Ref. p. 6] 1 Introduction 1 1 Introduction K. YAGI, G. MERCKLING, T.–U. KERN 1.1 General remarks To utilize energy resources efficiently and preserve the global environment, efforts are being made to raise the temperature at which high-temperature equipment is used at power and chemical plants. As a result, the conditions to which the structural components of these plants are exposed have become much more demanding. Structural components have been developed that endure these extreme conditions and some of them are now coming into use. It is therefore necessary to ensure the effective and safe use of these materials, to gain a full understanding of the characteristics of the new structural components, to evaluate their strengths, and to predict their life with greater accuracy. On the other hand, many of the world’s high-temperature plants were constructed as long ago as the 1970s and have deteriorated markedly with age. These aged plants are sometimes used under operating conditions different from those planned at the time of their construction. Therefore, the key issue is to be aware of the changes that take place in materials for structural components over time and to predict their remaining life with high accuracy. With regard to the prediction of the life of high temperature structural materials, the evaluation of their deterioration with time and the prediction of the remaining life of aged materials, it is essential to have a full knowledge of the characteristics of these materials and to be aware of the existence of material data that is a source of that knowledge. Creep characteristics are typical properties of high-temperature structural materials. Because the creep characteristics of structural materials in high-temperature plants are understood to be important in the design of boilers and pressure vessels, creep tests have been actively conducted since the 1930s [1, 2]. Creep data have been systematically obtained and published in the United States and European countries such as UK, Germany and Italy since the end of World War ll. Large-scale facilities and operating funds are required to obtain and register creep data, and in recent years it has become increasingly impractical for single organizations to be tasked with collecting systematic and long-term data. For this reason, it is increasingly important to share basic data and knowledge at the international level With the beginning of a new Landolt-Börnstein data collection series, the present data book was planned and compiled through the cooperation of European Creep Collaborative Committee (ECCC), German Creep Committee (GCC) and National Institute for Materials Science, Japan (NIMS). The purpose of the data book was to collate previously obtained creep data on major heat resistant steels and alloys as well as knowledge concerning creep characteristics. It could then serve as a basis for technological development to predict the life of structural materials, evaluate their deterioration with age and predict their technically usable life, as well as act as a resource for the design of safe structural components and safe maintenance of plants. More than four years were spent from planning to completion of this data book. However, this is a short period of time compared to the 10 years or more required to obtain service relevant creep data. The editors of this data book hope that it will help in the development of new technology as well as in the design and maintenance of safe power plants and comparable applications. 2 1 Introduction [Ref. p. 6 1.2 Status of creep database Research institutes, academic societies and private industries have collected and organized up to now creep data independently or through coordination as a group. Because of the need for special facilities and of constraints on funding and time, most long-term creep data have been collected on a national level or through programs run by academic societies. Typical data series published internationally are outlined below. 1.2.1 The ASTM data series The American Society for Testing and Materials (ASTM) published a collection of data on hightemperature strength as part of the Special Technical Publication (STP) series in the 1950s. Nearly 50 volumes have been published for the Data Series (DS) [3]. The features of this series are that the editors' analyses and the results of their evaluations are included in each volume. The description of data has not followed a prescribed format. 1.2.2 The BSCC high-temperature strength data series This is a data series compiled by the British Steelmakers Creep Committee (BSCC) in 1972, under the leadership of the British Steel Corporation [4]. The data series shows the results of high-temperature tensile testing and creep rupture testing on representative materials such as carbon steel, alloy steel and austenitic steel and follows a stipulated format. 1.2.3 The long-term data series by the Iron and Steel Institute of Germany The German Creep Committee with it’s secretary of Verein Deutscher Eisenhüttenleute (VDEh) compiled creep data on heat resistant steels in 1968 [5]. Data collection was made by a joint working group of steelmakers and equipment manufacturers. Data on carbon steel, low alloy steel, 12Cr steel and stainless steel are shown in a fixed format. Many years later, a data series on cast steels [6] and heat resistant alloys [7] were jointly published by Forschungsvereinigung Warmfeste Stähle (FWS) and Forschungsvereinigung Hochtemperaturwerkstoffe (FVHT) of VDEh and Forschungsvereinigung Verbrennungskraftmaschinen e.V. (FVV) in 1986 and 1987, respectively. 1.2.4 European Creep Collaborative Committee (ECCC) The ECCC was established to jointly acquire, collate and analyze creep data on metallic materials for high temperature plants in the European community in 1992. Actually 14 nations are members of the ECCC, including Germany, United Kingdom, Italy, France, Sweden, Denmark, Finland, Belgium, The Netherlands, Portugal, Austria, Switzerland, Czech Republic and Slovakia. The ECCC aims to harmonise and encourage European creep data generation, provide creep and creep rupture strength data as well as design relevant information to European standards, exchange information on material development, and develop rules for data generation, exchange and assessment [8]. Target materials are carbon steel and low alloy steel, 9-12% Cr steel, austenitic stainless steel, welded joints, bolts, and Ni base alloys. While Landolt-Börnstein New Series VIII/2B Ref. p. 6] 1 Introduction 3 experimental data have not been made public, the results assessed with proceduralised methods (e.g. BS PD 6605) and validated with the aid of innovative credibility checks [8] were presented to the public in 1999 [9]. Newer European standards, like EN 10028, EN 10216, EN 10222, contain creep strain and creep rupture strength data assessed by ECCC and derived from all over Europe, sometimes all over world collated experimental results. 1.2.5 Report on the mechanical properties of metals at elevated temperatures by the Iron and Steel Institute of Japan The High-temperature Research Committee (formerly called the Creep Committee) collected data and published five volumes of data series covering low alloy steel, stainless steel, carbon steel and cast iron, heat resistant alloys and welded joints [10]. 1.2.6 Creep data sheet published by NIMS (formerly called NRIM) In 1966, the National Institute for Materials Science (NIMS) launched a 100,000-hour creep rupture strength testing project on domestically produced high-temperature metallic materials. The results of these creep tests series were summarized in 49 kinds of NIMS (formerly called NRIM) creep data sheets and published in 122 volumes up to 2003 [11]. Although still in progress, the project is one of the largest in the world planned to obtain creep test data. A collection of microstructural photographs was also published, showing the microstructure of metal using long-term crept specimens obtained from this data sheet project [12]. 1.2.7 Others Academic societies have been producing data series limited to specific fields only. Those concerned with welded joints [13] and chemical equipment materials [14] have already been published. Creep data on products accumulated by industries have also been published as data series [15, 16]. 1.3 Testing procedures for obtaining creep data To obtain creep test data, a large-scale facility needs to be built. The tests are also time-consuming, making it impossible for one research organization alone to acquire all the required data. It is therefore important to conduct tests based on a shared method so that highly reliable test data can be obtained, exchanged and compared. To meet this need, different countries introduced standards for creep testing and creep rupture testing, and later their respective test standards were incorporated into ISO standards. Because of this background, the standards currently in use around the world are ISO [17], ASTM [18] of the United States and in the last years also the European standards EN [19]. The current ISO 204-1997 will be revised as a result of voting at ISO TC164-SC1. EN 10291:2000 [20] appears to have become the foundation for this amendment. In the revised plan, interrupted tests are allowed and specifications for temperature tolerance and accuracy in measurement of the cross-sectional area are modified. Landolt-Börnstein New Series VIII/2B 4 1 Introduction [Ref. p. 6 NIMS creep data have been produced not only in conformity with JIS but also with ISO and ASTM. With regard to temperature and load accuracies in particular, they are found to be better than the relevant standards, allowing the acquisition of data by performing high-accuracy creep tests [21]. During experiments that continue for more than 100,000 hours, there is a risk of exceeding the specified temperature range. In the NIMS creep data sheet, information on this problem is given for each data point. Temperature measurement during creep testing is generally made using a PR thermocouple, but PR thermocouples deteriorate during testing and the thermo-electromotive force declines. These results are published in the paper [22]. This type of information will be helpful in evaluating data and using it effectively. European creep data were produced according to several standards in the contributing Nations (DIN 50118, BS 3500, UNI 5111, etc.). A widespread overview on all European standards as well as on relevant laboratory intern testing practices formed the basement of the data generation recommendations stated in [19], which then further developed into EN 10291. European data collated in the ECCC programmes according to a specified recording scheme taking account of all testing details (see [19], Volume 4), were assessed for conformity with the minimum testing requirements as stated in Volume 3 of [19] before introduced in general assessment. New data, generated by the ECCC joint programmes, are mandatorily produced with testing procedures conformed to at least EN10291 or to the "high quality" testing recommendations in [19]. 1.4 Evaluation and assessment of creep data The determination of creep strength is a process which requires a high accuracy in the application of the pure testing technique as well as in the handling of the whole process, starting with the specimen manufacture and including the precision in the measurement of length changes during creep as well as the final strength computation. Therefore stringent procedures and specifications are necessary to both guarantee reliable test results and design relevant long-term creep and creep rupture strengths. The long term strength and creep behaviour of a material is dependent on several factors such as: • chemical composition, • way of manufacturing and heat treatment, and • component size and specimen location. The reliability of long-term properties of a particular material is fundamentally dependent on the material pedigree and raw test data verification, on the creep strength assessment method, its application procedure and on a critical evaluation of their credibility [23, 24, 25, 26]. The data assessment needs to rely on a sufficiently large data base, which must include a representative number of different casts of the same material grade and – possibly for a big amount of the casts – on several testing results with long durations in the intended application temperature range. Testing times should be sufficiently long to avoid extremely high extrapolations in time, and therefore the stress levels chosen for the specimens have to be well balanced to fulfil the statistical requirements. In Europe and Japan, the extrapolation rules allow time forecasts of three times the maximum testing time as this was originally suggested by the meanwhile withdrawn ISO 6303, e.g. for an extrapolation of a 100,000h (11.4 years) creep rupture strength, minimum data duration of 30,000h (3.4 years) is required in principle. If different casts of the same material grade are merged during the assessment, the evaluation with only statistical or mathematical tools does often not mirror the real material behaviour. The single cast trends and behaviour have also to be considered, and the assessment of the whole data population and of its sometimes huge scatter band needs to take this single cast information into account. Also the pedigree information for the single materials and of each cast of the same material grade needs to be carefully evaluated during the assessment in order to understand particular cast behaviour and to avoid erroneous conclusions based on numerous results belonging to casts with extraordinary surrounding properties. Landolt-Börnstein New Series VIII/2B Ref. p. 6] 1 Introduction 5 Europe developed in the last 10 years a quite rational and objective approach to creep data assessment, which bases on some fundamental statements: • Creep strength is considered reliable only if the available experimental data base conforms to given rules. They require a minimum amount of tested casts, a minimum number of tests per significant casts and a minimum number of tests with design relevant test durations in the range of temperatures and stresses expected to be technically relevant. • To assess creep strength, different methods for data evaluation are required to be applied contemporaneously to the same multi-cast, big sized and desirably long term test containing data base in order to ensure the true material behaviour from at least two distinct views. • A credibility check of the assessment results which were derived from test data is required before they are allowed to become strength values in order to ensure that failures and damages do not occur during the design life of the component, taking into account the scatter of properties in technical applications. This credibility check is codified in the ECCC Post Assessment Tests (PAT), which include three categories of physical, numerical and statistical tests, determining the degree of confidence in physical realism, test data description and extrapolation stability of the computed mathematical expression applying for becoming a creep strength prediction tool. Actually the majority of the creep strength data proposed for the new EN standards bases on this approach. In Japan, a Manual of Extrapolation Methods for Creep-rupture Strength Based on ISO 6303, in which Larson-Miller, Manson-Haferd and Manson-Brown parameter methods have been introduced as computer-aided extrapolation methods, was published on 1983 [26]. However, it is pointed out that longterm creep strength which is predicted using these current extrapolation methods is critically overestimated for advanced ferritic heat resistant steels. In order to improve long-term life prediction for 9-12Cr ferritic creep resistant steels, a new creep life prediction method is proposed in conjunction with a region partitioning method of stress vs. time to rupture diagrams [27]. The present book includes raw test data in the majority of the presentations. In some cases also computed strength values are included. The latter are determined by the mentioned rules. Additional statements on minimum data information requirements, testing techniques, minimum acceptability criteria and sound testing rules, data assessment procedures and post assessment tests are available in [23, 24, 28, 29]. 1.5 Application of creep data Design criteria under temperature conditions where creep properties have to be taken account of are determined by data on creep rupture strength, creep deformation rate, creep strain, etc. In ASME Sec. VIII-Div. 1, for example, allowable stress may be calculated from the minimum values obtained from the following: (1) 67% of the average value of 100,000-hour creep rupture strength (2) 80% of the minimum value of 100,000-hour creep rupture strength (3) 100% of the average value of stress that produces a creep rate of 0.01% per 1,000 hours In Europe and in Turbine and Power Plant industry generally, the recent trend has been to obtain allowable stress from 200,000-hour creep rupture strength. If a new material is used, creep testing is conducted to obtain its creep strength, from which an allowable stress can be defined. However, long-term creep strength is extrapolated using various methods for life prediction, since it is impossible to obtain data by conducting long-term creep testing under every condition. However, the prediction of creep strength is not simple and extrapolation from short-term creep data is not always reliable. The microstructure of metal changes during creep, and affects creep deformation and rupture life. Many life prediction methods have been proposed, but due to this problem Landolt-Börnstein New Series VIII/2B 6 1 Introduction none of them has been ideal. And even if so called Post Assessment Tests have been derived to establish a credibility criterion for data description and extrapolation functions, no mathematical relationship overcomes the need to obtain long-term creep data. Meanwhile, an additional challenge has appeared due to an increasing number of high-temperature plants which are still in use despite exceeding their design life, which cannot be replaced in short times or shut down. It has become an important task to some National Power Production Balances to keep these plants running by carefully evaluating the remaining life of these plants with a long history of use. In making this evaluation, an increased volume of abundant, more reliable and longer-term test data and microstructural information than those available at the time of plant design is essential. This data should include the changes in the microstructure of the metal during creep, the formation of creep damage and its growth, creep deformation, creep cracking behavior resulting from defects, the strength of welded joints, the effectiveness of multi-axiality on strength and failure, and creep rupture strength. 1.6 References [1] W. Cross: The Code, An authorized history of the ASME boiler and pressure vessel code, ASME, (1990), p.93 [2] H. Jungblut: Sonderstähle für den Dampfkesselbau. Mitt. VGB (1930), H.28, pp.141-146 [3] ASTM Data Series, example DS-11-S1 (1970); Carbon steel DS-47 (1971); Mo steel, Mn-Mo steel, Mn-Mo-Ni steel DS-50 (1970); 0.5Cr-0.5Mo steel, 1Cr-0.5Mo steel, 1.25Cr-0.5Mo-Si steel DS-6-S1 (1971); 2.25Cr-1Mo steel DS-5 8(1975); 3 to 9Cr steels DS-18 (1958); 12 to 27Cr steels DS-5-S1 (1965); Stainless steels DS-7-S1 (1968); Superalloys DS-20 (1960); Al alloys, Mg alloys [4] BSCC High Temperature Data, The Iron and Steel Institute, (1972) stahl-Eisen [5] Ergebnisse deutscher Zeitstandversuche langer Dauer, Verlag Stahl mbH, (1969) [6] Ergebnisse deutsche Zeitstandversuche langer Dauer an Stahlgusssorten nach DIN 17 245 - warmfester ferritischer Stahlguss -, Bericht FVW/FVV Nr.1-86, (1986) [7] Ergebnisse deutscher Zeitstandversuche langer Dauer an den hochwarmfesten Legierungen X 40 CoCrNi 20 20 (Typ S-590) und X 12 CrCoNi 21 20 (Typ N-155), Bericht FVHT/FVV Nr.2-87, (1987) [8] ECCC Recommendations 2001 “Creep Data Validation and Assessment Procedures”, Publ. ERA Technology Ltd., Leatherhead, UK, (2001) [9] ECCC Data Sheets, Publ. ERA Technology Ltd., Leatherhead, UK, (1999) [10] The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at Elevated Temperatures Vol. 1, Low ally steels (1972) Vol. 2, Stainless steels (1975) Vol. 3, Carbon steels and cast irons (1977) Vol. 4, Superalloys (1979) Vol. 5, Deposited metal, weld metal and welded joint (1985) [11] NIMS (former NRIM) Creep Data Sheets, No.0 to No.48, National Institute for Materials Science [12] National Research Institute for Metals: NRIM Creep Data Sheet, Metallographic Atlas of Long-term Crept Materials, No.M-1, (1999) [13] High Pressure Institute of Japan: High Temperature Strength Data Book of Welded Joint, (1967) Landolt-Börnstein New Series VIII/2B Ref. p. 6] 1 Introduction 7 [14] The Japan Petroleum Institute: High temperature creep rupture strength data of heat-resistant alloy and heat-resistant cast steel for oil refining and petrochemical equipment, (1979) [15] ESCHER WYSS: Zeitstandversuche an Staehlen, (1972) [16] Sumitomo Metal Industries, Ltd.: Creep Data Sheets, Sumitomo Seamless Tubes and Pipe, (1993) [17] ISO 204-1997, Metallic materials-Uninterrupted uniaxial creep testing in tension-Method of test [18] ASTM E 139-00, Standard Test Methods for Conducting Creep, Creep-Rupture, and Stress-Rupture Tests of Metallic Materials, Annual Book of ASTM Standards, Vol.03.01, (2001), pp.270-281 [19] ECCC Recommendations 2001 “Creep Data Validation and Assessment Procedures”, Publ. ERA Technology Ltd., Leatherhead, UK,, (2001) [20] EN 10291:2000, Metallic materials-Uniaxial creep testing in tension-Methods of test [21] National Research Institute for Metals: NRIM Materials Strength Data Sheet Technical Document, No.10, “Testing Plan and Testing Procedures or NRIM Creep Data Sheet Project’’, (1996) [22] H. Itoh, M. Egashira, H. Miyazaki, Y. Monma and S. Yokoi: Tetsu-to-Hagane, 72 (1986), 1944 [23] ECCC Recommendations 2001, Volume 3, ‘Recommendations for data acceptability criteria and the generation of creep, creep rupture, stress rupture and stress relaxation data’, Eds. Granacher J.,Holdsworth S.R., Klenk. A., Buchmayr B. & Gariboldi E., Publ. ERA Technology Ltd., Leatherhead, UK, (a) Part I: Generic recommendations for creep, creep rupture, stress rupture and stress relaxation data, (b) Part II: Creep data for welds, (c) Part III: Creep testing of PE- (ex service) materials. [24] ECCC Recommendations, 2001, Volume 5 ‘Guidance for the assessment of creep rupture, creep strain and stress relaxation data’, Eds. Holdsworth S.R. & Merckling G., Publ. ERA Technology Ltd, Leatherhead, UK, (a) Part I: Full-size datasets, (b) Part IIa: Sub-size datasets, (c) Part IIb: Weldment datasets, (d) Part III: Datasets for PE (ex-service) materials [25] Yokoi, S., Monma, Y.: Prediction of Long-time Creep-rupture Strength for High-temperature Materials; Tetsu-to-Hagane 65, No.7 (1979) 831 [26] Fujita, T., Monma, Y.: Accuracy of Extrapolation for Creep-rupture Strength and Standardization of Extrapolation Methods; Tetsu-to-Hagane, 70, No.3 (1984) 327 [27] Kimura, K., Kushima, H., Abe, F.: Improvement of Creep Life Prediction of High Cr Ferritic Creep Resistant Steels by Region Partitioning Method of Stress vs. Time to Rupture Diagram; J. Soc. Mat. Sci., Japan, 52, No.1 (2003) 57 [28] Holdsworth, S.R., Orr, J., Granacher, J., Merckling, G., Bullogh, C.K. on behalf of the ECCC-WG1 “Creep Data Collation and Assessment”: European Creep Collaborative Committee Activities on Creep Data Generation and Assessment Methodologies, in : D. Coutsouradis et. al. (editors): “Materials for Advanced Power Engineering”, 1994, Liege, 3.- 6.10.1994, Kluwer Accademic Publishers, p. 591 - 600 [29] National Research Institute for Metals : “Testing Plan and Testing Procedures for NRIM Creep Data Sheets Project”, NRIM Material Strength Data Sheet, Technical Document, No.10, (1996) Landolt-Börnstein New Series VIII/2B 2 Creep and rupture data of heat resistant steels - 2.1 Carbon steels 9 2 Creep and rupture data of heat resistant steels 2.1 Carbon steels 2.1.1 0.1C steel 2.1.1.1 Introduction This carbon steel for boiler and heat exchanger tubes is used as water tube, smoke tube, super-heater tube, air-preheater tube, etc. in boiler and as heat exchanger tube, condenser tube, catalyst tube, etc. in chemical and petrolic industries. The carbon steels are used only at temperatures lower than 400 °C, because they have not enough creep strength for higher temperatures. 2.1.1.2 Material standards, chemical and tensile requirements Table 1. Chemical requirements of 0.1C steel tubes; JIS STB340, ASTM A, BS360 and DIN St35.8 Standards Designation JIS ASTM BS DIN STB340 A 360 St35.8 C ≤0.18 0.06-0.18 ≤0.17 ≤0.17 Chemical composition [wt%] Si Mn P 0.30-0.60 ≤0.035 ≤0.35 0.27-0.63 ≤0.035 0.10-0.35 0.40-0.80 ≤0.035 0.10-0.35 0.40-0.80 ≤0.040 S ≤0.035 ≤0.035 ≤0.035 ≤0.040 Table 2. Tensile properties of 0.1C steel tubes at room temperature; JIS STB340 Tensile strength Yield strength Elongation [N/mm2] [N/mm2] [%] d ≥20 mm 20>d ≥10 mm d<10 mm ≥340 ≥175 ≥35 ≥30 ≥27 Landolt-Börnstein New Series VIII/2B Std.No. G3461 A178 3059-2 17175 10 2.1 Carbon steels 2.1.1.3 Creep properties of 0.1C steel tubes Information of fact on creep data for 0.1C steels can be obtained from [1], [2] and [3]. STB340 (0.12C steel) 500 400 300 200 100 80 400℃ 60 50 40 30 450℃ 500℃ 550℃ 100 101 Fig. 1. Creep rupture strength data of STB340; [1]. 102 103 104 105 Time to rupture (h) 2.1.1.4 References [1] The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at Elevated Temperatures, Vol. III Carbon Steels and Cast Irons, (1977), 195-232. [2] American Society for Testing Materials: Elevated-Temperature Properties of Carbon Steels, ASTM Special Technical Publication No. 180, (1955), 11-23. [3] The Iron and Steel Institute: BSCC High Temperature Data, (1972), 1-254. Landolt-Börnstein New Series VIII/2B Ref. p. 19] 2.1.2 0.2C-0.3C steel 11 2.1.2 0.2-0.3C steel 2.1.2.1 Introduction 0.2-0.3C steels are used as tubes for heat exchangers, boilers, superheaters and feedwater heaters in power plants, chemical and petrochemical plants. 0.2-0.3C steel plates are used for boilers and pressure vessels in power plants, chemical and petrochemical plants. Creep strength of the 0.2-0.3C steel is strongly influenced by small amounts of molybdenum through the strengthening effects of Mo-C and Mo-N atomic pairs in solid solution, as will be explained later. 2.1.2.2 Material standards, chemical and tensile requirements 2.1.2.2.1 0.2-0.3C steel tubes for heat exchangers Table 3. Chemical requirements of 0.2-0.3C steel tubes; JIS STB410, Japanese METI KA STB480, ASTM Gr. C, ASTM Gr. A-1 and ASTM Gr. C2 Chemical composition [wt%] Standards Designation Std. No C Si Mn P S JIS STB410 0.30-0.80 G3461 ≤0.32 ≤0.35 ≤0.035 ≤0.035 Japanese KA STB480 ≤0.30 0.29-1.06 ≥0.10 ≤0.048 ≤0.058 METI ASTM Gr. C A178 ≤0.35 ≤0.80 ≤0.035 ≤0.035 ASTM Gr. A-1 A210 ≤0.27 ≥0.10 ≤0.93 ≤0.035 ≤0.035 ASTM Gr. C 0.29-1.06 A210 ≤0.35 ≥0.10 ≤0.035 ≤0.035 ASTM Gr. C2 0.29-1.06 A556 ≤0.30 ≥0.10 ≤0.035 ≤0.035 2.1.2.3 0.2 - 0.3C steel plates for boilers and pressure vessels Table 4. Chemical requirements of 0.2-0.3C steel plates; JIS SB410, JIS SB480, JIS SGV410 Chemical composition [wt%] Standards Designation Thickness C Si Mn P S Mo [mm] ≤25 ≤0.24 JIS SB410 25 - 50 ≤0.035 ≤0.040 ≤0.27 0.15 - 0.30 ≤0.90 50 - 200 ≤0.30 ≤25 ≤0.31 JIS SB480 25 - 50 ≤0.035 ≤0.040 ≤0.33 0.15 - 0.30 ≤0.90 50 - 200 ≤0.35 ≤12.5 ≤0.21 12.5 - 50 ≤0.23 JIS SGV410 0.15 - 0.40 0.85 - 1.20 ≤0.030 ≤0.030 50 - 100 ≤0.25 100 - 200 ≤0.27 Landolt-Börnstein New Series VIII/2B Std. No G3103 G3103 G3118 12 2.1 Carbon steels Table 5. Chemical requirements of 0.2-0.3C steel plates; ASTM Gr. B, ASTM Gr. 60 and ASTM Gr. 70 Chemical composition [wt%] DesigStd. No Standards Thickness nation C Si Mn P S Mo [mm] ≤25 ≤0.20 25 - 50 0.45 ≤0.23 A204 0.15 - 0.40 ≤0.90 ASTM Gr. B ≤0.035 ≤0.035 0.60 50 - 100 ≤0.25 >100 ≤0.27 ≤25 ≤0.24 25 - 50 ≤0.27 ASTM Gr. 60 A515 50 - 100 ≤0.035 ≤0.035 ≤0.29 0.15 - 0.40 ≤0.90 100 - 200 ≤0.31 >200 ≤0.31 ≤25 ≤0.31 25 - 50 ≤0.33 ASTM Gr. 70 A515 50 - 100 ≤0.035 ≤0.035 ≤0.35 0.15 - 0.40 ≤1.20 100 - 200 ≤0.35 >200 ≤0.35 0.60 - 0.90 ≤12.5 ≤0.21 12.5 - 50 ≤0.23 50 - 100 A516 ASTM Gr. 60 ≤0.035 ≤0.035 ≤0.25 0.15 - 0.40 0.85 - 1.20 100-200 ≤0.27 >200 ≤0.27 ≤12.5 ≤0.27 12.5-50 ≤0.28 50-100 A516 ASTM Gr. 70 ≤0.30 0.15 - 0.40 0.85 - 1.20 ≤0.035 ≤0.035 100-200 ≤0.31 >200 ≤0.31 2.1.2.3 Creep properties of 0.2-0.3C steel tubes Information of fact on creep data for 0.2-0.3C steel tubes can be obtained from [1]. 2.1.2.3.1 Creep rupture data of 0.2-0.3C steel tubes The results of creep tests for 9 heats of JIS STB410 steel tubes are compiled in [1]. From this data sheet the data of rupture elongation, reduction of area and microstructures of as-received materials and crept specimens can be also obtained. Creep rupture strength data for 9 heats of 0.2C steel tubes (JIS STB410) is shown in Fig. 2 [1]. Very large heat-to-heat variation of creep rupture strength is observed over the whole range of creep test conditions from short-term to long-term. Differences in creep rupture strength are caused by differences in small amounts of molybdenum [2, 3]. Creep strength of the 0.2C steel is strongly influenced by small amounts of molybdenum through the strengthening effects of Mo-C and Mo-N atomic pairs in solid solution [4]. Landolt-Börnstein New Series VIII/2B Ref. p. 19] 2.1.2 0.2C-0.3C steel 13 500 Stress (MPa) 300 o 100 ○ 400 C 80 △ 450 C o o 60 □ 500 C n = 207 40 1 10 10 2 3 10 4 10 5 10 10 6 Fig. 2. Creep rupture strength data of 0.2C steel tubes (JIS STB410) according to [1]. n indicates the total number of data points. Time to rupture (h) 2.1.2.3.2 Creep rupture strength of 0.2-0.3C steel tubes Creep rupture strength was analyzed applying the Larson-Miller parameter method to NRIM creep rupture data on 0.2C steel tubes (JIS STB 410). The result is shown in Fig. 3. Sigmoidal inflection with a large scatter band is observed. 600 500 400 °C 450 °C 500 °C 400 Stress [MPa] 300 200 100 80 60 50 40 10 Average n = 207 Fig. 3. Master rupture curve obtained by Larson-Miller parameter method for 0.2C steel tubes (JIS STB 410); [1]. n indicates the total number of data points. 12 14 16 18 Larson-Miller-parameter TK [( log tR +15.753) [103 ] 2.1.2.3.3 Microstructural changes The typical initial microstructure of 0.2C steel tubes consists of ferritic and pearlitic grains. Optical micrographs of an as-received 0.2C steel tube are shown in Fig. 4. The bright grains are ferritic and the dark grains are pearlitic. Optical micrographs of 0.2C steel tube specimens creep ruptured after 138,403.7 h at 450 °C and 78 MPa are shown in Fig. 5. Coarsening of carbides within pearlitic grains is observed after long-term creep exposure at 450 °C. Changes in morphology and distribution of carbides within pearlitic grains are used as indicator of degradation of 0.2C steel due to long-term service at elevated temperatures. Landolt-Börnstein New Series VIII/2B 14 2.1 Carbon steels Fig. 4. Optical micrographs of as-received 0.2C steel tubes (etched in 4% nital); [1]. Fig. 5. Optical micrographs of 0.2C steel tube specimens (etched in picral) creep ruptured after 138,403.7 h at 450 °C and 78 MPa; [1]. 2.1.2.3.4 Creep deformation behavior of 0.2C steel tubes The creep deformation behavior of 0.2C steel tubes strongly depends on slight differences in chemical composition, heat treatment and initial microstructure. Creep rate vs. time curves of 0.2C steel tubes at 550 °C and 69 MPa are shown in Fig. 6 [5]. Heat-to-heat variation of creep deformation behavior is clearly observed on these 3 heats of 0.2C steel tubes. Creep rate vs. time curves of as-received and pre-aged 0.2C steel tubes at 550 °C and 69 MPa are shown in Fig. 7 [6]. Since creep deformation is strongly influenced by microstructural changes during creep exposure, complex creep deformation behavior observed for un-aged steel disappeares by preageing. Landolt-Börnstein New Series VIII/2B Ref. p. 19] 2.1.2 0.2C-0.3C steel 15 -2 -2 10 10 550oC-69MPa 550oC-69MPa -3 10 CAM -4 10 Creep rate (h-1) Creep rate (h-1) -3 CAH CAC -5 10 -4 10 ○ un-aged ● 100h aged △ 200h aged ▲ 300h aged □ 500h aged ■ 1,000h aged -5 10 -6 -6 10 10 -1 10 10 0 1 10 10 2 10 3 4 10 10 -1 10 Time (h) Fig. 6. Creep rate vs. time curves of 0.2C steel tubes at 550 °C and 69 MPa; [5]. 10 0 1 10 10 2 3 10 10 4 Time (h) Fig. 7. Effect of pre-ageing on creep deformation behavior of 0.2C steel tube; [6]. 2.1.2.3.5 Effect of molybdenum on creep rupture strength The creep deformation behavior of 0.2C steel tubes is strongly influenced by microstructural changes during creep exposure at elevated temperatures, as mentioned above. Creep strength decreases as a result of microsstructural changes and it becomes an inherent creep strength, which is the creep strength of the ferrite matrix itself, after long-term creep exposure [7, 8]. The inherent creep strength of 0.2C steel tubes is extremely improved by small amounts of molybdenum in solid solution [2, 3]. The very large heat-to-heat variation of long-term creep rupture strength for 0.2C steel tubes, as shown in Figs. 2 and 3, is caused by differences in the inherent creep strength due to a wide variety of molybdenum concentrations, even at low Mo levels of less than 0.02 mass%. Inherent creep strength of 0.2C steel tubes is increased by strengthening effects of Mo-C and Mn-C atomic pairs in solid solution [4]. Inherent creep strength is improved by small amounts of molybdenum, however, this effect is saturated at about 0.03 mass% of molybdenum [2, 3]. Therefore, the inherent creep strength obtained by addition of 0.03 mass% of molybdenum is the highest for 0.2C steel. It has been experimentally found that the inherent creep strength of ferritic creep resistant steels is almost the same independent of chemical composition, heat treatment condition and short-term creep strength [7, 8]. There is a good correspondence between common inherent creep strength for ferritic creep resistant steels and the highest inherent creep strength for 0.2C steel with addition of 0.03 mass% of molybdenum [2, 3]. 2.1.2.3.6 Estimated long-term creep strength The temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 9 heats of 0.2C steel tubes is shown in Fig. 8. The creep rupture strength curves shown in Fig. 8 were obtained by regression analysis using the Larson-Miller parameter. Landolt-Börnstein New Series VIII/2B 16 2.1 Carbon steels 800 600 500 400 Stress [MPa] 300 1000 h { Tensile strength 200 Fig. 8. Temperature depen-dence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 0.2C steel tubes (JIS STB 410); [1]. The dashed lines are the upper and lower 95 % confidence limit (±2σ, σ: standard deviation). 0.2% proof stress 100 80 60 50 40 350 100000 h 400 450 500 Temperature [°C] 550 600 2.1.2.4 Creep properties of 0.2-0.3C steel plates Information of fact on creep data for 0.2-0.3C steel plates can be obtained from [9]. 2.1.2.4.1 Creep rupture data of 0.2-0.3C steel plates The results of creep tests for 8 heats of JIS SB480 steel plates are compiled [9]. From this data sheet data of rupture elongation, reduction of area, minimum creep rate, time to specified strain and microstructures of as-received materials and crept specimens can be also obtained. Creep rupture strength data for 8 heats of 0.3C steel plates (JIS SB480) is shown in Fig. 9. Very large heat-to-heat variation of creep rupture strength is observed, especially in the lower temperature and higher stress condition. With increase in temperature and decrease in applied stress, heat-to-heat variation of creep rupture strength decreases. 500 Stress (MPa) 400 300 200 o ○ 400 C o △ 450 C 100 o 90 □ 500 C 80 n=117 70 60 0 1 10 10 Fig. 9. Creep rupture strength data of 0.3C steel plates (JIS SB480); [9]. n indicates the total number of data points. 2 10 3 10 4 10 10 5 10 6 Time to ruputre (h) Landolt-Börnstein New Series VIII/2B Ref. p. 19] 2.1.2 0.2C-0.3C steel 17 2.1.2.4.2 Creep rupture strength of 0.2-0.3C steel plates Creep rupture strength was analyzed applying the Orr-Sherby-Dorn parameter method to NRIM creep rupture data on 0.3C steel plates (JIS SB 480). The result is shown in Fig. 10. A very large scatter band of creep rupture strength is observed, especially in the higher stress condition. 1000 800 Stress [MPa] 600 500 400 300 400 °C 425 °C 450 °C 475 °C 500 °C 525 °C 550 °C 575 °C 200 100 80 Average n = 131 60 50 -19 -17 -13 -11 -9 -15 Orr-Sherby-Dorn parameter log tR -[247364/(19.1425 × TK )] Fig. 10. Master rupture curve by Orr-Sherby-Dorn parameter method for 0.3C steel plates (JIS SB 480); [9]. n indicates the total number of data points. 2.1.2.4.3 Microstructural changes The typical initial microstructure of 0.3C steel plates consists of ferritic and pearlitic grains. Optical micrographs of as-received 0.3C steel plates are shown in Fig. 11. The bright grains are ferritic and the dark ones are pearlitic. Optical micrographs of 0.3C steel plate specimens creep ruptured at 400, 450 and 500 °C are shown in Fig. 12, 13 and 14, respectively. Coarsening of carbides within pearlitic grains is observed after long-term creep exposure. By comparing the microstructures shown in Fig. 12, 13 and 14, carbide coarsening is more significantly observed in the specimens crept at higher testing temperatures. Fig. 11. Optical micrographs of as-received 0.3C steel plate (etched in 2 % nital); [9]. Landolt-Börnstein New Series VIII/2B 18 2.1 Carbon steels Fig. 12. Optical micrographs of a 0.3C steel plate specimen creep ruptured after 155,727.0 h at 400 °C and 333 MPa (etched in 2 % nital); [9]. Fig. 13. Optical micrographs of a 0.3C steel plate specimen creep ruptured after 122,103.2 h at 450 °C and 196 MPa (etched in 2 % nital); [9]. Fig. 14. Optical micrographs of a 0.3C steel plate specimen creep ruptured after 85,699.2 h at 500 °C and 88 MPa (etched in 2 % nital); [9]. Landolt-Börnstein New Series VIII/2B Ref. p. 19] 2.1.2 0.2C-0.3C steel 19 2.1.2.4.4 Estimated long-term creep strength The temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 8 heats of 0.3C steel plates is shown in Fig. 15 [9]. Creep rupture strength curves shown in Fig. 15 were obtained by regression analysis using the Orr-Sherby-Dorn parameter. 1000 800 60 50 350 400 1000 h { 100 80 { 200 100000 h 450 500 Temperature [°C] Tensile strength { 300 { Stress [MPa] 600 500 400 0.2% proof stress 550 600 Fig. 15. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 0.3C steel plates (JIS SB 480); [9]. 2.1.2.5 References [1] NRIM Creep Data Sheet, No. 7B, (1992). [2] Kimura, K., Kushima, H., Yagi, K., and Tanaka, C.: Proc. of JIMIS-7 on Aspects of High Temperature Deformation and Fracture in Crystalline Materials, Hosoi, Y., et al., eds., Nagoya, Japan, July 1993, The Japan Inst. Metals, (1993), 309-316. [3] Kimura, K., Kushima, H., Yagi, K., and Tanaka, C.: Tetsu-to-Hagane, 81, (1995), 757-762. [4] Onodera, H., Abe, T., Ohnuma, M., Kimura, K., Fujita, M., and Tanaka, C.: Tetsu-to-Hagane, 81, (1995), 821-826. [5] Kimura, K., Kushima, H., and Yagi, K.: Proc. of 10th Int. Conf. on the Strength of Materials, Oikawa, H., et al., eds., Sendai, Japan, August 1994, The Japan Inst. Metals, (1994), 645-648. [6] Kimura, K., Kushima, H., Abe, F., and Yagi, K.: Tetsu-to-Hagane, 82, (1996), 713-718. [7] Kimura, K., Kushima, H., Yagi, K., and Tanaka, C.: Tetsu-to-Hagane, 77, (1991), 667-674. [8] Kimura, K., Kushima, H., Yagi, K., and Tanaka, C.: Proc. of Inter. Conf. on Creep and Fracture of Engineering Materials and Structures, Wilshire, B., and Evans, R.W., eds., Swansea, UK, The Institute of Materials, 5, (1993), 555-564. [9] NRIM Creep Data Sheet, No. 17B, (1994). Landolt-Börnstein New Series VIII/2B 20 2.1 Carbon steels 2.1.3 C-Mn steel 2.1.3.1 Introduction C-Mn steels are used as tubes for boilers and heat exchangers in power plants, chemical and petrochemical plants. C-Mn steels shall be killed. C-Mn steel tubes are heat treated at a temperature of 900 °C or higher and followed by cooling in air. 2.1.3.2 Materials standards, and chemical and tensile requirements 2.1.3.2.1 C-Mn steel tubes for heat exchangers Table 6. Chemical requirements of C-Mn steel tubes; JIS STB 510, ASTM Gr. D. Chemical composition [wt%] Standards Designation C Si Mn P S JIS STB510 1.00~1.50 ≤0.25 ≥0.35 ≤0.035 ≤0.035 ASTM Gr. D 1.00~1.50 ≤0.27 ≥0.10 ≤0.030 ≤0.015 Std. No G3461 A178 2.1.3.3 Creep properties of C-Mn steel tubes Information on creep data for C-Mn steel tubes can be obtained from [1]. 2.1.3.3.1 Creep rupture data of C-Mn steel plates The results of creep tests for 2 heats of JIS STB510 steel tubes are compiled in [1]. From this data sheet the data of 0.2% proof stress, tensile strength, rupture elongation, reduction of area and microstructures of as-received materials and crept specimens can be also obtained. Creep rupture strength data of 2 heats of the 0.2C-1.3Mn silicon killed steel tubes (JIS STB510) is shown in Fig. 16 [1]. The slope of the stress vs. time to rupture curve at 400 °C increases with decrease in applied stress. The creep rupture curve at 450 °C indicates a slight inflection of sigmoidal shape. On the other hand, good linear relationship between stress and time to rupture is observed at 500 °C. 700 Stress (MPa) 500 300 ○ 400oC △ 450oC □ 500oC 100 80 60 0 10 n = 32 10 1 2 10 10 3 4 10 10 5 Fig. 16. Creep rupture strength data of 0.2C-1.3Mn silicon killed steel tubes (JIS STB510); [1]. n indicates the total number of data points. Time to rupture (h) Landolt-Börnstein New Series VIII/2B Ref. p. 22] 2.1.3 C-Mn steel 21 2.1.3.3.2 Microstructural change Initial microstructure of 0.2C-1.3Mn silicon killed steel tubes consists of ferritic and pearlitic grains. Optical micrographs in the as-received condition of 0.2C-1.3Mn silicon killed steel tubes are shown in Fig. 17. The bright grains are ferritic and the dark ones are pearlitic. Optical micrographs of the crept steel tubes are shown in Fig. 18. Pearlitic microstructure is broken due to carbide coarsening during creep exposure at elevated temperatures. Fig. 17. Optical micrographs of as-received 0.2C-1.3Mn silicon-killed steel tubes (etched in a solution of ethyl alcohol with 2 % picric acid ); [1]. Fig. 18. Optical micrographs of 0.2C-1.3Mn silicon-killed steel tubes creep ruptured after 30,530.3 h at 500 °C and 70 MPa (etched in a solution of ethyl alcohol with 2 % picric acid); [1]. 2.1.3.3.3 Estimated long-term creep strength The temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 9 heats of 0.2C-1.3Mn steel tubes is shown in Fig. 19 [1]. That of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for the same materials is shown in Fig. 20 [1]. Creep rupture strength curves shown in Fig. 19 and Fig. 20 were obtained by regression analysis using the Orr-Sherby-Dorn parameter. Landolt-Börnstein New Series VIII/2B 22 2.1 Carbon steels 1000 800 Stress [MPa] 100 h 200 100 80 60 50 40 350 Tensile strength { 300 { 600 500 400 0.2% proof stress 10000 h 400 450 500 Temperature [°C] 550 600 Fig. 19. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 0.2C-1.3Mn silicon killed steel tubes; [1]. The dashed lines are the upper and lower 95 % confidence limit (±2σ, σ: standard deviation). 1000 800 300 { Tensile strength 200 { Stress [MPa] 600 500 400 0.2% proof stress 1000 h 100 80 60 50 40 350 30000 h 400 450 500 Temperature [°C] 550 600 Fig. 20. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 0.2C1.3Mn silicon killed steel tubes; [1]. 2.1.3.4 Reference [1] NRIM Creep Data Sheet, No.40A, (2000). Landolt-Börnstein New Series VIII/2B Ref. p. 25] 2.1.4 0.25C cast 23 2.1.4 0.25C cast 2.1.4.1 Introduction The 0.25C cast material is a traditional unalloyed creep resistant cast steel. The grade is specified as GP240GH in EN 10213-2, material-no 1.0619. Typical features of the 0.25C cast material necessary to consider are summarized below: • • • • • • Melting processes: Electric arc, induction melting Heat treatment: Normalized, or quenched and tempered (cooling in furnace) Typical microstructure: Ferrite and pearlite Weldability: Easily weldable with similar weld metal High temperature applications: Casings of steam turbines, service temperatures up to about 450 °C Cast steel grade with similar chemical composition: ASTM A216 Grade WCA 2.1.4.2 Standard requirements Table 7. Chemical composition Standard Designation C Si Chemical composition [wt%] Mn P S EN 0213GP240GH 0.18 - 0.25 ≤0.60 ≤1.20 ≤0.030 ≤0.020(1) 2:1995 (1.0619) (1) The maximum admissible sulphur content is 0.030 % if the relevant wall thickness is not in excess of 28 mm. Table 8. Heat treatment and tensile properties at room temperature Min. 0.2 % Thickness proof strength Standard Designation Heat treatment [mm] [MPa] N:900 °C-980 °C EN10213GP240GH 240 Q:890 °C-980 °C 100 2:1995 (1.0619) T:600 °C-700 °C N: Normalized, Q: Quenched, T: Tempered Rp0.2 Min. elongation at rupture [%] 420-600 22 Rm min EN 600 400 500 300 Rm (MPa) Rp0,2 (MPa) Tensile strength [MPa] 200 100 400 300 200 100 0 0 0 100 200 300 Temperature (°C) 400 500 0 100 200 300 400 500 Temperature (°C) Fig. 21. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade GP240GH tested in creep rupture tests by the German Creep Committee; [1]. min EN: minimum values by EN 10213-2. Landolt-Börnstein New Series VIII/2B 24 2.1 Carbon steels Stress (MPa) 1000 broken 100 unbroken 400°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 22. Creep rupture strength data of cast steel grade GP240GH at 400 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 450°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 23. Creep rupture strength data of cast steel grade GP240GH at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 500°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 24. Creep rupture strength data of cast steel grade GP240GH at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B Ref. p. 25] 2.1.4 0.25C cast 25 2.1.4.3 Average creep rupture strength Table 9. Average creep rupture strength values indicated in EN 10213-2:1995 Average creep rupture strength [MPa] Temperature Time to rupture [°C] 10,000 h 100,000 h 200,000 h 400 205 160 145 450 132 83 71 500 74 40 32 2.1.4.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade GP240GH, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B 26 2.1 Carbon steels 2.1.5 C-Mn cast 2.1.5.1 Introduction For steel grade GP280GH (EN 10213-2, material-no 1.0625) C-Mn cast, a manganese content of 0.80 to 1.20 % is specified in EN 10213-2:1995. The manganese content may be increased if the specified maximum carbon content is reduced by 0.01 % for each 0.04 % Mn in excess of 1.20 % up to a maximum manganese content of 1.40 %. The increased manganese content promotes the creep rupture properties. Since 1989 the German Creep Committee has performed a number of qualification tests on quenched and tempered test materials of casts with 1.20 to 1.40 % Mn. The results of these tests are reported in this chapter. As expected the average creep rupture strength values of the casts are much higher than those indicated in EN 102132:1995 for steel grade GP280GH with a standard manganese content of 0.80 to 1.20 %. Typical features of GP280GH are summarized below: • • • • • Melting process: Electric arc, basic oxygen, argon oxygen decarburization, induction melting Heat treatment: Normalized, or quenched in air or water and tempered Typical microstructure: Ferrite and tempered bainite Weldability: Excellent weldability; weld metal of type E Mo should be used to obtain sufficient creep rupture strength of weldments High temperature applications: Casings of compressors (especially with very cold inlet and hot outlet), gas turbines, outer casings of steam turbines, valves, fittings; service temperatures up to 450 °C 2.1.5.2 Standard requirements Table 10. Chemical composition Standard Designation C Si Chemical composition [wt %] Mn P S EN 10213- GP280GH (1) (1) 0.80 - 1.20 0.18 - 0.25 ≤0.60 ≤0.030 ≤0.020(2) 2:1995 (1.0625) (1) The maximum admissible manganese content may be exceeded up to 1.40% if the maximum admissible carbon content is reduced by 0.01% per each 0.04% Mn in excess of 1.20%. (2) The maximum admissible sulphur content is 0.030% if the relevant wall thickness is not in excess of 28 mm. Table 11. Heat treatment and tensile properties at room temperature Min. 0.2 % Thickness proof strength Standard Designation Heat treatment [mm] [MPa] N:900°C-980°C EN 10213- GP280GH 280 Q:890°C-980°C 100 2:1995 (1.0625) T:600°C-700°C N: Normalized, Q: Quenched, T: Tempered Tensile strength [MPa] Min. elongation at rupture [%] 480-640 22 Landolt-Börnstein New Series VIII/2B Ref. p. 28] 2.1.5 C-Mn cast Rp0.2 min EN Rm 500 800 Rm (MPa) (MPa) 400 ,2 300 Rp 27 200 100 0 600 400 200 0 0 100 200 300 400 500 0 Temperature (°C) 100 200 300 400 500 600 Temperature (°C) Fig. 25. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade GP280GH tested in creep rupture tests by the German Creep Committee; [1]. min EN: minimum values by EN10213-2. Stress (MPa) 1000 broken unbroken 400°C_EN 100 100 1000 10000 100000 Test duration (h) Fig. 26. Creep rupture strength data of cast steel grade GP280GH at 400 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 450°C_EN 10 100 1000 10000 100000 Test duration (h) Fig. 27. Creep rupture strength data of cast steel grade GP280GH at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B 28 2.1 Carbon steels Stress (MPa) 1000 broken 100 unbroken 500°C_EN 10 100 1000 10000 100000 Test duration (h) Fig. 28. Creep rupture strength data of cast steel grade GP280GH at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. 2.1.5.3 Average creep rupture strength Table 12. Average creep rupture strength values indicated in EN 10213-2:1995 Average creep rupture strength [MPa] Temperature Time to rupture [°C] 10,000 h 100,000 h 200,000 h 400 210 165 450 135 85 500 75 42 2.1.5.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade GP280GH, compilation of test re-sults; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B Ref. p. 34] 2.2.1 0.5Mo steel 29 2.2 Low alloy steels 2.2.1 0.5Mo steel 2.2.1.1 Introduction 0.5Mo steels are applied for heat exchangers and piping systems in thermal power plants and are supplied for the plate members of pressure vessels. Mo, 0.5% of mass of the steel, increases creep rupture strength by both solid solution strengthening and carbide precipitation strengthening. Normalizing and tempering heat treatment processes produce ferrite and pearlite phase mixture in the microstructure of 0.5Mo steels. 2.2.1.2 Material standards, chemical and tensile requirements 2.2.1.2.1 0.5Mo steel tubes for heat exchangers of boiler application Table 13. Chemical requirements of 0.5Mo steel tubes; JIS STBA12 [1], ASTM A209 T1 T1 [3] Chemical composition [wt%] Standards Designation C Si Mn P S Mo 0.10 0.10 0.30 0.45 ≤ ≤ JIS STBA12 0.20 0.50 0.80 0.65 0.035 0.035 0.10 0.10 0.30 0.44 ≤ ≤ T1 0.20 0.50 0.80 0.65 0.025 0.025 ASTM 0.10 0.10 0.30 0.44 ≤ ≤ T1 0.20 0.50 0.80 0.65 0.025 0.025 [2] and A250 Std. No. G3462 A209 A250 2.2.1.2.2 0.5Mo steel pipes for steam conductors of boiler piping applications Table 14. Chemical requirements of 0.5Mo steel pipes; JIS STPA12 [1] and ASTM A335 P1 [4] Chemical composition [wt%] Standards Designation Std. No. C Si Mn P S Mo 0.10 0.10 0.30 0.45 ≤ ≤ JIS STPA12 G3458 0.20 0.50 0.80 0.65 0.035 0.035 0.44 0.10 0.10 0.30 ≤ ≤ A335 ASTM P1 0.65 0.20 0.50 0.80 0.025 0.025 Landolt-Börnstein New Series VIII/2B 30 2.2 Low alloy steels 2.2.1.2.3 0.5Mo steel plates for boiler and pressure vessel applications Table 15. Chemical requirements of 0.5Mo steel plates; JIS SB450M [1] and ASTM A204M Grade A [5] Chemical composition [wt%] Thickness t Standards Designation Std. No. [mm] C Si Mn P S Mo ≤0.18 ≤25 ≤0.21 0.15 - ≤ 25< t ≤50 0.45 ≤ ≤ JIS SB450M G3103 0.30 0.60 0.90 0.035 0.040 ≤0.23 50< t ≤100 ≤0.25 100< t ≤150 ≤0.18 ≤25 ≤0.21 0.15 - ≤ 0.45 - 25< t ≤50 ≤ ≤ ASTM Grade A A204M 0.40 0.60 0.90 0.035 0.030 ≤0.23 50< t ≤100 100< t ≤0.25 Table 16. Chemical requirements of 0.5Mo steel plates; JIS SB480M [1] and ASTM A204M Grade B [5] Chemical composition [wt%] Thickness t Standards Designation Std. No. [mm] C Si Mn P S Mo ≤0.20 ≤25 ≤0.23 0.15 - ≤ 0.45 - 25< t ≤50 ≤ ≤ JIS SB480M G3103 0.90 0.035 0.040 0.60 ≤0.25 0.30 50< t ≤100 ≤0.27 100< t ≤150 ≤0.20 ≤25 ≤0.23 0.15 - ≤ 25< t ≤50 0.45 ≤ ≤ ASTM Grade B A204M 0.90 0.035 0.035 0.60 ≤0.25 0.40 50< t ≤100 100< t ≤0.27 Table 17. Chemical requirements of 0.5Mo steel plates; JIS SBV1A [1] and ASTM A302M Grade A [6] Chemical composition [wt%] Thickness t Standards Designation Std. No. [mm] C Si Mn P S Mo ≤0.20 ≤25 0.15 - 0.95 - ≤ 0.45 ≤ JIS SBV1A G3119 ≤0.23 25< t ≤50 0.30 1.30 0.035 0.040 0.60 ≤0.25 50< t ≤150 ≤0.20 ≤25 0.15 - 0.95 - ≤ 0.45 ≤ ASTM Grade A A302M ≤0.23 25< t ≤50 0.40 1.30 0.035 0.035 0.60 50< t ≤0.25 Table 18. Chemical requirements of 0.5Mo steel plates; JIS SBV1B [1] and ASTM A302M Grade B [6] Chemical composition [wt%] Thickness t Standards Designation Std. No. [mm] C Si Mn P S Mo ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 ≤ ≤0.23 JIS SBV1B G3119 25< t ≤50 0.30 1.50 0.035 0.040 0.60 ≤0.25 50< t ≤150 ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 ≤ ≤0.23 ASTM Grade B A302M 25< t ≤50 0.40 1.50 0.035 0.035 0.60 ≤0.25 50< t Landolt-Börnstein New Series VIII/2B Ref. p. 34] 2.2.1 0.5Mo steel 31 Table 19. Chemical requirements of 0.5Mo steel plates; JIS SBV2 [1] and ASTM A302M Grade C [6] Thickness t Chemical composition [wt%] Std. No. Standards Designation [mm] C Si Mn P S Mo Ni ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 - 0.40 ≤ JIS SBV2 ≤0.23 25< t ≤50 G3119 0.30 1.50 0.035 0.040 0.60 0.70 ≤0.25 50< t ≤150 ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 - 0.40 ≤ ASTM Grade C ≤0.23 25< t ≤50 A302M 0.40 1.50 0.035 0.035 0.60 0.70 50< t ≤0.25 Table 20. Chemical requirements of 0.5Mo steel plates; JIS SBV3 [1] and ASTM A302M Grade D [6] Chemical composition [wt%] Thickness t Standards Desig-nation Std. No. [mm] C Si Mn P S Mo Ni ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 - 0.70 ≤ JIS SBV3 ≤0.23 25< t ≤50 G3119 0.30 1.50 0.035 0.040 0.60 1.00 ≤0.25 50< t ≤150 ≤0.20 ≤25 0.15 - 1.15 - ≤ 0.45 - 0.70 ≤ ASTM Grade D ≤0.23 25< t ≤50 A302M 0.40 1.50 0.035 0.035 0.60 1.00 50< t ≤0.25 2.2.1.3 Creep properties of 0.5Mo steel tubes The database [7] contains the creep data of 0.5Mo steel tubes, namely rupture data, minimum creep rate, rupture elongation, reduction of area and microstructures of crept specimens. 2.2.1.3.1 Creep rupture data of 0.5Mo steel tubes Fig. 29 shows the creep rupture data of STBA12 steel tubes of 12 heats. 2 Stress [N/mm ] 103 102 450 °C 500 °C 550 °C 10 10 102 Fig. 29. Creep rupture strength data of STBA12 according to data from [7]. 103 104 Time to rupture [h] Landolt-Börnstein New Series VIII/2B 105 106 32 2.2 Low alloy steels 2.2.1.3.2 Time-Temperature-Parametric prognostication of the creep rupture strength Fig. 30 shows Orr-Sherby-Dorn parametric plots of rupture data based on [7]. Creep rupture curve regression by a cubic expression predicts the creep rupture strength for times longer than that of the experiment at temperatures from 450 °C to 550 °C, Fig. 31. Stress (N/mm2) 1000 100 Fig. 30. Master rupture curve by Orr-SherbyDorn parameter method for 0.5Mo steel tubes; [7]. 450 °C 500 °C 550 °C TK: Temperature [K] tr: time to rupture OSDP fitting curve 10 -25 -23 -21 -19 -17 -15 OSDP = log tr - (348583/(19.1425 TK) Stress (N/mm2) 1000 100 450 °C 500 °C 550 °C Fig. 31. Estimated creep rupture curves for 0.5Mo steel tubes; [7]. 10 10 10 2 10 3 10 4 10 5 10 6 Time to rupture (h) Landolt-Börnstein New Series VIII/2B Ref. p. 34] 2.2.1 0.5Mo steel 33 2.2.1.4 Creep properties of 0.5Mo steel plates The database [8] contains creep data of 0.5Mo steel plates, namely rupture data, minimum creep rate, rupture elongation, reduction of area and microstructures of crept specimens. 2.2.1.4.1 Creep rupture data of 0.5Mo steel plates Fig. 32 shows the creep rupture data of SBV2 steel plates of 5 heats. Stress (N/mm2) 1000 100 450 °C Fig. 32. Creep rupture strength data of SBV2 according to data from [8]. 500 °C 550 °C 10 1 10 2 10 4 10 6 Time to rupture (h) 2.2.1.4.2 Time-Temperature-Parametric prognostication of the creep rupture strength Fig. 33 shows Manson-Haferd parametric plots of rupture data based on [8]. Creep rupture curve regression by a cubic expression predicts the creep rupture strength for times longer than that of the experiment at temperatures from 450 °C to 550 °C , Fig. 34. Stress (N/mm2) 1000 100 450°C 500 °C 550 °C Fig. 33. Master rupture curve by Manson-Haferd parameter method for 0.5Mo steel plates; [8]. MHP fitting curve 10 -6 Landolt-Börnstein New Series VIII/2B -5 -4 -3 MHP=[(log(tr)-11.169)/(Tk-530)] -2 34 2.2 Low alloy steels Stress (N/mm2) 1000 100 450 °C 500 °C 550 °C Fig. 34. Estimated creep rupture curves for 0.5Mo steel plates; [8]. 10 10 102 3 10 4 10 5 10 Time to rupture (h) 2.2.1.5 References [1] [2] [3] [4] [5] [6] [7] [8] JIS Handbook. ASTM Standard: A209/A209M (2001). ASTM Standard: A250/A250M (2001). ASTM Standard: A335/A335M (2001). ASTM Standard: A204/A204M (2001). ASTM Standard: A302/A302M (2001). National Research Institute for Metals: NRIM Creep Data Sheet, 8B (1991). National Research Institute for Metals: NRIM Creep Data Sheet, 18B (1987). Landolt-Börnstein New Series VIII/2B Ref. p. 37] 2.2.2 High strength steel 35 2.2.2 High strength steel 2.2.2.1 Introduction High strength steels are applied for pressure vessels. The application temperature range of the steels, categorized as silicon-manganese steels, is up to 350 °C. Therefore, allowable stresses are determined by the tensile stresses at service temperatures. Some steels are enhanced in tensile properties by MC type carbide precipitation strengthening. In order to obtain enough toughness and weldability for fabrication, the carbon, silicon and manganese contents are restricted in standards with respect to the parameters Ceq1 and PCM2 as described in JIS G3115 and in ISO 9328-4. Heat treatment manufacturing process is also given to unify the metallurgical microstructure as in JIS G3119 for instance. 2.2.2.2 Material standards, chemical and tensile requirements 2.2.2.2.1 High strength steel plates for pressure vessels Table 21. Chemical requirements of high strength steel plates; JIS SPV490 [1] and ISO P500TQ [2] Chemical composition [wt%] Thickness Standards Designation Std. No. t [mm] C Si Mn P S others 0.15 6< t ≤50 Ceq≤0.45 ≤ ≤ ≤ G3115 JIS SPV490 0.18 1.60 0.030 0.030 or PCM≤0.28 50< t ≤75 0.75 Cr≤2.0 Mo≤1.0 Ni≤2.0 Cu≤1.50 Nb≤0.06 0.70 - ≤ ≤ ≤ ≤ ISO P500TQ 9328-4 Ti≤0.20 3≤ t ≤70 0.20 0.55 1.70 0.030 0.030 V≤0.10 Al≤0.020 B≤0.005 N≤0.020 Zr≤0.15 2.2.2.2.2 High strength steel plates for general structures Table 22. Chemical requirements of high strength steel plates; JIS SM570[1], ASTM A678 C and A678 D [3] Chemical composition [wt%] Standards Designation Std. No. C Si Mn P S others ≤0.035 ≤0.035 ≤ ≤ ≤ G3106 JIS SM570 0.18 0.55 1.60 0.20 - 1.00 - ≤0.035 ≤0.04 ≤ A678 C 1.60 0.22 0.50 ASTM 0.15 - 1.15 - ≤0.035 V 0.04-0.11 ≤0.04 ≤ A678 D 1.50 N 0.01-0.03 0.22 0.50 1 2 Ceq = C+Si/24+Mn/6+Ni/40+Cr/5+Mo/4+V/14 PCM = C+Si/30+Mn/20+Cu/20+Ni/60+Cr/20+Mo/15+V/10+5B Landolt-Börnstein New Series VIII/2B 36 2.2 Low alloy steels 2.2.2.3 Creep properties of high strength steel plates The database [4] contains creep data of high strength steel plates, namely rupture data, rupture elongation, reduction of area, microstructures of as-received materials and crept specimens. 2.2.2.3.1 Creep rupture data of high strength steel plates Fig. 35 shows the creep rupture data of high strength steel plates of 21 heats. Several creep tests are still continuing. Stress (N/mm2) 1000 100 400°C 450°C 500°C 550°C 10 10 10 2 3 4 10 10 Time to rupture (h) 5 10 6 10 Fig. 35. Creep rupture strength data of high strength steel plates; [4]. 2.2.2.3.2 Time-Temperature-Parametric prognostication of creep rupture strength Fig. 36 shows Orr-Sherby-Dorn parametric plots of rupture data based on [4]. Creep rupture curve regression by a cubic expression predicts the creep rupture strength for times longer than that of the experimental data at temperatures from 400 °C to 550 °C, Fig. 37. 700 ○ 400 ℃ △ 450 ℃ □ 500 ℃ ▽ 550 ℃ Stress (MPa) 500 300 100 80 60 40 -22 ― Average n = 382 -20 Fig. 36. Master rupture curve by Orr-SherbyDorn parameter method for high strength steel plates; [4]. -18 -16 -14 -12 logtR - [ 284907 / ( 19.1425 × Tk ) ] Landolt-Börnstein New Series VIII/2B Ref. p. 37] 2.2.2 High strength steel 37 700 Stress ( MPa ) 500 300 400 ℃ 500 ℃ 100 80 60 40 101 450 ℃ 550 ℃ 102 103 104 105 Time to rupture ( h ) 106 Fig. 37. Estimated creep rupture curves for high strength steel plates; [4]. 2.2.2.4 References [1] [2] [3] [4] JIS Handbook. ISO Standard: 9328-4. ASTM Standard: A678 (2001). National Research Institute for Metals: NRIM Creep Data Sheet, 25B (1994). Landolt-Börnstein New Series VIII/2B 38 2.2 Low alloy steels 2.2.3 0.5Cr-0.5Mo steel 2.2.3.1 Introduction 0.5Cr-0.5Mo steels are used as tubes for heat exchangers, as pipes for high temperature service, as plates and forgings for pressure vessels of power plants, chemical and petrochemical plants. The creep strength of this steel is improved by addition of 0.5% of molybdenum. Oxidation and corrosion resistance are improved by addition of 0.5% of chromium. The creep strength is influenced by initial microstructure and changes in microstructure during creep exposure. Sigmoidal inflection of the stress vs. time to rupture curve is caused by decrease in creep strength and advent of inherent creep strength due to microstructural change during creep exposure, as will be mentioned later. The creep strength is affected by initial microstructure even for long-term creep exposure. The creep strength of steel with fully annealed ferrite and pearlite microstructure is higher than that of steel with martensitic and bainitic microstructures, as will be explained later. 2.2.3.2 Material standards, chemical and tensile requirements 2.2.3.2.1 0.5Cr-0.5Mo steel tubes for heat exchangers Table 23. Standards JIS ASTM Chemical requirements of 0.5Cr-0.5Mo steel tubes; JIS STBA 20, ASTM T2 Chemical composition [wt%] Designation C Si Mn P S Cr Mo STBA 20 0.10-0.20 0.10-0.50 0.30-0.60 ≤0.035 ≤0.035 0.50-0.80 0.40-0.65 T2 0.10-0.20 0.10-0.30 0.30-0.61 ≤0.025 ≤0.025 0.50-0.81 0.44-0.65 Std. No G3462 A213 2.2.3.2.2 0.5Cr-0.5Mo steel pipes for high temperature services Table 24. Standards JIS ASTM Chemical requirements of 0.5Cr-0.5Mo steel pipes; JIS STPA 20, ASTM P2 Chemical composition [wt%] Designation C Si Mn P S Cr Mo STPA 20 0.10-0.20 0.10-0.50 0.30-0.60 ≤0.035 ≤0.035 0.50-0.80 0.40-0.65 P2 0.10-0.20 0.10-0.30 0.30-0.61 ≤0.025 ≤0.025 0.50-0.81 0.44-0.65 Std. No G3458 A335 2.2.3.2.3 0.5Cr-0.5Mo steel plates for pressure vessels Table 25. Standards JIS ASTM Chemical requirements of 0.5Cr-0.5Mo steel plates; JIS SCMV 1-2, ASTM Gr.2 cl.2 Chemical composition [wt%] Designation C Si Mn P S Cr Mo SCMV 1-2 ≤0.21 0.55-0.80 ≤0.030 ≤0.030 0.50-0.80 0.45-0.60 ≤0.40 Gr.2 cl.2 0.05-0.21 0.15-0.40 0.55-0.80 ≤0.035 ≤0.035 0.50-0.80 0.45-0.60 Std. No G4109 A387 Landolt-Börnstein New Series VIII/2B Ref. p. 44] 2.2.3 0.5Cr-0.5Mo steel 39 2.2.3.2.4 0.5Cr-0.5Mo steel forgings for pressure vessels Table 26. Chemical requirements of 0.5Cr-0.5Mo steel forgings; JIS SFVA F2, ASTM F2 Standards Designation Std. No Chemical composition [wt%] C Si Mn JIS SFVA F2 ≤0.20 0.30-0.80 ≤0.60 ASTM F2 0.05-0.21 0.10-0.60 0.30-0.80 P ≤0.030 ≤0.040 S Cr Mo ≤0.030 0.50-0.80 0.45-0.65 G3203 ≤0.040 0.50-0.81 0.44-0.65 A182 2.2.3.3 Creep properties of 0.5Cr-0.5Mo steel tubes Information of fact on creep data for 0.5Cr-0.5Mo steel tubes can be obtained from [1] and [2]. 2.2.3.3.1 Creep rupture data of 0.5Cr-0.5Mo steel tubes The creep rupture strength of 0.5Cr-0.5Mo steel tubes obtained from available creep data sources is shown in Fig. 38. The results of creep test for 9 heats of JIS STBA 20 steel tubes are compiled in [1]. From this data sheet the data of rupture elongation, reduction of area, minimum creep rate, time to specified strain and microstructures of as-received materials and crept specimens can be also obtained. The creep rupture curve at 550 °C shows a sigmoidal shape, which is caused by changes in creep strength due to microstructural change during creep exposure, as will be explained later. 700 Stress (MPa) 500 300 100 80 60 ○ △ □ ▽ 40 -1 10 450oC 500oC 550oC 600oC 0 10 n=228 10 1 10 2 10 3 4 10 10 5 10 6 Fig. 38. Creep rupture strength data of JIS STBA 20; [1]. n indicates the total number of data points. Time to rupture (h) 2.2.3.3.2 Creep rupture strength of 0.5Cr-0.5Mo steel tubes Creep rupture strength was analyzed by applying the Manson-Haferd parameter method to NRIM creep rupture data on 0.5Cr-0.5Mo steel tubes (JIS STBA 20). The result is shown in Fig. 39. It should be noted that the heat-to-heat variation of creep rupture strength is very large under higher stress conditions, however, the scatter band of creep rupture strength under lower stress conditions is very narrow, in comparison with that under higher stresses. Decrease in heat-to-heat variation of creep rupture strength with decrease in applied stress is caused by decrease in creep strength and advent of inherent creep strength due to microstructural changes during long-term creep exposure at the elevated temperatures, as will be explained later [3, 4]. Landolt-Börnstein New Series VIII/2B 40 2.2 Low alloy steels Stress [MPa] 1000 800 600 500 400 300 450 °C 500 °C 550 °C 575 °C 600 °C 625 °C 200 100 80 60 50 Average 40 n = 231 30 -2.5 -4.5 -3.0 -3.5 -4.0 Manson-Haferd parameter [( log tR -18.087)/( TK -304.0 )] [×10 2 ] Fig. 39. Master rupture curve by Manson-Haferd parameter method for 0.5Cr-0.5Mo steel tubes (JIS STBA 20); [1]. n indicates the total number of data points. 2.2.3.3.3 Microstructural change The typical initial microstructure of 0.5Cr-0.5Mo steel tubes consists of ferritic and pearlitic grains. Optical micrographs of 0.5Cr-0.5Mo steel tubes are shown in Fig. 40. The bright grains are ferritic grains and the dark ones are pearlitic. Bright field TEM images within ferritic grains of 0.5Cr-0.5Mo steel tubes after crept and creep ruptured at 550 °C and stresses of 294, 196, 88 and 59 MPa are shown in Fig. 41 [3, 4]. In the specimen creep ruptured after 155.8 h under stress of 294 MPa (Fig. 41a), huge amounts of dislocations with a lot of very fine carbide particles are observed. After creep for 1,778.3 h under stress of 196 MPa (Fig. 41b), the dislocation density is still high and carbide particles are coarsened. After creep for 23,788.3 h under stress of 88 MPa (Fig. 41c), precipitation of many needle-like Mo2C carbides is observed and the dislocation density is low in comparison with that in specimens creep ruptured after short-term creep exposure. After long-term creep exposure for 112,776.4 h under stress of 59 MPa (Fig. 41d), further coarsening of carbide is observed and the dislocation density is significantly lowered. Fig. 40. Optical micrographs of as-received 0.5Cr-0.5Mo steel tubes (etched in 4 % natal); [1]. Landolt-Börnstein New Series VIII/2B Ref. p. 44] 2.2.3 0.5Cr-0.5Mo steel 41 Fig. 41. Bright field TEM images within ferritic grains of 0.5Cr-0.5Mo steel tubes after crept and creep ruptured at 550 °C at stresses of 294 (a), 196 (b), 88 (c) and 59 MPa (d); [3, 4]. Rupture times: a) tr = 155.8 h, b) tr = 1778.3h, c) tr = 23788.3 h, d) tr = 112776.4 h. 2.2.3.3.4 Inherent creep strength Stress vs. time to rupture curves of 0.5Cr-0.5Mo steel tubes at 550 and 600 °C are shown in Fig. 42 [3, 4]. Sigmoidal inflection is observed for the creep rupture curve at 550 °C. The slope of the curve increases with decrease in stress from 300 to 150 MPa, however, the curve turns to be gentle at about 100 MPa. Inflection of the curve at about 100 MPa is observed also at 600 °C, similar to that at 550 °C. Sigmoidal inflection of stress vs. time to rupture curves is caused by changes in creep strength due to microstructural change during creep exposure at elevated temperatures as shown in Fig. 41. Creep strength of 0.5Cr-0.5Mo steel tubes is strongly influenced by precipitation and coarsening of carbides and changes in dislocation density during long-term creep exposure. Changes in hardness within ferritic grains of 0.5Cr-0.5Mo steel tubes with increase in creep exposure time at 550 and 600 °C are shown in Fig. 43. With increase in creep exposure time, hardness decreases at both temperatures. However, the magnitude of the decrease in hardness decreases after about 10,000 h and 1,000 h of creep exposure at 550 and 600 °C, respectively. The hardness of crept 0.5Cr-0.5Mo steel tubes indicates an almost constant value from HV130 to HV150 for long-term creep exposure. Strengthening effects obtained by fine precipitates and high dislocation density are essentially lost during long-term creep exposure for about 10,000 h and 1,000 h at 550 and 600 °C, respectively. The constant hardness value observed for long-term creep exposure corresponds to that of the ferrite matrix itself, consequently, the creep strength after long-term creep exposure is the same as that of the ferrite matrix. The slope of the stress vs. time to rupture curve increases with decrease in applied stress, since creep strength decreases due to microstructural change, however, the creep strength decreases to that of the ferrite matrix after long-term creep exposure and the creep rupture curve turns to be gentle. Landolt-Börnstein New Series VIII/2B 42 2.2 Low alloy steels The creep strength corresponding to that of the ferrite matrix is constant and independent of creep exposure time, and it has been proposed as a concept of “Inherent Creep Strength” [3, 4]. Long-term creep strength of 0.5Cr-0.5Mo steel is governed by inherent creep strength. 250 500 550oC Vickers hardness (98N) Stress (MPa) 300 600oC 100 80 60 40 2 10 3 10 10 4 10 5 10 6 Time to rupture (h) Fig. 42. Stress vs. time to rupture curves of 0.5Cr0.5Mo steel tubes at 550 and 600 °C; [3, 4]. 550oC 200 150 600oC 100 2 10 3 10 10 4 10 5 10 6 Time to rupture (h) Fig. 43. Changes in hardness within ferritic grains with increase in creep exposure at 550 and 600 °C; [3, 4]. 2.2.3.3.5 Influence of initial microstructure on long-term creep strength The creep strength of 0.5Cr-0.5Mo steel is strongly influenced by initial microstructure, which results in large scatter of short-term creep strength as shown in Fig. 39. The microstructure of the steel is affected by heat treatment conditions. Bright field TEM images of 0.5Cr-0.5Mo steels subjected to various conditions of heat treatment are shown in Fig. 44. Martensitic microstructure (a), tempered martensitic microstructures (b,c), bainitic microstructure (d) and a complex of ferritic and pearlitic grains (e) are obtained by different heat treatment conditions. The creep rupture strengths of 0.5Cr-0.5Mo steels with different initial microstructures shown in Fig. 44 are shown in Fig. 45 [5, 6]. For creep exposure longer than 10,000 h, creep rupture strengths of the steels with martensitic microstructures are almost the same independent of tempering heat treatment prior to the creep test. Differences in microstructure due to tempering heat treatment essentially disappear during creep exposure for about 10,000 h at 575 °C. Long-term creep strength in the stress range below 50 MPa and creep rupture strength of furnace cooled steel with a complex of ferritic and pearlitic grains are higher than those of other steels with martensitic or bainitic microstructures. Although the creep strength in the range of stresses lower than about 50 MPa is thought to be inherent creep strength of the steel, creep strength of furnace cooled steel is clearly higher than that of other steels. In contrast to very high dislocation densities of steels with martensitic or bainitic microstructures in the as heat treated condition, the dislocation density of furnace cooled steels is significantly lower. Creep deformation can be carried with dislocations generated by applied stress high enough to produce them, even if the amount of dislocations is small in the furnace cooled condition. However, if the applied stress is such low that it can not produce enough dislocations for creep deformation, the creep rate should be very small. Long-term creep strength of 0.5Cr-0.5Mo steel is governed by inherent creep strength, which is independent of initial microstructure. However, long-term creep rupture strength of furnace cooled microstructure with very low dislocation density is higher than of other steels containing a lot of dislocations, since there are not enough dislocations for creep deformation. Landolt-Börnstein New Series VIII/2B Ref. p. 44] 2.2.3 0.5Cr-0.5Mo steel 43 Fig. 44. Bright field TEM images of 0.5Cr-0.5Mo steels in the as heat treated conditions of (a) quenched from 920 °C, (b) and (c) quenched from 920 °C followed by tempering at 650 °C, (d) quenched from 920 °C to 450 °C and isothermally transformed for 1 h and (e) furnace cooling from 920 °C; [5, 6] 200 Stress (MPa) 575oC 100 90 80 70 60 50 40 30 ○ Martensite o △ Tempered martensite (650 C/1h) o ▽ Tempered martensite (650 C/100h) □ Bainite o o ● Ferrite + Pearlite 20 1 10 10 2 10 3 10 4 10 5 6 10 Fig. 45. Creep rupture strength of 0.5Cr0.5Mo steels with different initial microstructures; [5, 6]. Time to rupture (h) 2.2.3.3.6 Estimated long-term creep strength The temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 9 heats of 0.5Cr-0.5Mo steel tubes is shown in Fig. 46 [1]. That of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for the same materials is shown in Fig. 47 [1]. Creep rupture strength curves shown in Fig. 46 and Fig. 47 were obtained by regression analysis using the Manson-Haferd parameter. Landolt-Börnstein New Series VIII/2B 44 2.2 Low alloy steels Stress [MPa] 1000 800 600 500 400 300 Tensile strength 0.2% proof stress 200 100 80 60 50 40 30 400 100 h 10000 h 450 500 550 Temperature [°C] 600 Stress [MPa] 1000 800 600 500 400 300 Tensile strength 0.2% proof stress 200 100 80 60 50 40 30 400 650 Fig. 46. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 0.5Cr0.5Mo steel tubes (JIS STBA 20); [1]. 1000 h 100000 h 450 500 550 Temperature [°C] 600 650 Fig. 47. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for 0.5Cr0.5Mo steel tubes (JIS STBA 20); [1]. 2.2.3.4 References [1] [2] [3] [4] National Research Institute for Metals: NRIM Creep Data Sheet, No.20B, (1994). Japan Pressure Vessel Research Committee: 0.5Mo and Cr-Mo steels Data Book, (1998). Kimura, K., Kushima, H., Yagi, K., and Tanaka, C.: Tetsu-to-Hagane, 77, (1991), 667-674. Kimura, K., Kushima, H., Yagi, K., and C. Tanaka: Proc. of Inter. Conf. on Creep and Fracture of Engineering Materials and Structures, Wilshire, B., and Evans, R.W., Swansea, eds., UK, The Institute of Materials, 5, (1993), 555-564. [5] Kimura, K., Kushima, H., Baba, E., Shimizu, T., Asai, Y., Abe, F., and Yagi, K.: Proc. of 5th Inter. Charles Parsons Turbine Conf. on Advanced Materials for 21st Century Turbines and Power Plant, Strang, A., et al. eds., Cambridge, UK, The Institute of Materials, 5, (2000), 558-571. [6] Kimura, K., Kushima, H., Baba, E., Shimizu, T., Asai, Y., Abe, F., and Yagi, K.: Tetsu-to-Hagane, 86, (2000), 542-549. Landolt-Börnstein New Series VIII/2B Ref. p. 53] 2.2.4 1Cr-0.5Mo steel 45 2.2.4 1Cr-0.5Mo steel 2.2.4.1 Introduction 1Cr-0.5Mo steels are used as tubes for heat exchangers and as plates for pressure vessels. The 1Cr-0.5Mo steel tubes were introduced in the 1950s. As the microstructure of this steel is strongly affected by heat treatment conditions and changes in microstructure are related with creep strength, the changes in microstructure during creep have been investigated. For this steel, M2C carbides precipitate in ferrite and M23C6 carbides precipitate in pearlite or in tempered bainite during creep. Studies on the effect of Al and N on creep strength have also been done. 1Cr-0.5Mo steel plates are used as materials for pressure vessels of petroleum refinery. For this steel, the reduction of creep ductility due to long-term service becomes a subject of investigation, and many studies have been done for the prevention of this creep embrittlement. 2.2.4.2 Material standards, chemical and tensile requirements 2.2.4.2.1 1Cr-0.5Mo steel tubes for heat exchangers Table 27. Chemical requirements of 1Cr-0.5Mo steel tubes; JIS STBA 22, ASTM T12, BS 620 and DIN 13CrMo44 Standards Designation JIS STBA 22 ASTM T12 BS 620 DIN 13CrMo44 C Si ≤0.15 ≤0.50 0.050.15 0.100.15 0.100.15 ≤0.50 0.100.35 0.100.35 Chemical composition [wt%] Std. No Mn P S Cr Mo Ni Others 0.300.80- 0.45G3462 ≤0.035 ≤0.035 0.60 1.25 0.65 0.300.80- 0.44A213 ≤0.025 ≤0.025 0.61 1.25 0.65 0.400.70- 0.45A1≤ 3606 ≤0.040 ≤0.040 ≤0.30 0.70 1.10 0.65 0.020 0.400.70- 0.4517175 ≤0.035 ≤0.035 0.70 1.10 0.65 Table 28. Tensile properties at room temperature of 1Cr-0.5Mo steel tubes; JIS STBA22 Tensile strength Yield strength Elongation [N/mm2] [N/mm2] [%] d<10 mm d≥20 mm 10≤d<20 mm ≥410 ≥205 ≥30 ≥25 ≥22 2.2.4.2.2 1Cr-0.5Mo steel plates for pressure vessels Table 29. Chemical requirements of 1Cr-0.5Mo steel plates; JIS SCMV 2, ASTM Gr.12, EN 13CrMo4-5 Chemical composition [wt%] Standards Designation Std.No C Si Mn P S Cr Mo Cu Others 0.400.80- 0.45JIS SCMV 2-2 ≤0.17 ≤0.40 G4109 ≤0.030 ≤0.030 0.65 1.15 0.60 0.05- 0.15- 0.400.80- 0.45A 387M ASTM Gr.12-cl.2 ≤0.035 ≤0.035 0.17 0.40 0.65 1.15 0.60 0.080.400.70- 0.40BS EN, 13CrMo4-5 10028-2 ≤0.35 ≤0.030 ≤0.025 ≤0.30 0.18 1.00 1.15 0.60 DIN EN Landolt-Börnstein New Series VIII/2B 46 2.2 Low alloy steels Table 30. Tensile properties at room temperature of 1Cr-0.5Mo steel plate; JIS SCMV 2-2. Tensile strength [N/mm2] Yield strength [N/mm2] Elongation [%] 450-590 ≥275 ≥22 2.2.4.3 Creep properties of 1Cr-0.5Mo steel tubes Information of fact on creep data for 1Cr-0.5Mo steel tubes can be obtained from [1], [3], [4] and [5]. 2.2.4.3.1 Creep rupture data of 1Cr-0.5Mo steel tubes Creep rupture strength data of 1Cr-0.5Mo steel tubes is shown in Fig. 50. The results of creep tests for 11 heats of STBA 22 steel tubes are compiled in [1]. From this data sheet the data of elongation, reduction of area and minimum creep rate, and microstructures of as-received materials and crept specimens can also be obtained. The relation of stress vs. time to rupture at 550 °C shows an inverse sigmoidal shape. This shape of the creep rupture curve is due to the fact that the creep deformation curve is changed complicatedly by microstructural evolutions during creep, as will be seen later. 2.2.4.3.2 Creep rupture strength of 1Cr-0.5Mo steel tubes It should be noted from Fig. 50 that creep rupture strength has a large scatter. The creep rupture strength is dependent on manufacturing conditions, chemical composition, and initial microstructure. This information is given in [1]. Creep rupture curves were analyzed using the Manson-Haferd method to NRIM creep data. The result is shown in Fig. 51, The creep rupture strength was estimated. Tensile strength 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 700 400 300 400 300 200 200 100 100 0 0 100 200 300 400 500 600 700 800 Test temperature (℃) 0 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 48. Tensile properties of 1Cr-0.5Mo steel tubes; [1]. Landolt-Börnstein New Series VIII/2B Ref. p. 53] 2.2.4 1Cr-0.5Mo steel 47 Tensile strength 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 700 400 300 400 300 200 200 100 100 0 0 0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800 Test temperature (℃) Test temperature (℃) Fig. 49. Tensile properties of 1Cr-0.5Mo steel plates; [2]. 500 500 °C 550 °C 600 °C 650 °C Stress [MPa] 300 100 80 60 40 n = 309 20 10 10 2 500 400 10 5 10 6 500 °C 550 °C 570 °C 580 °C 600 °C 625 °C 640 °C 650 °C 675 °C 300 200 Stress [MPa] 10 3 10 4 Time to rupture [h] Fig. 50. Creep rupture strength data of STBA 22; [1]. n indicates the total number of data points. 100 80 60 50 40 30 Average n = 315 20 -2.0 -4.0 -3.0 -2.5 -3.5 -4.5 Manson-Haferd parameter [( log tR -13.088)/( TK -510.0 )] [×10 2 ] Landolt-Börnstein New Series VIII/2B Fig. 51. Master rupture curve by Manson-Haferd parameter method for 1Cr-0.5Mo steel tubes. n indicates the total number of data points. 48 2.2 Low alloy steels 500 300 500 °C Stress [MPa] 550 °C 100 80 600 °C 650 °C 60 40 20 10 10 2 10 4 10 3 Time to rupture [h] 10 5 10 6 Fig. 52. Estimated creep rupture curves of STBA 22 steel tubes. 2.2.4.3.3 Microstructural changes The microstructure of 1Cr-0.5Mo steels changes during creep. The carbides precipitate, M2C in ferrite portion, and M23C6 in pearlite or bainite portion. The form of these carbides changes with aging time. The percentage of alloying elements in cementite for post-service material was tested at 823 K as a function of creep exposure time [7]. The material which was investigated in this paper was supplied in the form of pipe section, which had been removed from service after about 70,000 h at 838 K, and a nominal stress of 17.2 MNm−2. The service-exposed material contained a large amount of spheroidized M3C in the bainitic regions with M2C precipitates in the form of fine needles within the ferrite grains. It is suggested that these changes in the substitutional solute element concentrations in cementite could provide an aid to the estimation of effective exposure temperature for use in determining the remanent life of components. Continuous microstructural changes lead to property degradation; the reduction of the solid-solution Mo content and the increased interparticle spacing consequent on spherodization reduce creep resistance. The effect of heat treatment on creep rupture strength and microstructural change was investigated for annealed 1Cr-0.5Mo steel (Ann.) and for normalized and tempered one (NT) [8]. Based on the study on the change in creep rupture strength and carbide distribution, for as-heat-treated materials, the annealed steel has a larger amount of precipitates in ferrite and a higher creep strength. However, after long-term aging, there is no difference in the amount of precipitates between both steels, and the inversion of creep strength can be seen at longer times. 2.2.4.3.4 Creep deformation behavior and creep rupture strength Inverse sigmoidal shaped stress vs. time to rupture curves are observed for 1Cr-0.5Mo steels. The sigmoidal shape is caused by the transition of creep deformation behavior due to microstructural changes. Fig. 53 shows creep deformation, strain vs. time and creep rate vs. time curves, obtained under testing conditions where stress vs. time to rupture relations with inverse sigmoidal shape are observed. The creep rate curve has two minimum values in one curve. The creep rate curve of material pre-aged for 500 h at 873 K has one minimum value [9]. Fig. 54 shows the comparison of experimental and predicted creep rupture life of STBA 22 [9]. The creep deformation curve with two minimum values of creep rate was divided into two regions, Type I and Type II. The creep rupture life was predicted from each creep deformation analysis of Type I and Type II regions. For higher stresses and shorter times, experimental creep rupture life agrees well with the curves predicted from Type I creep deformation behavior, and for lower stresses and longer times, experimental Landolt-Börnstein New Series VIII/2B Ref. p. 53] 2.2.4 1Cr-0.5Mo steel 49 data agree well with the curves predicted from Type II. It is considered that since experimental short-term life of pre-aged material agree with the curve predicted from Type II, the change in controlling factor from Type I to Type II of creep rupture strength is caused by the change in controlling factor of creep deformation behavior due to microstructural evolution during creep. The relation of time to rupture vs. minimum creep rate of STBA 22 was investigated [10]. This relation is well known to be linear in double logarithmic scales. For Cr-Mo ferritic heat resistant steels, however, this relation has a large scattering, which is explained by the change in combination of controlling factor of time to rupture and minimum creep rate. 2.2.4.3.5 Effect of Al and N on creep rupture strength For carbon steels, the effect of Al and N on creep rupture strength has been investigated. However, for 1Cr-0.5Mo steels, this effect is more complicated because N interacts with Cr and Mo. The effect of Al and N on creep rupture strength of 1Cr-0.5Mo steel was examined [11]. Heat treatment conditions of this steel are 920 °C × 30 min → 720 °C × 25 min, AC. The creep rupture strength strongly depends on the amount of Al. Smaller amounts of Al produce higher creep rupture strength. All of nitrogen in the steel exists as CrN. This means that the detrimental effect of Al addition cannot be ascribed to the decrease in the amount of active N. The decrease in creep rupture strength due to Al addition is caused by grain refining effect of AlN. Fig. 55 shows the amount of soluble nitrogen in 1Cr-0.5Mo steel [12]. There is little amount of soluble N in low alloy steels, and strengthening due to soluble N is not expected for 1Cr-0.5Mo steel. 5 1 Cr-0.5Mo steel (JIS STBA 22) 300 3 2 Stress [MPa] Strain e [%] 4 500 a 823 K 88 MPa s / E = 0.509×10-3 1 0 b 100 80 873 K 60 Creep rate e [%/h] Calculated 40 10-3 Type I Type II un- aged pre-aged for 500h at 873 K 20 10 10-4 Measured Calculated 10-5 0 { 5000 { 10000 15000 Time t [h] Fig. 53. Creep deformation curves; [9]. Landolt-Börnstein New Series VIII/2B Type I Type II 20000 25000 10 2 10 4 10 3 Time to rupture [h] 10 5 10 6 Fig. 54. Comparison of experimental and predicted creep rupture life of STBA22; [9]. 50 2.2 Low alloy steels 100 1 Cr-0.5Mo steel 2.25 Cr-1Mo steel Extraction rate [10-6 %/°C ] 80 60 40 20 0 0 200 600 400 800 1000 Extraction temperature [°C ] 1200 Fig. 55. Extraction curves of nitrogen for as-received and crept 1Cr-0.5Mo steel and 2.25Cr-1Mo steel; [12]. 2.2.4.3.6 Estimated long-term creep rupture strength 800 600 500 400 { 200 { Stress [MPa] 300 100 80 60 50 40 30 20 450 Tensile strength 0.2% proof stress 1000 h 100000 h 500 550 600 Temperature [°C] 650 700 Fig. 56. Creep rupture strength of STBA 22 steel tubes [1]. The relations stress vs. temperature with the parameter time to rupture were estimated based on the most suitable master rupture curve, which was obtained from NRIM Creep Data using Manson-Haferd method. 2.2.4.4 Creep properties of 1Cr-0.5Mo steel plates Information of fact on creep data for 1Cr-0.5Mo steel plates can be obtained from [2], [3] and [5]. Creep rupture strength data of 1Cr-0.5Mo steel plates is shown in Fig. 57. The results of creep tests for 8 heats of SCMV 2 NT steel plates are compiled in [2]. From this data sheet the data of elongation and reduction of area, and microstructures of as-received materials can also be obtained. Landolt-Börnstein New Series VIII/2B Ref. p. 53] 2.2.4 1Cr-0.5Mo steel 51 500 Stress [MPa] 300 100 80 60 40 20 10 -1 450 °C 475 °C 500 °C 550 °C 600 °C 650 °C 1 10 10 3 10 2 Time to rupture [h] 10 4 10 5 10 6 Fig. 57. Creep rupture strength data of SCMV 2 NT; [2]. 2.2.4.4.1 Creep rupture strength of 1Cr-0.5Mo steel plates It should be noted from Fig. 57 that creep rupture strength has large scatter. The creep rupture strength depends on manufacturing conditions, chemical composition, and initial microstructure. This information is obtained from [2]. The master rupture curve, Fig. 58, was analyzed using the Orr-Sherby-Dorn method to NRIM creep data, which are shown in Fig. 57, and creep rupture strength was estimated, Fig. 59. 2.2.4.4.2 Creep properties of coarse grained 1Cr-0.5Mo steel The creep ductility of 1Cr-0.5Mo steels is low, and especially, the understanding of creep ductility at heat-affected zones (HAZ) is important for this steel. Fig. 60 shows the creep test results of smooth specimens and notched specimens for Cr-Mo steels [13]. The coarse grained heat affected zones of 1Cr-0.5Mo steel show notch weakening due to decrease in creep rupture ductility. The rupture ductility increases with increasing amount of Cr, and the material shows the notch strengthening. The influence of postweld heat treatment on creep properties has also been investigated [14]. The multiaxial creep properties of coarse grained 1Cr-0.5Mo steel were investigated [15]. The material is quenched and tempered, and has a microstructure comprising coarse grained tempered bainite with a prior austenite grain size of about 190 µm. The minimum creep rate stress index is in the range of 2-3 and the ductility is about 1 %. This material is creep brittle. The multiaxial stress rupture criterion (MSRC) of this steel varies with stress state; at high triaxiality (notch), MSRC is dependent on maximum principle stress, and at low triaxiality (shear), MSRC is dependent on both maximum principle stress and equivalent stress. Landolt-Börnstein New Series VIII/2B 52 2.2 Low alloy steels 100 500 °C 550 °C 600 °C 650 °C 300 100 80 550 °C 1Cr- 1/2 Mo 1 1/4 Cr- 1/2 Mo 2 1/4 Cr-1Mo 3Cr-1Mo 60 40 20 0 60 50 40 Average n = 158 30 20 -26 -24 -18 -22 -20 Orr-Sherby-Dorn parameter log tR -[390498/( 19.1425×TK )] Stress [kgf / mm 2 ] Stress [MPa] 200 80 Reduction of area [%] 600 500 400 30 25 20 15 10 Fig. 58. Master rupture curve by Orr-Sherby-Dorn parameter method for 1Cr-0.5Mo steel plates. n indicates the total number of data points. 0 open: smooth specimen solid: notched specimen 10 2 10 3 Time to rupture [h] 10 4 Fig. 60. Creep test result of smooth specimens and notched specimens for Cr-Mo steels; [13]. 500 Stress (MPa) o 500 C 340 o 550 C 180 o 600 C Fig. 59. Estimated creep rupture curves of SCMV 2 NT steel plates. o 650 C 20 101 102 103 104 105 106 Time to rupture (h) Landolt-Börnstein New Series VIII/2B Ref. p. 53] 2.2.4 1Cr-0.5Mo steel 53 2.2.4.4.3 Crack growth behavior in the creep range Components and structural parts are mostly subjected to strongly alternating loads during operation because of start-up and shut-down phases as well as load reversals. The understanding of crack growth behavior under creep-fatigue conditions is important. The crack growth rate for CT-specimens in tests with hold times compared with tests without hold times of creep-prestrained 13CrMo 44 was examined [16]. Hold times at maximum load caused additional creep damage and a further increase in the crack propagation rate. 2.2.4.5 References [1] NRIM Creep Data Sheet, No.1B, (1996). [2] NIMS Creep Data Sheet, No.35B, (2002). [3] The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at High Temperatures, Vol.I Low Alloy Steel, (1972). [4] Smith,G.V.: Evaluation of the Elevated Temperature Tensile and Creep-Rupture Prosperities of 1/2Cr-1/2Mo, 1Cr-1/2Mo, and 1-1/4Cr-1/2Mo-Si Steels, ASTM Data Series Publication DS 50, ASTM, (1973). [5] The British Steelmakers Creep Committee: BSCC high temperature data, (1972). [6] Krisch, A.: Proc.of Joint Intern. Conf. on Creep, (1963), Inst. Mech.Eng., p.1-81. [7] Afrouz, A., Collins, M.J., Pilkington, R.: Metals Techonology, 10 (1983), 461-463. [8] Yukitoshi, T., Nishida, K.: Journal of the Society of Meterials Science, Japan, 21 (1972), 204-211. [9] Kushima, H., Kimura, K., Abe, F., Yagi, K., Irie, H., Maruyama, K.: Tetsu-to-Hagane, 86 (2000) 131-137. [10] Kushima, H., Kimura, K., Yagi, K., Tanaka, C., Maruyama, K.: Proc. of 7th JIM Int..Symp. on Aspects of High Temperature Deformation and Fracture in Crystalline Materials, (1993), The Japan Insititue of Metals, 609-616. [11] Yukitoshi, T., Nishida, K.: Trans. ISIJ, 12 (1972), 429-434. [12] Shinya. N., Yokoi, S., Kushima, H., Imai, Y.: Tetsu-to Hagane, 67 (1981), S439. [13] Ishiguro, T., Tsukeda, T., Murakami, T.: Tetsu-to-Hagane, 69 (1983), S673. [14] Wu, Rui, Storesund, J., Sandstrom, R.: Materials Sccience and Techonology, 9 (1993), 773-780. [15] Browne, R. J., Flewitt, P. E., Lonsdale, D., Shammans, M. S., Soo, J. N.: Materials Science and Techonology, 7 (1991), 707-717. [16] Kullik, M., Maile, K.: Nuclear Engineering and Design, 199 (1990), 215-222. Landolt-Börnstein New Series VIII/2B 54 2.2 Low alloy steels 2.2.5 0.5Cr-0.5Mo-0.25V steel 2.2.5.1 Introduction 0.5Cr-0.5Mo-0.25V steel (14MoV6-3, 12MoCrV6-2-2) is primarily used as a steam pipe material in the normalized and tempered heat treatment condition. The microstructure is typically tempered bainite, the creep resistance being derived from a fine distribution of V4C3 precipitate. The requirements for 0.5Cr-0.5Mo-0.25V steel as 14MoV6-3 in EN 10216 replace those for BS 3604 (Grade 660) and DIN 17 175 (14MoV6-3). 2.2.5.2 Material standards, chemical composition and tensile requirements Table 31. Chemical requirements of 0.5Cr-0.5Mo-0.25V steel, 14MoV6-3 (EN 10216) Chemical composition [wt%] Stan- Std. Desigdard No. nation C Si Mn P S Cr Mo 0.15 - 0.35 - 0.70 - ≤ 0.60 - 0.70 ≤ EN 10216 14MoV6-3 0.10 0.15 0.40 0.50 0.025 0.020 0.30 V 0.28 0.22 Al ≤ 0.040 The material is usually supplied in the normalized and tempered condition. The recommended austenitizing temperature range is 930 - 990 °C with tempering in the range 680 - 750 °C. Table 32. Room temperature mechanical property requirements for 0.5Cr-0.5Mo-0.25V steel, 14MoV63 (EN 10216) StanStd. DesigHeat Thickness Rp0.2 Rm A Kv(RT) dard No. nation treat [mm] Nmm-2 [J] [Nmm-2] [%] 610 EN 10216 14MoV6-3 N+T 320 ≤40 ≥20 ≥40 460 610 EN 10216 14MoV6-3 N+T >40 310 ≥20 ≥40 460 Table 33. Minimum 0.2 % proof strength, Rp0.2, values at elevated temperatures for 0.5Cr-0.5Mo-0.25V steel, 14MoV6-3 (EN 10216) (wall thicknesses ≤60 mm) StanStd. DesigHeat Rp0.2 [Nmm-2] at a temperature [°C] of dard No. nation treat 100 150 200 250 300 350 400 450 500 550 EN 10216 14MoV6-3 N+T 282 276 267 241 225 216 209 203 200 197 2.2.5.3 Creep rupture strength The creep rupture strength of 0.5Cr-0.5Mo-0.25V steel is shown in Fig. 61. The analysis from which the data in the figure are derived was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found from their published data sheets [1]. The creep rupture properties have been obtained by analysis of (i) tube material with outer diameters in the range 162 - 521 mm and thicknesses of 19 - 89 mm, (ii) forgings with sections sizes in the range 381 - 508 mm. The test data were from 46 heats with test temperatures of 475 - 740 °C. The distribution of test durations is shown in Table 34. Landolt-Börnstein New Series VIII/2B Ref. p. 56] 2.2.5 0.5Cr-0.5Mo-0.25V steel 55 Table 34. Distribution of test durations used to derive the stress rupture properties of 14MoV6-3 (12MoCrV6-2-2). Number of test points at the various test durations 10,000 20,001 30,001 50,001 70,001 >100,000 h <10,000 h 20,000 h 30,000 h 50,000 h 70,000 h 100,000 h 331 (3) 81 (5) 30 (4) 29 (4) 11 (1) 13 (1) 5 (3) ( ) denotes unbroken tests The data were assessed using the BS PD6605 procedure and the following master equation was derived: ln(tu*) = β0 + β1log(σ) + β2σ + β3σ2 + β4T + β5/T where tu* is the predicted rupture time in hours, T is the absolute temperature and σ is the stress in Nmm-2. Table 35. The βi are constants with the following values β0 −39.7658730 β1 −8.43513298 β2 −0.00186616660 β3 −2.91037377×10−5 β4 0.00935613085 β5 49662.4102 STRENGTH, MPa 1000 100 10,000h 100,000h 200,000h 250,000h Fig. 61. Creep rupture strength data of 14MoV6-3 (12MoCrV6-2-2). 10 400 450 500 550 600 o TEMPERATURE, C Landolt-Börnstein New Series VIII/2B 650 56 2.2 Low alloy steels 2.2.5.4 Estimated long term creep rupture strength Based on the data shown in Fig. 61 the 100,000 h rupture strength values for a range of temperatures are as follows: 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] Temperature 450 460 470 480 490 500 510 520 Stress 305 276 249 224 200 177 155 135 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] Temperature 530 540 550 560 570 580 590 600 Stress 117 102 87 75 65 56 48 41 2.2.5.5 Reference [1] ECCC Data Sheet for 12MoCrV6-2-2, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). Landolt-Börnstein New Series VIII/2B Ref. p. 61] 2.2.6 1Cr-1Mo-V steel 57 2.2.6 1Cr-1Mo-V steel 2.2.6.1 Introduction 1Cr-1Mo-V steel forgings have been used as rotors for steam turbines during the application of high temperature steam in the 1950s. The manufacturing technologies of 1Cr-1Mo-V steel forgings have been investigated for turbine rotors of large size. The establishment of most suitable heat treatment conditions was important in order to obtain excellent creep properties for this steel. Because the microstructure changes during creep, these changes and the effecting factors on creep behavior have been studied. The performance of turbine rotors was improved by the development of manufacturing technology for high purity forgings. 2.2.6.2 Material standards, chemical and tensile requirements Material standard for 1Cr-1Mo-V steel forgings for turbine rotors and shafts is ASTM A470-94a, class 8. Table 36. Chemical requirements of 1Cr-1Mo-V steel forgings; ASTM A470-94a, class 8 Chemical composition [wt%] C Si Mn P S Ni Cr Mo V ASTM A470-94a 0.25-0.35 0.15-0.35 ≤1.00 ≤0.012 ≤0.015 ≤0.75 1.05-1.50 1.00-1.50 0.20-0.30 Standards Designation Table 37. Tensile properties at room temperature of 1Cr-1Mo-V steel forgings; ASTM A470-94a, class 8. Tensile strength Yield strength Elongation to radial body Reduction of area to radial body [MPa] [MPa] [%] [%] 725 - 860 ≥585 ≥14 ≥38 Table 38. Notch toughness requirements of 1Cr-1Mo-V steel forgings; ASTM A470-94a, class 8 Transition temperature FATT50 [°C] Room temperature impact [J] ≤121 ≥16 Tensile strength 1000 800 800 Stress (MPa) Stress (MPa) 0.2% proof stress 1000 600 400 200 0 600 400 200 0 100 200 300 400 500 600 700 Test temperature (℃) Fig. 62 Tensile properties of 1Cr-1Mo-V steel forgings [1]. Landolt-Börnstein New Series VIII/2B 0 0 100 200 300 400 500 Test temperature (℃) 600 700 58 2.2 Low alloy steels 2.2.6.3 Creep properties of 1Cr-1Mo-V steel forgings Information of fact on creep data for 1Cr-1Mo-V steel forgings can be obtained from [1] to [8]. 2.2.6.3.1 Creep rupture data of 1Cr-1Mo-V steel forgings Creep rupture strength data of 1Cr-1Mo-V steel forgings is shown in Fig. 63. 500 Stress [MPa] 300 100 80 60 40 10 450 °C 500 °C 525 °C 550 °C 575 °C 600 °C 625 °C 650 °C 675 °C 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 63. Creep rupture strength data of 1Cr-1Mo-V steel forgings; [1]. 2.2.6.3.2 Creep rupture strength of 1Cr-1Mo-V steel forgings The creep rupture data from Fig. 63 were analyzed using the Manson-Haferd parameter method. The master rupture curve is shown in Fig. 64 [1]. 800 600 500 400 Stress [MPa] 300 200 450 °C 500 °C 525 °C 550 °C 575 °C 600 °C 625 °C 650 °C 675 °C 100 80 60 50 Average 1) n = 229 (238) 40 30 -2.0 -3.0 -2.5 -3.5 -4.0 Manson-Haferd parameter [( log tR -17.145)/( TK -370.0 )] [×10 - 2 ] Fig. 64. Master rupture curve by Manson-Haferd parameter method for 1Cr-1Mo-V steel forgings; [1]. 1) The number in parenthesis includes the estimated values. Landolt-Börnstein New Series VIII/2B Ref. p. 61] 2.2.6 1Cr-1Mo-V steel 59 2.2.6.3.3 Effect of heat-treatment conditions on creep strength of 1Cr-Mo-V steel forgings The creep strength is an important property for turbine rotors, and toughness and thermal fatigue strength are also requested. The balance of these properties must be kept. Heat treatment conditions have been investigated in order to obtain the most suitable properties. Oil-quenching and tempering was at first used as heat treatment of rotor forgings, and air-cool normalizing and tempering was later introduced. High strength was easily obtained by oil-quenching, but quenching crack often happened. On the other hand, high strength could not be obtained by air-cooling. The heat treatment method using water sprays of fog was developed, and made it possible to control any cooling condition between oil-cooling and air-cooling. The turbine rotor with sound strength and toughness was manufactured using this method [2, 3]. A lot of research concerning effects of heat treatment on creep rupture notch strength was carried out. One case is shown in Fig. 65 [4]. 100 80 70 A Stress [1000 psi] 60 B 22 17 A B 50 13 14 40 Cooling Smooth Notch rate A 300°F/h B 400 °F/h Single lines are smooth-bar data Double lines are notch-bar data Numbers are rupture elongations [%] Rotor 30 20 1 10 9 10 3 10 2 Rupture time [h] 16 Fig. 65. Comparison of the 1000 °F stress-rupture properties of rotors A and B. Austenitized at 1750 °F, cooled as shown, and tempered at 1225 °F [4] 1 psi = 6.895 kPa. 10 4 2.2.6.3.4 Microstructural changes and long-term creep rupture properties for 1Cr-1Mo-V steel forgings Superior creep strength of 1Cr-1Mo-V steel forgings for turbine rotors is caused by precipitation strengthening due to finely distributed carbides. The degradation of high temperature strength properties is due to cohesion and enlargement of carbide particles, and caused by strength loss due to formation of voids and cracks during creep. Microstructural change is schematically presented in Fig. 66. For this steel, the cohesion and enlargement of grain boundary carbide particles during creep are remarkable. The formation of subgrains due to grain boundary migration is observed in the vicinity of enlarged grain boundary carbides, and low density precipitation areas of fine carbide particles are also observed along grain boundaries. The creep damage of this steel seems to be due to local recovery near grain boundaries, and not due to the formation of voids and cracks. The creep rupture ductility of 1Cr-1Mo-V steel is affected by impurity elements such as P, S, Sn, As, Sb and so on. The lowering of long-term creep rupture ductility is caused by formation of voids due to enlarged carbide particles at the grain boundaries and the linking of voids. The correlation between creep rupture ductility and numbers of grain boundary cavities is shown in Fig. 67 [6]. Landolt-Börnstein New Series VIII/2B 60 2.2 Low alloy steels Fig. 66. Schematic representations of microstructual change during creep; [5]. -5 -10 -15 80 600 500 400 60 300 40 Cavities [mm 2 ] D D/D [×10 4 ] 0 Reduction in area [%] 5 Reduction in area Density change, D D/D [×10 4 ] Grain boundary cavities [mm 2 ] 100 200 -20 20 -25 0 100 10 2 10 4 10 3 Time to rupture [h] 0 10 5 Fig. 67. Correlation between rupture ductility, density change and area of grain boundary cavities in specimens tested at 550 °C; [6]. 2.2.6.3.5 Creep crack growth property of 1Cr-1Mo-V steel forgings The understanding of creep crack growth properties of 1Cr-1Mo-V steel is important. The effect of specimen size on creep crack growth properties is shown in Fig. 68 [7]. The creep crack growth rate is dependent on the thickness of the specimen: The larger the thickness the faster the rate. This is due to the restriction of deformation to the direction of thickness at the crack tip. Landolt-Börnstein New Series VIII/2B Ref. p. 61] 2.2.6 1Cr-1Mo-V steel 61 10 d a /d t [mm/ h] 1Cr-Mo-V steel 538 °C 10- 1 W [mm] B [mm] 254.0 63.5 254.0 12.7 50.8 25.4 50.8 12.7 50.8 6.35 50.8 6.35 no S.G. 10- 2 10- 3 10- 1 1 10 10 2 Fig. 68. Effect of specimen thickness, B, on the relationship between creep crack growth rate da/dt and C* parameter; [7]. C * [kJ/m2 h ] 2.2.6.4 References [1] [2] [3] [4] [5] [6] [7] [8] National Research Institute for Metals: NRIM Creep Data Sheet, No.9B, (1990). Sakabe, K., Hori, K., Honma, R.: Tetsu-to-Hagane, 46 (1960), 1340-1342. Watanabe, J., Kumada, Y., Iwasaki, T.: Tetsu-to-Hagane, 52 (1966), 687-689. Werner, F.E., Eichelberger, T.W., Hann, E.K.: Trans.Amer.Soc.Metals, 52 (1960), 376-403. Matsuo, T., Kisanuki, T., Tanaka, R., Komatsu, S.: Tetsu-to-Hagane, 70 (1984), 565-572. Shin-ya, N., and Keown, S.R.: Material Science. 13 (1979), 89-93. Tabuchi, M., Kubo, K., and Yagi, K.: Engineering Fracture Mechanics, 40 (1991), 311-321. The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at High Temperatures, Vol. I, Low Alloy Steels, (1972). Landolt-Börnstein New Series VIII/2B 62 2.2 Low alloy steels 2.2.7 1.25Cr-0.5Mo steel 2.2.7.1 Introduction 2.2.7.1.1 1.25Cr-0.5Mo steel plates This material is normalized and tempered and used as plates for boilers and pressure vessels. The steel plate shall be made of the killed steel by hot rolling process. The steel plate shall be subjected to heat treatment either annealing or normalizing and tempering so that the normal grain size may be obtained. When high tensile strength is required, generally, the steel plate shall be subjected to normalizing and tempering. The maximum thickness of 1.25Cr-0.5Mo steel plates is 200 mm. 2.2.7.1.2 1.25Cr-0.5Mo steel tubes 1.25Cr-0.5Mo steel is used for boiler and heat exchanger seamless tubes. It is applied in alloy steel tubes, used for the purpose of heat exchange at the inside and outside of the tube, such as water tubes, smoke tubes, superheater tubes and air preheater tubes of boilers, or heat exchanger tubes, condenser tubes and catalyst tubes in the chemical and petroleum industries. However, it is not used for tubes in heating furnaces and heat exchangers at low temperatures. These steel tubes shall be made by the seamless process. Generally, tubes made of 1.25Cr-0.5Mo steel shall be subjected to heat treatments with isothermal annealed, fully annealed or normalized and tempered conditions. 2.2.7.2 Material standards, chemical compositions and tensile properties 2.2.7.2.1 1.25Cr-0.5Mo steel plates The following information was obtained from [1]. Table 39 shows the specification (SCMV 3 NT (JIS G 4109)) for the chemical composition of 1.25Cr0.5Mo steel plates and the analysis results of chemical compositions of typical three heats used for data treatment in this article. Moreover, Table 40 shows the heat treatment history of these three heats. Here, any test material has been normalized and tempered. The normalizing temperature shall be within the range of 875 to 1000 °C. After heating to the normalizing temperature, accelerated cooling such as liquid cooling, air-blasting or other appropriate methods may be performed to obtain the specified mechanical properties. Here, air-blasting has been applied to the test materials. The tempering temperature shall be above 620 °C. For the test materials, 630 °C as one-step tempering temperature or 710 °C and 700 °C as two-step tempering temperatures have been applied. Furthermore, Table 41 shows the specification for the tensile properties at room temperature. Table 39. Specification for chemical composition and analysis results for 1.25Cr-0.5Mo steel plates. Chemical composition [wt%] Standard/Heats C Si Mn P S Ni Cr Mo Fe SCMV 3 NT 0.44 0.36 0.940.40Rem. ≤0.17 ≤0.03 ≤0.03 (JIS G 4109) 0.86 0.69 1.56 0.70 Heat 1 0.15 0.61 0.6 0.009 0.013 0.35 1.2 0.51 Rem. Heat 2 0.16 0.66 0.56 0.015 0.015 0.05 1.27 0.51 Rem. Heat 3 0.13 0.52 0.54 0.009 0.011 0.05 1.1 0.48 Rem. Rem. = Remainder. Landolt-Börnstein New Series VIII/2B Ref. p. 66] 2.2.7 1.25Cr-0.5Mo steel 63 Table 40. Heat treatment history for 1.25Cr-0.5Mo steel plates. Thermal history Heat 1 920 °C × 1.5 h A.C. 710 °C × 1.5 h A.C. 700 °C × 2 h F.C. Heat 2 950 °C × 1.5 h A.C. 630 °C × 2.2 h A.C. Heat 3 930 °C × 1.5 h A.C. 630 °C × 2.2 h A.C Table 41. Specification of tensile properties for 1.25Cr-0.5Mo steel plates. Tensile properties Requirement Tensile strength 0.2 % proof stress Elongation [MPa] [MPa] [%] SCMV 3 NT 520 - 690 315 min. 22 min. (JIS G 4109) Reduction of area [%] - 800 800 700 700 y strength [MPa] 0.2 % proof Tensile strength [MPa] Fig. 69a - Fig. 69d show tensile strength, 0.2% proof strength, tensile elongation and reduction of area of 1.25Cr-0.5Mo steel plates from room temperature to 650 °C. The solid lines express the average level of the respective property. 600 500 400 300 200 600 500 400 300 200 100 100 0 0 0 100 200 300 400 500 600 0 700 100 200 Temperature [°C] Fig. 69a. Tensile strength of 1.25Cr-0.5Mo steel plates. 400 500 600 700 Fig. 69b. 0.2% proof strength of 1.25Cr-0.5Mo steel plates. 100 100 80 80 Reduction of area [%] Elongation [%] 300 Temperature [°C] 60 40 60 40 20 20 0 0 0 100 200 300 400 500 600 700 Temperature [°C] Fig. 69c. Tensile elongation of 1.25Cr-0.5Mo steel plate. Landolt-Börnstein New Series VIII/2B 0 100 200 300 400 500 600 700 Temperature [°C] Fig. 69d. Reduction of area of 1.25Cr-0.5Mo steel plates. 64 2.2 Low alloy steels Although the strong decrease of tensile strength is not indicated till about 400 °C, tensile strength decreases slightly near 100 °C and subsequently it increases slightly near 300 to 400 °C where it reaches a similar level as at room temperature. However, for temperatures above 500 °C, tensile strength decreases rapidly. 0.2% proof strength decreases gradually with increasing temperature above around 200 °C. For temperatures above 550 °C, degression becomes large. The tensile elongation curve inversely correlates with that of tensile strength. It increases strongly from near 500 °C. This tendency is the same also for the reduction of area. It should be noted that the scatter of these tensile properties comes from different heats. 2.2.7.2.2 1.25Cr-0.5Mo steel tubes The following information has been obtained [1]. Table 42 shows the specification (STBA23 (JIS G 3462)) for the chemical composition of 1.25Cr-0.5Mo steel tubes and the analysis results of chemical compositions of typical three heats used for data treatment in this article. Moreover, Table 43 shows the heat treatment history of these three heats. Here, any test material has been normalized and tempered. Annealing needs to be performed above 650 °C and it was carried out above 670 °C here. Furthermore, Table 44 shows the specification for the tensile properties at room temperature. Table 42. Specification for the chemical composition and analysis results for 1.25Cr-0.5Mo steel tubes. Chemical composition [wt%] Standard/Heats C Si Mn P S Ni Cr Mo Fe STBA 23 0.15 0.50 0.30 0.03 0.03 1.00 0.45 Rem. (JIS G3462) max. 1.00 0.60 max. max. 1.50 0.65 Heat 1 0.12 0.79 0.49 0.007 0.006 0.12 1.2 0.56 Rem. Heat 2 0.11 0.7 0.47 0.02 0.018 0.022 1.27 0.54 Rem. Heat 3 0.12 0.69 0.45 0.021 0.017 0.024 1.28 0.55 Rem. Table 43. Heat treatment history for 1.25Cr-0.5Mo steel tubes. Thermal history Heat 1 910 °C × 10 min → 670 °C × 70 min A.C. Heat 2 920 °C × 60 min → 740 °C × 90 min A.C. Heat 3 930 °C × 10 min → 690 °C × 70 min A.C. Table 44. Specification of tensile properties for 1.25Cr-0.5Mo steel tubes. Tensile properties Requirement Tensile strength 0.2% proof stress Elongation [MPa] [MPa] [%] STBA 23 ≥410 ≥205 ≥30 (JIS G3462) Reduction of area [%] - Fig. 70a - Fig. 70d show the tensile strength, 0.2% proof strength, tensile elongation and reduction of area of 1.25Cr-0.5Mo steel tubes from room temperature to 650 °C. The solid line expresses the average level of the properties. Tensile strength, 0.2% proof stress and tensile elongation show very similar behavior to 1.25Cr-0.5Mo steel plates (see above). Although the reduction of area tends to become a little lower near 300 °C, it increases with temperature beyond 300 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 66] 2.2.7 1.25Cr-0.5Mo steel 800 800 700 y strength [MPa] 0.2 % proof 700 600 Tensile strength [MPa] 65 500 400 300 200 100 600 500 400 300 200 100 0 0 0 100 200 300 400 500 600 700 0 100 200 Temperature [°C] 300 400 500 600 700 Temperature [°C] Fig. 70a. Tensile strength of 1.25Cr-0.5Mo steel tubes. 100 Fig. 70b. 0.2% proof strength of 1.25Cr-0.5Mo steel tubes. 100 80 Reduction of area [%] Elongation [%] 80 60 40 20 60 40 20 0 0 100 200 300 400 500 600 700 Temperature [°C] 0 0 100 200 300 400 500 600 700 Temperature [°C] Fig. 70c. tubes. Tensile elongation of 1.25Cr-0.5Mo steel Fig. 70d. Reduction of area of 1.25Cr-0.5Mo steel tubes. 2.2.7.3 Creep rupture properties of 1.25Cr-0.5Mo steels 2.2.7.3.1 1.25Cr-0.5Mo steel plates The creep rupture strength of 1.25Cr-0.5Mo steel plates is shown in Fig. 71. The creep tests were carried out in the temperature range from 500 °C to 650 °C with a 50 °C pitch and at stresses between 37 MPa and 431 MPa. The longest time to rupture is over 180,000 h. Even if there are more tests at low temperature, test data scatter is larger at the low temperature side. 2.2.7.3.2 1.25Cr-0.5Mo steel tubes The creep rupture strength of 1.25Cr-0.5Mo steel tubes is shown in Fig. 72. Creep tests were carried out in the temperature range from 500 to 650 °C with a 50 °C pitch and at stresses between 41 MPa and 373 MPa. The longest time to rupture is over 60,000 h. Even if there are more tests at low temperature, test data scatter is larger at the low temperature side. Landolt-Börnstein New Series VIII/2B 66 2.2 Low alloy steels 1.25Cr0.5Mo Steel Creep Rupture (Plates) Stress (MPa) 1000 100 T=500℃ T=550℃ T=600℃ T=650℃ 10 10-1 100 Fig. 71. Creep rupture strength data of 1.25Cr-0.5Mo steel plates. 101 102 103 104 105 106 Time to rupture (h) 1.25Cr0.5Mo Steel Creep Rupture (Tubes) Stress (MPa) 1000 100 T=500℃ T=550℃ T=600℃ T=650℃ 10 10-1 100 101 Fig. 72. Creep rupture strength data of 1.25Cr-0.5Mo steel tubes. 102 103 104 105 106 Time to rupture (h) 2.2.7.4 References [1] NRIM Creep Data Sheet, No. 21B, (1994). [2] NRIM Creep Data Sheet, No. 2A, (1976). Landolt-Börnstein New Series VIII/2B Ref. p. 73] 2.2.8 2.25Cr-1Mo steel 67 2.2.8 2.25Cr-1Mo steel 2.2.8.1 Introduction 2.25Cr-1Mo steel is widely used as tubes for boilers and heat exchangers and as components for pressure vessels. It is heat-treated in order to obtain suitable strength properties for use. 2.2.8.2 Material standards, chemical and tensile requirements 2.2.8.2.1 2.25Cr-1Mo steel tubes for boilers and heat exchangers Table 45. Chemical requirements of 2.25Cr-1Mo steel tubes; JIS STBA24, ASTM T22, BS622 and DIN 10CrMo 910 Standards Designation C STBA24 JIS ≤0.15 ASTM T22 0.05-0.15 BS 622 0.08-0.15 10CrMo 910 0.08-0.15 DIN Si ≤0.50 ≤0.50 ≤0.50 ≤0.50 Chemical composition [wt%] Mn P S Cr Mo 0.30-0.60 ≤0.030 ≤0.030 1.90-2.60 0.87-1.13 0.30-0.60 ≤0.025 ≤0.025 1.90-2.60 0.87-1.13 0.40-0.70 ≤0.040 ≤0.040 2.00-2.50 0.90-1.20 0.40-0.70 ≤0.035 ≤0.035 2.00-2.50 0.90-1.20 Ni ≤0.30 - Al ≤0.020 - Std.No. G3462 A213 3606 17175 Table 46. Tensile properties at room temperature of 2.25Cr-1Mo steel tubes; JIS STBA24, ASTM T22, BS622 and DIN 10CrMo 910 Tensile strength Yield strength Elongation Standards Designation [MPa] [MPa] [%] STBA24 JIS ≥410 ≥205 ≥30 ASTM T22 ≥415 ≥205 490-640 BS 622 ≥275 10CrMo 910 450-600 DIN ≥280 Tensile strength 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 600 300 300 200 200 100 100 0 0 100 200 300 400 500 600 700 0 0 Test temperature (℃) Fig. 73. Tensile properties of 2.25Cr-1Mo steel tubes; JIS STBA24 [1]. Landolt-Börnstein New Series VIII/2B 100 200 300 400 Test temperature 500 (℃) 600 700 68 2.2 Low alloy steels 2.2.8.2.2 2.25Cr-1Mo steel plates for boilers and pressure vessels Table 47. Chemical requirements of 2.25Cr-1Mo steel plates; JIS SCMV4-2, ASTM Gr.22-cl.2 and EN 10CrMo 9-10 Standards Chemical composition [wt%] Std.No. C Si Mn P S Cr Mo ≤0.17 ≤0.50 0.30-0.60 ≤0.030 ≤0.030 2.00-2.50 0.90-1.10 G4109 0.05-0.15 ≤0.50 0.30-0.60 ≤0.035 ≤0.035 2.00-2.50 0.90-1.10 A387M Designation JIS SCMV 4-2 ASTM Gr.22-cl.2 BS EN 10CrMo 9-10 0.08-0.14 ≤0.50 0.40-0.80 ≤0.030 ≤0.025 2.00-2.50 0.90-1.10 10028-2 DIN EN Table 48. Tensile properties at room temperature of 2.25Cr-1Mo steel plates; JIS SCMV4-2, ASTM Gr.22-cl.2 and EN 10CrMo 9-10. Tensile strength Yield strength Elongation Reduction of area Standards Designation [MPa] [MPa] [%] [%] 520-690 JIS SCMV 4-2 ≥315 ≥18 ≥45 515-690 ASTM Gr.22-cl.2 ≥310 BS EN 10CrMo 9-10 480-630 ≥310 DIN EN Tensile strength 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 700 400 300 400 300 200 200 100 100 0 0 100 200 300 400 500 600 700 0 0 100 Test temperature (℃) 200 300 400 500 600 700 Test temperature (℃) Fig. 74. Tensile properties of 2.25Cr-1Mo steel plates; JIS SCMV 4-2NT [2]. 2.2.8.2.3 Quenched–and-tempered 2.25Cr-1Mo steel plates; ASTM A542, cl.1, 2, 3, 4 and 4a Table 49. Chemical requirement of quenched-and-tempered 2.25Cr-1Mo steel plates; ASTM A542, TypeA. C ≤0.18 Si ≤0.50 Chemical composition according to product analysis [wt%] Mn P S Cr Mo Ni 0.25-0.66 ≤0.025 ≤0.025 1.88-2.62 0.85-1.15 ≤0.43 Cu ≤0.43 V ≤0.04 Landolt-Börnstein New Series VIII/2B Ref. p. 73] 2.2.8 2.25Cr-1Mo steel 69 Table 50. Tensile properties at room temperature of quenched-and-tempered 2.25Cr-1Mo steel plates; ASTM A542. Tensile strength Yield strength Elongation class [MPa] [MPa] [%] 725 - 860 1 ≥585 ≥14 795 - 930 2 ≥690 ≥13 655 - 795 3 ≥515 ≥20 585 - 760 4 ≥380 ≥20 585 - 760 4a ≥415 ≥18 Tensile strength 800 800 700 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 400 300 400 300 200 200 100 100 0 0 0 100 200 300 400 500 600 700 Test temperature (℃) 0 100 200 300 400 500 600 700 Test temperature (℃) Fig. 75. Tensile properties of quenched-and-tempered 2.25Cr-1Mo steel plates; ASTM A542, cl.1, 3 and 4a; [3]. 2.2.8.3 Creep properties of 2.25Cr-1Mo steels Information of fact on creep data for 2.25Cr-1Mo steels can be obtained from [1], [2], [3], [9] and [10]. 2.2.8.3.1 Creep rupture data of 2.25Cr-1Mo steels Creep rupture data of annealed 2.25Cr-1Mo steel tubes, normalized-and-tempered 2.25Cr-1Mo steel plates and quenched-and-tempered 2.25Cr-1Mo steel plates are shown in Fig. 76, Fig. 77 and Fig. 78, respectively. Landolt-Börnstein New Series VIII/2B 70 2.2 Low alloy steels 500 450 °C 475 °C 500 °C 525 °C 550 °C 600 °C 650 °C Stress [MPa] 300 100 80 60 40 20 10 10 2 10 3 10 4 Time to rupture [h] 10 5 Fig. 76. Creep rupture strength data of 2.25Cr-1Mo steel tubes; JIS STBA24; [1]. 10 6 500 Stress [MPa] 300 100 80 450 °C 475 °C 500 °C 525 °C 550 °C 600 °C 650 °C 60 40 20 1 10 2 10 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 77. Creep rupture strength data of 2.25Cr-1Mo steel plates; JIS SCMV 4-2NT; [2]. 700 500 Stress [MPa] 300 100 80 60 40 1 450 °C 475 °C 500 °C 525 °C 550 °C 575 °C 600 °C 650 °C 10 10 3 10 2 Time to rupture [h] 10 4 10 5 Fig. 78. Creep rupture strength data of quenched - and - tempered 2.25Cr-1Mo steel plates; ASTM A542; [3]. Landolt-Börnstein New Series VIII/2B Ref. p. 73] 2.2.8 2.25Cr-1Mo steel 71 2.2.8.3.2 Creep rupture strength of 2.25Cr-1Mo steels Creep rupture data of 2.25Cr-1Mo steel tubes was analyzed using the Manson-Haferd parameter method [1]. The master rupture curve obtained is shown in Fig. 79. 500 400 450 °C 475 °C 500 °C 525 °C 550 °C 600 °C 650 °C 300 Stress [MPa] 200 100 80 60 50 40 30 Average n = 294 (331) 20 -2.0 -3.0 -2.5 -3.5 -4.0 Manson-Haferd parameter [( log tR -16.053)/( TK -380 )] [×10 - 2 ] Fig. 79. Master rupture curve by Manson - Haferd parameter method for 2.25Cr-1Mo steel tubes; [1]. n indicates the total number of data points. The number in parenthesis includes the estimated values. 2.2.8.3.3 Effect of heat treatment conditions on long-term creep rupture strength of 2.25Cr-1Mo steel The long-term creep rupture strength of 2.25Cr-1Mo steels subjected to various heat treatment conditions is shown in Fig. 80. For shorter times, the creep rupture strength of quenched-and-tempered steel (Q.T.) is higher than that of annealed (Ann.) and of normalized-and-tempered steel (N.T.), because short-term creep rupture strength is dependent on tensile strength. However, long-term creep rupture strength is not related to any heat treatment condition, because differences in microstructure disappear due to changes in microstructure during creep [4]. 10 3 2.25Cr-1Mo steels Stress [MPa] Ann. N.T. Q.T. 10 2 10 16000 Fig. 80. Creep rupture strength properties of 2.25Cr-1Mo steels; [4]. 18000 20000 22000 24000 Larson-Miller parameter T [K] (20+log t r [ h]) Landolt-Börnstein New Series VIII/2B 72 2.2 Low alloy steels 2.2.8.3.4 Microstructual changes of 2.25Cr-1Mo steels Various precipitates such as ε-carbide, Fe3C, Mo2C, M7C3, M23C6, M6C etc. are formed in 2.25Cr-1Mo steels by heat treatment, during long heating, and during creep [5, 6]. Fig. 81 shows the carbide stability of 2.25Cr-1Mo steel during tempering. 800 M23C6 + Cr7C3 M23C6 + M6C Tempering temperature [°C ] 700 Fe3C + Cr7C3 + Mo2C 600 Fe3C + Mo2C 500 Fe3C 400 Fe3C + ε carbide 300 10 -1 1 2 10 10 Tempering time [h ] 10 3 4 Fig. 81. Carbide stability diagram of 2.25Cr-1Mo steel by Baker and Nutting; [5]. 10 The creep rupture curves of 2.25Cr-1Mo steel show inverse sigmoidal bending such as those of 1Cr0.5Mo steel. Fig. 82 shows the relationship between rupture life and minimum creep rate. It shows a large data scatter at longer rupture lifes and lower minimum creep rates. This scatter can be explained by the change in controlling factor of creep deformation and rupture life [7]. Time to rupture t r [h] 10 6 10 5 10 4 873 K 10 3 10 2 10 10 -6 2.25 Cr-1Mo steel Experimental data 723 K 773 K 823 K 823 K 873 K 923 K 923 K 723 K Predicted relations ( eI :30 %) emin I vs. tr I emin I vs. t r II 823 K 773 K Fig. 82. Comparison of measured results with predicted relations of time to rupture vs. minimum creep rate of 2.25Cr-1Mo steel; [7]. emin II vs. tr II 10 -5 10 -4 10 -3 10 -2 10 -1 Minimum creep rate, emin [% /h ] 1 2.2.8.3.5 Creep crack growth property of 2.25Cr-1Mo steels The shape of crack tip for CT specimens of 2.25Cr-1Mo steel shows tunneled creep crack growth. The electrical potential method for measuring tunneled crack growth was applied and a relationship between crack growth rate and C* integral was obtained as shown Fig. 83 [8]. Landolt-Börnstein New Series VIII/2B Ref. p. 73] 2.2.8 2.25Cr-1Mo steel 73 Creep crack growth rate d a /d t [mm /h] 1 10 -1 2.25Cr-1Mo steel 540 °C CT specimen (12.7, 6.4mmB) 10 -2 10 -3 da = 9.090×10- 3( C *) 0.818 dt (correlation coefficient = 0.956) 10 -4 10 -1 10 1 C *- Integral [kJ / m 2h ] without SG corrected by max.final crack length SG by Johnson’s eq. 10 2 Fig. 83. Relation between C*-integral and creep crack growth rate modified by the maximum final crack length for specimens without side grooves for 2.25Cr1Mo steel at 540 °C; [8]. SG means “side groove”. 2.2.8.4 References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] NRIM Creep Data Sheet, No.3B, (1986). NRIM Creep Data Sheet, No.11B, (1997). NRIM Creep Data Sheet, No.36A, (1991). Kushima, H., Kimura, K., Abe, F., Yagi, K., Irie, H., Maruyama, K.: Current Advances in Materials and Processes, 9 (1996), 1310. Baker, R.G., and Nutting, J.: The Iron and Steel Institute of Japan, 192 (1959), 257. Thomson, R.C., and Bhadeshia, H.K.D.H.: Materials Science and Technology, 10 (1994), 193-203. Yagi, K., Abe, F., Kimura, K., and Kushima, H.: Proc.of IUTAM Symposium on Creep in Structures, Kluwer Academic Publishers, (2001), 267-276. Fuji, A., Yamatani, I., Kitagawa, M., Ohtomo, A.: Tetsu-to-Hagane, 73 (1987), 1754-1761. The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at High Temperature, Vol.1, Low Alloy Steel, (1972). The British Steelmakers Creep Committee: BSCC high temperature data, (1972). Landolt-Börnstein New Series VIII/2B 74 2.2 Low alloy steels 2.2.9 2.25Cr-1.6W-V-Nb steel 2.2.9.1 Introduction 2.25Cr-1.6W-V-Nb ferritic steel (T23, P23; HCM2S) is used as water wall, superheater and reheater tubes, and header and main steam pipe in fossile fired boilers and heat recovery boilers. The steel has been developed for improving creep rupture strength of 2.25Cr-1Mo steel at elevated temperatures mainly by substituting Mo by W. The microstructure of the steel consists of a bainite matrix strengthened by M23C6 carbides located mainly along grain boundaries and finely dispersed VC carbides in the matrix. VC is fine and stable even after long term high temperature exposure. 2.2.9.2 Material standards, chemical and tensile requirements Tables 51 and 52 give the chemical requirements and the corresponding tensile requirements of 2.25Cr-1.6W-V-Nb steel tubes and pipes designated by the following standards: Japanese KA-STBA24J1, KA-STPA24J1, ASTM A213 T23, A335 P23, ASME Sec.I CC 2199. Table 51. Chemical requirements of 2.25Cr-1.6W-V-Nb steel tubes and pipes; Japanese KA-STBA24J1, KA-STPA24J1, ASTM A213 T23, A335 P23, ASME Sec.I CC 2199. DesigGrade nation Japanese KA-STBA METI 24J1 KA-STPA 24J1 ASTM- T23 A213 ASTM- P23 A335 C Si 0.04 - Mn P 0.10 - S - Chemical composition [wt%] Cr Mo W V Nb N 1.90 0.05 1.45 0.20 0.02 - Al - Std. No. B 0.0005 0.10 0.50 0.60 0.030 0.010 2.60 0.30 1.75 0.30 0.08 0.030 0.030 0.006 0.04 - 0.10 - - 1.90 0.05 1.45 0.20 0.02 - - 0.0005 ASME Sec I 0.10 0.50 0.60 0.030 0.010 2.60 0.30 1.75 0.30 0.08 0.030 0.030 0.006 CC 2199 Table 52. Tensile requirements of 2.25Cr-1.6W-V-Nb steel tubes and pipes; Japanese KA-STBA24J1, KA-STPA24J1, ASTM A213 T23, A335 P23, ASME Sec. I CC 2199. Minimal DesigStandard No. Grade TS1) YS2) elongation nation KA-STBA24J1 Japanese 510 MPa 400 MPa 20 % METI KA-STPA24J1 ASTM T23 ASME Sec. I A213 510 MPa 400 MPa 20 % CC 2199 ASTM P23 A335 1) TS: minimal tensile strength, 2) YS: minimal yield strength as 0.2% proof stress 2.2.9.3 Tensile properties of 2.25Cr-1.6W-V-Nb steel tubes 2.2.9.3.1 Tensile properties of 2.25Cr-1.6W-V-Nb steel tubes Fig. 84 shows tensile strength and yield stress data of 2.25Cr-1.6W-V-Nb steel tubes [1]. Their values are higher than those of T22 steel for all temperatures up to 650 °C. The corresponding tensile elongation and reduction of area data of 2.25Cr-1.6W-V-Nb steel tubes are available in the literature [1]. Landolt-Börnstein New Series VIII/2B Ref. p. 83] 2.2.9 2.25Cr-1.6W-V-Nb steel 75 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 0 100 200 300 400 500 Temperature [°C] 600 700 Fig. 84. Tensile strength (squares) and yield stress (circles) of 2.25Cr-1.6W-V-Nb steel tubes. 2.2.9.3.2 Tensile properties of 2.25Cr-1.6W-V-Nb steel pipe Fig. 85 shows tensile strength and yield stress data of 2.25Cr-1.6W-V-Nb steel pipes [1]. Their values are higher than those of P22 steel at all temperatures up to 650 °C. The corresponding tensile elongation and reduction of area data of 2.25Cr-1.6W-V-Nb steel pipes are available in [1]. 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 Fig. 85. Tensile strength (squares) and yield stress (circles) of 2.25Cr-1.6W-V-Nb steel pipes. 100 0 0 100 200 300 400 500 Temperature [°C] 600 700 2.2.9.4 Creep rupture properties of 2.25Cr-1.6W-V-Nb steel tubes and pipes 2.2.9.4.1 Creep rupture data of 2.25Cr-1.6W-V-Nb steel tubes Fig. 86 shows creep rupture data of 2.25Cr-1.6W-V-Nb steel tubes. The longest creep rupture time of 2.25Cr-1.6W-V-Nb steel tubes is about 40000 h at 550 °C. Their long-term creep strengths are very stable in the temperature range between 500 and 600 °C. Fig. 87 shows the Larson-Miller parameter plot of the creep rupture data with a master rupture curve and a 95 % confidence lower limit [1]. The best fitting was achieved with an optimized constant of 23.37. Landolt-Börnstein New Series VIII/2B 76 2.2 Low alloy steels 500 400 300 Stress [MPa] 500 °C 200 550 °C 100 80 500 °C 550 °C 600 °C 650 °C 600 °C Average curve 60 × ruptured due to substantial oxidation of specimen 40 1 × 10 2 10 3 Rupture time [h] 10 650 °C { 10 4 10 5 Fig. 86. Creep rupture strength data of 2.25Cr-1.6W-V-Nb steel tubes. 500 500 °C ×10 5h 400 Stress [MPa] 300 550 °C ×10 5h 200 100 80 60 40 17 600 °C ×10 5h 500 °C 550 °C 600 °C 650 °C average curve minimum curve 18 19 20 21 22 23 24 25 26 27 Larson-Miller-parameter T (23.37 + log t ) [×10 -3 ] Fig. 87. Larson-Miller parameter plot of the creep rupture data of 2.25Cr-1.6W-V-Nb steel tubes. 2.2.9.4.2 Creep rupture data of 2.25Cr-1.6W-V-Nb steel pipes Fig. 88 shows creep rupture data of 2.25Cr-1.6W-V-Nb steel pipes. The longest creep rupture time of 2.25Cr-1.6W-V-Nb steel pipes is about 50000 h at 600 °C. Their long-term creep strengths are very stable at temperatures between 500 and 600 °C. Fig. 89 shows the Larson-Miller parameter plot of the creep rupture data with a master rupture curve and a 95 % confidence lower limit [1]. The best fitting was achieved with an optimized constant of 19.95. 2.2.9.4.3 Creep data of 2.25Cr-1.6W-V-Nb steel tubes Fig. 90 shows minimum creep rate data of 2.25Cr-1.6W-V-Nb steel tubes measured at various stress levels at temperatures between 600 °C and 750 °C. Fig. 91 shows the Larson-Miller parameter plot of the minimum creep rate data of 2.25Cr-1.6W-V-Nb steel tubes with a master minimum creep rate curve. The best fitting was achieved with an optimized constant of 25.19. Landolt-Börnstein New Series VIII/2B Ref. p. 83] 2.2.9 2.25Cr-1.6W-V-Nb steel 77 500 400 Stress [MPa] 300 500 °C 200 550 °C 500 °C 550 °C 600 °C 650 °C 100 80 60 600 °C average curve 650 °C 40 1 10 2 10 3 Rupture time [h] 10 10 4 10 5 Fig. 88. Creep rupture strength data of 2.25Cr-1.6W-V-Nb steel pipes. 500 400 500 °C ×10 5h Stress [MPa] 300 550 °C ×10 5h 200 600 °C ×10 5h 100 80 60 40 15 625 °C ×10 5h 500 °C 550 °C 600 °C 650 °C average curve minimum curve 16 17 18 19 20 21 22 23 24 25 Larson-Miller-parameter T (19.95 + log t ) [×10 -3 ] Fig. 89. Larson-Miller parameter plot of the creep rupture data of 2.25Cr-1.6W-V-Nb steel pipes. 500 400 Stress [MPa] 300 200 500 °C 550 °C 100 80 500 °C 550 °C 600 °C 650 °C average curve 600 °C 60 650 °C 40 10 -2 Landolt-Börnstein New Series VIII/2B 10 -1 1 10 Minimum creep rate [% / 10 3 h] 10 2 Fig. 90. Minimum creep rate data of 2.25Cr-1.6W-V-Nb steel tubes. 10 78 2.2 Low alloy steels 500 500 °C 0.01 % /10 3h 400 Stress [MPa] 300 550 °C 0.01 % /10 3h 200 100 500 °C 550 °C 600 °C 650 °C 80 60 40 average curve 17 18 19 20 21 22 23 24 25 26 . Larson-Miller-parameter T (25.19 - log e ) [×10 -3 ] Fig. 91. Larson-Miller parameter plot of the minimum creep rate data of 2.25Cr-1.6W-V-Nb steel tubes. 2.2.9.4.4 Creep data of 2.25Cr-1.6W-V-Nb steel pipes Fig. 92 shows minimum creep rate data of 2.25Cr-1.6W-V-Nb steel pipes measured at various stress levels at temperatures between 600 °C and 750 °C . Fig. 93 shows the Larson-Miller parameter plot of the minimum creep rate data of 2.25Cr-1.6W-V-Nb steel pipes with a master minimum creep rate curve [1]. The best fitting was achieved with an optimized constant of 31.27. 500 400 300 Stress [MPa] 500 °C 200 550 °C 100 600 °C 500 °C 550 °C 600 °C 650 °C average curve 80 650 °C 60 40 10 -2 10 -1 1 10 Minimum creep rate [% / 10 3 h] 10 2 10 3 Fig. 92. Minimum creep rate data of 2.25Cr-1.6W-V-Nb steel pipes. Landolt-Börnstein New Series VIII/2B Ref. p. 83] 2.2.9 2.25Cr-1.6W-V-Nb steel 79 500 400 500 °C 0.01 % /10 3h Stress [MPa] 300 550 °C 0.01 % /10 3h 200 600 °C 0.01 % /10 3h 100 500 °C 550 °C 600 °C 650 °C 80 60 40 21 average curve 22 23 24 25 26 27 28 29 30 31 . Larson-Miller-parameter T (31.27 - log e ) [×10 -3 ] Fig. 93. Larson-Miller parameter plot of the minimum creep rate data of 2.25Cr-1.6W-V-Nb steel pipes. 2.2.9.5 Allowable stress of 2.25Cr-1.6W-V-Nb steel tubes and pipes Figs. 94 and 95 show the allowable tensile stresses determined for 2.25Cr-1.6W-V-Nb steel tubes and pipes (Japanese METI KA-STBA24J1 and KA-STPA24J1) according to the METI standard procedure comparing with those for the conventional steels ASME SA213-T22 and SA335-P22 (JIS STBA24 and STPA24). 180 Allowable tensile stress (MPa) 160 KA-STBA24J1 140 120 100 STBA24 80 60 40 20 0 0 100 200 300 400 500 600 700 800 Temperature (℃) Landolt-Börnstein New Series VIII/2B Fig. 94. Allowable tensile stress designated for 2.25Cr-1.6WV-Nb steel tubes (Japanese METI KA-STBA24J1). 80 2.2 Low alloy steels 180 Allowable tensile stress (MPa) 160 KA-STPA24J1 140 120 100 STPA24 80 60 40 20 Fig. 95. Allowable tensile stress designated for 2.25Cr1.6W-V-Nb steel pipes (Japanese METI KA-STPA24J1). 0 0 100 200 300 400 500 600 700 800 Temperature (℃) 2.2.9.6 Alloying philosophy of 2.25Cr-1.6W-V-Nb steel tubes Fig. 96 shows the alloying philosophy of 2.25Cr-1.6W-V-Nb steel tubes. The steel has been developed to improve the creep rupture strength of 2.25Cr-1Mo steel, which is mainly achieved by the combination of solid solution of W and (V,Nb) C dispersion hardening in fully tempered bainitic matrix. Addition of B enhances the bainitic microstructure and is found to improve the toughness of the steel to a great extent. Low C content has been chosen to improve the weldability of the steel and as a result no preheating and no post welding heat treatment (PWHT) is potentially required for some applications. Weldability Toughness Creep strength max.Hv≦350 Hardenability : B addition Solution Strengthening Low C-0.06mass% Fully tempered bainitic structure Precipitation Strengthening : V, Nb, B : High W No preheating and PWHT after welding* 0.06C-2.25Cr-1.6W-0.1Mo-0.25V-0.05Nb-B Matching welding filler used without PWHT * according to the limitation of the spec. Fig. 96. Alloying philosophy of 2.25Cr1.6W-V-Nb steel tubes. 2.2.9.7 Microstructural change of 2.25Cr-1.6W-V-Nb steel tubes Fig. 97 shows a calculated phase diagram of 2.25Cr-1.6W-V-Nb steel at 600 °C with changing Cr and C contents. The equilibrium phase diagram suggests that the final microstructure of 2.25Cr-1.6W-V-Nb steel consists of ferrite (α) + MX ((V,Nb)C) + M6C and may include a small amount of M23C6. Fig. 98 shows TEM micrographs of extraction replicas of 2.25Cr-1.6W-V-Nb steel normalized and tempered (a) and crept for 12567.6 h at 600 °C (b). In the tempered specimen, M23C6 is formed along prior austenitic grain boundaries and MX is formed along lath boundaries and in the bainitic matrix. M7C3 is occasionally observed along lath boundaries. In the crept specimen, on the other hand, no M23C6 and M7C3 are observed and instead blocky M6C is formed along the prior austenitic grain boundaries and fine MX remains along lath boundaries and in the bainitic matrix as shown in Fig. 99. It is noted that the pronounced lath structure is kept even after long-term creep deformation. Landolt-Börnstein New Series VIII/2B Ref. p. 83] 2.2.9 2.25Cr-1.6W-V-Nb steel 81 α + M 23C 6+M 6C +M X α + M X+M 6C Fig. 97. Calculated phase diagram of 2.25Cr-1.6W-V-Nb steel at 600 °C using Thermo-Calc. M23C 6 MX MX M7C3 1μm 1μm (a) normalized and tempered M6C MX M6C 1μm 1μm (b) crept for 12567.6 h at 600 °C Fig. 98. TEM micrographs of extraction replicas of 2.25Cr-1.6W-V-Nb steel normalized and tempered (a) and crept for 12567.6 h at 600 °C (b). Landolt-Börnstein New Series VIII/2B 82 2.2 Low alloy steels Formation of M6C means that the steel looses W and/or Mo in solution, which are the key elements for solid solution strengthening. It is, however, found that W is superior to Mo to retard the formation of M6C during long-term creep deformation. Fig. 100 shows the change in precipitated W in 2.25Cr-1.6W0.2Mo-V-Nb steel and Mo in 2.25Cr-1.0Mo-V-Nb steel during aging for up to 10000 h at temperatures between 550 °C and 650 °C. The lines indicate fitted curves assuming that the growth rate is controlled by the Johnson-Mehrl-Abrami theory. It is seen that in 2.25Cr-1.6W-0.2Mo-V-Nb steel the growth rate of M6C is 10 to 100 times slower that that in 2.25Cr-1.0Mo-V-Nb steel. This is one of the major reasons for the high creep strength of 2.25Cr-1.6W-V-Nb steel. 020 000 110 Fig. 99. TEM micrograph showing fine dispersion of MX in 2.25Cr-1.6W-V-Nb steel crept for 12567.6 h at 600 °C. 200 B :001 100nm 1.0 1.0 Experiment value 0.8 Fraction of W - precipitation Fraction of Mo - precipitation Experiment value 650 °C 0.6 600 °C 0.4 550 °C 0.2 0 1 0.8 650 °C 0.6 600 °C 0.4 0.2 550 °C 0 10 10 2 10 3 Aging time [h] (a) 2.25Cr-1.0Mo-V-Nb steel 10 4 10 5 1 10 10 2 10 3 Aging time [h] 10 4 10 5 (b) 2.25Cr-1.6W-0.2Mo-V-Nb steel Fig. 100. Changes in precipitated W in 2.25Cr-1.6W-0.2Mo-V-Nb steel and Mo in 2.25Cr-1.0Mo-V-Nb steel during aging for up to 10000 h at temperatures between 550 °C and 650 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 83] 2.2.9 2.25Cr-1.6W-V-Nb steel 83 2.2.9.8 Performance of service exposed tubes Detailed performance of service exposed tubes is available in [3], [6] and [7]. 2.2.9.9 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Masuyama, F., Yokoyama, T., Sawaragi, Y., and Iseda, A.: Materials for Advanced Power Engineering, Part 1, Kluwer Academic Publishers (1994), 173. [3] Sawaragi, Y., Kan, T., Yamadera, Y., Masuyama, F., Yokoyama, T., and Komai, N.: Proc. of the 6th International Conference on Materials for Advanced Power Engineering, Liege Forschungszentrum Jülich GmbH, 1998, p. 61. [4] Komai, N., Masuyama, F., Ishihara, I., Yokoyama, T., Yamadera, Y., Okada, H., Miyata, K., and Sawaragi, Y.: Advanced Heat Resistant Steels For Power Generation, The University Press, Cambridge (1998), 96. [5] Sawaragi, Y., Miyata, K., Yamamoto, S., Masuyama, F., Komai, N., Yokoyama, T.: Advanced Heat Resistant Steels For Power Generation, The University Press, Cambridge (1998), 144. [6] Miyata, K., Igarashi, M., and Sawaragi, Y.: ISIJ International, 39 (1999), 947. [7] Miyata, K., and Sawaragi, Y.: ISIJ International, 41 (2001), 281. Landolt-Börnstein New Series VIII/2B 84 2.2 Low alloy steels 2.2.10 3Cr-0.5Mo-V steel 2.2.10.1 Introduction 3Cr-0.5Mo-V steel (20CrMoV13-5) is primarily used as a material for seamless circular tubes for use mainly in chemical plants for high pressure applications at elevated service temperatures, which may also include simultaneous exposure to hydrogen or hydrogen containing fluids (e.g. boiler or heat exchanger tubes in petrochemical industry). The microstructure is typically bi-phase bainite and ferrite. Its creep resistance is due to structural stability and saturated bainite, the carbide distribution and solid solution hardening, which balances the lower strength of the ferrite phase. 20 CrMoV13-5 is relatively easy to cold and hot bend (pipes/tubes) and to weld by typical welding procedures for low alloy high temperature steels. 20CrMoV13-5 is suitable for use from 200 °C. 2.2.10.2 Material standards, chemical composition and tensile requirements Table 53. Chemical requirements of 3Cr-0.5Mo-V steel (20CrMoV13-5). Chemical composition [wt%] DesigStanStd. No. nation dard C Si Mn P S Cr Mo Ni Data 20CrMoV 0.17 0.15 0.30 ≤ 3.00 0.50 ≤ ECCC sheet 13-5 0.23 0.35 0.50 0.020 0.020 3.30 0.60 20CrMoV 0.17 0.15 0.30 ≤ 3.00 0.50 ≤ ≤ EN 10216-2 13-5-5 0.23 0.35 0.50 0.025 0.020 3.30 0.60 0.30 20CrMoV 0.17 0.15 0.30 ≤ 3.00 0.50 ≤ DIN 17176 13-5 0.23 0.35 0.50 0.025 0.020 3.30 0.60 V 0.45 0.55 0.45 0.55 0.45 0.55 Al ≤ 0.040 ≤ 0.040 ≤ 0.040 Cu ≤ 0.30 - Note: 20CrMoV13-5-5 EN 10216-2 supersedes 20CrMoV13-5 DIN 17176 specification. The material is usually supplied in quenched and tempered condition. The recommended quenching temperature range is 980 - 1030 °C with tempering in the range 680 - 730 °C, according to both of the standards and to the ECCC data sheet. Table 54. Room temperature mechanical property requirements for 3Cr-0.5Mo-V steel (20CrMoV13-5-5). StanDesigHeat Thickness t Rp0.2 Rm A Cv (RT)* Std. No. dard nation treat [mm] [Nmm-2] [Nmm-2] % [J] Data 20CrMoV 740 ECCC Q+T 1.6 < t < 100 590 sheet 13-5 880 740 20CrMoV 16 27 Q+T ≤100 590 EN 10216-2 880 13-5-5 740 20CrMoV 17 34 Q+T ≤100 590 DIN 17176 880 13-5 *The Charpy V-notch figure shown is in transverse direction. Table 55. Minimum 0.2% proof strength values at elevated temperatures for 3Cr-0.5Mo-V steel (20CrMoV13-5-5). Thickness Heat Rp0.2 [Nmm-2] at a temperature [°C] of Standard Designation [mm] treat 100 150 200 250 300 350 400 450 500 EN 10216-2 ≤ 60 Q+T 575 570 560 550 510 470 420 370 Landolt-Börnstein New Series VIII/2B Ref. p. 86] 2.2.10 3Cr-0.5Mo-V steel 85 2.2.10.3 Creep rupture strength The creep rupture strength of 20CrMoV13-5-5 is shown in Fig. 101. The analysis, from which the data in the figure were derived, was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found on their published data sheets [1]. 20CrMoV13-5 Stress [MPa] 1000 100 100,000h 10,000h Fig. 101. Creep rupture strength data of 3Cr-0.5Mo-V steel (20CrMoV13-5-5). 10 400 450 500 550 600 Temperature [°C] The creep rupture properties have been obtained by comparative analysis of strength values as reported in DIN 17176. 2.2.10.4 Estimated long term creep rupture strength Based on the data shown in Fig. 101 the 100,000 h rupture strength values for a range of temperatures are as follows: 100,000 h rupture strength [Nmm-2] at specified temperatures [°C] Temperature 420 430 440 450 460 470 Stress 420 370 310 260 220 190 480 165 100,000 h rupture strength [Nmm-2] at specified temperatures [°C] Temperature 490 500 510 520 530 540 Stress 145 127 114 101 87 74 550 59 The tabled values do not include any extended extrapolation in time or stress by more than a factor of 3, which is generally accepted as safe. Landolt-Börnstein New Series VIII/2B 86 2.2 Low alloy steels 2.2.10.5 References [1] ECCC Data sheet for 20CrMoV13-5-5, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, 1999. [2] DIN 17176, “Seamless Circular Steel Tubes for Hydrogen Service at Elevated Temperatures and Pressures; Technical Delivery conditions”, 1990. [3] EN 10216-2, “Seamless tubes for pressure purposes; Technical delivery conditions. Part 2: Nonalloy and alloy steel tubes with specified elevated temperature properties”, 2002 Landolt-Börnstein New Series VIII/2B Ref. p. 89] 2.2.11 5Cr-0.5Mo steel 87 2.2.11 5Cr-0.5Mo steel 2.2.11.1 Introduction 5Cr-0.5Mo steels are used as water tubes, smoke tubes, super-heater tubes, air preheater tubes and so on, in boilers, heat exchanger tubes, condenser tubes, catalyst tubes and so on, as well as in chemical and petrolic industries. Especially, 5Cr-0.5Mo steels are widely used in petrochemical industries, primarily because of high strength and corrosion resistance against crude oils containing hydrogen sulfide and other corrosive agents. 2.2.11.2 Material standards, chemical and tensile requirements Table 56. Chemical requirements of 5Cr-0.5Mo steel tubes; JIS STBA 25, ASTM T5 and BS 625 Standards Designation C JIS STBA 25 ≤0.15 ASTM T5 ≤0.15 BS 625 ≤0.15 Si ≤0.50 ≤0.50 ≤0.50 Mn 0.30-0.60 0.30-0.60 0.30-0.60 Chemical composition [wt%] P S Cr ≤0.030 ≤0.030 4.00-6.00 ≤0.025 ≤0.025 4.00-6.00 ≤0.030 ≤0.030 4.00-6.00 Mo Ni Al 0.45-0.65 0.44-0.65 0.45-0.65 ≤0.30 ≤0.020 Table 57. Tensile properties at room temperature of 5Cr-0.5Mo steel tubes; JIS STBA25. Tensile strength Yield strength Elongation [N/mm2] [N/mm2] [%] d <10 mm d ≥20 mm 10≤ d <20 mm ≥410 ≥205 ≥30 ≥25 ≥22 Tensile strength 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 700 400 300 400 300 200 200 100 100 0 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 102. Tensile properties of 5Cr-0.5Mo steel tubes [1]. Landolt-Börnstein New Series VIII/2B 0 0 100 200 300 400 500 600 700 Test temperature (℃) 800 88 2.2 Low alloy steels 2.2.11.3 Creep properties of 5Cr-0.5Mo steel Information of fact on creep data for 5Cr-0.5Mo steel can be obtained from [1] and [3]. 2.2.11.3.1 Creep rupture data of 5Cr-0.5Mo steel tubes Creep rupture strength data of 5Cr-0.5Mo steel tubes is shown in Fig. 103. Stress [MPa] 300 100 80 60 40 20 10 500 °C 550 °C 600 °C 650 °C 10 2 10 3 10 4 Time to rupture [h] Fig. 103. Creep rupture strength data of STBA 25; [1]. 10 5 10 6 2.2.11.3.2 Creep rupture strength of 5Cr-0.5Mo steel tubes It should be noted from Fig. 103 that creep rupture strength has a large scatter at higher stresses. The creep rupture strength is dependent on manufacturing conditions, chemical composition, and initial microstructure. This information is obtained from [1]. Creep rupture curves were analyzed using the Orr-Sherby-Dorn parameter method to NRIM creep data. The master rupture curve is shown in Fig. 104. 400 500 °C 550 °C 600 °C 650 °C 300 Stress [MPa] 200 100 80 60 50 40 30 Average n = 237 20 -22 -20 -18 -16 -24 Orr-Sherby-Dorn parameter log tR -[365457/(19.1425 × TK )] Fig. 104. Master rupture curve for 5Cr-0.5Mo steel tubes. n indicates the total number of data points. Note TK : absolute Temperature [K] T: test temperature [°C], and tR: time to rupture. Landolt-Börnstein New Series VIII/2B Ref. p. 89] 2.2.11 5Cr-0.5Mo steel 89 2.2.11.3.3 Microstructural changes Microstructural changes of long-term service-exposed process heater tube pipes of 5Cr-0.5Mo steels have been studied in [2]. The samples selected for this study have been used in the temperature range of 450 °C to 500 °C for about 20 to 25 years in oil refineries. The size, shape, position, distribution, and type of carbides in virgin steel have been found to have changed significantly due to prolonged exposure of 220,000 h in the temperature range from 450 °C to 500 °C. The sequence of carbide precipitation in 5Cr-0.5Mo steels seems to be as follows: M2C + M3C → M23C6 → M23C6 → M23C6 or M3C → M7C3 + M3C or M2C + M3C + M7C3 2.2.11.4 References [1] [2] [3] National Research Institute for Metals: NRIM Creep Data Sheet, No.12B, (1992). Das, S., Joarder, A.: Metallugical and Materials Transactions A, 28A (1997), 1607-1616. The Iron and Steel Institute of Japan: Report on the Mechanical Properties of Metals at High Temperatures, Vol. I Low Alloy Steels, (1972), pp.191-209. Landolt-Börnstein New Series VIII/2B 90 2.2 Low alloy steels 2.2.12 1.2Ni-Mo steel 2.2.12.1 Introduction 1.2Ni-Mo steel (15NiCuMo5-6-4, 9NiMoCuNb5-6-4) is primarily used as a steam pipe material for pressure purposes (e.g. in boiler feedwater lines) and for steam drums and boiler tanks (mainly bottoms) in the normalized and tempered heat treatment condition. The microstructure is typically tempered upper bainite. Its creep resistance is derived from the structural stability of the over saturated bainite, the carbide distribution and solid solution hardening. 1.2Ni-Mo steel is particularly suitable for use at temperatures around 300 °C due to enhanced ageing resistance and stands prolonged exposure in creep regime with no creep strength loss compared to other low alloyed structural steels. Practical experience nevertheless reported a tendency to embrittlement after long service periods (more than 100000 h), particularly related to weldment heat affected zones. 2.2.12.2 Material standards, chemical composition and tensile requirements Table 58. Chemical requirements of 1.2Ni-Mo steel, 9NiMoCuNb5-6-4, 15NiCuMo5-6-4 Standard Std. No. Data ECCC sheet Designation 9NiMoCuNb 5-6-4 15NiCuMoNb 5-6-4 9NiMnMoCrNb 5-4-4 EN 10216-2 ISO 9329-2 BS 3604:PT1 591 Chemical composition [wt%] C ≤ Si P 0.25 0.80 ≤ 0.17 0.50 0.25 ≤ 0.17 0.50 0.25 ≤ 0.17 0.50 0.10 0.25 0.17 0.50 Mn 1.20 0.80 1.20 0.80 1.20 0.80 1.20 0.030 ≤ 0.025 ≤ 0.030 ≤ 0.030 S ≤ Cr ≤ ≤ ≤ ≤ ≤ ≤ ≤ 0.025 0.30 0.020 0.30 0.030 0.30 0.030 0.30 Mo Ni Nb 0.25 0.50 0.25 0.50 0.25 0.40 0.25 0.50 1.00 1.30 1.00 1.30 1.00 1.30 1.00 1.30 0.015 0.045 0.015 0.045 0.015 0.045 0.015 0.045 Al ≤ Cu 0.50 0.050 0.80 0.50 ≤ 0.050 0.80 0.50 ≤ 0.020 0.80 0.50 ≤ 0.045 0.80 Note: 15NiCuMoNb5-6-4 EN 10216-2 supersedes the BS specification for grade 591. The material is usually supplied in normalized and tempered condition. According to the EN 10216-2 and ISO 9329-2 standards and the ECCC data sheet, the recommended austenitizing temperature range is 880 - 980 °C with tempering in the range 580 - 680 °C. According to the BS 3604:PT1(1990) standard, the austenitizing temperature is 900 - 980 °C with tempering at 580 - 660 °C. The material could be also supplied in quenched and tempered condition. In this case the recommended temperatures for heat treatment by the BS 3604:PT1(1990) standard are 880 - 930 °C for quenching and 620 - 690 °C for tempering. Table 59. Room temperature mechanical property requirements for 1.2Ni-Mo steel, 9NiMoCuNb5-6-4, 15NiCuMo5-6-4 StanHeat Thickness t Rp0.2 Rm A Cv (RT)* Std. No. Designation dard treat [mm] [Nmm-2] [Nmm-2] % [J] 610 Data 9NiMoCuNb N+T 1.6 < t < 100 ≥440 ECCC 780 Sheet 5-6-4 15NiCuMoNb 610 EN 10216-2 N+T ≤80 ≥440 ≥19 ≥27 5-6-4 780 610 9NiMnMoCrNb N+T ≤65 ISO 9329-2 ≥440 ≥19 ≥27 780 5-4-4 610 BS 3604:PT1 591 N+T ≥440 ≥20 760 610 BS 3604:PT1 591 Q+T ≥440 ≥20 760 *The Charpy V-notch figure shown is in transverse direction. Landolt-Börnstein New Series VIII/2B Ref. p. 92] 2.2.12 1.2Ni-Mo steel 91 Table 60. Minimum 0.2% proof strength values at elevated temperatures for 1.2Ni-Mo steel, 9NiMoCuNb5-6-4, 15NiCuMo5-6-4 Minimum 0.2% proof strength, Rp0.2 in Nmm-2 at a Thickness Heat treat temperature in °C of Standard Designation [mm] 100 150 200 250 300 350 400 450 15NiCuMo EN N+T 422 412 402 392 382 373 343 304 ≤80 5-6-4 2.2.12.3 Creep rupture strength The creep rupture strength of 15NiCuMo5-6-4 is shown in Fig. 105. The analysis, from which the data in the figure are derived, was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found in their published data sheets [1]. Stress [MPa] 1000 100 10,000h 100,000h Fig. 105. Creep rupture strength data of 15NiCuMo5-6-4. 10 350 400 450 500 550 Temperature [°C] The creep rupture properties have been obtained by comparative analysis of strength values as reported in VdTÜV Richtlinie 377/2. The test data used for the original analyses were related to several casts tested at temperatures of 400 - 500 °C. The available maximum test durations and distribution of casts per temperature are shown in Table 61. Landolt-Börnstein New Series VIII/2B 92 2.2 Low alloy steels Table 61. Distribution of casts from different sources and maximum test duration available to derive the stress rupture properties of 15NiCuMo5-6-4 Temperature [°C] 400 450 500 No. of casts Duration [h] No. of casts Duration [h] No. of casts Duration [h] 2 25,000 2 25,000 2 ≤13,241 3 15,000 5 2 25,000 ≤25,954 5 3 45,000 3 51,000 ≤77,160 Due to the comparative analysis assessment method, no master equation is available. 2.2.12.4 Estimated long term creep rupture strength Based on the data shown in Fig. 105 the 100,000 h rupture strength values for a range of temperatures are as follows: 100,000 h rupture strength at specified temperatures Temperature [°C] 400 410 420 430 440 Stress 373 349 325 300 273 450 245 100,000 h rupture strength at specified temperatures Temperature [°C] 460 470 480 490 500 Stress [Nmm-2] 210 175 139 104 69 - The tabled values do not include any extended extrapolation in time or stress by more than a factor of 3, which is generally accepted as safe. 2.2.12.5 NOTE Due to its tendency to embrittlement after prolonged exposure, 15NiCuMo5-6-4 is nowadays often replaced by 18NiCrMo2, which shows comparable high temperature strength, weldability and ageing resistance, but does not exhibit significant loss in rupture elongation and impact strength after service. 2.2.12.6 Reference [1] ECCC Data sheet for 9NiMoCuNb5-6-4, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). Landolt-Börnstein New Series VIII/2B Ref. p. 95] 2.2.13 1.4Cr-Mo steel 93 2.2.13 1.4Cr-Mo steel 2.2.13.1 Introduction 1.4Cr-Mo steel (Durehete 900) is used in fasteners for turbines and process plant and as boiler support rods. The steel was developed in the 1940’s as part of the Durehete series of creep resisting alloys. The composition was based on an existing high strength engineering steel, En20B (0.4%C, 1.2%Cr, 0.7%Mo). It derives its creep resistance [1] from a dispersion of Fe and Cr containing carbides, principally Fe3C and Cr7C3, and is suitable for use in applications up to 480 °C (900 °F). During exposure at the service temperature some Mo2C precipitates form which counteract reduction in strength due to coarsening of the Cr based carbides. 2.2.13.2 Material standards and chemical composition and tensile requirements Table 62. Chemical requirements of 1.4Cr-Mo steel, Durehete 900; EN 10269:1999 Chemical Composition [wt%] StanStd. No. Designation dard C Si Mn P S Cr 0.39 0.40 1.20 ≤ ≤ EN 10269:99 42CrMo5-6 ≤0.40 0.45 0.70 1.50 0.035 0.035 Mo 0.50 0.70 The material is usually supplied in the oil quenched and tempered condition. The recommended austenitizing temperature range is 840 - 870 °C with tempering in the range 600 - 700 °C. Table 63. Room temperature mechanical property requirements for 1.4Cr-Mo steel, Durehete 900; EN 10269:1999. StanHeat Diameter d Rp0.2 A Z Cv(RT) Rm Std. No. Designation dard treat [mm] [%] [J] [MPa] [MPa] [%] 860 ≤100 ≥700 ≥16 ≥50 ≥50 1060 EN 10269:99 42CrMo5-6 Q+T 850 100 <d ≤150 ≥640 ≥16 ≥50 ≥40 1000 Table 64. Minimum 0.2% proof strength values at elevated temperatures for 1.4Cr-Mo steel, Durehete 900; BS EN 10269:1999 Minimum 0.2% proof strength, Rp0.2 [Nmm-2] at a temperature DiaStan- DesigHeat [°C] of meter d dard nation treat [mm] 50 100 150 200 250 300 350 400 450 500 550 600 681+ 662 639 616 601 585 570 547 516 462 362 223 ≤100 EN 42CrMo5-6 Q+T 100 < 625+ 605 584 563 549 535 521 500 472 422 331 204 d ≤150 + values calculated by linear interpolation 2.2.13.3 Creep rupture strength The creep rupture strength of 42CrMo5-6 is shown in Fig. 106. The analysis, from which the data in the figure are derived, was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found from their published data sheets [2]. Landolt-Börnstein New Series VIII/2B 94 2.2 Low alloy steels 10 3 8 6 10000 h 30000 h 100000 h 200000 h Stress [MPa] 4 2 10 2 8 6×10 400 Fig. 106. Creep rupture strength data of 42CrMo5-6. 450 550 500 Temperature [°C] 600 The creep rupture properties have been obtained by analysis of bar material with sizes of 29 - 136 mm. The tensile properties of the material covered the range 660 - 830 Nmm-2 for Rp0.2 and 855 - 1060 Nmm-2 for Rm. The test data were available from 26 heats with test temperatures of 450 - 550 °C. The distribution of test durations is shown in Table 65. Table 65. Distribution of test durations used to derive the stress rupture properties of 42CrMo5-6. Number of test points at the various test durations 10,000 20,000 30,000 <10,000 h 20,000 h 30,000 h 50,000 h 151 18 9 (11) 4 (1) ( ) Denotes unbroken tests The data were assessed using the ISO 6303 procedure and the following master equation was derived: P(σ) = (log(tr*)−log(ta)) / (T−Ta)r = a + b(log σ) + c(log σ)2 + d(log σ)3 + e(log σ)4 where P(σ) is the creep rupture parameter, tr* is the predicted rupture time in hours, T is the absolute temperature and σ is the stress in Nmm-2. The remaining symbols are constants with the following values: log (ta) Ta r a b c d −2.4880708599 600 −1 −136047.7656 247130.3594 −164831.9531 48477.22266 e −5323.73877 2.2.13.4 Estimated long term creep rupture strength Based on the data shown in Fig. 106 the 100,000 h rupture strengths for a range of temperatures are as follows: 100,000 h rupture strengths at a range of temperatures Temperature [°C] 450 460 470 480 490 Stress [Nmm-2] 410* 346* 276* 219* 176 500 148 510 124 520 102 * Values which have involved extended time extrapolation Landolt-Börnstein New Series VIII/2B Ref. p. 95] 2.2.13 1.4Cr-Mo steel 95 2.2.13.5 References [1] Everson, H., Orr, J., and Dulieu, D., “Low Alloy Ferritic Bolting Steels for Steam Turbine Applications- The Evolution of the Durehete Steels”, ASM/EPRI Conference “Advances in Material Technology for Fossil Power Plant”, Chicago, (1987), pp.375-383. [2] ECCC Data Sheet for 42CrMo5-6, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). Landolt-Börnstein New Series VIII/2B 96 2.2 Low alloy steels 2.2.14 Cr-Mo-V-Ti-B steel 2.2.14.1 Introduction Cr-Mo-V-Ti-B steel (Durehete 1055) is used in fasteners for turbines and process plants and as boiler support rods. It is part of the Durehete series of creep resisting steels and was developed originally in the 1950’s in response to the increases in operating temperatures in steam power plants. The earlier alloy Durehete 900 was a CrMo base. Improved high temperature properties were obtained by the addition of V resulting in the 1%Cr, 1%Mo, 0.75%V steel, Durehete 950. Further improvements were obtained by adjusting the carbon and vanadium to near stoichiometric levels maximizing the elevated temperature strength to give the alloy Durehete 1050. However the high strength of this material was coupled with poor ductility which resulted in grain boundary cracking after relatively short exposures at 550 - 565 °C. Durehete 1055 was the result of further development to improve the ductility. Additions of Ti and B were made resulting in a finer austenite grain size. Further enhancement of the ductility, and hence a decrease in the susceptibility to grain boundary cracking, has been produced by control of residual levels principally phosphorus, arsenic, tin, antimony and copper. Durehete 1055 is suitable for use at temperatures up to 570 °C (approximately 1055 °F). 2.2.14.2 Material standard, chemical composition and mechanical property requirements Table 66. Chemical requirements for Cr-Mo-V-Ti-B steel, Durehete 1055; EN 10269:1999 Chemical composition [wt%] StanDesignation dard C Si Mn P S Cr Mo Ni Al B V Ti As Sn Cu 20CrMoVTiB 0.17 ≤ 0.35 ≤ 0.90 0.90 ≤ 0.015 0.001 0.60 0.07 ≤ ≤ ≤ ≤ EN 0.23 0.40 0.75 0.020 0.020 1.20 1.10 0.20 0.080 0.010 0.80 0.15 0.020 0.020 0.20 4-10 The material is usually supplied in the oil or water quenched and tempered condition. The recommended austenitizing temperature range is 970 - 990 °C with tempering in the range 680 - 720 °C. Table 67. Room temperature mechanical property requirements for Cr-Mo-V-Ti-B steel, Durehete 1055; EN 10269:1999 Stan- Std. Heat Diameter d Rp0.2 Rm A Z Cv(RT) Designation dard No. treat [mm] [MPa] [MPa] [%] [%] [J] 820 ≥ ≥ ≥ ≥ ≤100 1000 660 15 50 40 1026 20CrMoVTiB EN Q+T 9:99 4-10 820 ≥ ≥ ≥ ≥ 100 < d ≤ 160 1000 660 15 50 27 Table 68. Minimum 0.2% proof strength values at elevated temperatures for Cr-Mo-V-Ti-B steel, Durehete 1055; EN 10269:1999 Minimum 0.2% proof strength, Rp0.2 [Nmm-2] at a Heat Diameter StanDesignation temperature [°C] of treat [mm] dard 50 20CrMoVTiB Q+T ≤160 EN 4-10 + values calculated by linear interpolation 100 150 200 250 300 350 400 450 500 550 600 642+ 624 603 595 581 573 559 537 508 464 406 334 Landolt-Börnstein New Series VIII/2B Ref. p. 99] 2.2.14 Cr-Mo-V-Ti-B steel 97 2.2.14.3 Creep rupture strength The creep rupture strength of 20CrMoVTiB4-10 is shown in Fig. 107. The analysis, from which the data in the figure are derived, was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found from their published data sheets [1]. 10 3 8 10000 h 30000 h 100000 h 200000 h 6 Stress [MPa] 4 2 10 2 8 6×10 400 450 550 500 Temperature [°C] 600 650 Fig. 107. Creep rupture strength data of 20CrMoVTiB410 The creep rupture properties have been obtained by analysis of bar material with sizes of 19 - 190 mm. The tensile properties of the material covered the range 680 - 900 Nmm-2 for Rp0.2 and 830 - 1040 Nmm-2 for Rm. The test data were from 75 heats with test temperatures of 450 - 700 °C with the majority in the range 500 - 600 °C. The distribution of test durations are shown in Table 69. Table 69. Distribution of test durations used to derive the stress rupture properties of 20CrMoVTiB4-10 Number of test points at the various test durations 10,00020,00030,00050,00070,000>100,000 h <10,000 h 20,000 h 30,000 h 50,000 h 70,000 h 100,000 h 513 (26) 81 (11) 94 (11) 44 (8) 15 (2) 1 (2) 8 (2) ( ) Denotes unbroken tests The data were assessed using the ISO 6303 procedure and the following master equation was derived: P(σ ) = (log(tr*)−log(ta)) / (T−Ta)r = a + b(logσ) + c(logσ)2 + d(logσ)3 + e(logσ)4 where P(σ) is the creep rupture parameter, tr* is the predicted rupture time in hours, T is the absolute temperature and σ is the stress in Nmm-2. The remaining symbols are constants with the following values: log (ta) Ta r a b 10.523564339 590 1 −4.465617180 8.252388000 c d e −5.727178097 1.762619853 −0.2033182085 2.2.14.4 Creep properties from research papers At the sizes found in typical bolting applications after oil quenching from temperatures in the range 970 990 °C the microstructure of Durehete 1055 consists of fine grained bainite. Subsequent tempering in the range 680 - 720 °C produces a dispersion of V4C3 precipitates. The alloy derives its creep strength from these precipitates together with solid solution strengthening from chromium and molybdenum. The optimum creep properties are obtained by a vanadium addition of about 0.7%, which is close to the stoichiometric level for the carbon level of 0.2% in this alloy. Landolt-Börnstein New Series VIII/2B 98 2.2 Low alloy steels However the maximum creep life is associated with a minimum in the tensile ductility, Fig. 108. This is the result of regions close to grain boundaries which are denuded of precipitates where creep strain is concentrated. Additions of titanium and boron are made to alleviate this problem. The titanium leads to the formation of TiC precipitates in the proximity of the prior austenite grain boundaries although there is evidence that these are replaced by V4C3 particles during long term exposure at 550 - 600 °C. 100 10 20 10 1 Elongation [%] Rupture life [h] Tested at 600 °C / 324 MPa 0 0 0.2 0.8 0.4 0.6 Vanadium - content [%] 1.0 1.2 Fig. 108. Influence of vanadium level on rupture life (solid line) and ductility (dashed line). Further improvements in ductility were produced by controlling the levels of residual elements phosphorus, arsenic, tin, antimony and copper. The total residual content is described by the “R” factor given by: R = %P + 2.43 (%As) + 3.57 (%Sn) + 8.16 (%Sb) + 0.13 (%Cu) Elongation [%] (20000 h / 550 °C ) 40 30 20 10 0 0.05 0.10 ‘R’Value Fig. 109. Influence of residual content on rupture ductility. 0.15 The influence of the R value on the rupture ductility is illustrated in Fig. 109. There is a sharp increase in rupture elongation as the R value decreases, particularly at levels below 0.1. Detailed metallography has shown the presence of phosphorus and tin at grain boundaries. Landolt-Börnstein New Series VIII/2B Ref. p. 99] 2.2.14 Cr-Mo-V-Ti-B steel 99 2.2.14.5 Estimated long term creep rupture strength Based on the data shown in Fig. 107 the 100,000 h rupture strengths for a range of temperatures are as follows: 100,000 h rupture strengths [Nmm-2] at a range of temperatures [°C] Temperature 450 460 470 480 490 500 510 520 530 540 550 Stress 453 423 394 365 337 307 276 241 204 169 142 560 121 570 103 2.2.14.6 References [1] ECCC Data Sheet for 20CrMoVTiB4-10, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). [2] Everson, H., Orr, J., and Dulieu, D. “Low Alloy Ferritic Bolting Steels for Steam Turbine Applications- The Evolution of the Durehete Steels”, ASM/EPRI Conference “Advances in Material Technology for Fossil Power Plant”, Chicago, (1987), pp.375-383. Landolt-Börnstein New Series VIII/2B 100 2.2 Low alloy steels 2.2.15 Cr-Mo-V steel 2.2.15.1 Introduction Cr-Mo-V steel (21CrMoV5-7) is a frequently used creep resistant steel for fasteners and other parts in power plants. The steel was developed in the 1970´s based on the older steel grade 21CrMoV5-11 when long-term creep rupture tests showed that a Mo content of 0.7% is sufficient. The Ni content was limited to max. 0.6% for 21CrMoV5-7 to avoid long term brittlement. For dimensions >160 mm the through hardening could be improved by alloying a higher content of Ni (up to 0.8%, steel grade 21CrMoNiV4-7) The specified upper limit of tensile strength and solution temperature should not be exceeded in order to avoid notch weakness. Oil quenching or cooling in air after hardening is preferred to obtain appropriate toughness properties at room temperature combined with good creep rupture strength values and sufficient long term ductility. Typical microstructure: Mainly tempered bainite with parts of tempered martensite for high cooling rates at the grain boundary or parts of ferrite for low cooling rates in the grain centre. High temperature applications: Bolts, nuts, small forgings and other parts of steam turbines, compressors, gas turbines, valves, nozzles. Service temperature is up to 566 °C if oxidation is negligible or with surface protection, otherwise the limiting temperature is around 540 °C 2.2.15.2 Material standards, chemical composition and tensile requirements Table 70. Chemical requirements of 21CrMoV5-7 Chemical composition [wt%] Stan- Std. Designation dard No. C Si Mn P S Al Cr Mo 21CrMoV5-7 0.17 ≤ 0.40 ≤ 1.20 0.55 ≤ ≤ EN 10269 (1.7709) 0.25 0.40 0.80 0.030 0.030 0.030 1.50 0.80 21CrMoNiV4-7 0.17 0.15 0.35 ≤ 0.90 0.65 ≤ (1.6981) 0.25 0.35 0.85 0.030 0.035 1.20 0.80 21CrMoV5-11 0.17 0.30 0.30 ≤ 1.20 1.00 ≤ ≤ (1.8070) 0.25 0.60 0.60 0.035 0.035 0.030 1.50 1.20 Ni ≤ 0.60 0.20 0.80 ≤ 0.60 V 0.20 0.35 0.25 0.35 0.25 0.35 The material is usually supplied in quenched, in air or oil and tempered condition. The recommended austenitizing temperature range is 900 - 950 °C with tempering treatment temperature in the range 680 720 °C. Melting process: Electric arc. Forming process: Hot rolled or forged. Landolt-Börnstein New Series VIII/2B Ref. p. 103] 2.2.15 Cr-Mo-V steel 101 Table 71. Room temperature mechanical property requirements for 21CrMoV5-7 Heat Thickness Rp0.2 Std. Rm Designation Standard treat [mm] No [Nmm-2] [Nmm-2] 700 21CrMoV5-7 Q+T ≤160 EN 10269 ≥550 850 (1.7709) 700 21CrMoNiV4-7 Q+T ≤600 ≥550 850 (1.6981) 21CrMoV5-11 700 Q+T ≤250 ≥550 (1.8070) 850 A [%] 16 16 16 1000 1000 800 800 Tensile strength (MPa) 0.2% proof strength (MPa) Table 72. Minimum 0.2% proof strength values at elevated temperatures for 21CrMoV5-7 Minimum 0.2% proof strength, Rp0.2 [Nmm-2] at a Std. Heat Standard Designation temperature [°C] of No treat 50 100 150 200 250 300 350 400 450 500 21CrMoV5-7 EN 10269 Q+T 542 530 515 500 480 460 435 410 380 350 (1.7709) 600 400 type 21CrMoV5-7 type 21CrMoNiV4-7 200 type 21CrMoV5-11 600 400 type 21CrMoV5-7 type 21CrMoNiV4-7 type 21CrMoV5-11 200 min value EN10269 0 min value EN10269 0 0 100 200 300 400 500 600 0 100 200 Temperature (°C) 300 400 500 600 Temperature (°C) Fig. 110. Tensile properties, tests carried out by the German Creep Committee; [1]. 2.2.15.3 Creep rupture strength The ECCC [2] has made a data collection and assessment showing that the data of all the three steel grades were situated within the same acceptable scatter bands. The assessment was carried out using the DESA procedure [3]. The following master equation was derived: Larson-Miller [4] Parameter Model function PLM = (lg(t) + C ) τ τ = (δ + 273) / 1000 lg(t) = −C + B1/τ + (B2/τ)√σ + (B3/τ)(√σ)2 + (B4/τ)(√σ)3 where t = test duration in h, σ = stress in MPa, δ = temperature in °C Values for the constants: C 20.00 Landolt-Börnstein New Series VIII/2B B1 22.349564 B2 −0.195449 B3 0.002218 B4 −0.000251 102 2.2 Low alloy steels The equation is valid in the range of 420 °C to 550 °C and 100 h to 200,000 h. The results of the assessment were published in ECCC Data Sheets in 1999 [2]. The creep rupture strength values for 420 °C to 550 °C and for 10 000 h, 100 000 h and 200 000 h are given in EN 10269 [5]. 21CrMoV5-7 Stress [MPa] 1000 100 10,000h 30,000h 100,000h 200,000h Fig. 111. Creep rupture strength data of 21CrMoV 5-7. 10 400 450 500 550 600 Temperature [°C] The test data were available from 33 heats with test temperatures from 400 °C to 560 °C. The distribution of test durations is shown in Table 73. Table 73. Distribution of test durations used to derive the stress rupture properties of 21CrMoV 5-7. Number of test points at the various test durations 10,000 20,001 - 30,001 - 50,001 70,001 <10,000 h >100,000 h 20,000 h 30,000 h 50,000 h 70,000 h 100,000 h 190 (6) 38 (11) 16 (5) 27 (5) 15 (5) 7 (2) 7 (3) ( ) denotes unbroken tests Landolt-Börnstein New Series VIII/2B Ref. p. 103] 2.2.15 Cr-Mo-V steel 103 2.2.15.4 Estimated long term creep rupture strength Based on the data shown in Fig. 111 and on the ECCC data sheet [2] the 100,000 h rupture strength values and the 1% creep strength values for a range of temperatures are as follows: Temperature [°C] Stress [Nmm-2] 100,000 h rupture strengths at specified temperatures 420 430 440 450 460 399 375 350 325 300 470 274 480 249 Temperature [°C] Stress [Nmm-2] 100,000 h rupture strengths at specified temperatures 490 500 510 520 530 224 199 174 150 126 540 103 550 82 Temperature [°C] Stress [Nmm-2] 100,000 h 1% creep strengths at specified temperatures 420 430 440 450 460 470 365 340 315 288 262 235 480 208 Temperature [°C] Stress [Nmm-2] 100,000 h 1% creep strengths at specified temperatures 490 500 510 520 530 540 182 156 132 109 89 71 550 56 2.2.15.5 References [1] German Creep Commitee, VDEh, Düsseldorf. [2] European Creep Collaborative Commitee, BRITE-EURAM Thematic Network BET2-0509 "WELD-CREEP", (1999). [3] Granacher, J., and Oehl, M.: DESA Time-Temperature-Parameter Evaluation Method, Institut fur Werkstoffkunde, Darmstadt (1993). [4] Larson, F.R., and Miller, J.: A Time-Temperature Relationship for Rupture and Creep Stresses, Trans ASME 74 (1952). [5] EN 10269, Steels and nickel alloys for fasteners with specified elevated and/or low temperature properties, (1999). Landolt-Börnstein New Series VIII/2B 104 2.2 Low alloy steels 2.2.16 0.5Mo cast 2.2.16.1 Introduction The cast steel grade G20Mo5 (EN 10213-2, material-no 1.5419) represents the oldest type of the low alloy chromium free creep resistant cast steels. Due to the molybdenum content of 0.40 to 0.60 % the creep rupture strength values of G20Mo5 exceed those of the unalloyed cast steel grades. Industrial applications are reported since about 1920. The main features of G20Mo5 are summarized below: Melting process: Electric arc, induction melting. Heat treatment: Quenched in air or liquid medium, and tempered. Typical microstructure: Ferrite, tempered bainite and a small amount of pearlite. Weldability: Easily weldable with similar weld metal. High temperature applications: Casings of steam turbines, compressors, gas turbines, valves, nozzles; service temperatures up to about 500 °C. Cast steel grade with similar chemical composition: ASTM A 356 Grade 2. 2.2.16.2 Standard requirements Table 74. Chemical composition Chemical composition [wt %] C Si Mn P S Mo EN10213-2:1995 G20Mo5 (1.5419) 0.15 - 0.23 ≤0.60 0.50 - 1.00 ≤0.025 ≤0.020 (1) 0.40 - 0.60 (1) The maximum admissible sulphur content is 0.030 % if the relevant wall thickness is not in excess of 28 mm. Standard Designation Table 75. Heat treatment and tensile properties at room temperature. Min. 0.2 % Thickness Standard Designation Heat treatment proof strength [mm] [MPa] EN G20Mo5 Q:920°C-980°C 100 245 10213(1.5419) T:650°C-730°C 2:1995 Tensile strength [MPa] Min. elongation at rupture [%] 440-590 22 Landolt-Börnstein New Series VIII/2B Ref. p. 106] 2.2.16 0.5Mo cast Rp0.2 Rm min EN 700 500 600 400 Rm (MPa) R p0.2(MPa) 105 300 200 100 500 400 300 200 100 0 0 100 200 300 400 500 0 600 0 100 Temperature (°C) 200 300 400 500 600 Temperature (°C) Fig. 112. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade G20Mo5 tested in creep rupture tests by the German Creep Committee; [1]. min EN: minimum values by EN 10213-2. Stress (MPa) 1000 broken unbroken 450 °C_EN 100 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 113. Creep rupture strength data of cast steel grade G20Mo5 at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 500 °C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 114. Creep rupture strength data of cast steel grade G20Mo5 at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B 106 2.2 Low alloy steels Stress (MPa) 1000 broken 100 unbroken 550°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 115. Creep rupture strength data of cast steel grade G20Mo5 at 550 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. 2.2.16.3 Average creep rupture strength Table 76. Average creep rupture strength values indicated in EN 10213-2:1995: Time to rupture Temperature 10,000 h 100,000 h 200,000 h [°C] Average creep rupture strength [MPa] 400 360 310 290 450 275 205 180 500 160 85 70 550 66 30 23 2.2.16.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade G20Mo5, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B Ref. p. 109] 2.2.17 1.5Cr-0.5Mo cast 107 2.2.17 1.5Cr-0.5Mo cast 2.2.17.1 Introduction The cast steel grade G17CrMo5-5 (EN 10213-2, material-no 1.7357) was introduced in the 1940s. It represents one of the low alloy creep resistant cast steels with improved resistance to pressurized hydrogen. Because of the chromium content of 1.0 to 1.5 % the creep rupture strength values and yield strength values at elevated temperatures are higher than those of the cast steel type G20Mo5 without chromium addition. The main features of G17CrMo5-5 are summarized below: Melting process: Electric arc, induction melting. Heat treatment: Quenched in air and tempered (cooling in furnace). Typical microstructure: Tempered bainite and ferrite. Weldability: Easily weldable with similar weld metal. High temperature applications: Casings of steam turbines, compressors, gas turbines, valves, nozzles, chemical reactors; service temperatures up to about 530 °C. Cast steel grade with similar chemical composition: ASTM A 217 Grade WC6. 2.2.17.2 Standard requirements Table 77. Chemical composition. Chemical composition [wt%] C Si Mn P S Cr Mo 0.45EN10213G17CrMo5-5 0.150.50(1) 1.00≤0.60 ≤0.020 ≤0.020 1.50 0.65 2:1995 (1.7357) 0.20 1.00 (1) The maximum admissible sulphur content is 0.030 % if the relevant wall thickness is not in excess of 28 mm. Standard Designation Table 78. Heat treatment and tensile properties at room temperature. Min. 0.2 % Thickness proof strength Standard Designation Heat treatment [mm] [MPa] EN10213- G17CrMo5-5 Q: 920 °C - 960 °C 100 315 2:1995 (1.7357) T: 680 °C - 730 °C Landolt-Börnstein New Series VIII/2B Tensile strength [MPa] Min. elongation at rupture [%] 490-690 20 108 2.2 Low alloy steels Rp0.2 min EN Rm 600 800 400 Rm (MPa) R p0.2 (MPa) 500 300 200 100 0 600 400 200 0 0 100 200 300 400 500 600 0 100 Temperature (°C) 200 300 400 500 600 Temperature (°C) Fig. 116. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade G17CrMo5-5 tested in creep rupture tests by the German Creep Committee [1]. min EN: minimum values by EN 10213-2. Stress (MPa) 1000 broken unbroken 400°C_EN 100 100 1000 10000 100000 1000000 Test duration (h) Fig. 117. Creep rupture strength data of cast steel grade G17CrMo5-5 at 400 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken unbroken 450°C_EN 100 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 118. Creep rupture strength data of cast steel grade G17CrMo5-5 at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B Ref. p. 109] 2.2.17 1.5Cr-0.5Mo cast 109 Stress (MPa) 1000 broken 100 unbroken 500°C_EN 10 1 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 119. Creep rupture strength data of cast steel grade G17CrMo5-5 at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. 2.2.17.3 Average creep rupture strength Table 79. Average creep rupture strength values indicated in EN 10213-2:1995. Time to rupture Temperature 10,000 h 100,000 h 200,000 h Average creep rupture strength [MPa] 400 420 370 356 450 321 244 222 500 187 117 96 550 98 55 44 2.2.17.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade G17CrMo5-5, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B 110 2.2 Low alloy steels 2.2.18 2.25Cr-1Mo cast 2.2.18.1 Introduction The low alloy cast steel grade G17CrMo9-10 (EN 10213-2, material-no 1.7379) with improved resistance to high pressure hydrogen was introduced in the 1940s. Compared with G17CrMo5-5 the creep rupture strength values are improved above 450 °C by the higher content in molybdenum and chromium. Moreover the higher chromium content provides better resistance to oxidation. The main features of G17CrMo9-10 are summarized below: Melting process: Electric arc, argon oxygen decarburization. Heat treatment: Quenched in air, water spray or oil, and tempered (cooling in furnace). Typical microstructure: Tempered bainite and ferrite. Weldability: Easily weldable with similar weld metal: weldments exposed to high stresses should be welded by use of consumables with a carbon content ≥0.10 %. High temperature applications: Casings of steam turbines, compressors, gas turbines, valves, nozzles and chemical reactors; service temperatures up to about 570 °C. Cast steel grade with similar chemical composition: ASTM A217 Grade WC9. 2.2.18.2 Standard requirements Table 80. Chemical composition. Standard Designation C Si Chemical composition [wt %] Mn P S Cr Mo EN10213- G17CrMo9-10 (1) 0.13-0.20 ≤0.60 0.50-0.90 ≤0.020 ≤0.020 2.00-2.50 0.90-1.20 2:1995 (1.7379) (1) The maximum admissible sulphur content is 0.030 % if the relevant wall thickness is not in excess of 28 mm. Table 81. Heat treatment and tensile properties at room temperature. Min. 0.2% Thickness proof strength Standard Designation Heat treatment [mm] [MPa] EN10213- G17CrMo9-10 Q:930 °C - 970 °C 150 400 2:1995 (1.7379) T:680 °C - 740 °C Tensile strength [MPa] Min. elongation at rupture [%] 590-740 18 Landolt-Börnstein New Series VIII/2B Ref. p. 113] 2.2.18 2.25Cr-1Mo cast Rp0.2 min EN Rm 600 800 500 400 Rm (MPa) R p0.2(MPa) 111 300 200 100 0 600 400 200 0 0 100 200 300 400 500 600 0 Temperature °C 100 200 300 400 500 600 Temperature (°C) Fig. 120. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade G17CrMo9-10 tested in creep rupture tests by the German Creep Committee; [1]. min EN: minimum values by EN10213-2. Stress (MPa) 1000 broken 400°C_EN 100 1000 10000 100000 Time to rupture (h) Fig. 121. Creep rupture strength data of cast steel grade G17CrMo9-10 at 400 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken unbroken 450°C_EN 100 100 1000 10000 100000 1000000 Test duration (h) Fig. 122. Creep rupture strength data of cast steel grade G17CrMo9-10 at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B 112 2.2 Low alloy steels Stress (MPa) 1000 broken 100 unbroken 500°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 123. Creep rupture strength data of cast steel grade G17CrMo9-10 at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken unbroken 100 550°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 124. Creep rupture strength data of cast steel grade G17CrMo9-10 at 550 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 600°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 125. Creep rupture strength data of cast steel grade G17CrMo9-10 at 600 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B Ref. p. 113] 2.2.18 2.25Cr-1Mo cast 113 2.2.18.3 Average creep rupture strength Table 82. Average creep rupture strength values indicated in EN 10213-2:1995.l. Time to rupture Temperature 10,000 h 100,000 h 200,000 h [°C] Average creep rupture strength [MPa] 400 404 324 304 450 282 218 200 500 188 136 120 550 106 66 52 600 56 28 22 2.2.18.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade G17CrMo9-10, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B 114 2.2 Low alloy steels 2.2.19 1Cr-1Mo-V cast 2.2.19.1 Introduction G17CrMoV5-10 (EN 10213-2, material-no 1.7706) is the creep resistant cast steel grade which has been used for turbine and valve casings most frequently since 1960. Creep rupture strength and creep strength are high due to the vanadium content and the quenched and tempered microstructure, consisting mainly of tempered bainite. The specified upper limit of tensile strength and solution temperature should not be exceeded in order to avoid notch weakness. Oil quenching is preferred to obtain appropriate toughness properties at room temperature combined with excellent creep rupture strength values and sufficient long term ductility. The main features of G17CrMoV5-10 are summarized below: Melting process: Electric arc, argon oxygen decarburization, induction melting. Heat treatment: Quenched in air or liquid medium, and tempered (cooling in furnace). Typical microstructure: Mainly tempered bainite with a small amount of ferrite. Weldability: Weldable with similar weld metal; weldments exposed to high stresses (i.e. valves) should be welded by use of similar consumables with a carbon content ≥0.12 %; higher preheating and longer stress relief annealing (≥5 h) are necessary in comparison with other low alloy cast steel grades in order to ensure sufficient toughness properties which otherwise may be impaired due to the vanadium content; weldments exposed to low or moderate stresses may be welded with consumables of the type 2CrMo; weld metal of the type 2CrMo is also recommended when root layers are required to show high toughness properties. High temperature applications: Casings of steam turbines, compressors, gas turbines, valves, nozzles; service temperatures are up to about 570 °C if oxidation is negligible, otherwise the limiting temperature is around 530 °C. Cast steel grade with similar chemical composition: ASTM A 356 Grade 9. 2.2.19.2 Standard requirements Table 83. Chemical composition. Standard Designation C EN10213- G17CrMoV5-10 0.152:1995 (1.7706) 0.20 Si Mn 0.50≤0.60 0.90 Chemical composition [wt%] P S Cr Mo 1.20- 0.90≤0.020 ≤0.015 1.50 1.10 Table 84. Heat treatment and tensile properties at room temperature. Min. 0.2 % Thickness proof strength Standard Designation Heat treatment [mm] [MPa] EN10213- G17CrMoV5-10 Q:920 °C - 960 °C 150 440 2:1995 (1.7706) T:680 °C - 740 °C V 0.200.30 Other Sn: ≤0.025 Tensile Min. elongastrength tion at rupture [MPa] [%] 590-780 15 Landolt-Börnstein New Series VIII/2B Ref. p. 117] 2.2.19 1Cr-1Mo-V cast Rp0.2 min_EN Rm 800 1000 800 600 Rm (MPa) R p0.2 (MPa) 115 400 200 0 600 400 200 0 0 100 200 300 400 500 600 700 0 100 Temperature (°C) 200 300 400 500 600 700 Temperature (°C) Fig. 126. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade G17CrMoV5-10 tested in creep rupture tests by the German Creep Committee [1]. min EN: minimum values by EN 10213-2. Stress (MPa) 1000 broken unbroken 400°C_EN 100 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 127. Creep rupture strength data of cast steel grade G17CrMoV5-10 at 400 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken unbroken 450°C_EN 100 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 128. Creep rupture strength data of cast steel grade G17CrMoV5-10 at 450 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B 116 2.2 Low alloy steels Stress (MPa) 1000 broken unbroken 500°C_EN 100 100 1000 10000 100000 1000000 Test duration (h) Fig. 129. Creep rupture strength data of cast steel grade G17CrMoV5-10 at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken unbroken 100 550°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 130. Creep rupture strength data of cast steel grade G17CrMoV5-10 at 550 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 600°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 131. Creep rupture strength data of cast steel grade G17CrMoV5-10 at 600 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Landolt-Börnstein New Series VIII/2B Ref. p. 117] 2.2.19 1Cr-1Mo-V cast 117 2.2.19.3 Average creep rupture strength Table 85. Average creep rupture strength values indicated in EN 10213-2:1995. Time to rupture Temperature 10,000 h 100,000 h 200,000 h [°C] Average creep rupture strength [MPa] 400 463 419 395 450 340 275 254 500 229 171 157 550 151 96 83 600 80 28 19 2.2.19.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade G17CrMoV5-10, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c.o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B 118 2.3 High Cr steels 2.3 High Cr steels 2.3.1 9Cr-1Mo steel 2.3.1.1 Introduction Since its development for the oil industry in the 1930’s, 9Cr-1Mo steel (STBA 26, X11CrMo9-1+l1, +l2, X11CrMo9-1+NT) has become an internationally accepted material as reflected by the several national and international standards that exist to specify composition, heat treatment, minimum room temperature tensile and stress rupture properties [1]. In particular, 9Cr-1Mo steel is now established as a structural material for steam generator units by the UK nuclear industry following its successful service in the evaporators and parts of the superheaters of the Advanced Gas Cooled Reactor. Furthermore, the steel is also being used for the replacement superheater and reheater tube bundles now completing construction for the UK Prototype Fast Reactor. 2.3.1.2 Material standards, chemical and tensile requirements 2.3.1.2.1 9Cr-1Mo steel tubes for boilers and heat exchangers Table 86. Chemical requirements for 9Cr-1Mo steel tubes; JIS STBA 26, ASTM T9 and BS 629-470. Standard Designation JIS STBA 26 ASTM T9 ASTM T9 BS 629-470 C Si <0.15 0.25 1.00 <0.15 0.25 1.00 <0.15 0.25 1.00 <0.15 <1.00 Chemical composition [wt%] Mn P S Cr 0.3 0.6 0.3 0.6 0.3 0.6 0.3 0.6 <0.030 <0.030 8.00 10.00 <0.025 <0.025 8.00 10.00 <0.025 <0.025 8.00 10.00 <0.030 <0.030 8.00 10.00 Yield Others strength [MPa] 0.90 >205 1.10 0.90 >170 1.10 0.90 >205 1.10 0.90 - Al: >185 1.10 <0.02 Mo Tensile Std. strength No. [MPa] >410 G3462 >415 A199 >415 A213 470 620 3059-2 2.3.1.2.2 9Cr-1Mo steel pipes Table 87. Chemical requirements for 9Cr-1Mo steel pipes; JIS STPA 26, ASTM P9 and BS 629-470. Standard Designation JIS STPA 26 ASTM P9 BS 629 - 470 C Si <0.15 0.25 1.00 <0.15 0.25 1.00 <0.15 0.25 1.00 Chemical composition [wt%] Mn P S Cr 0.3 0.6 0.3 0.6 0.3 0.6 Yield Others strength [MPa] <0.030 <0.030 8.00 - 0.90 >205 10.00 1.10 <0.025 <0.025 8.00 - 0.90 >205 10.00 1.10 <0.030 <0.030 8.00 - 0.90 - Al: >185 10.00 1.10 <0.02 Mo Tensile Std. strength No. [MPa] >410 G3458 >415 A335 470 620 3604-1 2.3.1.3 Data sources for 9Cr-1Mo steel Information of fact on data for 9Cr-1Mo steel tubes can be obtained from [1], [2] and [3]. Landolt-Börnstein New Series VIII/2B Ref. p. 125] 2.3.1 9Cr-1Mo steel 119 2.3.1.4 Creep rupture data for 9Cr-1Mo steel tubes for boiler and heat exchangers, JIS STBA 26 2.3.1.4.1 Creep rupture data for 9Cr-1Mo steel tubes, JIS STBA 26 The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area and optical micrographs of as-received and crept specimens, has been published for 11 heats of 9Cr-1Mo steel, JIS STBA 26, in [2]. The details of tube production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for the 11 heats in [2]. The details of tube production and the chemical compositions are also given in [2]. The tensile and creep specimens, having a geometry of 6 mm in diameter and 30 mm in gauge length, were taken longitudinally from the middle of wall thickness of the tubes. Fig. 132 shows the 0.2% proof stress and tensile strength obtained by short-time tensile tests between room temperature and 700 °C. Tensile strength 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 600 300 300 200 200 100 100 0 0 100 200 300 400 500 600 700 800 0 0 Test temperature (℃) 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 132. Short-time tensile properties of 9Cr-1Mo steel, JIS STBA 26. Fig. 133 shows stress vs. time to rupture data for 11 heats of 9Cr-1Mo steel, JIS STBA 26, at temperatures between 550 and 700 °C. Fig. 133 exhibits a large heat-to-heat variation in time to rupture, which becomes more significant with increasing time and temperature. At 550 °C and 78 MPa, the time to rupture of the strongest heat is 1.3 × 105 hours, while that of the weakest heat is only 2.7 × 104 hours. It should be noted, however, that the observed heat-to-heat variation in time to rupture is not caused by data scattering, because each heat has its distinct stress dependence of time to rupture as shown in Fig. 134. The heat-to-heat variation in time to rupture comes from many factors, such as differences in production history, chemical composition and initial microstructure. 2.3.1.4.2 Estimated long-term creep rupture strength for 9Cr-1Mo steel tubes, JIS STBA 26 The creep rupture data shown in Fig. 133 were analyzed for each heat using the Larson-Miller parameter method. Fig. 135 shows the results for a heat (MEH) with an intermediate strength level among the 11 heats. The 105 h creep rupture strength was also estimated for the 11 heats. This is shown in Fig. 136 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. The regression equations for tensile and creep rupture strength are described in [1]. Landolt-Börnstein New Series VIII/2B 120 2.3 High Cr steels 300 550 °C 600 °C 650 °C 700 °C Stress [MPa] 200 100 80 60 50 40 30 Fig. 133. Creep rupture strength data for 9Cr- 1Mo steel, JIS STBA 26. n indicates the total number of data points. 20 n = 270 10 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 200 9Cr-1M o o Stress ( MPa ) 550 C ME B ME C ME D M EE ME F ME G ME H ME J ME L M EM ME N 100 90 80 70 Fig. 134. Creep rupture data for each heat of 9Cr-1Mo steel, STBA 26, at 550 °C. 60 10 2 10 3 10 4 10 5 T ime to ru pture ( h ) 2 00 o 55 0 C Stress ( MPa ) 1 00 o 600 C 50 o 65 0 C o 700 C 20 10 2 10 Fig. 135. Estimated creep rupture curves of 9Cr-1Mo steel STBA 26. 10 3 10 4 10 5 10 6 T ime to ruptu re ( h ) Landolt-Börnstein New Series VIII/2B Ref. p. 125] 2.3.1 9Cr-1Mo steel 121 800 600 500 400 300 Stress [MPa] 200 Tensile { strength { 0.2%stressproof 100 80 60 50 40 30 100000 h 20 10 500 550 600 650 Temperature [°C] 1000 h 700 750 Fig. 136. Estimated 105 h creep rupture strength for the 11 heats of 9Cr-1Mo steel, JIS STBA 26, as a function of temperature, together with 0.2% proof stress, tensile strength and 103 h creep rupture strength. 2.3.1.5 Creep behavior and microstructure of 9Cr-1Mo steel 2.3.1.5.1 Effect of secondary precipitation on the creep strength of normalized and tempered 9Cr-1Mo steel In order to demonstrate the importance of secondary precipitation on the creep and stress rupture properties and the difficulties in extrapolation of stress rupture data for design purposes, detailed microstructural examination has been made for laboratory creep tested specimens of 9Cr-1Mo steel at temperatures between 475 and 550 °C [5-7]. The material was received as 25 mm bar in the normalized (1000 °C, 1 h) and tempered (750 °C, 2 h) condition. The chemical composition was 8.6Cr-1.04Mo0.12C-0.69Si-0.48Mn-0.008S- 0.022P-0.22Ni- 0.05Cu (wt%). The stress-rupture data are presented in Fig. 137, together with the estimated ISO values (ISO 1971) for the rupture life for normalized and tempered 9Cr-1Mo steel. The composition and heat treatment combination for this steel provides appreciably greater strength than is predicted from the ISO data. At 475 °C, the curve is concave downwards, distinct inflexion points are obtained at 500 and 525 °C, whereas at 550 °C the curve is concave upwards. 450 400 350 475 °C 500 °C Stress [N /mm 2 ] 300 525 °C 250 550 °C I.S. O. 5 0 0° 200 C I.S. O. 5 2 150 5° C I.S .O. 100 650 °C 10 Landolt-Börnstein New Series VIII/2B 10 2 55 0° C 600 °C 10 3 Rupture time [h] 10 4 10 5 Fig. 137. Stress vs. time to rupture data for normalized and tempered 9Cr-1Mo steel bars compared with ISO data. 122 2.3 High Cr steels Fig. 138 shows the isochronal strain data up to 2 % at 475 °C. The log ε versus log σ lines generally diverge at 500, 525 and 550 °C with increasing strain and stress, but the opposite behavior occurs at 475 °C up to 1000 h testing. Divergence is often obtained with this steel, in which no period of steady state rate elongation occurs. Instead, after the initial primary extension, the creep rate continuously processes to failure. This can be attributed to recovery processes increasing at a greater rate than the strain hardening, i.e. microstructural degeneration is occurring such that the dislocation structure is not stabilized. At 475 °C, the divergence is not apparent until after 1000 h testing. At this temperature the strain-time curves generally show a period of steady state creep, more extensive than at higher temperatures, prior to rapid elongation to failure. Hence it appears that after 1000 h at 475 °C, degeneration of the microstructure becomes important and the isochronal log ε versus log σ lines diverge as at the higher temperatures. 450 Stress [N/mm 2 ] 400 0.5 % e 0.3 % e Temperature 475 °C 350 2.0 % e 300 1.0 % e 0.5 % e 0.3 % e 10 2 10 10 3 Time [h] 10 4 10 5 Fig. 138. Stress vs. time relationship for normalized and tempered 9Cr-1Mo steel bars at 475 °C. However, several creep strain-time curves have been obtained which show perturbations, a marked example of which is shown in Fig. 139. In this case, a steady state creep stage was established at low strain, followed by a period of accelerating creep and then by a further period of steady state creep. Other cases, where the perturbation occurs soon after primary extension, and at higher temperatures, have been obtained, but not at 550 °C. 10 Temperature 500 °C Stress 232 N/mm 2 Duplicate tests repeat test terminated test continuing Strain [%] 1.0 0.1 1 10 10 2 10 3 Time [h] 10 4 10 5 Fig. 139. Multi-stage secondary creep observed in normalized and tempered 9Cr-1Mo steel bars at 500 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 125] 2.3.1 9Cr-1Mo steel 123 The microstructure analysis concentrated mainly on the creep tested specimens at above and below the inflexion point at 500 °C shown on the stress rupture plot of Fig. 137. Some specimens tested at 475 and 550 °C were also examined. The microstructure of the gauge region of creep specimens above the inflexion (2000 h at 500 °C) shows that normal recovery creep events have commenced locally. The recovery processes have led to a local reduction in the intrinsic dislocation density, together with the onset of subcell formation and some regions of secondary precipitate. Below the inflexion point (3×104 h at 500 °C), recovery is again inhomogeneous, but additionally in those areas where recovery has occurred, significant secondary precipitation on or near dislocations has taken place. The secondary precipitate is up to 50 nm in diameter and precipitates separately or as a stack-like sequence of thin plates either on or near dislocations. The secondary precipitate is identified as M2X type carbonitrides with high Cr content, together with some substitutional Fe and Mo content. No secondary precipitate similar to that found in the gauge is visible, and hence the precipitation in the gauge occurs or is enhanced by the presence of creep strain. Examination of a 1.5×104 h test at 475 °C and 302 MPa shows a fine general precipitate of similar, or higher density, than that in the 500 °C, 3×104 h specimen’s gauge. However, the structure of a 550 °C, 132 MPa, 104 h specimen shows little or no such precipitate, and is very similar to the grip region of the 500 °C, 3×104 h specimen. It is concluded that the onset of secondary precipitation leads to modest increases in creep and rupture strength of normalized and tempered 9Cr-1Mo steel. Normal microstructural degeneration processes are perturbed under these circumstances giving rise to sigmoidal shaped creep and stress rupture curves. 2.3.1.5.2 Effect of heat treatment on the tensile strength of normalized and tempered 9Cr-1Mo steel The potential of 9Cr-1Mo steel for use in thick sections has been assessed by using simulation heat treatments [4]. This work involved the laboratory-scale cooling of bar samples to simulate waterquenching rates in cylindrical section up to 720 mm diameter (equivalent to 500 mm thick plate). The material, available as 20 mm diameter bars, originated from two commercial casts of 9Cr-1Mo steel manufactured by British Steel Corporation, one of the batches were from material produced by electroslag refining, the other by air melting. Bundles of 20 mm diameter bars were cooled from the austenitizing temperatures at rates simulating those at the centers of 375 and 500 mm thick plates during water quenching. Tables 88 and 89 give the chemical compositions and the heat treatment conditions, respectively, of 9Cr-1Mo steel examined. The experimental work was carried out in two separate phases : Phase 1 - an investigation of the effect of a 375 mm thick section simulation on tensile strength using relatively rapid furnace heating rates and short soak periods at austenitizing and tempering temperatures (Cast RM348). Phase 2 - as for phase 1, but extended to include the effects of a 500 mm thick plate simulation with similar heating rates and soak periods to those used commercially for large section forgings (Cast D9893). Duplicate tensile tests were carried out at room temperature and 525 °C. Table 88. Chemical compositions of 9Cr-1Mo steel for tensile tests. Identity RM348 (1) D9893 (2) Landolt-Börnstein New Series VIII/2B C 0.09 0.10 Si 0.84 0.66 Mn 0.46 0.50 Chemical composition [wt%] P S Cr Mo Ni Cu 0.018 0.007 9.8 1.00 0.1 0.1 0.030 0.008 8.85 0.95 0.21 0.15 Co 0.03 0.15 Al Sn 0.009 0.02 0.009 0.02 124 2.3 High Cr steels Table 89. Heat treatment conditions of 9Cr-1Mo steel for tensile tests. Austenititzing Phase Cast Identity Temp. Heating Cooling rate Temp. times rate times [°C/h] 1 RM348 920 °C 2000 Simulated 375 mm 700 °C, 2 h 1h thick WQ 780 °C, 2 h 980 °C 1h 2000 Simulated 375 mm thick WQ 980 °C, 1h 980 °C 15 h 980 °C 15 h 980 °C 15 h 980 °C 15 h WQ: Water quenched 2000 Simulated 375 mm thick WQ Simulated 375 mm thick WQ Simulated 375 mm thick WQ Simulated 375 mm thick WQ Simulated 375 mm thick WQ 2 D9893 30 30 30 30 Tempering Heating Cooling rate rate [°C/h] 1500 Air cooled as 20 mm diameter 1500 Air cooled as 20 mm diameter 700 °C, 2 h 1500 Air cooled as 20 mm diameter 700 °C, 2 h 1500 Air cooled as 20 mm diameter 770 °C 1500 Air cooled as 20 mm 2h diameter 770 °C 30 Air cooled as 20 mm 16 h diameter 770 °C 30 Furnace cooled 16 h 770 °C 30 Air cooled as 20 mm 16 h diameter 770 °C 30 Furnace cooled 16 h The results on 0.2% proof stress and tensile strength are summarized in Fig. 140 and 141, showing the effects of variations in heat treatment temperatures and section sizes, respectively. The information in Fig. 140 relates to the 0.84% Si steel (Cast RM348) and it is seen that austenitizing at 980 °C results in higher strength at room temperature, but lower values at 525 °C relative to those produced after austenitizing at 920 °C. The material tempered at 700 °C had a small strength advantage over material tempered at 780 °C for room temperature tests, but this trend was reversed for tests at 525 °C, presumably as a consequence of secondary precipitation. The results from Phases 1 and 2 when taken together as in Fig. 141, demonstrate that differences in cooling rate equivalent to water-quenching sections up to 500 mm thickness have little effect on the tensile properties. However, the results show significant strengthening effects of Si and further demonstrate that the strength is obtained relative to that from the more rapid laboratory-type treatments. Landolt-Börnstein New Series VIII/2B Ref. p. 125] 2.3.1 9Cr-1Mo steel 800 700 125 20 AC 550 (375) WQ 550 (375) WQ 720 (500) WQ LAB 980 0.84 LAB LAB 980 980 0.84 0.66 COM COM 980 980 0.66 0.66 COM COM 980 980 0.66 0.66 Bar dia. (plate thick) mm Tensile strength [MPa] Tensile strength [MPa] 700 600 500 400 300 920 920 700 780 980 980 700 780 600 500 400 300 aust.temp. [°C] temp.temp.[°C] heating rate St temp. [°C] silicon [%] 0.2 % Proof stress [MPa] 600 500 400 RT min.props. (BS3059) 20 °C 525 °C value not obtained-test fault 0.2 % Proof stress [MPa] 200 500 400 RT min.props. (BS3059) 20 °C 525 °C 300 200 AC AC AC AC FC AC FC cool rate from tempering 300 200 Fig. 140. Effect of heat treatment temperatures on 9Cr-1Mo steel simulated cooled as 375 mm thick WQ (Cast RM348). Fig. 141. Effect of heat treatment, composition and simulated bar size on tensile properties of 9Cr-1Mo steel. abbreviations in Fig. 140 and 141: LAB = laboratory-type rapid heating rate; COM = commercial-type slow heating rate; RT min. prop. = minimum value of 0.2% proof stress and tensile strength at room temperature. 2.3.1.6 References [1] [2] [3] [4] NRIM Creep Data Sheet, No. 19B, (1997). ASTM Data Series Publication DS50, (1973) The British Steelmakers Creep Committee (BSCC) High Temperature Data (1972) Orr, J., and Sanderson, S. J.: Proceedings of Topical Conference on Ferritic Alloys for Use in Nuclear Energy Technologies, Snowbird, Utah, June 19-23, (1983), 261-267. [5] Williams, K. R., Fidler, R. S. and Askins, M.C.: Proceedings of International Conference on Creep and Fracture of Engineering Materials and Structures, University College, Swansea, UK, (1981), pp.475 - 487. [6] Sanderson, S. J.: Metal Science 11 (1977), 490 - 492. [7] Sanderson, S. J.: Metal Science 12 (1978), 220 - 222. Landolt-Börnstein New Series VIII/2B 126 2.3 High Cr steels 2.3.2 9Cr-1Mo-V-Nb steel 2.3.2.1 Introduction 9Cr-1Mo-V-Nb steel was developed in the early 1980s [1]. It is improved in creep strength by precipitation strengthening of fine MX carbonitride with addition of vanadium and niobium. 9Cr-1Mo-VNb steel has already been widely used as tubes for heat exchangers, pipes for high temperature service, plates for pressure vessels, forged, rolled and cast steels for high temperature services. 2.3.2.2 Materials standards, and chemical and tensile requirements 2.3.2.2.1 9Cr-1Mo-V-Nb steel tubes for heat exchangers Table 90. Chemical requirements of 9Cr-1Mo-V-Nb steel tubes; Japanese METI KA STBA28 and ASTM T91 Chemical composition [wt%] Std. Standards Designation No C Si Mn P S Cr Japanese KA STBA 28 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 METI ASTM T91 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 A-213 Standards Japanese METI ASTM Designation Mo V Chemical composition [wt%] Nb Ni N sol. Al KA STBA 28 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 T91 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Std. No A-213 2.3.2.2.2 9Cr-1Mo-V-Nb steel pipes for high temperature services Table 91. Chemical requirements of 9Cr-1Mo-V-Nb steel pipes; Japanese METI KA STPA28 and ASTM P91 Chemical composition [wt%] Standards Designation Std. No C Si Mn P S Cr Japanese KA STPA 28 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 METI ASTM P91 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 A-335 Standards Japanese METI ASTM Designation Mo V Chemical composition [wt%] Nb Ni N sol. Al KA STPA 28 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 P91 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Std. No A-335 Landolt-Börnstein New Series VIII/2B Ref. p. 132] 2.3.2 9Cr-1Mo-V-Nb steel 127 2.3.2.2.3 9Cr-1Mo-V-Nb steel plates for pressure vessels Table 92. Chemical requirements of 9Cr-1Mo-V-Nb steel plates; Japanese METI KA SCMV28 and ASTM Gr.91 Chemical composition [wt%] Standards Designation Std. No C Si Mn P S Cr Japanese KA SCMV 28 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 METI ASTM Gr.91 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 A-387 Standards Japanese METI ASTM Designation Mo V Chemical composition [wt%] Nb Ni N sol. Al KA SCMV 28 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Gr.91 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Std. No A-387 2.3.2.2.4 9Cr-1Mo-V-Nb forged or rolled steel for high temperature services Table 93. Chemical requirements of 9Cr-1Mo-V-Nb forged or rolled steels; Japanese METI KA SFVAF28 and ASTM F91 Chemical composition [wt%] Standards Designation Std. No C Si Mn P S Cr Japanese KASFVAF28 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 METI ASTM F91 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 A-182 Standards Japanese METI ASTM Designation Mo V Chemical composition [wt%] Nb Ni N sol. Al KA SFVAF28 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 F91 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Std. No A-182 2.3.2.2.5 9Cr-1Mo-V-Nb steel castings for high temperature services Table 94. Chemical requirement of 9Cr-1Mo-V-Nb steel castings; Japanese METI KA SCPH91 and ASTM C12A Chemical composition [wt%] Standards Designation Std. No C Si Mn P S Cr Japanese KA SCPH91 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 METI ASTM C12A 0.08-0.12 0.20-0.50 0.30-0.60 ≤0.020 ≤0.010 8.00-9.50 A-217 Standards Japanese METI ASTM Landolt-Börnstein New Series VIII/2B Designation Mo V Chemical composition [wt%] Nb Ni N sol. Al KA SCPH91 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.03-0.07 ≤0.04 C12A 0.85-1.05 0.18-0.25 0.06-0.10 ≤0.40 0.030-0.070 ≤0.04 Std. No A-217 128 2.3 High Cr steels 2.3.2.3 Creep properties of 9Cr-1Mo-V-Nb steel Information of fact on creep data for 9Cr-1Mo-V-Nb steels can be obtained from [2 - 4]. 2.3.2.3.1 Creep rupture data of 9Cr-1Mo-V-Nb steel Results of creep tests for 3 heats of Japanese METI KA STBA28 steel tubes are given in [2]. From [2], data on tensile properties, rupture elongation, reduction of area, minimum creep rate, and microstructure of as-received materials can also be obtained. Creep rupture strength data of Japanese METI KA STBA28 steel tubes over a temperature range from 500 to 700 °C is shown in Fig. 142 [2]. The slope of stress vs. time to rupture curves increases with decrease in applied stress. This inflection of creep rupture curves is due to a change of the degradation mechanism from homogeneous recovery during short-term exposure to inhomogeneous recovery during long-term exposure, as will be explained later. Results of creep tests for 9Cr-1Mo-V-Nb steel tubes, pipes and plates are given in [3]. From [3] data on product form, size, chemical composition, heat treatment condition, tensile properties, rupture elongation and reduction of area can also be obtained. 500 ○ △ □ × ▽ Stress (MPa) 300 500 oC 550 oC 600 oC 650 oC 700 oC 100 80 60 Fig. 142. Creep rupture strength data of Japanese METI KA STBA 28; [2]. n indicates the total number of data points. 40 n=59 20 1 10 2 10 3 10 4 10 5 10 6 10 Time to rupture (h) Creep rupture strength of 9Cr-1Mo-V-Nb steel tubes, pipes and plates at 600 and 650 °C are shown in Fig. 143 and 144, respectively, for tempering temperatures between 760 °C and 790 °C [3]. Slightly higher creep rupture strength is observed for steels with lower tempering temperature, at both temperatures of 600 and 650 °C. Creep rupture ductility data of Japanese METI KA STBA28 steel tubes over a temperature range from 500 to 700 °C is shown in Fig. 145 [2]. 9Cr-1Mo-V-Nb steel has a good rupture ductility. In some cases, however, a decreasing tendency in rupture ductility is observed during long-term exposure. This effect is thought to be caused by inhomogeneous recovery in the vicinity of prior austenite grain boundaries, similar to inflection of creep rupture curves, as will be explained later. Landolt-Börnstein New Series VIII/2B Ref. p. 132] 2.3.2 9Cr-1Mo-V-Nb steel 129 300 Tempering ○ △ □ × o Stress (MPa) 600 C 200 temperature 790 oC 780 oC 765 oC 760 oC Fig. 143. Creep rupture strength of 9Cr-1Mo-V-Nb steels at 600 °C; [3]. 100 1 10 2 10 10 3 10 4 10 5 Time to rupture (h) Stress (MPa) 200 Tempering ○ △ □ × 100 90 80 70 60 temperature 790 oC 780 oC 765 oC 760 oC o 650 C 50 40 1 10 2 10 10 3 4 10 10 5 Fig. 144. Creep rupture strength data of 9Cr-1Mo-VNb steels at 650 °C; [3]. Time to rupture (h) Rupture elongation and reduction of area (%) 100 80 60 Open: Rupture elongation Solid: Reduction of area 40 20 0 1 10 Fig. 145. Creep rupture ductility of 9Cr-1Mo-V-Nb steels; [2]. 10 2 10 3 Time to rupture (h) Landolt-Börnstein New Series VIII/2B 10 4 5 10 130 2.3 High Cr steels 2.3.2.3.2 Creep deformation behavior and creep rupture strength Creep rate vs. strain curves of 9Cr-1Mo-V-Nb steel tubes at 600 °C and over the range of stresses from 100 to 200 MPa are shown in Fig. 146. Creep deformation consists of transient and accelerating creep stages and no obvious steady state creep stage is observed. With decrease in applied stress, the onset strain of the accelerating creep stage decreases from about 0.03 at 200 MPa to less than 0.01. 2.3.2.3.3 Microstructural change -1 Creep rate (h ) Heat treatment condition of 9Cr-1Mo-V-Nb steel is normalizing and tempering. Tempered martensitic microstructure is typical for the as heat treated condition of the steel. The influence of microstructures on mechanical properties and changes in microstructures during creep exposure of 9Cr-1Mo-V-Nb steel have been widely investigated [5-29]. It is well known that fine MX carbonitride of Nb(C, N) and V(C, N) is very stable at elevated temperatures and plays an important role in improving creep strength. 10 -1 10 -2 10 -3 10 -4 10 -5 10 -6 10 -7 200MPa 160MPa 140MPa 120MPa 110MPa 600oC Fig. 146. Creep rate vs. strain curves at 600oC of Japanese METI KA STBA 28; [5]. 100MPa 10 -4 10 -3 10 -2 10 -1 10 0 True strain Bright field TEM images of the steel in the as heat treated condition and the creep ruptured specimen are shown in Figure 147 [5]. During creep exposure at elevated temperatures, recovery of tempered martensitic microstructure, such as decrease in dislocation density and increases in lath width and subgrain size, takes place. Homogeneous progress in recovery is observed in the specimens creep ruptured during short-term exposure, as shown in Fig. 147(b) and (c). On the other hand, inhomogeneous progress in recovery is observed in the specimen creep ruptured after 34,141.0 h at 600 °C and 100 MPa, as shown in Fig. 147(d). The microstructure within grains is very fine, in contrast to significantly recovered regions in the vicinity of prior austenite grain boundaries. Although the creep exposure time of 34,141.0 h at 600 °C and 100 MPa is about three times longer than that of 12,858.6 h at 600 °C and 120 MPa, the subgrain size within grains of the former specimen is smaller than that of the latter one. Bimodal distribution of subgrain size is clearly observed only in the specimen creep ruptured at 600 °C and 100 MPa. Inhomogeneous recovery preferentially taking place in the vicinity of prior austenite grain boundaries is regarded to be a degradation mechanism during long-term creep exposure, in contrast to homogeneous recovery during short-term exposure. Inflection of creep rupture curves mentioned in section 2.3.2.3.1 is thought to be caused by such differences in recovery phenomena during short-term and long-term exposure. It seems that decrease in rupture ductility during long-term exposure (Fig. 145) and decrease in onset strain of accelerating creep stage with decrease in stress (Fig. 146) is also derived from inhomogeneous recovery preferentially taking place in the vicinity of prior austenite grain boundaries [5]. There are three types of precipitates in the as heat treated condition: M23C6 carbide, NbX (niobium carbonitride) and VX (vanadium carbonitride) [26]. Precipitation of Laves phase (Fe2Mo) takes place after short-term exposure at temperatures lower than 600 °C. The role of precipitation of Laves phase on creep strength has not yet been clearly understood. It has been reported that Laves phase improves creep Landolt-Börnstein New Series VIII/2B Ref. p. 132] 2.3.2 9Cr-1Mo-V-Nb steel 131 strength through a precipitation strengthening effect [29]. On the other hand, the possibility to decrease creep strength by reducing the solid solution strengthening effect of molybdenum has been also pointed out. Precipitation of modified Z-phase, a complex nitride of chromium, niobium and vanadium in a form of Cr(Nb,V)N [30], takes place after several thousand hours of creep exposure at elevated temperatures [26]. Changes in mean diameter of precipitates with increase in creep exposure time at 600 and 650 °C in 9Cr-1Mo-V-Nb steel tubes are shown in Fig. 148 [26]. The size of MX carbonitride is about 30 nm in the as heat treated condition and less than 100 nm even after long-term creep exposure. The coarsening rate of MX carbonitride is very small and MX carbonitride is finer than that of M23C6 carbide. Precipitation of modified Z-phase takes place after several thousand hours of creep exposure and its growth rate after nucleation is significantly large, in comparison with those of MX carbonitride and M23C6 carbide. Since modified Z-phase grows at the expense of fine MX carbonitride, its nucleation and rapid growth results in a decrease in number density of fine MX carbonitride and reduces creep strength during long-term exposure. Fig. 147. Bright field TEM images of 9Cr-1Mo-V-Nb steel (a) in the as tempered condition and creep exposed at 600 °C for (b) 971.2 h at 160 MPa, (c) 12,858.6 h at 120 MPa and (d) 34,141.0 h at 100 MPa [5]. ~ ~ ・ Solid line: 650oC Dashed line: 600oC Laves 103 Z phase M23C6 102 ・ ・ ~ ~ ~ ~ Mean diameter (nm) 104 Fig. 148. Changes in mean diameter of the precipitates in 9Cr-1Mo-V-Nb steel with increase in creep exposure time at 600 and 650 °C [26]. MX ・ ~ ~ 101 101 102 103 104 105 Time to rupture (h) 2.3.2.3.4 Long-term creep strength prediction Inflection of stress vs. time to rupture curves of 9Cr-1Mo-V-Nb steel makes it difficult to predict longterm creep strength from the short-term data. Creep rupture data of 9Cr-1Mo-V-Nb steel tubes in the temperature range from 500 to 700 °C is shown in Fig. 149. Creep rupture life predicted from short-term data up to 20,000 h using the Larson-Miller parameter with a best fit parameter constant of 38 are also indicated in the figure. Since the curve indicates inflection, predicted long-term creep rupture strength is extremely overestimated, especially at 600 and 650 °C. Landolt-Börnstein New Series VIII/2B 132 2.3 High Cr steels From the above point of view, new life prediction methods have been investigated on high chromium ferritic creep resistant steels. One of the proposed new life prediction methods is demonstrated in Fig. 150 on the same creep rupture data as shown in Fig. 149 [28]. Here, creep rupture data is divided into two groups of short-term and long-term exposure with a boundary condition of half of 0.2% proof stress at each temperature. Creep rupture data where the stresses are lower than half of 0.2% proof stress should be used for life prediction using the Larson-Miller parameter with a constant of 20. Proper results of longterm creep strength prediction are obtained with this proposed prediction method. 500 o 500 C o 550 C Stress (MPa) 300 o 100 80 600 C o 650 C 60 Fig. 149. Stress vs. time to rupture curves of 9Cr1Mo-V-Nb steel tubes and predicted long-term creep rupture life using the Larson-Miller parameter and a best fit parameter constant of 38. o 700 C 40 20 1 10 Predicted (C=38) 10 2 3 10 4 5 10 6 10 10 Time to rupture (h) 500 Stress (MPa) 300 o 500 C o 550 C 100 80 o 600 C 60 40 20 1 10 o 650 C 0.2% proof stress 2 2 10 o 700 C 3 10 4 10 10 5 6 Fig. 150. Stress vs. time to rupture curves of 9Cr1Mo-V-Nb steel tubes and predicted long-term creep rupture life by considering half of 0.2% proof stress [28]. 10 Time to rupture (h) 2.3.2.4 References [1] Sikka, V. K.: Proc. of Topical Conf. on Ferritic Alloys for Use in Nuclear Energy Technologies, Davis, J. W., and Michel, D. J., eds., TMS-AIME, Warrendale, Pennsylvania, USA, (1984), 317327. [2] National Research Institute for Metals: NRIM Creep Data Sheet, No.43, (1996). [3] The Iron and Steel Institute of Japan: Atlas of Stress-Strain Curves and Rupture Data at High Temperatures, (1994). [4] Japan Pressure Vessel Research Committee: 0.5Mo and Cr-Mo steels Data Book, (1998). [5] Kimura, K., Kushima, H., and Abe, F.: Key Engineering Materials, 171-174 (2000), 483-490. [6] Vitek, J.M., and Klueh, R.L.: Metall. Trans. A, 14A (1983), 1047-1055. [7] Jemian, P.R., Weertman, J.R., Long, G.G., and Spal, R.D.: Acta Metall. Mater., 39 (1991), 24772487. [8] Jones, W.B., Hills, C.R., and Polonis, D.H.: Metall. Trans. A, 22A (1991), 1049-1058. [9] Iseda, A., Sawaragi, Y., and Yoshikawa, K.: Tetsu-to-Hagane, 77 (1991), 582-589. [10] Brinkman, C.R., Gieseke, B., and Maziasz, P.J.: Proc. of Microstructures and Mechanical Properties of Aging Materials, Liaw, P.K. et al. eds., TMS, (1993), 107-115. Landolt-Börnstein New Series VIII/2B Ref. p. 132] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] 2.3.2 9Cr-1Mo-V-Nb steel 133 Hamada, K., Tokuno, K., and Takeda, T.: Nuc. Eng. Des., 139 (1993), 277. Ruggles, M.B., Cheng, S., and Krempl, E.: Mater. Sci. Eng., A186 (1994), 15-21. Tsuchida, Y., Takeda, T., and Tokunaga, Y.: Tetsu-to-Hagane, 80 (1994), 723-728. Ogata, T.: Soc.,J., Mat. Sci., Japan, 46 (1997), 25-31. Spigarelli, S., Kloc, L. and Bontempi, P.: Scripta Mater., 37 (1997), 399-404. Cadek, J., Sustek, V., and Pahutova, M.: Mater. Sci. Eng., A225 (1997), 22-28. Kloc, L., and Sklenicka, V.: Mater. Sci. Eng., A234-236 (1997), 962-965. Sawada, K., Maruyama, K., Komine, R., and Nagae, Y.: Tetsu-to-Hagane, 83 (1997), 466-471. Sawada, K., Takeda, M., Maruyama, K., Komine, R., and Nagae, Y.: Tetsu-to-Hagane, 84 (1998), 580-585. Orlova, A., Bursik, J., Kucharova, K., and Sklenicka, V.: Mater. Sci. Eng., A245 (1998), 39-48. Cerri, E., Evangelista, E., Spigarelli, S., and Boanchi, P.: Mater. Sci. Eng., A245 (1998), 285-292. Park, K.S., Masuyama, F., and Endo, T.: Tetsu-to-Hagane, 84 (1998), 526-533. Park, K.S., Masuyama, F., and Endo, T.: Tetsu-to-Hagane, 84 (1998), 553-558. Kushima, H., Kimura, K. and Abe, F.: Tetsu-to-Hagane, 85 (1999), 841-847. Spigarelli, S., Cerri, E., Bianchi, P., and Evangelista, E.: Mater. Sci. Technol., 15 (1999), 14331440. Suzuki, K., Kumai, S., Kushima, H., Kimura, K., and Abe, F.: Tetsu-to-Hagane, 86 (2000), 550-557. Kimura, K., Suzuki, K., Toda, Y., Kushima, H., and Abe, F.: Proc. of 7th Liege Conference on Materials for Advanced Power Engineering 2002, J. Lecomte-Beckers et al. eds., Forschungszentrum Jülich GmbH, Liege, Belgium, September 2002, 21 (2002), 1171-1180. Kushima, H., Kimura, K., and Abe, F.: Proc. of 7th Liege Conference on Materials for Advanced Power Engineering 2002, J. Lecomte-Beckers et al. eds., Forschungszentrum Jülich GmbH, Liege, Belgium, September 2002, 21 (2002), 1581-1590. Hald, J., and Korcakova, L.: ISIJ Inter., 43 (2003), 420-427. Strang, A., and Vodarek, V.: Mater. Sci. Technol., 12 (1996), 552. Landolt-Börnstein New Series VIII/2B 134 2.3 High Cr steels 2.3.3 9Cr-2Mo steel 2.3.3.1 Introduction The low carbon-9Cr-2Mo steel (STBA 27, SFVAF27) has been used as reheater and superheater tubes at high-temperature boilers in Japan [1]. In order to obtain higher creep rupture strength and higher oxidation resistance at around 600 °C than T22 (2 1/4 Cr-1Mo steel), a low carbon-9Cr-2Mo steel has been developed through the considerations shown in Fig. 151. At a servicing temperature of 600 °C, 7 to 9 % Cr is needed to prevent oxidation. From the point that a steel for high-temperature use must have enough oxidation resistance and must contain polygonal ferrite, 9 % Cr was chosen. The strengthening of 9 % Cr steel should be achieved by precipitation strengthening or solution-hardening which is effective for the stabilization of high-temperature strength, but the strengthening by precipitation is more remarkable than that by solid solution at high temperature. Next, heat treatment condition was considered. Commercial steels are often used in a fully annealed condition. The annealing treatment is advantageous for low Cr steels, but unfavorable for high Cr steels. Normalizing and tempering (NT) is usually favorable for high Cr steels. From the microstructural viewpoint, the decrease or removal of martensite is desirable. Alpha single phase material could be strengthened at high temperature, but coarse grain size leads to poor toughness and decreases such practical properties as flattening, flaring and weldability. These considerations led to the ideas of a duplex microstructure. The existence of polygonal ferrite is advantageous for both the stabilization of high-temperature strength and the decrease of tensile strength at room temperature. Further strengthening at high temperature was then considered. The decrease of carbon is favorable for both obtaining (α + γ) duplex phase at the normalizing temperature and for the improvement of weldability. Strong precipitation hardening elements, such as V, Ti and Nb, are strong ferrite-forming elements and have a tendency to become brittle during tempering. Increase in these kinds of elements accelerates weld cracking and makes it difficult to control ferrite content. From these considerations, 9Cr-Mo steel with simply higher Mo content, which is easy to fabricate, was proposed. Effect of chemical composition Servicing temperature: 600oC Oxidation resistivity High temperature strengthening Ti, Nb, V Mo (W) (Poor weldability) (No deleterious effect) 9%Cr Normalizing and temper (Excessive strength and poor weldability) (Formation of proeutectoid Ferrite is depressed) Annealing (Ferrite + Coarse carbide) 1) Modification of strength and Decrease of high temperature weldability strength and poor weldability 2) Increase and stabilization of high temperature strength Low C-9Cr-2Mo α+γ at Normalizing temperature α single phase at Normalizing temperature Fig. 151. Alloy design philosophy for development of low carbon-9Cr-2Mo steel. (Poor toughness and weldability) 2.3.3.2 Material standards, chemical and tensile requirements 2.3.3.2.1 9Cr-2Mo steel tube for boilers and heat exchangers Table 95. Chemical requirements for 9Cr-2Mo steel tube (JIS STBA 27) Chemical composition [wt%] Stan- Desigdard nation C Si Mn P S Cr Mo 1) STBA 27 2) <0.08 <0.50 0.3-0.7 <0.030 <0.030 8.00-10.00 1.80-2.20 Yield strength [MPa] >295 1) The Ministerial Ordinance for Providing the Technical Standard for Thermal Power Generating Facilities-1997 in Japan 2) Designation in the Ministerial Ordinance for Providing the Technical Standard for Thermal Power Generating Facilities-1997 in Japan. Landolt-Börnstein New Series VIII/2B Ref. p. 139] 2.3.3 9Cr-2Mo steel 135 Table 96. Chemical requirements for 9Cr-2Mo steel plate (JIS SFVAF 27) Chemical composition [wt%] Stan- Designation dard C Si Mn P S Cr Mo 1) SFVAF 27 2) <0.08 <0.50 0.3-0.7 <0.030 <0.030 8.00-10.00 1.80-2.20 Yield strength [MPa] >295 1) The Ministerial Ordinance for Providing the Technical Standard for Thermal Power Generating Facilities-1997 in Japan 2) Designation in the Ministerial Ordinance for Providing the Technical Standard for Thermal Power Generating Facilities-1997 in Japan 2.3.3.3 Data sources for 9Cr-2Mo steel tubes (JIS STBA 27) and plates (JIS SFVAF 27) Information of fact on data for 9Cr-2Mo steel tubes and plates can be obtained from NRIM Creep Data Sheet, No.46 (1997) [2]. 2.3.3.4 Creep rupture data for 9Cr-2Mo steel tubes for power boilers and 9Cr-2Mo steel plates for power plants 2.3.3.4.1 Creep rupture data for 9Cr-2Mo steel tubes (STBA27) and plates (SFVAF27) Creep rupture data and optical micrographs of as-received specimens have been obtained for 1 heat for tubes and 1 heat for plates [2]. The details of steel tube and plate production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available in [2]. The tensile and creep specimens had a geometry of 6 mm in gauge diameter and 32 mm in gauge length for the 9Cr-2Mo steel tubes, STBA 27, and 10 mm in gauge diameter and 52 mm in gauge length for the 9Cr-2Mo steel plates, SFVAF 27. Fig. 152 and 153 show the 0.2% proof stress and tensile strength obtained by short-time tensile tests for the 9Cr-2Mo steels STBA 27 and SFVAF 27, respectively, between room temperature and 750 °C. Fig. 154 and 155 show creep rupture data for 9Cr-2Mo steel tubes and plates, respectively. The estimation of 105 h creep rupture strength is not made in [2], because the test duration was too short. Tensile strength 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 700 400 300 400 300 200 200 100 100 0 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 152. Short-time tensile properties of 9Cr-2Mo steel, STBA 27 Landolt-Börnstein New Series VIII/2B 0 0 100 200 300 400 500 600 Test temperature (℃) 700 800 136 2.3 High Cr steels Tensile strength 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 600 300 300 200 200 100 100 0 0 100 200 300 400 500 600 700 0 800 0 100 200 Test temperature (℃) 300 400 500 600 700 800 Test temperature (℃) Fig. 153. Short-time tensile properties of 9Cr-2Mo steel, SFVAF 27 400 o 500 C Stress ( MPa ) o 550 C o 600 C 100 o 650 C o 700 C 10 1 10 10 2 10 3 10 4 10 5 10 Fig. 154. Creep rupture strength data for 9Cr-2Mo steel tubes, STBA 27. 6 T ime t o rup ture ( h ) 4 00 o 45 0 C o Stress ( MPa ) 50 0 C o 55 0 C o 60 0 C 1 00 o 65 0 C 10 0 10 1 10 10 2 10 3 10 4 10 5 10 6 Fig. 155. Creep rupture strength data for 9Cr-2Mo steel plates, SFVAF 27. T ime to rupture ( h ) Landolt-Börnstein New Series VIII/2B Ref. p. 139] 2.3.3 9Cr-2Mo steel 137 2.3.3.5 Creep behavior and microstructure of 9Cr-2Mo steel 2.3.3.5.1 Creep and creep rupture data for 9Cr-2Mo steel tubes and plates: Sumitomo data Fig. 156 shows stress vs. time to rupture data at 450, 500, 550, 600, 650, 675 and 700 °C for 5 heats of 9Cr-2Mo steel tubes and plates, satisfying the chemical requirements for STBA 27 and SFVAF 27 [3]. The total elongation of creep ruptured specimens is more than 20 %, which is enough ductility for practical use. 50 40 30 450 °C 500 °C Stress [kgf / mm 2 ] 20 550 °C 10 8 6 600 °C 4 650 °C 675 °C 2 Fig. 156. Creep rupture strength data for 9Cr-2Mo steel tubes and plates. 700 °C 1 10 10 2 10 3 Rupture time [h] 10 4 10 5 Fig. 157 compares stress vs. time to rupture data for 9Cr-2Mo steel at 600 °C with those for 2.25Cr-1Mo (T22) and 9Cr-1Mo (T9) steels. The 2.25Cr-1Mo steel exhibits a gentle slope at short times, but at long times the slope becomes steep. In comparison, the stress versus time to rupture curves of the 9Cr-1Mo and 9Cr-2Mo steels are nearly straight. Fig. 158 shows creep curves of 9Cr-2Mo steel plates at 550 °C. The 9Cr-2Mo steel exhibits larger primary creep strain but lower creep rate in the secondary or steady state creep region than those in 2.25Cr-1Mo steel. 30 9Cr-2Mo 2 1/4 Cr-1Mo 2 1/4 Cr-1 Mo 9 Cr-2 Mo 20 Strain [%] Stress [kgf / mm 2 ] 20 9 Cr-1 Mo 10 8 15.0 kg /mm 2 22.0 kg /mm 2 20.0 kg /mm 2 18.0 kg /mm 2 10 16.0 kg /mm 2 12.0 kg /mm 2 6 creep ruptured at 600 °C (1112 °F) 4 10 2 10 3 Time to rupture [h] 10 4 Fig. 157. Comparison of stress versus time to rupture curves of 2.25Cr-1Mo, 9Cr-1Mo and 9Cr-2Mo steels at 600 °C. Landolt-Börnstein New Series VIII/2B 0 1000 Time [h] 2000 Fig. 158. Creep curves of 9Cr-2Mo steel plates at 550 °C (solid lines), comparing with those of 2.25Cr1Mo steel (dotted lines). 138 2.3 High Cr steels Based on the creep curves in Fig. 158, the time to reach 1 % creep strain and the time to onset of tertiary or acceleration creep were evaluated. This is shown in Fig. 159. The time to reach tertiary creep after reaching 1 % creep strain is much longer for 9Cr-2Mo steel than for 2.25Cr-1Mo and 18Cr-8Ni-Ti steels. Time to 1 % creep strain [h] 10 4 9Cr-2Mo 2 1/4 Cr-1Mo 18-8-Ti 10 3 10 2 10 10 2 10 4 10 3 Time to onset of tertiary creep [h ] Fig. 159. Relationship between time to reach 1 % creep strain and time to onset of tertiary or acceleration creep for 9Cr-2Mo steel at 550 °C, comparing with that for 2.25Cr-1Mo and 18Cr-8Ni-Ti steels. The allowable stress based on ASME Code Section III, Case Interpretation 1592, was calculated from the high-temperature tensile strength and creep rupture strength. Fig. 160 shows the ASME allowable stress intensity value, defined as Smt value at 105 h, for 9Cr-2Mo steel together with those for various steels. The allowable stress of 9Cr-2Mo steel is 25 - 50 % higher than that of 2.25Cr-1Mo steel (T22) and 30 60 % higher than that of 9Cr-1Mo steel (T9) at temperatures higher than 550 °C. Stress intensity value [kg /mm2 ] 20 15 5 Smt [10 h] 10 21/4 Cr-1 Mo 9 Cr-2 Mo Type 304 Type 316 Alloy 800 H 5 0 300 400 500 600 Temperature [°C ] 700 800 Fig. 160. Comparison of allowable stress intensity value for various steels based on ASME case 1592. 2.3.3.5.2 Microstructure and strengthening factors of 9Cr-2Mo steel The microstructure of 9Cr-2Mo steel consists of tempered martensite and polygonal ferrite with fine M23C6 carbides [1]. Spheroidization of needle-like carbides and the formation of net-like carbides occur in tempered martensite during creep at 600 °C. The precipitation behavior of carbides can be detected by the measurement of Cr or Mo as carbides. Analysis of electrolytically extracted residues revealed that the amount of Mo as carbides increases more slowly than that in normalized and tempered 2.25Cr-1Mo steel Landolt-Börnstein New Series VIII/2B Ref. p. 139] 2.3.3 9Cr-2Mo steel 139 (T22) and annealed 9Cr-1Mo steel (T9). Half of the total Mo remains in solution in the 9Cr-2Mo steel. From microstructural observations, the strengthening factors of the 9Cr-2Mo steel are summarized as follows. Positive strengthening factors are: the precipitation of needle-like carbides within ferrite, the formation of net-like carbides and slow growth of globular carbides within tempered martensite. Factors that contribute to the stabilization of a microstructure are: the existence of polygonal ferrite, 1 % of Mo in solution. The strengthening of the 9Cr-2Mo steel is not ascribed to only one strengthening factor, but to the summing up of the aforementioned factors. 2.3.3.6 References [1] Yukitoshi, T., Nishida, K., Oda, T. and Daikoku, T.: Journal of Pressure Vessel Technology, Transactions of the ASME, (1976), 173 - 178. [2] National Research Institute for Metals (NRIM) Creep Data Sheet, No.46, (1998). [3] Yukitoshi, T., Yoshikawa, K., Tokimasa, K., Shida, Y. and Inaba, Y.: Tetsu-To-Hagane, 65 (1979), 876 - 885. Landolt-Börnstein New Series VIII/2B 140 2.3 High Cr steels 2.3.4 9Cr-0.5Mo-1.8W-V-Nb-B steel 2.3.4.1 Introduction 9Cr-0.5Mo-1.8W-V-Nb-B steel is used for heat exchangers and piping systems in Ultra Super Critical steam conditioned thermal power plants [1]. In order to achieve higher creep rupture strength than that of Mod. 9Cr steel, Gr. 91 of ASME standard, tungsten was replaced by molybdenum improving the creep rupture strength of the ferritic heat resistant steel designated as KA-STBA29 for METI and as Gr. 92 for ASME. Other alloying elements, niobium, vanadium and nitrogen, have also been optimized with respect to the creep properties through precipitation strengthening by fine carbonitride distribution in the lath interior [2]. Boron stabilizes the tempered martensitic sub-grain structure during creep deformation by segregation at the lath boundaries and the surface of M23C6 type carbides [3]. 2.3.4.2 Material standards, chemical and tensile requirements 2.3.4.2.1 9Cr-0.5Mo-1.8W-V-Nb-B steel tubes for heat exchanger or boiler applications Table 97. Chemical composition of 9Cr-0.5Mo-1.8W-V-Nb steel tubes; KA-STBA29 and 213 T92 [4] Chemical composition [wt%] Standards Designation C Si Mn P S Cr Mo 0.07 0.30 8.50 0.30 ≤ ≤ ≤ METI KA-STBA29 0.13 0.60 0.60 0.50 0.020 0.010 9.50 8.50 0.30 0.30 0.07 ≤ ≤ ≤ ASTM Gr. T92 0.60 0.60 0.13 0.020 0.010 9.50 0.50 Standards Designation METI KA-STBA29 ASTM Gr. T92 W 1.50 2.00 1.50 2.00 Ni ≤ 0.40 ≤ 0.40 Chemical composition [wt %] V Nb N Al 0.15 0.04 0.030 ≤ 0.25 0.09 0.070 0.04 0.15 0.04 0.03 ≤ 0.25 0.09 0.07 0.04 ASTM SAStd. No. SA-213 Std. No. B 0.001 0.006 0.001 0.006 SA-335 2.3.4.2.2 9Cr-0.5Mo-1.8W-V-Nb-B steel pipes for steam conductors or boiler piping application Table 98. Chemical composition of 9Cr-0.5Mo-1.8W-V-Nb steel pipes; KA-STPA29 and 335 P92 [5] Chemical composition [wt%] Standards Designation C Si Mn P S Cr Mo 8.50 0.30 0.30 0.07 ≤ ≤ ≤ METI KA-STPA29 0.60 0.60 0.13 0.020 0.010 9.50 0.50 8.50 0.30 0.30 0.07 ≤ ≤ ≤ ASTM Gr. P92 0.60 0.60 0.13 0.020 0.010 9.50 0.50 Standards Designation METI KA-STPA29 ASTM Gr. P92 W 1.50 2.00 1.50 2.00 Ni ≤ 0.40 ≤ 0.40 Chemical composition [wt%] V Nb N Al 0.15 0.04 0.030 ≤ 0.25 0.09 0.070 0.04 0.15 0.04 0.03 ≤ 0.25 0.09 0.07 0.04 ASTM SAStd. No. SA-335 Std. No. B 0.001 0.006 0.001 0.006 SA-335 Landolt-Börnstein New Series VIII/2B Ref. p. 143] 2.3.4 9Cr-0.5Mo-1.8W-V-Nb-B steel 141 2.3.4.3 Creep properties of 9Cr-0.5Mo-1.8W-V-Nb steel tubes [6] contains creep data of 9Cr-0.5Mo-1.8W-V-Nb-B steel tubes, namely rupture data, minimum creep rate, rupture elongation and reduction of area of cross section. 2.3.4.3.1 Creep rupture data of 9Cr-0.5Mo-1.8W-V-Nb steel tubes Fig. 161 shows the creep rupture data of 9Cr-0.5Mo-1.8W-V-Nb-B steel tubes of 7 heats [6]. Creep test duration is still continuing and is at about 55,000 h. All the rupture data satisfy the ASME Gr. 92 standard requirement. 1000 T ube Stress (MPa) 550 ℃ 600 ℃ 100 650 ℃ 750 ℃ 700 ℃ Fig. 161. Creep rupture strength data of KA-STBA29; [6]. 10 1 10 100 1000 10000 100000 T ime (h) 2.3.4.3.2 Time-Temperature-Parametric prognostication of creep rupture strength Fig. 162 shows the Larson Miller Parametric plots of the rupture data based on [6]. Creep rupture curve regression by a cubic expressionpredicts the creep rupture strength for times longer than that of the experiment between 550 °C and 750 °C, Fig. 163. 1000 1000 Stress (MPa) Stress (MPa) 550 ゚C 100 100 600 ゚C 650 ゚C 750 ゚C 10 ----- Average 10 25000 27000 29000 700 ゚C 1 31000 33000 35000 37000 39000 10 100 1000 10000 100000 1000000 Rupture T ime (h) Larson-Miller-parameter TK (32.896118 + log tr ) Fig. 162. Master rupture curve by Larson-Miller parameter method for 9Cr-0.5Mo-1.8W-V-Nb-B steel tubes. Landolt-Börnstein New Series VIII/2B Fig. 163. Estimated creep rupture curves of 9Cr-0.5Mo1.8W-V-Nb-B steel tubes. 142 2.3 High Cr steels 2.3.4.4 Creep properties of 9Cr-0.5Mo-1.8W-V-Nb steel pipes [6] contains creep data of 9Cr-0.5Mo-1.8W-V-Nb-B steel pipes, namely rupture data, minimum creep rate, rupture elongation and reduction of area of cross section. 2.3.4.4.1 Creep rupture data of 9Cr-0.5Mo-1.8W-V-Nb steel pipes Fig. 164 shows creep rupture data of 9Cr-0.5Mo-1.8W-V-Nb-B steel pipes of 9 heats [6]. Creep test duration is still continuing and is at about 70,000 h. All the rupture data satisfy the ASME Gr. 92 standard requirement. 1000 Pipe Stress (MPa) 550 ℃ 600 ℃ 100 650 ℃ 700 ℃ 750 ℃ Fig. 164. Creep rupture strength data of KA-STPA29; [6]. 10 1 10 100 1000 10000 100000 T ime (h) 2.3.4.4.2 Time-Temperature-Parametric prognostication of the creep rupture strength Fig. 165 shows the Larson Miller Parametric plots of the rupture data based on [6]. Creep rupture curve regression by a cubic expression predicts the creep rupture strength for times longer than that of the experiment between 550 °C and 750 °C [6], Fig. 166. 1000 550 ゚C Stress (MPa) Stress (MPa) 1000 100 100 600 ゚C 650 ゚C ----10 25000 750 ゚C 30000 35000 40000 45000 Larson-Miller-parameter TK (35.277449 + log tr ) Fig. 165. Master rupture curve by Larson-Miller parameter method for 9Cr-0.5Mo-1.8W-V-Nb steel pipes. 700 ゚C 10 1 10 100 1000 10000 100000 1000000 Rupture T ime (h) Fig. 166. Estimated creep rupture curves of 9Cr-0.5Mo-1.8W-V-Nb steel pipes. Landolt-Börnstein New Series VIII/2B Ref. p. 143] 2.3.4 9Cr-0.5Mo-1.8W-V-Nb-B steel 143 2.3.4.5 Effect of tungsten content on creep properties of 9Cr-0.5Mo-1.8W-V-Nb steel Precipitated W [mass %] Precipitated W [mass %] Precipitated W [mass %] Optimized tungsten content in 9Cr-0.5Mo-1.8W-V-Nb steel increases the creep rupture strength at high temperatures [7]. Tungsten delays the microstructure evolution by solid solution dragging in the same manner as molybdenum. An excess of tungsten in thermodynamic equilibrium at service temperature precipitates as Fe2W type intermetallic compound, Laves phase. Fig. 167 shows the tungsten precipitation during aging [8]. After saturation of precipitation in amount, Laves phase ripens at the sub-grain boundary, and possibly affects the microstructure evolution delaying the dynamic recrystallization. 1.5 1.26 % 600 °C 1.2 0.9 0.6 0.3 0 1.5 650 °C 1.2 0.99 % 0.9 0.6 0.3 0 1.5 700 °C 1.2 0.9 0.58 % 0.6 Fig. 167. time. 0.3 0 1 10 10 3 10 2 Aging time [h] 10 4 Tungsten precipitation behavior with aging 10 5 2.3.4.6 References [1] Fujita, T.: COST-EPRI Workshop, Shaffhausen (1996). [2] Masumoto, H., Sakakibara, M., Takahashi, T., and Fujita, T.: EPRI, 1st. Conf. Improved Coal-Fired Power Plants, Palo Alto 5 (1986) 205. [3] Naoi, H., Mimura, H., Ohgami M., Morimoto, H., Tanaka, T., Yagaki, Y., and Fujita, T.: Proc. EPRI/National Power Conf., New Steel for Advanced Plant up to 620°C, London, May 11 (1995), 1. [4] ASTM Standard: A213/A213M-99a (2001). [5] ASTM Standard: A335/A335M (2001). [6] Muraki, T.: Private communication “Nippon Steel Creep Database” (2000) [7] Hasegawa, Y., Muraki, T., and Ohgami, M.: 123rd committee heat resistant materials and alloys, 39, No. 3 (1998) 275. [8] Hasegawa, Y., Muraki, T., Ohgami, M., and Mimura, H.: Proceedings of the 8th International Conference on Creep and Fracture of Engineering Materials and Structures (1999) 427. Landolt-Börnstein New Series VIII/2B 144 2.3 High Cr steels 2.3.5 9Cr-1Mo-1W-V-Nb-N steel 2.3.5.1 Introduction 9Cr-1Mo-1W-V-Nb-N steel (X11CrMoWVNb9-1-1) is used for tubing, headers and piping, but also for large forgings. The maximum service temperature for tubes and pipes is limited to 625 °C. The steel was developed in Europe in parallel to the grade P92 and is also well known under the designation E911. The material shows a pure martensitic microstructure after tempering. The steel has a good weldability. Preheating up to 150 °C at least is recommended, during welding the temperature should not exceed 350 °C. After welding it is essential for the steel to cool down to a temperature below 100 °C, in order to allow the complete transformation into martensite. The above mentioned parameters depend on the type and thickness of the component to be welded. Thin structures may be welded below 150 °C and also allowed to cool down at room temperature. Post heat treatment should be done at 740 - 770 °C. The holdtime at PWHT temperature depends on the thickness of the material. 2.3.5.2 Material standards, chemical and tensile requirements 2.3.5.2.1 X11CrMoWVNb9-1-1 for seamless tubes Table 99. Heat treatment of X11CrMoWVNb9-1-1 seamless tubes for pressure purposes; VdTÜV Werkstoffblatt 522:2001 Quenching 1040 - 1080 °C / Air VdTÜV Werkstoffblatt 522/2 Tempering 750 - 780 °C/ Air Table 100. Chemical requirements of X11CrMoWVNb9-1-1; VdTÜV Werkstoffblatt 522/2:2001 Chemical composition [wt%] Designation steel number C Si Mn P S Cr Ni Mo W Nb V Al N B 8.50 0.10 0.90 0.90 0.06 0.18 0.050 0.0005 ≤ X11CrMoW 0.09 0.10 0.30 ≤ 0.13 0.50 0.60 0.020 0.010 9.50 0.40 1.10 1.10 0.10 0.25 0.040 0.900 0.005 VNb9-1-1 1.4905 Table 101. Tensile requirements of X11CrMoWVNb9-1-1 at room temperature; VdTÜV Werkstoffblatt 522/2:2001 Tensile requirements Standard Designation/steel number Yield Tensile Elongation Impact energy strength strength after fracture Charpy-V-testpiece T Q T Q [MPa] [MPa] [%] [%] [J] [J] VdTÜV X11CrMoWVNb9-1-1 620 - 850 ≥19 ≥450 ≥17 ≥68 ≥41 Werkstoffblatt 1.4905 522/2 T longitudinal, Q transverse direction 2.3.5.2.2 X11CrMoWVNb9-1-1 for forgings and rolled or forged bars for pressure purposes Table 102. Heat treatment of X11CrMoWVNb9-1-1 forgings and rolled or forged bars for pressure purposes; VdTÜV Werkstoffblatt 522/3:2001 Quenching 1040 - 1080 °C / Oil VdTÜV Werkstoffblatt 522/2 Tempering 750 - 780 °C/ Air Landolt-Börnstein New Series VIII/2B Ref. p. 149] 2.3.5 9Cr-1Mo-1W-V-Nb-N steel 145 Table 103. Chemical requirements of X11CrMoWVNb9-1-1; VdTÜV Werkstoffblatt 522/3:2001 Chemical composition [wt%] Designation steel number C Si Mn P S Cr Ni Mo W Nb V Al N B 8.50 0.10 0.90 0.90 0.06 0.18 0.050 0.0005 X11CrMoW 0.09 0.10 0.30 0.13 0.50 0.60 0.020 0.010 9.50 0.40 1.10 1.10 0.10 0.25 0.040 0.900 0.005 VNb9-1-1 1.4905 Table 104. Tensile requirements of X11CrMoWVNb9-1-1 at room temperature; VdTÜV Werkstoffblatt 522/3:2001 Standard Designation/ steel number VdTÜV X11CrMoWVNb9-1-1 Werkstoffblatt 522/2 1.4905 Tensile requirements Range of Yield Tensile Elongation significant strength strength after fracture dimensions T Q [%] [%] [mm] [MPa] [MPa] 620 ≤500 ≥450 ≥19 ≥17 850 Impact energy Charpy-V-testpiece T Q [J] [J] ≥68 ≥41 T longitudinal, Q transverse direction Fig. 168. Microstructure of X11CrMoWVNb9-1-1 (as received state). 2.3.5.3 Mechanical properties of X11CrMoWVNb9-1-1 seamless tubes, forgings 1000 minimum values tensile strength VdtÜV 522 minimum values yield strength VdtÜV 522 Stress σ (MPa) 800 600 400 200 0 0 100 200 300 400 Temperature T (°C) Landolt-Börnstein New Series VIII/2B 500 600 700 Fig. 169. High temperature tensile strength and yield strength of X11CrMoWVNb9-1-1 according to VdTÜV 522: 2001 [1] 146 2.3 High Cr steels 800 E911 UTS [2] E911 YS [2] E911 UTS [8] E911 YS [8] 700 Stress σ (MPa) 600 500 400 300 200 100 0 0 100 200 300 400 500 600 700 800 Fig. 170. High temperature tensile strength (UTS) and yield strength (YS) of X11CrMoWVNb9-1-1 (E911) [2], [8]. Temperature T (°C) 2.3.5.4 Creep properties of X11CrMoWVNb9-1-1 2.3.5.4.1 Creep strength of X11CrMoWVNb9-1-1 seamless tubes and forgings 1000 Stress σ (MPa) Tubes Welded pipes Pipes 100 10 100 1000 10000 100000 Fig. 171. Creep rupture strength data of E911 (X11CrMoWVNb9-1-1) at 625 °C [2]. The data of tubes are slightly above the pipes. Short term tests with cross weld specimens of pipes are at the lower band of the parent material in the short term test duration. Time to rupture tR (h) 1000 Stress σ (MPa) P91 E911 100 Fig. 172. Creep rupture strength data of E911 (X11CrMoWVNb9-1-1) and P91 (both pipes) at 650 °C [2]. E911 material shows a factor 3 to 5 longer rupture time at the same constant stress in comparison to P91 steel. 10 10 100 1000 10000 100000 Time to rupture tR (MPa) Landolt-Börnstein New Series VIII/2B Ref. p. 149] 2.3.5 9Cr-1Mo-1W-V-Nb-N steel 147 Stress σ (MPa) 1000 610 °C, heat A, broken 640 °C, heat A, broken 550 °C, heat B, broken 600 °C, heat B, broken 600 °C, heat B, unbroken 650 °C, heat B, broken 650 °C, heat B, unbroken 550 °C, VdTÜV 522 600°C, VdTÜV 522 610 °C, VdTÜV 522 640 °C, VdTÜV 522 650 °C, VdTÜV 522 550 °C, broken [8] 550 °C, unbroken [8] 600 °C, broken [8] 600 °C, unbroken [8] 650 °C, broken [8] 650 °C, unbroken [8] 100 10 10 100 1000 10000 100000 1000000 Fig. 173. Creep rupture strength data of steel grade E911 (X11CrMoWVNb9-1-1) in dependence of temperature (3 heats, tubes) [3], [8] and average creep rupture strength values indicated in VdTÜV 522/2. Stress σ (MPa) Test duration t (h) Fig. 174. Creep rupture strength data of steel grade E911 (X11CrMoWVNb9-1-1) of parent material and cross weld specimens at 600 °C [3], [8] and average creep rupture strength values indicated in VdTÜV 522/2. Cross weld specimens show lower creep strength in comparison to the parent material, caused by failure in the heat affected zone. 100 Crossweld, MAW, broken Crossweld, MAW, unbroken Parent material, broken Parent material, unbroken Crossweld, SAW, broken 600 °C, VdTÜV, parent material Parent material, broken [8] Parent material, unbroken [8] 10 100 1000 10000 100000 Stress σ (MPa) Test duration t (h) 100 Crossweld, MAW, broken Crossweld, MAW, unbroken Parent material, broken Parent material, unbroken Crossweld, SAW, broken 650 °C, VdTÜV, parent material Weld material, broken [8] Crossweld, broken [8] 10 100 1000 10000 Test duration t (h) Landolt-Börnstein New Series VIII/2B 100000 Fig. 175. Creep rupture strength data of the steel grade E911 (X11CrMoWVNb9-1-1) of parent material and cross weld specimens at 650 °C [3], [8] and average creep rupture strength values indicated in VdTÜV 522/2. Cross weld specimens show lower creep strength in comparison to the parent material, caused by failure in the heat affected zone. 148 2.3 High Cr steels 2.3.5.4.2 Fact creep data of X11CrMoWVNb9-1-1 tubes Information of fact on creep data for X11CrMoWVNb9-1-1 tubes and forgings is given in [4, 6, 7]. 2.3.5.4.3 Microstructural change The typical microstructure of X11CrMoWVNb9-1-1 is a martensitic structure. A high dislocation density and relatively fine carbide precipitates at the martensite lath boundaries can be observed. In the initial state Nb and NbV-rich MX particles as well as M23C6 carbides can be observed. The nucleation of Laves phase and Z phase can be observed after creep at 600 °C. In this context a change in the chemical composition of both M23C6 carbides as well as MX carbides could be observed [5]. 2.3.5.4.4 Creep crack growth Creep crack growth may occur at defects in components operated in the high temperature regime. The assessment of crack growth at defects is based on fracture mechanics and the relevant data. The crack growth rate was measured using fracture mechanic specimens (CT, Cs -side grooved CT, D) with different ratios of crack start length a0 to specimen width W. The stress situation at crack tip was calculated using the creep fracture mechanics parameter C*. 1 10 -7 a [mm/h] 10 -2 10 -3 230 (1035) 282 282 (1799) (1271) 178 (304) 220 175 (674) (305) 10 -4 10 -5 10 -6 10 -5 sn0 = 204 MPa -8 (K l0 = 688 N/mm 3/2 ) 10 320 (1443) 10 -9 178 (901) 10 -10 320 282 176 (951) 179 (862) (709) (679) 140 (454) Cs25 Cs50 CT100 a0 / W 0.55 0.55 0.55 10 -11 D30 D60 D15 a0 / W 0.25 0.45 0.2 0.1 0.2 10 -12 10 -4 10 -3 10 -2 C * [N/mmh] 10 -1 1 10 a [m/s] 10 -1 Fig. 176. Crack growth rate in dependence on the parameter C* (based on the load line displacement rate) for different specimens types and sizes for E911 (forgings). Cs25, Cs50, CT100 – CT specimens with thickness 25 and 50 mm (side grooved), 100 mm (not side grooved), D15, D30, D60– double edge notched specimens, thickness 15 mm; σn0 nominal stress, KI0 stress intensity factor at the beginning of the test [6]. 2.3.5.4.5 Estimated long term creep rupture strength Table 105. Average values of creep rupture strength of X11CrMoWVNb9-1-1 for seamless tubes. Long term data is partly based on extended time and stress extrapolations; [1]. Time to rupture Temperature [°C] [104 h] [105 h] Average creep rupture strength [MPa] 480 322 288 490 305 271 500 288 255 510 271 239 520 255 223 Landolt-Börnstein New Series VIII/2B Ref. p. 149] Temperature [°C] 530 540 550 560 570 580 590 600 610 620 630 640 650 2.3.5 9Cr-1Mo-1W-V-Nb-N steel 149 Time to rupture [104 h] [105 h] Average creep rupture strength [MPa] 239 208 224 193 21 182 197 166 182 150 167 135 154 121 140 108 128 95 115 83 104 72 93 62 82 53 2.3.5.5 References [1] VdTÜV-Werkstoffblatt 522 09 (2001): Warmfester Stahl X11CrMoWVNb9-1-1. TÜV Verlag GmbH, Postfach 9030 60, 51123 Köln. [2] Gianfrancesco, A. Di., and Merckling, G.: The Italian effort to the development of 9 to 12 % Chromium steels for power plant applications. International Colloquium on the occasion of the 50th anniversary of the German Creep Committee, November 25 (1999) Düsseldorf. Verein Deutscher Eisenhüttenleute VDEh. [3] Klenk, A., Maile, K., Theofel, H., and Husemann, R.-A.: Long term behaviour of weldments of modern power plant steels. Creep 7, Proceedings of the 7th International Conference on Creep and Fatigue at elevated Temperatures, Japan Society of Mechanical Engineers Tokyo, Japan (2001) 8791. [4] Husemann, R.U.: Abschlussbericht und Zusammenfassung der Ergebnisse des FDBR-/VGBForschungsvorhabens „Qualifizierung von Werkstoffen zum Einsatz in Dampferzeugeranlagen mit erhöhten Temperaturen“, AVIF-Vorhaben A77 (1999). Wirtschaftsverband Stahlbau und Energietechnik e. V., Düsseldorf. [5] Maile, K., Klenk, A., and Zies, G.: Determination of Microstructural Parameters for 9 % Cr Steels. Proceedings of the 8th Japanese-German Joint Seminar on Structural Integrity and NDE in Power Engineering, Tokyo (2001) 511-518. [6] Berger, C., Granacher,J., Kostenko,J., Roos, E., Maile, K., and Schellenberg, G.: Kriechrissverhalten ausgewählter Kraftwerksbaustähle in erweitertem, praxisnahem Parameterbereich, Abschlussbericht des AVIF-Vorhabens Nr. A78 des IfW der TU-Darmstadt und der MPA der Universität Stuttgart (1999), Forschungskuratorium Maschinenbau e. V., Frankfurt. [7] Klenk, A., Maile, K.: Nachweis der Langzeiteigenschaften von Schweißverbindungen moderner Stähle für den Einsatz in Dampferzeugern im Bereich bis 620 °C. Abschlussbericht AVIF Vorhaben A129 der MPA Stuttgart, 2002. Wirtschaftsverband Stahlbau und Energietechnik e.V., Düsseldorf. [8] Bendick, W.: Neue Entwicklungen für warmfeste Rohre im Kraftwerksbau. 3R international (40), Heft 5/2001 264-268. Landolt-Börnstein New Series VIII/2B 150 2.3 High Cr steels 2.3.6 12Cr steel 2.3.6.1 Introduction 12Cr stainless steels are used as wrought bars, plates, sheets, strips, wire rods, billets and forgings. It is hardenable corrosion and heat resistant martensitic chromium steel. Microstructure and stability at elevated temperatures are strongly influenced by heat treatment condition. Changes in microstructure during creep exposure and creep strength properties have been investigated, in conjunction with creep deformation behavior. 2.3.6.2 Materials standards, chemical and tensile requirements 2.3.6.2.1 12Cr steel Table 106. Chemical requirements of 12Cr steel; JIS SUS403 and ASTM 403 Chemical composition [wt%] StanDesigdards nation C Si Mn P S Cr 11.50JIS SUS403-B ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 SUS40311.50JIS ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 HP 13.00 SUS40311.50JIS ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 CP 13.00 SUS40311.50JIS ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 WR 13.00 11.50ASTM 403 ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 11.50ASTM 403 ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 11.50ASTM 403 ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 11.50ASTM 403 ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 11.50ASTM 403 ≤0.15 ≤0.50 ≤1.00 ≤0.040 ≤0.030 13.00 Std. No Ni ≤0.60 G4303 ≤0.60 G4304 ≤0.60 G4305 ≤0.60 G4308 ≤0.60 A176 - A276 - A314 - A473 - A479 Table 107. Product forms of 12Cr steel; JIS SUS403 and ASTM 403 Standards Designation Std. No Product form JIS SUS403-B G4303 bar JIS SUS403-HP G4304 plate, sheet and strip JIS SUS403-CP G4305 plate, sheet and strip JIS SUS403-WR G4308 wire rod ASTM 403 A176 plate, sheet and strip ASTM 403 A276 bar and shape ASTM 403 A314 billet and bar for forging ASTM 403 A473 forging ASTM 403 A479 bar and shape Landolt-Börnstein New Series VIII/2B Ref. p. 155] 2.3.6 12Cr steel 151 2.3.6.3 Creep properties of 12Cr steels Information of fact on creep data for 12Cr stainless steels can be obtained [1] and [2]. 2.3.6.3.1 Creep rupture data of 12Cr steel bars The results of creep tests for 9 heats of JIS SUS 403-B steel bars are given in [1]. Here, data on rupture elongation, reduction of area, minimum creep rate, time to specified strain and microstructures of asreceived materials and crept specimens are aloso given. Creep rupture strength of 9 heats of 12Cr stainless steel bars (JIS SUS 403-B) are shown in Fig. 177. It should be noted that the creep rupture strength of the steels shows a large scatter over the range of tested temperatures from 450 to 600 °C. Heat-to-heat variation is caused by differences in initial microstructure. The martensitic microstructure is strongly influenced by manufacturing condition, especially heat treatment condition. The initial microstructure of the 12Cr stainless steel influences its stability during creep exposure at elevated temperatures and results in large differences in creep rupture strength, as will be described later. 500 Stress (MPa) 300 100 80 ○ ● △ ▲ 60 40 10 450 oC 500 oC 550 oC 600 oC n=226 -1 0 10 10 1 10 2 10 3 10 4 10 5 10 6 Fig. 177. Creep rupture strength data of 9 heats of SUS 403-B steel bars; [1]. n indicates the total number of data points. Time to rupture (h) 2.3.6.3.2 Creep rupture strength of 12Cr stainless steel bars Creep rupture strength data of 9 heats of 12Cr stainless steel bars are shown in Fig. 178. It should be noted that creep rupture strength of 12Cr stainless steel bars shows a large heat-to-heat variation. Microstructure is strongly dependent on heat treatment conditions and influences the creep strength of the steel. Heat treatment conditions and creep rupture strength of 3 heats of 12Cr stainless steel bars are shown in Table 108 and Fig. 179, respectively. Differences in creep rupture strength of these 3 heats of 12Cr stainless steel bars are attributed to differences in heat treatment condition as shown in Table 108. The lowest creep rupture strength of heat C is caused by an extremely high tempering temperature of 750 °C. Rapid decrease in creep rupture strength with increase in creep exposure of heat B is due to low temperature before quenching, as will be explained in conjunction with microstructures later. Landolt-Börnstein New Series VIII/2B 2.3 High Cr steels 800 600 500 400 450 °C 475 °C 500 °C 525 °C 550 °C 575 °C 600 °C Stress [MPa] 300 200 100 80 60 50 40 30 500 400 300 Stress (MPa) 152 200 100 90 80 70 60 50 40 30 16000 Average n = 231 20 -26 -16 -24 -20 -18 -22 Orr-Sherby-Dorn parameter log tR -[354987/(19.1425 × TK )] ○ heat A △ heat B □ heat C 17000 18000 19000 20000 21000 22000 23000 Larson-Miller parameter (T(K)(21+Log tR(h))) Fig. 179. Creep rupture strength of 3 heats of 12Cr stainless steel bars; [3]. Fig. 178. Master rupture curve by Orr-Sherby-Dorn parameter method for 12Cr stainless steel bars; [1]. TK = T + 273.15, T: test temperature [°C] and tR: time to rupture [h]. n indicates the total number of data points. Table 108. Heat treatment conditions of 3 heats of 12Cr stainless steel bars; [3]. Standard & Designation heats Heat treatment conditions Forged 980 °C / 0.5 h / Oil quenching heat A 640 °C / 2 h / Air cooling 630 °C / 2 h / Air cooling Forged JIS G4303 SUS403-B heat B 950 °C / 1 h / Oil quenching 650 °C / 2 h / Air cooling Hot rolled heat C 970 °C / 0.5 h / Oil quenching 750 °C / 1 h / Water quenching 2.3.6.3.3 Microstructural change The typical initial microstructure of 12Cr stainless steel is tempered martensite. Optical micrographs of a 12Cr stainless steel bar are shown in Fig. 180. Bright field TEM images of 3 heats of 12Cr stainless steel bars in the as-received and crept conditions at 600 °C and 61 MPa are shown in Fig. 181 [3]. A very fine tempered martensitic microstructure is observed on heats A and B in the as-received condition. On the other hand there is a significantly recovered microstructure even in the as-received condition on heat C, since the tempering temperature of 750 °C is extremely high, in contrast to 630 and 650 °C of heats A and B, respectively. The tempered martensitic microstructure of heat A is very stable during creep exposure up to about 2000 h at 600 °C and 61 MPa. With increase in creep exposure time, however, recovery of tempered martensitic microstructure proceeds very rapidly in heat B. In contrast to the homogeneous tempered martensitic microstructure of heat A in the as-received condition, that of heat B is inhomogeneous and contains small amounts of ferritic grains, as can be seen in Fig. 181 (f). The inhomogeneous microstructure of heat B in the as-received condition is caused by a slightly lower temperature of 950 °C before quenching, comparing to 980 °C of heat A. Landolt-Börnstein New Series VIII/2B Ref. p. 155] 2.3.6 12Cr steel 153 Fig. 180. Optical micrographs of as-received 12Cr stainless steel bars (etched in 4% natal); [1]. Differences in heat treatment condition strongly influence the initial microstructure and stability during creep exposure at elevated temperatures. Different changes in microstructure during creep exposure of 3 heats of 12Cr stainless steel bars are clearly observed as changes in hardness, as shown in Fig. 182 [3]. Hardness of heat B is almost the same as that of heat A in the as-received condition, however, it decreases rapidly with increase in creep exposure time, corresponding to changes in microstructures. Fig. 181. Bright field TEM images of 3 heats of 12Cr stainless steel bars in the as-received and crept conditions at 600 °C and 61 MPa [3]. ti: creep exposed time before interrupting, tr: time to rupture Landolt-Börnstein New Series VIII/2B 154 2.3 High Cr steels ~ ~~ ~ 200 ~ ~ 600oC-61MPa 240 heat A heat B heat C 160 120 Asreceived Fig. 182. Changes in hardness of the 3 heats of 12Cr stainless steel bars with increase in creep exposure time at 600 °C and 61 MPa; [3]. Ruptured ~ ~ Vickers hardness (98N) 280 2 3 4 10 10 5 10 10 Time (h) 2.3.6.3.4 Creep deformation behavior and creep rupture strength Differences in initial microstructure and its stability strongly influence creep deformation behavior. Creep rate vs. time curves of 3 heats of 12Cr stainless steel bars at 500 °C - 177 MPa and 600 °C - 61 MPa are shown in Fig. 183 and 184, respectively. Under the creep test condition of 500 °C - 177 MPa, differences in creep strength of the 3 heats are clearly observed. Differences in creep strength of these 3 heats correspond to differences in initial microstructure, as shown in Fig. 181. Creep rupture life of heat B is about five times longer than that of heat C and that of heat A is about five times longer that that of heat B. On the other hand, creep deformation behavior of heat B under the creep test condition of 600 °C 61 MPa is affected by rapid progress in recovery of tempered martensitic microstructure during creep exposure, as shown in Fig. 181. Creep rate of heat B is smaller than that of heat C and almost the same as that of heat A in the beginning of creep deformation up to about 100 h. However, heat B shows minimum creep rate and onset of accelerating creep stage after about 200 - 300 h, which is significantly earlier than for heat A (about 3,000 h). Consequently, difference in creep rupture life of heats B and C is very small in comparison with the difference observed under the creep test condition of 500 °C-177 MPa. Such rapid acceleration of creep rate for heat B is caused by rapid progress in recovery of tempered martensitic microstructure, as shown in Fig. 181. Differences in initial microstructure strongly influence short-term creep strength. The stability of microstructure during creep exposure at elevated temperatures significantly affects long-term creep strength. Very large heat-to-heat variations of creep rupture strength of 12Cr stainless steels, as shown in Fig. 177 and 178, are caused by differences in initial microstructure and its stability at elevated temperatures, which is strongly influenced by heat treatment condition. -3 -3 10 10 heat C -4 Creep rate (h ) 10 10 -1 -1 Creep rate (h ) heat C heat B -4 -5 10 -6 10 500 C-177MPa 0 1 10 -6 o 600 C-61MPa -7 10 2 10 3 10 4 10 heat A 10 heat A o 10 heat B -5 10 5 10 Time (h) Fig. 183. Creep rate vs. time curves of 3 heats of 12Cr stainless steel bars at 500 °C and 177 MPa; [3]. -7 10 0 10 10 1 10 2 3 10 4 10 10 5 Time (h) Fig. 184. Creep rate vs. time curves of 3 heats of 12Cr stainless steel bars at 600 °C and 61 MPa; [3]. Landolt-Börnstein New Series VIII/2B Ref. p. 155] 2.3.6 12Cr steel 155 2.3.6.3.5 Estimated long-term creep rupture strength The temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 9 heats of 12Cr stainless steel bars are shown in Fig. 185 [1]. Those of 0.2% proof stress, tensile strength and creep rupture strength at 1,000 and 100,000 h for the same materials are shown in Fig. 186 [1]. Creep rupture strength curves shown in Fig. 185 and 186 were obtained by regression analysis using the Orr-Sherby-Dorn parameter. {{ 100 80 60 50 40 30 20 400 450 500 550 Temperature [°C] 0.2% proof stress 100 h { 200 Tensile strength { Stress [MPa] 1000 800 600 500 400 300 10000 h 600 650 Fig. 185. Temperature dependence of 0.2% proof stress, tensile strength and creep rupture strength at 100 and 10,000 h for 12Cr stainless steel bars; [1]. 1000 800 200 { Stress [MPa] 300 100 80 60 50 400 450 500 550 Temperature [°C] { {{ 600 500 400 Tensile strength 0.2% proof stress 1000 h 100000 h 600 650 Fig. 186. Temperature dependence of 0.2% proof stress, tensile strength and creep-rupture strength at 1,000 and 100,000 h for 12Cr stainless steel bars; [1]. 2.3.6.4 References [1] National Research Institute for Metals: NRIM Creep Data Sheet, No.13B, (1994). [2] ASM International: Atlas of Creep and Stress-Rupture Curves, (1988). [3] Kushima, H., Kimura, K., Yagi, K., and Tanaka, C.: Tetsu-to-Hagane, 81 (1995), 214-219. Landolt-Börnstein New Series VIII/2B 156 2.3 High Cr steels 2.3.7 12Cr-0.6Mo-0.3V-0.4Nb-N steel 2.3.7.1 Introduction 12Cr-0.6Mo-0.3V-0.4Nb-N steel (H46) is produced as forging quality bars and billets (blading bars) and bars (rounds, squares, hexagons and flats) for use in rotating blades of steam and combustion turbines, disks, rotor shafts and bolts. H46 was developed by William Jessop, UK in the 1950s for hightemperature applications up to 650 °C through modification of H40 (3Cr-0.5Mo-0.5W-0.8V steel) by increasing the Cr content to 11 - 12 % and adding Nb to substitute for W in H40. The V content was also reduced to 0.3 % to avoid the agglomeration of V4C3 in the temperature range of 600 - 650 °C. 2.3.7.2 Materials standards, and chemical and tensile requirements Table 109 and Table 110 show the chemical requirements and tensile requirements of 12Cr-0.6Mo-0.3V0.4Nb-N steel (H46, JIS G4311 SUH600), respectively. Table 111 shows the chemical compositions and heat treatment conditions of the H46 steels tested, which were produced in the UK and Japan in the 1950s. Table 112 lists the tensile properties of three heats of H46 steels. Fig. 187 shows the elevated temperature tensile properties of H46 steel [1]. Table 109. Chemical requirements of 12Cr-0.6Mo-0.3V-0.4Nb-N steel (H46, JIS G4311 SUH600) Chemical composition [wt%] Stan- DesigStd. dard nation No. C Si Mn P S Cr Ni Mo V Nb N JIS SUH600 0.15∼ ≤0.50 0.50∼ ≤0.040 10.00∼ ≤0.60 ≤0.60 0.30∼ 0.10∼ 0.20∼ 0.05∼ G4311 0.20 1.00 13.00 0.90 0.40 0.60 0.10 Table 110. Tensile requirements of 12Cr-0.6Mo-0.3V-0.4Nb-N steel (H46, JIS G4311 SUH600) Standard Designation 0.2% yield Tensile Elongation Reduction Hardness* Std. No. strength strength [%] of area [%] [HB] [MPa] [MPa] JIS SUH600 G4311 ≥685 ≥830 ≥15 ≥30 ≤321 * ≤269 for as-annealed Table 111. Chemical compositions of H46 steels tested [1], [2] Chemical composition [wt%] Steel Heat treatment C Si Mn P S Cr Ni Mo A 1150 °C AC+ 0.16 0.3 0.7 NA NA 11.6 NA 0.6 670~690 °C AC B 1040 °C OC+ 0.15 0.4 0.6 NA NA 11.5 NA 0.45 620 °C WC C 1150 °C AC+ 0.13 0.15 0.79 0.008 0.028 11.47 NA 0.58 680 °C AC D 1150 °C AC+ 650 °C AC 0.16 Producer V 0.3 Nb N 0.25 NA Jessop 0.30 0.25 NA Jessop 0.35 0.28 0.046 Jessop 0.18 0.66 0.012 0.014 11.90 0.12 0.17 0.30 0.26 NA Nippon Special Steel NA: Not available Landolt-Börnstein New Series VIII/2B Ref. p. 160] 2.3.7 12Cr-0.6Mo-0.3V-0.4Nb-N steel 157 Table 112. Tensile properties of H46 steels at room temperature [1], [2] Steel Yield strength Tensile strength Elongation (0.2% offset) [MPa] [MPa] [%] A 693* 919 17 C 866 1040 18 D 853 955 21 * 0.1% offset Reduction of area [%] 60 51 59 1100 Tensile strength 900 800 700 600 0.1 % offset yield strength 500 80 400 60 300 Reduction of area 40 200 100 20 Elongation 0 50 150 250 350 450 Temperature [°C] 550 650 0 750 Elongation, reduction of area [%] Yield strength, tensile strength [MPa] 1000 Fig. 187. Elevated temperature tensile properties of H46 steel (A); [1]. 2.3.7.3 Creep properties 2.3.7.3.1 Creep rupture data [1], [2] Figs. 188 [1], 189 [2] and 190 show the creep rupture stress vs. time to rupture diagrams for three heats of H46. H46 shows stable creep rupture strength at temperatures from 400 to 550 °C. However, strengths at temperatures of 600 °C and above drop rapidly with longer time, except heat D shown in Fig. 190. Heat D was normalized at a relatively low temperature followed by rapid cooling, and was also tempered at a lower temperature, which is different from the other heats. Figs. 191 and 192 respectively show the creep rupture elongation and reduction of area for heat D of H46 steel. 3000 2000 400℃ 500℃ 550℃ 600℃ 650℃ 700℃ 1000 700 Stress (MPa) 500 300 200 100 70 50 30 20 10 101 Landolt-Börnstein New Series VIII/2B Fig. 188. Creep rupture strength data of H46 steel (A); [1]. 102 103 104 Time to rupture (h) 105 106 158 2.3 High Cr steels 700 400℃ 450℃ 500 500℃ 8.3 Stress (MPa) 6.9 5.0 300 550℃ 8.6 200 11.8 9.8 6.1 3.6 8.8 6.8 100 8.4 70 50 Values designate rupture elongation in %. 102 650℃ 600℃ 700℃ 103 Time to rupture (h) 104 105 Fig. 189. Creep rupture strength data of H46 steel (B); [2]. 1000 700 550℃ 600℃ 650℃ 700℃ 500 300 Stress (MPa) 200 100 70 50 30 20 Fig. 190. Creep rupture strength data of H46 steel (D). 10 101 102 103 Time to rupture (h) 30 20 80 Reduction of area [%] 550 °C 600 °C 650 °C 700 °C 40 Elongation [%] 105 100 50 60 40 550 °C 600 °C 650 °C 700 °C 20 10 0 10 104 10 2 10 3 10 5 10 4 Time to rupture [h] Fig. 191. Creep rupture elongation of H46 steel (D). 0 10 10 2 10 3 10 5 10 4 Time to rupture [h] Fig. 192. Creep rupture reduction of area of H46 steel (D). Landolt-Börnstein New Series VIII/2B Ref. p. 160] 2.3.7 12Cr-0.6Mo-0.3V-0.4Nb-N steel 159 2.3.7.3.2 Creep deformation behavior Fig. 193 [2] shows stress vs. time to 0.1% creep strain of H46 steel in the temperature range from 500 °C to 650 °C. Fig. 194 shows creep deformation curves, strain vs. time at 600 °C, for the stress range from 108 MPa to 294 MPa for heat D of H46 steel. Fig. 195 shows Larson-Miller plots of the average creep strain rate obtained from time to given strain (0.1%, 0.2% and 0.3%) creep test data at temperatures from 550 °C to 700 °C, also for heat D of H46 steels. In the medium stress range of around 100 MPa, averaged strain rates scatter more widely than in the lower stress range, meaning that the creep curves have greater curvature at around 100 MPa than at other stresses. 300 Stress (MPa) 500℃ 200 550℃ 100 600℃ 650℃ 0 101 Fig. 193. Stress vs time to 0.1% creep strain of H46 steel (C); [2]. 103 102 104 1000 800 600 108 MPa 115 MPa 127 MPa 5 147 MPa 6 260 MPa 186 MPa Time (h) 400 300 2 1 0 Stress [MPa] 294 MPa 3 200 219 MPa Strain [%] 4 0.1 % 0.2 % 0.3 % 100 80 60 40 30 20 2000 6000 4000 Time [h] 8000 Fig. 194. Creep curves of H46 steel (D). Landolt-Börnstein New Series VIII/2B 10000 10 9 10 11 12 13 . 14 Larson-Miller-parameter T (10 - log e ) [×10 -3 ] 15 Fig. 195. Larson-Miller plots of average creep strain rate obtained from the time to given creep strain against stress for H46 steel (A). 160 2.3 High Cr steels 2.3.7.3.3 Creep mechanism [3] The minimum creep rate ε&m of heat D of H46 steel is plotted against creep stress (normalized with Young’s modulus) σ/E and reciprocal temperature in Figs. 196 (a) and (b), respectively. The stress exponent changes at σ/E=8.5×10−4, and this value appears to be independent of temperature. The stress exponents are 4.7 and 8.4 over the low and high stress ranges, respectively, and are temperature independent. In Fig. 196 (a) the two points at 600 °C under σ/E=4.1×10−4 and 4.7×10−4 deviate from what is expected from other data points. The creep curves under these conditions are completely different in shape from those under the other conditions. Since the testing temperatures are close to the Curie temperature (720 °C for 11.8Cr steel) the Arrhenius plot in Fig. 196 (b) is not straight as is the case with diffusivity. An average activation energy for ε&m over the range studied is 508 kJ/mol, being substantially greater than that for self-diffusion (360 kJ/mol). Temperature T (℃) 10-6 700℃ ( ) 650℃ 600℃ 700 650 10-3 10-7 σ/E=1×10-3 10 . εm (s-1) . εm (h-1) . εm (s-1) 10-5 10-9 10-5 10-9 0.5×10-3 10-6 10 ( ) ( ) 10-4 -8 . 10 -8 -10 550 10-3 10-4 550℃ 600 10-6 10 -10 10-7 10-11 0.3 0.5 εm (h-1) 10-7 10-6 0.7 1.0 σ/E (10- 3) (a) 2.0 3.0 10-7 10-11 1.00 1.05 1.10 1.15 T-1 (10- 3K- 1) (b) 1.20 1.25 Fig. 196. (a) stress and (b) temperature dependence of minimum creep rate ε&m of H46 steel (D) (Creep stress s is normalized with Young’s modulus E) [3]. 2.3.7.4 References [1] Briggs, J.Z., and Parker, T.D. (eds): The Super 12%Cr Steels, Climax Molybdenum CD. Michigan, (1982). [2] William Jessop, UK: Data Sheets, Jessop H46, (1956). [3] Maruyama, K., Harada, C., and Oikawa, H.: Trans. Iron and Steel Inst. Japan, 26 (1986), 212. Landolt-Börnstein New Series VIII/2B Ref. p. 169] 2.3.8 12Cr-1Mo-1W-0.3V steel 161 2.3.8 12Cr-1Mo-1W-0.3V steel 2.3.8.1 Introduction Steels of the 12Cr-1Mo-1W-0.3V type, specified as JIS SUH 616-B and ASTM S 42200, are used as turbine blades at around 500 °C in modern steam power plants. Because of high operating temperatures of such components, creep and creep rupture data are required by designer. 2.3.8.2 Materials standards and chemical requirements Table 113. Chemical requirements for 12Cr-1Mo-1W-0.3V steel bars; JIS SUH 616-B and ASTM S 42200. Chemical composition [wt%] StanDesigStd. dard nation C No. Si Mn P S Ni Cr Mo W V JIS SUH 0.20- <0.50 0.50 - <0.040 <0.030 0.50 - 11.00 - 0.75 - 0.75 - 0.20 - G4311 616-B 0.25 1.00 1.00 13.00 1.25 1.25 0.30 ASTM S 42200 0.20 - <0.75 0.75 - <0.040 <0.030 0.50 - 11.50 - 0.75 - 0.75 - 0.15 - A565 0.25 1.25 1.00 13.50 1.25 1.25 0.30 2.3.8.3 Data sources for 12Cr-1Mo-1W-0.3V steel Information of fact on data for 12Cr-1Mo-1W-0.3V steel bars can be obtained from [1], [2], [3]. 2.3.8.4 Creep and creep rupture data for 12Cr-1Mo-1W-0.3V steel bars for turbine blades, JIS SUH 616-B 2.3.8.4.1 Creep rupture data for 12Cr-1Mo-1W-0.3V steel bars, JIS SUH 616-B The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area, minimum creep rate and optical micrographs of as-received and crept specimens, has been obtained for 9 heats of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B, in [1]. The details of steel bar production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are additionally available for the 9 heats in [1]. Fig. 197 shows the 0.2% proof stress and tensile strength, of the 9 heats of 12Cr-1Mo-1W-0.3V steel bars, JIS SUH 616-B, in [1]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 50 mm in gauge length, were taken longitudinally from square bars of 50 mm by 50 mm side, obtained by short-time tensile tests between room temperature and 650 °C. Fig. 198 shows stress vs. time to rupture data for the 9 heats of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B, at temperatures between 500 and 650 °C. Fig. 198 exhibits a large heat-to-heat variation in time to rupture, which becomes more significant with increasing time and temperature. At 550 °C and 157 MPa, the time to rupture of the strongest heat is 105 h, while that of the weakest one is only 2×104 h. It should be noted, however, that the observed heat-to-heat variation in time to rupture is not caused by data scattering, because each heat exhibits its distinct stress dependence of time to rupture as shown in Fig. 199. The heat-to-heat variation in time to rupture comes from many factors, as will be described later. Landolt-Börnstein New Series VIII/2B 162 2.3 High Cr steels Tensile strength 1200 1000 1000 800 800 Stress (MPa) Stress (MPa) 0.2% proof stress 1200 600 400 200 0 600 400 200 0 100 200 300 400 500 600 0 700 0 100 Test temperature (℃) 200 300 400 500 600 700 Test temperature (℃) Fig. 197. Short-time tensile properties of 12Cr-1Mo-1W-0.3V steel bars, JIS SUH 616-B. 800 Stress [MPa] 600 500 400 300 500 °C 550 °C 600 °C 650 °C 200 100 80 60 50 40 30 n = 258 20 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 198. Creep rupture strength data for 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B. n indicates the total number of data points. 500 12Cr-1Mo-1W -0.3V 400 Stress ( MPa ) o 550 C 300 RAA RAB RAC RAD RAE RAF RAG RAH RAJ 200 100 10 2 Fig. 199. Creep rupture strength data for each heat of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B, at 550 °C. 10 3 10 4 10 5 Tim e to rupture ( h ) Landolt-Börnstein New Series VIII/2B Ref. p. 169] 2.3.8 12Cr-1Mo-1W-0.3V steel 163 2.3.8.4.2 Estimated long-term creep rupture strength for 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B The creep rupture data shown in Fig. 198 were analyzed for each heat using the Manson-Haferd parameter method. The solid curves in Fig. 200 are based on the Manson-Haferd parameter for the RAF heat which showed an intermediate strength level among the 9 heats. 105 h creep rupture strength was also estimated for the 9 heats. This is shown in Fig. 201 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. 1000 o Stress ( MPa ) 500 C o 550 C 10 0 o 6 00 C o 65 0 C Fig. 200. Estimated creep rupture curves of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B. 10 2 10 10 3 10 4 10 5 10 6 T ime to ruptu re ( h ) Tensile strength 0.2% proof stress { 1000 h { 100000 h { Stress [MPa] { 1000 800 600 500 400 300 200 100 80 60 50 40 30 20 450 500 550 600 Temperature [°C] 650 700 Fig. 201. Estimated 105 h creep rupture strength for the 9 heats of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B. 2.3.8.4.3 Creep strain data of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B The stress vs. time to reach 0.5, 1, 2 and 5 % total strain, time to tertiary creep and time to rupture for the heat RAB (Fig. 199) of 12Cr-1Mo-1W-0.3V steel are obtained from [1]. The relationship between stress and minimum creep rate is shown for the 9 heats in Fig. 202. The relationship between time to rupture and minimum creep rate is shown for the 9 heats in Fig. 203. Landolt-Börnstein New Series VIII/2B 2.3 High Cr steels 600 500 400 10 6 300 10 5 500 °C 550 °C 600 °C 650 °C n = 124 200 Time to rupture [h] Stress [MPa] 164 100 80 60 50 40 500 °C 550 °C 600 °C 650 °C n = 126 30 20 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 -1 10 4 10 3 10 2 1 Fig. 202. Stress vs. minimum creep rate for 12Cr1Mo-1W-0.3V steel. The corres-ponding data of time to rupture are included in Fig. 198. n indicates the total number of data points. 10 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 -1 1 Fig. 203. Time to rupture versus minimum creep rate for 12Cr-1Mo-1W-0.3V steel. The corresponding data of time to rupture are included in Fig. 198. n indicates the total number of data points. 2.3.8.5 Creep behavior and microstructure of 12Cr-1Mo-1W-0.3V steel 2.3.8.5.1 Effect of high aluminum content on the log term creep properties of 12Cr-1Mo-1W-0.3V steel The origin of differences in long term creep properties was investigated using the selected 4 heats, RAB, RAD, RAG and RAJ, of the 9 heats in [1] at temperatures between 500 and 650 °C [4]. Fig. 204 shows the creep rupture data for the 4 heats. Metallurgical examination after exposure at 600 °C showed that the microstructure and the dissolved concentration of Mo and W in the matrix were similar among the 4 heats and had no correlation with their rupture strength. The heats RAD and RAJ, containing low aluminum content less than 0.007 mass%, showed high strength at long times. Thermal aging at 600 °C prior to creep test decreases the creep rupture strength at 550 °C, which is more significant for the heats RAB and RAG with high aluminum content than for the heats RAD and RAJ with low aluminum content. This is shown in Fig. 205. Aluminum nitride AlN forms in the heats RAB and RAG (high aluminum content) during thermal aging at 600 °C, as shown in Fig. 206. Therefore, it appears that a high aluminum content reduces the nitrogen concentration in solution due to the precipitation of AlN during prolonged rupture test and leads to deterioration in rupture strength. The rupture ductility variation among the different heats is suggested to arise from the differences in prior austenite grain size, aluminum content and copper content. The heat RAJ with fine grains, low aluminum content of 0.005 mass%, and low copper content of 0.03% showed a high ductility over a wide test range. Landolt-Börnstein New Series VIII/2B Ref. p. 169] 2.3.8 12Cr-1Mo-1W-0.3V steel RAB RAD RAG RAJ 60 50 40 Stress [kgf/mm 2 ] 165 500 °C 30 20 550 °C 10 600 °C 5 650 °C 10 2 10 10 3 Time to rupture [h] 10 4 Fig. 204. Creep rupture strength data for the 4 heats, RAB, RAD, RAG and RAJ, of 12Cr-1Mo-1W0.3V steel. 10 5 50 12Cr-Mo-W-V Stress [kgf/mm 2 ] 40 RAB RAD RAG RAJ 30 20 Rupture strength (550 °C, 100 hr) 10 as-received 10 2 10 3 10 4 Heating time at 600 °C [h] 10 5 Fig. 205. Creep rupture strength of 4 heats of 12Cr-1Mo1W-0.3V steel at 550 °C and 102 h, as a function of heating time at 600 °C prior to creep test at 550 °C. 2.3.8.5.2 Creep deformation behavior and microstructure evolution during creep of 12Cr-1Mo1W-0.3V steel, JIS SUH 616-B The creep deformation behavior and microstructural evolution during creep were investigated for the 12Cr1Mo-1W-0.3V steel, JIS SUH 616-B, at 600 °C, comparing with those for a simple 12Cr steel, SUS 403-B without Mo, W and V [5,6]. Main focus was placed on the effect of vanadium addition to 12Cr steel on the degradation during creep deformation. Fig. 207 shows the creep rate vs. time curve of the RAJ heat of 12Cr1Mo-1W-0.3V steel at 600 °C and 137 MPa, comparing with that of the 12Cr steel at 600 °C and 47 MPa. The creep specimens had a size of 8 mm in diameter and of 50 mm in gage length. The time to rupture was almost the same for both steels; 5124 and 6084 h for the 12Cr-1Mo-1W-0.3V and 12Cr steel, respectively. Both creep rate versus time curves consist of two stages: the transient and tertiary creep stages. No steady state creep stage was observed. The minimum creep rate of the 12Cr-1Mo-1W-0.3V steel is about half of that of the 12Cr steel, although the time to rupture of the former is slightly shorter than that of the latter. It should be also noted that the acceleration of creep rate, defined as d ε& /dt, in the tertiary creep stage, was larger in the 12Cr-1Mo-1W-0.3V steel by a factor of two than in the 12Cr steel. Landolt-Börnstein New Series VIII/2B 166 2.3 High Cr steels 0.03 0.015 12 Cr-Mo-W-V 12 Cr-Mo-W-V RAB RAD RAG RAJ 0.010 0.02 Al as AIN [%] N as nitride [%] RAB RAD RAG RAJ 0.01 0.005 0 as-received 10 2 0 as-received 10 2 10 4 10 3 Heating time at 600 °C [h] 10 3 Heating time at 600 °C [h] 10 4 Fig. 206. Increase in nitrogen and aluminum as aluminum nitride AlN during thermal aging at 600 °C, by alcohol iodine method. 10 -6 0 1000 Time [h] 2000 3000 4000 5000 6000 10 -3 12Cr 873K, 47MPa Prior creep testing specimens 3 10 - 7 3 10 -4 t r = 21.9 10 6s 3 10 - 8 3 3 -10 10 -6 a 10 10 - 6 12CrMoWV 873K, 137MPa Prior creep testing specimens 3 10 - 7 10 -3 3 10 -4 3 t r = 18.4 10 6s 10 - 8 3 10 - 9 10 3 Creep rate [h -1] Creep rate [s -1] 10 - 9 3 10 - 5 3 -10 3 10 - 5 3 10 -6 b 0 10 Time [10 6 s] 20 Fig. 207. Creep rate vs. time curves of the 12Cr and the 12Cr-1Mo-1W-0.3V steels at 600 °C - 47 MPa and 600 °C - 137 MPa, respectively. After interruption of the creep tests for the 12Cr-1Mo-1W-0.3V steel at 600 °C and 137 MPa and for the 12Cr steel at 600 °C and 47 MPa (Fig. 207) at several different times, the creep specimens were machined to a smaller size of 6 mm in gage diameter and of 30 mm in gage length to eliminate any mechanical damages developed near surface during the previous creep tests. Then the creep tests were re-started at higher stress conditions for the 12Cr-1Mo-1W-0.3V steel at 600 °C and 225 MPa and for the 12Cr steel at 600 °C and 84 MPa. The results are shown in Figure 208. The previous creep test (Fig. 207) is denoted as Landolt-Börnstein New Series VIII/2B Ref. p. 169] 2.3.8 12Cr-1Mo-1W-0.3V steel 167 the first stage creep test, while the later one (Fig. 208) as the enhanced stress creep test. The minimum creep rate in the enhanced stress creep test becomes larger with increasing creep-interrupted time in the first stage creep testing both the 12Cr-1Mo-1W-0.3V and 12Cr steels. In the enhanced stress creep test, the minimum creep rate of the creep-interrupted specimen at 4000 h (14.4 Ms) was only five times larger in the 12Cr steel than that of the as-tempered specimen without being subjected to the first stage creep test, while two orders of magnitude larger in the 12Cr-1Mo-1W-0.3V steel. 1 3 10 3 3 10 3 3 10 4 3 14.4 106s 3 10 Time [h] 3 10 2 12Cr 873K 84MPa 10.8 106s 7.2 106s -5 10 1.08 106s 6 3.6 10 s 3 6 1.8 10 s 3 Creep rate [s -1] 10 10 10 - 3 0.36 106s -7 3 -8 3 As tempered 10 -4 a 10 - 4 3 10 - 5 3 12CrMoWV 873K 225MPa 6 14.4 10 s 3 10 10 3 10 - 2 3 -6 10 -1 10.8 106s -6 3 10 - 2 3 3.6 106s 3 -7 1.08 106s 10 - 3 As tempered 3 10 -4 3 10 - 8 b 3×10 8 -3 10 10 -1 Creep rate [h -1] 10 -4 3 3 10 - 2 3 10 -1 3 1 Time [10 6 s ] 3 10 3 10 2 Fig. 208. Creep rate vs. time curves of the creepinterrupted 12Cr and 12Cr-1Mo-1W-0.3V steel specimens at 84 and 225 MPa, respectively, at 600 °C. The Vickers hardness and the half-value width of an X-ray diffraction peak at (211) were measured to evaluate the overall softening during the first stage creep test shown in Fig. 208. The results are shown in Fig. 209 as a function of t/tr. The overall softening is mainly caused by the coarsening of carbide precipitates and by the annihilation of pre-existing dislocations. The large decrease in hardness and halfvalue width occurs in the transient creep stage rather than in the tertiary creep stage. The hardness and half-value width at the time of rupture in the 12Cr-1Mo-1W-0.3V steel is still larger than those of the 12Cr steel on an as-tempered condition. The 12Cr-1Mo-1W-0.3V steel exhibited tempered martensitic microstructure in as-tempered condition. The TEM observations showed that the density of precipitated carbides and dislocations remained high within laths even after 4000 h (14.4 Ms) of the first stage creep test. At the minimum creep rate stage of the first stage creep test, a recovered zone with a low density of precipitated carbides and dislocations started to form along prior austenite grain boundaries. The average width of this recovered zone increased with increasing testing time. The local softening due to the development of the recovered zone is mainly responsible for the acceleration of creep rate. The loss of creep resistance proceeds due to local softening along prior austenite grain boundaries, accompanied by the decrease in density of V4C3 carbides and dislocations in the recovered zone. Landolt-Börnstein New Series VIII/2B 168 2.3 High Cr steels Hardness [HV :98N] 350 873 K 300 12CrMoWV, 137MPa 250 12Cr, 47MPa 200 150 Half - value width [° ] 2.2 12CrMoWV, 137MPa 2.0 1.8 1.6 12Cr, 47MPa 0 0.2 0.4 0.6 Normalized time t / t r Fig. 209. Vickers hardness and the half-value width of an X-ray diffraction peak at (211) as a function of normalized time t/tr during the first stage creep test. 0.8 1.0 2.3.8.5.3 Heat-to-heat variation in long term creep strength of 12Cr-1Mo-1W-0.3V steel, JIS SUH 616-B The heat-to-heat variation in long term creep strength was investigated for the 9 heats of 12Cr-1Mo-1W0.3V steel by analyzing the creep rupture data in [7]. The concentrations of the major alloying elements C, Si, Mn, Cr, Mo and V are not very different among the 9 heats [5]. Therefore, these parameters are excluded as main explanation of the observed heat-to-heat variation in time to rupture. Then our interest is concentrated on the effect of minor alloying elements. It has been well known for ferritic and austenitic heat resistant steels that nitrogen causes a beneficial effect on the long term creep rupture strength but that Al causes a deteriorative effect. Fig. 210(a) shows that a monotonous decrease in time to rupture with an increase in Al content is not observed, suggesting that the time to rupture of the 12Cr-1Mo-1W-0.3V steel is not directly related with the Al content and other factors should be taken into account. The time to rupture is again plotted in Figure 210(b) as a function of effective nitrogen concentration, N − Al − Ti in at %. The effective nitrogen concentration is defined as the nitrogen concentration available for the formation of fine vanadium nitrides. Because Al is a stronger nitride forming element than Cr and V, the effective nitrogen concentration is reduced by the formation of AlN. Titanium is also known as a strong nitride forming element. The time to rupture increases with increasing effective nitrogen concentration, which becomes more significant with decreasing stress and increasing time. The creep rate versus time curves in Fig. 211 show that the creep rate is not much different in the transient region among the different heats but that the onset of acceleration creep occurs at shorter times in the high-Al heat than in the low-Al heat. This results in higher minimum creep rate and shorter rupture time in the high-Al heat than in the low-Al heat. The microstructure evolution was investigated by several researchers. Yokoi and co-workers [4] investigated the formation of AlN during aging at 600 °C for some heats with different Al content. Their results show that AlN is already present after heat treatment and before creep test and that additional precipitation of AlN occurs during aging at 600 °C. On the other hand, Watanabe and co-workers reported that preferential recovery occurs in the vicinity of prior austenite grain boundaries during creep at 600 °C [6]. Landolt-Börnstein New Series VIII/2B 10 5 10 4 10 3 2.3.8 12Cr-1Mo-1W-0.3V steel o 550 C 176 235 294 333 MPa MPa MPa MPa Time to rupture ( h ) Tim e to rupture ( h ) Ref. p. 169] (a) 0 0.01 0.02 0.03 0.04 10 5 10 4 10 3 o 550 C 176 MPa 235 294 333 (b) 0 0.05 169 0.04 0.08 Fig. 210. Time to rupture of 12Cr1Mo-1W-0.3V steel at 550 °C, as a function of Al content in mass % and of effective nitrogen concentration, N(nitrogen)-Al-Ti in at %. The corresponding creep rupture data are shown in Fig. 199. 0.12 N - Al - Ti ( at % ) Al content ( m ass % ) o Creep rate ( 1 / h ) 650 C, 69 M P a 10 -3 10 -4 10 -5 10 R AG , 0.0 37% Al R AA, 0.030% Al R AJ, 0.005% Al -2 10 -1 10 0 10 1 10 2 10 3 10 4 Fig. 211. Creep rate vs. time curves of the 3 heats containing different aluminum content at 650 °C and 69 MPa. T ime ( h ) Based on above results, it is concluded that Al promotes the preferential recovery in the vicinity of prior austenite grain boundaries, which may be promoted by the formation of AlN, because this consumes available fine vanadium nitrides. The preferential recovery in the vicinity of prior austenite grain boundaries accelerates the onset of acceleration creep. This reduces the time to rupture. 2.3.8.6 References [1] [2] [3] [4] National Research Institute for Metals: NRIM Creep Data Sheet, No.10B, (1998). ASTM Data Series Publication DS50, (1973). The British Steelmakers Creep Committee (BSCC) High Temperature Data (1972). Yokoi, S., Shin-ya, N. and Kori, M.: Journal of the Society of Materials Science, Japan, 26 (1977), 241-247. [5] Matsuo, T., Kikuchi, M., Watanabe, T. and Monma, Y.: Proceedings of the Fifth International Conference on Creep of Materials, Lake Buena Vista, Florida, USA, 18-21 May (1992), 271-279. [6] Watanabe, T. and Monma, Y., Matsuo, T. and Kikuchi, M.: Report of the 123rd Committee on HeatResisting Metal and Alloys, Japan Society for the Promotion of Science, Vol.32 (1991) 137-148. [7] Abe, F.: Proceedings of NRIM-MPA Workshop on Creep and Fatigue Performance of High Cr Steels for Elevated Temperature Plants, Tsukuba, Japan (2001), 1-10. Landolt-Börnstein New Series VIII/2B 170 2.3 High Cr steels 2.3.9 12Cr-1Mo-V steel 2.3.9.1 Introduction 12Cr-1Mo-V steel (X20CrMoV12-1; X20CrMoV(W)12-1, X22CrMoV12-1) has been widely used for tubing, headers and piping in Europe. The steel was developed in the 1960s together with a modification for bars and forgings with an increased C-content (0.20 - 0.26 %) - X22CrMoV12-1 as well as a modification with an additive of W - X22CrMoWV12-1, X20CrMoWV12-1. The maximum long term service temperature for tubes and pipes is generally limited to 565 °C. Due to the high Cr- and Mo-content X20CrMoV12-1 steel shows a distinctive martensitic microstructure, which permits its use as thick pipe material. If the standard cooling down in air to room temperature is applied a residual austenite content of approximately 2 - 5 % could be stated, influenced by the specific chemical composition of the heat. A change in the standardized heat treatment conditions leads to modifications in the microstructure and thus to a decrease of the long term creep strength. X20CrMoV12-1 steel demonstrates high creep rupture ductility also in the long term service range. As a consequence the sensitivity to the formation of creep cavities is low compared with that of low alloyed steels. This should be considered if the damage state and life expenditure of the component is evaluated by means of the replica technique and the consequent appearance of cavities. The steel is sensitive to intergranular stress corrosion if hardening (austenizing and cooling down) is not followed by tempering. The steel may be welded if the relevant measures required for the material are observed. Specific care is required in welding: correct pre and post weld heat treatment should be done in order to avoid cracking. Pre heating up to 450 °C is necessary in dependence of thickness. After welding an intermediate cooling down below 130 °C should be performed in order to optimize the martensite formation in the deposit material (if similar to X20CrMoV12-1) and heat affected zone. Post heat treatment should be done at a temperature ranging from 750 °C to 770 °C. 2.3.9.2 Materials standards, chemical and tensile requirements 2.3.9.2.1 X20CrMoV12-1 seamless tubes for pressure purposes Table 114. Heat treatment of X20CrMoV12-1 seamless tubes for pressure purposes; DIN 17175:1979 DIN 17175 Austenizing temperature / cooling medium 1020 - 1070 °C / Air Tempering temperature / cooling medium 730 - 780 °C/ Air Table 115. Chemical requirements of X20CrMoV12-1; DIN 17175:1979 Chemical composition [wt%] Standard Designation/ steel number C Si Mn P S Cr Mo DIN X20CrMoV12-1 0.17 ≤0.50 ≤1.00 ≤0.030 ≤0.030 10.00 0.80 17175 1.4922 0.23 12.50 1.20 Ni 0.30 0.80 V 0.25 0.35 Table 116. Mechanical properties of X20CrMoV12-1 at room temperature; DIN 17175:1979 Tensile requirements Standard Designation/ steel number Thickness Yield Tensile Elongation Impact energy stress strength after fracture Charpy-V-testpiece L T L T [mm] [MPa] [MPa] [%] [%] [J] [J] DIN X20CrMoV12-1 490 Not listed ≥17 ≥14 ≥16, ≤60 ≥34 17175 1.4922 T transverse direction, L longitudinal direction Landolt-Börnstein New Series VIII/2B Ref. p. 179] 2.3.9 12Cr-1Mo-V steel 171 2.3.9.2.2 X20CrMoNiV11-1-1 seamless tubes for pressure purposes Table 117. Heat treatment of X20CrMoNiV11-1-1-1; ISO 9329-2:1997 ISO 9329 Austenizing temperature / cooling medium 1020 - 1080 °C / Air Tempering temperature / cooling medium 730 - 780 °C/ Air Table 118. Chemical requirements of X20CrMoNiV11-1-1; ISO 9329-2:1997 Chemical composition [wt%] Standard Designation/ steel number C Si Mn P S Cr Mo Ni V ISO 9329 X20CrMoNiV11-1-1 0.17 0.15 ≤1.00 ≤0.030 ≤0.030 10.00 0.80 0.30 0.25 0.23 0.50 12.50 1.20 0.80 0.35 Table 119. Mechanical properties of X20CrMoNiV11-1-1 at room temperature; ISO 9329-2:1997 Tensile requirements Standard Designation/steel number Thickness Yield Tensile Elongation Impact energy stress strength after fracture Charpy-Vtestpiece L T T L [mm] [MPa] [MPa] [%] [%] [J] [J] ISO 9329 X20CrMoNiV11-1-1 490 Not listed ≥17 ≥14 ≥16, ≤60 ≥27 ≥35 T transverse direction, L longitudinal direction 2.3.9.2.3 X21CrMoV12-1 for large forgings for components in turbine and generator equipment; SEW 555 Table 120. Heat treatment of X21CrMoV12-1; SEW 555:2001 Austenizing temperature / cooling medium The heat treatment used to achieve the SEW specified properties is left up to the 555 manufacturer, if this is not agreed in the order. Tempering temperature / cooling medium The customer shall be advised. Table 121. Chemical requirements of X21CrMoV12-1; SEW 555:2001 Chemical composition [wt%] Standard Designation/ steel number C Si Mn P S Cr Mo 0.30 11.00 0.80 SEW X21CrMoV12-1 0.20 ≤0.020 ≤0.007 ≤0.20 0.80 12.50 1.20 555 1.4926 0.26 Ni 0.30 0.80 Table 122. Tensile requirements of X21CrMoV12-1; SEW 555:2001 Tensile requirements Standard Designation Range of 0.2 % Tensile Elongation Reduction significant proof strength after of area dimensions strength fracture after fracture T Q T Q [mm] [MPa] [MPa] [%] [%] [%] [%] SEW X21CrMoV12-1 1500 600 750 ≥14 ≥11 ≥40 ≥40 555 1.4926 900 T and Q correspond to the relevant direction to the fibre flow Landolt-Börnstein New Series VIII/2B V 0.25 0.35 Impact energy Charpy-Vtestpiece T Q [J] [J] ≥20 ≥12 172 2.3 High Cr steels 2.3.9.2.4 X20CrMoV11-1 for forgings and rolled or forged bars for pressure purposes; ISO 93272:1997; EN 10222-2:2000 Table 123. Heat treatment of X20CrMoV11-1; ISO 9327-2:1997; EN 10222-2:1999 ISO 9327 Austenizing temperature / cooling medium 1020 - 1070 °C / cooling air, oil, water Tempering temperature 730 - 780 °C Table 124. Chemical requirements of X20CrMoV11-1; ISO 9327-2:1997; EN 10222-2:1999 Chemical composition [wt%] Standard Designation/ steel number C Si Mn P S Cr Mo Ni ISO 0.17 0.30 ≤0.40 0.30 ≤0.035 ≤0.030 10.00 0.80 X20CrMoV11-1 0.23 9327 1.00 12.50 1.20 1.00 1.4922 0.17 0.30 EN ≤0.40 0.30 ≤0.025 ≤0.015 10.00 0.80 0.23 1.00 12.50 1.20 0.80 10222 V 0.20 0.35 0.20 0.35 Table 125. Tensile requirements of X20CrMoV11-1; ISO 9327-2:1997; EN 10222-2:2000 Tensile requirements Standard Designation Range of 0.2 % Tensile Elongation Impact energy significant proof strength after fracture Charpy-V-testpiece dimensions strength x y x-y y-x [mm] [MPa] [MPa] [%] [%] [J] [J] ISO ≤100 ≥39 ≥27 X20CrMoV11-1 >100, ≤200 9327 500 700 - 850 ≥16 ≥16 ≥31 ≥27 1.4922 ≥14 ≥27 ≥24 >250, ≤300 EN ≤10 ≥39 500 700 -850 ≥16 ≥14 10222 ≥27 >100, ≤250 ≥31 >250, ≤330 ≥27 x, y acc. ISO 1546; x, x-y longitudinal; y, y-x transverse Fig. 212. Microstructure of X20CrMoV12-1 (as received state). Landolt-Börnstein New Series VIII/2B Ref. p. 179] 2.3.9 12Cr-1Mo-V steel 173 2.3.9.3 Mechanical properties of X20CrMoV12-1 2.3.9.3.1 X20CrMoV12-1, X22CrMoV12-1, X20CrMoWV12-1, X22CrMoWV12-1 for seamless tubes and bars 1400 Group 1, without W Group 1, with W Group 2, without W Group 2, with W Group 3, without W Group 3, with W 1200 Stress σ (MPa) 1000 800 600 400 200 Fig. 213. High temperature tensile strength of X20CrMo(W)V12-1. 0 0 100 200 300 400 500 600 700 800 900 100 Test temperature T (°C) The data of Fig. 212 is published in [1] from which data on proof stress, elongation and reduction of area can also be obtained. The plot includes data with different heat treatment, consequently the data has to be divided into the following groups with different tensile strength at room temperature: Group 1 2 3 Yield strength [MPa] ≥490 ≥589 ≥785 Tensile strength [MPa] 638 - 883 785 - 932 ≥932 It has to be considered that the heat treatment applied to group 2 and 3 heats however does not correspond to the specified conditions in the codes and standards cited above. 2.3.9.4 Creep properties of X20CrMoV12-1 2.3.9.4.1 Creep strength of X20CrMoV12-1, X20CrMoWV12-1 bars and tubes The creep rupture strength of X20CrMoV12-1, X20CrMoWV12-1 bars and tubes obtained from published literature is shown in the following. The results of 13 heats of X20CrMo(W)V12-1 are shown in Fig. 214. The data of this figure is published in [1] from which data on stress, elongation and reduction of area of the individual creep tests can also be obtained. In the figure only test results of heats with a heat treatment which corresponds to the specified conditions in the codes and standards cited above are plotted. A significant loss in creep strength at 600 °C especially in the long term range could be observed. This gives the reason for the limitation of maximum service temperature of this type of steel. Landolt-Börnstein New Series VIII/2B 174 2.3 High Cr steels Stress σ(MPa) 1000 500 °C with W 550 °C with W 550 °C without W 600 °C with W 100 1 10 Fig. 214. Creep rupture strength of X20CrMo(W) V12-1; [1]. 100 1000 10000 100000 Time to rupture t (h) 1000 Stress σ (MPa) broken unbroken 500°C DIN 17175 Fig. 215. Creep rupture strength data of steel grade X20CrMoV12-1 at 500 °C (10 heats, bars and tubes) obtained by the German Creep Committee [2], and average creep rupture strength values indicated in DIN17175. 100 10 100 1000 10000 100000 1000000 Test duration t (h) Stress σ (MPa) 1000 100 broken unbroken 550°C DIN 17175 10 10 100 1000 10000 100000 1000000 Fig. 216. Creep rupture strength data of steel grade X20CrMoV12-1 at 550 °C (27 heats, bars and tubes) obtained by the German Creep Committee [2], and average creep rupture strength values indicated in DIN17175. Test duration t (h) Landolt-Börnstein New Series VIII/2B Ref. p. 179] 2.3.9 12Cr-1Mo-V steel 175 1000 Stress σ (MPa) broken unbroken 600°C DIN 17175 100 Fig. 217. Creep rupture strength data of steel grade X20CrMoV12-1 at 600 °C (23 heats, bars and tubes) obtained by the German Creep Committee [2], and average creep rupture strength values indicated in DIN17175. 10 10 100 1000 10000 100000 1000000 Test duration t (h) 1000 Stress σ (MPa) broken unbroken 100 Fig. 218. Creep rupture strength data of steel grade X20CrMoV12-1 at 600 °C (5 heats, bars and tubes) obtained by the German Creep Committee; [2]. 10 10 100 1000 10000 100000 1000000 Test duration t (h) 2.3.9.4.2 Fact creep data of X20CrMoV12-1 tubes, bars and forgings The information of fact creep data for X20CrMoV12-1 tubes, bars and forgings can be obtained from [1]. More actual data of heats in accordance to DIN 17175 is available in [2]. 2.3.9.4.3 Microstructural change The typical microstructure X20CrMoV12-1 is a needle shaped martensitic structure. The martensite needles are decorated with precipitations. Using the lightmicroscope no significant change in the microstructure due to service exposure is visible. The typical martensitic needle shaped microstructure is very stable. Laves phase could only be stated after long term service exposure or at non-acceptable high temperatures. In the long term range the precipitates at the needle boundaries will grow. An incipient dissolution of the needle shaped microstructure could be observed, Fig. 219. However this is not an indication of exhaustion or damage of the material. Landolt-Börnstein New Series VIII/2B 176 2.3 High Cr steels Fig. 219. As received state (a) crept state (b) (550 °C/118 MPa/51447 h), X20CrMoV12-1. Incipient dissolution of the needle shaped microstructure due to the growth of carbides. The formation of creep cavities could be observed at the prior austenite grain boundaries. Also nonmetallic inclusions as MnS are preferred locations for the nucleation of creep cavities. Contents of S and P considerably below the allowed upper limit given in the standard are advantageous. Due to the coalescence with non-metallic inclusions a careful metallographic preparation is necessary in order to identify creep cavities. Especially if the replica technique is used to detect creep damage at components preferably mechanical polishing should be used. If electropolishing and etching is used there is a risk that inclusions will be removed from the matrix and the subsequent hole will be identified as creep cavity. Detailed information about the creep damage development in X20CrMoV12-1 could be obtained in [3]. 2.3.9.4.4 Effect of W, Mo and V on creep rupture strength Investigations, done by [1] realized that W does not cause an improvement of the creep strength, see Fig. 220. Optimized creep strength will be obtained if 0.5 - 1 % Mo is balanced by 0.15 - 0.35 % V. Also the content of C should not fall below the lower bound given in the standard, Fig. 221 [4]. 2.3.9.4.5 Effect of heat treatment on long term creep rupture strength Investigations and failures at components [5] revealed that especially low quenching temperatures will cause a decrease of the creep strength. The mechanical properties like tensile strength are no guarantee for optimized creep rupture strength. Any deviation from the typical needle shaped martensitic microstructure will cause a drop in the creep strength. A ferritic matrix with carbides is not acceptable. The presence of Laves phase in the as received state is an indication of wrong heat treatment. Landolt-Börnstein New Series VIII/2B Ref. p. 179] 2.3.9 12Cr-1Mo-V steel 177 1000 Stress σ (MPa) 550 °C with W 550 °C without W 100 10 100 1000 10000 100000 Fig. 220. Effect of W on creep rupture strength of X20CrMoV12-1 with heat treatment according to the requirements of the cited standards. The content of W ranges from 0.013 to 0.59 %. No increase of creep strength could be observed; [1]. Creep strength test heat / average creep strength V Time to rupture t (h) 1.4 1.2 M+20% 1.0 M 0.8 M-20% 500 °C 550 °C 575 °C 580 °C 600 °C 0.6 Fig. 221. Optimal creep strength will be obtained at C contents higher than 0.17%. M: average value. Forgings, bars Pipes, plates 0.11 0.13 0.15 0.17 0.19 0.21 0.23 0.25 0.27 C content [%] 550 °C Stress [N /mm 2 ] 10 2 10 2 Fig. 222. Austenitizing temperatures below the recommended ones in the relevant codes will lead to a decrease in the creep rupture strength of X20CrMoV12-1; [6]. 600 °C mean value lower scatter bound 10 650 °C 10 10 2 Landolt-Börnstein New Series VIII/2B 10 3 Rupture time [h] 10 4 10 5 L = air Rp/Rp0.2 [N/mm2] Rm [N/mm2] ■ 1/2 h, 920 °C/L; 2 h, 780 °C/L * 1/2 h, 925 °C/L; 2 h, 780 °C/L 459 558 724 755 ○ 1/2 h, 975 °C/L; 2 h, 750 °C/L 605 805 ● 1/2 h, 1000 °C/L; 2 h, 750 °C/L 603 810 ◆ 1/2 h, 1050 °C/L; 2 h, 750 °C/L 606 814 178 2.3 High Cr steels 2.3.9.4.6 Creep crack growth Creep crack growth may occur at defects in components operated in the high temperature regime. The assessment of crack growth at defects is based on fracture mechanics and the relevant data. The crack growth rate was measured using fracture mechanic specimens (CT, Cs -side grooved CT, D) with different ratios of crack start length a0 to specimen width W. The stress situation at crack tip was calculated using the creep fracture mechanics parameter C*. 10 -1 X22 CrMoV 121, AMB, J = 550 °C 10 -2 10 -3 a = 0.14×(C *) [mm/h] sn0 [MPa] CT20 383 CT20 250 CT20 200 CT100 250 CT40 250 CT40 233 D9 304 D9 255 D9 210 10 -4 10 10 -5 10 -6 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 C * [N/mmh] 10 2 10 1 Fig. 223. Crack growth rate in dependence of the parameter C* (based on load line displacement rate) for different specimen types and sizes of X22CrMoV12-1 (forgings). CT20, CT100, CT40 – CT specimens with thickness 20, 100 and 40 mm, D9 – double edge notched specimens, thickness 9 mm, σn0 nominal stress at begin of the test; [7, 8, 9]. 10 -1 10 -8 X22 CrMoV 12 1, 220sa/AMB, J = 550 °C 10 -2 sn0 = 312 MPa (K l0 = 830 N/mm 3/2 ) 246 (654) a [mm/h] a [mm/h] 10 0.86 10 -9 10 -3 10 10 -10 209 (556) -4 200 (345) 10 -5 145 160 (381) (276) 240 (422) a0 / W Cs20 D9 0.55 0.4 10 -11 10 -12 10 -6 10 -5 10 -4 10 -3 10 -2 C * [N/mmh] 10 -1 Fig. 224. Crack growth rate in dependence of the parameter C* (based on load line displacement rate) for different specimen types of X20CrMoV12-1 (seamless tube). Cs20 – side grooved CT specimens (thickness 20 mm), D9 – double edge notched specimens (thickness 9 mm); [7, 8, 9]. 1 Landolt-Börnstein New Series VIII/2B Ref. p. 179] 2.3.9 12Cr-1Mo-V steel 179 2.3.9.4.7 Estimated long term creep rupture strength Table 126. Average values of creep rupture strength of X20CrMoV12-1, X20CrMoNiV11-1-1 for seamless tubes, X20CrMoV12-1 for forgings and rolled or forged bars according to the relevant standards DIN 17175, ISO 9327 and ISO 9329. Long term data is partly based on extended time and stress extrapolations. Temperature °C 500 510 520 530 540 550 560 570 580 590 600 Temperature °C 500 510 520 530 540 550 560 570 580 590 600 Time to rupture (h) 105 2•105 104 105 2•105 2.5•105 Average creep rupture strength (MPa) DIN 17175 ISO 9329 294 235 215 290 237 221 215 274 211 191 264 212 196 190 253 186 167 240 189 172 167 232 167 147 217 167 151 145 213 147 128 196 146 130 125 192 128 111 176 127 112 107 173 112 96 157 109 95 90 154 96 81 139 93 80 76 136 82 68 123 80 68 65 119 70 58 107 68 58 56 101 59 48 93 59 50 48 104 Time to rupture (h) 105 2•105 104 105 2•105 2.5•105 Average creep rupture strength (MPa) EN 10222 ISO 9327 292 236 218 294 248 234 229 269 212 194 274 225 213 208 247 188 170 253 202 190 185 225 167 149 232 180 167 161 205 147 129 213 159 143 137 184 128 112 192 139 122 117 165 111 96 173 121 104 100 147 95 81 154 104 89 84 130 81 68 136 88 76 72 113 69 58 119 75 64 60 97 59 49 101 63 53 50 104 2.3.9.5 References [1] Ergebnisse deutscher Zeitstandversuche langer Dauer. Verlag Stahleisen mbH (1969). [2] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade G17CrMoV5-10, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c.o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D) (2001). [3] Guideline for the assessment of microstructure and damage development of creep exposed materials for pipe and boiler components. VGB-TW 507, VGB Technische Vereinigung der Großkraftwerksbetreiber e. V., Essen. [4] Jesper, H., and Kautz, H. R.: Eigenschaften, Verarbeitung und Bewährung des Stahles X20CrMo(W)V 12 1 im Kraftwerk. VGB Konferenz, Werkstoffe und Schweißtechnik im Kraftwerk (1985), VGB Technische Vereinigung der Großkraftwerksbetreiber e. V., Essen. Landolt-Börnstein New Series VIII/2B 180 2.3 High Cr steels [5] Wachter, O., Müsch, H., and Bendick, W.: Zeitstandschädigung an Komponenten in Frischdampfleitungen aus dem Werkstoff X 20 CrMoV 12 1. VGB Konferenz „Werkstoffe und Schweißtechnik im Kraftwerk (1991), VGB Technische Vereinigung der Grosskraftwerksbetreiber e. V., Essen. [6] Fabritius, H., and Weber, H.: Zur Betriebssicherheit von Anlagen nach langer Betriebsbeanspruchung im Zeitstandbereich. Sonderheft VGB-Konferenz „Werkstoffe und Schweißtechnik im Kraftwerk (1976), S. 179-217. VGB Technische Vereinigung der Grosskraftwerksbetreiber e. V., Essen. [7] Granacher, J., Tscheuschner, R., Mao, T. S., Maile, K., and Bareiss, J.: Anwendung numerischer Verfahren zur Auswertung von Kriechrissversuchen am Stahl X 22CrMoV 12. Schädigungsmechanismen und Bruch, Berichtsband der 28. Tagung in Bremen. Deutscher Verband für Materialforschung und –prüfung, Berlin. [8] Granacher, J., Tscheuschner, R., Maile, K., and Eckert, W.: Rissverhalten warmfester Stähle im Kriech- und Kriechermüdungsbereich. Abschlussbericht zum AiF-Vorhaben Nr.7251 (1992), MPA Stuttgart und IfW Darmstadt. [9] Granacher, J., Kostenko, Y., Maile, K., and Schellenberg, G.: Kriechrissverhalten ausgewählter Kraftwerksstähle in erweitertem, praxisnahem Parameterbereich. Abschlussbericht zum Vorhaben Nr.186 (1998), Forschungskuratorium Maschinenbau e.V.; Frankfurt. Landolt-Börnstein New Series VIII/2B Ref. p. 188] 2.3.10 12Cr-1Mo-1W-V-Nb steel 181 2.3.10 12Cr-1Mo-1W-V-Nb steel 2.3.10.1 Introduction 12Cr-1Mo-1W-V-Nb ferritic steel (HCM12) is used as water wall, superheater and reheater tubes in fossile fired boilers and black liquor recovery boilers. The steel has been developed for improving creep rupture strength of 410 type ferritic steel at elevated temperatures mainly by substituting a part of Mo by W. The microstructure of the steel consists of 15 - 30 % delta-ferrite and tempered martensitic matrix strengthened by M23C6 carbide mainly along grain boundaries and fine dispersed (V,Nb)(C,N) carbonitride in matrix. (V,Nb)(C,N) is fine and stable even after long term creep exposure at high temperatures. 2.3.10.2 Material standards, chemical and tensile requirements Tables 127 and 128 give the chemical requirements and the corresponding tensile requirements of 12Cr1Mo-1W-V-Nb steel tubes and pipes which are designated by the standards: Japanese METI KASUS410J2TB, VD-TÜV 510 HCM12. Table 127. Chemical requirements of 12Cr-1Mo-1W-V-Nb steel tubes; Japanese METI KASUS410J2TB, VD-TÜV 510 HCM12. Designation Grade Japanese METI VD-TÜV 510 KA-SUS 410J2TB HCM12 C 0.14 0.14 Si 0.50 0.50 Mn 0.30 0.70 0.30 0.70 Chemical composition [wt%] P S Cr Mo 11.00 0.80 0.030 0.030 13.00 1.20 11.00 0.80 0.030 0.030 13.00 1.20 W 0.80 1.20 0.80 1.20 V 0.20 0.30 0.20 0.30 Nb 0.20 0.20 Table 128. Tensile requirements of 12Cr-1Mo-1W-V-Nb steel tubes; Japanese METI KA-SUS410J2TB, VD-TÜV 510 HCM12. Designation Grade Min. TS1) Min. YS2) Min. elongation Japanese METI KA-SUS 410J2TB 590 MPa 390 MPa 20 % VD-TÜV 510 HCM12 588 MPa 392 MPa 20 % 1) TS; tensile strength, 2) YS; yield strength as 0.2% proof stress 2.3.10.3 Tensile properties of 12Cr-1Mo-1W-V-Nb steel tubes Fig. 225 shows tensile strength and yield stress data of 12Cr-1Mo-1W-V-Nb steel tubes [1]. They are higher than those of T9 steel at all temperatures up to 650 °C. The corresponding tensile elongation and reduction of area data of 12Cr-1Mo-1W-V-Nb steel tubes are available in [1]. 2.3.10.4 Creep rupture properties of 12Cr-1Mo-1W-V-Nb steel tubes 2.3.10.4.1 Creep rupture data of 12Cr-1Mo-1W-V-Nb steel tubes Fig. 226 shows creep rupture data of 12Cr-1Mo-1W-V-Nb steel tubes with average curves according to the Larson-Miller parameter method shown in Fig. 227 [1]. The longest creep rupture time of 12Cr-1Mo1W-V-Nb steel tubes is about 60000 h at 650 °C. Their long term creep strengths are very stable in the temperature range between 500 and 700 °C. Fig. 228 shows a Larson-Miller parameter plot of the creep rupture data of 12Cr-1Mo-1W-V-Nb steel tubes with a master rupture curve and a 95 % confidence lower limit. The best fitting was achieved with an optimized constant of 30.21. Landolt-Börnstein New Series VIII/2B 182 2.3 High Cr steels 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 0 100 200 300 400 500 Temperature [°C] 600 700 Fig. 225. Tensile strength (circles) and 0.2% proof stress (triangles) data of 12Cr-1Mo-1W-V-Nb steel tubes. 500 400 Stress [MPa] 300 500 °C 200 550 °C 600 °C 100 500 °C 550 °C 600 °C 650 °C 700 °C average curve 80 60 40 1 650 °C Fig. 226. Creep rupture data of 12Cr-1Mo-1W-V-Nb steel tubes. 700 °C 10 2 10 3 Rupture time [ h] 10 10 4 10 5 500 500 °C ×10 5h 400 Stress [MPa] 300 550 °C ×10 5h 600 °C ×10 5h 200 650 °C ×10 5h 100 80 60 40 24 500 °C 550 °C 600 °C 650 °C 700 °C 25 average curve minimum curve 26 27 28 29 Fig. 227. Larson-Miller parameter plot of the creep rupture data of 12Cr-1Mo-1W-V-Nb steel tubes. 30 31 32 33 34 Landolt-Börnstein New Series VIII/2B Ref. p. 188] 2.3.10 12Cr-1Mo-1W-V-Nb steel 183 2.3.10.4.2 Creep data of 12Cr-1Mo-1W-V-Nb steel tubes Fig. 228 shows minimum creep rate of 12Cr-1Mo-1W-V-Nb steel tubes measured at various stress levels between 500 °C and 700 °C with fitted curves according to the Larson-Miller parameter method. Fig. 229 shows a Larson-Miller parameter plot of the minimum creep rate of 12Cr-1Mo-1W-V-Nb steel tubes with a master minimum creep rate curve. The best fitting was achieved with an optimized constant of 48.32. 500 400 Stress [MPa] 300 200 500 °C 500 °C 550 °C 600 °C 650 °C 700 °C average curve 550 °C 600 °C 100 80 60 650 °C 700 °C 40 10 -2 10 -1 500 10 2 10 3 500 °C 0.01%/10 3h 400 550 °C 0.01%/10 3h 300 Stress [MPa] 1 10 Minimum creep rate [% / 10 3 h] Fig. 228. Minimum creep rate data of 12Cr-1Mo-1W-V-Nb steel tubes 600 °C 0.01%/10 3h 200 650 °C 0.01%/10 3h 100 80 60 500 °C 550 °C 600 °C 650 °C 700 °C average curve 40 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 Larson-Miller-parameter T (48.32 + log e ) [×10 -3 ] Fig. 229. Larson-Miller papameter plot of the minimum creep rate data of 12Cr-1Mo-1W-V-Nb steel tubes. 2.3.10.5 Allowable stress of 12Cr-1Mo-1W-V-Nb steel tubes and pipe Fig. 230 shows the allowable tensile stress determined for 12Cr-1Mo-1W-V-Nb steel tubes (Japanese METI KA-SUS410J2TB) according to the METI standard procedure comparing with that for conventional 9%Cr steel, ASME SA213-T9 (JIS STBA26). Landolt-Börnstein New Series VIII/2B 184 2.3 High Cr steels 180 Allowable tensile stress (MPa) 160 KA-SUS410J2TB 140 120 100 STBA26 80 60 40 Fig. 230. Allowable tensile stress determined for 12Cr1Mo-1W-V-Nb steel tubes (Japanese METI KASUS410J2TB). 20 0 0 100 200 300 400 500 600 700 800 Temperature (℃) 2.3.10.6 Alloying philosophy of 12Cr-1Mo-1W-V-Nb steel tubes Fig. 231 shows the alloying philosophy of 12Cr-1Mo-1W-V-Nb steel tubes. The steel has been developed for superheater and reheater tubes used in plants operated at high temperatures between 540 °C and 625 °C. 12%Cr matrix is chosen for corrosion resistance to steam oxidation and hot corrosion at high temperatures. High temperature creep strength is achieved by using Mo and W in solid solution and fine precipitation of VC (or (V,Nb)(C,N)) carbide. To optimize the weldability and formability, the C content is reduced, which causes formation of delta-ferrite to some extent. Fig. 232 shows change in Charpy impact values with respect to the amount of delta-ferrite in 12Cr model steels. It can be seen that the toughness of the steels can be maintained reasonably high when keeping the amount of delta-ferrite below 35 %. Fig. 233 shows the change in the amount of delta-ferrite with respect to Creq calculated for the model steels. It is concluded that the Creq of the steel should be kept below 12.5 to suppress too much delta-ferrite and the resultant poor toughness. Service steam temperature; up to 625℃ High temperature strength V, Nb Mo, W Weldability Toughness 0.2V-0.05/0.1Nb Corrosion resistance 12%Cr Steel Weldability Formability Martensitic steel 0.2C 0.1C Dual phase steel δ phase < 35% 0.10C-12Cr-1Mo-0.25V-0.05/0.1Nb Ac1 = 886℃ 1050℃Norma. + 800/830℃ Temper Long-term creep strength Fig. 231. Alloying philosophy of 12Cr-1Mo-1W-V-Nb steel tubes. Landolt-Börnstein New Series VIII/2B Ref. p. 188] 2.3.10 12Cr-1Mo-1W-V-Nb steel 200 160 140 60 120 δ - ferrite (%) Impact value at 20℃ (J/cm2 ) Creq = Cr+6Si+4Mo+1.5W+11V+5Nb+12sol.Al+8Ti - (40C+30N+2Co+Cu+4Ni+2Mn) 80 δ = 35% 180 185 100 80 60 40 20 0 40 δ = 35% 20 0 20 40 60 80 δ - ferrite (%) 100 Fig. 232. Change in Charpy impact values with respect to the amount of δ -ferrite in 12Cr model steels. 0 5 10 15 Creq (mass%) 20 25 Fig. 233. Change in the amount of delta-ferrite with respect to Creq calculated for the model steels. Fig. 234 shows effects of Nb and V contents on the estimated 10000 h creep rupture strength of 12Cr1Mo-1W-V-Nb model steels at 600 °C. Highest creep strength is obtained by the combination of V from 0.2 % to 0.3 % and Nb from 0 % to 0.1 %. Fig. 235 shows effects of Mo and W contents on creep rupture strength of 12Cr-Mo-W-V-Nb model steels at 600 °C. The creep rupture strength increases with increasing Moeq (=Mo+1/2W). It is found that the toughness decreases more than 1.5 % with increasing Moeq which is due to increase in the amount of delta-ferrite. It is therefore concluded that the combination of 1 % Mo and 1 % W is the best for creep strength with enough toughness. 0.5 600 °C ×104 h creep rupture strength [MPa] Maximum 0.4 V content [mass %] 126 0.3 142 132 152 140 151 0.2 133 147 139 120 101 127 137 123 127 123 0.1 0 0 0.1 0.2 Nb content [mass %] 0.3 0.4 Fig. 234. Effects of Nb and V contents on the estimated 10000 h creep rupture strength of 12Cr-1Mo-1W-V-Nb model steels at 600 °C. 2.3.10.7 Microstructure of 12Cr-1Mo-1W-V-Nb steel tubes Fig. 236 shows the microstructure of 12Cr-1Mo-1W-V-Nb steel tubes normalized at 1050 °C and tempered at 815 °C. The microstructure of the steel consists of about 20 % delta-ferrite and tempered martensite. Landolt-Börnstein New Series VIII/2B 186 2.3 High Cr steels 10 5 Mo + 1/2 W = 1.5 5 Creep rupture time [h] (A) 10 4 (B) 5 Increase of δ-ferrite lower toughness 10 3 A 5 10 2 0 1 2 3 Mo + 1/2 W [ mass %] B - Element W Mo Mo + W 4 5 Fig. 235. Effects of Mo and W contents on creep rupture strength of 12Cr-Mo-W-V-Nb model steels at 600 °C. Steel A: 0.1C-12CrMoWVNb, 600 °C × 147 MPa Steel B: 0.2C-12CrMoWV, 600 °C × 152 MPa Fig. 236. Optical micrographs of 12Cr-1Mo-1W-V-Nb steel tubes normalized and tempered showing the duplex micro-structure consisting of delta-ferrite and tempered martensite. Fig. 237 shows a typical CCT (Continuous Cooling Transformation) diagram determined for 12Cr-1Mo1W-V-Nb steel after heating at 1050 °C. Martensitic microstructure with delta ferrite is easily obtained even with a fairly slow cooling. It is also noted that the Ac1 temperature is very high, which is advantageous for establishing a long-term microstructural stability by tempering at higher temperatures. Fig. 238 shows the effect of tempering temperature on long term creep strength of 12Cr-1Mo-1W-VNb steel tubes. With increasing testing temperature and decreasing stress level the creep rupture lives of the specimens tempered at 800 °C becomes much longer than those of the ones tempered at 750 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 188] 2.3.10 12Cr-1Mo-1W-V-Nb steel 1000 187 Ac3 931 °C 900 Ac1 886 °C Temperature T [°C] 800 F+C 700 600 500 400 Ms 300 Vickers hardness 200 349 352 100 10 344 329 279 293 275 199 180 10 3 10 4 10 2 Cooling time from Ac 3 temperature [s] 10 5 Fig. 237. A typical CCT diagram determined for 12Cr-1Mo-1W-VNb steel after heating at 1050 °C. 400 300 600 °C Stress [MPa] 200 650 °C 100 80 60 600 °C 650 °C Temperature ×1h AC 750 °C 800 °C 40 10 10 2 10 3 Time to rupture [ h] 10 4 10 5 Fig. 238. Effect of tempering temperature on long term creep strength of 12Cr-1Mo-1W-V-Nb steel tubes. 2.3.10.8 Performance of service exposed tubes Fig. 239 shows changes in tensile properties and toughness of 12Cr-1Mo-1W-V-Nb steel tubes after service exposure for up to 16 years in the Wakayama Kyodo Power Station No.3 boiler which has been operated with outlet steam temperatures of 543 °C for reheater (RH) and 571 °C for superheater (SH) tubes. The tensile properties after the service exposure have not changed much. Toughness reduced to some extent after 1 year exposure but saturated to high level even after 16 years exposure. More detailed performance of the service exposed tubes is available in [3]. Landolt-Börnstein New Series VIII/2B 2.3 High Cr steels 800 80 600 60 400 40 200 20 0 Elongation [%] Tensile strength, Yield stress [MPa] 188 0 SH RH Impact value at 0 °C [J/cm 2 ] 100 80 60 40 20 0 0 5 10 Service time [a] 15 Fig. 239. Change in tensile properties and toughness of 12Cr-1Mo-1W-V-Nb steel tubes after service exposure at the Wakayama Kyodo Power Station No.3 boiler. Open circles: SH; Full circles: RH. 2.3.10.9 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Iseda, A., Sawaragi, Y., Teranishi, H., Kubota, M., and Hayase, Y.: The Sumitomo Search No.40 (1989), 41. [3] Iseda, A., Sawaragi, Y., Ogawa, K., Kubota, M., and Hayase, Y.: The Sumitomo Search No.48 (1992), 21. [4] Nishimura, N., and Masuyama, F.: Materials for Advanced Power Engineering, Part 1, Kluwer Academic Publishers (1994), 351. Landolt-Börnstein New Series VIII/2B Ref. p. 191] 2.3.11 12Cr-1Mo-Ni-V cast 189 2.3.11 12Cr-1Mo-Ni-V cast 2.3.11.1 Introduction The 12Cr-1Mo-Ni-V cast steel grade GX23CrMoV12-1 (EN 10213-2, material-no 1.4931) was introduced in the 1960s. Among the steel grades specified in EN 10213-2:1995, GX23CrMoV12-1 shows the maximum creep rupture strength values and the highest oxidation resistance. The excellent creep rupture strength is mainly related to a stable microstructure composed of tempered martensite and small vanadium carbides. If the wall thickness is less than about 100 mm quenching in air is sufficient to produce a martensite microstructure. Lower cooling rates from austenite temperature promote the transformation to ferrite and carbides rather than martensite. Large amounts of ferrite, however, are detrimental to the creep rupture properties, and may reduce the creep rupture strength values by about 30 % at temperatures above 530 °C. For this reason sections thicker than about 100 mm have to be quenched in oil. The high oxidation resistance at temperatures up to 600 °C is ensured by the high chromium content of 11.3 to 12.2 %. The main features of GX23CrMoV12-1 are summarized below: Melting process: Electric arc, argon oxygen decarburization, induction melting. Heat treatment: Quenched in air or oil, and tempered (cooling in furnace). Typical microstructure: Tempered martensite. Weldability: Weldable with similar weld metal; the welding should be performed in the austenite or austenite/martensite temperature range; after welding cooling below 100 °C is necessary before stress relief annealing. High temperature applications: Casings of steam turbines, compressors, gas turbines, valves, nozzles; service temperatures up to about 600°C. 2.3.11.2 Standard requirements Table 129. Chemical composition Chemical composition [wt%] Standard Designation C Si Mn P S EN 10213-2: 1995 GX23CrMoV12-1 0.20(1.4931) 0.25 0.50≤ 0.40 0.80 Cr 11.30- 1.00≤ ≤ 0.030 0.020 12.20 1.20 Table 130. Heat treatment and tensile properties at room temperature StanDesignation Heat treatment Thickness Min. 0.2 % dard proof strength [mm] [MPa] EN GX23CrMoV12-1 Q:1030°C-1080°C 150 540 10213(1.4931) T:700°C-780°C 2:1995 Landolt-Börnstein New Series VIII/2B Mo Ni V 0.25≤ 1.00 0.35 Other W: ≤0.50 Tensile Min. elongastrength tion at rupture [MPa] [%] 740 880 15 190 2.3 High Cr steels min_EN Rm 800 1000 600 800 Rm (MPa) R p0.2 (MPa) Rp0.2 400 200 0 600 400 200 0 0 100 200 300 400 500 600 0 100 200 300 400 500 600 Temperature (°C) Temperature (°C) Fig. 240. Tensile properties Rp0.2 and Rm of the test materials of cast steel grade GX23CrMoV12-1 creep rupture tested by the German Creep Committee; [1]. min EN: minimal values by EN 10213-2. Stress (MPa) 1000 broken unbroken 500°C_EN 100 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 241. Creep rupture strength data of cast steel grade GX23CrMoV12-1 at 500 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995. Stress (MPa) 1000 broken 100 unbroken 550°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 242. Creep rupture strength data of cast steel grade GX23CrMoV12-1 at 550°C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:1995 Landolt-Börnstein New Series VIII/2B Ref. p. 191] 2.3.11 12Cr-1Mo-Ni-V cast 191 Stress (MPa) 1000 broken 100 unbroken 600°C_EN 10 10 100 1000 10000 100000 1000000 Test duration (h) Fig. 243. Creep rupture strength data of cast steel grade GX23CrMoV12-1 at 600 °C obtained by the German Creep Committee [1], and average creep rupture strength values indicated in EN 10213-2:199. 2.3.11.3 Average creep rupture strength Table 131. Average creep rupture strength values indicated in EN 10213-2:1995. Time to rupture Temperature 10000 h 100000 h 200000 h [°C] Average creep rupture strength [MPa] 400 504 426 394 450 383 309 279 500 269 207 187 550 167 118 103 600 83 49 39 2.3.11.4 Reference [1] Results of German long term creep rupture tests; Contribution to the Landolt-Börnstein Creep Data Book; Cast steel grade GX23CrMoV12-1, compilation of test results; Forschungsvereinigung Warmfeste Stähle, c. o. Verein Deutscher Eisenhüttenleute, Düsseldorf (D), (2001). Landolt-Börnstein New Series VIII/2B 192 2.3 High Cr steels 2.3.12 11Cr-0.4Mo-2W-Cu-V-Nb steel 2.3.12.1 Introduction 11Cr-0.4Mo-2W-Cu-V-Nb ferritic steel (T122, P122; HCM12A) is used as superheater and reheater tubes, and header and main steam pipe in fossile fired boilers. The steel has been developed for improving creep rupture strength and corrosion resistance of T91 type 9%Cr steels at elevated temperatures. The microstructure consists of tempered martensitic matrix strengthened by M23C6 carbide mainly along grain boundaries and fine dispersed MX such as (V, Nb)(C, N) carbonitride in matrix. MX is fine and stable even after long term creep exposure at high temperatures. 2.3.12.2 Material standards, and chemical and tensile requirements Tables 132 and 133 give the chemical requirements and the corresponding tensile requirements of 11Cr0.4Mo-2W-Cu-V-Nb steel tubes and pipes which are designated by the standards: Japanese KASUS410J3TB, KA-SUS410J3TP, ASTM A213-T122, A335-P122, ASME Sec. I CC 2180. Table 132. Chemical requirements of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes and pipes; Japanese KASUS410J3TB, KA-SUS410J3TP, ASTM A213-T122, A335-P122, ASME Sec. I CC 2180. Designation Japanese METI ASTMA213 ASTMA335 Grade (1) (2) T122 P122 Std. No. Cu 0.30 1.70 0.30 ASME SecI 0.14 0.50 0.70 0.020 0.010 0.50 12.50 0.60 2.50 0.30 0.10 0.100 0.040 0.005 1.70 CC2180 C 0.07 0.14 0.07 Si 0.50 - Mn 0.70 - P 0.020 - S 0.010 - Chemical composition [wt%] Ni Cr Mo W V 10.00 0.25 1.50 0.15 0.50 11.50 0.60 2.50 0.30 10.00 0.25 1.50 0.15 Nb 0.04 0.10 0.04 N 0.040 0.100 0.040 Al 0.040 - B 0.005 - (1): KA-SUS410J3TB (2): KA-SUS410J3TP Table 133. Tensile requirements of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes and pipes; Japanese KASUS410J3TB, KA-SUS410J3TP, ASTM A213-T122, A335-P122, ASME Sec. I CC 2180. Min. Standard No. Designation Grade Min. TS1) Min. YS2) elongation KA-SUS410J3TB Japanese METI 620 MPa 400 MPa 20 % KA-SUS410J3TP ASTM A213 T122 ASME Sec. I 620 MPa 400 MPa 20 % CC 2180 ASTM A335 P122 1) TS; tensile strength, 2) YS; yield strength as 0.2% proof stress 2.3.12.3 Tensile properties of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes 2.3.12.3.1 Tensile properties of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes Fig. 244 shows tensile strength and yield stress data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes [1]. They are higher than those of T91 type 9%Cr steels in all the temperatures up to 700°C. The corresponding tensile elongation and reduction of area data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes are available in the literatures [1,4]. Landolt-Börnstein New Series VIII/2B Ref. p. 199] 2.3.12 11Cr-0.4Mo-2W-Cu-V-Nb steel 193 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 0 100 200 300 400 500 Temperature [°C] 600 700 800 Fig. 244. Tensile strength (circles) and yield stress (triangles) data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes. 2.3.12.3.2 Tensile properties of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes Fig. 245 shows tensile strength and yield stress data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes [1]. They are higher than those of P91 type steels at temperatures up to 700 °C. The corresponding tensile elongation and reduction of area data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes are available in [1]. 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 0 100 200 300 400 500 Temperature [°C] 600 700 800 Fig. 245. Tensile strength (circles) and yield stress (triangles) data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes. 2.3.12.4 Creep rupture properties of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes and pipes 2.3.12.4.1 Creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes Fig. 246 shows creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes with average curves assessed by the Larson-Miller parameter method [1]. The longest creep rupture time of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes is about 30000 h at 600 °C. Their long term creep strength is stable at temperatures between 550 °C and 650 °C. Fig. 247 shows a Larson-Miller parameter plot of creep rupture data of 11Cr-0.4Mo2W-Cu-V-Nb steel tubes with a master rupture curve and a 95 % confidence lower limit. The best fitting was achieved with an optimized constant of 34.64. Landolt-Börnstein New Series VIII/2B 194 2.3 High Cr steels 500 400 300 550 °C Stress [MPa] 200 600 °C 100 650 °C 80 60 40 30 1 550 °C 600 °C 650 °C 700 °C average curve 700 °C 10 2 10 3 Rupture time [ h] 10 10 4 10 5 Fig. 246. Creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes. 500 550 °C ×10 5h 400 600 °C ×10 5h 300 Stress [MPa] 200 650 °C ×10 5h 100 80 60 40 30 29 550 °C 600 °C 650 °C 700 °C average curve minimum curve Fig. 247. Larson-Miller parameter plot of the creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes. 30 31 32 33 34 35 36 37 38 39 Larson-Miller-parameter T (34.64 + log t ) [×10 -3 ] 2.3.12.4.2 Creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes Fig. 248 shows creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes with average curves assessed by the Larson-Miller parameter method [1]. The longest creep rupture time of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes is about 45000 h at 650 °C. Their long term creep strength is very stable at temperatures between 550 °C and 650 °C. Fig. 249 shows a Larson-Miller parameter plot of creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes with a master rupture curve and a 95 % confidence lower limit. The best fitting was achieved with an optimized constant of 35.20. Landolt-Börnstein New Series VIII/2B Ref. p. 199] 2.3.12 11Cr-0.4Mo-2W-Cu-V-Nb steel 195 500 400 300 550 °C Stress [MPa] 200 600 °C 100 650 °C 80 550 °C 600 °C 650 °C 700 °C average curve 60 40 30 1 700 °C 10 2 10 3 Rupture time [ h] 10 10 4 Fig. 248. Creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes. 10 5 500 550 °C ×10 5h 400 600 °C ×10 5h 300 Stress [MPa] 200 650 °C ×10 5h 100 80 60 550 °C 600 °C 650 °C 700 °C average curve minimum curve 40 30 29 Fig. 249. Larson-Miller parameter plot of creep rupture data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes. 30 31 32 33 34 35 36 37 38 39 Larson-Miller-parameter T (35.20 + log t ) [×10 -3 ] 2.3.12.4.3 Creep data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes Fig. 250 shows minimum creep rate data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes measured at various stress levels at temperatures between 550 °C and 700 °C with curves fitted by the Larson-Miller parameter method [1]. Fig. 251 shows a Larson-Miller parameter plot of the minimum creep rate data of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes with a master minimum creep rate curve. The best fitting was achieved with an optimized constant of 49.86. 2.3.12.4.4 Creep data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes Fig. 252 shows minimum creep rate data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes measured at various stress levels at temperatures between 550 °C and 700 °C with curves fitted by the Larson-Miller parameter method [1]. Fig. 253 shows a Larson-Miller parameter plot of the minimum creep rate data of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes with a master minimum creep rate curve. The best fitting was achieved with an optimized constant of 41.42. Landolt-Börnstein New Series VIII/2B 196 2.3 High Cr steels 500 400 500 550 °C 0.01% /10 3h 400 300 300 600 °C 0.01% /10 3h 550 °C 200 Stress [MPa] Stress [MPa] 200 600 °C 100 80 650 °C 100 80 550 °C 600 °C 650 °C 700 °C average curve 60 40 700 °C 30 10-2 650 °C 0.01% /10 3h 1 10 10-1 10 2 3 Minimum creep rate [% / 10 h] 550 °C 600 °C 650 °C 700 °C 60 40 10 3 Fig. 250. Minimum creep rate data of 11Cr-0.4Mo2W-Cu-V-Nb steel tubes. average curve 30 39 40 41 42 43 44 45 46 47 48 49 Larson-Miller-parameter T (49.86 + log e ) [×10 -3 ] Fig. 251. Larson-Miller parameter plot of the minimum creep rate of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes. 500 400 500 300 300 550 °C 0.01% /10 3h 400 600 °C 0.01% /10 3h 550 °C 200 Stress [MPa] Stress [MPa] 200 600 °C 100 80 650 °C 60 40 30 10-2 700 °C 550 °C 600 °C 650 °C 700 °C average curve 1 10-1 10 10 2 Minimum creep rate [% / 103h] 10 3 Fig. 252. Minimum creep rate data of 11Cr-0.4Mo-2WCu-V-Nb steel pipes. 650 °C 0.01% /10 3h 100 80 60 40 30 39 550 °C 600 °C 650 °C 700 °C average curve 40 41 42 43 44 45 46 47 48 49 Larson-Miller-parameter T (41.42 + log e ) [×10 -3 ] Fig. 253. Larson-Miller parameter plot of the minimum creep rate of 11Cr-0.4Mo-2W-Cu-V-Nb steel pipes. 2.3.12.5 Allowable stress of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes and pipe Figs. 254 and 255 show the allowable tensile stresses determined for 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes and pipes (Japanese METI KA-SUS410J3TB and KA-SUS410J3TP) according to the METI standard procedure comparing with those for the conventional steels ASME SA213-T91 and SA335-P91 (Japanese METI KA-STBA28 and KA-STPA28). Landolt-Börnstein New Series VIII/2B Ref. p. 199] 2.3.12 11Cr-0.4Mo-2W-Cu-V-Nb steel 180 180 160 160 KA-SUS410J3TB 140 120 Allowable tensile stress (MPa) Allowable tensile stress (MPa) 197 KA-STBA28 100 80 60 40 KA-SUS410J3TP 140 120 KA-STBA28 100 80 60 40 20 20 0 0 0 0 100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800 Temperature (℃) Temperature (℃) Fig. 254. Allowable tensile stress determined for 11Cr0.4Mo-2W-Cu-V-Nb steel tubes (Japanese METI KASUS410J3TB). Fig. 255. Allowable tensile stress determined for 11Cr0.4Mo-2W-Cu-V-Nb steel pipe (Japanese METI KASUS410J3TP). 2.3.12.6 Alloying philosophy of 11Cr-0.4Mo-2W-Cu-V-Nb steel 11Cr-0.4Mo-2W-Cu-V-Nb steel has been developed for improving creep rupture strength and corrosion resistance of P91 type 9%Cr steels above 600 °C, which is mainly achieved by a higher Cr content and substitution of a part of Mo by W. It is also noted that in order to suppress δ - ferrite formation for thick wall pipes Cu addition is chosen among the γ forming elements shown in Fig. 256. Cu is the γ forming element which does not reduce Ac1 temperature much and does not enhance coarsening of M23C6 carbide unlike Ni and Mn. Cu addition allows the combination of a higher Cr content with high W and Mo contents. 40 Base; 0.1C-11Cr steel Addition [mass %] a forming element 2W DAc 1 [°C ] 1Cr 1Mo 0 2Cu 0.5Ni -40 -4 0.05N Cr eq = Cr+6Si+4Mo+1.5W +11V+5Nb+8Ti+12Al -40C-30N-4Ni-2Mn -Cu-2Co [mass %] Fig. 256. Comparison of alloying elements with respect to changes in Ac1 temperature and Creq of 0.1C-11Cr model steels. g forming element -2 Landolt-Börnstein New Series VIII/2B 0 D Cr eq [mass %] 2 4 198 2.3 High Cr steels 2.3.12.7 Microstructural change of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes Fig. 257 shows a typical CCT diagram determined for 11Cr-0.4Mo-2W-Cu-V-Nb steel after heating at 1050 °C. Full martensitic microstructure is easily obtained even with a very slow cooling. It is noted that Ac1 temperature is over 800 °C, which is advantageous for a long-term microstructural stability by taking tempering at higher temperatures. 1000 Ac3 904 °C Austenitized at 1050 °C × 5 min 900 Ac1 805 °C Temperature T [°C] 800 700 600 500 400 300 200 100 1 Vickers hardness 10 428 422 437 425 420 416 433 452 481 2 3 10 10 Cooling time from Ac 3 temperature [s] 10 4 408 10 5 Fig. 257. A typical CCT diagram determined for 11Cr-0.4Mo-2WCu-V-Nb steel after heating at 1050 °C. Fig. 258 shows TEM micrographs of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes normalized and tempered, and service exposed for 20508 h in the Wakayama Kyodo Power Station No.3 boiler which has been operated with an outlet steam temperature of 571 °C [8]. It can be seen that in the specimen normalized and tempered VN type MX ((V,Nb)(C,N)) is finely dispersed in matrix with coherency strain, while in the specimen service exposed fine VN still remains in matrix with a smaller coherency strain. 2.3.12.8 Performance of service exposed tubes More detailed performance data of service exposed tubes is available in [7] and [8]. Landolt-Börnstein New Series VIII/2B Ref. p. 199] 2.3.12 11Cr-0.4Mo-2W-Cu-V-Nb steel VN VN 110 α 100 α 010 α VN 100nm 100nm (a) Bright field image 100 α 199 (b) Dark field image 010 α VN Laves 110 α 100nm (c) Bright field image 100nm (d) Dark field image Fig. 258. TEM micrographs of 11Cr-0.4Mo-2W-Cu-V-Nb steel tubes normalized and tempered (a and b), and service exposed for 20508 h (c and d) at 571 °C. 2.3.12.9 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Sawaragi, Y., Iseda, A., Ogawa, K., and Masuyama, F.: Materials for Advanced Power Engineering, Part 1, Kluwer Academic Publishers (1994), p.309. [3] Iseda, A., Sawaragi, Y., Kato, S., and Masuyama, F.: Proc. of the Fifth International Conf. on Creep Materials, Florida, (1992), 389. [4] Sawaragi, Y., Igarashi, M., Iseda, A., Yamamoto, S., and Masuyama, F.: Sumitomo Kinzoku Vol.47 No.4 (1995), 29. [5] Ogawa, K., Iseda, A., Sawaragi, Y., Matsumoto, S., and Masuyama, F.: Sumitomo Kinzoku Vol.47 No.4 (1995), 39. [6] Sawaragi, Y., Kan, T., Yamadera, Y., Masuyama, F., Yokoyama, T., and Komai, N.: Proc. of the 6th International Conf. on Materials for Advanced Power Engineering (1998) Liege, Forschungszentrum Julich GmbH, 62. [7] Sawaragi, Y., Miyata, K., Yamamoto, S., Masuyama, F., Komai, N., and Yokoyama, T.: Advanced Heat Resistant Steels For Power Generation, The University Press, Cambridge (1998), p.144. [8] Miyata, K., Sawaragi, Y., Okada, H., Masuyama, F., Yokoyama, T., and Komai, N.: ISIJ International, Vol. 40 (2000), 1156. Landolt-Börnstein New Series VIII/2B 200 2.3 High Cr steels 2.3.13 12Cr-2.6W-2.5Co-0.5Ni-V-Nb steel 2.3.13.1 Introduction 12Cr-2.6W-2.5Co-0.5Ni-V-Nb steel (NF12) was developed by Nippon Steel Corporation, Japan in the mid-1990s for boiler tubing and pipe work applications for power plants with high steam parameters. The targeted creep rupture strength of NF12 steel is at least 1.3 times higher than that of NF616 (P92) steel. Demonstrative fabrication of full size header and main steam pipe components has been conducted, although the steel has not yet been used for practical applications. 2.3.13.2 Material standards, chemical and tensile requirements [1] NF12 steel is not specified in any codes or standards. Table 134 shows the chemical compositions of tubes and plates produced from NF12 steel on a trial basis and subjected to creep and characterization tests. The test materials were melted in a vacuum induction furnace or in an electric furnace and then cast into 20 kgf to 1000 kgf weight ingots. Hot rolling equipment produced 15 mm thick plate specimens and a hot extrusion machine formed seamless tube specimens with wall thickness from 8.1 to 9.0 mm and outer diameter from 45 to 50.8 mm. Specimens were austenitized in the range from 1070 °C to 1100 °C, quenched in air, and then tempered in the range from 770 to 800 °C. Figs. 259 and 260 show elevated temperature tensile properties and Charpy impact properties of NF12 steel, respectively. Table 134. Chemical compositions of NF12 steels [1]. Chemical composition [wt%] Product C Si Mn Cr Mo W Nb V Tube 0.092 0.03 0.51 10.79 0.13 2.47 0.064 0.20 Tube 0.094 0.19 0.50 11.35 0.16 2.57 0.070 0.20 Plate 0.077 0.26 0.57 12.11 0.15 2.75 0.071 0.23 Plate 0.078 0.22 0.47 10.85 0.14 2.60 0.068 0.20 Ni 0.51 0.41 0.58 0.51 Co 1.95 1.49 2.68 1.91 B 0.002 0.004 0.083 0.003 N 0.046 0.040 0.050 0.048 1000 Yield strength, Tensile strength (MPa) Tensile strength Yield strength (0.2% offset) 800 600 400 200 0 Fig. 259. Elevated temperature tensile properties of NF12 steel; [1]. 0 100 200 300 400 500 600 700 800 Temperature (℃) Landolt-Börnstein New Series VIII/2B Ref. p. 203] 2.3.13 12Cr-2.6W-2.5Co-0.5Ni-V-Nb steel 100 250 200 80 Toughness Crystallinity 150 60 100 40 50 20 0 -80 -60 -40 -20 0 20 Temperature (℃) 40 Cristallinity (%) Charpy impact value (J/cm2) 201 Fig. 260. Charpy impact properties of NF12 steel; [1]. 0 80 60 2.3.13.3 Creep properties 2.3.13.3.1 Creep rupture data [1] Fig. 261 shows the creep rupture stress vs. time to rupture relationship for NF12 steel tubes and plates at temperatures from 600 °C to 750 °C. Fig. 262 shows creep rupture elongation and reduction of area against time to rupture. There is no major difference in creep rupture ductilities among the different testing temperatures of NF12 steel. 1000 700 500 Stress (MPa) 300 200 600℃ 100 70 50 650℃ 700℃ 30 750℃ 20 10 100 101 102 103 Time to rupture (h) Landolt-Börnstein New Series VIII/2B 104 Fig. 261. Creep rupture strength data of NF12 steel; [1]. 105 202 2.3 High Cr steels 100 600℃ Elongation, Reduction of area (%) 90 650℃ 80 700℃ Reduction of area 70 60 750℃ Elongation 50 40 30 Fig. 262. Creep rupture elongation and reduction of area of NF12 steel; [1]. 20 10 0 100 101 102 103 104 105 Time to rupture (h) 2.3.13.3.2 Estimated creep strength [1] Fig. 263 shows the extrapolated 100,000 h creep rupture strength of NF12 steel compared with those of NF616 (P92) steel and Mod.9Cr-1Mo (T91) steel by means of the Larson-Miller parametric method. The extrapolated creep rupture strength for NF616 steel is about 1.3 times higher than that of Mod.9Cr-1Mo steel. The creep rupture strength of NF12 steel is expected to be about 1.3 to 1.5 times higher than that of NF616 steel, depending on the extrapolation method. It can thus be inferred that the creep rupture strength of NF12 steel is around 1.6 times higher than that of Mod.9Cr-1Mo, and sometimes up to 1.9 times higher. 300 Estimated stress for 105h (MPa) NF12 250 200 NF616 (P92) 150 Mod. 9Cr-1Mo (P91) 100 Fig. 263. Extrapolated creep rupture strength of NF12 steel comparing with NF616 steel and Mod. 9Cr-1Mo steel; [1]. 50 0 500 550 600 Temperature (℃) 650 700 The allowable stresses of NF12 steel were developed based on the ASME criteria and are compared with NF616 steel and Mod.9Cr-1Mo steel in Fig. 264. The allowable stresses for NF616 steel and NF12 steel tend to be much higher compared with those of Mod.9Cr-1Mo steel in the relatively high temperature region. At 600 °C the allowable stress for NF616 steel is 1.3 times higher than that of Mod.9Cr-1Mo steel, and the stress for NF12 steel is 1.6 times higher than that for Mod.9Cr-1Mo steel. Landolt-Börnstein New Series VIII/2B Ref. p. 203] 2.3.13 12Cr-2.6W-2.5Co-0.5Ni-V-Nb steel 203 200 NF12 180 NF616 (P92) Allowable stress (MPa) 160 140 Mod. 9Cr-1Mo (P91) 120 100 80 60 Fig. 264. Allowable stresses of NF12 steel comparing with NF616 steel and Mod. 9Cr-1Mo steel; [1]. 40 20 0 0 100 200 300 400 Temperature (℃) 500 600 700 2.3.13.4 Reference [1] Ohgami, M., Hasegawa, Y., Naoi, H., and Fujita, T.: IMechE Conf. Trans. 1997-2, Advanced Steam Plant-New Materials and Plant Design and Their Practical Implications for Future CCGT and Conventional Power Stations, (1997), 115. Landolt-Börnstein New Series VIII/2B 204 2.3 High Cr steels 2.3.14 12Cr-3W-3Co-V-Nb-Ta-Nd-N steel 2.3.14.1 Introduction 12Cr-3W-3Co-V-Nb-Ta-Nd-N steel (SAVE12) was developed by Sumitomo Metal Industries, Ltd., Japan in the mid-1990s for thick wall pipes applicable to main steam pipes and headers of power plants with high steam parameters. This steel has higher creep rupture strength at elevated temperatures up to 630 °C than Mod.9Cr-1Mo steel (P91), NF616 (P92) steel and HCM12A (P122) steel. To date, laboratory heat has been used for studies of creep strength and for characterization tests, and the steel has not yet been used for practical applications. However, several lengths of tubings have been installed in a large capacity power boiler for field exposure testing. 2.3.14.2 Material standards, chemical and tensile requirements SAVE12 steel is not specified in any codes or standards. Table 135 [1] shows ranges of chemical compositions of SAVE12 steel vacuum induction melted in the laboratory as a 150 kgf ingot for creep strength studies, and subsequently processed by hot forging into 25 mm thick plates. The plates were normalized for 1 hour at temperatures between 1000 °C and 1200 °C, air cooled, and tempered at 550 °C to 800 °C, followed again by air-cooling. The plates subjected to creep rupture tests were normalized for 0.5 h at 1050 °C and tempered for 1.5 h at 780 °C. Fig. 265 [1] shows changes in hardness with Co content of the specimens as a function of the LarsonMiller parameter (LMP) for 0.1C-10Cr-0∼5Co-2.6W-0.2Mo-0.2V-0.05Nb-0.05N-0.005B steel normalized and tempered at 600 °C to 820 °C. Table 135. Chemical composition of SAVE12 steel; [1]. Chemical composition [wt%] Product C Si Mn P S Cr Mo W Co V Nb 2.0 0 0.15 0 Plate 0.07 0.05 0.01 ≤0.015 ≤0.001 8.0 0 ∼ ∼ ∼ ∼ ∼ ∼ ∼ ∼ ∼ 13.0 0.50 3.5 7.0 0.35 0.10 0.13 0.75 1.00 Ta 0 ∼ 0.15 Nd 0 ∼ 0.15 Hf 0 ∼ 0.15 N 0.01 ∼ 0.09 B 0 ∼ 0.0008 450 0% Co 1% Co 400 Hardness(HV) 3% Co 5% Co 350 Fig. 265. Changes in hardness with Co content of specimens as a function of Larson-Miller Parameter (LMP) for 0.1C10Cr-0~5Co-2.6W-0.2Mo0.2V-0.05Nb-0.05N-0.005B steels normalized and tempered; [1]. 300 250 200 28 30 32 34 36 T (35+log t) × 10- 3 38 40 Landolt-Börnstein New Series VIII/2B Ref. p. 205] 2.3.14 12Cr-3W-3Co-V-Nb-Ta-Nd-N steel 205 2.3.14.3 Creep properties [1] Fig. 266 shows creep rupture stress vs. time to rupture relations of SAVE12 plates normalized for 0.5 h at 1050 °C and tempered for 1.5 h at 780 °C. It is found that the creep rupture strength increases with increasing Co content as in the case of softening resistance of the steels, see Fig. 265. The most marked increase in creep rupture strength with Co content has been obtained for specimens tested at 600 °C. At higher testing temperatures with low stress levels, the increase in creep rupture strength with Co content is smaller than at 600 °C. 500 Stress(MPa) 300 200 600℃ 100 70 50 0% Co Fig. 266. Creep rupture properties of 0.1C-10Cr0~5Co-2.6W-0.2Mo-0.2V0.05Nb-0.05N-0.005B steels normalized for 0.5 h at 1050 °C and tempered for 1.5 h at 780 °C; [1]. 650℃ 1% Co 3% Co 700℃ 5% Co 101 102 103 104 105 Time to rupture(h) 2.3.14.4 Reference [1] Igarashi, M., and Sawaragi, Y.: Proc. International Conf. Power Engineeering-97, Vol.2, Tokyo, (1997), 107. Landolt-Börnstein New Series VIII/2B 206 2.4 Austenitic stainless steels 2.4 Austenitic stainless steels 2.4.1 18Cr-8Ni steel 2.4.1.1 Introduction Austenitic stainless steels, such as type 304 (18Cr-8Ni), 316 (18Cr-12Ni-Mo), 321 (18Cr-10Ni-Ti) and 347 (18Cr-12Ni-Nb) steels, are widely used as high-temperature components, such as boilers and superheaters, which require good mechanical properties and corrosion resistance at temperatures up to 650 - 700 °C [1-2]. Among the stainless steels, type 304 steel exhibits the most simple chemical composition and hence the most simple microstructure where M23C6 carbides and σ phase precipitate at high temperature. The microstructures of other stainless steels are more complicated. 2.4.1.2 Material standards, chemical and tensile requirements 2.4.1.2.1 18Cr-8Ni stainless steel tubes for boilers and heat exchangers Table 136. Chemical and tensile requirements for 18Cr-8Ni stainless steel tubes for boilers and heat exchangers; JIS SUS 304 HTB, ASTM TP 304 H, BS 304 S 51. Chemical composition [wt%] Standard Designation Std. No. C Si Mn P S Ni Cr JIS SUS 304 0.04-0.10 <0.75 <2.00 <0.040 <0.030 8.00-11.00 18.00-20.00 G3463 HTP ASTM TP 304 H 0.04-0.10 <0.75 <2.00 <0.040 <0.030 8.0-11.0 18.0-20.0 A213, A249 BS 304 S 51 0.04-0.10 <1.00 <2.00 <0.040 <0.030 8.00-11.00 17.0-19.0 3059-2 Standard Designation Yield strength [MPa] JIS SUS 304 >205 HTP ASTM TP 304 H >205 >515 BS 490-690 304 S 51 >230 Tensile strength Std. No. [MPa] >520 G3463 A213, A249 3059-2 2.4.1.2.2 18Cr-8Ni stainless steel plates Table 137. Chemical and tensile requirements for 18Cr-8Ni stainless steel plates; JIS SUS 304-HP, ASTM S 30400, BS 304 S 31, DIN X5CrNi 1810, ISO L-No.6 X5CrNi 18-9. Chemical composition [wt%] StanDesignation Std. No. dard C Si Mn P S Ni Cr N JIS SUS 304-HP <0.08 <1.00 <2.00 <0.045 <0.030 8.0018.00G4304 10.50 20.00 ASTM S 30400 <0.08 <0.75 <2.00 <0.045 <0.030 8.0018.00<0.10 A240, 10.50 20.00 A666 BS 304 S 31 <0.07 <1.00 <2.00 <0.045 <0.030 8.0-11.0 17.0-19.0 1449-2 DIN C5CrNi1810 <0.07 <1.00 <2.00 <0.045 <0.030 8.5-10.5 17.0-19.0 17441 ISO L-No6 <0.07 <1.00 <2.00 <0.045 <0.015 8.0017.00X5CrNi 18-9 10.50 19.50 Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel Table 137 cont. Standard Designation JIS ASTM BS DIN ISO SUS 304-HP S 30400 304 S 31 C5CrNi1810 L-No6 X5CrNi 18-9 Yield strength [MPa] >205 >205 Tensile strength [MPa] >520 >515 207 Std. No. G4304 A240, A666 1449-2 17441 2.4.1.3 Data sources for 18Cr-8Ni stainless steel Information of fact on data for 18Cr-8Ni stainless steel can be obtained from [3], [4], [5] and [6]. 2.4.1.4 Creep and creep rupture data for 18Cr-8Ni stainless steel for boiler and heat exchanger seamless steel tubes, JIS SUS 304H TB 2.4.1.4.1 Creep rupture data for 18Cr-8Ni stainless steel tubes, JIS SUS 304H TB The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area, minimum creep rate and optical micrographs of as-received and crept specimens, has been obtained for the 9 heats in [3]. The details of steel tube production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for each heat in [3] Fig. 267 shows the 0.2% proof stress and tensile strength of the 9 heats of 18Cr-8Ni stainless steel, JIS SUS 304 HTB, [3], obtained by short-time tensile tests between room temperature and 700 °C. The tensile and creep specimens, having a geometry of 6 mm in diameter and 30 mm in gauge length, were taken longitudinally from the middle of wall thickness of the tubes. Fig. 268 shows stress vs. time to rupture data for 9 heats of 18Cr-8Ni steel, JIS SUS 304 HTB, at temperatures between 600 and 750 °C. Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 100 200 300 400 500 600 Test temperature (℃) 700 800 0 0 100 200 300 400 600 Test temperature (℃) Fig. 267. Short-time tensile properties of 18Cr-8Ni stainless steel tubes, JIS SUS 304 HTB. Landolt-Börnstein New Series VIII/2B 500 700 800 208 2.4 Austenitic stainless steels 300 o 60 0 C o 62 5 C o 65 0 C o Stress ( MPa ) 67 5 C o 70 0 C o 72 5 C 100 80 o 75 0 C o 77 5 C o 80 0 C 60 o 82 5 C o 85 0 C 40 n = 28 7 20 1 10 10 2 10 3 10 4 10 5 10 Fig. 268. Creep rupture strength data for 18Cr-8Ni stainless steel tubes, JIS SUS 304 HTB. n indicates the total number of data points. 6 Time to ru ptu re ( h ) 2.4.1.4.2 Estimated long-term creep rupture strength for 18Cr-8Ni stainless steel tubes, JIS SUS 304H TB The creep rupture data shown in Fig. 268 were analyzed for each heat using the Manson-Haferd parameter method. Fig. 269 shows the resulting master rupture curve for all data. The estimated stress vs. time to rupture curves for the heat ABE which shows an intermediate strength level among the 9 heats are shown in Fig. 270. The 105 h creep rupture strength was also estimated for the 9 heats. This is shown in Fig. 271 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. 400 600 °C 625 °C 650 °C 675 °C 700 °C 725 °C 750 °C 775 °C 800 °C 825 °C 850 °C 300 Stress [MPa] 200 100 80 60 50 40 30 20 Average n = 289 (309) -1.0 -4.0 -3.0 -2.5 -1.5 -3.5 -2.0 Manson-Haferd parameter [( log tR -10.378)/( TK - 650 )] [×10 - 2 ] Fig. 269. Master rupture curve using the MansonHaferd parameter for the 9 heats of 18Cr-8Ni steel tube, JIS SUS 304 HTB. n indicates the number of data points used for analysis. In brackets the total number of data points is given. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 209 30 0 o Stress ( MPa ) 6 00 C 10 0 80 60 o 6 50 C 40 o 700 C o 75 0 C 20 10 10 2 10 3 10 4 10 5 10 6 Fig. 270. Estimated creep rupture strength curves for the heat ABE of 18Cr-8Ni steel tube, JIS SUS 304 HTB. Ti me to rupture ( h ) 500 400 300 Stress [MPa] Tensile strength { 100 80 { 200 0.2% proof stress 1000 h 60 50 40 100000 h 30 20 575 600 625 650 700 675 Temperature [°C] 725 750 775 Fig. 271. Estimated 105 h creep rupture strength for the 9 heats of 18Cr-8Ni steel tube, JIS SUS 304 HTB. 2.4.1.4.3 Creep strain data of 18Cr-8Ni stainless steel tubes, JIS SUS 304H TB [3] contains the creep strain data for the heat ABE of 18Cr-8Ni steel tubes, JIS SUS 304 HTB. The stress vs. time to reach 0.5, 1, 2 and 5 % total strain, time to tertiary creep and time to rupture are obtained from [3]. The relationship between stress and minimum creep rate is shown Fig. 272. The relationship between time to rupture and minimum creep rate is shown in Fig. 273. Landolt-Börnstein New Series VIII/2B 210 2.4 Austenitic stainless steels 300 10 6 10 5 Time to rupture [h] Stress [MPa] 200 100 80 600 °C 650 °C 700 °C ABE n = 20 60 50 40 10-6 10-5 10-4 10-3 10-2 10-1 Minimum creep rate [%/h] 10 3 600 °C 650 °C 700 °C ABE n = 15 10 2 30 20 10-7 10 4 1 Fig. 272. Stress vs. minimum creep rate for the heat ABE of 18Cr-8Ni steel tubes, JIS SUS 304 HTB at 600, 650 and 700 °C. n indicates the total number of data points. 10 10-7 10-6 10-5 10-4 10-3 10-2 10-1 Minimum creep rate [%/h] 1 Fig. 273. Time to rupture vs. minimum creep rate for the heat ABE of 18Cr-8Ni steel tube, JIS SUS 304 HTB at 600, 650 and 700 °C. n indicates the total number of data points. 2.4.1.5 Creep rupture data for 18Cr-8Ni stainless steel plates for reactor vessels, JIS SUS 304-HP The complete set of creep rupture data, such as creep rupture time, total elongation, reduction of area and optical micrographs of as-received and crept specimens, has been obtained for the 2 heats in [4]. The details of steel plate production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for each heat in [4]. Fig. 274 shows the 0.2% proof stress and tensile strength of the 2 heats of 18Cr-8Ni stainless steel in [4], obtained by short-time tensile tests between room temperature and 850 °C. The tensile and creep specimens, having a geometry of 10 mm in diameter and 50 mm in gauge length, were taken longitudinally from the middle of plates. Fig. 275 shows stress vs. time to rupture data for the 2 heats of 18Cr-8Ni steel plates, JIS SUS 304HP, at temperatures between 450 and 700 °C. The 105 h creep rupture strength was estimated for the 2 heats. This is shown in Fig. 276 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 211 Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 100 200 300 400 500 600 700 0 800 0 100 Test temperature (℃) 400 500 600 700 800 450 °C 475 °C 500 °C 525 °C 550 °C 575 °C 600 °C 625 °C 650 °C 675 °C 700 °C 400 300 200 Stress [MPa] 300 Test temperature (℃) Fig. 274. Short-time tensile properties of 18Cr-8Ni steel, JIS SUS 304-HP. 500 200 100 80 60 50 40 30 n = 71 20 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 275. Creep rupture strength data for the 2 heats of 18Cr-8Ni steel plates, JIS SUS 304-HP. n indicates the total number of data points. 800 600 500 400 100 80 60 50 40 30 450 Tensile strength { 200 { Stress [MPa] 300 0.2% proof stress 1000 h Fig. 276. Estimated 105 h creep rupture strength for the 2 heats of 18Cr-8Ni steel plates, JIS SUS 304-HP. 100000 h 500 Landolt-Börnstein New Series VIII/2B 550 650 600 Temperature [°C] 700 750 800 212 2.4 Austenitic stainless steels 2.4.1.6 Creep rupture data for welded joints of 18Cr-8Ni stainless steel plates 2.4.1.6.1 Submerged arc welded joints of 18Cr-8Ni stainless steel plates The complete set of creep rupture data, such as creep rupture time, total elongation, reduction of area and optical micrographs of as-received and crept specimens for submerged arc welded joints of 18Cr-8Ni stainless steel plates are given in [4]. The details of base metal plates and the chemical compositions of the 2 heats AbW and AbX of 18Cr-8Ni stainless steel are also given in [4]. The details of submerged arc welding procedure, the welding conditions, and the chemical compositions of filer wires and 308 weld metals can also be obtained from [4]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 100 mm in gauge length, were taken longitudinally from the middle of plates. The weld metal was located at the center of specimen gauge, as shown in Fig. 277. Fig. 278 and 279 show the 0.2% proof stress and tensile strength, obtained by short-time tensile tests for submerged arc welded joints of the heats AbW and AbX, respectively. Fig. 280 and 281 show stress vs. time to rupture data for submerged arc welded joints of 18Cr-8Ni steel plates at temperatures between 500 and 700 °C. The corresponding total elongation and reduction of area are available in [4]. Fig. 277. Test specimen of welded joints. Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 0 100 200 300 400 500 600 Test temperature (℃) 700 800 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 278. Short-time tensile properties of submerged arc welded joints of the heat AbW of 18Cr-8Ni steel. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 213 Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800 Test temperature (℃) Test temperature (℃) Fig. 279. Short-time tensile properties of submerged arc welded joints of the heat AbX of 18Cr-8Ni steel. 500 400 500 °C 550 °C 600 °C 625 °C 650 °C 675 °C 700 °C 300 Stress [MPa] 200 100 80 60 50 40 n = 79 30 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 280. Creep rupture data for submerged arc welded joints of the heat AbW of 18Cr-8Ni steel. n indicates the total number of data points. 500 400 500 °C 550 °C 600 °C 650 °C 700 °C 300 Stress [MPa] 200 100 80 60 50 40 n = 192 30 10 Landolt-Börnstein New Series VIII/2B 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 281. Creep rupture data for submerged arc welded joints of the heat AbX of 18Cr-8Ni steel. n indicates the total number of data points. 214 2.4 Austenitic stainless steels The 105 h creep rupture strength was estimated for submerged arc welded joints, using the data in Fig. 280 and 281. An example of results estimated is shown in Fig. 282 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. 800 600 500 400 100 h 100 80 60 50 40 30 450 Tensile strength { 200 { Stress [MPa] 300 0.2% proof stress 10000 h 550 500 650 600 Temperature [°C] 750 700 800 Fig. 282. Estimated 105 h creep rupture strength for the submerged arc welded joint JAA of the heat AbW of 18Cr-8Ni steel plates. 2.4.1.6.2 Electron beam welded joints of 18Cr-8Ni stainless steel plates The complete set of creep rupture data, such as creep rupture time, total elongation, reduction of area and optical micrographs of as-received and crept specimens for electron beam welded joints of 18Cr-8Ni stainless steel plates is given in [4]. The details of electron beam welding procedure and welding conditions for the base metal, heat AbX, are also given in [4]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 100 mm in gauge length, were taken longitudinally from the middle of plates. The weld metal was located at the center of specimen gauge, as shown in Fig. 277. Fig. 283 shows the 0.2% proof stress and tensile strength, obtained by short-time tensile tests for electron beam welded joints of the heat AbX. Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 0 100 200 300 400 500 600 700 800 Test temperature (℃) 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 283. Short-time tensile properties of electron beam welded joints. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 215 Fig. 284 shows stress vs. time to rupture data for electron beam welded joints of 18Cr-8Ni steel plates at temperatures between 475 and 700 °C. The corresponding total elongation and reduction of area are available in [4]. The 105 h creep rupture strength was estimated using the data in Fig. 284. An example is shown in Fig. 285 for electron beam welded joints, as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. 500 475 °C 500 °C 525 °C 550 °C 575 °C 600 °C 650 °C 700 °C 400 300 Stress [MPa] 200 100 80 60 50 40 n = 44 30 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 284. Creep rupture strength data for electron beam welded joints of the heat AbX of 18Cr8Ni steel. n indicates the total number of data points. 800 600 500 400 Stress [MPa] 300 Tensile strength 200 0.2% proof stress 100 80 60 50 40 30 450 1000 h 100000 h 500 550 600 Temperature [°C] 650 700 750 Fig. 285. Estimated 105 h creep rupture strength for the electron beam welded joint JCA of the heat AbX of 18Cr-8Ni steel plates. 2.4.1.6.3 Narrow-gap gas tungsten arc welded joints of 18Cr-8Ni stainless steel plates The complete set of creep rupture data, such as creep rupture time, total elongation, reduction of area and optical micrographs of as-received and crept specimens for narrow-gap gas tungsten arc welded joints of 18Cr-8Ni stainless steel plates is given in [4]. The details of the narrow-gap gas tungsten arc welding procedure and welding conditions for the base metal, heat AbX, are also given in [4]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 100 mm in gauge length, were taken longitudinally from the middle of plates. The weld metal was located at the center of specimen gauge, as shown in Fig. 277. Fig. 286 shows the 0.2% proof stress and tensile strength obtained by short-time tensile tests for narrow-gap gas tungsten arc welded joints of the heat AbX. Landolt-Börnstein New Series VIII/2B 216 2.4 Austenitic stainless steels Fig. 287 shows stress vs. time to rupture data for narrow-gap gas tungsten arc welded joints of 18Cr-8Ni steel plates at temperatures between 475 and 700 °C. The corresponding total elongation and reduction of area are available in [4]. The 105 h creep rupture strength was estimated using the data in Fig. 287. This is shown in Fig. 288 for the narrow-gap gas tungsten arc welded joint, as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 0 100 200 300 400 500 600 0 700 100 Test temperature (℃) 200 300 400 500 600 700 Test temperature (℃) Fig. 286. Short-time tensile properties of narrow-gap gas tungsten arc welded joints. 500 475 °C 500 °C 525 °C 550 °C 575 °C 600 °C 650 °C 700 °C 400 300 Stress [MPa] 200 100 80 60 50 40 30 10 n = 21 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 287. Creep rupture strength data for narrow-gap gas tungsten arc welded joints of the heat AbX of 18Cr-8Ni steel plates. n indicates the total number of data points. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 217 800 600 500 400 Tensile strength Stress [MPa] 300 200 0.2% proof stress 100 80 60 50 40 30 450 1000 h 100000 h 500 550 600 Temperature [°C] 650 700 750 Fig. 288. Estimated 105 h creep rupture strength for the narrow-gap gas tungsten arc welded joint of the heat AbX of 18Cr-8Ni steel plates. 2.4.1.7 Microstructure data of 18Cr-8Ni austenitic steel 2.4.1.7.1 Creep fracture modes of 18Cr-8Ni austenitic steel The microstructure observations by optical, scanning and transmission electron microscopes were carried out on the longitudinal cross-section of the specimens after creep-rupture. The creep fracture modes were characterized by the analysis of microstructure near the fracture portion and are shown for the two heats ABA and ABE in Fig. 289 [7-9]. The heat ABA exhibits a steep decrease in creep rupture strength at long times, while the heat ABE exhibits an intermediate level of creep rupture strength among the 9 heats examined in [3]. The creep fracture modes for the two heats ABA and ABE are divided to one transgranular fracture (denoted by T) and three types of intergranular fracture: the wedge-type cracking (denoted by W), the creep cavitation associated with M23C6 carbides at grain boundaries (denoted by C ) and the σ/matrix interface cracking along grain boundaries (denoted by σ), as shown in Fig. 289. The results suggest that the creep fracture modes at long times above 104 h are closely connected with the precipitation behavior of M23C6 carbides and σ phase. 2.4.1.7.2 Microstructure evolution in 18Cr-8Ni austenitic steel The microstructure evolution during thermal aging under no stress has been examined by several researchers [10, 11] for austenitic stainless steels, 304H, 316H, 321H and 347H steels, for up to 5×104 h at temperatures between 600 (873) and 800 °C (1073 K). But these studies are limited to specimens tested in periods not exceeding 6×104 h. Recently, the microstructural evolution during creep and during thermal aging has comprehensively been investigated for JIS SUS 304HTB steel after long-term creep rupture tests for up to 1.8×105 h, using specimens tested in the NRIM Creep Data Sheet Project [12, 13]. JIS SUS 304HTB steel is one of the most popular austenitic heat resistant steels. A number of micrographs were recently published for SUS 304HTB steel as ‘Metallographic Atlas of Long-Term Crept Materials’ [14], parallel with the NRIM Creep Data Sheets. The Metallographic Atlas contains not only series of micrographs showing the microstructure evolution during creep for up to 105 h but also the relating data such as time-temperature-precipitation (TTP) diagrams, histograms describing the distributions of precipitates and creep-voids, and creep damage parameters. The TTP diagram was constructed for the heat ABE, using the head or grip portion under no stress of the crept specimens. This is shown in Fig. 290. Only the M23C6 carbides precipitate in the specimens at short times less than about 104 h at 650 °C, but both M23C6 carbides and σ phase appear Landolt-Börnstein New Series VIII/2B 218 2.4 Austenitic stainless steels at long times above about 104 h. The TEM micrographs clearly show that the M23C6 carbides are observed in the form of cube-like particles in Widmanstätten distributions in the matrix and in the form of chains of enlarged particles along grain boundaries, while the σ phase is observed in the form of large and irregular shapes on grain boundaries and of needles in the matrix. The mean size of M23C6 carbides in the specimen head portion is plotted in Fig. 291 as a function of time. In the initial stage of precipitation in the matrix, the size of M23C6 particles is approximately described by d ∝ t1/2, suggesting diffusion-controlled growth of the M23C6 carbides from supersaturated solid solution. The slope of the size vs. time curves decreases at long times and the particle size reaches about 0.05 - 0.07 µm at 105 h at 600 - 700 °C. For the M23C6 carbides at grain boundaries, the slope of the size-time curves also decreases at long times similar as in the matrix, although the size is much larger than that in the matrix. T Stress [kgf /mm 2 ] 20 10 8 6 700 °C 725 °C 750 °C 775 °C 800 °C T C s 4 T :Transgranular creep fracture W :Wedge-type cracking 2 C :Cavity formation s :Cracking at sigma / austenite interface 1 20 10 8 6 s within grain 750 700 650 M23C6 within grain 600 550 s creep damage test 2 10 2 10 10 3 10 4 Time to rupture [h] M23C 6 carbide Grain boundary 10-1 Matrix 1/2 600 °C 650 °C 700 °C M23C6 on grain boundary 500 10 -1 1 10 10 2 Time [h] 10 3 10 4 10 5 Fig. 290. Time-Temperature-Precipitation (TTP) diagram for the specimen head portion of the heat ABE of JIS SUS 304HTB. 10 5 1 Particle size of M23C6 carbide [ m ] Temperature [°C] 800 } 4 No precipitation M23C6 on grain boundary M23C6 M23C6+s on grain boundary M23C6+s s on grain boundary 850 W C Fig. 289. Stress vs. time to rupture and creep fracture modes for the heats ABA (left) and ABE (right) of JIS SUS304HTB. 900 heat B 40 Stress [kgf /mm 2 ] 600 °C 625 °C 650 °C 675 °C W heat A 40 10-2 10-1 1 10 10 3 10 2 Time [ h] 10 4 10 5 10 6 Fig. 291. Mean size of M23C6 carbides in the specimen head portion of crept specimens under no stress as a function of time. Specimen: heat ABE of JIS SUS 304HTB. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 219 Area fraction [ %] The size, area fraction and number density of the σ phase on grain boundaries as a function of time are shown in Fig. 292. Although the σ phase was observed to have irregular shapes, the particle was assumed to be spherical having equal volume and the diameter of the sphere was regarded as the size of σ phase. The area fraction, corresponding to the amount of precipitated σ phase, is much larger in the gauge portion than in the head portion, indicating an acceleration effect of stress and/or strain on the σ phase precipitation. In the head portion under no stress, the number of σ phase particles significantly increases with time, while the size increases only slightly. In the gauge portion under stress, on the other hand, the number density of σ phase particles decreases or is constant with time, while the size significantly increases with time. These results indicate that the rate-determining process of the precipitation of the σ phase on grain boundaries is mainly the nucleation at new sites in the head portion under no stress. However, in the gauge portion under stress, the nucleation is almost completed in the initial stage of precipitation and the major process of precipitation is the growth. The available nucleation sites are restricted to grain boundaries perpendicular to stress direction in the gauge portion, while all grain boundaries are available for the nucleation in the head portion. 10 s phase on grain boundary 600 °C open:specimen head 650 °C solid:specimen gauge 700 °C 1 Number density [mm-2 ] 10 -1 104 8 6 4 2 103 Particle size [mm 2 ] 102 10 1 10 -1 104 Fig. 292. Area fraction, number density and particle size of σ phase on grain boundaries in the heat ABE, as a function of time. 2 4 6 8 105 Time [h] 2.4.1.7.3 Creep voids in 18Cr-8Ni austenitic steel The creep voids were observed to form during creep, which is more significant at lower stress and longer time conditions. The area fraction and number density of creep voids were measured on the SEM micrographs, after interruption of the creep tests at several creep strains. The development of creep voids Landolt-Börnstein New Series VIII/2B 220 2.4 Austenitic stainless steels during creep is shown in Fig. 293, as a function of time normalized by time to rupture tr. The creep voids form at the later stage of creep substantially above t/tr = 0.5 and significantly develop just before creeprupture above t/tr = 0.9. The creep voids were observed to form at the interface between the σ phase on grain boundaries and austenite matrix, reflecting the σ/matrix interface cracking along grain boundaries shown in the creep fracture mode diagram in Fig 289. 0.06 Area fraction of creep void [%] Area fraction 0.05 750 °C, 37 MPa, t r = 26500.7h 700 °C, 53 MPa, t r = 29289.5h 650 °C, 61 MPa, t r = 100491.4h 0.04 0.03 0.02 0.3 0.01 0.4 0.5 0.6 0.7 0.8 Life consumption rate t/tr 0.9 1.0 0 Number density of creep void [mm-2 ] 100 Number density 80 60 40 Fig. 293. A parameter, area fraction and number density of creep voids in the heat ABE of JIS SUS304HTB, as a function of t/tr. The A parameter is defined as the fraction of grain boundaries on which creep voids have formed. 20 0 0.3 0.4 0.5 0.6 0.7 0.8 Life consumption rate t /tr 0.9 1.0 2.4.1.7.4 Change in hardness of 18Cr-8Ni austenitic steel Fig. 294 shows the Vickers hardness of the specimen head portion under no stress and of the specimen gauge portion under stress of the heat ABE, as a function of time. The Vickers hardness in as-received condition was 160. The specimen head portion under no stress exhibits two step age hardening: shortterm age hardening for times less than 103 h and long-term age hardening for times above 104 h. The short-term and long-term age hardening results from the precipitation of M23C6 carbides and σ phase, respectively. In the gauge portion of creep-ruptured specimens, the hardness decreases with time for all temperatures, except for 600 °C where it has an increasing tendency at long times above 104 h. The change in hardness with time for the gauge portion results from the change in dislocation density produced by creep deformation as well as from precipitation hardening due to M23C6 carbides and σ phase, as described above. It should be noted that the solid lines in Fig. 294 are connecting the data points Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 221 for the creep-ruptured specimens which were tested at different stress levels as shown in Fig. 289. In general, resultant dislocation density and resultant dislocation arrangements in the specimens are strongly influenced by stress level and test duration in the creep rupture testing. This suggests that the solid lines in Fig. 293 cannot represent the test duration dependence alone but that they also involve the effect of stress level. In order to exclude a possible influence of stress level, the change in hardness was measured as a function of time during creep at a constant load condition [14]. The creep tests were carried out at 650 °C and at three different stress levels, 177, 118 and 61 MPa at which the time to rupture tr was 71.9, 2621.3 and 100491.4 h, respectively. The creep tests were interrupted at several strains as indicated by the arrows in Fig. 295 using different specimens and then the hardness was measured. Fig. 296 shows the change in hardness during creep as functions of time and normalized time t/tr. In this figure, the hardness in the specimen head portion under no stress is also shown by the dotted line for comparison. The hardening behavior during creep at 650 °C depends on stress levels as well as on the precipitation of M23C6 carbides and σ phase. At a high stress of 177 MPa, the hardness increases up to t/tr = 0.7, then decreases slightly and again increases just before creep-rupture. The hardening during creep is much larger than the age hardening, indicating that the hardening during creep is mainly caused by strain hardening. Strain hardening disappears with decreasing stress and increasing test duration. At a low stress of 61 MPa, hardening during creep is approximately the same as age hardening for almost the whole range of test duration except for the final stage of creep where softening occurs similar as at 118 MPa. This suggests that hardening during creep is determined substantially by precipitation hardening due to M23C6 carbides at short times and due to σ phase at long times above 105 h. For estimating material degradation or remaining life for JIS SUS 304HTB austenitic steel components, which are usually operated under stress presumably less than 61 MPa, the hardness can be approximated by age hardening under no stress, except for the final stage just before creep-rupture. Fig. 294 and 295, see next page. a 240 650 °C, 177 MPa, tr = 71.9 h 650 °C, 118 MPa, tr = 2621.3 h 650 °C, 61 MPa, tr = 100491.4 h 650 °C, thermal aging as-received 220 200 Vickers hardness [HV5 ] 180 160 10 2 0 10 10 3 Time [h] 10 5 10 4 240 b 220 200 180 160 0 Landolt-Börnstein New Series VIII/2B 0.2 0.4 0.6 Normalized time t /t r 0.8 1.0 Fig. 296. Vickers hardness of the heat ABE of JIS SUS 304HTB during creep, as functions of (a) time and (b) normalized time t/tr at 650 oC. 222 2.4 Austenitic stainless steels 260 240 220 200 ruptured 650 °C, 177 MPa, t r = 71.9 h 0.40 specimen head as-received 550 °C 600 °C 650 °C 700 °C 750 °C 0.30 0.20 Vickers hardness [HV5 ] 180 160 0.10 :interrupted times 140 0 120 260 0 0.30 specimen gauge 10 20 30 40 50 70 80 ruptured 650 °C, 118 MPa, t r = 2621.3 h 240 60 0.25 Creep strain 220 200 180 0.20 0.15 160 0.10 140 0.05 120 0 10 10 2 10 3 Time [h] 10 4 10 5 10 6 Fig. 294. Vickers hardness of the specimen head and gauge portions of the heat ABE of JIS SUS304HTB, as a function of time. 0 0 500 1000 1500 2000 2500 3000 0.20 650 °C, 61 MPa, tr = 100491.4 h ruptured 0.15 0.10 → Fig. 295. Creep curves of the heat ABE of SUS 304HTB at 177, 118 and 61 MPa at 650 °C. 0.05 0 0 20000 40000 60000 80000 100000 120000 Time [h] 2.4.1.7.5 Heat-to-heat variation in creep rupture strength of 18Cr-8Ni austenitic steel The heat-to-heat variation in long term creep rupture strength has been investigated for JIS SUS 304HTB steel in order to clarify the correlation between long term creep rupture strength and minor elements [12, 15]. The materials examined were the 9 heats of JIS SUS 304HTB. As given in [3], the concentrations of impurities, such as Mo, Ti, Al and N, are widely different among the 9 heats. Fig. 297 shows their creep rupture data at 600 and 700 °C. At a low temperature of 600 °C, the heat-to-heat variation in time to rupture is very large over the whole stress range examined. The time to rupture of the heat ABL, which is the strongest of the steels at 600 °C, is about 10 times longer than that of the heat ABD, which is the weakest one. It should be noted that the heat-to-heat variation is not caused by data scattering, because each heat exhibits distinct stress dependence of time to rupture. At a high temperature of 700 °C, the heatto-heat variation in time to rupture is not large at high stress and short time conditions less than 104 h but it becomes more significant again with increasing test duration at low stress and time conditions longer than 104 h. Austenite grain size and hardness were not different so much among the 9 heats in as-received condition. The concentrations of major alloying elements C, Si, Mn, Ni and Cr were also not different among the 9 heats. Therefore, these parameters are excluded as main explanation of the observed heat-toheat variation in time to rupture. It has been well known for ferritic and austenitic heat resistant steels that nitrogen causes a beneficial effect on the long-term creep rupture strength but that Al causes a Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 223 deteriorative effect. Proposed mechanisms responsible for reducing creep resistance by Al are the reduction of dissolved nitrogen or fine vanadium nitrides by the formation of large AlN, the refinement of grain size, the change in distribution of NbN and M23C6, leaving precipitation-free regions around AlN, and the promotion of grain boundary cracks associated with AlN at grain boundaries [17-20]. Al is a stronger nitride forming element than Cr, V ad Nb. 200 ABA ABB ABC ABD ABE ABF ABL ABM ABN 100 80 60 10 2 10 3 10 4 Tim e to rupture ( h ) 10 SUS 304H o 700 C 100 Stress ( MPa ) Stress ( MPa ) 150 SUS 304H o 600 C 300 5 80 ABA ABB ABC ABD ABE ABF ABL ABM ABN 60 40 25 10 2 10 3 10 4 10 5 Time to rupture ( h ) Fig. 297. Creep rupture data for the 9 heats of SUS 304HTB at 600 and 700 °C. Fig. 298 shows the time to rupture of the 9 heats at 600 °C-137 MPa and 700 °C-47 MPa, as a function of Al content, where the 105 h-data are included. The content of Al is high only in the heat ABA (0.047 mass %) while it is low (0.010 to 0.015 mass %) and not substantially different among the other heats. In Fig. 298 there is no distinct relationship between the time to rupture and the content of Al, while the time to rupture differs widely from about 104 h to about 105 h at approximately the same content of Al of 0.010 to 0.015 mass %. This suggests other factors as well as Al can affect the time to rupture. Titanium is also known to form large nitrides during the manufacturing process, because it is a strong nitride forming element. Fig. 299 shows the time to rupture of the 9 heats at 700 °C, as a function of available nitrogen concentration which is defined as the concentration of nitrogen free from AlN and TiN and is given by Nav = Nt − Al – Ti (1) where Nt is the total amount of nitrogen in the steel, Al and Ti are the content of Al and Ti in the steel in at %. The formation of stoichiometric compounds AlN and TiN is assumed. The time to rupture simply increases with increasing of Nav at long times above 104 h at 700 °C, while the dependence of Nav is split into two lines having approximately the same slope at short times. The line with longer time to rupture among the two split lines represents the data for the heats ABA, ABL, ABM and ABN, which contain more (Nb+Ta) than the other heats. The presented results indicate that precipitation strengthening due to Nb-carbides is effective at short times. Fig. 300 shows the extremely fine distribution of Nb-carbides in the heat ABN (6064.8 h) of SUS 304 HTB steel, after creep rupture testing at 650 °C and 137 MPa. Fig. 301 compares stress vs. time to rupture of the heats with different contents of (Nb+Ta) but the same amounts of Nav at an intermediate temperature of 650 °C. The difference in time to rupture between the two heats with high and low contents of (Nb+Ta) disappears with increasing test duration, because of agglomeration of Nb-carbides during creep. The time to rupture is substantially the same between the heats with the same amount of Nav at about 105 h. At long times, the heat-to-heat variation in time to rupture is explained by the variation in Nav. Landolt-Börnstein New Series VIII/2B 224 2.4 Austenitic stainless steels 5 10 SUSo 304 HTB 105 700 C o 600 C, 137 MPa o 700 C, 47 MPa 104 0 0.01 0.02 0.03 0.04 Time to Rupture, t / h Time to Rupture, t / h SUS 304 HTB 3 10 47 MPa 69 MPa 98 MPa 102 0.05 0 0.04 0.08 0.12 Available Nitrogen Concentration (at %) Total Al Content ( mass % ) Fig. 298. Time to rupture of the 9 heats of SUS 304HTB, as a function of Al content. 4 10 Fig. 299. Time to rupture for SUS 304 HTB steel at 700 °C as a function of available nitrogen concentration defined by Nav = N−Al−Ti, where the concentrations are in at %. Fe b Intensity I Cr Ni Nb Fig. 300. (a) TEM micrograph and (b) EDX analysis of the heat ABN (6064.8 h) of JIS SUS 304 HTB steel, after creep rupture testing at 650 °C and 137 MPa, showing the precipitation of extremely fine Nbcarbonitrides. Nb V 0 10.240 Energy E [keV] 20.470 Fig. 302 shows schematic drawings of the difference in time to rupture between the heats with high and low (Nb+Ta) and between the heats with high and low available nitrogen concentrations Nav. The first increase in heat-to-heat variation with increasing test duration, which is more pronounced at a lower temperature of 600 °C, is caused by precipitation strengthening due to very fine Nb-carbides having a size of 10 nm or less. The precipitation strengthening due to Nb-carbides disappears by about 105 h at 650 °C, because of their agglomeration during creep. This causes the reduction of heat-to-heat variation. The second increase in heat-to-heat variation at long times is more pronounced at a higher temperature of 700 °C and at long times above 104 h, but it does not appear at 600 °C for up to 105 h. The available nitrogen concentration, defined as the concentration of nitrogen free from AlN and TiN, clearly explains the second heat-to-heat variation. Accelerated void formation in the heat ABA containing Al as high as 0.047 mass% also decreases the creep strength at long times. Landolt-Börnstein New Series VIII/2B Ref. p. 225] 2.4.1 18Cr-8Ni steel 225 200 SUS 304 HTB o 650 C (a) Stress, σ / MPa 100 90 N AV 80 = 0.043 - 0.044 (at %) heat ABC, 0.36 Mo, 0.01 Nb+Ta heat ABN, 0.31 Mo, 0.04 Nb+Ta 70 60 200 (b) 100 90 N AV 80 heat ABD, 0.06 Mo, 0.01 Nb+Ta 70 heat ABM, 0.32 Mo, 0.03 Nb+Ta 60 10 Fig. 301. Stress vs. time to rupture at 650 °C for (a) the heats ABC and ABN with available nitrogen concentration of 0.043-0.044 at % and for (b) the heats ABD and ABM with available nitrogen concentration of 0.092 at %. = 0.092 (at %) 10 2 3 10 4 5 10 10 Logarithm of time to rupture Time to Rupture, t / h Nav : available nitrogen concentration Nav = N - Al(sol) - Ti (at %) Middle Nav High Nb+Ta High Nav Middle Nav Low Nb+Ta Middle Nav Low Nav Low temp. & short time Fig. 302. Schematic drawings showing the difference in time to rupture between the heats with high and low Nb+Ta and between the heats with high and low Nav. High temp. & long time 2.4.1.8 References [1] Sourmail, T.: Material Science and Technology, 17 (2001), 1-14. [2] Pickering, F.B.: in ‘Stainless steels 84’, The Institute of Metals, London (1985), pp.2-28. [3] National Research Institute for Metals (NRIM) Creep Data Sheet, No.4B, (1986) for 18Cr-8Ni stainless steel, JIS SUS 304H TB. [4] National Research Institute for Metals (NRIM) Creep Data Sheet, No.32A, (1995) for 18Cr-8Ni stainless steel, JIS SUS 304-HP. [5] ASTM Data Series Publication DS 5-S1, (1965) [6] Elevated temperature properties for steels for pressure purpose, Part I, British Standards Institution (BSI), (1990) Landolt-Börnstein New Series VIII/2B 226 2.4 Austenitic stainless steels [7] Shinya, N., Kyono, J., Tanaka, H., Murata, M. and Yokoi, S.: Tetsu to Hagane, 69 (1983) 16681675. [8] Shinya, N., Tanaka, H., Murata, M., Kaise, M. and Yokoi, S.: Tetsu to Hagane, 71 (1985) 114-120. [9] Tanaka, H., Murata, M., Kaise, M. and Shinya, N.: Tetsu to Hagane, 74 (1988) 2009-2016. [10] Biss, V. A. and Sikka, V. K.: Metall. Trans. 12A (1981), 1360-1362. [11] Minami, Y., Kimura, H. and Ihara, Y.: Mater. Sci. Technol. 2 (1986), 795-806. [12] Murata, M., Tanaka, H., Abe, F. and Irie, H.: Key Engineering Materials, Trans Tech Publications, Switzerland, 171-174 (2000), 513-520. [13] Abe, F., Tanaka, H., Murata, H., Irie, H. and Yagi, K.: Proc. 4th Japan-China Bilateral Symposium on High Temperature Strength of Materials, Tsukuba, Japan, (2001), 83-88. [14] National Research Institute for Metals Creep Data Sheet, Metallographic Atlas of Long-Term Crept Materials, Nat. Res. Inst. for Metals, Tsukuba, No.M-1 (1999). [15] Tanaka, H., Murata, M., Abe, F. and Irie, H.: Materials Science and Engineering, A319 (2001) 788791. [16] Miyazaki, H., Tanaka, H., Murata, M. and Abe, F.: J. Japan Institute of Metals, 66 (2002), 12781286. [17] Yukitoshi. T. and Nishida, K.: Trans. ISIJ, 12 (1972) 429-434. [18] Shinya, N., Kyono, J., Tanaka, H., Murata, M. and Yokoi, S.: Tetsu-To-Hagane, 69 (1983) 16681675. [19] Schirra, M. and Anderko, K.: Steel Research, 61 (1990) 242-250. [20] Naoi, H., Ohgami, M., Liu, X. and Fujita, T.: Metall. Trans., 28A (1997) 1195-1203. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 227 2.4.2 18Cr-12Ni-Mo steel 2.4.2.1 Introduction The molybdenum-containing AISI type 316 (SUS316HTB, SUS316-HP, SUS316-B, X2CrNiMo17-12-2, X5CrNiMo17-12-2, X6CrNiMoTi17-12-2, X2CrNiMoN17-13-3, X2CrNiMo17-12-2, SS 2343, X3CrNiMoBN17-13-3) stainless steel has been used within the power-generating industry. A common usage is as superheater tubing exposed to high temperatures of 650 °C or higher [1]. It has higher creep strength than the unstabilized molybdenum-free AISI type 304 steel and better resistance to heat-affected zone cracking during welding than the niobium- and titanium-stabilized grades, i.e. AISI types 347 and 321. However, in some circumstances it can become embrittled after prolonged exposure at elevated temperatures as a result of the formation of carbide and intermetallic phases. Moreover, it is now known that large cast-to-cast variations exist in this grade of steel. Its long-term ductility can vary from below 10 % to over 100 %. The demand of high reliability in modern plants, especially nuclear, requires a substantial reduction in material variability. 2.4.2.2 Materials standards, and chemical and tensile requirements 2.4.2.2.1 18Cr-12Ni-Mo stainless steel tubes for boilers and heat exchangers Table 138. Chemical and tensile requirements for 18Cr-12 Ni-Mo stainless heat exchangers; JIS SUS 316 HTB, ASTM TP 316 H, BS 316 S 33. Chemical composition [wt%] StanDesignation dard C Si Mn P S Ni JIS SUS 316 0.04<0.75 <2.00 <0.040 <0.030 11.00HTB 0.10 14.00 ASTM TP 316 H 0.04<0.75 <2.00 <0.040 <0.030 11.00.10 14.0 ASTM TP 316 H 0.04<0.75 <2.00 <0.040 <0.030 11.00.10 14.0 BS 316 S 33 <0.07 1.00 <2.00 <0.040 <0.030 11.014.0 Standard JIS Designation Yield strength [MPa] SUS 316 >205 HTB ASTM TP 316 H >205 ASTM TP 316 H >205 BS 316 S 33 >245 Landolt-Börnstein New Series VIII/2B Tensile Std. strength [MPa] No. >520 G3463 >515 >515 410-710 A213 A249 3606 steel tubes for boilers and Cr 16.0018.00 16.018.0 16.018.0 16.5018.50 Mo 2.003.00 2.003.00 2.003.00 2.503.00 Std. No. G3463 A213 A249 3606 228 2.4 Austenitic stainless steels 2.4.2.2.2 18Cr-12Ni-Mo stainless steel plates Table 139. Chemical and tensile requirements for 18Cr-8 Ni stainless steel plates; JIS SUS ASTM S 31600, BS 316 S 31, DIN X5CrNi 17122, ISO L-No.26 X5CrNiMo 17-22-2. Chemical composition [wt%] StanDesignation dard C Si Mn P S Ni Cr Mo N JIS SUS 316<0.08 <1.00 <2.00 <0.045 <0.030 11.00- 16.00- 2.00HP 14.00 18.00 3.00 ASTM S 31600 0.04- <0.75 <2.00 <0.040 <0.030 11.00- 16.0- 2.00- <0.1 0.10 14.00 18.0 3.00 BS 316 S 31 0.04- <0.75 <2.00 <0.040 <0.030 10.5- 16.0- 2.00.10 13.5 18.0 2.5 DIN X5CrNiMo <0.07 <1.00 <2.00 <0.040 <0.030 10.5- 16.50- 2.017122 13.5 18.50 2.5 ISO L-No26 <0.07 <1.00 <2.00 <0.045 <0.030 10.0- 16.0- 2.0<0.11 X5CrNiMo 13.0 18.0 3.0 17-12-2 Standard JIS ASTM BS DIN ISO Designation SUS 316-HP S 31600 316 S 31 X5CrNiMo 17122 L-No26 X5CrNiMo 17-12-2 Yield strength [MPa] >206 >205 Tensile strength [MPa] >520 >515 316-HP, Std. No. G4304 A240, A666 1449-2 17441 Std. No. G4304 A240, A666 1449-2 17441 2.4.2.2.3 18Cr-12Ni-Mo stainless steel bars Table 140. Chemical and tensile requirements for 18Cr-8 Ni stainless steel bars; JIS SUS 316-B, ASTM S 31600, BS 316 S 31, DIN X5CrNi 17122, ISO L-No.26 X5CrNiMo 17-22-2. Chemical composition [wt%] StanDesignation Std. dard No. C Si Mn P S Ni Cr Mo N JIS SUS 316-B <0.08 <1.00 <2.00 <0.045 <0.030 11.00- 16.00- 2.00G4303 14.00 18.00 3.00 ASTM S 31600 0.04- <0.75 <2.00 <0.040 <0.030 11.00- 16.0- 2.00- <0.1 A276, 0.10 14.00 18.0 3.00 A493 BS 316 S 31 0.04- <0.75 <2.00 <0.040 <0.030 10.5- 16.0- 2.00.10 13.5 18.0 2.5 DIN X5CrNiMo <0.07 <1.00 <2.00 <0.040 <0.030 10.5- 16.50- 2.01654-5 17122 13.5 18.50 2.5 ISO L-No26 <0.07 <1.00 <2.00 <0.045 <0.030 10.0- 16.0- 2.0<0.11 X5CrNiMo 13.0 18.0 3.0 17-12-2 Standard JIS ASTM BS DIN ISO Designation SUS 316-HP S 31600 316 S 31 X5CrNiMo 17122 L-No26 X5CrNiMo 17-12-2 Yield strength [MPa] >206 >205 Tensile strength [MPa] >520 >515 Std. No. G4304 A240, A666 1449-2 17441 Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 229 2.4.2.3 Data sources for 18Cr-12Ni-Mo stainless steel Information of fact on data for 18Cr-12Ni-Mo stainless steel can be obtained from [2], [3], [5] and [6]. 2.4.2.4 Creep rupture data for 18Cr-12Ni-Mo stainless steel for boiler and heat exchanger seamless steel tubes, JIS SUS 316H TB 2.4.2.4.1 Creep and creep rupture data for 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316H TB The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area, minimum creep rate and optical micrographs of as-received and crept specimens, has been obtained for 9 heats in [2]. The details of steel tube production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for each heat in [2]. The tensile and creep specimens used in [2], having a geometry of 6 mm in diameter and 30 mm in gauge length, were taken longitudinally from the middle of wall thickness of the tubes. Fig. 303 shows the 0.2% proof stress and tensile strength obtained by short-time tensile tests between room temperature and 750 °C. Fig. 304 (next page) shows the stress vs. time to rupture data for the 9 heats of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB, at temperatures between 600 and 750 °C. The fact data are available in [2]. Tensile strength 0.2% proof stress 700 700 600 600 400 Stress (MPa) Stress (MPa) 500 300 500 400 200 300 100 0 0 100 200 300 400 500 600 Test temperature (℃) 700 800 200 0 100 200 300 400 500 600 700 800 Test temperature (℃) Fig. 303. Short-time tensile properties of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB. 2.4.2.4.2 Estimated long-term creep rupture strength for 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316H TB The creep rupture data shown in Fig. 304 were analyzed for each heat using the Manson-Haferd parameter method. Fig. 305 shows the estimated 105 h creep rupture strength for the 9 heats as a function of temperature. In this figure, the 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength are also included. Landolt-Börnstein New Series VIII/2B 230 2.4 Austenitic stainless steels 500 400 300 600 °C 650 °C 700 °C 750 °C Stress [MPa] 200 100 80 60 50 40 30 20 n = 319 10 3 10 4 Time to rupture [h] 10 5 800 600 500 400 300 Stress [MPa] 200 100 80 60 50 40 30 0.2% proof stress 10 6 1000 h 20 10 550 Tensile strength { 10 2 { 10 10 Fig. 304. Creep rupture strength data for 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB. n indicates the total number of data points. 100000 h 600 700 650 Temperature [°C] 750 800 Fig. 305. Estimated 105 h creep rupture strength for the 9 heats of 18Cr-12Ni-Mo stainless steel tube, JIS SUS 316 HTB. 2.4.2.4.3 Creep strain data of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316H TB [2] contains the creep strain data for the heat AAL of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB. The stress vs. time to reach 0.5, 1, 2 and 5 % total strain, time to tertiary creep and time to rupture are obtained from [2]. The total strain is defined as instantaneous strain and creep strain, which are produced at loading and during creep, respectively. The relationship between stress and minimum creep rate is shown in Fig. 306. The relationship between time to rupture and minimum creep rate is shown in Fig. 307. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 231 Fig. 306. Stress vs. minimum creep rate for the heat AAL of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB at 600, 650, 700 and 750 °C. n indicates the total number of data points. Fig. 307. Time to rupture vs. minimum creep rate for the heat AAL of 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316 HTB at 600, 650, 700 and 750 °C. n indicates the total number of data points. 2.4.2.5 Creep rupture data for 18Cr-12Ni-Mo stainless steel plates for reactor vessels, JIS SUS 316HP 2.4.2.5.1 Creep rupture data for 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area, minimum creep rate and optical micrographs of as-received and crept specimens, has been obtained for 2 heats in [3]. The details of steel plate production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for each heat in [3]. The details of plate production and the chemical compositions, respectively, of the 2 heats of 18Cr12Ni-Mo stainless steel plates, JIS SUS316-HP, are given in [3]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 50 mm in gauge length, were taken longitudinally from the middle of thickness of the plates. Fig. 308 shows the 0.2% proof stress and tensile strength obtained by shorttime tensile tests between room temperature and 850 °C. Fig. 309 shows the stress vs. time to rupture data for the 2 heats of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP, at temperatures between 600 and 850 °C. The fact data are available in [3]. Landolt-Börnstein New Series VIII/2B 232 2.4 Austenitic stainless steels Tensile strength 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 600 300 200 200 100 100 0 300 0 200 400 600 800 0 1000 0 200 Test temperature (℃) 400 600 800 1000 Test temperature (℃) Fig. 308. Short-time tensile properties of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP. 50 0 o 6 00 C 30 0 o 6 50 C o Stress ( MPa ) 700 0 C o 7 50 C o 8 00 C 10 0 80 o 8 50 C 60 40 20 10 1 n = 57 10 2 1 03 10 4 10 5 10 6 Fig. 309. Creep rupture strength data for 18Cr-12NiMo stainless steel plates, JIS SUS 316-HP. n indicates the total number of data points. T ime to rupture ( h ) 2.4.2.5.2 Estimated long-term creep rupture strength for 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP The creep rupture data shown in Fig. 309 were analyzed for each heat using the Manson-Haferd parameter method. Fig. 310 shows the resulting master rupture curve for all data. The 105 h creep rupture strength was also estimated for the 2 heats. This is shown in Fig. 311 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 400 600 °C 625 °C 650 °C 675 °C 700 °C 750 °C 775 °C 800 °C 850 °C 300 200 Stress [MPa] 233 100 80 60 50 40 30 Fig. 310. Master rupture curve based on the MansonHaferd parameter method for the 2 heats of 18Cr-12NiMo stainless steel plates, JIS SUS 316-HP. n indicates the total number of data points. 20 Average n = 60 10 -4.0 -1.0 -5.0 -3.0 -2.0 Manson-Haferd parameter [( log tR -9.223)/( TK - 720 )] [×10 - 2 ] 500 400 300 200 { Stress [MPa] { 100 80 60 50 40 1000 h 30 20 500 Tensile strength 0.2% proof stress 100000 h 550 600 750 700 650 Temperature [°C] 800 850 900 Fig. 311. Estimated 105 h creep rupture strength for the 2 heats of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP. 2.4.2.5.3 Creep strain data of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP [3] contains creep strain data for 2 heats of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP. The stress vs. time to reach 0.5, 1, 2 and 5 % total strain, time to tertiary creep and time to rupture for the AaA heat can also be obtained from [3]. The total strain is defined as instantaneous strain and creep strain, which are produced at loading and during creep, respectively. The relationship between stress and minimum creep rate is shown Fig. 312. The relationship between time to rupture and minimum creep rate is shown in Fig. 303. Landolt-Börnstein New Series VIII/2B 234 2.4 Austenitic stainless steels 300 Stress [MPa] 200 100 80 600 °C 60 50 650 °C 40 30 700 °C 20 750 °C 800 °C 850 °C n = 28 10 8 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 600 °C 625 °C 650 °C 675 °C 700 °C 750°C 775 °C 800 °C 850 °C 10 -1 Fig. 312. Stress vs. minimum creep rate for the heats AaA and AaB of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP at 600, 650, 700, 750, 800 and 850 °C. n indicates the total number of data points. 1 10 6 600 °C 625 °C 650 °C 675 °C 700 °C 750°C 775 °C 800 °C 850 °C Time to rupture [h] 10 5 10 4 10 3 Fig. 313. Time to rupture vs. minimum creep rate for the heats AaA and AaB of 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP at at 600, 650, 700, 750, 800 and 850 °C. n indicates the total number of data points. 10 2 n = 28 10 1 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 -1 1 2.4.2.6 Creep rupture data for 18Cr-12Ni-Mo-middle nitrogen-low carbon stainless steel plates, JIS SUS 316-HP The creep rupture data, such as creep rupture time, total elongation and reduction of area, and optical micrographs of as-received specimens, have been obtained for one heat in [4]. The details of steel plate production, processing, thermal history, austenite grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical composition, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available in [4]. Fig. 314 shows the 0.2% proof stress and tensile strength of the 1 heat of 18Cr-12Ni-Mo-middle nitrogen-low carbon stainless steel plates, JIS SUS316-HP , obtained by short-time tensile tests between room temperature and 800 °C; [4]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 50 mm in gauge length, were taken longitudinally from the middle of plates. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 235 Tensile strength 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 600 300 200 300 200 100 100 0 0 0 200 400 600 800 1000 0 200 400 600 800 1000 Test temperature (℃) Test temperature (℃) Fig. 314. Short-time tensile properties of 18Cr-12Ni-Mo-middle nitrogen-low carbon stainless steel plates, JIS SUS 316-HP. Fig. 315 shows the stress vs. time to rupture data for 18Cr-12Ni-Mo-middle nitrogen-low carbon stainless steel plates, JIS SUS 316-HP, at temperatures between 500 and 750 °C. The fact data are available in [4]. Stress ( MPa) 1000 100 o 50 0 C o 55 0 C Fig. 315. Creep rupture strength data for 18Cr-12NiMo-middle nitrogen-low carbon stainless steel plate, JIS SUS 316-HP. o 60 0 C o 65 0 C 70 0oC o 10 10 75 0 C 2 3 4 10 10 10 Time to rupture ( h ) 5 10 2.4.2.7 Creep rupture data for 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B 2.4.2.7.1 Creep rupture data The complete set of creep and creep rupture data, such as creep rupture time, total elongation, reduction of area, minimum creep rate and optical micrographs of as-received and crept specimens, has been obtained for the 6 heats in [5]. The details of steel bar production, processing, thermal history, austenite Landolt-Börnstein New Series VIII/2B 236 2.4 Austenitic stainless steels grain size number, Rockwell hardness and volume fraction of non-metallic inclusions before creep test, the chemical compositions, the 0.2% proof stress and ultimate tensile strength data at high temperature are also available for each heat in [5]. Fig. 316 shows the 0.2% proof stress and tensile strength of the 6 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS316-B obtained by short-time tensile tests between room temperature and 850 °C; [5]. The tensile and creep specimens, having a geometry of 10 mm in diameter and 50 mm in gauge length, were taken longitudinally from the middle of bars. Fig. 317 shows the stress vs. time to rupture data for the 6 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B, at temperatures between 600 and 850 °C. The fact data are available in [5]. Tensile strength 700 600 600 500 500 400 400 Stress (MPa) Stress (MPa) 0.2% proof stress 700 300 300 200 200 100 100 0 0 200 400 600 800 0 1000 0 200 Test temperature (℃) 400 600 800 1000 Test temperature (℃) Fig. 316. Short-time tensile properties of 18Cr-12Ni-Mo-middle nitrogen-low carbon stainless steel plates, JIS SUS 316-HP. 50 0 o 60 0 C o 30 0 65 0 C o Stress ( MPa ) 70 0 C o 75 0 C o 80 0 C o 10 0 80 85 0 C 60 Fig. 317. Creep rupture strength data for 18Cr-12NiMo stainless steel bars, JIS SUS 316-B. n indicates the total number of data points. 40 n = 1 66 20 10 1 10 2 3 10 10 4 10 5 T ime to rupture ( h ) Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 237 2.4.2.7.2 Estimated long-term creep rupture strength for 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B The creep rupture data shown in Fig. 317 were analyzed for each heat using the Manson-Haferd parameter method. Fig. 318 shows the resulting master rupture curve for all data. The 105 h creep rupture strength was also estimated for the 6 heats. This is shown in Fig. 319 as a function of temperature, together with 0.2% proof stress, ultimate tensile strength and 103 h creep rupture strength. 400 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 300 Stress [MPa] 200 100 80 60 50 40 30 Fig. 318. Master rupture curve based on the MansonHaferd parameter method for the 6 heats of 18Cr-12NiMo stainless steel bars, JIS SUS 316-B. n indicates the total number of data points. 20 Average n = 166 10 -1.0 -4.0 -2.0 -5.0 -3.0 Manson-Haferd parameter [( log tR -8.447)/( TK - 720 )] [×10 - 2 ] 500 400 300 200 { Stress [MPa] { 100 80 60 50 40 30 1000 h 20 10 500 Tensile strength 0.2% proof stress 100000 h 550 600 650 750 700 Temperature [°C] 800 850 900 Fig. 319. Estimated 105 h creep rupture strength for the 9 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B. 2.4.2.7.3 Creep strain data of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B [5] contains creep strain data for 6 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B. The stress vs. time to reach 0.5, 1, 2 and 5 % total strain, time to tertiary creep and time to rupture are obtained from [5]. The relationship between stress and minimum creep rate is shown in Fig. 320. The relationship between time to rupture and minimum creep rate is shown in Fig. 321. Landolt-Börnstein New Series VIII/2B 238 2.4 Austenitic stainless steels 300 200 Stress [MPa] 600 °C 100 80 60 50 40 700 °C 650 °C 30 20 750 °C 800 °C 850 °C 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C Fig. 320. Stress vs. minimum creep rate for the 6 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B at 600, 650, 700, 750, 800 and 850 °C. n indicates the total number of data points. n = 68 10 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 6 1 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 10 5 Time to rupture [h] 10 -1 10 4 10 3 10 2 n = 68 10 1 10 -7 10 -6 10 -4 10 -5 10 -3 Minimum creep rate [%/h] 10 -2 10 -1 Fig. 321. Time to rupture vs. minimum creep rate for the 6 heats of 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B at 600, 650, 700, 750, 800 and 850 °C. n indicates the total number of data points. 2.4.2.8 Microstructure data of 18Cr-12Ni-Mo stainless steel 2.4.2.8.1 Creep fracture modes of JIS SUS316HTB steel The creep fracture modes were characterized for the two heats AAF and AAL of JIS SUS316HTB steel [2] by analysis of the microstructure near the fracture portion [7-9]. This is shown in Fig. 322. The heat AAF contained a high Al concentration (0.095 wt% Al), while the heat AAF contained a low Al concentration (0.017 wt% Al). The microstructure observations by optical, scanning and transmission electron microscopes were carried out on the longitudinal cross-section of the specimens after creeprupture. The creep fracture modes are divided to transgranular fracture (denoted by T) and three types of intergranular fracture: the wedge-type cracking at triple point (denoted by W), the intergranular cavitation associated with M23C6 carbides at grain boundaries (denoted by C ) and the σ/matrix interface cracking along grain boundaries (denoted by σ), as shown in Fig. 322. The results suggest that the creep fracture modes at long times above 104 h are closely connected with the precipitation behavior of M23C6 carbides and σ phase. The precipitation of M23C6 carbides at grain boundaries promotes the transition from wedgetype cracking to intergranular cavitation, and the precipitation of σ phase at grain boundaries leads to the Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 239 σ/matrix interface cracking. Al contents above 0.03 wt% lead to the precipitation of AlN associated with the grain boundary σ phase. The precipitation of AlN accelerates the σ/matrix interface cracking, resulting in the reduction of creep rupture strength and ductility at long times. 30 20 600 °C 700 ° C 10 725 775 800 Stress [kgf / mm2 ] 5 Heat F 625 °C 650 ° C 675 ° C °C °C 75 0° °C C 3 30 600 °C Heat L 650 °C 20 700 ° 10 625 °C 675 ° C 725 ° C C 750 ° C 5 3 Transgranular creep fracture Wedge-type cracking Cavity formation Cracking at s/matrix interface Cracking at c/matrix interface 10 2 775 ° C 10 3 10 4 Time to rupture [h] 10 5 Fig. 322. Stress vs. time to rupture and creep fracture modes for the heats AAF (Heat F) and AAL (Heat L) of JIS SUS316HTB steel. 2.4.2.8.2 Microstructure evolution in JIS SUS3164HTB steel The microstructure evolution during thermal aging under no stress and during creep has been examined by several researchers [10-16] for type 316 stainless steel at temperatures between 600 (873) and 800 °C (1073 K). But these studies are limited to specimens tested in periods not exceeding 6×104 h. Recently, the microstructure evolution during creep and during thermal aging has been comprehensively investigated for SUS 316HTB steel after long-term creep rupture tests over 105 h, using specimens tested in the NIMS Creep Data Sheet Project [8-9]. A number of micrographs were recently published for SUS 316HTB steel as ‘Metallographic Atlas of Long-Term Crept Materials’ [8], parallel with the NIMS Creep Data Sheets. The Metallographic Atlas of Long-Term Crept Materials contains not only series of micrographs showing the microstructure evolution during creep for up to 105 h but also the relating data such as timetemperature-precipitation (TTP) diagrams, histograms describing the distributions of precipitates and creep-voids, and creep damage parameters. The TTP diagram was constructed for the heat AAL, using the head or grip portion of the crept specimens under no stress. This is shown in Fig. 323. Only the M23C6 carbides precipitate in the specimens at short times less than about 103 h at 650 °C but Laves and σ phases also appear at long times above about 103 and 104 h, respectively. The χ phase appears at long times in the temperature range between 750 and 900 °C. The TEM micrographs clearly show that the M23C6 carbides are observed in form of cube-like particles in Widmanstätten distributions in the matrix and in form of chains of enlarged particles along grain boundaries, as shown in Fig. 324. The Laves phase is observed in rod shape in the matrix, while the σ and χ phases are in form of large and irregular shapes on grain boundaries. Landolt-Börnstein New Series VIII/2B 240 2.4 Austenitic stainless steels Fig. 323. Time-Temperature-Precipitation (TTP) diagram for the specimen head portion of the heat AAL of JIS SUS 316HTB steel. Fig. 324. TEM micrographs of the heat AAL of JIS SUS 316HTB steel after aging under no stress. The change in particle size of M23C6 carbides, Laves phase and σ phase is shown as a function of time for the heat AAL of JIS SUS316HTB steel in Fig. 325 and Fig. 326. A series of optical, scanning and transmission electron micrographs are included in the Metallographic Atlas of Long-Term Crept Materials [8]. The area fraction, corresponding to the amount of precipitated σ phase, is much larger in the gauge portion under stress than in the head portion under no stress, indicating an acceleration effect of stress and/or strain on the σ phase precipitation, as shown in Fig. 326. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 241 The concentrations of the major components Cr, Fe, Mo and Ni in the M of M23C6 carbides were measured on extracted replicas by EDX in SEM. The summation of metallic elements is assumed to be 100 %. The results are shown in Fig. 327 as a function of time. At 650 °C, the concentration of Cr increases from about 50 - 55 % at 102 h to about 60 % at 105 h in the specimen head, while that of Fe decreases from 25 % at 102 h to 15 % at 105 h. Because the equilibrium concentration of Cr in the M23C6 carbides is much higher than the concentration of Cr in the matrix, it is considered that at first the M23C6 carbides precipitate with a Cr concentration much lower than the equilibrium one and that the concentration of Cr in the M23C6 carbides gradually increases during exposure at high temperatures toward the equilibrium one. The change in the concentrations of Cr and Fe with time shifts to shorter times with increasing temperature, suggesting a diffusion-controlled process. The change in the concentrations of Cr and Fe with time was accelerated under stress. In the Laves phase and σ phase, the concentrations of Fe, Cr, Mo and Ni do not change so much with time, as shown in Fig. 328 and Fig. 329. There was also no difference in concentrations between the specimen head and gauge portions. The present results indicate that the Laves phase and σ phase, having the equilibrium concentrations of Fe, Cr, Mo and Ni, precipitate from the initial stage. This is quite different from the remarkable change in concentrations for the M23C6 carbides during high temperature exposure. Fig. 325. Change in particle size of (a) M23C6 carbides and (b) Laves phase within grains in specimen head portion as a function of time for the heat AAL of JIS SUS316HTB steel. Landolt-Börnstein New Series VIII/2B 242 2.4 Austenitic stainless steels Fig. 326. Change in area fraction, number density and particle size of σ phase on grain boundaries in specimen head and gauge portions as a function of time for the heat AAL of JIS SUS316HTB steel. 2.4.2.8.3 Change in hardness in JIS SUS3164HTB steel Fig. 330 shows the Vickers hardness of the specimen head portion under no stress and the specimen gauge portion under stress of the heat AAL of JIS SUS316HTB steel, as a function of time. The Vickers hardness in as-received condition was 160. The specimen head portion under no stress exhibits hardening with time for up to 105 h or more, indicating precipitation hardening, although detailed relationship between the hardening and precipitation behavior is not clear. Presumably, the short-term and long-term age hardening results from the precipitation of M23C6 carbides and intermetallic compounds, respectively. The gauge portion of specimens, creep-ruptured at short times less than 103 h, exhibits hardening compared with the as-received condition and the hardness decreases with time for up to 105 h or more. The change in hardness with time for the gauge portion results from the change in dislocation density produced by creep deformation as well as from the precipitation hardening described above. It should be noted that the solid lines in Fig. 330 are connecting the data points for the creep-ruptured specimens which were tested at different stress levels as shown in Fig. 322. In general, resultant dislocation density and resultant dislocation arrangements in the specimens are strongly influenced by stress level and test duration in the creep rupture testing. This suggests that the solid lines in Fig. 330 cannot represent the test duration dependence alone but that they also involve the effect of stress level. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 80 2.4.2 18Cr-12Ni-Mo steel 80 550 °C 60 40 20 Chemical composition of M in M23 C 6 carbide [ %] 600 °C 60 Fe Cr Mo Ni 40 243 20 10 10 10 2 80 650 °C 10 3 10 4 10 5 10 6 10 10 10 2 80 700 °C 60 60 40 40 20 20 10 10 10 2 80 750 °C 10 3 10 4 10 5 10 6 10 10 10 2 10 4 10 5 10 6 10 3 10 4 Time [h] 10 5 10 6 10 3 60 40 Fig. 327. Change in chemical composition of M in M23C6 carbides within grains in specimen head portion as a function of time for the heat AAL of JIS SUS316HTB steel. 20 10 10 50 10 3 10 4 Time [h] 10 2 10 5 10 6 50 550 °C 600 °C 40 30 20 40 Fe Cr Mo Ni 30 20 Chemical composition of Laves phase [ %] 10 10 0 10 10 2 50 650 °C 40 10 3 10 4 10 5 10 6 0 10 50 10 4 10 5 10 6 10 3 10 4 Time [h] 10 5 10 6 10 3 700 °C 40 30 30 20 20 10 10 0 10 10 2 50 750 °C 40 10 2 10 3 10 4 10 5 10 6 0 10 10 2 30 Fig. 328. Change in chemical composition of Laves phase within grains in specimen head portion as a function of time for the heat AAL of JIS SUS316HTB steel. 20 10 0 10 10 2 10 3 10 4 Time [h] Landolt-Börnstein New Series VIII/2B 10 5 10 6 244 60 50 2.4 Austenitic stainless steels 40 30 20 Chemical composition of s phase [ %] 60 550 °C 600 °C 50 Fe Cr Mo Ni 10 0 10 10 2 60 650 °C 50 40 No precipitation 30 20 10 3 10 4 10 5 10 0 10 6 10 60 10 4 10 5 10 6 10 3 10 4 Time [h] 10 5 10 6 10 3 700 °C 50 40 10 2 40 30 30 20 20 10 0 10 10 2 60 750 °C 50 10 3 10 4 10 5 10 0 10 6 10 10 2 40 30 Fig. 329. Change in chemical composition of σ phase within grains in specimen head portion as a function of time for the heat AAL of JIS SUS316HTB steel. 20 10 0 10 10 2 260 10 5 10 6 Specimen head as - received 550 °C 600 °C 650 °C 700 °C 750 °C 240 220 200 180 Vickers hardness [HV5] 10 3 10 4 Time [h] 160 140 120 260 Specimen gauge 240 220 200 180 160 140 120 1 10 10 2 10 4 10 3 Time [h] 10 5 10 6 Fig. 330. Comparison of Vickers hardness for specimens tested at various temperatures, (a) specimen head and (b) gauge portions of the heat AAL of JIS SUS316HTB steel. Landolt-Börnstein New Series VIII/2B Ref. p. 246] 2.4.2 18Cr-12Ni-Mo steel 245 30 650 °C, 88 MPa, t r = 55367.0 h 700 °C, 61 MPa, t r = 34728.8 h 750 °C, 37 MPa, t r = 32781.8 h Creep strain [%] 25 20 15 10 5 Fig. 331. Creep curves and creep-interruption conditions for creep void observations for the heat AAL of JIS SUS316HTB steel. open :interrupted points solid :ruptured points 0 0 10000 20000 30000 40000 Time [h ] 50000 60000 A parameter 0.3 A parameter 750 °C, 37 MPa, t r = 32781.8 h 700 °C, 61 MPa, t r = 34728.8 h 650 °C, 88 MPa, t r = 55367.0 h 0.2 0.1 0 0.04 Area fraction of creep voids [%] Area fraction 0.03 0.02 0.01 0 250 Number density of creep voids [mm2 ] Number density 200 150 100 Fig. 332. A parameter, area fraction and number density of creep voids as a function of life consumption rate t/tr for the heat AAL of JIS SUS316HTB steel. 50 0 0 Landolt-Börnstein New Series VIII/2B 0.2 0.8 0.4 0.6 Life consumption rate, t / t r 1.0 246 2.4 Austenitic stainless steels 2.4.2.8.4 Creep voids in JIS SUS316HTB steel The creep voids were observed to form during creep, which is more significant at lower stress and longer time conditions. The area fraction and number density of creep voids were measured on the SEM micrographs, after interruption of the creep tests at several creep strains, as shown in Fig. 331. The development of creep voids during creep is shown in Fig. 332, as a function of time normalized by time to rupture tr. The creep voids form at the later stage of creep substantially above t/tr = 0.4. The creep voids were observed to form mainly at the interface between the σ phase on grain boundaries and austenite matrix, reflecting the σ/matrix interface cracking along grain boundaries shown in the creep fracture mode diagram in Fig. 322. 2.4.2.9 References [1] Lai, J. K. L.: Materials Science and Engineering, 61 (1983), 101-109. [2] National Research Institute for Metals (NRIM) Creep Data Sheet, No.6B (2000) for 18Cr-12Ni-Mo stainless steel tubes, JIS SUS 316H TB. [3] National Research Institute for Metals (NRIM) Creep Data Sheet, No.14B (1988) for 18Cr-12Ni-Mo stainless steel plates, JIS SUS 316-HP. [4] National Research Institute for Metals (NRIM) Creep Data Sheet, No.45 (1997) for 18Cr-12Ni-Momiddle N-low C hot rolled stainless steel plate, JIS SUS 316-HP. [5] National Research Institute for Metals (NRIM) Creep Data Sheet, No.15B (1988) for 18Cr-12Ni-Mo stainless steel bars, JIS SUS 316-B. [6] Elevated temperature properties for steels for pressure purpose, Part I, British Standards Institution (BSI), (1990). [7] Shinya, N., Tanaka, H., Murata, M., Kaise, M. and Yokoi, S.: Tetsu-To-Hagane, 71 (1985), 114120. [8] National Institute for Material Science Creep Data Sheet, Metallographic Atlas of Long-Term Crept Materials, National Institute for Materials Science, Tsukuba, No.M-2 (2003). [9] Tanaka, H., Murata, M., Abe, F. and Yagi, K.: Proceedings of the 28th MPA-Seminar, Stuttgart University, Stuttgart, Germany (2002), 38.1-38.10. [10] Lai, J. K. and Wickents, A.: Acta Metall., 27 (1979), 217-230. [11] Mimino, T., Kinoshita, K., Shinoda, T. and Minegishi, I.: Tetsu-To-Hagane, 54 (1968), 464-472. [12] Morris, D. G. and Harries, D. R.: Metal Science, 12 (1978), 525-549. [13] Weiss, B. and Stickler, R.: Metallurgical Transactions, 3 (1972), 851-866. [14] Lai, J. K. L.: Materials Science and Engineering, 58 (1983), 195-209. [15] Lai, J. K. L.: Materials Science and Engineering, 61 (1983), 101-109. [16] Minami, Y., Kimura, H. and Ihara, Y.: Mater. Sci. Technol. 2 (1986), 795-806. Landolt-Börnstein New Series VIII/2B 2.4.3 18Cr-10Ni-Ti steel 247 2.4.3 18Cr-10Ni-Ti steel 2.4.3.1 Introduction 18Cr-10Ni-Ti steel is an austenitic stainless steel with an addition of about 0.4 wt% Ti on 18Cr-10Ni base compositions. This steel was developed in order to improve the corrosion resistance of 18Cr-10Ni steels. However, it is widely used as super-heater and/or re-heater tubes in boilers because its creep rupture strength is higher than that of 18Cr-10Ni steel. In the 1950s there was a burst problem of boiler tubes consisting of 18Cr-10Ni-Ti steel in the USA. The reason was the low creep rupture strength due to lower solution heat treatment temperature. After that higher solution heat treatment temperature was specified and coarse grain was required. 2.4.3.2 Chemical composition Chemical requirements of 18Cr-10Ni-Ti steel tubes are shown in Table 141. Table 141. Chemical requirements of 18Cr-10Ni-Ti steel. Chemical composition [wt%] Standards Designation C Si Mn P S Ni 0.049.00JIS SUS321HTB ≤0.75 ≤2.00 ≤0.030 ≤0.030 0.10 13.00 0.049.00ASTM TP321H ≤0.75 ≤2.00 ≤0.040 ≤0.030 0.10 13.0 0.049.00BS 321S51 ≤1.00 ≤2.00 ≤0.040 ≤0.030 0.10 12.0 9.0DIN X6CrNiTi1810 ≤0.08 12.0 Cr 17.0020.00 17.020.0 17.019.0 17.019.0 Ti 4×C% - 0.60 4×C% - 0.60 5×C% - 0.80 5×C% - 0.80 2.4.3.3 Mechanical properties The mechanical requirements of this steel is as follows: Tensile strength is more than 520 MPa. Yield strength is more than 205 MPa. Elongation is more than 35 % in the case of outer diameter of tubes over 20 mm. 2.4.3.4 Creep rupture properties The creep rupture data of 18Cr-10Ni-Ti steel tubes is shown in Fig. 333 [1]. From [1], data on elongation, reduction of area, minimum creep rate and microstructure of as-received materials and crept specimens can also be obtained. Landolt-Börnstein New Series VIII/2B 248 2.4 Austenitic stainless steels 500 600℃ 650℃ 700℃ 750℃ 400 300 Stress (MPa) 200 100 90 80 70 60 50 40 Fig. 333. Creep rupture strength data of 18Cr-10Ni-Ti steel; [1]. n indicates the total number of data points. 30 20 n=278 10 1 10 2 10 3 10 4 10 5 10 6 Time to rupture (h) Average creep rupture strength of 18Cr-10Ni-Ti steel predicted from curvilinear regression using the Manson-Haferd parameter method is summarized in Table 142. Table 142. Average creep rupture strength of 18Cr-10Ni-Ti steel [MPa] Temperature 100 h 1,000 h 10,000 h 100,000 h 600 °C 307 244 166 100 650 °C 238 167 106 64 700 °C 168 110 70 750 °C 114 76 40 2.4.3.5 Reference [1] National Research Institute for Metals: NRIM Creep Data Sheet, No. 5B (1987). Landolt-Börnstein New Series VIII/2B 2.4.4 18Cr-12Ni-Nb steel 249 2.4.4 18Cr-12Ni-Nb steel 2.4.4.1 Introduction 18Cr-12Ni-Nb steel is an austenitic stainless steel with an addition of about 0.8 wt% Nb on 18Cr-12Ni base compositions. It was developed in order to improve the corrosion resistance of 18Cr-10Ni steels. However, it is widely used as super-heater and/or re-heater tubes in boilers because its creep rupture strength is higher than that of 18Cr-10Ni steel. 2.4.4.2 Chemical composition Chemical requirements of 18Cr-12Ni-Nb steel tubes are shown in Table 143. Table 143. Chemical requirements of 18Cr-12Ni-Nb steel. Chemical composition [wt%] Standards Designation C Si Mn P S Ni 0.04≤1.00 ≤2.00 ≤0.030 ≤0.030 9.00JIS SUS347HTB 13.00 0.10 0.04≤0.75 ≤2.00 ≤0.040 ≤0.030 9.00ASTM TP347H 0.10 13.0 0.04≤1.00 ≤2.00 ≤0.040 ≤0.030 9.0BS 347S51 0.10 13.0 9.0≤0.08 DIN X6CrNiNb1810 12.0 Cr 17.0020.00 17.0020.0 17.019.0 17.019.0 Nb 8×C% -1.00 8×C% -1.0 10×C% -1.2 10×C% -1.00 2.4.4.3 Mechanical properties The mechanical requirements of this steel is as follows: Tensile strength is more than 520 MPa. Yield strength is more than 205 MPa. Elongation is more than 35 % in the case of outer diameter of tubes over 20 mm. 2.4.4.4 Creep rupture properties The creep rupture data of 9 heats obtained from [1] is shown in Fig. 334. From [1] data on elongation, reduction of area, minimum creep rate and microstructure of as-received materials and crept specimens can also be obtained. Landolt-Börnstein New Series VIII/2B 250 2.4 Austenitic stainless steels 500 400 600℃ 300 700℃ 650℃ 750℃ Stress (MPa) 200 100 90 80 70 60 50 40 Fig. 334. Creep rupture strength data of 18Cr-12Ni-Nb steel; [1]. n indicates the total number of data points. 30 n=206 20 10 1 10 2 10 3 10 4 10 5 Time to rupture (h) The creep rupture strength of 9 heats predicted from curvilinear regression using the Manson-Haferd parameter method is summarized in Table 144. There is a large difference in creep rupture strength between the heats. Table 144. Creep rupture strength of 18Cr-12Ni-Nb steel tubes [MPa] Temperature 100 h 1,000 h 10,000 h 100,000 h 600 °C 283-308 222-303 153-242 85-181 650 °C 223-290 157-223 95-165 53-109 700 °C 161-220 103-155 59-102 38-60 750 °C 111-167 64-114 43-70 2.4.4.5 Reference [1] National Research Institute for Metals: NRIM Creep Data Sheet, No. 28B (2001). Landolt-Börnstein New Series VIII/2B Ref. p. 257] 2.4.5 Fine grained 18Cr-12Ni-Nb steel 251 2.4.5 Fine-grained 18Cr-12Ni-Nb steel 2.4.5.1 Introduction Fine-grained 18Cr-12Ni-Nb austenitic steel (TP347HFG) is widely used as superheater and reheater tubes in fossile fired boilers. The steel has been developed for improving steam oxidation resistance of conventional TP347H stainless steel by grain refinement through a specially established thermomechanical process. The microstructure consists of a austenitic fine-grained matrix strengthened by M23C6 carbides mainly along grain boundaries and finely dispersed NbC carbides in the matrix. NbC is fine and stable even after long-term creep exposure at high temperatures. 2.4.5.2 Material standards, and chemical and tensile requirements Tables 145 and 146 give the chemical requirements and the corresponding tensile requirements for finegrained 18Cr-12Ni-Nb steel tubes which are designated by the standards; ASTM A213 TP347HFG, ASME Sec. I CC 2159, EN 10216-5 Table 145. Chemical requirements of fine-grained 18Cr-12Ni-Nb steel tubes; ASTM A213 TP347HFG, ASME Sec. I CC 2159, EN 10216-5. Chemical composition [wt%] DesigGrade Std. No. nation C Si Mn P S Ni Cr Nb+Ta 0.06 ≤ 9.00 17.0 ≤ (Nb+Ta)/C ≤ ≤ ≤ A213 ASTM TP347HFG 0.10 0.75 2.00 0.040 0.030 13.0 20.0 1.0 >8 0.06 ≤ 9.00 17.0 ≤ (Nb+Ta)/C ≤ ≤ ≤ EN TP347HFG 10216-5 0.10 0.75 2.00 0.040 0.030 13.0 20.0 1.0 >8 Table 146. Tensile requirements of fine-grained 18Cr-12Ni-Nb steel tubes; ASTM A213 TP347HFG, ASME Sec. I CC 2159, EN 10216-5 Designation Grade Min. TS1) Min. YS2) Min. elongation Standard No. ASTM TP347HFG 550 MPa 205 MPa 35 % A213 EN TP347HFG 550 MPa 205 MPa 35 % 10216-5 1) TS; Tensile strength, 2) YS; Yield strength as 0.2% proof stress 2.4.5.3 Tensile properties of fine-grained 18Cr-12Ni-Nb steel tubes Fig. 335 shows tensile strength and yield stress data of fine-grained 18Cr-12Ni-Nb steel tubes [1]. They are higher than those of conventional TP347H steel for temperatures up to 750 °C. The corresponding tensile elongation and reduction of area data of fine-grained 18Cr-12Ni-Nb steel tubes are in the same level of those of TP347H steel, which are available in [1], [3] and [4]. Landolt-Börnstein New Series VIII/2B 252 2.4 Austenitic stainless steels 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 100 200 300 400 500 Temperature [°C] 600 700 800 Fig. 335. Tensile strength (circles) and yield stress (triangles) data of fine-grained 18Cr-12Ni-Nb steel tubes. 2.4.5.4 Creep rupture properties of fine-grained 18Cr-12Ni-Nb steel tubes 2.4.5.4.1 Creep rupture data of fine-grained 18Cr-12Ni-Nb steel tubes Fig. 336 shows creep rupture data of fine-grained 18Cr-12Ni-Nb steel tubes with average curves according to the Larson-Miller parameter method [1]. The longest creep rupture time of fine-grained 18Cr-12Ni-Nb steel tubes is about 60000 h at 600 °C. Their long term creep strength is very stable and no degradation in creep strength is expected at temperatures up to 750 °C. Fig. 337 shows a Larson-Miller parameter plot of the creep rupture data of fine-grained 18Cr-12Ni-Nb steel tubes with a master rupture curve and a 95% confidence lower limit. The best fitting was achieved with the optimized constant of 19.14. 500 400 300 Stress [MPa] 200 650 °C 700 °C 750 °C 800 °C 600 °C 100 80 60 600 °C 650 °C 700 °C 750 °C 800 °C Average curve 40 20 10 1 10 10 2 10 3 Rupture time [h] 10 4 10 5 Fig. 336. Creep rupture strength data of fine-grained 18Cr-12NiNb steel tubes. Landolt-Börnstein New Series VIII/2B Ref. p. 257] 2.4.5 Fine grained 18Cr-12Ni-Nb steel 500 400 300 600 °C ×10 5h 650 °C ×10 5h 200 Stress [MPa] 253 700 °C ×10 5h 100 80 60 600 °C 650 °C 700 °C 750 °C 800 °C average curve minimum curve 40 20 10 16 17 18 19 20 21 22 23 24 25 26 Larson-Miller-parameter T (19.14 + log t ) [×10 -3 ] Fig. 337. Larson-Miller parameter plot of the creep rupture data of fine-grained 18Cr-12Ni-Nb steel tubes. 2.4.5.4.2 Creep data of fine-grained 18Cr-12Ni-Nb steel tubes Fig. 338 shows minimum creep rate data of fine-grained 18Cr-12Ni-Nb steel tubes measured at various stress levels in the temperature range between 600 °C and 900 °C with average curves according to the Larson-Miller parameter method [1]. Fig. 339 shows a Larson-Miller parameter plot of the minimum creep rate data of fine-grained 18Cr-12Ni-Nb steel tubes with a master minimum creep rate curve. The best fitting was achieved with the optimized constant of 32.88. 500 400 300 600 °C 200 Stress [MPa] 650 °C 100 700 °C 80 60 750 °C 40 20 800 °C 850 °C 10 10 -2 Landolt-Börnstein New Series VIII/2B 10 -1 900 °C Average curve 1 10 Minimum creep rate [% /10 3 h] 10 2 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 900 °C 10 3 Fig. 338. Minimum creep rate data of fine-grained 18Cr-12NiNb steel tubes. 254 2.4 Austenitic stainless steels 500 400 300 600 °C 0.01%/10 3h 650 °C 0.01%/10 3h 700 °C 0.01%/10 3h Stress [MPa] 200 100 80 60 750 °C 0.01%/10 3h 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 900 °C 40 20 average curve 10 26 Fig. 339. Larson-Miller parameter plot of the minimum creep rate data of fine-grained 18Cr-12Ni-Nb steel tubes. 28 40 36 30 32 34 38 Larson-Miller-parameter T (32.88 + log e) [×10 -3 ] 2.4.5.5 Allowable tensile stress of fine-grained 18Cr-12Ni-Nb steel tubes Fig. 340 shows the allowable stress designated for fine-grained 18Cr-12Ni-Nb steel according to the ASME standard procedure comparing with that for the conventional steel TP347H. 180 Allowable tensile stress (MPa) 160 TP347HFG 140 120 100 80 TP347H 60 40 20 Fig. 340. Allowable tensile stress for fine-grained 18Cr12Ni-Nb steel tubes according to the ASME standard. 0 0 100 200 300 400 500 600 700 800 Temperature (℃) 2.4.5.6 Manufacturing process of fine-grained 18Cr-12Ni-Nb steel tubes Fig. 341 shows the manufacturing process of fine-grained 18Cr-12Ni-Nb steel tubes, which is characterized by the double stage heat treatment to achieve fine grain microstructure with very fine dispersion of NbC in the matrix. In the new process, NbC resolves into the matrix during the pre-solution treatment at higher temperatures and re-precipitates finely in the matrix during the subsequent solution treatment at lower temperatures. This gives rise to the fine grain microstructure with very fine dispersion of NbC in the matrix. Landolt-Börnstein New Series VIII/2B Ref. p. 257] 2.4.5 Fine grained 18Cr-12Ni-Nb steel 255 Fine NbC precipitation Cold working CW≧30% Fine NbC dissolution Solution Pre-solution Fig. 342 shows the initial microstructures of fine-grained 18Cr-12Ni-Nb steel tubes and conventional TP347H steel. Homogeneous and very fine grain structure has been achieved by applying the double stage heat treatment in the new process. Fig. 343 shows the change in the amount of Nb precipitated as NbC after pre-solution treatment at various temperatures. More NbC precipitated when applying the lower temperature solution treatment after a higher temperature pre-solution treatment. Fig. 344 shows the effect of the final-solution treatment temperature on the grain size of fine-grained 18Cr-12Ni-Nb steel tubes and the conventional TP347H steel. The grain size of fine-grained 18Cr-12NiNb steel tubes is much smaller than that of the conventional steel even with increasing the solution treatment temperature. This has been achieved by more precipitation of fine NbC carbides during the presolution treatment at lower temperatures. TP347HFG CW 20~30% Conventional TP347H ASTM ASTM G.S No. 8 G.S No. 4~5 Fig. 341. A comparison of manufacturing processes for fine-grained 18Cr-12Ni-Nb steel and the conventional TP347H steel tubes. Left: New process; right: conventional process. (a) Fine-grained 18Cr-12Ni-Nb steel (b) conventional TP347H Fig. 342. Optical micrographs of the fine grain microstructure in fine-grained 18Cr-12Ni-Nb steel by taking the double stage heat treatment (a) and of the microstructure in conventional TP347H steel (b). Landolt-Börnstein New Series VIII/2B 256 2.4 Austenitic stainless steels 0.8 0.6 0.4 0.2 0 12 Pre-solution treatment ○ 1250℃× 10min ● 1300℃× 10min 10 Grain size [ASTM No.] Extracted Nb content (%) 1.0 Precipitated Nb as NbC during final-solution treatment As presolution 1100 1150 1200 1250 Solution treatment temperature ( ℃ ) Fig. 343. Effects of pre- and final-solution treatment temperatures on the amount of NbC precipitation. 8 6 4 new process conventional process 2 0 1100 1300 1200 Solution treatment temperature [°C] Fig. 344. Effect of solution treatment temperatures on grain size and the resultant creep strength of finegrained 18Cr-12Ni-Nb steel. 2.4.5.7 Corrosion resistance of fine-grained 18Cr-12Ni-Nb steel tubes Inner-scale thickness (µm) Fig. 345 shows the oxidation behavior of fine-grained 18Cr-12Ni-Nb steels with different grain size tested at 650 °C and 700 °C. It can be seen that the steam oxidation resistance is improved by reduction of the grain size. Steam oxidation resistance is found to be achieved by the thin and tight protective Cr2O3 corundum type inner oxide layer formed in the fine-grained steel (see Fig. 346). 650℃ □ ○ △ 100 700℃ ■ TP347H( GS6) TP347HFG(GS8) ▲ ● TP347HFG(GS9) 50 20 In steam 10 500 Outer scale 1000 Fig. 345. Steam oxidation resistance of fine-grained 18Cr-12Ni-Nb steel tested at 650 °C and 700 °C. 3000 Time (h) Inner scale Metal Outer scale Inner scale Metal Fe3O4 Fe3O4 Cr2O3 (Fe,Cr)3O4 Cr2O3 a) Fine-grained (Fe,Cr)3O4 Fig. 346. Schematic illustrations of oxide layers to be formed in fine- and coarse-grained steels. b) Coarse-grained Landolt-Börnstein New Series VIII/2B Ref. p. 257] 2.4.5 Fine grained 18Cr-12Ni-Nb steel 257 2.4.5.8 Microstructural change of fine-grained 18Cr-12Ni-Nb steel during long term creep exposure Fig. 347 shows TEM micrographs of crept specimens from fine-grained 18Cr-12Ni-Nb and coarsegrained TP347H steel. The initial microstructures are completely different from each other. In finegrained 18Cr-12Ni-Nb steel fine NbC carbide precipitates homogeneously and acts as obstacle against dislocation motion even after creep exposure, resulting in higher creep strength. In conventional TP347H steel the size and distribution of NbC carbide is inhomogeneous, which is the main reason for lower creep strength. As-solution treated 1µm crept at 750℃, 98 MPa crept at 650℃, 196 MPa ruptured after 643h ruptured after 2958h (a) Fine-grained 18Cr-12Ni-Nb steel (TP347HFG) ruptured after 399h ruptured after 9746h (177MPa) (b) Conventional TP347H with coarse-grain Fig. 347. TEM micrographs of the crept specimens from fine-grained 18Cr-12Ni-Nb steel and the conventional TP347H steel with coarse-grain. 2.4.5.9 Performance of service exposed tubes Performance of service exposed tubes is available in [7] and [9]. 2.4.5.10 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Teranishi, H., Yoshikawa, K., Fujikawa, H., Kubota, M., Tokimasa, K., and Miura, M.: Proc. of Int.Conf. on Coatings and Bi-Metallics for Energy Systems Chemical Process Environment, (1984). [3] Teranishi, H., Fujikawa, H., Yoshikawa, K., Kubota, M., Yamamoto, S.: Sumitomo Metals, 36 (1984), 134. [4] Yukitoshi, T., Yoshikawa, K., Teranishi, Y.: Tetsu-to-Hagane, 70 (1984), 1962. [5] Yuzawa, H., Teranishi, H., Fujikawa, H., Yoshikawa, K., Kubota, M.: The Thermal and Nuclear Power, 36 (1985), 1325. [6] Teranishi, H., Yoshikawa, K., and Sawaragi, Y.: Proc. of Int. Conf. on Creep, (1986), 233. [7] Teranishi, H., Sawaragi, Y., Kubota, M., Hayase, Y.: The Sumitomo Search, No.38 (1989), 63. [8] Sawaragi, Y., Teranishi, H., Iseda, A., Yoshikawa, K.: Sumitomo Metals, 42 (1990), 260. [9] Sawaragi, Y., Otsuka, N., Senba, H., and Yamamoto, S.: Sumitomo Search, No.56 (1994), 34. Landolt-Börnstein New Series VIII/2B 258 2.4 Austenitic stainless steels 2.4.6 16Cr-13Ni-Nb steel 2.4.6.1 Introduction 16Cr-13Ni-Nb steel (X8CrNiNb16-13, 1.4961, 16-13Nb) is a creep resisting austenitic steel used primarily in Germany. It has a similar composition to AISI Type 347 and is used for components in gas and steam turbines, turbo-rotor wheels, turbine rotor power plants, superheater and heat exchanger tubings and steam pipes. 2.4.6.2 Material standards, chemical composition and tensile requirements Table 147. Chemical requirements of X8CrNiNb16-13 concerning EN 10028-7 (plate) and EN 10216-5 (tube). Chemical composition [wt%] StanStd. No Designation dard C Si Mn P S Cr Ni Others 0.04 0.30 15.00 12.00 Nb ≥ EN 10028-7 X8CrNiNb16-13Nb ≤1.50 ≤0.035 ≤0.015 0.10 0.50 17.00 14.00 10×C-1.2 0.04 0.30 15.00 12.00 Nb ≥ EN 10216-5 X8CrNiNb16-13Nb ≤1.50 ≤0.035 ≤0.015 0.10 0.50 17.00 14.00 10×C-1.2 X8CrNiNb16-13Nb is usually solution heat treated at 1050 to 1110°C. Table 148. Room temperature minimum mechanical property requirements for X8CrNiNb16-13 Rp1.0 Rm Rp0.2 Standard Std. No. Designation [Nmm-2] [Nmm-2] [Nmm-2] EN 10028-7 X8CrNiNb16-13 205 245 510 Table 149. Minimum 0.2% and 1.0% proof strength values at elevated temperatures for X8CrNiNb16-13 Minimum 0.2% (Rp0.2) and 1.0% (Rp1.0) proof strength, at StanStd. No. Designation various temperatures. dard T [°C] 100 150 250 350 450 500 550 Rp1.0 [Nmm-2] 175 157 137 128 118 118 113 EN 10028-7 X8CrNiNb16-13 Rp0.2 [Nmm-2] 205 186 167 157 147 147 142 2.4.6.3 Creep rupture strength The creep rupture strength of X8CrNiNb16-13 is shown in Fig. 348. The analysis from which the data in the figure are derived was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found from their published data sheets [1]. The test data were available from 28 casts with test temperatures of 500 - 800 °C. The test distribution of test durations are shown in Table 150. Table 150. Distribution of test durations used to derive the stress rupture properties of X8CrNiNb 16-13. Number of test points at the various test durations 20,001- 30,00170,001<10,000 h 10,000-20,000 h 50,001-70,000 h >100,000 h 30,000 h 50,000 h 100,000 h 209 28 17 13 12 (5) (7) 1 (4) ( ) denotes unbroken tests The assessment was made by the German Creep Committee in 1969 by using the graphical method [2, 3]. Landolt-Börnstein New Series VIII/2B Ref. p. 259] 2.4.6 16Cr-13Ni-Nb steel 259 1000 Stress [MPa] 10,000h 100,000h 200,000h 100 Fig. 348. Creep rupture strength data of X8CrNiNb16-13. 10 550 600 650 700 750 800 Temperature [°C] 2.4.6.4 Estimated long term creep rupture strength Based on the data shown in Fig. 348 the 100,000 h and 200,000 h rupture strength values for a range of temperatures are as follows: 100,000 h rupture strengths at specified temperatures Temperature [°C] 580 590 600 610 620 630 640 650 660 Stress [Nmm-2] 129 119 108 98 89 80 72 64 57* Temperature [°C] Stress [Nmm-2] 100,000 h rupture strengths at specified temperatures 670 680 690 700 710 720 730 50* 44* 39* 34* 30* 27* 25* 740 22* 750 20* Temperature [°C] Stress [Nmm-2] 200,000 h rupture strengths at specified temperatures 580 590 600 610 620 630 640 115* 105* 94* 85* 77* 69* 61* 650 53* 660 47* 740 17* 750 15* 200,000 h rupture strengths at specified temperatures Temperature [°C] 670 680 690 700 710 720 730 Stress [Nmm-2] 41* 36* 31* 27* 25* 22* 19* * Values which have involved extended time extrapolation. 2.4.6.5 References [1] ECCC Data sheet for X8CrNiNb16-13, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). [2] G. Bandel and H. Gravenhorst: Verhalten warmfester Stähle im Zeitstandversuch bei 500 bis 700°C, Teil II. Auswertungsverfahren, Archiv Eisenhüttenwes. 28 (1957), pp.253-258. [3] ECCC- WG1 Recommendations “Data Assessment” volume 5, part 1, app. D5; European Creep Collaborative Committee (1996). Landolt-Börnstein New Series VIII/2B 260 2.4 Austenitic stainless steels 2.4.7 18Cr-9Ni-3Cu-Nb-N steel 2.4.7.1 Introduction 18Cr-9Ni-3Cu-Nb-N austenitic steel (SUPER304H) is used as superheater and reheater tubes in fossile fired boilers. The steel has been developed for substituting conventional 304H and 321H steels by the addition of copper and nitrogen to increase creep strength at elevated temperatures and toughness after long term exposure at high temperatures. The microstructure consists of an austenitic matrix strengthened by M23C6 carbides mainly along grain boundaries and finely dispersed Cu-phase and NbCrN nitrides in the matrix. The Cu-phase is fine and coherent to the matrix which gives rise to a significant increase in creep strength at elevated temperatures. NbCrN is also fine and stable even after long term exposure at high temperatures. No σ phase is expected to form even after 100000 h in the temperature range between 600 and 800 °C, which is mainly achieved by stabilization of the austenitic matrix with copper and nitrogen. 2.4.7.2 Material standards, chemical and tensile requirements Tables 151 and 152 give the chemical requirements and the corresponding tensile requirements of 18Cr9Ni-3Cu-Nb-N steel tubes which are designated by the standards; Japanese METI KA-SUS304J1HTB, ASTM A213 UNS No.S30432 (ASME Sec. I CC 2328). Table 151. Chemical requirements of 18Cr-9Ni-3Cu-Nb-N steel tubes; Japanese SUS304J1HTB, ASTM A213 UNS No.S30432 (ASME Sec. I CC 2328), and EN 10216-5. Chemical composition [wt%] DesigGrade nation C Si Mn P S Ni Cr Nb N Cu Al 7.50 17.00 0.30 0.05 2.50 Japanese (1) 0.07 ≤ ≤ ≤ ≤ METI 0.13 0.30 1.00 0.040 0.010 10.50 19.00 0.60 0.12 3.50 7.50 17.00 0.20 0.05 2.50 0.003 ASTM (2) 0.07 ≤ ≤ ≤ ≤ 0.13 0.30 1.00 0.040 0.010 10.50 19.00 0.60 0.12 3.50 0.030 7.50 17.00 0.20 0.05 2.50 0.003 EN (3) 0.07 ≤ ≤ ≤ ≤ 0.13 0.30 1.00 0.040 0.010 10.50 19.00 0.60 0.12 3.50 0.030 (1) KA-SUS304J1HTB; (2) UNS No. S30432; (3) SUPER304H METI KA- B Std. No. 0.001 A213 0.010 0.001 10216 0.010 -5 Table 152. Tensile requirements of 18Cr-9Ni-3Cu-Nb-N steel tubes; Japanese METI KASUS304J1HTB, ASTM A213-01 UNS No.S30432 (ASME C.C.2328), and EN 10216-5. Designation Grade Min. TS1) Min. YS2) Min elongation Standard No. Japanese METI KA-SUS304J1HTB 590 MPa 235 MPa 35 % ASTM UNS No.S30432 590 MPa 235 MPa 35 % A213 EN SUPER304H 590 MPa 235 MPa 35 % 10216-5 1) TS; tensile strength, 2) YS; yield strength as 0.2% proof stress 2.4.7.3 Tensile properties of 18Cr-9Ni-3Cu-Nb-N steel tubes Fig. 349 shows tensile strength and yield stress data of 18Cr-9Ni-3Cu-Nb-N steel tubes [1], [3] and [4]. They are higher than those of TP304H steel for temperatures up to 750 °C. The corresponding tensile elongation and reduction of area data of 18Cr-9Ni-3Cu-Nb-N tubes are in the same level as those of TP304H steel, which are available in [1]. Landolt-Börnstein New Series VIII/2B Ref. p. 264] 2.4.7 18Cr-9Ni-3Cu-Nb-N steel 261 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 100 200 300 400 500 Temperature [°C] 600 700 800 Fig. 349. Tensile strength (circles) and yield stress (triangles) data of 18Cr-9Ni-3Cu-Nb-N steel tubes. 2.4.7.4 Creep rupture properties of 18Cr-9Ni-3Cu-Nb-N steel tubes 2.4.7.4.1 Creep rupture data of 18Cr-9Ni-3Cu-Nb-N steel tubes Fig. 350 shows creep rupture data of 18Cr-9Ni-3Cu-Nb-N steel tubes with average curves assessed by the Larson-Miller parameter method [1]. The longest creep rupture datum of 18Cr-9Ni-3Cu-Nb-N steel tubes is over 85000 h at 600 °C. Their long-term creep strength is very stable and no degradation in creep strength is expected for temperatures up to 750 °C. Fig. 351 shows a Larson-Miller parameter plot of the creep rupture data of 18Cr-9Ni-3Cu-Nb-N steel tubes with a master rupture curve and a 95 % confidence lower limit. The best fitting was achieved with an optimized constant of 19.68. 500 400 Stress [MPa] 300 600 °C 200 650 °C 100 80 60 600 °C 650 °C 700 °C 750 °C average curve 40 10 Landolt-Börnstein New Series VIII/2B 10 2 700 °C 750 °C 10 3 Rupture time [h] 10 4 10 5 Fig. 350. Creep rupture strength data of 18Cr-9Ni-3Cu-Nb-N steel tubes. 262 2.4 Austenitic stainless steels 500 600 °C ×10 5h 400 Stress [MPa] 300 650 °C ×10 5h 200 700 °C ×10 5h 750 °C ×10 5h 100 600 °C 650 °C 700 °C 750 °C 80 60 40 17 average curve minimum curve Fig. 351. Larson-Miller parameter plot of the creep rupture data of 18Cr-9Ni-3Cu-Nb-N steel tubes. 18 19 20 21 22 23 24 25 26 27 Larson-Miller-parameter T (19.68 + log t ) [×10 -3 ] 2.4.7.4.2 Creep data of 18Cr-9Ni-3Cu-Nb-N steel tubes Fig. 352 shows minimum creep rate data of 18Cr-9Ni-3Cu-Nb-N steel tubes measured at various stress levels in the temperature range between 600 °C and 750 °C with average curves according to the LarsonMiller parameter method [1]. Fig. 353 shows a Larson-Miller parameter plot of the minimum creep rate data of 18Cr-9Ni-3Cu-Nb-N steel tubes with a master curve. The best fitting was achieved with an optimized constant of 26.96. 500 400 300 Stress [MPa] 600 °C 200 650 °C 100 700 °C 600 °C 650 °C 700 °C 750 °C 80 60 750 °C 40 average curve 10 -2 10 -1 1 10 Minimum creep rate [% /10 3 h] 10 2 10 3 Fig. 352. Minimum creep rate data of 18Cr-9Ni-3Cu-Nb-N steel tubes. Landolt-Börnstein New Series VIII/2B Ref. p. 264] 2.4.7 18Cr-9Ni-3Cu-Nb-N steel 263 500 400 600 °C 0.01%/10 3h Stress [MPa] 300 650 °C 0.01%/10 3h 200 700 °C 0.01%/10 3h 100 600 °C 650 °C 700 °C 750 °C 80 60 40 20 Fig. 353. Larson-Miller parameter plot of the minimum creep rate data of 18Cr-9Ni-3Cu-Nb-N steel tubes. average curve 21 22 23 24 25 26 27 28 29 30 Larson-Miller-parameter T (26.96 + log e) [×10 -3 ] 2.4.7.5 Allowable stress of 18Cr-9Ni-3Cu-Nb-N steel tubes Fig. 354 shows the allowable stress determined for 18Cr-9Ni-3Cu-Nb-N steel (Japanese METI KA-SUS 304J1HTB) according to the METI standard procedure comparing with that for the conventional steel, ASME SA213-TP347H (Japanese METI KA-SUSTP347HTB). 180 T ensile region Allowable tensile stress (MPa) 160 Solid solution strengthening (N) 140 120 KA-SUS304J1HTB C reep region Precipitation strengthening Nb (C,N) NbCrN M 23C6 Cu phase 100 KA-SUSTP347HTB 80 60 40 20 0 0 100 200 300 400 500 600 700 800 Temperature (℃) Fig. 354. Allowable tensile stress determined for 18Cr-9Ni-3Cu-Nb-N steel tubes. 2.4.7.6 Microstructural change of 18Cr-9Ni-3Cu-Nb-N steel tubes The microstructural change in 18Cr-9Ni-3Cu-Nb-N steel tubes after aging for up to 10000 h in the temperature range between 600 °C and 750 °C is available in [3] and [4]. There is no significant microstructural change observed even after aging for 10000 h at 750 °C. A detailed TEM observation of Landolt-Börnstein New Series VIII/2B 264 2.4 Austenitic stainless steels the specimens aged for 3000 h in the temperature range between 600 °C and 750 °C has shown that fine coherent Cu phase is dispersed in the matrix as well as fine NbCrN nitrides and no harmful blocky precipitation such as σ phase is found. This fine dispersion of the precipitates is the major strengthening mechanism of this steel in creep regions at higher temperatures, which is schematically depicted in Fig. 354. 2.4.7.7 Performance of service exposed tubes Performance of service exposed tubes is available in [5] and [8]. 2.4.7.8 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Sawaragi, Y., and Hirano, S.: Proc. of Int. Conf. on New Alloys for Pressure Vessels and Piping, (1990). [3] Sawaragi, Y., Otsuka, N., Ogawa, K., Kato, S., and Hirano, S.: Sumitomo Metals, 43 (1991), 24. [4] Sawaragi, Y., Otsuka, N., Ogawa, K., Kato, S., and Hirano, S.: The Sumitomo Search, No.48 (1992), 50. [5] Sawaragi, Y., Otsuka, N., Senba, H., and Yamamoto, S.: Sumitomo Search, No.56 (1994), 34. [6] Sawaragi, Y., Hirano, S., and Masuyama, F.: Proc. of Int. Conf. on Microstructure and Mechanical Properties of Aging Materials, (1992). [7] Ogawa, K., Sawaragi, Y., Otsuka, N., Hirata, H., Natori, A., and Matsumoto, S.: ISIJ International, 35 (1995), 1258. [8] Kan, T., Sawaragi, Y., Yamadera, Y., and Okada, H.: Proc. of 6th Liege Conf. on Materials for Advanced Power Engineering, (1998), 60. [9] Senba, H., Sawaragi, Y., Ogawa, K., Natori, A., and Kan, T.: Materia, 41 (2002), 120. Landolt-Börnstein New Series VIII/2B 2.4.8 18Cr-10Ni-Ti-Nb steel 265 2.4.8 18Cr-10Ni-Ti-Nb steel 2.4.8.1 Introduction 18Cr-10Ni-Ti-Nb steel (TEMPALOY A-1) is a austenitic stainless steel made by adding small amounts of Ti and Nb to SUS304H for precipitation strengthening in order to improve its long-term creep rupture strength. Its allowable stress at 650 °C for 105 h is 1.5 times that of conventional SUS321H and SUS347H. It is suitable as material for super-heater tubes and re-heater tubes in boilers. 2.4.8.2 Chemical composition Chemical requirement of 18Cr-10Ni-Ti-Nb steel tube is shown in Table 153. Table 153. Chemical requirement of 18Cr-10Ni-Ti-Nb steel (mass%) Chemical requirements [wt%] Designation C Si Mn P S Ni Cr Ti KA-SUS 0.07- ≤1.00 ≤2.00 ≤0.040 ≤0.030 9.00- 17.50- ≤0.20 321J1HTB 0.14 12.00 19.50 Nb ≤0.40 (Ti+Nb/2)/C 0.6-2.5 2.4.8.3 Mechanical properties The room temperature mechanical requirements are as follows: tensile strength is more than 520 MPa, yield strength is more than 205 MPa, and elongation is more than 35 % in the case of outer diameter of tubes over 20 mm. 2.4.8.4 Creep and rupture properties The creep rupture data obtained from NKK co. is shown in Fig. 355 [1]. The average creep rupture strength predicted using the Larson-Miller parameter method is summarized in Table 154. Table 154. Average creep rupture strength of 18Cr-10Ni-Ti-Nb steel [MPa] Temperature 100 h 1,000 h 10,000 h 100,000 h 600 °C 304 240 191 139 650 °C 225 162 123 93 700 °C 157 108 74 58 750 °C 111 78 54 34 Landolt-Börnstein New Series VIII/2B 266 2.4 Austenitic stainless steels 400 600 650 700 750 800 300 Stress (MPa) 200 100 90 80 70 60 50 40 30 20 10 1 10 2 3 4 10 10 Time to rupture (h) 10 5 10 6 Fig. 355. Creep rupture strength data of 18Cr-10Ni-TiNb steel obtained from NKK co. 2.4.8.5 Reference [1] NKK Technical Bullitin: TEC. No.243-312 Boiler Tubing. Landolt-Börnstein New Series VIII/2B Ref. p. 269] 2.4.9 20Cr-25Ni-1.5Mo-NbTiBN steel 267 2.4.9 20Cr-25Ni-1.5Mo-NbTiBN steel 2.4.9.1 Introduction 20Cr-25Ni-1.5Mo-NbTiBN steel [1] is designed for superheater tubes for Ultra Super Critical power plants. The high chromium content improves corrosion resistance, and the well-balanced Nb, Ti and N contents increase creep rupture strength compared with conventional austenitic heat resistant steels. 20Cr25Ni-1.5Mo-NbTiBN steel is designated as KA-SUS310J2TB in METI standard with a creep rupture strength of 86 MPa at 700 °C for 100,000 h. 2.4.9.2 Material standards, chemical and tensile requirements Table 155. Chemical requirements of 20Cr-25Ni-1.5Mo-NbTiBN steel tubes for superheater tubes; KA-SUS310J2TB Chemical composition [wt%] StanDesignation dards C Si Mn P S Cr Mo METI KA-SUS310J2TB ≤0.10 ≤1.00 ≤1.50 ≤0.030 ≤0.010 19.00-23.00 1.00-2.00 Standards Designation METI KA-SUS310J2TB Ni 22.0028.00 Nb 0.100.40 N 0.100.25 Ti 0.020.20 B 0.0020.010 2.4.9.3 Creep properties of 20Cr-25Ni-1.5Mo-NbTiBN steel tubes [2] contains creep data of 20Cr-25Ni-1.5Mo-NbTiBN steel tubes, namely rupture data, minimum creep rate, rupture elongation and reduction of area. 2.4.9.3.1 Creep rupture data of 20Cr-25Ni-1.5Mo-NbTiBN steel tubes Fig. 356 shows the creep rupture data of 20Cr-25Ni-1.5Mo-NbTiBN steel tubes of 6 heats. Creep tests continue over 50,000 h. 1000 Stress (MPa) 600°C 650°C 100 700°C 750°C 800°C 850°C 950°C Fig. 356. Creep rupture strength data of 20Cr-25Ni1.5Mo-NbTiBN steel tubes; [2]. 900°C 10 10 100 1000 Time to Rupture (h) Landolt-Börnstein New Series VIII/2B 10000 100000 268 2.4 Austenitic stainless steels 2.4.9.3.2 Time-Temperature-Parametric prognostication of the creep rupture strength Fig. 357 shows the Larson-Miller Parametric plot of the rupture data [2]. Fig. 358 shows a creep rupture curve regression by a fifth-degree expression predicting the creep rupture strength for times longer than that of the experiment for temperatures between 600 °C and 850 °C. 18000 20000 22000 800°C,105h 750°C,105h 700°C,105h 10 16000 650°C,105h 100 600°C,105h Stress (MPa) 1000 24000 26000 Fig. 357. Master rupture curve by LarsonMiller parameter method for 20Cr-25Ni1.5Mo-NbTiBN steel tubes. LMP=[T+273.15][17.825+log(tr)] 1000 Stress (MPa) 600°C 650°C 100 700°C 850°C 900°C 950°C 750°C 800°C 10 10 100 1000 10000 Fig. 358. Estimated creep rupture curves of 20Cr-25Ni1.5Mo-NbTiBN steel tubes. 100000 Time to Rupture (h) 2.4.9.3.3 Microstructural changes during creep [3] Fig. 359 shows an optical and an electron micrograph of steel crept at 700 °C for 5,000 h. Mainly, three types of precipitates are observed in the crept specimens: Massive particles (type A) of 0.4 - 0.5 µm in width, string Cr-Nb nitrides (type B) of less than 0.03 µm in width and fine granular and needle-like M23C6 carbides (type C) of less than 0.2 µm in width. The long-term creep properties are presumed to be due to the many fine precipitates, which are very fine particles and string type and needle type precipitates, the depression of coarsening of the precipitates by Nb and Ti, and the absence of precipitation of σ-phase. Landolt-Börnstein New Series VIII/2B Ref. p. 269] Cr 2.4.9 20Cr-25Ni-1.5Mo-NbTiBN steel 269 b a c Ni Cr Si Mo Fe Mo Nb Nb Cr Nb Mo Fe Ni Mo Fe Mo Fig. 359. Optical and electron micrographs and EDX analyses of steel crept at 700 °C for 5,000 h; [3]. 2.4.9.4 References [1] Kikuchi, M., Sakakibara, M., Otoguro, Y., Mimura, H. Takahashi, T., and Fujita, T.: The International Conference on High Temperature Alloys, Petton (1985). [2] Nippon Steel Corporation: Nippon Steel Creep Database (2000). [3] Takahashi, T., Sakakibara, M., Kikuchi, M., Ogawa, T., Araki, S., and Fujita, T.: Tetsu-to-Hagane, 76 (1990), No. 7, 1131. Landolt-Börnstein New Series VIII/2B 270 2.4 Austenitic stainless steels 2.4.10 21Cr-32Ni-Ti-Al steel 2.4.10.1 Introduction 21Cr-32Ni-Ti-Al steel (Alloy 800H) is a version of Alloy 800 having higher creep and rupture strength. The two alloys have the same chemical composition with the exception that the carbon content of Alloy 800H is restricted to the upper portion of the standard range for Alloy 800. In addition to a controlled carbon content, Alloy 800H receives an annealing treatment that produces a coarse grain size.This alloy is popularly useful for applications involving long term exposure to elevated temperatures or corrosive atmospheres. It is used in chemical and petrochemical processing and often used in domestic appliances for sheathing on electric heating elements. 2.4.10.2 Material standards, chemical and tensile requirements Chemical requirements of 21Cr-32Ni-Ti-Al steel plates are shown in Table 156. Table 156. Chemical requirements of 21Cr-32Ni-Ti-Al steel plates ; JIS NCF800H, ASTM B409, UNS 8810. Chemical composition [wt%] Specification C Cr Mn Cu Ni P S Si JIS NCF800H 0.050.10 19.00 23.00 ≤1.50 ≤0.75 30.00 35.00 ≤0.030 ≤0.015 ≤1.00 ASTM B409 0.050.10 19.00 23.00 ≤1.50 ≤0.75 30.00 35.00 - ≤0.015 ≤1.00 UNS No.8810 0.050.10 19.00 23.00 1.50 0.75 30.00 35.00 0.015 0.75 Others Al:0.15-0.60 Ti:0.15-0.60 Bal: Fe Al:0.15-0.60 Ti:0.15-0.60 Bal: Fe Al:0.15-1.00 Ti:0.15-0.60 Bal: Fe 2.4.10.3 Creep properties of 21Cr-32Ni-Ti-Al steel plates Information of fact on creep data for 21Cr-32Ni-Ti-Al steel plates can be obtained from [1]. 2.4.10.3.1 Creep rupture data of 21Cr-32Ni-Ti-Al steel plates The creep rupture strength of 21Cr-32Ni-Ti-Al steel plates obtained from [1]is illustrated in Fig. 360. Data on elongation, reduction of area and minimum creep rate is shown in Fig. 361-Fig. 364. Landolt-Börnstein New Series VIII/2B Ref. p. 272] 2.4.10 21Cr-32Ni-Ti-Al steel 600 500 400 300 600 °C 700 °C 800 °C 900 °C 1000 °C 200 Stress [MPa] 271 100 80 60 50 40 30 20 10 8 6 5 4 3 10 Fig. 360. Creep rupture strength data of 21Cr-32Ni-Ti-Al steel plates. n indicates the total number of data points. n = 155 100 10 2 10 3 10 4 Time to rupture [h] 600 °C 100 80 80 60 60 40 40 n = 22 600 °C 0 n = 22 700 °C 80 60 40 20 n = 28 100 100 Reduction of area [%] Elongation [%] 100 0 10 6 20 20 0 10 5 60 40 20 0 800 °C 80 800 °C 80 60 60 40 20 20 Landolt-Börnstein New Series VIII/2B n = 28 100 40 n = 38 0 10 5 10 10 2 10 3 10 4 Time to rupture [h] 700 °C 80 10 6 0 10 n = 38 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 Fig. 361. Elongation and reduction of area at 600, 700 and 800 °C for 21Cr-32Ni-Ti-Al steel plates. n indicates the total number of data points in each diagram. 272 2.4 Austenitic stainless steels 100 900 °C 80 80 60 60 40 40 20 0 n = 40 100 1000 °C 80 Reduction of area [%] Elongation [%] 100 20 0 1000 °C 80 60 40 40 20 20 10 6 n = 40 100 60 n = 27 0 10 5 10 10 2 10 3 10 4 Time to rupture [h] 900 °C n = 27 0 10 5 10 10 2 10 3 10 4 Time to rupture [h] 400 300 600 °C 700 °C 800 °C 900 °C 1000 °C 10 5 100 80 60 Time to rupture [h] Stress [MPa] 10 6 10 6 200 40 20 10 8 6 4 10 -7 Fig. 362. Elongation and reduction of area at 900 and 1000 °C for 21Cr-32Ni-Ti-Al steel plates. n indicates the total number of data points in each diagram. 600 °C 700 °C 800 °C 900 °C 1000 °C n = 52 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 -1 10 4 10 3 10 2 n = 52 10 1 Fig. 363. Stress vs. minimum creep rate for 21Cr32Ni-Ti-Al steel plates. n indicates the total number of data points. 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 Minimum creep rate [%/h] 10 -1 1 Fig. 364. Time to rupture vs. minimum creep rate for 21Cr-32Ni-Ti-Al steel plates. n indicates the total number of data points. 2.3.4.10.4 Reference [1] National Research Institute for Metals: NRIM Creep Data Sheet, 27B (2000). Landolt-Börnstein New Series VIII/2B 2.4.11 22Cr-15Ni-NbBN steel 273 2.4.11 22Cr-15Ni-NbBN steel 2.4.11.1 Introduction 22Cr-15Ni-NbBN (TEMPALOY A-3) is a steel with corrosion resistance equal to, and high temperature strength greater than that of Incoloy 800H, and has superior economic efficiency. It is suited for use in environments of 700 °C or higher. Other high Cr steels containing more than 20 % Cr include SUS309 and SUS310, but their high temperature strength is low. Its high temperature strength is improved by Nb(C,N) and M23C6 formed by adding Nb and N to 22 %Cr-15 %Ni. SUS310 and other high Cr steels become brittle as large quantities of the σ-phase are precipitated during long use. The σ-phase precipitation of 22Cr-15Ni-NbBN is equal to that of 18 %Cr-8 %Ni type steel, providing it with suitable toughness after long-term use. Its Ni content lower than that of SUS310 and Incoloy 800H provides superior economic benefits. 2.4.11.2 Chemical composition Chemical requirement of 22Cr-15Ni-NbBN steel is shown in Table 157. Table 157. Chemical requirement of 22Cr-15Ni-NbBN steel. Designation Chemical composition [wt%] C Si Mn P S Ni Cr KA-SUS 0.03- ≤1.00 ≤2.00 ≤0.040 ≤0.030 14.50- 21.00309J4HTB 0.10 16.50 23.00 Nb 0.500.80 B N ≤0.005 0.100.20 2.4.11.3 Mechanical requirements The room temperature mechanical requirements of this steel are as follows: tensile strength is more than 590 MPa, yield strength is more than 235 MPa, elongation is more than 35 % in the case of outer diameter of tubes over 20 mm. 2.4.11.4 Creep rupture properties The creep rupture data obtained from NKK co. [1] is shown in Fig. 365. Landolt-Börnstein New Series VIII/2B 274 2.4 Austenitic stainless steels 500 400 300 Stress (MPa) 200 100 90 80 70 60 50 600℃ 650℃ 700℃ 750℃ 800℃ 40 30 20 101 102 103 104 105 Fig. 365. Creep rupture strength data of 22Cr-15NiNbBN steel; [1]. Time to rupture (h) 2.4.11.5 Reference [1] NKK Technical Bullitin: TEC. No. 243-312 Boiler Tubing. Landolt-Börnstein New Series VIII/2B Ref. p. 278] 2.4.12 23Cr-18Ni-3Cu-1.5W-Nb-N steel 275 2.4.12 23Cr-18Ni-3Cu-1.5W-Nb-N steel 2.4.12.1 Introduction 23Cr-18Ni-3Cu-1.5W-0.4Nb-0.2N steel (SAVE25) has been used for superheater and reheater tubings in power boilers in field exposure test experiences since June 1999, and has been approved as a ministerial ordinance material by METI Japan. SAVE25 was developed by Sumitomo Metal Industries, Ltd., Japan in the 1990s to improve creep rupture strength and to obtain a high corrosion resistance by optimizing chemical composition as well as to achieve relatively low cost. The chromium content is 23 %, based on requirements for hot corrosion and steam oxidation resistance. Nitrogen, as a substitute element for nickel, is sufficient at 0.2 % for stabilizing an austenite structure. Copper and tungsten are characteristic alloying elements to improve creep strength. 2.4.12.2 Material standards, chemical and tensile requirements Table 158 and Table 159 respectively show the chemical and tensile requirements of 23Cr-18Ni-3Cu1.5W-Nb-N steel tubes approved by METI in the ministerial ordinance interpretation designated as KASUS310J3TB. Fig. 366 shows charpy impact values at 0 °C of SAVE25 steel aged for 3000 h. Table 158. Chemical requirements of 23Cr-18Ni-3Cu-1.5W-Nb-N steel (SAVE25) Stan- Designation dard METI KA-SUS310J3TB Chemical composition [wt%] C Si Mn P S Ni Cr W Cu Nb N 0.05∼ ≤1.50 ≤2.00 ≤0.030 ≤0.010 15.00~ 21.00~ 0.80~ 2.00~ 0.30~ 0.15~ 22.00 24.00 2.80 4.00 0.60 0.30 0.12 Table 159. Tensile requirements of 23Cr-18Ni-3Cu-1.5W-Nb-N steel (SAVE25) Standard Designation Yield strength [MPa] Tensile strength [MPa] Elongation [%] METI KA-SUS310J3TB ≥650 2295 ≤30 120 Charpy impact value (J/cm2) 600℃ 650℃ 100 700℃ 750℃ 80 60 40 20 0 500 1000 1500 2000 2500 3000 Fig. 366. Charpy impact values at 0 °C of the SAVE25 steel aged for up to 3000 h; [1]. Aging time (h) 2.4.12.3 Creep properties 2.4.12.3.1 Creep rupture data and creep rupture strength The chemical compositions of SAVE25 steel tubes used for creep rupture testing are listed in Table 160. These tubes were melted in a VIF forged from 180 kg ingots, hot-extruded, cold-drawn and solution heattreated at 1150 - 1175 °C . Landolt-Börnstein New Series VIII/2B 276 2.4 Austenitic stainless steels The creep rupture properties of SAVE25 steel are shown in Fig. 367. The creep rupture master-curve of the Larson-Miller parameter method is shown in Fig. 368. Table 160. Chemical compositions of SAVE25 steel tested [1]. Chemical composition [wt%] Product C Si Mn Ni Cr W Cu Nb N Tube A 0.10 0.13 0.48 19.8 22.6 1.47 3.51 0.44 0.22 Tube B 0.10 0.14 0.48 16.7 22.6 2.51 3.50 0.45 0.18 Tube C 0.10 0.14 0.49 15.3 22.7 1.48 3.52 0.45 0.20 500 Stress (MPa) 300 200 650℃ 700℃ 100 750℃ 70 50 Fig. 367. Creep rupture strength data of SAVE25 steel; [1]. 800℃ 100 101 102 103 104 105 Time to rupture (h) 500 650℃ 700℃ 300 750℃ Stress (MPa) 800℃ 200 100 Fig. 368. Creep rupture master-curve of SAVE25 steel by Larson-Miller parametric method; [1]. 70 50 16 18 20 22 24 26 T (17.9817+log t) × 10- 3 2.4.12.3.2 Creep deformation behavior Fig. 369 compares the creep curves of 0.75Mo and 1.5W steels having base composition of 23Cr-20Ni3Cu-0.12N with the same Mo equivalents. It is found that the tertiary creep of the 1.5W steel is retarded, due to the fact that σ phase precipitation and carbide/nitride coarsening are suppressed, thus resulting in higher creep strength. Landolt-Börnstein New Series VIII/2B Ref. p. 278] 2.4.12 23Cr-18Ni-3Cu-1.5W-Nb-N steel 277 1.5 Elongation (%) 800℃,78.4MPa 1.0 0.75Mo 0.5 1.5W Fig. 369. Effect of 0.75% Mo and 1.5% W on creep curves of 23Cr-20Ni-3Cu-0.12N steels; [1]. 0 0 200 400 Time (h) 600 800 2.4.12.3.3 Effect of chemical compositions on creep strength Fig. 370 shows that the creep rupture strength at 700 °C and 156.8 MPa increases remarkably with the addition of 2.5 to 3.5 % Cu. 2400 Cu solubility Time to rupture (h) 2200 2000 1800 1600 1400 700℃ 156.8MPa 1200 0 1 2 Cu content (mass %) 3 4 Fig. 370. Effect of Cu content on creep rupture strength of 23Cr-15.5Ni-2.5W-0.2N steels; [2]. Fig. 371 shows that the creep rupture strength of 1 % Mo steel is much lower than that of 1.5 % W steel, although the Mo-equivalent (=Mo + 1/2W) of 1 % Mo steel is higher than that of 1.5 % W steel. Chemical analysis of extracted residues in the 1 % Mo steel revealed that about 90 % of the alloyed Mo is dissolved even after long-term aging at 650 - 800 °C . Most of the alloyed Mo seems to be still in solution during the long-term creep stage and contributes to creep rupture strength by solid solution strengthening. Time to rupture (h) 3000 650℃ 235.2MPa 700℃ 156.8MPa 1Mo 1Mo 750℃ 98MPa 2000 1000 700 500 Landolt-Börnstein New Series VIII/2B 1.5W 1.5W 1Mo 1.5W Fig. 371. Effect of Mo and W on creep rupture strength of 23Cr-20Ni-3Cu-Mo-W0.12N steels; [2]. 278 2.4 Austenitic stainless steels 2.4.12.4 Estimated creep strength Allowable stresses of SAVE25 developed based on the ASME criteria are compared with those of HR3C steel (ASME SA-213 TP310HCbN) and TP347H steel in Fig. 372. The allowable stress of SAVE25 at 700 °C is 60 MPa, which is 36 % higher than that of HR3C steel and 88 % higher than that of TP347H. 180 Allowable tensile stress (MPa) 160 SAVE25 140 HR3C 120 100 TP347H 80 60 Fig. 372. Allowable stresses of SAVE25 steel compared with HR3C steel and TP347H steel; [1]. 40 20 0 200 400 Temperature (℃) 600 800 2.4.12.5 References [1] Semba, H., Igarashi, M., Sawaragi, Y., and Iseda, A.: Proc. International Conf. Advanced Materials and Processes, Munich, Germany, (2001), 1. [2] Semba, H., Igarashi, M., and Sawaragi, Y.: Proc. International Conf. Power Engineering-97, Vol.2, Tokyo, (1997), 125. Landolt-Börnstein New Series VIII/2B Ref. p. 282] 2.4.13 23Cr-45Ni-6W-Nb-Ti-B steel 279 2.4.13 23Cr-45Ni-6W-Nb-Ti-B steel 2.4.13.1 Introduction 23Cr-45Ni-6W-Nb-Ti-B steel (HR6W) was developed by Sumitomo Metal Industries, Ltd., Japan in the 1980s for heat exchanger tubings such as power boiler superheaters and reheaters, steam generators and chemical plants operated at very high temperatures of around 700 °C. HR6W steel has a high creep rupture strength compared with conventional high alloy steels such as Hastelloy X, Alloy 800H and Incoloy 807 due to the solution strengthening effect of W and N and the precipitation strengthening effect provided by a fine Laves phase, M23C6 and nitrides. The corrosion resistance properties of HR6W steel, such as steam oxidation resistance and hot corrosion resistance are superior to those of 18Cr-8Ni stainless steels due to the higher Cr content. 2.4.13.2 Material standards, chemical and tensile requirements [1] HR6W steel is not specified in any codes or standards except the internal specifications of Sumitomo Metal Industries, Ltd. Table 161 shows the chemical requirements for HR6W steel by Sumitomo Metal Industries, Ltd. Table 2 lists the chemical composition of HR6W steel used for creep rupture and characterization tests, as well as Hastelloy X, Alloy 800H and Incoloy 807 for comparison. Fig. 373 shows Charpy impact values at 0 °C for HR6W steel aged for 3,000 h, as compared to the competitive alloys. Table 161. Chemical requirements of HR6W steel Chemical composition [wt%] Product C Si Mo P S Ni Cr W Ti Nb Tube ≤0.10 ≤1.00 ≤2.00 ≤0.030 ≤0.030 35.0-45.0 21.0-25.0 4.0-8.0 ≤0.20 ≤0.40 Table 162. Chemical compositions of alloys tested [1] Chemical composition [wt%] Alloy C Si Mn Ni Cr Mo V Ti Nb M3 0.08 0.42 1.20 42.21 22.91 2.98 0.07 0.19 M5 0.07 0.40 1.21 44.20 22.77 4.91 0.08 0.18 W5 0.08 0.42 1.16 41.69 22.64 5.07 0.07 0.18 W7 0.08 0.39 1.20 44.15 22.76 7.38 0.09 0.16 Hastelloy X 0.07 0.38 0.70 44.80 22.47 8.71 1.10 Alloy 800H 0.08 0.43 0.97 33.86 21.08 0.53 Incoloy 807 0.07 0.43 0.97 38.82 20.41 4.55 0.30 0.95 Landolt-Börnstein New Series VIII/2B Others 0.0034 B 0.0032 B 0.0033 B 0.0030 B 1.1 Co 0.43 Al 0.38 Al, 7.7 Co 280 2.4 Austenitic stainless steels 160 120 100 80 Impact value after aging for 3000h Impact value before aging 140 Charpy impact value (J/cm2) 0.6 M3 M5 W5 W7 Hastelloy X Alloy 800H Incoloy 807 60 40 0.4 0.2 20 0 700 750 0 800 700 Aging temperature (℃) 750 800 Aging temperature (℃) Fig. 373. Charpy impact properties of test alloys at 0 °C after 3000 h aging; [1]. 2.4.13.3 Creep properties 2.4.13.3.1 Creep rupture data and creep rupture strength [1] Fig. 374 shows the creep rupture properties for HR6W steel. The 100,000 h extrapolated creep rupture strength at 700 °C is estimated to be over 90 MPa. 300 Stress (MPa) 200 700℃ 100 750℃ 70 50 800℃ 102 103 104 105 Fig. 374. Creep rupture strength data of HR6W steel; [1]. Time to rupture (h) 2.4.13.3.2 Effect of chemical compositions on creep properties [1] The creep rupture strength of four alloys (M3, M5, W5, W7) is superior to that of Alloy 800H, and the rupture strength levels of the alloys containing W (W5 and W7) are higher than those of the alloys containing Mo (M3 and M5), as shown in Fig. 375. The creep rupture ductilities for alloy M5 with 5 % Mo and alloy W7 with 7 % W are shown in Fig. 376. The rupture elongation and the reduction of area deteriorate with increased testing temperature and Landolt-Börnstein New Series VIII/2B Ref. p. 282] 2.4.13 23Cr-45Ni-6W-Nb-Ti-B steel 281 time in M5, with inferior creep rupture strength. In W7, having excellent rupture strength, the deterioration in creep rupture ductility is smaller than that in M5; in particular the change of the reduction of area in W7 is small even after higher temperature and longer term testing. Fig. 377 shows that lowering of the W content to 3 % results in decreased creep rupture strength. 19 200 T (18 + log t ) [ 10 3 ] 20 21 22 200 23 5 700 °C ×10 h 700 °C 100 W [%] W5 5.07 W7 7.38 750 °C Stress [MPa] Stress [MPa] 100 50 200 M3 M5 Hasteloy X 50 200 5 700 °C ×10 h 700 °C 100 100 Mo [%] M3 2.98 M5 4.91 750 °C 50 W5 W7 Alloy 800 H Incoloy 807 50 10 2 10 3 10 4 Time to rupture [h] 10 5 21 22 23 24 T (20 + log t ) [ 10 3 ] 25 Fig. 375. Creep rupture properties for test alloys M3, M5, W5, and W7; [1]. Alloy M5 700℃ 750℃ E1. (4.91% Mo)R.A W7 Elongation, Reduction of area (%) E1. (7.38% W) R.A 100 80 60 40 Fig. 376. Comparison of creep rupture ductility between alloys M5 (4.91% Mo) and W7 (7.38% W); [1]. 20 0 102 103 104 Time to rupture (h) Table 163. Chemical compositions of Alloys A, B and C given in Fig. 377. Chemical composition [wt%] Alloy C Ni Cr W Ti Nb B A 0.083 42.75 23.12 6.58 0.07 0.16 0.0042 B 0.080 40.60 23.08 5.03 0.07 0.15 0.0038 C 0.085 35.56 22.98 3.10 0.07 0.15 0.0035 Landolt-Börnstein New Series VIII/2B 282 2.4 Austenitic stainless steels Alloy 700℃ 750℃ A B C Stress (MPa) 300 200 100 Fig. 377. Effect of W content on creep rupture strength of 23Cr-45Ni-Nb-Ti-B steels; [1]. 70 50 10 102 103 104 105 Time to rupture (h) 2.4.13.4 Reference [1] Sawaragi, Y., Hayase, Y., and Yoshikawa, K.: Proc. International Conf. Stainless Steels, Chiba, Japan (1991), 633. Landolt-Börnstein New Series VIII/2B Ref. p. 285] 2.4.14 25Cr-12Ni steel 283 2.4.14 25Cr-12Ni steel 2.4.14.1 Introduction 25Cr-12Ni steel is a cast heat resistant stainless steel. It is basically austenitic, but in some composition balance of Cr, Ni and C, partially it is duplex of ferritic and austenitic. The partially ferritic alloy is adapted to operating conditions that are subjected to changes in temperature level and applied stress. The wholly austenitic alloy is used extensively in high temperature applications because of its combination of relatively high strength and oxidation resistance at temperatures up to 1100 ºC. 2.4.14.2 Chemical composition Chemical requirements of 25Cr-12Ni steel are shown in Table 164. Table 164. Chemical requirements of 25Cr-12Ni steel Chemical composition [wt%] StanDesigdards nation C Si Mn P 0.20JIS SCH13 ≤2.00 ≤2.00 ≤0.040 0.50 0.20ASTM HH ≤2.00 ≤2.00 ≤0.04 0.50 0.20ASTM Type I ≤1.75 ≤2.50 ≤0.05 0.45 0.20ASTM Type II ≤1.75 ≤2.50 ≤0.05 0.45 Type I: partially feritic Type II: wholly austenitic S Ni 11.00≤0.040 14.00 11.00≤0.04 14.00 10.00≤0.05 14.00 10.00≤0.05 14.00 Cr 24.0028.00 24.0028.00 23.0028.00 23.0028.00 Mo N ≤0.50 ≤0.20 ≤0.20 2.4.14.3 Mechanical properties The mechanical requirements of this steel is shown in Table 165. Table 165. Mechanical property requirements of 25Cr-12Ni steel. Standards Designation Yield strength Tensile strength [N/mm2] [N/mm2] JIS SCH13 ≥235 ≥490 ASTM HH ≥240 ≥535 ASTM Type I, II ≥550 2.4.14.4 Creep rupture properties The creep rupture data of 25Cr-12Ni steel obtained from [1] is shown in Fig. 378. From [1] data on elongation and reduction of area can also be obtained (Fig. 379 and Fig. 380). Landolt-Börnstein New Series VIII/2B 284 2.4 Austenitic stainless steels Stress (MPa) 200 700℃ 800℃ 900℃ 950℃ 100 90 80 70 60 50 40 30 20 10 101 102 103 104 105 Fig. 378. Creep rupture strength data of 25Cr-12Ni steel. n indicates the total number of data points. Time to rupture (h) n = 88 Fig. 379, see next page n = 20 100 900 °C 80 80 60 60 40 40 20 0 100 n = 15 950 °C 80 Reduction of area [%] Elongation [%] 100 100 950 °C 80 40 40 20 20 10 6 n = 15 0 60 10 5 10 2 10 3 10 4 Time to rupture [h] 900 °C 20 60 0 10 n = 20 0 10 Fig. 380. Elongation and reduction of area at 900 and 950 ºC for 25Cr-12Ni steel. n indicates the total number of data points in each diagram. 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 Landolt-Börnstein New Series VIII/2B Ref. p. 285] 100 n = 29 100 700 °C 80 80 60 60 40 40 20 20 0 0 100 n=5 100 750 °C 80 80 60 60 40 40 20 0 100 n = 27 Reduction of area [%] Elongation [%] 2.4.14 25Cr-12Ni steel 80 40 40 20 20 0 0 80 100 850 °C 60 40 40 20 20 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 750 °C n = 27 800 °C n=5 850 °C 80 60 0 10 n=5 80 60 n=5 700 °C 0 60 100 n = 29 20 100 800 °C 285 0 10 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 Fig. 379. Elongation and reduction of area at 700, 750, 800 and 850 ºC for 25Cr-12Ni steel. n indicates the total number of data points in each diagram. 2.4.14.5 Reference [1] National Research Institute for Metals: NRIM Creep Data Sheet, 37A (1992). Landolt-Börnstein New Series VIII/2B 286 2.4 Austenitic stainless steels 2.4.15 25Cr-20Ni steel 2.4.15.1 Introduction 25Cr-25Ni centrifugally cast steel is a heat resistant and high corrosion resistant alloy having similar chemical composition as type 310 stainless steel but a rather high carbon content. It is popularly used in chemical plant pipings or reactors, especially in steam or ethylene reformer tubes. 2.4.15.2 Materials standards, and chemical requirements Table 166. Chemical requirements of 25Cr-20Ni steel castings; JIS SCH21, ASTM A351 HK40, ACI HK40, BS 310 310C45 and DIN 17465 1.4848 Chemical composition [wt%] Specification C Cr Mn Mo Ni P S Si Others N: ≤0.2 JIS SCH21 0.35-0.45 23-27 ≤1.5 0.04 ≤0.5 19-22 0.04 ≤1.75 Bal: Fe ASTM A351 HK40 0.35-0.45 23-27 1.5 19-22 0.04 0.04 1.75 Bal: Fe Bal: Fe ACI HK40 0.2-0.6 24-28 ≤2 ≤0.5 18-22 ≤0.04 ≤0.04 1.75 22-27 ≤1.5 0.04 BS 310 310C45 ≤0.5 ≤0.5 19-22 0.04 ≤1.75 Bal: Fe DIN 17465 1.4848 0.3-0.5 24-26 0.5-1.5 19-21 0.045 0.03 1-2.5 Bal: Fe 2.4.15.3 Creep properties of 25Cr-20Ni steel castings Information of fact on creep data for 25Cr-20Ni steel castings can be obtained from [1]. 2.4.15.3.1 Creep rupture data of 25Cr-20Ni steel castings The creep rupture strength of 25Cr-20Ni steel castings obtained from the available creep data source is illustrated in Fig. 381. The results of creep tests from 14 JIS SCH21 heat cast tubes are given in [1]. Data on elongation, reduction of area, minimum creep rate and microstructures of as-received and crept specimens can also be obtained from [1]. Log-log plots of relations between stress and time to rupture in the temperature range 800 - 1000 °C are almost of a linear shape but tend to be slightly inverse sigmoidal. 2.4.15.3.2 Creep rupture strength of 25Cr-20Ni steel castings The creep rupture time at each stress level is widely scattered, and almost a 0.8 - 1.0 order of magnitude difference can be found (Fig. 381). There are no significant differences of the data scattering tendency between the test temperatures. The creep rupture strength depends on manufacturing conditions, chemical composition, and initial microstructure. In particular, the rupture strength of castings is influenced by casting condition and initial (as-cast) microstructure. The master rupture curve obtained by the Larson-Miller parameter method for centrifugally cast 25Cr20Ni steel tubes is illustrated in Fig. 382. A set of of Larson-Miller parameters fitted to all creep-rupture data in [1] is given in Table 167. Landolt-Börnstein New Series VIII/2B Ref. p. 291] 2.4.15 25Cr-20Ni steel 287 100 800℃ 900℃ 1000℃ 10 n=211 10 1 10 2 10 3 10 4 10 5 10 6 Fig. 381. Creep rupture strength data of centrifugally cast 25Cr-20Ni steel tubes. n indicates the total number of data points. Time to rupture (h) 200 800 °C 870 °C 900 °C 982 °C 1000 °C 1050 °C 1100 °C Stress [MPa] 100 80 60 50 40 30 20 10 8 6 4 12 average curve n = 263 18 20 16 14 Larson-Miller-parameter TK ( log t R-10.315) [10 3 ] Fig. 382. Master rupture curve obtained by the LarsonMiller parameter method for centrifugally cast 25Cr-20Ni steel tubes; [1]. n indicates the total number of data points. Table 167. A set of Larson-Miller parameters fitted to all creep-rupture data in [1] according to log tR=(T+273.15)−1[b0+b1log S+b2 (log S)2]−C n C b0 b1 b2 263 1.031462 × 10 2.204935 × 104 −3.439566 × 103 −4.937139 × 102 2.4.15.3.3 Elongation and reduction of area of ruptured specimens Elongation and reduction of area of ruptured specimens tested at 800, 900 and 1000 °C as a function of time to rupture are shown in Fig. 383. The ductility of the specimens tested at 800 °C and 900 °C is almost constant and not high, approximately some percent. The ductility of the specimens tested at 1000 °C up to 104 h has a similar tendency as those tested at lower temperatures, however, it increases with increasing time for rupture times longer than 103 h. Landolt-Börnstein New Series VIII/2B 288 2.4 Austenitic stainless steels 100 100 800 °C 80 80 60 60 40 40 20 20 0 0 n = 70 100 900 °C Reduction of area [%] 100 Elongation [%] n = 72 80 60 40 20 800 °C n = 70 900 °C n = 71 1000 °C 80 60 40 20 0 0 100 n = 72 n = 71 1000 °C 100 80 80 60 60 40 40 20 20 0 10 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 0 10 10 5 10 2 10 3 10 4 Time to rupture [h] 10 6 Fig. 383. Elongation and reduction of area of ruptured specimens tested at 800, 900 and 1000 °C as a function of time to rupture. n indicates the total number of data points in each diagram. 2.4.15.3.4 Microstructural change The microstructure of centrifugally cast 25Cr-20Ni steel tubes varies with cast condition. Fig. 384 is an example set of variation in as-cast microstructure from [1]. Large directed grain structures (TAA and TAG) or rather fine equiaxed grain structure (TAD and TAF) can be found. As reported in [2], there is no clear relationship between grain size and creep rupture strength in this alloy. The microstructure of 25Cr-20Ni steels changes during creep deformation (Fig. 385: All the data from cast TAA of Fig. 384). The microstructure of as-cast materials is an austenitic matrix having dendritic structure with primary carbides along dendrite interfaces. With increasing creep temperature and/or creep time, carbide coarsening and coalescencing takes place. Under the creep conditions tested below 900 °C, fine carbides precipitate around the final solidified zone during creep tests. There are some reports that σ phase precipitates are found during creep deformation. The σ phase morphology and quantity very depend on the alloy chemistry. In general, massive σ phase, which precipitates after long creep (more than 30000 h) beside coarsened carbide, can be a creep void initiation site. Details are described later. 2.4.15.3.5 Creep deformation process in 25Cr-20Ni steel As seen in Fig. 385, voids at/along dendrite interfaces can be found at low magnified structures. At a higher magnification observations reveals that voids initiate within the primary carbides. An estimated process of creep damage progress is as follows: A. void initiation at dendrite interface, especially at primary carbides B. connection of adjoining voids C. microcrack initiation D. crack propagation Landolt-Börnstein New Series VIII/2B Ref. p. 291] 2.4.15 25Cr-20Ni steel 289 There are reports on the relationship between creep strength and σ phase precipitation [3]. In general, a σ/matrix interface tends to be a creep crack initiation and propagation site. Time to rupture of alloys involving more σ phase are short. Therefore, improved alloy design avoids σ phase precipitation. For example, PHACOMP alloy design method was applied and improved alloys have been developed [4]. 800 °C 900 °C 1000 °C Fig. 385. A comparison of microstructure after creep ruptured at similar times as a function of test temperature. Landolt-Börnstein New Series VIII/2B 290 2.4 Austenitic stainless steels Fig. 384. Variation in microstructure of centrifugally cast 25Cr-20Ni steel. Landolt-Börnstein New Series VIII/2B Ref. p. 291] 2.4.15 25Cr-20Ni steel 291 2.4.15.4 References [1] National Research Institute for Metals Japan: NRIM Creep Data Sheet, 16B (1990). [2] Ohta, S., and Kori, M.: Report of the 123rd Committee on Heat-Resisting Metals and Alloys, Japan Society for the Promotion of Science, 20, No.1 (1984) 97 in Japanese. [3] Ohta, S., and Kori, M.: Annmonia to Kougyou, 31 (1978) 1 in Japanese. [4] Kihara, S., Ohtomo, A., Shinozaki, S., Saiga, Y., and Kawasumi, Y: J. Jpn. Petrol. Inst. 24 (1981) 27. Landolt-Börnstein New Series VIII/2B 292 2.4 Austenitic stainless steels 2.4.16 25Cr-20Ni-Nb-N steel 2.4.16.1 Introduction 25Cr-20Ni-Nb-N austenitic steel (TP310HCbN; HR3C) is used as superheater and reheater tubes in fossile fired, black liquor recovery and refuse fired boilers. The steel has been developed for improving 310 type stainless steel by the addition of niobium and nitrogen to increase creep strength at elevated temperatures. The microstructure consists of an austenitic matrix strengthened by M23C6 carbide mainly along grain boundaries and finely dispersed NbCrN nitride in the matrix. NbCrN is fine and stable even after long term creep exposure at high temperatures. No σ phase has been found after more than 30000 h in the temperature range between 600 and 800 °C, which is achieved by optimizing the Ni-balance. 2.4.16.2 Material standards, and chemical and tensile requirements Tables 168 and 169 give the chemical requirements and the corresponding tensile requirements of 25Cr20Ni-Nb-N steel tubes which are designated by the standards; Japanese METI KA-SUS310J1TB, ASTM A213 TP310HCbN (ASME Sec. I CC 2115), and EN 10216-5. Table 168. Chemical requirements of 25Cr-20Ni-Nb-N steel tubes; Japanese METI KA-SUS310J1TB, ASTM A213 TP310HCbN (ASME Sec. I CC 2115), and EN 10216-5. Chemical composition [wt%] DesigGrade Std.No. nation C Si Mn P S Ni Cr Nb N Japanese 17.0 23.0 0.20 0.15 KA≤ ≤ ≤ ≤ ≤ SUS310J1TB 0.10 1.50 2.00 0.030 0.030 23.0 METI 27.0 0.60 0.35 0.04 ≤ 17.00 24.00 0.20 0.15 ≤ ≤ ≤ ASTM TP310HCbN A213 0.10 0.75 2.00 0.030 0.030 23.00 26.00 0.60 0.35 17.0 23.0 0.20 0.15 10216≤ ≤ ≤ ≤ ≤ EN TP310HCbN 0.10 1.50 2.00 0.030 0.030 23.0 27.0 0.60 0.35 5 Table 169. Tensile requirements of 25Cr-20Ni-Nb-N steel tubes; Japanese METI KA-SUS310J1TB, ASTM A213 TP310HCbN (ASME Sec. I CC 2115), and EN 10216-5. Min. Standard No. Designation Grade Min. TS1) Min. YS2) elongation Japanese KA660 MPa 295 MPa 30 % METI SUS310J1TB ASTM TP310HCbN 665 MPa 295 MPa 30 % SA213-01 EN HR3C 665 MPa 295 MPa 30 % 10216-5 1) TS; tensile strength, 2) YS; yield strength as 0.2% proof stress 2.4.16.3 Tensile properties of 25Cr-20Ni-Nb-N steel tubes 2.4.16.3.1 Tensile properties of 25Cr-20Ni-Nb-N steel tubes Fig. 386 shows tensile strength and yield stress data of 25Cr-20Ni-Nb-N steel tubes [1], [2] and [5]. They are higher than those of TP310S steel at all temperatures up to 750 °C. The corresponding tensile elongation and reduction of area data of 25Cr-20Ni-Nb-N steel tubes, which are also available in [1], [2] and [5], are at the same level as those of TP310S steel at temperatures below 300 °C but much better above 300 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 296] 2.4.16 25Cr-20Ni-Nb-N steel 293 1000 Tensile strength,Yield stress [MPa] 900 800 700 600 500 400 300 200 100 0 100 200 300 400 500 Temperature [°C] 600 700 800 Fig. 386. Tensile strength (circles) and yield stress (triangles) data of 25Cr-20Ni-Nb-N steel tubes. 2.4.16.4 Creep rupture properties of 25Cr-20Ni-Nb-N steel tubes 2.4.16.4.1 Creep rupture data of 25Cr-20Ni-Nb-N steel tubes Fig. 387 shows creep rupture data of 25Cr-20Ni-Nb-N steel tubes with average curves assessed by the Larson-Miller parameter method [1]. The longest creep rupture datum of 25Cr-20Ni-Nb-N steel tubes is about 90000 h at 700 °C. Their long-term creep strength is very stable and no degradation in creep strength is expected at temperatures up to 750 °C. Fig. 388 shows a Larson-Miller parameter plot of the creep rupture data of 25Cr-20Ni-Nb-N steel tubes with a master rupture curve and a 95 % confidence lower limit. The best fitting was achieved with an optimized constant of 16.96. 500 400 300 Stress [MPa] 600 °C 200 650 °C 100 80 60 40 700 °C 600 °C 650 °C 700 °C 750 °C average curve 1 Landolt-Börnstein New Series VIII/2B 10 750 °C 10 2 10 3 Rupture time [h] 10 4 10 5 Fig. 387. Creep rupture data of 25Cr-20Ni-Nb-N steel tubes. 294 2.4 Austenitic stainless steels 500 600 °C ×10 5h 400 Stress [MPa] 300 650 °C ×10 5h 200 700 °C ×10 5h 100 600 °C 650 °C 700 °C 750 °C 80 60 40 14 average curve minimum curve Fig. 388. Larson-Miller parameter plot of the creep rupture data of 25Cr-20Ni-Nb-N steel tubes. 15 16 17 18 19 20 21 22 23 24 Larson-Miller-parameter T (16.96 + log t )[×10 -3 ] 2.4.16.4.2 Creep data of 25Cr-20Ni-Nb-N steel tubes Fig. 389 shows minimum creep rate data of 25Cr-20Ni-Nb-N steel tubes measured at various stress levels at temperatures between 600 °C and 750 °C with fitted curves obtained by the Larson-Miller parameter method shown in Fig. 390 [1]. Fig. 390 shows a Larson-Miller parameter plot of the minimum creep rate data of 25Cr-20Ni-Nb-N steel tubes with a master curve. The best fitting was achieved with an optimized constant of 19.06. 500 400 Stress [MPa] 300 200 600 °C 650 °C 100 600 °C 650 °C 700 °C 750 °C average curve 80 700 °C 60 750 °C 40 10 -2 10 -1 1 10 Minimum creep rate [% / 10 3 h] 10 2 10 3 Fig. 389. Minimum creep rate data of 25Cr-20Ni-Nb-N steel tubes. Landolt-Börnstein New Series VIII/2B Ref. p. 296] 2.4.16 25Cr-20Ni-Nb-N steel 295 500 400 600 °C 0.01%/10 3h Stress [MPa] 300 650 °C 0.01%/10 3h 200 700 °C 0.01%/10 3h 100 600 °C 650 °C 700 °C 750 °C 80 60 average curve 40 13 14 15 16 17 18 19 20 21 22 23 Larson-Miller-parameter T (19.06 + log e ) [×10 -3 ] Fig. 390. Larson-Miller parameter plot of the minimum creep rate data of 25Cr-20Ni-Nb-N steel tubes. 2.4.16.5 Allowable stress of 25Cr-20Ni-Nb-N steel tubes Fig. 391 shows the allowable stress determined for 25Cr-20Ni-Nb-N steel (Japanese METI KASUS310HCbN) according to the METI standard procedure comparing with that for the conventional steel ASME SA213-TP347HTB (Japanese METI KA-SUSTP347HTB). 180 KA-SUS310J1TB Allowable tensile stress (MPa) 160 140 120 100 KA-SUSTP347HTB 80 60 40 Fig. 391. Allowable tensile stress determined for 25Cr20Ni-Nb-N steel tubes according to the Japanese METI standard. 20 0 0 100 200 300 400 500 600 700 800 Temperature ( ℃) 2.4.16.6 Microstructural change of 25Cr-20Ni-Nb-N steel tubes The microstructural change in 25Cr-20Ni-Nb-N steel tubes after aging for up to 10000 h in the temperature range between 600 °C and 750 °C is available in [2] and [4]. There is no significant microstructural change observed even after aging for 10000 h at 750 °C. A detailed TEM observation of the specimens aged for 3000 h in the temperature range between 600 °C and 750 °C has shown that fine NbCrN nitride dispersion is identified in the matrix and no harmful blocky precipitation such as σ phase is found. Landolt-Börnstein New Series VIII/2B 296 2.4 Austenitic stainless steels 2.4.16.7 Performance of service exposed tubes Performance of service exposed tubes is available in [5]. 2.4.16.8 References [1] Sumitomo seamless tubes and pipe Creep Data Sheets, Sumitomo Metal Industries, (1993). [2] Sawaragi, Y., Teranishi, H., Makiura, H., Miura, M., and Kubota, M.: Sumitomo Metals, 37 (1985), 66. [3] Sawaragi, Y.: The Journal of Japan Welding Society, 58 (1989), 193. [4] Sawaragi, Y., Teranishi, Y., Iseda, A., Yoshikawa, K.: Sumitomo Metals, 42 (1990), 260. [5] Natori, A., Sawaragi, Y.: Sumitomo Metals, 45 (1993), 96. [6] Sawaragi, Y., Teranishi, H., and Yoshikawa, K.: Proc. of Int. Conf. on Creep, Tokyo, (1986), 239. [7] Yoshikawa, K., Sawaragi, Y., and Yuzawa, H.: Proc. of Int. Conf. on Improved Coal-Fired Power Plants, EPRI, Palo Alto, (1986), 5. [8] Sawaragi, Y., Teranishi, H., Iseda, A., and Yoshikawa, K.: The Sumitomo Search, No.44 (1990), 146. Landolt-Börnstein New Series VIII/2B Ref. p. 300] 2.4.17 25Cr-35Ni steel 297 2.4.17 25Cr-35Ni steel 2.4.17.1 Introduction This material is used as centrifugally cast tubes and cast blocks of 25Cr-35Ni-0.4C steel for reformer furnaces. It is a heat resisting steel casting and is manufactured by the centrifugal casting process or the mould casting process. Heat treatment is not performed, but this steel is used as-casted. 2.4.17.2 Material standards, chemical compositions and tensile properties The following information is obtained from [1]. Table 170 shows the specification (SCH 24(JIS G 5122)) of the chemical composition of 25Cr-35Ni0.4C steel and analysis results for the chemical compositions of three typical heats used for data treatment in this article. Three heats were made by the centrifugal casting process and one heat was made by the mould casting process. The chemical compositions are almost equivalent and there is little difference between the heats and the casting processes. Table 170. Specification of chemical composition and analysis results for 25Cr-35Ni-0.4C steel SCH24(JIS G 5122) and HP(ASTM). Chemical composition [wt%] Product C Si Mn P S Ni Cr Fe Requirement 0.35-0.75 ≤2.00 ≤2.00 ≤0.040 ≤0.040 33.0-37.0 24.0-28.0 Rem. Cast tube (typical Heat 1 0.48 0.83 1.01 0.009 0.005 34.47 25.64 Rem. example) Heat 2 0.48 0.97 0.81 0.014 0.009 35.63 27.49 Rem. Heat 3 0.42 0.82 1.02 0.01 0.018 34.4 24.75 Rem. Cast block Heat 1 0.47 0.9 0.97 0.008 0.009 35.02 26.11 Rem. Table 171 shows the specification of the tensile properties at room temperature and the test results of the heats tested here. As for the heat resisting steel castings which were made by the centrifugal casting process, the difference between the heats is small. However, the tensile strength of the heat resisting steel casting made by the mould casting process is quite low compared with those of the heats made by the centrifugal casting process. Although the 0.2% proof stress shows the same tendency, the difference is small compared with the tensile strength. Moreover, the tensile elongation and the reduction of area of the mould casted heat are quite low compared with the centrifugal casted heat. Table 171. Specification of tensile properties HP(ASTM). Product Tensile properties Tensile strength [MPa] Requirement ≥440 Cast tubes Heat 1 490 (typical example) Heat 2 530 Heat 3 510 Cast block Heat 4 400 for 25Cr-35Ni-0.4C steel SCH24(JIS G 5122) and 0.2% proof stress [MPa] ≥235 245 260 250 230 Elongation [%] ≥5 10 15 16 9 Reduction of area [%] 13 12 16 11 Next, the high temperature tensile properties will be reviewed. First, the tensile properties of the heat resisting steel casting made by the centrifugal casting process are shown below. Fig. 392 a - d show the tensile strength, 0.2% proof stress, tensile elongation and reduction of area from room temperature to 900 °C. The solid lines express the average level for each tensile property. The decrease of tensile strength is relatively large in the low temperature region up to near 200 °C , but after that, the tensile Landolt-Börnstein New Series VIII/2B 298 2.4 Austenitic stainless steels 600 600 500 500 400 400 0.2 % proof stress [MPa] Tensile strength (MPa) strength is almost constant up to near 400 °C . Then, a large decrease takes place in the higher temperature region, especially the fall of tensile strength is remarkable at 700 °C or more. The tendency of 0.2% proof stress is almost the same as that of tensile strength up to near 600 °C. However, proof stress rises near 700 °C and at higher temperatures it decreases again.. The tensile elongation and the reduction of area are in a tendency completely contrary to 0.2% proof stress, and there is a phenomenon of falling near 700 °C. 300 200 300 200 100 100 0 0 0 200 400 600 800 0 1000 200 70 70 60 60 Reduction of area (%) Elongation (%) 600 800 1000 800 1000 b a 50 40 30 50 40 30 20 20 10 10 0 0 0 200 400 600 800 1000 0 Temperature (℃) c 400 Temperature (℃) Temperature (℃) 200 400 600 Temperature (℃) d Fig. 392. Tensile strength (a), 0.2% proof stress (b), elongation (c) and reduction of area (d) for 25Cr-35Ni-0.4C steel made by centrifugal casting process. Next, the tensile properties of the heat resisting steel casting manufactured by the mould casting process are shown in Fig. 393 a - d. The tensile strength is lower than that of the steel manufactured by the centrifugal casting process at room temperature. Although the tensile strength tends to decrease with increasing temperature, the degree of the decrease is relatively small. The tensile strength of both steels becomes almost equivalent near 800 °C. 0.2% proof strength of both steel casts is very similar, but there is no increase of 0.2% proof strength near 700 °C in the mould cast heat resisting steel. Although tensile elongation and reduction of area are lower than those of the steel manufactured by the centrifugal casting process , they become almost equivalent at 400 °C or more. The mould casted steels tend to higher values up to 700 °C and then decrease again up to 800 °C, whereas the centrifugally casted steels have a minimum at about 700 °C and then strongly increase up to 800 °C. Landolt-Börnstein New Series VIII/2B 2.4.17 25Cr-35Ni steel 700 700 600 600 500 500 0.2 % proof stress [MPa] Tensile strength (MPa) Ref. p. 300] 400 300 200 299 400 300 200 100 100 0 0 0 200 400 600 800 0 1000 200 600 800 1000 800 1000 b a 70 70 60 60 Reduction of area (%) Elongation (%) 400 Temperature (℃) Temperature (℃) 50 40 30 50 40 30 20 20 10 10 0 0 0 200 400 600 800 1000 0 Temperature (℃) c 200 400 600 Temperature (℃) d Fig. 393. Tensile strength (a), 0.2% proof stress (b), elongation (c) and reduction of area (d) for 25Cr-35Ni-0.4C steel made by the mould casting process. 2.4.17.3 Creep rupture properties of 25Cr-35Ni steels Fig. 394 shows the creep rupture strength of 25Cr-35Ni-0.4C steel manufactured by the centrifugal casting process. Creep tests were carried out at temperatures in 50 °C pitch from 850 °C to 1000 °C and at stresses between 10 MPa and 69 MPa. The longest time to rupture was over 50,000 h. The test data shows a slightly larger scattering for high temperatures. Fig. 395 shows the creep rupture strength of 25Cr-35Ni-0.4C steel manufactured by the mould casting process. Although there are less data points as in Fig. 394, it can be said that the creep rupture strength is at an equivalent level for both steels. However, there is a tendency that the degree of the decreasing of creep rupture strength in the mould steel casting is lower than that in the centrifugal steel casting for 1000 °C and 1100 °C. Landolt-Börnstein New Series VIII/2B 300 2.4 Austenitic stainless steels Stress (MPa) 100 10 T=850℃ T=900℃ T=950℃ T=1000℃ T=1100℃ 101 102 Fig. 394. Creep rupture strength data for 25Cr-35Ni0.4C steel made by the centrifugal casting process. 103 104 105 Time to rupture (h) Stress (MPa) 100 10 T=850℃ T=900℃ T=950℃ T=1000℃ T=1100℃ 101 102 Fig. 395. Creep rupture strength data for 25Cr-35Ni0.4C steel made by the mould casting process. 103 104 105 Time to rupture (h) 2.4.17.4 Reference [1] National Research Institute for Metals : NRIM Creep Data Sheet, No. 38A, (1991). Landolt-Börnstein New Series VIII/2B Ref. p. 308] 2.4.18 27Cr-32Ni-Nb-Ce steel 301 2.4.18 27Cr-32Ni-Nb-Ce steel 2.4.18.1 Introduction 27Cr-32Ni-Nb-Ce steel (Grade X6NiCrNbCe 32-27, also called AC 66) is a development based on alloy 800. Originally it was invented to be used in coal gasification plants with process gases including H2S, SO2, HCl, CO etc. operating at 950 °C. It is characterized by an austenitic microstructure with 28 % chromium, 32 % nickel and 0.05 % - 0.10 % cerium. Owing to its generally good corrosion resistance, further applications were found in waste incineration plants in which AC 66 tubes have been successfully operated as super-heater bundles at 500 to 600 °C. The material has a fully austenitic grain structure (Fig. 396) with a high thermal stability. The mechanical properties remain unchanged after exposure up to 30,000 h at temperatures up to 1000 °C. Embrittlement due to intermetallic phases like the σ phase does not occur. Fig. 396. Tenitic structure of AC 66. For tubes and pipes with a wall thickness of less than 20 mm, grain sizes of ASTM 5-7 are usually obtained. A grain size of ASTM 3-4 must be assumed for pipes with larger wall thickness. 2.4.18.2 Material standards, chemical composition and tensile requirements Table 172. Chemical requirements of X6NiCrNbCe 32-27 steel tubes concerning: ASTM A 213, A 321, VdTÜV data sheet 497 (Grade-no. 1.4877) and EN 10095. Std. Chemical composition [wt%] Designation Standard No. C Si Mn P S Cr Ni Al Nb Ce A213 UNS S 0.04 26.0 31.0 0.6 0.05 ASTM ≤0.30 ≤1.0 ≤0.020 ≤0.015 ≤0.025 A312 33228 0.08 28.0 33.0 1.0 0.10 0.04 26.0 31.0 0.6 0.05 VdTÜV 497 1.4877 ≤0.30 ≤1.0 ≤0.015 ≤0.010 ≤0.025 0.08 28.0 33.0 1.0 0.10 X6NiCrNbCe 0.04 26.0 31.0 0.6 0.05 EN 10095 ≤0.30 ≤1.0 ≤0.020 ≤0.010 ≤0.025 32-27 0.08 28.0 33.0 1.0 0.10 The formation of protective oxide layers is guaranteed by the high chromium content of about 27 %, which is high enough to ensure the healing of the scale cracks caused by mechanical or temperatureinduced stressing. Scale spalling due to temperature changes has been significantly reduced through the addition of cerium. The limitation of the aluminium and silicon contents is necessary in order to ensure the required resistance to internal oxidation. The niobium content improves the tensile properties. Landolt-Börnstein New Series VIII/2B 302 2.4 Austenitic stainless steels Normally all products are delivered in a solution annealed condition with an annealing temperature between 1120 °C and 1180 °C, according to the VdTÜV data sheet 497. According to the EN 10095 standard, the recommended annealing temperature range is 1050 - 1150 °C. Table 173. Room temperature mechanical property requirements for X6NiCrNbCe 32-27. Rp0.2: Minimum 0.2% proof strength; Rp1.0: Minimum 1.0% proof strength; Rm: Tensile strength. Section size Rp0.2 Rp1.0 Rm Standard Std. No. Designation Product [mm] [Nmm-2] [Nmm-2] [Nmm-2] VdTÜV 497 1.4877 Plate 185 500-750 ≤30 VdTÜV 497 1.4877 Bar 185 500-750 ≤250 VdTÜV 497 1.4877 Tube <180 185 215 500-750 EN 10095 X6NiCrNbCe32-27 Plate 180 500-750 ≤75 EN 10095 X6NiCrNbCe32-27 Bar 180 500-750 ≤160 Table 174. Minimum 0.2% and 1.0% proof strength values and tensile strength values at elevated temperatures for X6NiCrNbCe 32-27 Std. Minimum 0.2% proof strength, Rp0.2 [Nmm-2] at a temperature [°C] of Designation Standard No 100 200 300 350 400 450 500 550 600 650 700 VdTÜV 497 1.4877 160 140 120 110 105 100 95 90 90 85 80 Standard VdTÜV Standard VdTÜV Std. No 497 Std. No 497 Designation 1.4877 Designation 1.4877 Minimum 1.0% proof strength, Rp1.0 [Nmm-2] at a temperature [°C] of 100 200 300 350 400 450 500 550 600 650 700 190 170 145 135 130 125 115 110 110 105 100 100 450 Minimum Rm [Nmm-2] at a temperature [°C] of 200 300 350 400 450 500 550 600 650 430 410 400 390 380 370 360 340 300 700 250 2.4.18.3 Creep rupture strength Creep tests [3], [4] and [8] have been carried out on X6NiCrNbCe 32-27 (AC 66) in the temperature range between 600 and 950 °C. The test results are represented in Fig. 397 in form of a Larson-Miller plot. With a few exceptions all rupture points are included within a scatterband of ± 30 % in stress. 2.6 2.4 2.2 2.0 Log (σ) 1.8 1.6 1.4 1.2 Data Mean Line 1.0 0.8 Fig. 397. Larson-Miller plot of creep rupture strength of AC 66 (Data: 600 - 950 °C, 3.8 - 320 MPa; scatterband: ±30 % in stress). 0.6 0.4 16 18 20 22 24 26 28 T (16.76 + log t R) / 1000 Landolt-Börnstein New Series VIII/2B Ref. p. 308] 2.4.18 27Cr-32Ni-Nb-Ce steel 303 Since the material originally was developed for application in coal gasification plants, most tests were carried out between 850 and 950 °C (Fig. 398 to 400). 100 Stress (MPa) 850°C 10 Data Mean Line 1 10 100 1000 10000 100000 100 Au, Z (%) 80 60 40 Fig. 398. Test results on creep rupture strength and ductility at 850 °C (Mean line acc. Larson-Miller evaluation; scatterband: + 30 % in stress). Au Z 20 0 10 Landolt-Börnstein New Series VIII/2B 100 1000 Time (h) 10000 100000 304 2.4 Austenitic stainless steels 100 Stress (MPa) 900°C 10 Data Mean Line 1 10 100 1000 10000 100000 100 Au, Z (%) 80 Au Z 60 40 20 0 10 100 1000 Time (h) 10000 100000 Fig. 399. Test results on creep rupture strength and ductility at 900 °C (Mean line acc. Larson-Miller evaluation; scatterband: + 30 % in stress). Landolt-Börnstein New Series VIII/2B Ref. p. 308] 2.4.18 27Cr-32Ni-Nb-Ce steel 305 100 Stress (MPa) 950°C 10 Data Mean Line 1 10 100 1000 10000 100000 100 Au, Z (%) 80 Au Z 60 40 Fig. 400. Test results on creep rupture strength and ductility at 950 °C (Mean line acc. Larson-Miller evaluation; scatterband: + 30 % in stress). 20 0 10 100 1000 Time (h) 10000 100000 The upper half of the figures shows creep rupture strength with respect to time, including the mean line and scatterband from the Larson-Miller evaluation. In the lower half the accompanying rupture ductility values are given, i.e. rupture elongation (Au) and reduction of area (Z). In most cases high ductility values of more than 20 % are obtained. The tests have been performed both in air and in simulated coal gasification atmosphere, but no difference with respect to the test atmosphere could be observed. Only a limited number of tests have been carried out at lower temperatures (Fig. 401). The values follow the trend as given by the Larson-Miller mean lines. Landolt-Börnstein New Series VIII/2B 306 2.4 Austenitic stainless steels 1000 600°C 650°C Stress (MPa) 700°C 750°C 100 800°C 600°C 650°C 700°C 750°C 800°C Fig. 401. Creep test results at 600, 650, 700, 750 and 800 °C (Mean lines acc. Larson-Miller evaluation). 10 10 100 1000 10000 100000 Time (h) Fig. 402 shows the characteristic strength properties which are used for design. The mean line of the mean 105 h creep rupture intersects the lines of minimum 0.2% and 1.0% proof strength in the range of 630 to 660 °C. A design below that temperature range uses strength values which are not time dependent. 180 160 5 Rm (10 h) 140 Strength (MPa) 120 100 Rp1.0 (Min) 80 Rp0.2 (Min) 60 40 20 0 500 Fig. 402. Design strength values of AC 66. 600 700 800 900 1000 Temperature (°C) The creep rupture strength of X6NiCrNbCe 32-27 is shown in Fig. 403. The analysis from which the data in the figure are derived was carried out as part of the activities of the European Creep Collaborative Committee and additional details can be found in their published data sheets [9]. Landolt-Börnstein New Series VIII/2B Ref. p. 308] 2.4.18 27Cr-32Ni-Nb-Ce steel 307 1000 10,000h 100,000h Stress [MPa] 100 10 Fig. 403. Creep rupture strength of X6NiCrNbCe 3227. 1 500 600 700 800 900 1000 Temperature [°C] The creep rupture properties have been obtained by comparative analysis of strength values as reported in VdTÜV data sheet 497. Due to the comparative analysis assessment method, no master equation is available. The test data used for the original analyses were related to several casts tested at temperatures of 580 950 °C. 2.4.18.4 Estimated long term creep rupture strength Based on the data shown in Fig. 403 the 100,000 h rupture strength values for a range of temperatures are as follows: Temperature Stress 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] 580 590 600 610 620 630 640 650 160 150 140 130 120 111 101 92 660 83 670 74 Temperature Stress 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] 680 690 700 710 720 730 740 750 66 58 52 45 39 34 30 27 760 24.5 770 22 Landolt-Börnstein New Series VIII/2B 308 2.4 Austenitic stainless steels Temperature Stress 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] 780 790 800 810 820 830 840 850 20 18 16 14.5 13 11.5 10 9 860 8 Temperature Stress 100,000 h rupture strengths [Nmm-2] at specified temperatures [°C] 870 880 890 900 910 920 930 7 6.3 5.6 5 4.5 4 3.6 950 3 940 3.3 All of the values have involved extended extrapolation Other 104 h and 105 h creep rupture strength values between 580 and 1000 °C are listed for AC 66 steel in [1]. 2.4.18.5 References [1] VdTÜV data sheet 497: High-Temperature Rolled and Forged Steel; X5 NiCrCeNb 32-27; GradeNo 1.4877 [in German], 1998. [2] Lindemann, J., and Schendler, W.: Ein neuer Fe-Ni-Cr-Werkstoff (AC 66) für Komponenten in Combined-cycle Kraftwerken sowie in modernen Müllverbrennungsanlagen. VGB Kraftwerkstechnik 71 Jahrgang, Heft 8, August (1991), Seite 746-754 [in German]. [3] Final Report WE 998 B; 23rd. February (1989) of TÜV RHEINLAND. [4] Bendick, W., Lindemann, J., Schendler, W.: Development of a New High-temperature Alloy for Coal Gasification; Combined Cycle Processes and Waste Incinceration High-temperature Materials for Power Engineering, Sept. 24-27, (1990); Liège, Belgium. [5] Final Report Legierungsentwicklung für den Wärmetauscher der Wasserdampf-Kohlevergasung 01.01. (1982) - 31.12. (1988), Bergbauforschung, Mannesmann Forschungsinstitut [in German]. [6] R. Plür: Experience with and Measures for the Reduction of Corrosion and Flue Gas-side Deposition on the Heating Surfaces of the Boilers of GMVA Niederrhein GmbH VGB Kraftwerkstechnik Vol.70, No. 8, August (1990), 589-596 [7] AC 66: Iron-nickel-chrome alloy for high temperature service; MANNESMANN EDELSTAHLROHR; information paper Edition (1992). [8] Collected data of the MANNESMANN FORSCHUNGSINSTITUT GmbH, Duisburg. [9] ECCC Data sheet for X6NiCrNbCe 32-27, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). Landolt-Börnstein New Series VIII/2B Ref. p. 311] 2.4.19 30Cr-50Ni-2Mo-Ti-Zr-B steel 309 2.4.19 30Cr-50Ni-2Mo-Ti-Zr-B steel 2.4.19.1 Introduction 30Cr-50Ni-2Mo-Ti-Zr-B steel (TEMPALOY CR30A, or CR30A for short) was developed by NKK, Japan in the 1980s for heat exchanger tubings such as boiler superheaters and reheaters, steam generators, chemical plants operated at very high temperatures of around 700 °C and in severely corrosive environments. The CR30A steel features well-balanced hot corrosion resistance through increased Cr content, high temperature creep rupture strength by alloying with Mo and improved fabricability and weldability by means of the addition of Ti, Zr and B. The creep rupture strength of CR30A is comparable to that of 17-14CuMo. The hot corrosion resistance of CR30A under the environmental conditions of 1 % SO2 containing gas with equivalent amounts of 5 % O2, 15 % CO2 and N2, and molten ash with 34 %Na2SO4 - 41 % K2SO4 - 25 % Fe2O3 is much better than that of Alloy 617 and Alloy 800H at 700 °C. 2.4.19.2 Material standards, chemical and tensile requirements [1] CR30A steel is not specified in any codes or standards except the internal specifications of NKK. Table 175 and Table 176 respectively show the requirements for the chemical composition and tensile properties specified by NKK. The tensile properties at room temperature are almost equivalent to those of 18Cr-8Ni stainless steels. Fig. 404 shows the absorbed energies obtained by Charpy impact tests at 0 °C using full size specimens with a 2 mm V-notch [2]. Table 175. Typical chemical composition of CR30A steel; [1]. Chemical composition [wt%] Product C Si Mn Ni Cr Mo Al Ti Zr B Fe Tube 0.06 0.2 0.1 50 30 2 0.1 0.2 0.03 0.005 Bal. Table 176. Typical tensile properties of CR30A steel at room temperature; [1]. Product Yield strenth (0.2% offset) Tensile strength Elongation [MPa] [MPa] [%] Tube 279 612 75 2.4.19.3 Creep properties [2], [3] 2.4.19.3.1 Creep rupture data and creep rupture strength Table 177 lists the chemical compositions of the steels tested, which were melted as 150 kg ingots and solution treated at 1180 °C for 0.5 h after rolling the plate to a 15 mm thickness. Fig. 405 shows the creep rupture stress vs. time to rupture diagram for CR30A steel in the temperature range of 600 °C to 1000 °C. The Larson-Miller plot of the creep rupture data for CR30A steel is shown in Fig. 406. The creep rupture strength of CR30A is comparable to that of 17-14CuMo steel. The 100,000 h rupture strengths obtained by linear extrapolation of the stress vs. time to rupture curves of CR30A steel at 650 °C and 700 °C are 147 MPa and 108 MPa, respectively. However, the Larson-Miller plot yields rather conservative estimations, i.e., 125 MPa for 650 °C and 843 MPa for 700 °C. Landolt-Börnstein New Series VIII/2B 310 2.4 Austenitic stainless steels Temperature [°C ] v E0 [J] 900 66 45 49 800 90 40 27 66 53 29 80 45 27 14 53 26 600 180 150 130 500 374 382 330 300 1000 3000 Aging time [h] 700 Fig. 404. Time-Temperature-Absorbed energy map at 0 °C for CR30A steel; [2]. 10000 Table 177. Chemical compositions of alloys tested; [3]. Chemical composition [wt%] Alloy C Si Mn P S Ni Cr Mo Al Ti Zr N Fe CR30A 0.058 0.27 0.20 0.001 0.0007 50.99 30.52 2.11 0.14 0.181 0.027 0.0016 Bal. ZD3 0.004 0.32 0.22 0.001 0.0007 56.19 24.12 2.89 0.21 0.200 0.029 0.0022 Bal. 500 46 38 43 300 40 200 Stress (MPa) 36 38 31 32 20 44 18 19 3132 30 24 22 23 14 12 23 23 13 17 17 26 59 45 61 650℃ 750℃ 65 57 74 800℃ 45 40 600℃ 700℃ 49 63 70 50 13 26 18 61 70 15 18 47 100 36 49 42 46 30 20 43 43 30 51 1000℃ 32 102 101 900℃ 41 Values designate rupture elongation in %. 103 104 105 Fig. 405. Creep rupture strength data of CR30A steel; [1]. Time to rupture (h) 500 550℃ 600℃ 650℃ 700℃ 750℃ 800℃ 900℃ 1000℃ 300 Stress (MPa) 200 100 70 50 30 20 10 18 20 22 24 26 28 30 Fig. 406. Creep rupture master curve of CR30A steel by Larson-Miller parametric method; [3]. T (20+log t) × 10- 3 Landolt-Börnstein New Series VIII/2B Ref. p. 311] 2.4.19 30Cr-50Ni-2Mo-Ti-Zr-B steel 311 2.4.19.3.2 Microstructural changes during creep The excellent long-term creep rupture strength was found to be due to a high density and uniform dispersion of intergranular precipitates in the bcc chromium phase. Very fine M23C6 carbide also precipitates at the dislocation lines within the grains of austenite during creep, which contributes to enhanced creep strength. 2.4.19.3.3 Creep deformation Creep deformation was measured at 600 °C and 294 MPa for the as-solution treated steel, for steel aged at 700 °C for 1000 h to precipitate α' in the grains, and for a model alloy (ZD3 in Table 177) simulating a single phase structure of γ which appears as a matrix of the aged material. Fig. 407 shows creep curves for these three specimens. The solution-treated steel exhibited a 5 times longer rupture time against ZD3 with a single phase of γ, and the minimum creep rate was 3.5×10−4 h−1 which is 1/5 of that of ZD3. These enhancements of creep in solution-treated steel are considered to be due to the dense precipitations of M23C6 at the dislocation lines. Aged steel with precipitations of α' in the γ grain exhibited a rupture time of twice as long as that of solution-treated steel. In this aged steel most of the M23C6 precipitated at the grain boundaries. 30 Fe-30Cr-50Ni-0Mo 700 °C, 1000 h aged 25 Stress [MPa] 20 ZD3 solution treated Fe-30Cr-50Ni-2Mo solution treated 15 10 5 0 100 200 300 400 Time [h] 500 600 Fig. 407. Creep curves at 650 °C - 294 MPa for ZD3 solution treated and Fe-30Cr-50Ni-2Mo steel solution treated and aged at 700 °C for 1000 h; [3]. 2.4.19.4 References [1] Tamura, M., and Murase, S.: NKK Technical Review, No.56, (1989), 93. [2] Tamura, M., Yamanouchi, N., Tanimura, M., and Murase, S.: Proc. (1985) Exposition and Symposium on Industrial Heat Exchanger Technology, Pittsburgh, PA., (1985), 273. [3] Yamanouchi, N., Shirada, T., Tamura, M., Matsuo, T., and Kikuchi, M.: Tetsu-to-Hagane, 76 (1990), 1179. Landolt-Börnstein New Series VIII/2B 312 2.4 Austenitic stainless steels 2.4.20 21Cr-11Ni-Si-N-Ce steel 2.4.20.1 Introduction 21Cr-11Ni-Si-N-Ce steel (EN 1.4835, X9CrNiSiNCe 21-11-2, UNS S30815) is an austenitic stainless steel designed primarily for use at temperatures exceeding 550 °C, i.e. in the temperature range where creep is controlling the mechanical strength and where oxidation resistance is of importance. EN 1.4835 is represented in the standard EN 10095 [1]. The trade name of EN 1.4835 is 253MA [2]. In comparison with traditional stainless steels, EN 1.4835 has an increased nitrogen content and has been microalloyed with rare earth metals (REM). The most suitable temperature range is 850 - 1100 °C, since structural changes below 850 °C can lead to reduced impact toughness at room temperature. Since the steel is optimized for high temperature service the resistance to aqueous corrosion is limited. EN 1.4835 is used in a number of high temperature applications for example for components within iron, steel, and non-ferrous industries; engineering industry; energy conversion plants, and cement industry. Like other austenitic steels, EN 1.4835 can be formed in hot and cold condition. However, as a result of the relatively high nitrogen content, the mechanical strength is higher and consequently greater deformation forces will be required. Also the ability to strain harden must be taken into consideration in connection with machining. The steel has good weldability and can be welded using shielded metal arc (SMA) welding with covered electrode or gas shielded welding. The latter method has given the best creep properties for welds. 2.4.20.2 Material standards, chemical composition and tensile properties Table 178. Chemical requirements of X9CrNiSiNCe 21-11-2. Standard Std. No. Designation EN 10095 ECCC Data sheet C 0.05 X9CrNiSiNCe 21-11-2 0.12 X9CrNiSiNCe 21-11-2 0.05 (X7CrNiSiNCe 21-11) 0.10 Chemical composition [wt%] Si Mn P S Cr Ni 1.40 20.00 10.00 ≤1.00 ≤0.045 ≤0.015 22.00 12.00 2.50 1.40 20.00 10.00 ≤0.80 ≤0.040 ≤0.030 22.00 12.00 2.00 N 0.12 0.20 0.14 0.20 Table 179. Room temperature mechanical property requirements for X9CrNiSiNCe 21-11-2. StanHeat Thickness Rp0.2 Rp1.0 Rm Std. No. Designation dard treat [mm] [MPa] [MPa] [Nmm-2] X9CrNiSiNCe 21-11- Solution 650 EN 10095 310 350 ≤75 2 annealed 850 X9CrNiSiNCe 21-11Solution 640 ECCC Data sheet 2 295 345 ≤30 annealed 850 (X7CrNiSiNCe 21-11) Ce 0.03 0.08 0.03 0.08 A [%] 33 - Table 180. Minimum 0.2% proof strength values at elevated temperatures for X9CrNiSiNCe 21-11-2. Standard Designation Thickness Heat treat [mm] Avesta 1.4835 Polarit [2] ≤75 Solution annealed Minimum 0.2% proof strength, Rp0.2 [MPa] at a temperature [°C] of 50 100 200 300 400 500 600 700 280 230 185 170 160 150 140 130 Landolt-Börnstein New Series VIII/2B Ref. p. 314] 2.4.20 21Cr-11Ni-Si-N-Ce steel 313 2.4.20.3 Creep rupture strength The creep rupture strength of X9CrNiSiNCe 21-11-2 is shown in Fig. 408. The values have been derived from experimental creep data using the free temperature time temperature parameter. This was carried out as part of the activities of the European Creep Collaborative Committee [3] and [4]. Rupture strength, MPa 200 X9CrNiSiNCe 21-11-2 100 10000 h 100000 h 200000 h 50 20 10 5 500 Fig. 408. Creep rupture strength data of X9CrNiSiNCe 21-11-2; [3], [4]. 600 700 800 900 1000 1100 Temperature, °C 2.4.20.4 Estimated long term creep rupture strength Values from Fig. 408 as well as from EN 10095 are summarized in Table 181 [1] and [3]. Table 181. Creep strength to rupture and to 1% strain of X9CrNiSiNCe 21-11-2 Standard Std. No. Criterion ECCC ECCC ECCC EN Data sheet Data sheet Data sheet 10095 Rupture Rupture Rupture Rupture Temperature [°C] 550 600 650 700 750 800 850 900 950 1000 1050 1100 EN 10095 1% strain EN 10095 1% strain 10,000 h 100,000 h 200,000 h 10,000 h 100,000 h 10,000 h 100,000 h 208.3 138.2 91.8 61.2 41.2 28.2 19.6 14 10.3 7.8 6.1 5.0 149.4* 88.2 54.4* 35.1* 23.5* 16.3 11.8 8.7 6.7* 5.3* 4.2* 3.5* 135.2* 77.0* 46.5* 29.6* 19.8* 13.9* 10.1* 7.6* 5.9* 4.7* - EN 10095 Rupture 157 88 126 80 63 35 45 26 27 15 19 11 13 8 10 6 7* 4* 5* 3* * : Values which have involved extended time extrapolation (more than a factor of three in time) - : Values which have involved extended stress extrapolation Landolt-Börnstein New Series VIII/2B 314 2.4 Austenitic stainless steels The errors in the ECCC values in Table 181 due to the uncertainties in the evaluation procedure, are about 5 % of the values or 1 MPa whichever is the largest. In spite of this the values in Table 181 are given with 2 to 4 figures to avoid unnecessary loss in precision. 2.4.20.5 References [1] European Standard EN 10095 “Heat-resisting steels and nickel alloys” (1999). [2] High Temperature Stainless Steel, Data sheet, AvestaPolarit (2002). [3] ECCC Data sheet for of X7CrNiSiNCe 21-11, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). [4] Lindé, L, Sandström, R, Gommans, R, Spindler, M. W., An Evaluation of Creep Rupture Data for the New European Standard for Stainless Steels-Edition 3, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep (1999). [5] Lindé, L, Sandström, R, Creep rupture of the 21Cr 11Ni Si N Rem Stainless steel 253MA- Data collation and assessment, Swedish Institute for Metals Research, Report IM-3572 (1998). Landolt-Börnstein New Series VIII/2B Ref. p. 318] 2.4.21 15Cr-10Ni-1Mo-Mn-Nb-V-B steel 315 2.4.21 15Cr-10Ni-1Mo-Mn-Nb-V-B steel 2.4.21.1 Introduction 15Cr-10Ni-1Mo-Mn-Nb-V-B steel (X10CrNiMoMnNbVB 15-10-1, Esshete 1250) is an austenitic steel made by Corus in the UK. It is well established as superheater boiler tube material in UK power stations [1] and has an approximately 30 % creep strength advantage over Type 316, which is a recognized standard for similar applications. Esshete 1250 is readily welded with either inert gas welding with wires/rods or metal arc welding with covered electrodes. In addition to its application as boiler tubing Esshete 1250 has been used for piping and headers in super critical plant [1]. Furthermore, warm working can increase the tensile and creep properties of Esshete 1250. This enables the material to be used for bolting applications [2]. In the solution treated condition the microstructure of Esshete 1250 typically consists of dispersed niobium carbides in an austenite matrix. The microstructure of boiler tubing is fine equiaxed austenite grains, mainly of size ASTM 9 but some at ASTM 7 or 8. Long trails of Nb(CN) particles and a fine background dispersion of carbides in broad bands aligned with the longitudinal direction of the tube wall are also present. 2.4.21.2 Material standards and chemical composition and tensile requirements Table 182. Chemical requirements of X10CrNiMoMnNbVB 15-10-1 (Esshete 1250) steel tubes for pressure purposes concerning EN 10216-5, ASTM A213 and BS 3605 Part 1. Chemical composition [wt%] Stan- Std. Designation dard No. C Si Mn P S Cr Ni Mo Nb V B X10CrNiMoMn 0.06 0.20 5.50 ≤ 14.0 9.0 0.80 0.75 0.15 0.003 ≤ EN 10216-5 NbVB 15-10-1 0.15 1.00 7.00 0.035 0.015 16.0 11.0 1.20 1.25 0.40 0.009 0.06 0.20 5.50 ≤ 14.0 9.0 0.80 0.75 0.15 0.003 ≤ ASTM A213 UNS S 215000 0.15 1.00 7.00 0.040 0.030 16.0 11.0 1.20 1.25 0.40 0.009 3605 0.06 0.20 5.50 ≤ 14.0 9.0 0.80 0.75 0.15 0.003 ≤ BS 215S15 Part 1 0.15 1.00 7.00 0.040 0.030 16.0 11.0 1.20 1.25 0.40 0.009 X10CrNiMoMnNbVB 15-10-1 (Esshete 1250) tubes are usually solution heat treated at a temperature range of 1050 to 1150 °C. Table 183. Room temperature minimum mechanical property requirements for X10CrNiMoMnNbVB 15-10-1 (Esshete 1250). R Rp1.0 Rm Standard Std. No. Designation p0.2 -2 [Nmm-2] [Nmm ] [Nmm-2] 540 3605 215S15 220 270 BS 740 Part 1 Section size ≤250 mm Table 184. Minimum 0.2% and 1.0% proof strength values at elevated temperatures for X10CrNiMoMnNbVB 15-10-1 (Esshete 1250). DesigMinimum 0.2% proof strength, Rp0.2 [Nmm-2] at a temperature [°C] of Standard Std. No. nation 100 150 200 250 300 350 400 450 500 550 600 650 3605 215S15 188 171 161 153 148 145 144 141 139 136 133 130 BS Part 1 Section size ≤250 mm Landolt-Börnstein New Series VIII/2B 316 2.4 Austenitic stainless steels Table 184 cont. Standard Std. No. 3605 Part 1 BS Designation Minimum 1.0% proof strength, Rp1.0 [Nmm-2] at a temperature [°C] 100 150 200 250 300 350 400 450 500 550 600 650 215S15 232 210 195 190 187 184 182 179 178 175 170 165 Section size ≤250 mm 2.4.21.3 Creep rupture strength Creep rupture tests have been carried out on X10CrNiMoMnNbVB 15-10-1 (Esshete 1250) in the temperature range between 550 and 950 °C. In addition to the data reported in [3], a considerable quantity of long term creep rupture tests were performed by British Steel and ERA Technology Ltd in the UK. The data are from 218 casts and the test durations extend to 178,988 h (at 700 °C), 143,109 h (at 650 °C) and 153,491 h (at 600 °C). 1000 Stress [MPa] 10,000h 30,000h 100,000h 200,000h 250,000h 100 Fig. 409. Creep rupture strength data of X10CrNiMoMnNbVB 15-10-1 (Esshete 1250). 10 550 600 650 700 750 800 Temperature [°C] Not continuous line denotes extended time extrapolation. The creep rupture test results at 600 to 800 °C have been analyzed in [4] using the standard ISO 6303 method. The extent of the data that were analyzed is shown in Table 4. Landolt-Börnstein New Series VIII/2B Ref. p. 318] 2.4.21 15Cr-10Ni-1Mo-Mn-Nb-V-B steel Table 185. Distribution of test durations used to derive the stress rupture properties of X10CrNiMoMnNbVB 15-10-1 (Esshete 1250). Number of test points at the various test durations 10,000 20,001 30,001 50,001 70,001 <10,000 h 20,000 h 30,000 h 50,000 h 70,000 h 100,000 h 1227 (17) 102 (3) 58 (2) 51 (18) 17 (9) 13 (25) 317 >100,000h 9 ( ) denotes unbroken tests The master curve, that was derived with the ISO 6303 method, is described by: P (σ ) = a + b (logσ ) + c (logσ ) 2 + d (logσ ) 3 + e (logσ ) 4 = log t - log t a (T - Ta ) r where P(σ) is the creep rupture parameter; T is the temperature in Kelvin; t is the time to rupture in hours; 2 σ is the stress in N/mm ; r is a temperature exponent; and a, b, c, d, e, r, Ta and log ta are constants (see the following table. log( ta ) Ta r a b c d e −18.431352615 0 −1 −336414.5313 799872.0625 −654687.0625 234517.4219 −31193.5293 2.4.21.4 Creep deformation behavior The creep strength (1 % plastic strain) data for X10CrNiMoMnNbVB 15-10-1 have been assessed using the Larson Miller parameter to predict isochronous curves for up to 100,000 h at 600 to 700 °C. 300 [h] 100 1000 3000 10000 20000 30000 50000 100000 Stress [N/mm 2 ] 200 100 80 60 40 20 600 Landolt-Börnstein New Series VIII/2B 700 800 Temperature [°C] 900 Fig. 410. Isochronous creep curves for X10 CrNiMoMnNbVB 15-10-1. 318 2.4 Austenitic stainless steels 2.4.21.5 Estimated long term creep rupture strength Based on the data shown in Fig. 409 the 100,000 h, 200,000 h and 250,000 h rupture strength values for a range of temperatures are as follows: 100,000 h rupture strengths at specified temperatures Temperature [°C] 600 610 620 630 640 650 660 670 Stress [Nmm-2] 199 185 167 147 122 100 84 74 100,000 h rupture strengths at specified temperatures Temperature [°C] 680 690 700 710 720 730 740 750 Stress [Nmm-2] 66 59 54 49 45 40* 36* 30* * Values which have involved extended time extrapolation 200,000 h rupture strengths at specified temperatures Temperature [°C] 600 610 620 630 640 650 660 Stress [Nmm-2] 183 165 143 118 97 82 72 200,000 h rupture strengths at specified temperatures Temperature [°C] 670 680 690 700 710 720 730 Stress [Nmm-2] 64 58 52 48 43 39 35* * Values which have involved extended time extrapolation 250,000 h rupture strengths at specified temperatures Temperature [°C] 600 610 620 630 640 650 660 Stress [Nmm-2] 177 158 134 109* 90* 78* 69* 250,000 h rupture strengths at specified temperatures Temperature [°C] 670 680 690 700 710 720 Stress [Nmm-2] 62* 56* 51* 46* 42* 37* * Values which have involved extended time extrapolation 2.4.21.6 References [1] Orr, J., Nileshwar, V. B., Esshete 1250: An advanced austenitic stainless steel for power station tubes, piping and headers, Stainless steels ’84 Conference, Gottenburg, Sept (1994). [2] Orr, J., Everson, H., Parkin, G., Warm Worked Esshete 1250: A high strength bolting steel, in Performance of Bolting Materials in High Temperature Plant Applications, IOM London, UK, (1995). [3] Murray, J.D., Hacon, J. Wannell P. H., The high-temperature properties of a advances austenitic steel: Esshete 1250, in High-Temperature Properties of Steels, ISI Publication 97, The Iron and Steels Institute, London, UK, (1967). [4] Burton, D., Orr, J., Dulieu, D., An Assessment of The Stress Rupture Properties of Esshete 1250, British Steel Report No. S/RSC/S1122/2/88/E, (1988). [5] ECCC Data sheet for X10CrNiMoMnNbVB 15-10-1, European Creep Collaborative Committee, BRITE EURAM Thematic Network BET2-0509 “Weld Creep”, (1999). Landolt-Börnstein New Series VIII/2B 3 Superalloys - 3.1 Fe-base alloys 319 3 Creep and rupture data of superalloys 3.1 Fe-base alloys 3.1.1 Fe-15Cr-26Ni-Mo-Ti-V alloy 3.1.1.1 Introduction Fe-15Cr-26Ni-Mo-Ti-V (A286, AISI660, JIS SUH660, ASTM S 66286) alloy is one of the gamma prime precipitation strengthened type iron-base superalloys. This alloy was developed in the 1950s based on German Tinidur alloy and has been widely used as jet engine and gas turbine components such as wheels, disks, blades, shafts, casings and bolts up to about 650 °C because of its good strength, toughness and oxidation resistance [1]. It contains 2 - 3 % Ti plus Al to precipitate gamma prime phase [Ni3(Al,Ti)], 25 % Ni to stabilize austenitic structure, 15 % Cr for corrosion resistance and Mo for improving solid solution strengthening and stabilizing gamma prime phase [2]. Because A286 has also good strength and toughness at cryogenic temperatures, it is used as a cryogenic structural material. It is primarily used as wrought alloy and used after solid solution heat treatment at about 900 - 1000 °C and aging heat treatment at about 700 - 760 °C for gamma prime precipitation [3]. 3.1.1.2 Material standard and chemical composition The chemical composition requirement in JIS G 4311 [3], which is nearly the same as for AMS 5805D, and the mechanical property requirement [3] is given in Table 186. The mechanical properties of the A286 alloy are given in [1], [4], and [5]. Table 186. Chemical composition and mechanical property requirement in JIS G 4311 (1) Chemical composition requirement C Si Mn ≤0.08 ≤1.00 ≤2.00 Chemical composition [wt%] P S Ni Cr Mo 24.00- 13.50- 1.00≤0.040 ≤0.030 27.00 16.00 1.50 V 0.100.50 Ti 1.902.35 Al ≤0.35 B 0.0010.010 (2) Mechanical property requirement Proof stress Tensile strength Elongation Reduction of area [N/mm2] [N/mm2] [%] [%] ≥590 ≥900 ≥15 ≥18 3.1.1.3 Tensile properties 0.2 % proof stress and tensile strength of A286 alloy are shown in Fig. 411 [4]. 3.1.1.4 Creep and rupture properties Creep rupture curves of iron-base A286 alloy at 550 to 700 °C are shown in Fig. 412 [4]. The effect of grain-size on creep strength of this alloy is shown in Fig. 413 [1]. The rupture-stresses from 100 to 100,000 h as a function of temperatures are available in Fig. 414. Minimum creep rate for A286 alloy is reported as shown in Fig. 415 [4]. Landolt-Börnstein New Series VIII/2B 320 3.1 Fe-base alloys Tensile strength 1200 1000 1000 800 800 Stress (MPa) Stress (MPa) 0.2% proof stress 1200 600 400 200 0 600 400 200 0 100 200 300 400 500 600 700 0 800 0 100 200 Test temperature (℃) 300 400 500 600 700 800 Test temperature (℃) Fig. 411. 0.2% proof stress and tensile strength of Fe base A286 superalloy; [4]. 800 700 600 550℃ 600℃ 650℃ 700℃ 500 400 Stress (MPa) 300 200 100 90 80 70 60 Fig. 412. Creep rupture strength data of iron-based A286 alloy of 3 heat turbine discs; [4]. n indicates the total number of data points. n=79 1 10 102 103 104 105 106 Time to ruputure (h) Landolt-Börnstein New Series VIII/2B Ref. p. 322] 3.1.1 Fe-15Cr-26Ni-Mo-Ti-V alloy 321 100 A-286 sheet 100-hour rupture strength [ksi ] 60 40 1300 F 20 1400 F 10 6 1500 F 4 1600 F 2 1 1 2 4 6 10 20 40 60 100 Grain size [ µm ] Fig. 413. Effect of grain size on creep strength of A286; [1]. 1 ksi = 6.89476 MPa 200 400 2000 100 h { 600 500 400 300 Tensile strength 0.2% proof stress { Stress [MPa] 1000 800 200 10000 h 100 80 60 500 550 600 a 700 650 Temperature [°C] 800 750 2000 600 500 400 300 { 200 100 80 60 500 b Landolt-Börnstein New Series VIII/2B Tensile strength 0.2% proof stress { Stress [MPa] 1000 800 1000 h Fig. 414. Temperature dependence of creep rupture strength from 100 to 100000 h; [4]. 100000 h 550 600 700 650 Temperature [°C] 750 800 322 3.1 Fe-base alloys 1000 800 Stress [MPa] 600 500 400 300 550 °C 200 600 °C 100 650 °C 700 °C Fig. 415. Stress vs. minimum creep rate for A286 ironbased superalloy; [4]. n indicates the total number of data points. n = 27 80 60 10-7 550 °C 600 °C 650 °C 700 °C 10-6 10-5 10-4 10-3 10-2 Minimum creep rate [%/h] 10-1 1 3.1.1.5 References [1] [2] [3] [4] [5] Aerospace Structural Metals Handbook, vol.2, code 1601 (1987). The superalloys, ed. by Sims, C. T., and Hagel, W. C., John Wiley & Sons (1972) pp. 20-21. JIS G4311-1991, Heat-resisting steel bars (1991). NRIM Creep Data Sheet, No.22B (1993). Report on the mechanical properties of metals at elevated temperatures, Vol.IV Superalloys, The Iron and Steel Institute of Japan (1979) pp. 1-21. Landolt-Börnstein New Series VIII/2B Ref. p. 326] 3.1.2 Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy 323 3.1.2 Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy 3.1.2.1 Introduction Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy (S590, X40CoCrNi2020) is a member of the well-known 20Co-20Cr-20Ni group of superalloys, which were considered outstanding for high temperature service. It is the strongest of these iron base alloys and is distinguished by its long time stability at high temperature [1]. Its usage for wheels, shafts and buckets for gas turbines and for forgings requires high strength up to 1500 °F and oxidation resistance up to 1800 °F. Flat products and castings are also available; [2] and [3]. The alloy was introduced as S590 for gas turbine buckets in the 1940s [4]. The high creep strength of S590 is obtained by additions of 4 % Mo, 4 % W, 4 % Nb for strengthening the matrix and 0.4 % C for carbide precipitation [5]. The 20 % Cr content of the alloy improves oxidation resistance, while both 20 % Ni and Co additions help stabilize the austenite matrix [6]. 3.1.2.2 Chemical composition and material preparation The chemical compositions shown in Table 187 were reported by the manufacturers except for Al and N, for which the analysis was carried out at NRIM [7]. The chemical requirements coincide with S590 and AMS 5770B(revision 5770D). Material preparation conditions are shown in Table 188. The bars were sampled in 1969. Table 187. Chemical composition of Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars NRIM reference code Requirement fBA fBB fBC C Si Mn P S Chemical composition [wt-%] Ni Cr Mo Cu W 0.38~ 0.48 0.43 0.43 0.40 ≤ 1.00 0.37 0.47 0.56 ≤ 2.00 1.27 1.51 1.18 ≤ 0.040 0.008 0.019 0.005 ≤ 0.030 0.013 0.023 0.003 18.50~ 21.50 20.28 19.79 19.85 19.00~ 22.00 20.26 19.98 20.25 3.50~ 4.50 4.26 3.92 4.12 ≤ 0.50 0.06 0.06 0.05 3.50~ 4.50 4.23 3.98 4.20 Co Al N 18.50~ 3.50~ 21.50 4.50 20.10 0.010 0.0083 4.48 20.09 0.030 0.0114 4.10 19.85 0.044 0.044 3.92 Table 188. Materials preparation of Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars. NRIM Type of Size of Deoxidation Product Dimen Processing and Austenite reference melting ingot process form -sions thermal history grain size code [t] [mm] number fBA 0.15 Al-killed 20 D Hot rolled 7.1 150 L 1204 °C/1 h WQ 760 °C/10 h AC HFIVF fBB 0.10 Al-Ca-Si20 D Hot rolled 7.2 Bar killed 580 L 1190 °C/1 h WQ 760 °C/10 h AC fBC ESR 1.28 20 D Hot rolled 7.4 2000 L 1204 °C/1 h WQ 760 °C/10 h AC HFIVF: high frequency induction vacuum furnace Landolt-Börnstein New Series VIII/2B Nb+Ta Rockwell hardness [HRC] 22 23 24 324 3.1 Fe-base alloys 3.1.2.3 Mechanical properties The mechanical properties of Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars are shown in Fig. 416, obtained from [7]. 0.2 % proof stress 1200 800 800 Stress [MPa] 1000 Stress [MPa] 1000 600 400 upper 95% PI average lower 95% PI 0 200 400 600 Test temperature [°C] 200 800 0 1000 80 80 70 70 Reduction of area [%] 90 60 50 40 20 200 800 1000 1000 800 1000 Reduction of area 10 400 600 Test temperature [°C] 800 40 20 n = 38 400 600 Test temperature [°C] 50 30 0 200 n = 38 60 30 0 0 100 90 10 upper 95% PI average lower 95% PI n = 38 Elongation 100 Elongation [%] 600 400 200 0 Tensile strength 1200 0 n = 38 0 200 400 600 Test temperature [°C] Fig. 416. Short time tensile properties of Fe-20Cr-20Ni-20Co-W-Mo- (Nb+Ta) alloy bars. n indicates the total number of data points. 3.1.2.4 Creep rupture properties The creep rupture properties of Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars are shown in Fig. 417 to 419, which are obtained from [7]. Fig. 417 shows stress vs. time to rupture data at 650, 700, 750 and 800 °C for Fe-20Cr-20Ni-20Co-WMo-(Nb+Ta) alloy bars. The solid curves are based on the Larson-Miller parameter method for all available data at various temperatures. Landolt-Börnstein New Series VIII/2B Ref. p. 326] 3.1.2 Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy 325 500 650 °C 700 °C 750 °C 800 °C 400 300 Stress [MPa] 200 100 80 60 50 40 30 10 Fig. 417. Creep rupture strength data for Fe-20Cr-20Ni-20Co-WMo-(Nb+Ta) alloy bars. n indicates the total number of data points. n = 83 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 418 (next page) shows elongation and reduction of area data at 650, 700, 750 and 800 °C for Fe20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars. It shows the tendency that elongation and reduction of area are decreasing with increasing temperature and rupture times. Fig. 419 shows the master rupture curve obtained by the Larson-Miller parameter method for Fe-20Cr20Ni-20Co-W-Mo-(Nb+Ta) alloy bars. It should be noted that the creep rupture strength has some scatter at high values of this parameter, corresponding to the scatter in creep rupture strength for long times at 750 and 800 °C in Fig. 417. 500 400 300 650 °C 700 °C 750 °C 800 °C Stress [MPa] 200 100 80 60 average curve 40 n = 83 (88)1) 30 18 24 19 20 25 26 22 21 23 Larson-Miller-parameter TK (log t R -18.597) [×10 3 ] Landolt-Börnstein New Series VIII/2B Fig. 419. Master rupture curve by the Larson-Miller parameter method for Fe-20Cr-20Ni-20Co-W-Mo(Nb+Ta) alloy bars. n indicates the total number of data points. 326 3.1 Fe-base alloys 100 100 650 °C 650 °C 80 80 60 60 40 40 20 20 0 n = 23 0 n = 23 100 100 700 °C 700 °C 80 60 60 40 40 Reduction of area [%] 80 Elongation [%] 20 0 n = 23 100 750 °C 80 20 0 100 750 °C 80 60 60 40 40 20 20 0 100 n = 23 n = 17 0 100 n = 17 800 °C 800 °C 80 80 60 60 40 40 20 20 0 10 n = 20 10 2 3 10 10 Time to rupture [h] 4 10 5 0 10 n = 20 10 2 10 3 10 4 Time to rupture [h] 10 5 Fig. 418. Elongation and reduction of area at 650, 700, 750 and 800 °C for Fe-20Cr-20Ni-20Co-W-Mo-(Nb+Ta) alloy bars. n indicates the total number of data points in each diagram. 3.1.2.5 References [1] [2] [3] [4] [5] [6] [7] Aerospace Structural Metals Handbook, Volume I, Ferrous Alloys, 1963, Code 1603, p. 1. Metal Handbook, 8th Edition, Vol.1 Properties and Selection of Metals, AMS (1961), p. 487. Aeronautical Material Specification, AMS5770B (1951). Buergel, R.; Materialwise Werkstofftech , Vol.23, No.8, (1992) 287-292. Matsunaga, Y.; Stainless Steel-Heat Resisting Alloy, Seibunndou Shinkousya (1963) p. 231. Imai, Y.; High Temperature Materials Handbook, Asakura Shoten, (1965) p. 92. NRIM Creep Data Sheet, No.23B, Fe based 20Cr-20Ni-20Co-W-Mo-(Nb+Ta)bars, (1989). Landolt-Börnstein New Series VIII/2B Ref. p. 330] 3.1.3 Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy 327 3.1.3 Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy 3.1.3.1 Introduction Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy (N-155, JIS SUH 616) is an iron-based superalloy containing 20 % Co, 20 % Ni and 21 % Cr. It also contains smaller amounts of Mo, W, and Nb for improved solution strengthening at elevated temperatures, but little or no precipitation strengthening is obtainalble. N-155 is single phase austenitic and hardenable primarily by cold working or by hot-cold working and has good forming, welding, and brazing characteristics. N-155 is used up to approximately 1500 °F (815 °C) and utilized primarily in low-stress applications up to approximately 2000 °F (1093°C), where oxidation resistance is the most significant requirement [1]. The high contents of chromium and cobalt contribute to good hot corrosion resistance. N-155 has been widely used in gas turbine engines, heat exchangers, and other high temperature applications [2]. 3.1.3.2 Chemical composition The chemical compositions shown in Table 189 were reported by the manufacturers except for Al and B, for which the analysis was carried out at NRIM [3]. The chemical requirements coincide with JIS G4311 SUH 661. Materials preparation conditions are shown in Table 190. The bars were sampled in 1971. Table 189. Chemical composition of Fe based 21Cr-20Ni-20Co-3Mo-2.5W-(Nb+Ta)-N alloy NRIM reference code Requirement fFG fFH fFJ C Si Mn P S Chemical composition [wt-%] Ni Cr Mo W Co 0.080.16 0.14 0.12 0.13 ≤ 1.00 0.65 0.53 0.79 1.002.00 1.91 1.56 1.37 ≤ 0.040 0.005 0.006 0.012 ≤ 0.030 0.006 0.006 0.008 19.0021.00 20.16 20.25 20.77 20.0022.50 21.52 20.10 20.12 2.503.50 3.03 2.88 2.78 2.003.00 2.48 2.54 2.10 Al B N 18.500.1021.00 0.20 19.75 <0.01 0.001 0.161 19.35 0.049 <0.001 0.133 18.43 0.055 0.001 0.110 Table 190. Material preparation of Fe based 21Cr-20Ni-20Co-3Mo-2.5W-(Nb+Ta)-N alloy NRIM Type of Size of Deoxidation Product Dimen Processing and Austenite reference melting ingot process form -sions thermal history grain size code [kgf] [mm] number fFG 150 Si-Al-killed 20 D Forged 6.1 HFIF 150 L 1177 °C/1 h WQ fFH ESR 1100 25 D Forged 5.8 5000 L 1150 °C/1 h WQ Bar 800 °C/15 h AC fFJ HFIVF 100 C-killed 20 D Forged 5.7 2740 - 1180 °C/0.5 h 3930 L WQ 816 °C/4 h AC HFIF: high frequency induction furnace, ESR: electroslag remelting, HFIVF: high frequency induction vacuum furnace Landolt-Börnstein New Series VIII/2B Nb+ Ta 0.751.25 1.07 1.02 0.86 Rockwell hardness [HRB] 94 94 92 328 3.1 Fe-base alloys 3.1.3.3 Mechanical properties The mechanical properties of Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings are shown in Fig. 420 [3]. 0.2 % proof stress 900 900 800 800 700 700 600 upper 95% PI average lower 95% PI 500 400 500 400 300 200 200 100 100 0 200 400 600 Test temperature [°C] 800 0 1000 Elongation 100 90 90 80 80 70 70 60 50 40 20 10 10 400 600 Test temperature [°C] 800 1000 800 1000 Reduction of area 40 20 200 1000 50 30 0 800 60 30 0 0 upper 95% PI average lower 95% PI 200 400 600 Test temperature [°C] 100 Reduction of area [%] Elongation [%] 600 300 0 Tensile strength 1000 Stress [MPa] Stress [MPa] 1000 0 0 200 400 600 Test temperature [°C] Fig. 420. Short-time tensile properties of Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. 3.1.3.4 Creep and rupture properties The creep rupture properties of Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings are shown in Fig. 421 to 424 [3]. Fig. 421 shows the stress vs. time to rupture at 550, 650, 750 and 850 °C for iron based 21Cr-20Ni20Co-Mo-(Nb+Ta)-N alloy forgings. Landolt-Börnstein New Series VIII/2B Ref. p. 330] 3.1.3 Fe-21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy 329 1000 500 Stress [MPa] 300 100 50 30 550 °C 650 °C 750 °C 850 °C 10 1 10 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 421. Creep rupture strength data for iron based 21Cr20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. Fig. 422 (next page) shows the elongation and reduction of area at 550, 650, 750 and 850 °C for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. Fig. 423 shows stress vs. minimum creep rate for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. Fig. 424 shows time to rupture vs. minimum creep rate for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)N alloy forgings. 1000 10 6 550 °C 650 °C 750 °C 850 °C 500 105 Time to rupture [h] Stress [MPa] 300 550 °C 650 °C 750 °C 850 °C 100 50 30 104 103 102 10 10-6 10-5 10-4 10-3 10-2 10-1 1 Minimum creep rate [% / h ] Fig. 423. Stress vs. minimum creep rate for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. Landolt-Börnstein New Series VIII/2B 10 10-6 10-5 10-4 10-3 10-2 10-1 1 Minimum creep rate [% /h] Fig. 424. Time to rupture vs. minimum creep rate for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. 330 3.1 Fe-base alloys 100 100 550 °C 550 °C 80 80 60 60 40 40 20 20 0 0 100 100 650 °C 650 °C 80 60 60 40 40 Elongation [%] 20 0 100 750 °C 80 Reduction of area [%] 80 20 0 100 750 °C 80 60 60 40 40 20 20 0 100 0 100 850 °C 850 °C 80 80 60 60 40 40 20 20 0 1 10 10 4 10 3 10 2 Time to rupture [h] 10 5 10 6 0 1 10 10 4 10 3 10 2 Time to rupture [h] 10 5 10 6 Fig. 422. Elongation and reduction of area at 550, 650, 750 and 850 °C for iron based 21Cr-20Ni-20Co-Mo-(Nb+Ta)-N alloy forgings. 3.1.3.5 References [1] Superalloys II, High temperature materials for aerospace and industrial power (1987). [2] Aerospace structural materials handbook, code 1602. [3] NRIM Creep Data Sheet, No. 33A, Fe based 21Cr-20Ni-20Co-3Mo-2.5W-(Nb+Ta)-N Superalloy for Gas Turbine Blades, 1999. Landolt-Börnstein New Series VIII/2B Ref. p. 335] 3.2.1 Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B alloy 331 3.2 Ni-base alloys 3.2.1 Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B alloy 3.2.1.1 Introduction Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B (Inconel 713C, Alloy713C) alloy is one of the gamma prime precipitation strengthened type nickel-base superalloys with most excellent high temperature creep strength. Ti, Al, Nb and Ta which combine with Ni to form gamma prime contribute precipitation strengthening and Cr and Mo which form carbides contribute to grain boundary strengthening [1]. This alloy also has very good oxidation, hot corrosion and thermal shock resistance up to about 1000 °C. Therefore it is in widespread use as turbine blades, vanes etc. [1, 2]. It is also used as connectors or pullrods in high temperature mechanical testing machines. Inconel 713C is usually produced by vacuum melting and casting and used in as-cast condition. 3.2.1.2 Material standard and chemical composition The chemical composition requirement given in ASM is shown in Table 191. The mechanical properties of Inconel 713C reported here are given in [2], [3] and [4]. Table 191. Chemical composition requirement in AMS. Chemical composition [wt%] C Mn Si S Cr Mo Nb+Ta Ti Al B Zr Min. 0.08 - 12.00 3.80 1.80 0.50 5.50 0.005 0.05 Max 0.20 0.25 0.50 0.015 14.00 5.20 2.80 1.00 6.50 0.015 0.15 AMS Fe 2.5 Cu Co Ni balance 0.50 1.00 3.2.1.3 Tensile properties 0.2% proof stress and tensile strength of Inconel 713C alloy are shown in Fig. 425 [3, 4] and Fig. 426 [2-4]. 3.2.1.4 Creep and rupture properties Creep rupture curves of Inconel 713C alloy are shown in Fig. 427 [3], Fig. 428 [4] and Fig. 429 [2]. 1,000, 10,000 and 30,000 h rupture-stresses as a function of temperatures are available in Fig. 430 [3, 4]. Minimum creep rate for Inconel 713C is reported as shown in Fig. 431 and Fig. 432 [2, 3]. Landolt-Börnstein New Series VIII/2B 332 3.2 Ni-base alloys Tensile strength 1000 800 800 600 600 Stress (MPa) Stress (MPa) 0.2% proof stress 1000 400 200 0 400 200 0 200 400 600 800 1000 0 1200 0 200 Test temperature (℃) 400 600 800 1000 1200 Test temperature (℃) Fig. 425. 0.2% proof stress and tensile strength of Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B superalloy; [3]. Fig. 427, see next page Ni-13Cr-6Al-4Mo-2Cb-0.7Ti as cast bar 80 70 60 Tensile stress 50 120 80 40 0 40 Stress [kg f / mm 2 ] 80 Yield stress [ksi] Tensile stress [ksi] 120 750 °C 850 °C 40 30 20 Yield stress 1200 0 1400 1600 1800 Temperature [°F] 2000 Fig. 426. Tensile (circles) and yield stress (squares) of Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B superalloy; [2]. 1 ksi = 6.89476 MPa 10 1 10 10 3 10 2 Time to rupture [h] 10 4 Fig. 428. Creep rupture curve of Ni-13Cr-4.5Mo-0.75Ti6Al-(Nb+Ta)-Zr-B; [4]. Landolt-Börnstein New Series VIII/2B Ref. p. 335] 3.2.1 Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B alloy 333 500 850 °C 900 °C 950 °C 1000 °C 400 300 Stress [MPa] 200 100 80 850 °C 60 50 40 Fig. 427. Creep rupture strength data of Ni-13Cr-4.5Mo-0.75Ti6Al-(Nb + Ta)-Zr-B superalloy including 8 heats; [3]. n indicates the total number of data points. 900 °C 950 °C 30 20 10 1000 °C n = 187 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Ni-13 Cr-6 Al-4 Mo-2 Cb-0.7 Ti vac melt, vac cast bar 100 Stress [ksi ] 1350 F 50 1500 F 20 1700 F 1800 F 10 5 10 2000 F 2 10 2 2 5 10 3 2 Rupture time [h] 5 5 10 4 Ni-13 Cr-6 Al-4 Mo-2 Cb-0.7 Ti as-cast, various sources, vac melt, cast in vac or inert atm 100 Stress [ksi ] 1350 F 50 1500 F 1600 F 20 1700 F 1900 F 10 1800 F Fig. 429. Creep rupture curves of Ni-13Cr-4.5Mo-0.75Ti6Al-(Nb+Ta)-Zr-B superalloy; [2]. 1 ksi = 6.89476 MPa 2000 F 5 10 2 Landolt-Börnstein New Series VIII/2B 5 10 2 2 5 10 3 2 Rupture time [h] 5 10 4 334 3.2 Ni-base alloys 500 400 300 Stress [MPa] 200 100 h 100 80 60 50 40 10000 h 30 20 800 850 a 1000 900 950 Temperature [°C] 1050 500 400 300 Stress [MPa] 200 100 80 1000 h 60 50 40 30 Fig. 430. Temperature dependence of creep rupture strength from 100 to 100,000 h; [3]. 100000 h 20 800 850 b 1000 900 950 Temperature [°C] 1050 300 200 Stress [MPa] 100 100 80 60 50 40 30 850 °C 900 °C 950 °C 1000 °C 850 °C 900 °C 950 °C 1000 °C n = 65 20 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 Minimum creep rate [% / h] Fig. 431. Stress vs. minimum creep rate for Ni-13Cr4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B superalloy; [3]. 1 Landolt-Börnstein New Series VIII/2B Ref. p. 335] 3.2.1 Ni-13Cr-4.5Mo-0.75Ti-6Al-(Nb+Ta)-Zr-B alloy 335 Ni-13 Cr-6 Al-4 Mo-2 Cb-0.7 Ti 100 as-cast bar, vac melt, vac cast 1350 F 1500 F Stress [ksi ] 50 1700 F 20 Minimum creep rate 10 10 − 4 2 5 10 − 3 2 5 10 − 2 2 Minimum creep rate [% / h ] 5 10 − 1 Fig. 432. Stress vs. minimum creep rate for Ni-13Cr 4.5Mo - 0.75Ti-6Al-(Nb + Ta) - Zr-B superalloy; [2]. 1 ksi = 6.89476 MPa 3.2.1.5 Creep crack growth properties Creep crack growth properties of Ni-10Cr-15Co-3Mo-5Ti-6Al-V-B (IN100) and Ni-13Cr-4.5Mo-0.75Ti-6Al(Nb+Ta)-Zr-B (Inconel 713C) superalloys obtained in NIMS using CT specimen [5] are shown in Fig. 433. 1 d a /d t [mm /h ] 10 1 10 2 IN 100, 732 °C IN 100, 850 °C Inconel 713 C, 900 °C Inconel 713 C, 1000 °C 10 3 10 4 10 2 10 1 C * [kJ /m 2 h ] 1 10 Fig. 433. Creep crack growth rate vs. C* relations of Ni10Cr-15Co-3Mo-5Ti-6Al-V-B (IN100) and 13Cr-4.5Mo0.75Ti-6Al-(Nb+Ta)-Zr-B (Inconel 713C) superalloys; [5]. 3.2.1.6 References [1] [2] [3] [4] The superalloys, ed. by Sims, C. T., and Hagel, W. C., John Wiley & Sons (1972). Aerospace Structural Metals Handbook, vol.5, code 4119 (1976). NRIM Creep Data Sheet, No.29B (1990). Report on the mechanical properties of metals at elevated temperatures, Vol. IV Superalloys, The Iron and Steel Institute of Japan (1979). [5] Tabuchi, M., Kubo, K., Yagi, K., Yokobori, A. T. Jr., and Fuji, A., Eng. Fract. Mech., 62 (1999), 4760. Landolt-Börnstein New Series VIII/2B 336 3.2 Ni-base alloys 3.2.2 Ni-10Cr-15Co-3Mo-5Ti-6Al-V-B alloy 3.2.2.1 Introduction Ni-10Cr-15Co-3Mo-5Ti-6Al-V-B alloy (IN-100 alloy) is a nickel-base precipitation hardenable, vacuum cast superalloy possessing high rupture strength up to about 1040 °C. The high percentage of aluminum and titanium and the low refractory metal content make IN-100 alloy particularly attractive on strength to density basis. The alloy has been successfully cast and utilized in a variety of shapes from turbine blades, vanes and nozzles to integral wheels. Because of the high content of gamma prime precipitate that constitutes one of the strengthening components of the alloy, the equilibrium solution temperature approaches the solidus, so the alloy is usually used in the as-cast condition. IN-100 alloy has been widely known as a cast superalloy, because the alloy was not hot worked due to its high content of gamma prime precipitate. Recently, however, there has been considerable development of a powder metallurgy product which permits working of the alloy. At high temperatures the powderconsolidated product has been found to show superplasticity, thus many possibilities in fabrication-toshape of wrought complex components can be available. However, because no public specification is available for the powder-consolidated IN-100 alloy, only data for as-cast condition are contained in this sheet. 3.2.2.2 Material standards, chemical and mechanical requirements As with other high strength superalloys, deterioration of strength after long time exposure at elevated temperatures is of major concern with IN-100 alloy. It has been widely accepted that electron vacancy concentration is useful in indicating the susceptibility of an alloy to form σ phase [1]. The electron vacancy number, Nv, of IN-100 alloy of nominal composition is 2.46. Nv values over 2.50 generally indicate that an alloy is susceptible to σ phase formation. When IN-100 alloy was originally introduced, the suggested range for titanium extended from 4.5 to a maximum of 5.5 %. Compositions toward the top side of this range exhibited σ phase formation. For example, a 5.3Ti alloy with Nv 2.70, contained σ phase which detracted from rupture life. The maximum titanium level then was reduced to the AMS specification value of 5.0 %. This change eliminated the deleterious effects of σ phase formation on material properties without sacrificing any properties desired [1]. Also, because of the same reason, GE’s new spec. C50T77C specifies that the maximum titanium content is 4.4 % while their original spec. C50T77A specifies it as 5.5 % [2]. Although AMS5397B was only a public specification for IN-100 alloys, please note that the specification has been declared “NONCURRENT” by the Aerospace Materials Division, SAE, in November 1995 [3]. Table 192. Chemical requirement of AMS5397B Chemical composition [wt%] C Mn Si P S Cr Co Mo Ti Al Ti+Al B V Zr Fe Ni max. 0.20 0.10 0.10 0.015 0.015 11.00 17.00 4.00 5.00 6.00 11.00 0.02 1.20 0.09 1.00 remainder min. 0.15 8.00 13.00 2.00 4.50 5.00 10.00 0.01 0.70 0.03 Table 193. Mechanical requirements of AMS5397B Tensile properties Condition Min. tensile Min. yield stress at Min. elongation strength 0.2 % offset in 4D as-cast 795 MPa 655 MPa 5% Stress-rupture properties Min. rupture Min. elongation life in 4D 23 h 4% Landolt-Börnstein New Series VIII/2B Ref. p. 340] 3.2.2 Ni-10Cr-15Co-3Mo-5Ti-6Al-V-B alloy 337 3.2.2.3 Mechanical properties Tensile properties of IN-100 alloy are shown in Table 194 (raw data) and Fig. 434 [1]. Table 194. Tensile properties of IN-100 alloy Test temp. 0.2% yield strength Tensile strength [°C] [MPa] [MPa] 21 849 1014 538 883 1090 649 890 1111 732 876 1097 816 814 994 927 504 738 1038 283 442 1200 Elongation [%] 9.0 9.0 6.0 6.5 6.0 6.0 6.0 Reduction of area [%] 11.0 11.0 7.0 7.2 7.2 7.2 8.0 20 Tensile Strength 18 1000 16 Reduction of Area Ductility (%) Stress (MPa) 14 0.2% Yield Strength 800 600 400 12 10 8 6 Elongation 4 200 2 0 0 0 200 400 600 800 1000 1200 Test temperature (OC) 0 200 400 600 800 1000 1200 Test temperature (OC) Fig. 434. Typical tensile properties of as-cast IN-100 alloy. 3.2.2.4 Creep and rupture properties Stress-rupture data for IN-100 alloy are shown in Fig. 435 and Table 195 (raw data) [1]. Coarse grain (>1/8”) and fine grain (<1/16”) castings have exhibited nearly identical creep rupture lives. 10, 100 and 1000 h rupture-stresses as function of temperature are shown in Fig. 436 [1]. Landolt-Börnstein New Series VIII/2B 338 3.2 Ni-base alloys Table 195. Stress-rupture data on as-cast IN-100 alloy Coarse grain (>1/8”) Temp Stress Life [h] Elong. R. o. a. Temp. [°C] [MPa] [%] [%] [°C] 104 115 9 13 982 1038 83 278 9 17 62 705 11 14 927 200 45 11 12 173 82 11 12 899 982 90 1779 9 15 816 83 2440 12 23 345 15 7 7 927 131 3468 13 18 899 207 1322 6 11 587 16 6 10 816 518 82 5 6 380 806 9 9 760 587 202 6 690 52 2 5 732 621 355 3 6 552 1468 3 8 R.o.a. : Reduction of area Fine grain (<1/16”) Stress Life [h] Elong. [MPa] [%] 200 43 14 124 526 12 242 183 11 173 1013 11 207 970 7 621 9 7 414 771 7 345 1548 8 R. o. a. [%] 16 19 12 16 14 6 10 14 1000 732OC Stress (MPa) 816OC 927OC 982OC 100 1038OC IN-100 alloy 4.80% Ti : Fine grain : Coarse grain Fig. 435. Creep rupture strength data for as-cast IN-100 alloy. 10 1 10 100 1000 10000 Time (h) Landolt-Börnstein New Series VIII/2B Ref. p. 340] 3.2.2 Ni-10Cr-15Co-3Mo-5Ti-6Al-V-B alloy 339 1000 IN-100 alloy 4.80% Ti 800 Stress (MPa) 100h 10h 600 1000h 400 200 Fig. 436. Typical stress-rupture properties of as-cast IN-100 alloy 0 700 800 900 1000 1100 Temperature ( C) O Long-time creep data on as-cast IN-100 alloy are shown in Table 196 (raw data) and Fig. 437 [1]. Table 196. Long-time creep data on as-cast IN-100 alloy Coarse grain (>1/8”) Temp. Stress Time for total creep strain of [°C] [MPa] [h] 0.1% 0.2% 0.5% 1.0% 732 816 927 982 1038 690 621 552 587 518 380 345 131 200 173 90 83 104 83 62 Landolt-Börnstein New Series VIII/2B Min. creep rate [%/h] 1.0 2.0 8.0 26.0 0.0291 5.0 10.0 44.0 135.0 0.0050 25.0 175.0 500.0 800.0 0.0014 0.2 1.9 5.6 0.1300 2.0 2.5 7.7 28.0 0.0185 50.0 170.0 395.0 560.0 0.0010 0.4 1.8 2.9 5.8 0.0320 80.0 200.0 1000.0 1760.0 0.0004 1.5 7.0 16.0 25.0 0.0310 2.5 7.0 19.0 35.0 0.0350 60.0 175.0 625.0 1175.0 0.0006 75.0 195.0 750.0 1380.0 0.0005 2.7 6.0 25.0 58.0 0.0144 8.0 20.0 62.0 140.0 0.0060 4.0 15.0 90.0 270.0 0.0028 Fine grain (<1/16”) Temp. Stress Time for total creep strain of [°C] [MPa] [h] 0.1% 0.2% 0.5% 1.0% 816 899 927 982 621 414 207 242 173 124 0.10 7.50 55.00 5.00 60.00 30.00 0.15 40.00 190.00 15.00 120.00 88.00 0.40 170.00 440.00 45.00 260.00 165.00 Min. creep rate [%/h] 1.85 0.2800 340.00 0.0025 570.00 0.00091 79.00 0.0010 480.00 2850.00 0.0030 340 3.2 Ni-base alloys 750 0.5% creep strain 600 1.0% creep strain 816OC 732OC 700 550 Stress-rupture Stress (MPa) Stress (MPa) 650 600 550 0.1% creep strain 500 Stress-rupture 500 450 400 0.1% creep strain 0.2% creep strain 350 450 400 0.2% creep strain 0.5% creep strain 1.0% creep strain 300 1 10 100 1000 10000 1 10 Time (h) 400 927OC 10000 982OC 230 1.0% creep 210 190 300 Stress (MPa) Stress (MPa) 1000 250 0.5% creep strain 1.0% creep strain 350 100 Time (h) Stress-rupture 250 200 0.1% creep strain 150 1 Stress-rupture 150 130 110 0.1% creep strain 90 70 0.2% creep strain 100 170 10 100 0.2% creep strain 0.5% creep strain 50 1000 10000 Time (h) 1 10 100 1000 Time (h) 120 1038 C 110 1038OC Stress (MPa) 100 90 Stress-rupture 80 70 60 0.5% creep strain 50 1.0% creep strain 40 1 10 100 1000 10000 Time (h) Fig. 437. Creep curves for as-cast IN-100 alloy 3.2.2.5 References [1] International Nickel Co., Engineering Properties of IN-100 Alloy. [2] Aerospace Structural Metals Handbook, vol.5, code 4212 (1978). [3] Aerospace Materials Division, SAE, Aerospace Material Specification, AMS5397C (1995). Landolt-Börnstein New Series VIII/2B 10000 Ref. p. 344] 3.2.3 Ni-15.5Cr-8Fe alloy 341 3.2.3 Ni-15.5Cr-8Fe alloy 3.2.3.1 Introduction Ni-15.5Cr-8Fe (Inconel 600) alloy is one of the oxidation-resistant type superalloys based on the Ni-Cr alloy system [1]. Because Inconel 600 has good workability, weldability and corrosion resistance, it is extensively used for heat exchanger tubes in chemical and nuclear power plants. Because this alloy is used as the steam generator tubing in nuclear power plants, there are many researches concerning not only creep but also stress corrosion cracking (SCC) and fatigue properties. The protective Cr2O3 scale contributes to corrosion-resistance and Fe is a solid solution strengthening element. This wrought alloy is used after annealing at about 1000 °C. 3.2.3.2 Material standard and chemical composition The chemical composition requirement of JIS [2-4] is shown in Table 197, which is nearly the same as in ISO4955. The mechanical properties of Inconel 600 are reported in [5] for bars, plates and tubes, in [6] and [7]. Table 197. Chemical composition requirement in JIS G 4904 Chemical composition [wt%] C Si Mn P S Ni Cr F Cu NCF600TB ≤0.15 ≤0.50 ≤1.00 ≤0.030 ≤0.015 ≥72.00 14.00-17.00 6.00-10.00 ≤0.50 JIS G 4904 3.2.3.3 Tensile properties 0.2% proof stress and tensile strength of Inconel 600 alloy are shown in Fig. 438 [5]. The yield strength and tensile strength are shown in Fig. 439 [6]. Tensile strength 800 700 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 800 400 300 400 300 200 200 100 100 0 0 200 400 600 800 1000 1200 0 0 200 Test temperature (℃) Fig. 438. 0.2% proof stress and tensile strength of Ni-15.5Cr-8Fe alloy; [5]. Landolt-Börnstein New Series VIII/2B 400 600 800 Test temperature (℃) 1000 1200 342 3.2 Ni-base alloys 120 100 Tensile stress 60 40 Yield stress 20 120 80 0 40 Elongation Elongation [%] Stress [ksi] 80 0 -400 0 800 1200 400 Temperature [°F] Fig. 439. Yield and tensile strength of Inconel 600 alloy; [6]. 1 ksi = 6.89476 MPa 1600 3.2.3.4 Creep and rupture properties Stress vs. creep rupture time relations of Inconel 600 alloy are shown in Fig. 440 [5]. Creep strain and rupture data is shown in Fig. 441 [6]. 1,000, 10,000 and 30,000 h rupture-stresses as functions of temperature are shown in Fig. 442 [5]. 500 400 300 600 °C 700 °C 800 °C 900 °C 1000 °C Stress [MPa] 200 100 80 60 50 40 30 20 10 8 10 n = 103 10 2 10 3 10 4 Time to rupture [h] 10 5 10 6 Fig. 440. Creep rupture strength data of Inconel 600 alloys including bars, plates and tubes; [5]. n indicates the total number of data points. Landolt-Börnstein New Series VIII/2B Ref. p. 344] 3.2.3 Ni-15.5Cr-8Fe alloy 343 Fig. 441, see next page 800 600 500 400 300 100 80 60 50 40 30 { { Stress [MPa] 200 Tensile strength 0.2% proof stress 20 1000 h 10 8 a 6 800 600 500 400 300 100 80 60 50 40 30 { Tensile strength { 0.2% proof stress { Stress [MPa] 200 Tensile strength 20 10 8 b 6 800 600 500 400 300 10000 h 100 80 60 50 40 30 { Stress [MPa] 200 0.2% proof stress 20 10 8 6 500 c Landolt-Börnstein New Series VIII/2B Fig. 442. Temperature dependence of creep rupture strength from 1,000 to 30,000 h; [5]. 30000 h 600 700 800 Temperature [°C] 900 1000 1100 344 3.2 Ni-base alloys 20 Inconel alloy 600 0.060 in sheet 2050 F, 2 h Stress [ksi ] 10 5 1500 F 2 1 10 0.5 5 10 Rupture 10 5 1300 F 2 1 0.5 5 Elongation% Rupture 1650 F 2 Total creep and rupture Tested in argon 1 20 0.5 1 Inconel alloy 600 0.060 in sheet CW 20 % + 1900 F, 41/2 min 1300 F Stress [ksi ] 10 5 2 0.5 1 2 0.5 1 2 5 2 10 R 0.5 1 2 5 10 Rupture e, percent 5 1500 F 1650 F Total creep and rupture 10 Tested in argon Rupture 1 10 10 2 Time [h] 10 3 Fig. 441. Creep strain and rupture curves of Inconel 600 alloy; [6]. 1 ksi = 6.89476 MPa 10 4 3.2.3.5 References [1] [2] [3] [4] [5] [6] [7] The superalloys, ed. by Sims, C. T., and Hagel, W. C., John Wiley & Sons (1972) p. 294. JIS G4901-1991, Corrosion-resisting and heat-resisting superalloy bars. JIS G4902-1991, Corrosion-resisting and heat-resisting superalloy plates and sheets. JIS G4904-1991, Seamless nickel-chromium-iron alloy heat exchanger tubes. NRIM Creep Data Sheet, No.41A (1999). Aerospace Structural Metals Handbook, vol.4, code 4101 (1967). Report on the mechanical properties of metals at elevated temperatures, Vol. IV Superalloys, The Iron and Steel Institute of Japan (1979). Landolt-Börnstein New Series VIII/2B Ref. p. 347] 3.2.4 Ni-15.5Cr-2.5Ti-0.7Al-1Nb-7Fe alloy 345 3.2.4 Ni-15.5Cr-2.5Ti-0.7Al-1Nb-7Fe alloy 3.2.4.1 Introduction Ni-15.5Cr-2.5Ti-0.7Al-1Nb-7Fe (Inconel X-750, JIS NCF750, ISO NW7750) is one of the precipitation hardened nickel chromium alloys. These alloy families were developed from the solid-solution strengthened Ni-15.5Cr-8Fe alloy (Inconel 600) by addition of titanium and aluminum to form gamma prime phase for precipitation strengthening [1, 2]. Addition of 1 % Nb gives Inconel X-750. Because Inconel X-750 has not only high creep strength but also good formability, weldability and corrosion resistance, it is widely used for aerospace applications such as rotors, blades, wheels and bolts etc. up to about 1000 °C [2]. It has also excellent properties at cryogenic temperatures, therefore it is used for bolts, springs etc. at various temperatures. This wrought alloy is normally used in the precipitation hardened condition after solid-solution at about 1150 °C and ageing heat treatment whose condition is dependent on desired properties of products. 3.2.4.2 Material standard and chemical composition The chemical composition requirement given in JIS G 4901 [3] is shown in Table 1, which is nearly the same as ISO 9723. The mechanical properties of Inconel X-750 alloy can be obtained in NRIM Creep Data Sheet 39A [4], Aerospace structural metals handbook [2] and the report on the mechanical properties of metals at elevated temperatures [5]. Table 198. Chemical composition requirement in JIS G 4901 Standard Chemical composition [wt%] C Si Mn P S Ni Cr Cu Ti Al Nb+Ta JIS G 4901 14.002.25- 0.40- 0.70≤0.50 ≤0.08 ≤0.50 ≤1.00 ≤0.030 ≤0.015 ≥70.00 17.00 2.75 1.00 1.20 Fe 5.009.00 3.2.4.3 Tensile properties 0.2% proof stress and tensile strength of Inconel X-750 are shown in Fig. 443 [4]. Tensile strength 1200 1000 1000 800 800 Stress (MPa) Stress (MPa) 0.2% proof stress 1200 600 400 400 200 200 0 600 0 200 400 600 800 1000 0 0 Test temperature (℃) Fig. 443. 0.2% proof stress and tensile strength of Inconel X-750 alloy; [4]. Landolt-Börnstein New Series VIII/2B 200 400 600 Test temperature (℃) 800 1000 346 3.2 Ni-base alloys 3.2.4.4 Creep and rupture properties Stress vs. creep rupture relations of Inconel X-750 alloy are shown in Fig. 444 [4] and Fig 445 [2]. The creep rupture stresses from 100 to 30,000 h as functions of temperature are given in Fig. 446 [4]. The relation between stress and minimum creep rate is given in Fig. 447 [2]. Stress [MPa] 900 700 600 500 400 300 600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 900 °C 200 100 70 60 50 40 30 Fig. 444. Creep rupture strength data of Ni based 15.5Cr-2.5Ti0.7Al-1Nb-7Fe superalloy bars; [4]. n indicates the total number of data points. n = 100 20 1 10 2 10 10 3 10 4 Time to rupture [h] 10 5 10 6 10 7 Fig. 446, see next page IN X-750 bar 2100 F, 2h, AC+1550 F, 24 h, Ac+1300 F, 20 h, AC 2 1000 F 1100 F 1000 F 1100 F 100 1350 F Stress [ksi ] 10 Stress [ksi ] IN X-750 bar 1625 F, 24 h, AC+1300 F, 20 h, Ac 1200 F 50 10 1500 F 1800 F 1 10 -1 1700 F 1350 F 1600 F 1500 F 10 1 10 3 10 2 10 Rupture time [h] 10 4 10 5 Fig. 445. Creep rupture curves of Inconel X-750 alloy bar; [2]. 1 ksi = 6.89476 MPa 1 10 10 2 3 Creep rate [ %/10 h] Fig. 447. Stress vs. minimum creep rate for Inconel X-750 superalloy; [2]. 1 ksi = 6.89476 MPa Landolt-Börnstein New Series VIII/2B Ref. p. 347] 3.2.4 Ni-15.5Cr-2.5Ti-0.7Al-1Nb-7Fe alloy 347 2000 Tensile strength { 100 h 0.2% proof stress { 100 80 60 50 40 30 a 20 Tensile strength { 200 { Stress [MPa] 1000 800 600 500 400 300 0.2% proof stress 10000 h 2000 Stress [MPa] 1000 800 600 500 400 300 200 100 80 60 50 40 30 20 550 1000 h 30000 h 600 650 b 700 750 800 Temperature [°C] 850 900 950 1000 Fig. 446. Temperature dependence of creep rupture stress from 100 to 30000 h; [4]. 3.2.4.5 References [1] [2] [3] [4] [5] The superalloys, ed. by Sims, C. T., and Hagel, W. C., John Wiley & Sons (1972) p. 16. Aerospace Structural Metals Handbook, vol.4, code 4105 (1981). JIS G 4901-1999, Corrosion-resisting and heat-resisting superalloy bars. NRIM Creep Data Sheet, No. 39A (1992). Report on the mechanical properties of metals at elevated temperatures, Vol.IV Superalloys, The Iron and Steel Institute of Japan (1979) pp. 219-228. Landolt-Börnstein New Series VIII/2B 348 3.2 Ni-base alloys 3.2.5 Ni-15Cr-28Co-Mo-Ti-Al alloy 3.2.5.1 Introduction Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al alloy is one of the γ’ strengthened superalloys. This alloy has been developed for high temperature service in the 1940s. The commercial designation of this alloy is “Inconel Alloy 700”. The alloy is available in form of bars and forgings. Chemical properties are similar to Waspaloy [1]. 3.2.5.2 Chemical composition and material preparation The conditions of material preparation are shown in Table 199. The chemical compositions shown in Table 200 were analyzed by NRIM [2] and reported by the manufactures. The chemical requirements coincide with Inconel 700. Table 199. Details of Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al superalloy bars (1) NRIM Type of Size of ingot Product Dimensions(3) Processing and reference melting(2) thermal history form code [mm] [t] iBA CE 0.3 20D Forged 1600L Bar 1200 °C/2 h AC iBB HFIVF 0.5 20D 870 °C/24 h AC 140L Austenite grain size number(4) 2.4 Rockwell hardness [HRC] 36 2.4 36 (1) The bars were sampled in 1969. Details other than grain size number and hardness are as reported by the manufactures. (2) CE: consumable electrode vacuum melt, HFIVF: high frequency induction vacuum furnace. (3) D: diameter, L: length (4) JIS G 0551-1977, “Method of Austenite Grain Size Test for Steel’’ Table 200. Chemical composition (product analysis) of Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al superalloy bars Chemical composition [wt-%](1) S Ni Cr Mo Cu Co Ti (3) ≤0.015 bal 13.0 1.0 ≤0.50 24.0 1.75 ~17.0 ~4.5 ~34.0 ~2.75 0.13 0.09 0.09 0.002 0.003 46.90 14.40 3.74 0.01 28.88 2.36 0.14 0.12 0.08 0.001 <0.005 bal(3) 15.13 3.63 tr(3) 27.91 2.26 NRIM reference code C Si Mn P Requirement(2) ≤0.20 ≤1.00 ≤2.00 iBA iBB Al B N* 2.50 ~3.50 3.07 0.0059 0.0039 2.99 0.005 0.0030 Fe ≤4.0 0.24 0.72 (1) The chemical composition given above was reported by the manufactures except for the elements marked with an asterisk, for which the analysis was carried out at NRIM. (2) The chemical requirements coincide with Inconel 700 and with AISI 687. (3) bal: balance, tr: trace 3.2.5.3 Mechanical properties The tensile properties of Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al alloy are shown in Fig. 448 which is obtained from [3]. The solid curves represent the average; the broken curves are the upper and lower 95% PI (prediction intervals). Landolt-Börnstein New Series VIII/2B Ref. p. 350] 3.2.5 Ni-15Cr-28Co-Mo-Ti-Al alloy Tensile strength 1600 1400 1400 1200 1200 1000 1000 Stress [MPa ] Stress [MPa ] 0.2 % proof stress 1600 800 600 Upper 95 % PI Average Lower 95 % PI 400 200 0 600 0 Elongation 100 70 60 50 40 30 n = 24 Reduction of area 90 Reduction of area [%] 80 Upper 95 % PI Average Lower 95 % PI 200 90 Elongation [%] 800 400 n = 24 100 349 80 70 60 50 40 30 20 20 10 n = 24 0 0 200 400 600 800 1000 Test temperature [°C] 10 n = 24 0 0 200 400 600 800 1000 Test temperature [°C] Fig. 448. Short-time tensile properties of Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al superalloy bars. 3.2.5.4 Creep rupture properties The creep rupture properties of Nickel based 15Cr-28Co-4Mo-2.5Ti-3Al alloy bars are shown in Fig. 449 and Fig. 450 which are obtained from [2]. Fig. 449 shows stress vs. time to rupture data at 700, 725, 750, 800, 825 and 850 °C for nickel based 15Cr-28Co-4Mo-2.5Ti-3Al alloy bars. Fig. 450 shows the master rupture curve assessed by MansonHaferd parameter method. Landolt-Börnstein New Series VIII/2B 350 3.2 Ni-base alloys 800 300 700 °C 725 °C 750 °C 800 °C 825 °C 850 °C 200 700 °C Stress [MPa] 600 500 400 750 °C 100 80 60 50 40 10 Fig. 449. Creep rupture strebgth data for Nickel based 15Cr- 28Co - 4Mo - 2.5Ti - 3Al superalloy bars. n indicates the total number of data points. 800 °C 850 °C n = 62 10 2 10 3 10 4 Time to rupture [h] 825 °C 10 5 10 6 800 600 500 400 Stress [MPa] 300 700 °C 725 °C 750 °C 800 °C 825 °C 850 °C 200 100 80 60 average n = 62 50 40 -2.7 -2.5 -1.9 -1.7 -2.3 -2.1 Manson-Haferd parameter [( log tR -26.696)/( TK )] [×10 - 2 ] Fig. 450. Master rupture curve by Manson-Haferd parameter method for nickel based 15Cr-28Co-4Mo2.5Ti-3Al superalloy bars. n indicates the total number of data points. The creep data including time to reach specific total strain and minimum creep rate of nickel based 15Cr28Co-4Mo-2.5Ti-3Al alloy bars are available from [2]. 3.2.5.5 References [1] Aerospace Structural Metals Handbook, Volume I, Non-ferrous Alloys, 1963, Code 4201, p.1 [2] National Research Institute for Metals: NRIM Creep Data Sheet, No.24B, (1989). [3] NRIM Creep Data Sheet, No.23B, 1989 Landolt-Börnstein New Series VIII/2B Ref. p. 355] 3.2.6 Ni-19Cr-18Co-4Mo-3Ti-3Al-B alloy 351 3.2.6 Ni-19Cr-18Co-4Mo-3Ti-3Al-B alloy 3.2.6.1 Introduction This material is a Nickel based U500 superalloy (19Cr-18Co-4Mo-3Ti-3Al-B-Bal. Ni) which is applied for gas turbine blades etc. and is manufactured in casting or forging form. It has shown excellent resistance to hot corrosion attack and structural stability for long time service requirements. It is used at high temperatures up to 1000 °C. 3.2.6.2 Material standards, chemical compositions and tensile properties Information can be obtained from [1]. 3.2.6.2.1 Nickel based 19Cr-18Co-4Mo-3Ti-3Al-B superalloy castings Table 201 shows a requirement range for the chemical composition of Nickel based 19Cr-18Co-4Mo-3Ti3Al-B superalloy castings (U500) which coincides with the requirements of AMS5384 and U500. Moreover, the chemical composition analysis results of the three heats used for data treatment are shown in Table 201. These analysis results are almost equivalent. Table 202 shows the heat treatment conditions of each heat. The treatment conditions of solid solution, high temperature aging and final aging are almost equal for each heat. Table 201. Requirement of chemical composition and analysis results for U500 casting alloy. Chemical composition [wt %] S Cr Mo Cu Co ≤0.015 16.0- 3.0- ≤0.10 16.020.0 5.0 20.0 ≤0.002 ≤0.005 19.51 4.12 trace 18.89 0.002 0.008 18.5 4.14 0.03 18.15 18.57 4.4 ≤0.05 18.81 ≤0.002 0.01 C Si Mn P ≤0.10 ≤0.30 ≤0.20 - Requirement* Heat 1 0.07 Heat 2 0.09 Heat 3 0.09 0.02 0.12 0.13 trace 0.07 0.12 Ti 2.503.25 2.88 3.16 2.93 Al 2.503.25 3.13 2.96 3.04 B 0.0030.010 0.005 0.009 0.01 N - Fe ≤2.0 0.004 0.2 0.006 0.23 0.001 0.12 * The chemical requirements coincide with AMS5384 Table 202. Heat treatment history for U500 casting alloy. Thermal history Heat 1 1149 °C × 4 h AC, 1080 °C × 4 h AC, 760 °C × 16 h AC Heat 2 1149 °C × 4 h AC, 1079 °C × 4 h AC, 760 °C × 16 h AC Heat 3 1149 °C × 4 h AC, 1080 °C × 4 h AC, 760 °C × 16 h AC Table 203 shows the requirements of tensile strength and tensile elongation at 649 °C. Fig. 451 (a)-(d) show the tensile properties from room temperature up to 1000 °C. The tensile strength has the tendency to slightly decrease up to about 600 °C and then to increase near 700 °C. After that the strength falls rapidly at high temperatures. 0.2% proof stress shows a similar tendency. The tensile elongation ranges between 5 and 20 % from room temperature up to 900 °C and the temperature dependence is not large. However, the elongation at 1000 °C is 15 to 20 %. The reduction of area differs largely between the test materials and a remarkable variation is seen. Although there is a slight decrease of reduction of area between 700 and 800 °C, the reduction of area indicates rapid increasing at temperatures above 800 °C. This reversely corresponds well with the tendency for tensile strength. Landolt-Börnstein New Series VIII/2B 352 3.2 Ni-base alloys 1400 1400 1200 1200 0.2% Proof stress (MPa) Tensile strength (MPa) Table 203. Requirement of tensile properties at 649 °C for U500 casting alloy. Tensile properties (at 649 °C) Tensile strength 0.2% proof stress Elongation Reduction of area [MPa] [MPa] [%] [%] Requirement ≥827 ≥7 1000 800 600 1000 800 600 400 400 200 200 0 0 0 200 400 600 800 0 1000 200 70 70 60 60 Reduction of area (%) Elongation (%) 600 800 1000 800 1000 b a 50 40 30 50 40 30 20 20 10 10 0 0 200 400 600 800 0 1000 0 200 Temperatura (℃) c 400 Temperature (℃) Temperature (℃) 400 600 Temperature (℃) d Fig. 451. Tensile strength (a), 0.2% proof stress (b), tensile elongation (c) and reduction of area (d) for U500 casting alloy. 3.2.6.2.2 Nickel based 19Cr-18Co-4Mo-3Ti-3Al-B superalloy forgings Table 204 shows a requirement range for the chemical composition of Nickel based 19Cr-18Co-4Mo-3Ti3Al-B superalloy forgings (U500) which coincides with the requirements of AMS5751A and U500. Moreover, the chemical composition analysis results of the three heats used for data treatment are shown in Table 204. These analysis results are almost equivalent except for the higher Fe content in heat 3 compared to the other two heats. There is no large difference of chemical composition between castings and forgings. Landolt-Börnstein New Series VIII/2B Ref. p. 355] 3.2.6 Ni-19Cr-18Co-4Mo-3Ti-3Al-B alloy 353 Table 204. Requirement of chemical composition and the analysis results for U500 forging alloy. Requirement* Heat 1 Heat 2 Heat 3 Chemical composition [wt %] S Cr Mo Cu Co ≤0.015 15.0- 3.0- ≤0.15 13.020.0 5.0 20.0 0.004 0.002 0.01 19.23 4.13 trace 18.47 0.02 0.001 0.003 16.86 3.78 trace 18.2 0.002 0.002 0.009 19.25 4.12 0.01 18.8 C Si Mn P ≤0.15 ≤0.75 ≤0.75 0.07 0.06 0.08 0.01 0.01 0.02 Ti 2.503.25 3.02 2.76 2.86 Al 2.503.25 3.1 2.66 2.81 B 0.0030.010 0.009 0.007 0.0065 N - Fe ≤4.0 0.005 0.22 0.006 0.73 0.007 2.32 * The chemical requirements coincide with AMS5384 Table 205 shows the heat treatment conditions of each heat. The treatment conditions of solid solution, high temperature aging and final aging are almost equal for each heat. Compared with castings, a 170 °C lower solid solution temperature is applied for forgings. Table 205. Heat treatment history for U500 forging alloy. Thermal history Heat 1 1180 °C × 4 h AC, 843 °C × 24 h AC, 760 °C × 16 h AC Heat 2 1179 °C × 4 h AC, 843 °C × 24 h AC, 760 °C × 16 h AC Heat 3 1179 °C × 4 h AC, 843 °C × 24 h AC, 760 °C × 16 h AC Table 206 shows the requirements of tensile properties at 649 °C. Compared with the castings in Table 203, the minimum requirement of tensile strength is about 350 MPa higher. Fig. 452 (a)-(d) show the tensile properties of forgings from room temperature up to 1000 °C. Although the tensile strength decreases slightly from room temperature up to 200 °C, it is almost constant up to near 700 °C. At higher temperatures, the tensile strength decreases rapidly. Although the forgings are 200 to 300 MPa higher in tensile strength than the castings from room temperature up to about 800 °C, at temperatures above 900 °C, a big difference is no longer seen between castings and forgings. The 0.2% proof stress stays almost constant from room temperature up to near 700 °C and rapidly decreases at temperatures above 700°C. The difference of proof stress between castings and forgings is smaller than that of tensile strength. However, 0.2% proof stress of the forgings is about 100 MPa higher than that of the castings up to near 700 °C. Although the tensile elongation is about 10 %, like for castings, up to near 600 °C, it rapidly increases at higher temperatures. The reduction of area shows a similar tendency. Table 206. Requirement of tensile properties at 649 °C for U500 forging alloy. Tensile properties (at 649 °C) Tensile strength 0.2% proof stress Elongation Reduction of area [MPa] [MPa] [%] [%] Requirement ≥1172 ≥758 ≥6 ≥10 3.2.6.3 Creep rupture properties of Ni-19Cr-18Co-4Mo-3Ti-3Al-B alloy 3.2.6.3.1 Nickel based 19Cr-18Co-4Mo-3Ti-3Al-B superalloy castings Fig. 453 shows the creep rupture test results of superalloy U500 castings. The creep tests were carried out in the temperature range from 700 °C to 900 °C in 50 °C pitch and 1000 °C was also selected. The creep stresses were adopted between 29 MPa and 608 MPa. Landolt-Börnstein New Series VIII/2B 354 3.2 Ni-base alloys 1400 1200 1200 0.2 % proof stress [MPa] Tensile strength (MPa) 1400 1000 800 600 400 1000 800 600 400 200 0 200 0 200 400 600 800 0 1000 200 70 70 60 60 Reduction of area (%) Elongation (%) 600 800 1000 800 1000 b a 50 40 30 50 40 30 20 20 10 10 0 0 0 200 400 600 800 1000 0 200 Temperature (℃) c 400 Temperature (℃) Temperature (℃) 400 600 Temperature (℃) d Fig. 452. Tensile strength (a), 0.2% proof stress (b), tensile elongation (c) and reduction of area (d) for U500 forging alloy. 3.2.6.3.2 Nickel based 19Cr-18Co-4Mo-3Ti-3Al-B superalloy forgings Fig. 454 shows the creep rupture test results of superalloy U500 forgings. The creep tests were carried out in the temperature range from 700 °C to 900 °C in 50 °C pitch and 1000 °C was also selected. The creep stresses were adopted between 24 MPa and 608 MPa. Comparison of Fig. 453 and Fig. 454 shows that the difference of creep rupture strength for forgings and castings is low at temperatures of 850 °C or less. However, the decrease of the creep rupture strength of forgings is larger than that of castings at temperatures above 900 °C. Landolt-Börnstein New Series VIII/2B Ref. p. 355] 3.2.6 Ni-19Cr-18Co-4Mo-3Ti-3Al-B alloy 355 Stress (MPa) 1000 100 T=700℃ T=750℃ T=800℃ T=850℃ T=900℃ T=1000℃ 10 1 10 100 1000 104 105 Fig. 453. Creep rupture strength data for U500 casting alloy. Time to rupture (h) Stress (MPa) 1000 100 T=700℃ T=750℃ T=800℃ T=850℃ T=900℃ T=1000℃ Fig. 454. Creep rupture strength data for U500 forging alloy. 10 1 10 100 1000 104 105 Time to rupture (h) 3.2.6.4 Reference [1] National Research Institute for Metals : NRIM Creep Data Sheet, No.34B, (1993). Landolt-Börnstein New Series VIII/2B 356 3.3 Co-base alloys 3.3 Co-base alloys 3.3.1 Co-20Cr-20Ni-Mo-W-Ni alloy 3.3.1.1 Introduction This material is Co-based S-816 superalloy (20Cr-20Ni-4Mo-4W-4Nb-4 Fe-Bal. Co) which is applied to blades, bolts, springs etc. for gas turbines. It is superior in corrosion resistance and is used in the high temperature region up to about 900 °C. Although it has been manufactured by casting or rolling processes, only data of rolling material is dealt with in this data book. The following heat treatments have been performed: solid solution treatment or solid solution treatment with subsequent aging treatment. 3.3.1.2 Material standards and chemical compositions This information on this alloy is obtained from [1]. Table 207 shows the typical chemical composition and the analysis results for two heats of S-816 superalloy (AISI 671). Both heats were almost equivalent in chemical composition. Table 208 shows the typical heat treatment conditions and the thermal history of the two heats. Although the solid solution treatment was performed at 1180 °C for all test materials, for the aging process, either no aging, 760 °C or 816 °C has been applied. Table 207. Typical chemical composition and the analysis results for S-816 alloy. Chemical composition [wt%] Standard/ heat C Si Mn P S Ni Cr Mo Co Nb W AISI (S-816) 0.38 0.7 1.5 20 20 4 43 4 4 Nominal Heat 1 0.37 0.37 1.31 0.006 0.019 19.6 20.4 4.3 42.7 3.6 4.2 Heat 2 0.35 0.64 1.58 0.004 0.017 19.7 20.1 4 42.2 3.9 4.3 Table 208. Typical heat treatment conditions and the thermal history for S-816 alloy. Heat treatment Standard/ heat Solution treatment Aging AISI (S-816) 1180 °C × 1 h WQ 760 °C × 16 h AC Nominal 1180 °C × 1 h WQ Heat 1 1180 °C × 1 h WQ 816 °C × 14 h AC 1180 °C × 1 h WQ 760 °C × 14 h AC Heat 2 1180 °C × 1.5 h WQ 760 °C × 16 h AC 3.3.1.3 Creep rupture properties of alloy S-816 The influence of heat and aging condition on the creep rupture strength is shown in this chapter. Fig. 455 shows all the creep rupture test results of superalloy S-816 dealt with in this data book. The creep tests were carried out at temperatures from 600 °C to 850 °C in 50 °C pitch and at stresses which were selected between 78 MPa and 785 MPa. Landolt-Börnstein New Series VIII/2B Ref. p. 361] 3.3.1 Co-20Cr-20Ni-Mo-W-Ni alloy 357 Stress (MPa) 1000 100 T=600℃ T=700℃ T=750℃ T=800℃ T=850℃ Fig. 455. Creep rupture strength data for Co-20Cr-20Ni-Mo-W-Ni alloy S-816. 10 10 100 1000 104 Time to rupture (h) Fig. 456 (a) - (c) show the creep rupture strength of Heat 1 which is either not aged or aged at 760 °C or 816 °C. Fig. 457 shows creep rupture strength of Heat 2. As for Heat 1, the creep rupture data are obtained only from the 760 °C aged material. Stress (MPa) 1000 100 Fig. 456 a. Creep rupture strength data of Heat 1 of Co20Cr-20Ni-Mo-W-Ni alloy S-816 without aging treatment. T=600℃ T=700℃ T=800℃ T=850℃ 10 100 1000 Time to rupture (h) Landolt-Börnstein New Series VIII/2B 104 358 3.3 Co-base alloys Stress (MPa) 1000 100 T=600℃ T=700℃ T=800℃ T=850℃ 10 Fig. 456 b. Creep rupture strength data of Heat 1 of Co20Cr-20Ni-Mo-W-Ni alloy S-816 aged at 760 °C. 100 1000 104 Time to rupture (h) Stress (MPa) 1000 100 T=600℃ T=700℃ T=800℃ T=850℃ 10 Fig. 456 c. Creep rupture strength of Heat 1 data of Co-20Cr-20NiMo-W-Ni alloy S-816 aged at 816 °C. 100 1000 104 Time to rupture (h) Landolt-Börnstein New Series VIII/2B Ref. p. 361] 3.3.1 Co-20Cr-20Ni-Mo-W-Ni alloy 359 Stress (MPa) 1000 100 T=700℃ T=750℃ T=800℃ 10 Fig. 457. Creep rupture strength data of Heat 2 of Co-20Cr-20NiMo-W-Ni alloy S-816. 100 1000 104 Time to rupture (h) All creep rupture test results were compared and the influence of heat and aging treatment condition were summarized in Fig. 458. Fig. 458 a shows the influence of aging treatment condition on test results at 600 °C for Heat 1. Although there is some uncertainty due to data scatter, the decrease in strength for longer times becomes smaller by aging treatment. Moreover, by increasing aging temperature from 760 °C to 816 °C, the decrease in creep rupture strength for longer times becomes smaller. [ ] 1000 900 Stress (MPa) 800 700 600 500 Heat1, S.T.=1180℃, Aging Less Heat1, S.T.=1180℃, Aging=816℃ Heat1, S.T.=1180℃, Aging=760℃ 400 Fig. 458 a. Influence of heat and aging treatment condition on test results for Co-20Cr-20Ni-Mo-WNi alloy S-816 at 600 °C. 300 10 100 1000 104 Time to rupture (h) Fig. 458 b shows the influence of aging treatment condition on test results at 700 °C for Heat 1 and Heat 2. Because data has large scatter, the influence of aging treatment and aging temperature on the creep rupture strength is not clear. The creep rupture strength is influenced by the difference of heat, and Heat 2 is lower than Heat 1 in creep rupture strength. Landolt-Börnstein New Series VIII/2B 360 3.3 Co-base alloys 700 600 Stress (MPa) 500 400 300 200 Heat1, Heat1, Heat1, Heat2, S.T.=1180℃, S.T.=1180℃, S.T.=1180℃, S.T.=1180℃, Aging Less Aging=816℃ Aging=760℃ Aging=760℃ Fig. 458 b. Influence of heat and aging treatment condition on test results for Co-20Cr-20Ni-Mo-WNi alloy S-816 at 700 °C. 100 10 100 1000 104 Time to rupture (h) Fig. 458 c similarly shows the results of creep rupture strength at 800 °C. The same tendency as in the case of 700 °C can be seen. Stress (MPa) 500 300 100 80 Heat1, Heat1, Heat1, Heat2, 60 S.T.=1180℃, S.T.=1180℃, S.T.=1180℃, S.T.=1180℃, Aging Less Aging=816℃ Aging=760℃ Aging=760℃ Fig. 458 c. Influence of heat and aging treatment condition on test results for Co-20Cr-20Ni-Mo-WNi alloy S-816 at 800 °C. 40 10 100 1000 104 Time to rupture (h) Fig. 458 d is the result of creep rupture strength at 850 °C. Also in this case, the existence of aging treatment and the effect of aging temperature on creep rupture strength is difficult to assess. Landolt-Börnstein New Series VIII/2B Ref. p. 361] 3.3.1 Co-20Cr-20Ni-Mo-W-Ni alloy 361 Stress (MPa) 300 100 80 60 40 Heat1, S.T.=1180℃, Aging Less Heat1, S.T.=1180℃, Aging=816℃ Heat1, S.T.=1180℃, Aging=760℃ Fig. 458 d. Influence of heat and aging treatment condition on test results for Co-20Cr-20Ni-Mo-WNi alloy S-816 at 850 °C. 20 10 100 1000 104 Time to rupture (h) 3.3.1.4 Reference [1] Report on The Mechanical Properties of Metals at Elevated Temperatures: The Iron and Steel Institute of Japan, (1975). Landolt-Börnstein New Series VIII/2B 362 3.3 Co-base alloys 3.3.2 Co-25Cr-10Ni-7.5W-B alloy 3.3.2.1 Introduction Although the creep strength of Co-base alloys is smaller than that of Ni-base alloys, recently they are used in turbine applications in a secondary position to Ni-base alloys because of their advantages in hotcorrosion resistance and thermal-shock resistance [1, 2]. Co-25Cr-10Ni-7.5W-B (X-45) is a daughter of X-40, which was first introduced in the 1940s. These alloys have higher carbon content, because they are basically strengthened by carbide precipitation. The carbides are mainly M23C6 because of high Cr content [1]. Tungsten is a solid solution strengthening element [2]. Although the creep strength of X-45 is lower than that of X-40 due to the lower carbon content, weldability and phase stability is improved. X-45 is used for nozzle vane partitions in industrial turbines and some aircraft engines. X-45 is normally used in as cast condition, but sometimes solution heat treatment is applied. 3.3.2.2 Materials standard and chemical composition The chemical composition requirement of ASTM A567 Grade 13 (discontinued 1987) is shown in Table 209. The mechanical properties of X-45 are reported in [2], [3], and [4]. Table 209. Chemical composition requirement of Co-25Cr-10Ni-7.5W-B (X-45) superalloy castings ASTM Chemical composition [wt%] A567 Si Mn P S Ni Cr W B Fe Grade13 C 0.20- 0.75- 0.409.50- 24.5- 7.00- 0.005X-45 ≤0.04 ≤0.04 ≤2.00 0.30 1.00 1.00 11.50 26.5 8.00 0.015 3.3.2.3 Tensile properties The 0.2% proof stress and tensile strength of X-45 alloy are shown in Fig. 459 [3]. The yield strength and tesnsile strength of X-45 alloy are shown in Fig. 460 [2]. Tensile strength 800 700 700 600 600 500 500 Stress (MPa) Stress (MPa) 0.2% proof stress 800 400 300 400 300 200 200 100 100 0 0 200 400 600 800 1000 Test temperature (℃) 0 0 200 400 600 800 1000 Test temperature (℃) Fig. 459. 0.2% proof stress and tensile strength of X-45 alloy [3]. Landolt-Börnstein New Series VIII/2B Ref. p. 365] 3.3.2 Co-25Cr-10Ni-7.5W-B alloy 363 Ultimate strength, Ftu , and Yield strength, Fty [ksi ] 150 X-45, As cast Ftu 100 80 60 Fty 40 20 Electroslag remelted Vacuum-arc remelted 0 400 1200 800 Temperature [F ] 1600 2000 Fig. 460. Yield strength and tensile strength of X-45 alloy [2]. 1 ksi = 6.89476 MPa 3.3.2.4 Creep and rupture properties Stress vs. creep rupture time relations of X-45 alloy are shown in Fig. 461 [3]. 10, 100, 1,000, 10,000 and 100,000 h rupture-stresses as a function of temperatures are available in Fig. 462 [3] and 463 [2]. Minimum creep rate for X-45 alloy castings are reported as shown in Fig. 464 [3]. g 500 750℃ 800℃ 850℃ 900℃ 950℃ 300 100 80 60 40 Fig. 461. Creep rupture strength data of X-45 alloy; [3]. n indicates the total number of data points. n=103 20 10 1 10 2 10 3 10 4 Time to rupture (h) Landolt-Börnstein New Series VIII/2B 10 5 10 6 364 3.3 Co-base alloys 800 { { Stress [MPa] 600 500 400 300 200 100 80 Tensile strength 0.2% proof stress 100 h 60 50 40 30 a 10000 h 20 800 { { Stress [MPa] 600 500 400 300 200 100 80 60 50 40 30 20 600 650 700 100000 h 750 850 900 800 Temperature [°C] Stress [MPa] Rupture stress [ksi] 1000 200 10 h 100 h 1000 h 30 20 15 100 80 750 °C 60 50 800 °C 40 30 10 8 20 6 4 1000 950 Fig. 462. Temperature dependence of creep rupture strength from 100 to 100,000 h; [3]. 300 100 80 40 0.2% proof stress 1000 h b 60 Tensile strength 1200 1400 Temperature [F] 1600 1800 Fig. 463. Temperature dependence of creep rupture strength from 10 to 1,000 h; [2]. 1 ksi = 6.89476 MPa 850 °C 900 °C 950 °C 750 °C 800 °C 850 °C 900 °C 950 °C n = 48 10 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 Minimum creep rate [% / h] 1 Fig. 464. Stress vs. minimum creep rate for X-45 superalloy castings; [3]. Landolt-Börnstein New Series VIII/2B Ref. p. 365] 3.3.2 Co-25Cr-10Ni-7.5W-B alloy 365 3.3.2.5 Referecnes [1] [2] [3] [4] The superalloys, ed. by Sims, C. T., and Hagel, W. C., John Wiley & Sons (1972) p.145. Aerospace Structural Metals Handbook, vol.5, code 4305 (1985). NRIM Creep Data Sheet, No.30B (1988). Report on the mechanical properties of metals at elevated temperatures, Vol. IV Superalloys, The Iron and Steel Institute of Japan (1979). Landolt-Börnstein New Series VIII/2B