?K^ooo'az PINSTECH/NMD-116 IHTER6RAHULAR CORROSION OF INCOLOY 8 0 0 BY ELECTROCHEMICAL POTERTIOKINETIC REACTIVATION AND HUEY TEST METHODS SOHAIL UR RAHMAN NAZAR HUSSAIN K. A. SHAHID (NUCLEAR MATERIALS DIVISION) Pakistan Institute of Nuclear Science and Technology Nflore, Islamabad. March, 1986. PINSTECH/NMD-116 INTERGRANULAR CORROSION OF INCOLOY 800 BY ELECTROCHEMICAL POTENTfOKINETIC REACTIVATION AND HUEY TEST METHODS Sohail ur Rahman Nazar Hussain K.A. Shahid Nuclear Materials Division Pakistan Institute; of Nuclear Science and Technology Mi lore, Islamabad. CONTENT Page S/NO. Description 1. ABSTRACT 2. INTRODUCTION 1 3. EXPERIMENTAL 1 4. RESULT fc DISCUSSION 3 5. CONCLUSION 6 6. BIBLIOGRAPHY 7 7. TABLES 8. FIGURES 8-il ABSTRACT To measure the degree of sensitization (DOS) quantitatively in stainless steels an Electro­ chemical Potentiokinetic Reactivation (EPR) method was developed. Here in this report the reliability and reproducibility of this technique was studied. The test was also extended to quantify the DOS in Incoloy-800 and efforts made to correlate it with ASTM A 262-Practice C; Huey Test, the investigation was performed by annealing the specimens at different temperatures around and within the sensitization range of material and testing by both the methods. The results measured by potentiokinetic reactivation method and the Huey test were not in correspondence with each other. The reproduci­ bility of EPR method was found to be good. 1. INTRODUCTION A technique was developed * 'to measure the degree of sensitization quantitatively in thermally treated stainless (2) steels of type 304 t> 304 L. Elsewhere , the method was correlated and compared to ASTM Procedure A-262 Practice E. Sensitized nickel-rich chromium-bearing alloys behave, similar to the sensitized austenitic stainless steels, according to the generally accepted model for intergranular corrosion involving precipitation of Cr-rich carbides accompanied by narrow Cr-depleted zones adjacent to the grain boundaries. The objective of the present investigation is to establish a relationship between the Huey Test and the new EPR technique with respect to Alloy 800-H. In relation to the electrochemical evaluation of the degree of sensitization, efforts have been made to correlate the parameters of the part of polarization curve of Incoloy 800 in sulphuric acid with intergranular corrosion. A summary of different methods is found in Ref. (3). To quantify the degree of sensitization through Huey Test, the material exhibiting high corrosion rates with increasing tendency in later periods is usually rejected. 2. EXPERIMENTAL Composition of the material used in this study is shown in Table 1. Only one heat of alloy-800 was employed for the purpose of investigation. The specimens were annealed in the range of 500°C - 1000°C for one and two hours. EPR TEST The arrangement for EPR testing consisted of a Wenklng ST 72 potentiostat, a Wenking SNP 72 stepping potentiometer coupled to Houston Instruments 2000 X-Y-recorder. Measure­ ments on flat specimens about 10 x 10 mm were carried out -2 in the type of one liter, 5 neck flask specified in ASTM G 5-72 * . An AISI 304 SS wire, 1.0 mm thick and 300 mm long was soldered to the side opposite the test surface. The entire assembly was then mounted in Epokwick resin 10-15 mm deep by placing a glass tube in a 25 mm diameter mold in the fashion as shown in figure 1. The specimens were sequentially polished to a final 1 um finish and rinsed with triple distilled water and acetone just before testing. Masking tape was then applied to the surface of 2 the specimen so as to allow only 19.63 mm of the area exposed to the solution. For each test, a fresh solution 4 of IN H SO with 0.97 g/1 KSCN was used. Two high density graphite auxiliary electrodes, necessary wiring and a saturated calomel electrode completed the cell. An electric hot plate was used to maintain the temperature of solution at 30°C ± 1°C. The solution was purged with nitrogen or argon and stirred magnetically before and during the run. The test was started by immersing the mounted specimen taking care not to expose the S.S wire to the solution. After 2 minute immersion to establish corrosion potential, which is near -350 mV Vs SCE, the potential was scanned to 200 mV and held there for 2 minutes. The potential was then traversed back to the original corrosion potential at a rate of 6V/h. 4 ) 2 HUEY TEST This widely used test consists of exposure of samples to boiling 65% nitric acid for five 48 hour periods. The samples used in this study were fabricated from 1 mm thick sheet of the material under investigation and had the following dimensions; 50 x 20 millimeters. A 4 mm diameter hole was provided to facilitate its suspension from glass cradles. A 2 liter round bottom flask fitted with a reflux condenser, contact thermometer and heating mantle constituted the experimental set up. 65% nitric acid of Analar grade was used for experiments. Specimens after each period of exposure were washed, dried and weighed. Data was established and samples were studied by metallographic examination. 3 - RESULTS AND DISCUSSION EPR TEST Typical polarization curve of alloy 800 can be seen in Pigure 2. The test conditions of the EPR method are given in Table II. Idea behind the EPR method is to judge the extent of impoverishment in chromium, it is therefore necessary to choose a comparative measurement from which the reduction of the total activation as a result of the formation of a weak passive layer would follow. Polarization and reactivation curves at various heat treatments are shown in Figure 3a & b. The practical absence of the reactivation peaks in Figure 3a (i) and its propagating height with increasing degree of sensitization can be clearly observed. In order to numerically express the suscepitibility to intergranular corrosion or the degree of sensitization, a number of writers have proposed various methods (5-8). For our evaluation of results we used the reactivation charge Pa for different temperatures. Pa was measured from time-current curve. Sensitized specimens are easily activateu and show high value of Pa, Table V. Grain boundary penetration can also be seen on the specimen surface after exposure, figure 4. Values of current above 10 uA only were taken into account to calculate the quantity Pa. The heat treatment experiments were carried out in the furnace of a dilatometer which had to be modified for this purpose. Argon was used to displace the air present in the furnace. With the behaviour observed in case of specimens between 650°C and 850°C, it was thought that something must have gone wrong with these heat treatments because in case of these few specimens the reactivation peaks were almost of the height of active peaks. A delay in arresting the required temperature was thought to be the offender. So in order to make sure of correct heat treatments the whole set of experiments was repeated. Reproduction of sensitized specimens was conducted in a different tubular furnace* The specimens were then subjected to EPR tests under conditions shown in Table II. The results deduced from this second set of tests were in excellent agreement with the previous one. -4 - The ASTM grain size number was not decided practically but the value of 4.5 given by the manufacturer was relied upon. The maximum value of Pa is for specimens sensitized from 700°C and 8OO C. The EPR method moves the peak of sensitization curve towards higher temperatures. 0 HUEY TEST The effect of the acid on the material was measured by determining the loss of weight of the specimen after each period and the total of the test periods. The corrosion rate pertaining to each specimen was calculated from the following equation; R = KW DAT where, R = the rate in mpy, mro/yr, in, penetration per month. K = constant, depends upon units of penetration desired. W * Weight loss in milligrams. A = Total surface area in square inches. D * Density of the material in g/cc. T = Duration of the test period in hours. Table 111 shows the tabulation of sensitization treatments at different temperatures. The results of Huey tests are given in Table IV. The ASTM A 262-C does not give criterion to enable determination of whether the test results indicate intergranular corrosion susceptibility of material being -5 tested. When the data shows increasing weight loss for successive 48 hr test periods, this should indicate intergranular corrosion. This test readily detects sensitization effects due to carbide precipitation. However, for certain grades of stainless steels this test is sensitive to a phase which does not cause intergranular corrosion. Figure 6, a graph of loss of weight in milligrams versus the number of periods of test, depicts the behaviour of alloy at various heat treatments. From the results in Table IV the sensitization range for one and two hour treatments is about 600°C-700°C. Figures 4 & 5 show the micro-strucu*._e of the alloy at various heat treatment after exposure to 65% boiling nitric acid. A temperature - corrosion rate graph for the alloy is shown in figure 7. Rates in mils per year are plotted for various temperatures on semilog paper because the range of rates represented is over 100 fold. Certain tests were disconti­ nued after specimen failed during examination, therefore these points are connected by dotted lines. The temperature for maximum sensitization for one hour exposure is about 620°C. It should be noted ' ' that Huey test does not assess the resistance of material to pure boiling nitric acid, but rather to the acid plus corrosion products. The standard test is, therefore self accelerating and becomes more selective as corrosion rate increases. Because of the absence of molybdenum from the alloy matrix, the high corrosion rates leading to failure of certain specimens can only be attributed to the presence of chromium ion in the solution. These appear to have been admitted as corrosion products of heavily sensitized specimens. The chromium ions are known to accelerate the rate of attack to an appreciable extent . it must also be noted that at potentials greater than 1.2V SHE the addition of Cr to Fe decreases resistance to dissolution. However, below 1.2V SHE the reverse is true. Because the boiling nitric acid test considers the extent of grain boundary attack, which occurs in Cr-depleted areas, in an aggressive corrodent at a potential set by the solution and the potential of Huey test lies in a range which is very near to 1.2V SHE, it gives us a picture that it may be responsible for high attack on some samples. 4. CONCLUSION According to the test results the alloy 800-H seems to be prone to intergranular corrosion attack in sensitized condition both by the standard boiling 65% nitric acid test and by the electrochemical potentio kinetic reactivation test. However, the EPR method tends to move the sensitization peak towards higher temperatures. The two methods could not be correlated because of their difference in detecting the peak sensitization of the material. Nevertheless, the reproducibility of EPR method has been found good. B I B L I O G R A P H Y W.L.Clarke, N.M. Romero, and J.C. Oanko "Delection of sensitization in stainless steel using electrochemical techniques". General Electric Company Report GEAP-21382, August 1976 and NACE Corrosion Conf. Paper No. 180, SanPranciso CA, March, 1977. W.L. Clarke, V.M. Romero, "Detection of sensitization stainlles steel: 11. EPR Method for nondestructive field tests". General Electric Company Report CEAP-1297. February, 1978. Cowan, R.L, & Tedmon, Jr. C.S., Advances in Corrosion Science and Technology, Vol. 3, 1973, PP-293-395 (New York:Plenum Press). ASTM GS-72 standard Reference Method for Haling Potentiostatic and potentio dynemic, Anodic Polarization Measure­ ments. ASTM, Philadelphia, Pennsylvania. Sohail Rehman, Study of intercrystalline corrosion Internal Report PINSTECH/NM0-116. W.L. Clarke, R.L. Cowan, W.L. Walker, "Comparative Methods Measuring Degree of Sensitization in S.S." Intergrar.ular corrosion of stainless Alloys ASTM STP 656, R.F. Steigerwald, Ed, ASTM, Philadelphia, Pennsylvania, P. 99, 1978. W.B. Delong, American Society for Testing Materials, Special Technical Publication No. 93. UK.C-1 Owrtcol CoomiUoa of Test *>teriol {Alloy 9BO-H) lest Qiocnsfons Nsey-Test SO x 30 « 1 M crt-rest .1963 Cm row* Eleae»t mmml « S Ti ill Cr «i C F» Co 0.05 B.S 32.1 0.38 0 . M 0.38 •5.87 0.083 TABUS-11 BPR Test Conditions Electrolyte 0.5* H S 0 Temperature 30»C i 1>C Specinen Surface Finish. 1 u* (diaeond paste) Initial potential B corr. VS SCE. Vertex Potential • 200 «V . Vertex Delay 2 win. Scan rate l.tt •V/sec. Dn-aeration Argon 1 litre/ain. 2 4 S * 0.97 9/1 » .33/ - * - TABLE-III Sensitizat ion Annealing Tines and Temperatures For Huey Test Specimens. Code of Specimens Sensitized for 1 hr 1 2 1 4 S t 7 t » 10 11 12 1) 14 IS 1* 17 1» 1* 20 21 22 21 24 Sensitized for 2 hr • 2 - 2 - 400 400 500 500 550 550 600 600 600 600 - 610 - 620 650 650 700 700 750 750 800 800 - S-50-IA S-50-2A S-55-1A - S-40-lAj S-40-2AJ S-*0-lA S-*0-2A S-62-1A S-62-2A S-65-IA S-*S-2A S-70-1A S-70-2A S-7S-1A S-7S-2A - •c As received H-A*-l H-AK-2 - Sensitization Heat Treatment Temperature S-45-1B S-45-2B S-50-1B S-50-2B S-55-1B S-55-2B S-60-1B S-60-2B S-65-IB S-65-2B S-70-IB S-70-2B S-75-1B S-75-2B S-BO-IB S-80-2B - 10 - TABLE-IV CORROSION RATE OF INCOLOY 800 BY HUEY TEST Corrosion Rate at Time Periods, 48 hrs each Sensitization Sensitization Time (hrs.) Temperature(C°) (mpy) 5 th 1st 2nd 3rd 4 th 1. 2. 500 4 4 4 5 6 550 23 31 37 52 59 600 347 ND ND ND ND 650 106 173 ND ND ND 700 5 6 8 9 10 800 5 5 7 8 9 26 50 55 62 ND ND ND ND 5 500 I* 550 143 455 ND ND 600 520 ND ND ND 650 375 522 ND ND 700 43 304 498 ND 800 4 4 4 4 ND: Not determinable. - 11 - TABLE-V The Reactivation Charge fa of the Specimens Sensitized For One Hour Only in the EPtt-Test. Code of Specimens 1) 2) 31 4) 5) 6) 7) 8) 91 101 11) H-AR-I S-50-1A S-55-1A S-60-1A S-65-1A S-70-1A S-75-1A S-80-1A S-85-1A S-90-1A S-95-1A Sensitization Heat Treatment Temperature °C As received 500 550 600 650 700 750 800 850 900 950 _ r . Reactivation Charge Pa(mc/Cm ) 0 41 77 69 220 440 420 364 294 264 161 Fig. 1 SPECIMEN ASSEMBLY FOR EPR TESTING pr. ssi vi! pesr.ive transpassivr; trar.spassive U!:nV) v Fiij.2 TY iCAL ANODIC POLARIZATION PLOT OF ALLOY 800 trans passive" trunspossivr 0-2V 0 3 5 V AS RECEIVED (1) 5-50 'J??. 1A ( 2 ) S-55-1AO) FIG. 3 a *-'• -003V OSV , •' .;V (tf'/V +0-2V S - 6 0 - 1 A (4) S-65-1A(5) S-70-1AC6) CHARACTERISTIC POTErjTIODYNAMIC CURVES OF ALLOY 800 WITH VARYING DEGREES OF SFMSITIZ AT ION DRAWN IN ACCORDANCE WITH THE DESCRIBED PROCEDURE • ; . - \ -0.35V U.?iV 035/ S-75-1AU) 5 - 8 0 - 1 A (8) s-es-tAO) FIG. 3 b + 0.2V -»0 ." V -0;O\ S-9O-1AO0) r -0 - Y 5-95-lA(11) + \' Q2 * 0 2V 02V CHARACTERISTIC POTENTIODYNAMIC CURVES OF ALLOY 800 WITH VARYING DEGREES OF SENSITI­ ZATION DRAWN IN ACCORDANCE WITH THE DESCRIBED PROCEDURE. v 590 o 550 600 600 iT-yfc ." ; " *•!""•• - 500 Ih b ! 550 Ih b ] FIG. U. MICROSTRUCTURES OF ALLOY 800 AFTER EXPOSURE TO Q) EPR TESTING b) 65V. BOILING NITRIC ACID r 620 l h 650 1h -<r* 750 lh FIG.5.MICR0STRUCTURES OF ALLOY 800 AFTER EXPOSURE TO BOILING 65V. NITRIC ACIO LJ a »< a ui a. Z f 4 I N I fNf <-• £ *>*. « « ^ ^» ^""• ~~ 1 ^"T» — ! ^^I •~i; «.**•• T ^ v £* K \r> CM r : m O i / » o < m f u> u> r- c^» <o 1 I I iM xOO<JP<][Kj -1* < >- o a X UI o u. o o (6UJ) ssr»| iqfii*M l \ $ 21,0 hr 43 hr 96 br 1 U hr 1100 " 1300 1^00 o A D O 1700 Temperature F( 1 HR Exposure) FIG 7 EFFECT OF HEAT TREATMENTS ON EVALUATION TEST RATE OF ALLOY 800-H IJL Printino Corporation of Pafcittan Pros, Islamabad