Unique Stainless Steel Materials and Processing For High Strength With Reduced Magnetic Performance Tom Stuart, Delphi Corporation Chris Schade, Hoeganaes Corporation Francis Hanejko, Hoeganaes Corporation Abstract A new automotive part was designed having property requirements incorporating high yield and tensile strengths with good ductility, while at the same time requiring reduced magnetic performance. This combination of properties precludes the use of iron and low alloy materials because of their intrinsic magnetic response. In an effort to satisfy both requirements, type 200 stainless steel powders were prepared and processed into both mechanical property test specimens and magnetic toroids. Processing of the compacted samples was optimized to give the required strength characteristics with required minimal magnetic response. This paper will detail the types of stainless materials utilized and unique processing developed to accomplish these conflicting requirements. The mechanical and magnetic properties will be presented. Introduction The driving force for this study was the development of a new application that had the following design criteria: ¾ High yield and tensile strengths; ideally the yield strength should approach 100,000 psi (~700 MPa). ¾ Ductility should be as high as possible with a 2% minimum tensile elongation. ¾ Magnetic permeability response of the pressed and sintered component should be nearly zero. This prevents flow restrictions when used in conjunction with a magneto-rheological fluid. ¾ As-sintered net shape part without the need for sizing or secondary machining. Initial modeling for this device utilized an aluminum alloy (type 7175) that was extensively machined to produce the final component (Figure 1). Part complexity made machining difficult; P/M processing offered significant cost reduction opportunities if all desired design criteria were met. Figure 1: Schematic of application, parts are located top and bottom of drawing. Initially, high strength low alloy irons were considered. Alloys containing 0.8% graphite would provide the required strength; however, magnetic response of these materials was still in excess of design requirements (permeability >200). P/M austenitic stainless steels also were considered but these alloys lack the necessary yield strength and tensile strength required in this application. Space restrictions within the final device precluded the extensive redesign and larger part required to accommodate reduced strength of the 316 alloy. Wrought 200 series stainless steels have the high strength and austenitic stainless steel magnetic response. [1] The 200 series stainless steels contain relatively low amounts of nickel but also are alloyed with nitrogen for strengthening and as an austenite-forming element. Currently, there are no P/M equivalents to the 200 series stainless steels; prealloyed nitrogen dramatically reduces compressibility. A material and processing scheme was needed that would simulate the magnetic and mechanical property response of 200 series stainless steels while the advantages of using P/M. This paper will outline the material and processing parameters evaluated to achieve the desired design parameters. Experimental Procedure Materials investigated The materials evaluated in this study are listed in Table 1. All alloys were prepared at Hoeganaes Corporation’s pilot atomization facilities and were premixed with 0.75% Acrawax C. Particle size analyses of these materials were comparable to commercially available stainless steel alloys (-100 mesh with ~40% -325 mesh). Graphite was added as Asbury 3203 natural graphite. Alloy “C” is a commercially available 316 austenitic stainless alloy; it was incorporated into this study as a baseline for comparison. Alloy “D” is a duplex stainless steel (ferritic / austenitic microstructure); wrought alloys of this type possess high strength. [2] Table 1 Alloys Investigated in this Study Alloy ID A B C D E Cr, wt% 17.0 17.0 17.0 22.2 17.0 Alloy Composition Ni, wt % Si, wt% Mo, wt% 4.0 0.8 0 4 0.8 1.0 9.0 0.8 2.0 5.5 1.0 3.4 4.0 0.8 1.0 Cb, wt% 0 0 0 0 0.50 Gr, wt% 0.35 0.35 0 0 0.35 Samples prepared In order to satisfy the key design requirements, it was imperative to determine the yield strength, tensile strength, and magnetic response of the various materials. The following samples were prepared: ¾ TRS bars compacted at 40 tsi (550 MPa) and 50 tsi (690 MPa) ¾ “MPIF” Dog bone tensile bars compacted at 40 tsi (550 MPa) and 50 tsi (690 MPa) ¾ Magnetic toroids (2.0 inch (50 mm) OD x 1.8 inch (45 mm) ID x 0.25 inch tall (6 mm)) were compacted at 40 tsi (550 MPa) and 50 tsi (690 MPa) Compaction pressures of 40 tsi (550 MPa) and 50 tsi (690 MPa) were selected because of the high strength / high-density requirements. Sintering and post sintering heat treatment Sintering was performed at the temperatures and atmosphere conditions listed in Table 2. Time at temperature was ~40 minutes for each condition. Tempering of the samples was investigated because the alloy content of these materials has a significant potential of forming martensite during cooling. Similar to sinter-hardening alloys, tempering was investigated as a means to improve the mechanical property response. Table 2 Sintering and Tempering Conditions Evaluated Sintering Temperature 2150 °F (1175 °C) 2300 °F (1260 °C) 2350 °F (1290 °C) 2350 °F (1290 °C) Sintering Atmosphere 90 v/o nitrogen and 10 v/o hydrogen 90 v/o nitrogen and 10 v/o hydrogen 90 v/o nitrogen and 10 v/o hydrogen 50 v/o nitrogen and 50 v/o hydrogen 2350 °F (1290 °C) 100 v/o hydrogen Tempering None None None None, 900 °F (480 °C), 1100 °F (595 °C) None, 900 °F (480 °C), 1100 °F (595 °C) Results Mechanical property test results Green densities for the two compaction pressures and five test materials are shown in Figure 2. Compressibility of the 316 (austenitic stainless steel) is superior to the ferritic grades. It is noteworthy that the compressibility of these materials is low in comparison to traditional pure iron and low alloy irons. Thus, it will be imperative that sinter densification occur to facilitate attainment of the mechanical properties required for this application. 6.80 40 tsi (550 MPa) 50 tsi (690 MPa) Green Density, g/cm³ 6.60 6.40 6.20 6.00 5.80 5.60 5.40 A B C D E Material ID Figure 2: Compressibility of the five alloys studied, all compacted at room temperature with 0.75% admixed Acrawax C. Sintered densities, dimensional change (DC), and tensile properties for the five materials are presented as Tables 3 through 7. All data shown represent sintering times of ~40 minutes at temperature. Table 3 As Sintered Properties of Alloy A (17% Cr, 4% Ni, 0.8% Si, 0.35% Gr) Sinter Cond. 1175 °C, 90 / 10 1260 °C, 90 / 10 1290° C, 90 / 10 1290°C, 50 / 50 1290°C, 100 Compact Sinter tsi (MPa) g/cm³ 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 6.57 6.77 6.68 6.90 6.70 6.92 6.73 6.96 6.80 6.94 DC, % TRS, 10³ psi (MPa) YS, 10³ psi (MPa) UTS, 10³ psi (MPa) El,% -0.79 -0.71 -1.37 -1.35 -1.50 -1.47 -1.61 -1.65 -2.36 -1.90 151 (1040) 174 (1200) 160 (1605) 188 (1295) 144 (995) 210 (1450) 177 (1220) 187 (1290) 245 (1690) 278 (1915) 53.9 (370) 59.6 (410) 52.2 (360) 56.9 (390) 53.6 (370) 57.5 (395) 59.3 (415) 62.5 (430) 59.9 (415) 62.6 (431) 83.6 (575) 94.0 (650) 83.0 (570) 89.4 (620) 82.8 (570) 87.9 (605) 98.3 (675) 90.9 (625) 126.2 (870) 142.2 (980) 1.8 2.0 2.5 3.2 2.7 3.5 1.6 2.4 4.5 5.6 Table 4 As Sintered Properties of Alloy B (17% Cr, 4% Ni, 0.8% Si, 1.0 % Mo, 0.35% Gr) Sinter Cond. 1175 °C, 90 / 10 1260 °C, 90 / 10 1290 °C, 90 / 10 1290 °C, 50 / 50 1290 °C, 100 Compact, tsi (MPa) Sinter g/cm³ DC, % TRS, 10³ psi (MPa) YS, 10³ psi (MPa) UTS, 10³ psi (MPa) EL,% 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 6.53 6.77 6.67 6.92 6.68 6.93 6.70 6.98 6.86 7.01 -1.13 -1.02 -1.83 -1.75 -1.9 -1.88 -2.04 -2.04 -3.14 -2.62 157 (1080) 186 (1280) 186 (1280) 209 (1440) 203 (1400) 221 (1525) 210 (1450) 210 (1450) 239 (1650) 272 (1875) 56.9 (390) 61.7 (425) 59.3 (410) 60.7 (420) 60.7 (420) 63.0 (435) 64.4 (445) 65.9 (455) 54.7 (375) 60.3 (415) 88.5 (610) 98.7 (680) 93.2 (640) 93.4 (645) 93.8 (645) 95.2 (655) 104.7 (720) 104.7 (720) 125.8 (865) 138.8 (955) 2.0 2.4 2.3 3.0 2.4 3.1 2.7 3.0 6.6 7.0 Table 5 As Sintered Properties of Alloy C (17% Cr, 9% Ni, 0.8% Si, 2% Mo) Sinter Cond. 1175 °C, 90 / 10 1260 °C, 90 / 10 1290 °C, 90 / 10 1290 °C, 50 / 50 1290 °C, 100 Compact, tsi (MPa) Sinter g/cm³ DC, % TRS, 10³ psi (MPa) YS, 10³ psi (MPa) UTS, 10³ psi (MPa) EL, % 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 6.60 6.84 6.70 6.93 6.73 6.96 6.76 6.97 6.80 7.01 -0.43 -0.37 -1.01 -0.87 -1.17 -1.03 -1.31 -1.11 -1.68 -1.46 125 (860) 147 (1015) 142 (980) 177 (1220) 147 (1015) 161 (1110) 163 (1125) 177 (1220) 145 (1000) 157 (1080) 48.7 (335) 56.0 (385) 50.7 (350) 55.7 (385) 51.0 (350) 55.8 (385) 53.5 (370) 55.9 (385) 39.2 (270) 40.7 (280) 58.4 (405) 67.9 (370) 64.7 (445) 72.8 (500) 64.0 (440) 74.9 (515) 70.0 (485) 77.4 (535) 62.3 (430) 68.1 (470) 2.9 4.0 6.5 8.3 6.4 9.7 7.2 11.5 17.4 21.1 Table 6 As Sintered Properties of Alloy D (%Cr, %Ni, %Si, %Gr) Sinter Cond. 1175 °C 90 / 10 1260 °C, 90 / 10 1290 ° C 90 / 10 1290 °C, 50 / 50 1290 °C, 100 Compact, tsi (MPa) Sinter g/cm³ DC, % TRS, 10³ psi (MPa) YS, 10³ psi (MPa) UTS, 10³ psi (MPa) EL,% 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 6.10 6.39 6.22 6.49 6.57 6.79 7.03 7.20 7.06 7.20 -0.48 -0.46 -1.17 -1.07 -3.15 -2.70 -5.36 -4.60 -6.21 -5.33 113 (780) 133 (915) 132 (915) 156 (1075) 192 (1325) 214 (1475) 194 (1340) 197 (1360) 200 (1380) 202 (1395) 44.8 (310) 52.8 (364) 47.3 (325) 54.4 (375) 61.5 (425) 66.8 (460) 64.4 (445) 61.0 (420) 61.2 (420) 61.9 (425) 58.7 (405) 70.0 (485) 65.8 (455) 75.7 (520) 88.4 (610) 95.8 (660) 81.4 (560) 80.9 (560) 81.7 (565) 84.1 (580) 1.1 1.4 2.1 2.6 4.7 5.3 5.5 7.6 13.3 10.8 Table 7 As Sintered Properties of Alloy E (17% Cr, 4% Ni, 0.8% Si, 1.0% Mo, 0.50% Cb, 0.35% Gr) Sinter Cond. Compact, tsi (MPa) Sinter, g/cm³ DC, % TRS, 10³ psi (MPa) YS, 10³ psi (MPa) UTS, 10³ psi (MPa) EL, % 2150F, 90 / 10 2300 F, 90 / 10 1290°C 90 / 10 1290°C 50 / 50 1290°C 100 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 40 (550) 50 (690) 6.27 6.53 6.39 6.67 6.45 6.72 6.53 6.77 6.82 7.00 -0.32 -0.28 -1.00 -0.97 -1.35 -1.27 -1.82 -1.61 -3.70 -3.05 100 (700) 123 (850) 125 (850) 147 (1000) 138 (950) 157 (1075) 141 (1000) 170 (1175) 222 (1550) 226 1550) 42.8 (295) 50.0 (345) 46.4 (320) 54.4 (375) 49.3 (340 55.3 (380) 53.1 (365) 57.3 (395) 57.9 (400) 65.5 (450) 53.6 (370) 63.8 (440) 63.2 (435) 74.4 (515) 64.9 (445) 73.6 (505) 70.3 (485) 78.6 (540) 102.3 (705) 104.3 (720) 1.2 1.3 3.1 3.8 4.4 5.1 4.7 8.0 5.7 5.7 As-sintered tensile properties show these 5 alloys develop the required 2% minimum tensile ductility following sintering at 2300 °F (1260 °C) or 2350 °F (1290 °C). The commercially available 316 have the highest ductility of all alloys; however, the yield strength and tensile strength are significantly below the design objectives. Alloy A and Alloy B possess the highest tensile strength but the yield strength at approximately 60,000 psi (415 MPa) is below the design parameter. Another important aspect of the data present in Table 3 through Table 7 is the DC after sintering. As depicted in Figure 1, the component has a complex geometry with critical “cored” details, any sintering distortion will affect the in-service performance of this part. Thus over the range of green densities studied, DC response should remain constant to prevent component distortion; thus eliminating the need for a sizing operation. Alloys A, B, C, and E show uniform DC at the two densities for the sintering conditions evaluated. Alloy D (duplex phase) exhibits a large variation in DC with minor changes in green densities. This implies that Alloy D has a greater tendency to distort during sintering, thus this alloy was deleted from further evaluation. One of the stated design criteria was a yield strength approaching 100,000 psi (690 MPa). The tensile data developed and presented in Table 3 through Table 7 fall short of this objective. Consequently, tempering of Alloys A, B, and E was investigated what effect it had on mechanical properties. Presented in Table 8 through Table 10 are the tensile data for materials A, B & E as a function of tempering temperatures, all tempering was done for 1 hour at temperature in a 100% nitrogen atmosphere. As stated earlier, the tempering response in these alloys occurs because of their high hardenability producing martensite during cooling. Tempering acts to stress relieve the material, increasing the yield strength and tensile strength. For brevity, the tensile data shown in the subsequent table represents the 50 tsi (690 MPa) compaction condition. Initially, a tempering temperature as low as 400 °F (205 °C) was investigated; however, no significant response was observed until a temperature of 900 °F (480 °C) was utilized. This tempering temperature is consistent with the tempering response of the wrought 200 series stainless steel. Table 8 Tempering Response for Material A (17% Cr, 4% Ni, 0.8% Si, 0.35% Gr) Density, g/cm³ 6.77 6.90 6.92 6.96 6.96 6.96 6.94 6.94 6.94 Sinter Cond, ° C 1175 1260 1290 1290 1290 1290 1290 1290 1290 Temper °C None None None None 480 595 None 480 595 YS, 10³ psi (MPa) TS, 10³ psi (MPa) 59.6 (415) 56.9 (415) 57.5 (400) 62.5 (430) 70.5 (490) 62.0 (430) 62.6 (435) 89.4 (620) 76.5 (530) 94.0 (650) 89.4 (620) 87.6 (605) 90.9 (625) 87.4 (600) 94.0 (650) 142.2 (980) 134.8 (931) 117.6 (813) El, % 2.0 3.2 3.5 2.4 1.3 3.1 5.6 2.7 5.9 Hardness, HRA 59 55 55 52 51 50 60 62 54 Table 9 Tempering Response for Material B (17% Cr, 4% Ni, 0.8% Si, 1.0% Mo, 0.35% Gr) Density, g/cm³ 6.77 6.92 6.93 6.98 6.98 6.98 7.01 7.01 7.01 Sinter Cond, ° C 1175 1260 1290 1290 1290 1290 1290 1290 1290 Temper °C None None None None 480 595 None 480 595 YS, 10³ psi (MPa) 61.7 (425) 60.7 (420) 63.0 (435) 65.9 (455) 73.9 (510) 69.5 (480) 60.3 (415) 84.5 (585) 76.0 (525) TS, 10³ psi (MPa) 98.7 (685) 93.4 (650) 95.2 (655) 104.7 (725) 104.3 (715) 105.4 (725) 138.8 (960) 142.0 (980) 121.6 (840) El, % 2.4 3.0 3.1 3.0 2.3 4.0 7.0 6.8 6.8 Hardness, HRA 59 56 56 55 56 55 59 61 56 Table 10 Tempering Response for Material B (17% Cr, 4% Ni, 0.8% Si, 1.0% Mo, 0.50% Cb, 0.35% Gr) Density, g/cm³ 6.53 6.67 6.72 6.77 6.77 6.77 7.00 7.00 7.00 Sinter Cond, ° C 1175 1260 1290 1290 1290 1290 1290 1290 1290 Temper °C None None None None 480 595 None 480 595 YS, 10³ psi (MPa) 50.0 (345) 54.4 (370) 55.3 (380) 57.3 (395) 57.4 (395) 58.6 (405) 65.6 (450) 86.6 (600) 89.3 (615) TS, 10³ psi (MPa) 63.8 (440) 74.4 (510) 73.6 (510) 78.6 (545) 78.8 (545) 78.7 (545) 104.3 (715) 115.9 (800) 110.3 (760) El, % 1.3 3.8 5.1 8.0 9.1 8.4 5.7 5.3 5.4 Hardness, HRA 52 49 48 47 48 48 55 57 58 Tempering of Alloy A, Alloy B, and Alloy D developed yield strengths greater than 70,000 psi (485 a) approaching the 100,000-psi (690 MPa) design criteria. The highest mechanical properties were achieved with sintering at 2350 °F (1290 °C) in 100% hydrogen. However, as will be discussed in the subsequent section, this sintering conditions results in a magnetic permeability greater than 200 precluding its use in this application. Alloy A and Alloy B show minor improvements in the yield strength up to ~ 70,000 psi (480 MPa) with tempering at 900 °F (480 °C) subsequent to sintering in a 90 v/o nitrogen and 10 v/o hydrogen or 50 v/o nitrogen and 50 v/o hydrogen atmosphere. Magnetic Properties The magnetic data of the various materials are summarized in Table 11. The 316 stainless (Alloy C) has no magnetic response, Alloy D was not tested because of its DC response. For brevity, only data at compaction conditions of 50 tsi are presented. Testing was done at 15 Oersteds. The key in this testing was to determine the magnetic response and determine which material and processing produced nearly zero magnetic response. Table 11 Magnetic Response at 15 Oersteds of Various Alloys Material A A A B B B E E Sintering Temperature, °C 1175 1260 1290 1175 1260 1290 1175 1290 Sintering Atmos %N2/%H 90 / 10 90 / 10 50 / 50 90 / 10 90 / 10 50 / 50 90 / 10 50 / 50 Permeability 5 2 30 4 3 83 3 45 Bs at 15 Oe, Gauss 92 55 850 77 70 1010 48 1400 From the data in Table 11, sintering in a 90/10 atmosphere gave almost no magnetic response (approaching paramagnetic conditions). [3] Increasing the amount of hydrogen in the atmosphere to 50% and then to 100%, increased the permeability to approximately 50 and then to >200, respectively. [4] Thus from this part of the study, it was determined that sintering in the 90 v/o nitrogen and 10 v/o hydrogen at either 2300 °F (1260 °C) or 2350 °F (1290 °C) was necessary to give the required magnetic response and mechanical properties. Additionally, the necessity of sintering in 90 v/o nitrogen and 10 v/o hydrogen eliminates Alloy E because its sintered density and mechanical properties are lower than Alloy A or Alloy B under these processing conditions. Alloy B is the preferred material system because it has the highest strength. Discussion This investigation focused on material and processing selection to produce a part that possesses good mechanical properties but almost zero magnetic response. Of the alloys chosen, Alloy B (17% Cr, 4 % Ni, 0.8 % Si, 1.0 % Mo) has the highest level of mechanical properties, consistent DC, and low magnetic response if sintered in a 90 v/o nitrogen and 10 v/o hydrogen atmosphere. Increasing the amount of hydrogen in the sintering atmosphere improves the mechanical properties but results in increased permeability. Shown in Figure 3 is test data developed on components relative to the machined aluminum model material. The ideal response is that represented by the top three curves: one is the aluminum standard and two P/M components sintered at 2350F in 90 v/o nitrogen and 10 v/o hydrogen. Note the nearly identical response of developed force vs. velocity. The lower response curve in Figure 3 represents sintering at 2350F in a 50/50 atmosphere. Note the degradation in response. This lower response is because of the increased permeability affecting the magneto-rheological fluid. Figure 3: Test data illustrating effect of magnetic permeability on component response Sintering in high nitrogen atmospheres results in nitrogen pick up of the components as shown in Table 12. The nitrogen acts both to strengthen the stainless steel and pins the magnetic domains, thus giving the desired overall response. Mechanical property test results and FEA showed the reduced yield strength necessitated thickening of the central region of the component. However, the increase in thickness dimension was less than required if a 316 austenitic steel was specified. Table 12 Nitrogen Pick-up with Sintering Temperature and Atmosphere Sintering Temperature, °C 1175 1260 1290 1290 1290 Sintering Atmosphere (v/o N2 / v/o H2) 90 / 10 90 / 10 90 / 10 50 / 50 0 / 100 Nitrogen Content, % 0.63 0.63 0.71 0.22 0.03 Conclusions From this study, the following conclusions were reached ¾ It was possible to produce a 200 series stainless steel that produced yield strengths of ~ 70, 000 psi (480 MPa) with the magnetic permeability response of less than 5, as required for the new part design. The optimum alloy had the following composition: (17 % Cr, 4 % Ni, 0.80% Si, 1.0 % Mo) ¾ A minimum sintering temperature of 2300 °F (1260 °C) was required to produce the sinter densification to give the required mechanical properties. ¾ Sintering atmosphere was critical, a 90 v/o nitrogen and 10 v/o hydrogen atmosphere is optimal to promote the nitrogen pick-up to give the increase in mechanical strength plus the reduced magnetic response. ¾ FEA modeling of the reduced strength showed that an increase in thickness of the central region of the part was necessary. ¾ Actual component performance demonstrated that the P/M parts had identical service performance to machined wrought aluminum parts. ¾ Dimensional stability of the parts is critical to insure proper function and eliminate the need for a sizing step after sintering. References: 1. Making, Shaping and Treating of Steel, edited by Harold McGannon, United States Steel, Ninth Edition, 1970, p 1164 – 1184. 2. The International Molybdenum Association, “Practical Guideline for the Fabrication of Duplex Stainless Steels”, Edited by Technical Marketing Resources, Inc. Pittsburgh, PA 2001. 3. Richard Bozorth, “Ferromagnetism”, D. Van Nostrand Company, Princeton,NJ,1951. 4. H. Kopech, H. Rutz, P. dePoutiloff, “Effects of Powder Processing on Soft Magnetic Performance of 400-Series Stainless Steel Parts”