US3772005A - Corrosion resistant ultra high strength stainless steel - Google Patents

Corrosion resistant ultra high strength stainless steel Download PDF

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Publication number
US3772005A
US3772005A US00080341A US3772005DA US3772005A US 3772005 A US3772005 A US 3772005A US 00080341 A US00080341 A US 00080341A US 3772005D A US3772005D A US 3772005DA US 3772005 A US3772005 A US 3772005A
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percent
stainless steel
accordance
molybdenum
chromium
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US00080341A
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J Debarbadillo
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

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  • the corrosion resistant nature of the stainless steels is attributable mainly to an ability to assume what is commonly referred to as the passive state.
  • This is an inherent phenomenon due principally to composition and involves the formation of a thin, continuous, rather tenacious film (mostly chromium oxides) about the surface, the film acting as a barrier to penetration by corrodents.
  • the passive film is all too frequently ruptured. This usually occurs at localized areas and the ruptured sites tend to form crevices or pits, conditions most conducive to attack.
  • flaws or imperfections may be (a) unintentionally induced, e.g., nicks, scratches, dents and the like, or (b) formed as the result of natural processes, e.g., through the adherence of barnacles or other marine organisms, or (c) inescapably brought about, stranded cable, valve seats, etc., being illustrative.
  • the chlorides are notorious for their ability to materially assist in the breakdown of passive film.
  • ferritic or martensitic stainless steels might offer enhanced resistance to seawater attack, they often are not only difficultly workable but in the production of various products they generally lack sufficient ductility at the given high strength level to be formed or fabricated into certain desired forms, e.g., twisting wire into stranded cable.
  • a further object of the invention is to provide strong, corrosion resistant stranded cable and other articles such as fasteners, reinforcing members, springs, cold forgings, etc.
  • FIG. 1 is a graphical'representation correlating the herein described Ferrite Index and Austenite Index
  • FIG. 2 is also a graphical representation correlating the herein described Ferrite Index and Austenite Sta bility Index.
  • the subject invention contemplates stainless steels containing (in weight per cent) from about 14 to 27.65 percent chromium, from 3 to 12 percent molybdenum, at least one of, and most advantageously both, nickel and cobalt in amounts up to 17.5 percent nickel and up to about 25.5 percent cobalt, carbon in a small but effective amount, e.g., 0.01 percent, up to 0.3 percent, up to 0.3 percent nitrogen, the sum of the carbon plus nitrogen not exceeding 0.3 percent, up to 2 percent silicon, up to 5 percent manganese with the balance being essentially iron, the steels being characterized in the annealed condition by a predominantly austenitic microstructure, the austenite, however, being of such instability that a relatively high rate of work hardening is achieved through progressive strain-induced transformation of at least a portion of the austenite to martensite.
  • the Corrosion Indicator comprised of chromium plus twice the molybdenum be greater than 28.5 and that the percentages of the alloying constituents be otherwise controlled so as to give correlated Ferrite Index, Austenite Index and Austenite Stability Index values with regard to the diagrams depicted in FIGS. 1 and 2.
  • the Ferrite Index is given by the relationship %Cr %Mo 1.5 (%Si) about 22 to 30.65
  • Corrosion Indicator While it is difiicult to assess the individual effects of each of the essential constituents owing to their interdependency, it is decidedly beneficial in consistently achieving a high level of corrosion resistance that the Corrosion Indicator be at least 30 or 31. While this value can be lowered to near 28.5, resistance to aggressive corrosive environments is reduced.
  • the sum of the respective percentages of chromium plus molybdenum can be as high as 30.65 percent, it is much preferred that this total sum not exceed about 27.5 or 28 percent.
  • the primary reason for this stems from the need to minimize the occurrence of delta ferrite, a phase which promotes hot working difficulties (e.g., decomposition of ferrite to brittle intermetallic compounds) and which, among other things, tends to result in a lower rate of work hardening by reducing the volume of austenite available for transformation to martensite. This can result in lower strength. Up to 5 or 6 percent delta ferrite can be tolerated but it is advantageous that it not exceed 2 or 3 percent by volume.
  • compositions within area DEF are deemed outstanding, particularly with a combined chromium plus molybdenum content of at least 24 percent since, in addition to being devoid of detrimental amounts of delta ferrite, they exhibit a high rate of work hardening at room temperature. This precludes or greatly minimizes any need for working at below room temperature, say, down to l00F., as would be required for compositions falling between line F H and line CB of FIG. 1, the temperature decreasing as CB is approached. Alloys within the area DEI-IG not only give excellent results but for the most part are the least costly.
  • the high tensile strengths characteristic of the steels is brought about by a combination of work hardening of the austenite accompanied by strain-induced transformation of at least a portion of the austenite to martensite.
  • the steels must be austenitic as annealed. But, even should a steel be completely austenitic upon cooling from annealing temperature, if it is too stable, the desired level of strength will not be achieved.
  • the proper balance is brought about through correlation of the above described Indices, particularly the Ferrite and Austenite Stability lndices as reflected by FIG. 2.
  • 00- balt plays a significant role in that while it promotes the formation of austenite during annealing, it only mildly depresses the M temperature. If it were to depress the M, temperature to the degree of, say, nickel or chromium, then the alloy might be too stable to be work hardened such that a strain-induced transformation could readily by achieved. At best, unnecessary low work hardening temperatures and attendant problems would be likely.
  • a cobalt range of from 15 to 25 percent is distinctly beneficial.
  • alloys below and to the left of line JK work harden too rapidly to be of commercial interest, whereas compositions above ML are too stable. From RS to ML work hardening should be carried out at below about room temperature. Steels exhibiting increasing strength are obtained with compositions away from RS and toward .IK. Within the area defined by PQRS, excellent strengths can be achieved and wire in the fully worked condition exhibits sufficient ductility for the Wrap" and Kink tests described herein. As the area contiguous to .II( is approached from PQ, the rate of work hardening increases and some difficulty may be experienced in respect of the higher percentages of reduction accomplished through working.
  • silicon and manganese contents not exceed about 1 and 2 percent, respectively.
  • Silicon is a strong ferrite stabilizer and as the amount thereof is increased where is required either the presence of higher nickel and/or cobalt contents (thus adding to cost) or the use of lesser amounts of chromium and/or molybdenum, (thus in a given case likely detracting from corrosion resistance).
  • Manganese tends to promote the formation of sigma and this can be harmful.
  • Moderate to severe crevice denotes a weight loss above
  • Table 1 To conduct corrosion tests a number of compositions l0 an p I0 100 milligrams, there being p g but within the invention, Table 1, were prepared using a a greater degree of discoloration plus grooving. To be vacuum induction furnace (except Alloy 6 which was within the present invention, the weight loss should not melted in argon and poured in air). The materials embe greater than about 20 milligrams for the test deployed were of high purity, e.g., the electrolytic forms scribed.
  • the weight loss should not exof iron, nickel and cobalt being used together with moceed about 10 milligrams.
  • Specimens of the A inch plates were annealed at 2200F. for one hour and water quenched, surface subjected to intermediate thermal treatments (Table III).
  • the b inch bars were machined and first drawn to 0.103 inch or 0.062 inch diameter on a draw bench using copper plate and soap lubricant, the copper plate being removed and the specimen annealed where necessary.
  • the wires were drawn down to final desired diameter using diamond dies and oil lubricant. Three specimens of each composition were drawn, usually a reduction in area of 90, 98 and 99 percent being performed.
  • the Kink test comprised making a loop of wire and drawing tight by hand such that virtually no light appeared through the kink.
  • the Wrap test consisted of forming successive contiguous turns of the wire about its own 15 boosted by thermal treatment as will be seen from a perusal of Table 11]. As to Alloys 20 and 21, these failed to pass both the Kink and Wrap tests and thus their use for stranded cable would be unsuitable although they would be useful for fasteners, particularly coldthreaded fasteners, and other cold worked products such as sheet, reinforcing bar, etc.
  • Heat Treatment A comprised reducing the rod to a 51 mil diameter and then heat treating at 800F. for 15 minutes and thereafter drawing to desired diameter.
  • Heat Treatment 8 a temperature of 1000F. was used whereas in Heat Treatment C" a temperature of 1200F. was employed.
  • Heat Treatment B was, in effect, an aging treatment with Heat Treatment C diameter. being an austenitic reversion treatment, i.e., the mar- TABLE 11 Cr Mo Co Ni C Si Mn Red LTS Kink Wrap Alloy No ⁇ percentl (percent!
  • Thermal treatments A and C readily reflect that substantial increase in strength can be obtained.
  • the data further reflect that an aging treatment, Heat Treatment B, should be avoided because of the tendency toward severe embrittlement.
  • the temperature should be from about 500F. or 700F. but should not exceed about 900F. or possibly 950F., unless the structure of the steel is first transformed back to austenite by reversion as illustrated by Treatment C. If an austenite reversion treatment is used, it should be followed by a significant amount of subsequent cold reduction to minimize possible loss in corrosion resistance.
  • the period for intermediate thermal treatment can be extremely short, e.g., 1 minute.
  • the work hardened product should contain at least about 10 percent to not more than about 60 percent martensite.
  • steels having the following compositions have been found to be particularly advantageous from the overall viewpoint of corrosion resistance, strength and ductility: from about 16 to 22 percent chromium, about 4 to 8.5 percent molybdenum, the Corrosion Indicator being at least 30, from 2.5 to 6.5 percent nickel about to 25 percent cobalt, about 0.01 to 0.15 percent carbon, up to 0.1 percent nitrogen, the sum of the carbon plus nitrogen not exceeding about 0.2 percent, up to .75 percent silicon, up to about 2 percent manganese and the balance essentially iron.
  • compositional range which gives outstanding results has from 17 to 20 percent chromium, 5.5 to 7.5 percent molybdenum, the Corrosion Indicator being about 30.5 or more, about 3 to 5 percent nickel, about 17 percent to 23 percent cobalt, 0.01 to 0.08 percent carbon, up to 0.04 percent nitrogen, up to 0.75 percent silicon, up to l or 2 percent manganese, with iron being essentially the balance.
  • the constituents must be formulated such that a correlation of the Ferrite, Austenite and Austenite Stability Indices is represented by a point within the areas ABCA and JKLMJ, particularly DEF and PQSR, of FIGS. 1 and 2, respectively.
  • balance or balance essentially used in referring to the iron content does not exclude the presence of other elements commonly present as incidental constituents, e.g., deoxidizing and cleansing elements (zirconium, boron, calcium, magnesium, and titanium) and impurities ordinarily associated therewith in amounts which do not affect the basic characteristics of the alloy.
  • deoxidizing and cleansing elements zirconium, boron, calcium, magnesium, and titanium
  • impurities ordinarily associated therewith in amounts which do not affect the basic characteristics of the alloy.
  • a small but effective amount e.g., 0.25 percent, up to 2 percent columbium can be employed, particularly in conjunction with carbon contents not exceeding 0.06 or 0.08 percent to improve corrosion resistance.
  • Tantalum can be used in lieu of columbium, two parts of tantalum for one part of columbium.
  • Columbium particularly is a rather strong ferrite promoter and if used, should be assigned a value of unity in computing the Ferrite Index. Up to 5 percent copper can be present. Constituents such as sulfur, phosphorus, hydrogen and oxygen should be maintained at low levels consistent with good commercial practice.
  • a stainless steel consisting essentially of from 14 to 27.65 percent chromium, about 3 to 12 percent molybdenum, up to 17.5 percent nickel, cobalt present in an amount up to about 25.5 percent, the sum of the chromium plus twice the molybdenum being greater than 28.5, carbon up to 0.3 percent, up to 0.3 percent nitrogen, the sum of the carbon plus nitrogen not exceeding 0.3 percent, up to 2 percent silicon, up to 5 percent manganese and the balance essentially iron, the Ferrite Index being correlated with the Austenite Index so as to represent a point within the area ABCA of FIG. 1 and with the Austenite Stability Index so as to represent a point within the area JKLMJ of FIG. 2 of the accompanying drawing.
  • a stainless steel in accordance with claim 1 containing at least 1 percent nickel and 15 percent cobalt.
  • a stainless steel in accordance with claim 2 containing from 0.01 to 0.08 percent carbon, the sum of the carbon plus nitrogen not exceeding 0.2 percent.
  • a stainless steel in accordance with claim 2 containing about 16 to 22 percent chromium, about 4 to 8.5 percent molybdenum, the chromium plus twice the molybdenum being at least about 30, about 2.5 to 6.5 percent nickel, about 15 to 25 percent cobalt, about 0.01 to 0.15 percent carbon, up to 0.0l percent nitrogen, the sum of the carbon plus nitrogen not exceeding 0.2 percent, up to about 0.75 percent silicon and up to about 2 percent manganese.
  • a stainless steel in accordance with claim 2 containing 17 to 20 percent chromium, 5.5 to 7.5 percent molybdenum, the sum of the chromium plus twice the molybdenum being at least 30.5, 3 to 5 percent nickel, 17 to 23 percent cobalt, 0.01 to 0.08 percent carbon, up to 0.04 percent nitrogen, up to 0.75 percent silicon and up to 2 percent manganese.
  • a stainless steel consisting essentially of from 14 to 27.65 percent chromium, about 3 to 12 percent molybdenum, being up to 17.5 percent nickel, cobalt present in an amount up to about 25.5 percent, the sum of the chromium plus twice the molybdenum being greater than 28.5, carbon up to 0.3 percent, up to 0.3 percent nitrogen, the sum of the carbon plus nitrogen not exceeding 0.3 percent, up to 2 percent silicon, up to 5 percent manganese, up to 2 percent columbium, up to 4 percent tantalum, the sum of the percentage of columbium plus one-half the percentage of tantalum being up to 2 percent, up to 5 percent copper, and the balance essentially iron, the Ferrite Index being correlated with the Austenite Index so as to represent a point within the area ABCA of FIG. 1 and with the Austenite Stability Index so as to represent a point within the area JKLMJ of FIG. 2 of the accompanying drawing.
  • a stainless steel in accordance with claim 19 containing at least 2 percent nickel, at least 15 percent cobalt, and in which the sum of the chromium plus twice the molybdenum is at least 30.
  • a stainless steel in accordance with claim 19 which contains at least 15 percent cobalt and a small but effective amount of columbium up to 2 percent to improve corrosion resistance.

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929520A (en) * 1971-12-23 1975-12-30 Lars Ivar Hellner Corrosion-resistant austenitic-ferritic stainless steel
US4007073A (en) * 1974-10-15 1977-02-08 Felix Lvovich Levin Method of producing articles having alternating magnetic and non-magnetic portions from continuous metal blanks
US4018132A (en) * 1974-06-18 1977-04-19 Tokai Cold Forming Co., Ltd. Connecting-rod bolt
DE2703756A1 (de) * 1976-02-02 1977-08-04 Avesta Jernverks Ab Austenitischer nichtrostender stahl mit hohem mo-gehalt
DE3510331C1 (de) * 1985-03-22 1985-12-05 Thyssen Edelstahlwerke AG, 4000 Düsseldorf Dental-Gusslegierung
US4588440A (en) * 1984-06-28 1986-05-13 Hydro Quebec Co containing austenitic stainless steel with high cavitation erosion resistance
US4626116A (en) * 1984-03-06 1986-12-02 Hitachi Metals, Ltd. Head for wire dot printer
US4751046A (en) * 1986-06-30 1988-06-14 Hydro Quebec Austenitic stainless steel with high cavitation erosion resistance
US4856323A (en) * 1987-04-06 1989-08-15 Mitsubishi Denki Kabushiki Kaisha Steering torque detecting device
US5514328A (en) * 1995-05-12 1996-05-07 Stoody Deloro Stellite, Inc. Cavitation erosion resistent steel
US20040016497A1 (en) * 1994-12-20 2004-01-29 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US20040156737A1 (en) * 2003-02-06 2004-08-12 Rakowski James M. Austenitic stainless steels including molybdenum
US7181847B2 (en) * 2000-10-24 2007-02-27 Boehler Edelstahl Gmbh & Co. Kg Process for manufacturing a cylindrical hollow body and hollow body made thereby
US20070221396A1 (en) * 2004-05-19 2007-09-27 Hiromu Izumida Composite Wire for Wire-Harness and Process for Producing the Same
DE102008005803A1 (de) * 2008-01-17 2009-07-23 Technische Universität Bergakademie Freiberg Bauteil aus höher kohlnstoffhaltigem austenitischem Stahlformguss, Verfahren zu deren Herstellung und deren Verwendung
US7985304B2 (en) 2007-04-19 2011-07-26 Ati Properties, Inc. Nickel-base alloys and articles made therefrom
WO2020105885A1 (ko) * 2018-11-19 2020-05-28 한국기계연구원 열간가공성 및 인장 특성이 우수한 보론 함유 스테인리스강 및 그 제조 방법

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1513157A (en) * 1974-10-28 1978-06-07 Langley Alloys Ltd Corrosion resistant steels
EP0009881B2 (en) * 1978-10-03 1987-07-08 Deloro Stellite Limited Cobalt-containing alloys
JPS5658954A (en) * 1979-10-22 1981-05-22 Japan Atom Energy Res Inst Solid solution hardening type iron alloy
CN115029644B (zh) * 2022-06-23 2023-04-11 西安必盛激光科技有限公司 提高扎管芯棒自润滑性和热强性的粉末及激光熔覆方法

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US2083524A (en) * 1931-11-27 1937-06-08 Payson Peter Corrosion resistant alloy
US2115733A (en) * 1935-06-25 1938-05-03 Rustless Iron & Steel Corp Alloy and manufactures
US2141016A (en) * 1936-11-19 1938-12-20 Payson Peter Alloy steel
US2159725A (en) * 1938-03-19 1939-05-23 Electro Metallurg Co Corrosion resistant steel
US2294803A (en) * 1942-02-18 1942-09-01 Rich Mfg Corp Valve
US2306662A (en) * 1934-01-20 1942-12-29 Rustless Iron & Steel Corp Alloy
US2398702A (en) * 1941-02-26 1946-04-16 Timken Roller Bearing Co Articles for use at high temperatures
US2801916A (en) * 1954-08-24 1957-08-06 Jessop William & Sons Ltd Ferrous alloys for high temperature use
US3152934A (en) * 1962-10-03 1964-10-13 Allegheny Ludlum Steel Process for treating austenite stainless steels
US3563729A (en) * 1968-04-16 1971-02-16 Crucible Inc Free-machining corrosion-resistant stainless steel
US3592634A (en) * 1968-04-30 1971-07-13 Armco Steel Corp High-strength corrosion-resistant stainless steel

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2083524A (en) * 1931-11-27 1937-06-08 Payson Peter Corrosion resistant alloy
US2306662A (en) * 1934-01-20 1942-12-29 Rustless Iron & Steel Corp Alloy
US2115733A (en) * 1935-06-25 1938-05-03 Rustless Iron & Steel Corp Alloy and manufactures
US2141016A (en) * 1936-11-19 1938-12-20 Payson Peter Alloy steel
US2159725A (en) * 1938-03-19 1939-05-23 Electro Metallurg Co Corrosion resistant steel
US2398702A (en) * 1941-02-26 1946-04-16 Timken Roller Bearing Co Articles for use at high temperatures
US2294803A (en) * 1942-02-18 1942-09-01 Rich Mfg Corp Valve
US2801916A (en) * 1954-08-24 1957-08-06 Jessop William & Sons Ltd Ferrous alloys for high temperature use
US3152934A (en) * 1962-10-03 1964-10-13 Allegheny Ludlum Steel Process for treating austenite stainless steels
US3563729A (en) * 1968-04-16 1971-02-16 Crucible Inc Free-machining corrosion-resistant stainless steel
US3592634A (en) * 1968-04-30 1971-07-13 Armco Steel Corp High-strength corrosion-resistant stainless steel

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929520A (en) * 1971-12-23 1975-12-30 Lars Ivar Hellner Corrosion-resistant austenitic-ferritic stainless steel
US4018132A (en) * 1974-06-18 1977-04-19 Tokai Cold Forming Co., Ltd. Connecting-rod bolt
US4007073A (en) * 1974-10-15 1977-02-08 Felix Lvovich Levin Method of producing articles having alternating magnetic and non-magnetic portions from continuous metal blanks
DE2703756A1 (de) * 1976-02-02 1977-08-04 Avesta Jernverks Ab Austenitischer nichtrostender stahl mit hohem mo-gehalt
US4626116A (en) * 1984-03-06 1986-12-02 Hitachi Metals, Ltd. Head for wire dot printer
US4588440A (en) * 1984-06-28 1986-05-13 Hydro Quebec Co containing austenitic stainless steel with high cavitation erosion resistance
DE3510331C1 (de) * 1985-03-22 1985-12-05 Thyssen Edelstahlwerke AG, 4000 Düsseldorf Dental-Gusslegierung
US4751046A (en) * 1986-06-30 1988-06-14 Hydro Quebec Austenitic stainless steel with high cavitation erosion resistance
US4856323A (en) * 1987-04-06 1989-08-15 Mitsubishi Denki Kabushiki Kaisha Steering torque detecting device
US20040016497A1 (en) * 1994-12-20 2004-01-29 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US6691758B2 (en) 1994-12-20 2004-02-17 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US6857458B2 (en) 1994-12-20 2005-02-22 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US20050051251A1 (en) * 1994-12-20 2005-03-10 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US7082978B2 (en) 1994-12-20 2006-08-01 The Goodyear Tire & Rubber Company Tires with high strength reinforcement
US5514328A (en) * 1995-05-12 1996-05-07 Stoody Deloro Stellite, Inc. Cavitation erosion resistent steel
US7181847B2 (en) * 2000-10-24 2007-02-27 Boehler Edelstahl Gmbh & Co. Kg Process for manufacturing a cylindrical hollow body and hollow body made thereby
US20040156737A1 (en) * 2003-02-06 2004-08-12 Rakowski James M. Austenitic stainless steels including molybdenum
US20070221396A1 (en) * 2004-05-19 2007-09-27 Hiromu Izumida Composite Wire for Wire-Harness and Process for Producing the Same
US7491891B2 (en) * 2004-05-19 2009-02-17 Sumitomo (Sei) Steel Wire Corp. Composite wire for wire-harness and process for producing the same
US7985304B2 (en) 2007-04-19 2011-07-26 Ati Properties, Inc. Nickel-base alloys and articles made therefrom
US20110206553A1 (en) * 2007-04-19 2011-08-25 Ati Properties, Inc. Nickel-base alloys and articles made therefrom
US8394210B2 (en) 2007-04-19 2013-03-12 Ati Properties, Inc. Nickel-base alloys and articles made therefrom
DE102008005803A1 (de) * 2008-01-17 2009-07-23 Technische Universität Bergakademie Freiberg Bauteil aus höher kohlnstoffhaltigem austenitischem Stahlformguss, Verfahren zu deren Herstellung und deren Verwendung
WO2020105885A1 (ko) * 2018-11-19 2020-05-28 한국기계연구원 열간가공성 및 인장 특성이 우수한 보론 함유 스테인리스강 및 그 제조 방법

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CA956148A (en) 1974-10-15
IT939544B (it) 1973-02-10
FR2111283A5 (en)van) 1972-06-02
BE773908A (fr) 1972-04-13
NO127307B (en)van) 1973-06-04
DE2150731A1 (de) 1972-05-31

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