STAINLESS STEEL AISI GRADES FOR PM APPLICATIONS Chris Schade Hoeganaes Corporation Cinnaminson, NJ 08077 John Schaberl Ancor Specialties Ridgway, PA 15853 Alan Lawley Drexel University Philadelphia, PA 19104 ABSTRACT Applications requiring stainless steels are growing at a rate of about 5% annually. Opportunities for using powder metallurgy (PM) exist, but additional grades not covered by MPIF Standard 35 are required. The American Iron and Steel Institute (AISI) has standards for a broad range of stainless steels that can be used in many applications, but the compositions of these grades must be modified to be conducive to manufacture by conventional PM techniques. Several of these grades have been produced as standard press and sinter powders. The physical properties, mechanical properties and microstructures of these various grades are reviewed to serve as a guideline for PM parts manufacturers and potential applications of these grades are addressed. INTRODUCTION MPIF Standard 351 lists the most common grades of stainless steel used by PM parts manufacturers. These include austenitic grades such as 303L, 304L and 316L, and ferritic grades such as 409L, 410L, 430L and 434L. However, with the continued growth of stainless steel there exists many opportunities for specialized stainless steel grades not covered by MPIF Standard 35. These include applications requiring enhanced physical properties, corrosion resistance, weldability and machinability. There are additional grades covered by the American Iron and Steel Institute (AISI) that can be manufactured by conventional press and sinter powder metallurgy (PM), Figure 1. The AISI designation for these alloys is well known with the number series 200 and 300 referring to austenitic stainless steels and the 400 series covering the ferritic and martensitic stainless steels. Letter designations attached to the end of the number series indicate modifications to the composition.2 Many societies such as the Society for Automotive Engineers (SAE) and the American Society for Testing and Materials (ASTM) use the AISI specification with the latter adding physical property specifications.3 SAE and ASTM have worked together to create the unified numbering system (UNS) for metals and alloys, which is recognized globally and can be used as a cross-reference internationally. 4 Other references covering both wrought and cast grades of stainless steel are available.5-6 Figure 1. Available stainless steel alloy systems.3 There are hundreds of commercially available stainless steel compositions, fabricated by multiple processing steps which modify their properties. Fortunately these stainless steels can be classified into several distinct categories. These include austenitic, ferritic, martensitic, precipitation hardening, and duplex stainless steels. For convenience the development of additional PM grades of stainless steel will adhere to these categories. ALLOY PREPARATION AND TESTING The powders used in this study were produced by water atomization with a typical particle size (100 w/o) <150 µm (–100 mesh) and with 38 to 48 w/o <45 µm (-325 mesh). All the alloying elements were prealloyed into the melt prior to atomization, unless otherwise noted. Admixed copper, molybdenum and nickel powders were used to make some compositions and are so designated in the tables of chemical composition. The stainless powders were mixed with 0.75 w/o Acrawax C lubricant. Samples for transverse rupture (TR) and tensile testing were compacted uniaxially at 690 MPa (50 tsi). All the test pieces were sintered in a high temperature Abbott continuous-belt furnace at 1260 °C (2300 °F) for 45 min in hydrogen with a dewpoint of –40 oC (-40 °F), unless otherwise noted. Prior to mechanical testing, green and sintered density, dimensional change (DC), and apparent hardness, were determined on the tensile and TR samples. Five tensile specimens and five TR specimens were tested for each composition. The densities of the green and sintered steels were determined in accordance with MPIF Standard 42 and tensile testing followed MPIF Standard 10. Impact energy specimens were tested in accordance with MPIF Standard 40. Apparent hardness measurements were conducted on tensile, TR and impact specimens, following MPIF Standard 43. Rotating bending fatigue (RBF) specimens were machined from test blanks that were pressed at 690 MPa (50 tsi) and sintered at 1260 oC (2300 oF). The dimensions of the test blanks were 12.7 mm x 12.7 mm x 100 mm. RBF tests were performed using rotational speeds in the range of 7,000-8000 rpm at R equal -1 using four fatigue machines simultaneously. Thirty specimens were tested for each alloy composition, utilizing the staircase method to determine the 50% survival limit and the 90% survival limit for 107 cycles (MPIF Standard 56). Metallographic specimens of the test materials were examined by optical microscopy in the polished and etched (glyceregia) conditions. Etched specimens were used for microindentation hardness testing, per MPIF Standard 51. Salt spray testing on TR bars was performed in accordance with ASTM Standard B 11703. Five TR bars per alloy (prepared as previously described) were tested. The percent area of the bars covered by red rust was recorded as a function of time. The level of corrosion was documented photographically. RESULTS AND DISCUSSION Ferritic Stainless Steels For PM applications, the ferritic stainless steels are by far the most widely used grades, reflecting their application in the automotive industry. Examples are ABS sensor rings and muffler exhaust flanges. Chromium is the major alloy constituent of the ferritic grades along with minor additions of other ferrite stabilizers such as silicon and niobium (Table I). In general, the 400 series, ferritic stainless steels contain 11 to 27 w/o Cr, are magnetic, have moderate ductlity and corrosion resistance and are relatively weak at high temperatures.7-8 In order to form the passive oxide layer a minimum of about 11 w/o Cr is required. Table I: Composition of PM Ferritic Stainless Steels (w/o) AISI S40940 410L1 S41000 416L S41603 430L1 S43000 434L1 S43400 436 S43600 439 S43035 441 S44100 446 S44600 446 S44626 409L 1 UNS 1 C 0.03 Max. 0.03 Max. 0.03 Max. 0.12 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. S .030 Max. .030 Max. .150 .300 .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. P .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. .040 Max. Si 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. Cr 10.5 11.7 11.5 13.0 11.5 13.0 16.0 18.0 16.0 18.0 16.0 18.0 16.0 18.0 16.0 18.0 23.0 27.0 25.0 27.5 Ni .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. 1.0 Max. 1.0 Max. Cu .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. Mn 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. Mo .50 Max. .50 Max. .50 Max. .50 Max. 0.75 1.25 0.75 1.25 .50 Max. .50 Max. Nb .40 .60 --------.40 .60 .40 .60 1.00 --- --- 0.75 1.50 .05 .20 Covered by MPIF Standard 35 The early use of these grades was limited by the amount of carbon and nitrogen in the alloys. With higher levels of carbon and nitrogen, the ductile to brittle transition can occur at low temperatures. However, with the advent of argon-oxygen-decarburization (AOD), lower values of nitrogen and carbon have been acheieved and the ductility of these grades has been greatly enhanced.9 The effect of carbon and nitrogen can furthur be reduced by the addition of niobium which combines with the interstitial elements to prevent sensitization. Niobium is also a ferrite stabilizer which helps to prevent the formation of martensite in the alloys. In general, the oxidation resistance and mechancial properties (Table II) increase as the chromium level increases. The addition of other alloying elements to the base compositions can enhance certain properties. For example, in the case of 434L, when molybdenum is added, the resistance of the alloy to corrosion by road salt is increased. Niobium is added to several stainless steel grades to prevent the formation of chromium carbides which leads to intergranular corrosion (409L,436 and 439). This is particularly important when welding ferritic stainless steels, since the formation of chromium carbides is rapid and difficult to avoid. Sulfur can be added to enhance the machinability of ferritic stainless steels. In AISI 416L, sulfur is prealloyed prior to atomization, and the element combines with manganese during solidification to form managnese sulfides that assist in machining. This technique has been used in the PM grade of 303L for many years. Table II: Mechanical Properties of PM Ferritic Stainless Steels Impact AISI 409L 410L 416L 430L 434L 436 439 441 446 446 UNS S40940 S41000 S41603 S43000 S43400 S43600 S43035 S44100 S44600 S44626 ft.lbs.f 107 164 110 121 140 42 37 9 67 46 (J) 143 220 147 162 188 56 50 12 90 62 Green Sintered Density Density (g/cm3) (g/cm3) 6.56 7.08 6.66 7.25 6.52 7.16 6.59 7.15 6.52 7.11 6.40 6.81 6.32 6.81 6.29 6.38 6.25 6.96 6.23 6.99 TRS (ksi) 147 177 128 193 141 122 109 75 154 127 (MPa) 1011 1218 881 1328 970 839 750 516 1060 874 Apparent Hardness (HRB) 63 64 56 60 61 59 56 32 67 75 UTS (ksi) 56 57 51 52 57 46 48 29 55 62 (MPa) 385 392 351 358 392 316 330 200 378 427 0.20% OFFSET Elongation (ksi) 35 33 29 31 36 33 33 23 40 50 (MPa) 241 227 200 213 248 227 227 158 275 344 (%) 15.4 17.0 16.3 14.8 13.7 7.7 11.6 3.5 12.0 11.6 Superferritics have been developed for increased oxidation or scaling resistance. In general, the higher the chromium content the higher the oxidation rsistance. Additions of molybdenum and niobium can enhance oxidation resistance even further. Figure 2 shows that the oxidation resistance of S44626 (containing molybdenum) and S44100 (containing 1 w/o niobium) approach that of high chromium-nickel grades such as 310L and Hasteloy X (a superalloy). 20 Hastelloy X Super Ferritic 310L 441 409Cb % of Initial Weight 15 10 5 0 800 850 900 950 1000 1050 1100 1150 1200 o Temperature ( C) Figure 2. Weight gain (in air) as a function of temperature for selected oxidation resistant alloys. Austenitic Stainless Steels The AISI 300 austenitic series stainless steels contain nickel and chromium and have excellent corrosion resistance in diverse environments. The properties of austenite are generally described as nonmagnetic, with a relatively low yield strength, high ductility and excellent impact toughness. Austenitic stainless steels behave in a manner similar to that of low carbon steels but with enhanced high temperature strength and oxidation resistance. Depending on chemical composition, these stainless steels can resist scaling up to 1095 oC (2000 oF). Conversely, austenitic stainless steels can be used in low temperature applications where their high toughness levels are compatible with cryogenic applications. Based on Table III, there exists a wide range of 300 series stainless steels suitable for a variety of applications. This table also includes stainless steel grades commonly used by the PM industry and detailed in MPIF Standard 35, namely 303L, 304L and 316L. With the increased use of PM stainless parts an exploration of other grades listed in Table III would appear to be timely. Table III: Composition of PM Austenitic Stainless Steels (w/o) 1 AISI UNS 302B S30215 303L1 S30300 304L1 S30403 304Cu S30430 309Cb S30940 310S S31008 316L1 S31603 316Cb S31640 317L S31703 321L S32100 904L N08904 C 0.03 Max. 0.03 Max. 0.03 Max. 0.12 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.03 Max. 0.02 Max. S .030 Max. .150 .300 .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. .030 Max. Si 2.0 3.0 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.5 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. 1.0 Max. Cr 17.0 19.0 17.0 19.0 17.0 19.0 17.0 19.0 22.0 24.0 24.0 26.0 16.0 18.0 16.0 18.0 18.0 20.0 17.0 19.0 19.0 23.0 Ni 8.0 10.0 8.0 10.0 8.0 10.0 8.0 10.0 12.0 16.0 19.0 22.0 10.0 14.0 10.0 14.0 11.0 15.0 9.0 12.0 23.0 28.0 Cu .50 Max. .50 Max. .50 Max. 3.0 4.0 .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. 1.0 2.0 Mo .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. .50 Max. 2.00 3.00 2.00 3.00 3.00 4.00 .50 Max. 4.0 5.0 Nb --------.40 .60 ----.40 .60 --.40 .60 --- Covered by MPIF Standard 35 There is a growing need to weld PM austenitic stainless steel parts to other structures. In doing so the normal grades of stainless steel (304L and 316L) are susceptible to sensitization, particularly in areas adjacent to the weld. Sensitization is the process by which chromium combines with carbon to form chromium carbides. The chromium is removed from areas close to the grain boundaries and leaves these areas depleted of chromium, with attendant susceptibility to intergranular corrosion. The formation of chromium carbides is enhanced by temperature and generally occurs in austenitic stainless steels at temperatures between 480 oC and 815 oC (900 oF and 1500 oF). The cooling rate resulting from the welding process is generally slow which increases the likelihood of chromium carbide formation. Increased carbon levels due to insufficient lubricant burn-off can also increase the chance of sensitization. In order to avoid postweld heat-treatment, stabilized grades of austenitic stainless steels have been developed. In order to prevent the chromium from forming carbides, strong carbide-forming elements have been added to the austenitic grades of stainless steel. In AISI grades 309Cb, 316Cb and 321L, titanium and niobium were added for this reason. In PM products, the use of niobium is preferred because water atomization oxidizes the titanium. Table IV lists the mechanical properties of these niobium-stabilized austenitic PM grades. In general, due to the addition of niobium and the formation of carbides, the ductility and impact toughness of these grades are slightly lower than those of the non-stabilized grades. However, in general, this decline in mechanical properties is small, and can be compensated for by an increase in the level of other elements (such as nickel and chromium). Due to the formation of the carbides, the creep resistance of these grades of stainless steel is improved. Table IV: Mechanical Properties of PM Austenitic Stainless Steels Impact AISI 302B 303L 304L 304Cu 309Cb 310S 316L 316Cb 317L 321L 904L UNS S30215 S30300 S30403 S30430 S30940 S31008 S31603 S31640 S31703 S32100 N08904 ft.lbs.f 70 63 60 64 25 38 77 73 66 53 44 (J) 94 84 80 86 34 51 103 98 88 71 59 Green Sintered Density Density (g/cm3) 6.44 6.60 6.57 6.73 6.45 6.42 6.74 6.56 6.72 6.66 6.52 (g/cm3) 6.72 6.97 6.90 6.86 6.76 6.80 7.13 6.88 7.01 6.90 6.80 TRS (ksi) 210 205 180 129 119 139 138 137 162 128 130 (MPa) 1445 1410 1238 888 819 956 949 943 1115 881 894 Apparent Hardness (HRB) 56 48 55 28 62 63 56 51 61 57 56 UTS (ksi) 59 55 61 55 63 61 61 51 70 54 55 (MPa) 406 378 420 378 433 420 420 351 482 372 378 0.20% OFFSET Elongation (ksi) 32 28 35 30 41 41 32 29 42 32 33 (MPa) 220 193 241 206 282 282 220 200 289 220 227 (%) 24.8 25.4 22.4 20.0 14.9 14.5 27.0 15.0 22.0 16.2 14.8 Other alloying elements, such as molybdenum, can be added to the austenitic stainless steels to improve corrosion resistance. Molybdenum, when added at levels between 2 w/o and 4 w/o improves resistance to oxidation, pitting and crevice corrosion. The addition of molybdenum also tends to improve both room and high temperature properties such as tensile strength and creep. The mechanical properties of AISI 317L are cited in Table IV and the corrosion resistance is illustrated in Figure 3. Currently PM fabricators sinter austenitic grades in a hydrogen/nitrogen atmosphere to increase strength (MPIF Standard 35: grades SS-304N and SS-316N). In so doing, significant chromium nitride formation occurs, which is detrimental to the overall corrosion resistance of the alloy. The addition of molybdenum is beneficial if both corrosion resistance and strength are required. (a) (b) (c) Figure 3. Representative appearance of salt spray specimens: (a.) 304L, (b.) 316L, (c.) 317L. More highly alloyed 300 series stainless steels are available that are designed to resist oxidation at high temperatures while maintaining a high degree of tensile strength and creep resistance. These alloys rely on the formation of the chromium oxide film for protection from corrosion, but the additional nickel and silicon in these alloys helps to form a more ductile scale, which increases its adherence to the base metal. The adherent scale is particularly important when service conditions involve cyclic temperatures. The properties of several of these PM grades (302B, 304L and 310L) are listed in Table IV and the relative oxidation resistance of these grades is shown in Figure 4. 1.4 304L 302B 310L 1.2 % of Initial Weight 1 0.8 0.6 0.4 0.2 0 600 700 800 900 1000 1100 o Temperature ( C) Figure 4. Oxidation of 300 series stainless steels. 1200 As with the other categories of stainless steels, there exists “super austenitics” where increased levels of nickel, copper, and molybdenum provide superior or specialized corrosion resistance. However, for the PM grades of these alloys the increased alloy content has a negative impact on powder compressibility and therefore on overall density. In consequence, care has to be taken to ensure that the increased corrosion resistance and enhanced mechanical properties gained by the increase in alloy content are not offset by a reduction in achievable density. Type 904 stainless steel is considered a “super austenitic” stainless steel. Martensitic Stainless Steels Martensitic steels in the 400 series are similar to the ferritic stainless steels in that they contain chromium in the range of 11 w/o to 18 w/o but also contain other elements such as nickel Table V. The martensitic stainless steels are magnetic and are generally used in applications where hardness and/or wear resistance is required. When heat-treated they can achieve high strength and when tempered, they can exhibit some ductility. Essentially, these steels achieve mechanical properties comparable with those of a heattreatable low alloy steel but with enhanced corrosion resistance, although their corrosion resistance is the lowest of any of the stainless steel categories. MPIF standard 35 recognizes SS-410-90HT as a martensitic alloy. For this grade, the sintering atmosphere contains a high level of nitrogen, and the alloys form high temperature austenite, which transforms to martensite on cooling. Table V: Composition of PM Martensitic Stainless Steels (w/o) C S Si Cr Ni Cu Mo Nb 0.03 .030 1.0 12.0 1.25 .50 .50 S41400 --414M Max. Max. Max. 15.0 2.50 Max. Max. 0.03 .030 1.0 12.0 4.0 1.5 1.5 S41426 --414M Max. Max. Max. 15.0 7.0 2.0 2.0 0.03 .030 1.0 11.5 3.5 .50 .5 S41500 --415M Max. Max. Max. 14.0 5.5 Max. 1.0 .15 .030 1.0 12.0 .50 .50 .50 S42000 --420M .30 Max. Max. 14.0 Max. Max. Max. 0.75 .030 1.0 16.0 .50 .50 .75 S44003 --440BM 0.95 Max. Max. 18.0 Max. Max. Max. 0.95 .030 1.0 16.0 .50 .50 .75 S44004 --440CM 1.20 Max. Max. 18.0 Max. Max. Max. 0.15 .030 1.5 11.5 1.0 3.0 .50 410LCu J91151 --Max. Max. Max. 14.0 Max. 5.0 Max. M Designates material made from a mix of a base powder and additives such as nickel, graphite, copper and molybdenum. AISI UNS Other AISI martensitic grades of stainless steel, such as 420,440A, 440B and 440C, can be processed by adding graphite to ferritic grades of stainless steels such as 410L and 430L. Table VI gives the properties of 420L, 440B and 440C made by this approach. The level of carbon added to the alloy dictates the mechanical properties of the martensitic stainless steel. The higher the carbon content, the larger the extent of chromium carbide formation, and the higher the strength and apparent hardness of the alloy. Table VI: Mechanical Properties of PM Martensitic Stainless Steels Impact AISI UNS ft.lbs.f (J) 410LCu 414 414 415M J91151 S41400 S41426 S41500 13 50 21 26 17 67 28 35 415PA 420 440B 440B HT 440C 440C HT S41500 S42000 S44003 S44003 S44004 S44004 11 24 20 3 13 3 15 32 27 4 17 4 Green Sintered Density Density (g/cm3) (g/cm3) 6.43 6.84 6.55 6.95 6.62 7.00 6.69 7.03 6.17 6.68 6.58 6.58 5.56 5.56 6.52 6.86 6.82 6.76 6.91 6.90 (ksi) (MPa) Apparent Hardness (HRB) (ksi) (MPa) (%) 249 223 209 253 1713 1534 1438 1741 95 90 89 96 116 98 100 108 798 674 688 743 89 75 76 80 612 516 523 550 2.7 3.7 2.5 2.9 178 172 134 128 169 155 1225 1183 922 881 1163 1066 83 67 93 29/c 94 37/c 98 57 67 74 79 65 674 392 461 509 544 447 73 37 42 70 61 62 502 255 289 482 420 427 2.3 2.2 2.0 0.6 2.2 0.6 TRS 0.20% OFFSET Elongation UTS (ksi) (MPa) AISI 415M = Powder Mix, AISIPA = Prealloy. A major drawback to carbon-containing martensitic stainless steels is their relatively poor corrosion resistance and ductility. Low carbon-containing martensitic stainless steels can be produced by adding nickel, molybdenum and copper to form martensitic stainless steels with improved toughness and corrosion resistance. Table V cites the composition of several martensitic stainless steels made by adding nickel, copper and molybdenum. Nickel and copper are austenite formers, while molybdenum improves properties via solid solution strengthening; this element is responsible for improving high temperature properties. While the apparent hardness of these alloys is slightly inferior to that of heattreated carbon-containing martensitic stainless steels, other mechanical properties such as tensile strength, toughness and ductility are superior. These grades of stainless steel also exhibit superior corrosion resistance which reflects the absence of carbide formation and hence sensitization, as shown in Figure 5. Figure 5. (a) (b) (d) (e) (c) Representative appearance of salt spray specimens: (a.) 440B, (b.) 440C, (c.) 410Lcu, (d.) super-martensitic admixed, (e.) super-martensitic prealloyed As with other categories of stainless steels, super-martensitic stainless steels can be formed by adding high levels of nickel, copper and molybdenum. For PM alloys the prealloyed materials are usually low in compressibility but can exhibit superior corrosion resistance due to their high alloy content. Precipitation-Hardening Stainless Steels Precipitation hardening stainless steels are not defined by their microstructure, but rather by strengthening mechanism. These grades may have austenitic, semi-austenitic or martensitic microstructures and can be hardened by aging at moderately elevated temperatures, 480 oC to 620 oC (900 oF to 1150 oF). The strengthening effect is due to the formation of intermetallic precipitates from elements such as copper or aluminum. These alloys generally have high strength and high apparent hardness while exhibiting superior corrosion resistance compared with martensitic stainless steels. Heat treatments can be used to vary the properties of the alloys and involve short times (1 h) at temperatures ranging from 480 oC to 620 oC (900 oF to 1150 oF). The aging treatment can take place in either air or in nitrogen, depending on the surface appearance required. However, these alloys should not be subjected to welding or in service temperatures above the heat-treatment temperature because strength can be lost due to overaging. The AISI designation for these alloys is the 600 series of stainless steels, but most are more commonly known by their alloy name, for example, 15-5PH, 17-4PH and17-7PH. The aluminum-containing precipitation hardening alloys are difficult to process by the PM route due to their high affinity for nitride formation and the difficulty in reducing aluminum oxide during sintering. Table VII and VIII give the chemical compositions and mechanical properties of several precipitation hardening alloys produced by conventional PM techniques. 17-4PH is a martensitic grade in which ductility and toughness are generally higher than in the carbon-containing martenstitc grades. The mechanical properties of 17-4PH can be increased by 15% by aging at 538 oC (1000 oF) for 1 h. Applications for this alloy exist in the food, chemical and aerospace industries. Table VII: Composition of PM Precipitation Hardening Stainless Steels (w/o) AISI UNS 17-4PH S17400 410LCu J91151 633M S35000 C 0.03 Max. .15 .30 0.07 0.11 S .030 Max. .030 Max. .030 Max. Si 1.0 Max. 1.0 Max. 1.0 Max. Cr 15.0 17.0 12.0 14.0 16.0 17.0 Ni 3.0 5.0 .50 Max. 4.0 5.0 Cu 3.0 5.0 .50 Max. .50 Max. Mo .50 Max. .50 Max. 2.50 3.25 Nb .15 .45 ----- 633 is a semi-austenitic precipitation hardening stainless steel offering improved corrosion resistance compared with martensitic precipitation hardening alloys. These alloys are used for parts requiring high strength at moderately elevated temperatures. Depending on the aging treatment, the ductility and toughness of this alloy can approach those of the austenitic stainless steels. The microstructure of the alloy is a mixture of austenite, martensite and small quantities of ferrite. Table VIII: Mechanical Properties of PM Precipitation Hardening Stainless Steels Impact AISI 17-4PH 17-4PH Aged 410LCu 410LCu Aged 633 633 AGED UNS S17400 S17400 J91151 J91151 S35000 S35000 ft.lbs.f 10 6 21 22 65 67 (J) 13 8 28 29 87 90 Green Sintered Density Density (g/cm3) (g/cm3) 6.39 6.66 6.39 6.66 6.50 6.98 6.50 6.98 6.57 7.23 6.57 7.24 TRS (ksi) 220 273 219 245 218 265 (MPa) 1514 1878 1507 1686 1500 1823 Apparent Hardness (HRB) 81 93 88 94 94 96 0.20% OFFSET Elongation UTS (ksi) 92 119 99 113 111 113 (MPa) 633 819 681 777 764 777 (ksi) 60 100 76 94 63 85 (MPa) 413 688 523 647 433 585 (%) 2.8 1.7 3 3.5 4.5 8.7 Usage of the precipitation-hardening alloys is generally limited by the high cost of the alloying elements. Recently, a lower cost PM precipitation hardening alloy has been introduced based on UNS J91151 (a cast grade). 10 This alloy has only 13 w/o chromium and utilizes the precipitation of copper to provide a low cost-high strength alloy with moderate corrosion resistance. Table VIII shows that the mechanical properties approach those of 17-4PH, while still maintaining a level of corrosion resistance that is better than that of the high carbon martensitic grades. Duplex Stainless Steels Table IX: Composition of PM Duplex/Dual Phase Stainless Steels (w/o) AISI UNS Duplex- 329M S32900 Duplex- 2205 S32205 Duracor/3Cr12 S41003 C 0.08 Max. 0.03 Max. .15 .30 S .030 Max. .030 Max. .030 Max. Si 1.0 Max. 1.0 Max. 1.0 Max. Cr 23.0 28.0 21.0 23.0 10.5 12.5 Ni 2.5 5.0 4.5 6.5 1.50 Max. Cu .50 Max. 3.0 5.0 .50 Max. Mo 1.00 2.00 2.50 3.50 .50 Max. Nb ------- Technically, duplex steels are stainless steels that contain two phases.3 Duplex stainless steels are more-accurately defined as alloys containing a mixed microstructure of ferrite and austenite. New alloys being developed that contain mixtures of ferrite and martensite are generally termed dual-phase.11 Compositions of PM Duplex/Dual Phase stainless steels are listed in Table IX. A major advantage of these stainless steel grades is that each phase imparts improved properties to the alloy. (a) (b) Figure 6. Representative microstructures of (a) duplex stainless steel: (b) dual-phase stainless steel. Duplex stainless steels are ferritic stainless steels (Figure 6(a)) containing chromium and molybdenum to which austenite formers (primarily nickel) have been added to ensure that austenite is present at room temperature. Duplex stainless steels have several advantages over the austenitic grades including high strength, acceptable toughness, and superior corrosion resistance, particularly to chloride stress corrosion cracking. The mechanical properties of a duplex stainless steel (2205) are shown in Table X. Table X: Mechanical Properties of PM Duplex/Dual Phase Stainless Steels Green Sintered Density Density Impact AISI UNS ft.lbs.f (J) Duplex- 329M Duplex- 2205 Duracor/3Cr12 S32900 S32205 S41003 46 82 49 62 110 66 3 (g/cm ) 6.27 6.48 6.62 3 (g/cm ) 7.07 7.20 7.34 (ksi) (MPa) Apparent Hardness (HRB) 179 202 278 1232 1390 1913 50 81 88 TRS 0.20% OFFSET Elongation UTS (ksi) (MPa) (ksi) (MPa) (%) 76 84 107 523 578 736 67 62 82 461 427 564 7.7 10.8 3.1 Dual phase stainless steels vary in composition but are generally non-austenitic (Figure 6(b)) and magnetic, containing 11 w/o Cr. The chemistry of the alloy is balanced by ferrite formers and austenite formers. The austenite transforms to martensite upon cooling resulting in a mixture of ferrite and martensite. Because of the low cost of the alloy it is used as a replacement for plain carbon steels where increased corrosion resistance is needed. The martensite in the alloy allows the material to be used in applications requiring strength and wear resistance. The properties of a PM version of this stainless steel (S41003) are cited in Table X. FATIGUE BEHAVIOR OF PM STAİNLESS STEELS Fatigue tests were performed on some of the high strength PM alloys developed. The results of these tests,in terms of the 90% survival limit, are compared with those of other stainless steel fatigue data by Shah et al. 12 in Figure 7. The latter study study compared the fatigue strength of various stainless steels as a function of tensile strength. Tensile Strength (MPa) 100 200 300 400 500 600 700 50 420 Dual Phase Fatigue Endurance Limit (KSI) 45 800 410LCu Aged 900 345 295 410LCu Martensitic 40 409LNi 35 409LNi-HC 410HT DUPLEX 245 17-4PH 409LE 30 195 430L 25 430N2 434L 20 145 434N 410L 15 95 10 Fatique Endurance Limit MPa) 0 45 5 0 40 50 60 70 80 90 100 110 120 130 -5 140 Tensile Strength (KSI) Figure 7. Fatigue endurance limit (90% survival) as a function of tensile strength. The excellent fatigue response of these alloys is attributed to their high tensile strength. In general, fatigue crack propagation rates in PM steels are high and the fatigue limit is dictated by crack initiation rather than by crack propagation. Resistance to crack initiation increases as the tensile strength increases. All the PM alloys included in Figure 7 have high tensile strengths, and therefore high fatigue endurance limits. It appears that the addition of copper, nickel, and molybdenum, results in harder martensite, which has a positive effect on fatigue strength. CONCLUSIONS • Many AISI grades of stainless steel can be made via conventional water atomization and press and sinter PM. These grades are not currently covered by MPIF Standard 35, but provide a range of properties and corrosion resistance that can lead to increased opportunities for PM parts producers. • These PM grades can be made as prealloys, or admixed nickel, copper and molybdenum powders can be added to the base stainless steel. • In ferritic grades, higher levels of chromium, niobium and sulfur can lead to improved mechanical properties, corrosion resistance and machinability. • The addition of carbon to low chromium PM alloys results in martensitic stainless steels with increased strength and apparent hardness. Additions of nickel, copper and molybdenum produce low carbon martensitic stainless steels with increased toughness and corrosion resistance. • Niobium, when added to PM austenitic stainless steels, improves weldability. Increases in the molybdenum content of austenitic stainless steels can increase strength and enhance corrosion resistance. Increases in chromium, nickel and silicon levels enhance oxidation resistance. • Several precipitation hardening alloys with a range of mechanical properties, microstructure and attendant corrosion resistance can be produced by conventional PM processes. • Mixed microstructure stainless steels exhibiting excellent mechanical properties and corrosion resistance can be produced by conventional PM processes. • Fatigue response of the high strength PM alloys is a function of their tensile strength. REFERENCES Materials Standards for PM Structural Parts, 2007, Metal Powder Industries Federation, Princeton, NJ. 2. J.R. Davis, Alloying: Understanding the Basics, 2001, ASM International, Materials Park OH. 3. J. Beddoes and J. G. Parr, Introduction to Stainless Steels, 1999, ASM International, Materials Park, OH. 4. J.D. Redmond, Metals and Alloys in the Unified Numbering System, 10th Edition, 2004, Joint Publication of the Society of Automotive Engineers, Inc. and the American Society for Testing and Materials. 5. J.E. Bringas, Stainless Steel Data Book, 1992, CASTI Publishing Inc., Edmonton, Alberta, Canada. 6. H. Cobb, Steel Products Manual- Stainless Steels, 1999, Iron and Steel Society, Warrendale, PA. 7. T.R. Albee, P. DePoutiloff, G. Ramsey and G.E. Regan, “Enhanced Powder Metal Materials for Exhaust System Applications,” SAE Paper No. 970281, SAE International, Warrendale, PA, USA.1997. 8. T. Hubbard, K. Couchman and C. Lall, “Performance of Stainless Steel PM Materials in elevated Temperature Applications,” SAE Paper No. 970422, SAE International, Warrendale, PA, USA.1997. 9. R.J. Causton, T. Cimino-Corey, and C.T. Schade “Improved Stainless Steel Process Routes,” Advances in Powder Metallurgy and Particulate Materials – 2003, compiled by R. Lawcock and M. Wright, Metal Powder Industries Federation, Princeton, NJ, 2003, part 2 pp.1-13. 10. A. Lawley, R.Doherty, P. Stears and C.T. Schade, “Precipitation Hardening Stainless Steels,” Advances in Powder Metallurgy and Particulate Materials – 2006, compiled 1. by W. R. Gasbarre and J.W. von Arx, Metal Powder Industries Federation, Princeton, NJ, 2006, part 7 pp.141-153. 11. A. Lawley, E. Wagner, and C.T. Schade, “Development of a High-Strength-DualPhase P/M Stainless Steel,” Advances in Powder Metallurgy and Particulate Materials – 2005, compiled by C. Ruas and T. Tomlin, Metal Powder Industries Federation, Princeton, NJ, 2005, part 7 pp.78-89. 12. S.O. Shah, J.R. McMillen, P.K. Samal and L.F. Pease, “Mechanical Properties of High Temperature Sintered P/M 409LE and 409LNi Stainless Steels Utilized in the Manufacturing of Exhaust Flanges and Oxygen Sensor Bosses,” SAE Paper No. 2003-01-0451, SAE International, Warrendale, PA 15096, USA, 2003.
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