US3552950A - High temperature corrosion resistant fe-g-ni-mn alloy - Google Patents

High temperature corrosion resistant fe-g-ni-mn alloy Download PDF

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Publication number
US3552950A
US3552950A US646130A US3552950DA US3552950A US 3552950 A US3552950 A US 3552950A US 646130 A US646130 A US 646130A US 3552950D A US3552950D A US 3552950DA US 3552950 A US3552950 A US 3552950A
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alloys
corrosion
nickel
chromium
alloy
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Gene R Rundell
Alvin E Nehrenberg
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Simonds Saw and Steel Co
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Simonds Saw and Steel Co
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

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  • This invention pertains to high temperature, corrosion resistant, age hardenable, austenitic alloys,'and moref'particularly to an essentially medium tolow carbon, low silicon, nickel-manganese-chromium-iron alloy .of this type, preferably containing aluminum and titanium as age hardening elements, and wherein manganese is present in substantial amount along with nickel in critically restricted amount for imparting high elevated temperature corrosion resistance to the combustion products of leaded gasoline fuels.
  • an alloy steel commonly known as 2l-4N has been widely used for automotive exhaust valves.
  • This steel nominally containsabout 21% chromium, 10% manganese, 4% nickel, 05% carbon, 0.4% nitrogen, and the balance substantially iron.
  • the steel is hardened by the precipitation of carbides and nitrides, and is characterized by unusually high tensile strengthand hardness for 'an austenitic alloyaIn-addition it has good resistance to corrosion in the combustion products of leaded gasoline fuels.
  • V t I H There are a number of requirements to. be met by an alloy or alloy steelto render it suitable for use in internal combustion engine valves and valve partsrSuch-analloy should be austenitic for reasons of strength at valve operating' temperatures on the order of 1200-1600 F. Also the austenitic alloy should be hardenable by precipitation of a stable phase such as carbides or intermetallic compounds to provide resistance to wear and to indentation. Also the alloy must have adequate corrosion resistance to the combustion products of leadedengine, fuels.
  • Inconel .750 has a corrosion rate in molten .lead oxide of less than 3.0 gram per sq. decimeter, but its cost is several times that of 21-4N steel which has a corrosion rate of about 20.0 gms./dm. As shown below the alloy of the present invention has a corrosion rate in molten lead oxide of about 10.0 gms./dm. which places it between the iron-base alloy, 21-4N, and the nickel-base alloy, 750.
  • the blank is surface ground on both ends to a length of .444 inch, and is finished by hand grinding on dry 240 grit paper over the complete surface.
  • the specimen is measured, degreased in methanol, and weighed to the nearest tenth of a milligram. It is then placed in a small magnesia crucible, covered with 40 grams of lead oxide, heated to a temperature of 1675 F., and held for an hour. After cooling to room temperature the specimen is broken out of the lead oxide, scraped to remove the loose lead oxide, and immersed in a molten solution of caustic soda and soda ash (1075 to 1100 F.) for several minutes.
  • the specimen is broken out of the lead oxide, scraped to remove the loose lead oxide, and immersed in a molten solution of caustic soda and soda ash (1075 to 1100 F.) for several minutes.
  • FIG. 1 is a graphical showing of the corrosion rate in molten lead oxide of the various'iron-chromium-nickel alloys, with both high and low silicon contents.
  • FIG. 2 is a similar graphical showing of other ironchromium-nickel alloys containing titanium and aluminum as age hardening elements.
  • FIG. 3 is a similar graphical showing of other ironnickel-chromium alloys which also contain manganese as well as titanium and aluminum in varying amounts.
  • FIG. 4 is a similar graphical showingof various ironnickel-chromium-manganese alloys which contain titanium and aluminum.
  • FIG. 5 is a graphical showing of the elevated temperature, creep-rupture properties of an alloyaccording to the invention and of the analysis set forth therein.
  • One objective of the research program resulting in this invention was to survey the corrosion behavior of simple Fe-Cr-Ni alloys which were treated essentially as ternary alloys, in order to determine a suitable base composition for further work.
  • Alloys were made with nickel contents in the range 20 to and chromium contents in the range 5 to 30%. Both elements were varied independently of the other except that combinations of nickel and chromium were avoided that did not produce fully austenitic alloys. Silicon and manganese contents consistent with normal steelmaking practice (.2 to 3% and .3 t o .4%,respectively) were OORROSION RATES OF SIMPLE Fe-Cr-Ni CAST ALLOYS (O 0.05% MAX., RESIDUALS NIL) [Corrosion rate, gms./drn. at indicated nickel and chromium contents] Cr content, percent Nickel content, percent:
  • the corrosion rates of the 5 Cr and 20 Cr alloys are plotted as a function of nickel content in the upper two curves of FIG. 1, and serve to indicate the potent effect of nickel on corrosion resistance.
  • low-silicon alloys do not exhibit increasing corrosion rates with decreasing nickel below about 40%. This appears to be fundamental to alloys of low silicon, and is indicated by the horizontal extension of the low silicon graphs to-the left in FIG. v1 below the 40% Ni level, which implies a maximum corrosion rate of about 16 to 22 grams for Fe-base, Fe-Cr-Ni alloys. According to this figure, the only way'of achieving lower corrosion rates is' to increase the nickel content above 40%. h As pointed out above, one of the requirements for a suitable alloy for internal combustion engine valve "applications is that it be hardenable'by the precipitation of a stable phase, such as carbides or intermetallic com pounds. Obviously, the addition of elements to promote hardening could affect the corrosion behavior of the simple alloys having corrosion resistant properties as above described.
  • FIGS. 1 and 2 are also evident from FIGS. 1 and 2 that nickel exerts the most influence on the corrosion resistance of these alloys, and it is useful to consider the. effect of other elements in terms of the nickel content required for a given corrosion.rate..
  • the term critical nickel content will be used to denote the nickel content required for a corrosion rate of less than grams per square decimeter.
  • the effect of adding titanium and aluminum is to increase the nickel content from 45 to about 60% v I FIG. 2 also indicates that the objective ofdeveloping an alloy of lower cost than Inconel 750,. cannot be realized in Fe-Cr-Ni alloys containing titanium and aluminum, since a reduction in nickel from about 75% for Inconel 750 to 60% is not sufficient to affect the cost appreciably.
  • the corrosion rate will be less than 15 gms./dm If the chromium is less than the amount indicated the corrosion rate will exceed 55 gms./dm
  • Equation 1 is written with silicon as the independent variable. However, if chromium is to be considered as an independent variable, Equationl may be transposed in accordance with Equation 2 below: 1
  • alloys VS 54 and VS 55 containing. Ni, 10% Cr, 0.3O.34% Si and about 2.83.6% Ti and Al did not have a chromium content equal to that calculated from Equation 1, yet the corrosion resistance was very good. This serves to illustrate that chromium and silicon variations do not affect corrosion resistance independently of nickel.
  • the amount of chromium required can be considerably lower for the 70% nickel alloys than for alloys containing less than about 40% nickel. Since the objective in practicing this invention is to provide good corrosion resistance at low cost, primary concern is with the effects of chromium and silicon at intermediate nickel contents where Equation 1 is valid.'
  • the amoun'tof jnickel that may be replaced is about six times the manganese (both have about equal atomic weight); Only about half of the nickel otherwise required maybe thus replaced.
  • Manganese has a completely difiYerent function in the alloys of this invention than in known types of iron-base austeniticstainless' steels, such as those containing low nickel, high manganese, carbon, and nitrogen.
  • the func tion of manganese in such alloys ' is to stabilize the aus tenitic structure in the absence of'suflicient nickel. From a consideration of the similar corrosion resistance of high manganese stainless steels such as'-21'4N. and'ordinary stainless steels such' as Type 304, it is evident that manganese is not required to impart corrosion resistance thereto.
  • the alloys of this invention on' the other hand, contain TABLE VIL-TENSILE PROPERTIES OF HIGH MANGANESE Fe-Or-Ni ALLOYS HARDENED WITH Ti AND Al Strength, 1,000
  • - limit is dictated by tensile ductility which drops off sharply chromium, 2% Ti, 1% Al, markedly improves the corrowith hardener contents in excess of about 4%. sion resistance thereof.
  • An age hardenable alloy characterized in having a corrosion rate in molten lead oxide as measured in a magnesia crucible of less than about 15 grams per square decirneter, said alloy consisting essentially of up to 0.5% carbon, up to 0.3% nitrogen, up to 0.6% silicon, up to 5% in total amount of at least one metal of the group MO, W and V and combinations thereof, up to 4% copper, up to 0.2% boron, 1.5 to 3% titanium, 0.8 to 1.5% aluminum, 12 to chromium with the chromium content at least equal to 16+43.5 percent silicon, 34 to nickel, 4 to 20% manganese, the nickel content being selected relative to the manganese content to provide said corrosion rate, and the balance substantially iron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US646130A 1967-06-14 1967-06-14 High temperature corrosion resistant fe-g-ni-mn alloy Expired - Lifetime US3552950A (en)

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JP (1) JPS4931848B1 (https=)
FR (1) FR1570154A (https=)
GB (1) GB1206666A (https=)
SE (1) SE345878B (https=)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3778256A (en) * 1970-12-28 1973-12-11 Hitachi Ltd Heat-resistant alloy for a combustion liner of a gas turbine
US3833358A (en) * 1970-07-22 1974-09-03 Pompey Acieries Refractory iron-base alloy resisting to high temperatures
US3859082A (en) * 1969-07-22 1975-01-07 Armco Steel Corp Wrought austenitic alloy products
US3900316A (en) * 1972-08-01 1975-08-19 Int Nickel Co Castable nickel-chromium stainless steel
US3947266A (en) * 1974-05-17 1976-03-30 Carondelet Foundry Company Corrosion-resistant alloys
US4088478A (en) * 1974-04-24 1978-05-09 Carondelet Foundry Company Corrosion-resistant alloys
US4278465A (en) * 1979-11-02 1981-07-14 Carondelet Foundry Company Corrosion-resistant alloys
US4409025A (en) * 1981-01-12 1983-10-11 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4419129A (en) * 1981-01-12 1983-12-06 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4442068A (en) * 1981-10-12 1984-04-10 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4448749A (en) * 1981-10-12 1984-05-15 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4560408A (en) * 1983-06-10 1985-12-24 Santrade Limited Method of using chromium-nickel-manganese-iron alloy with austenitic structure in sulphurous environment at high temperature
US5660938A (en) * 1993-08-19 1997-08-26 Hitachi Metals, Ltd., Fe-Ni-Cr-base superalloy, engine valve and knitted mesh supporter for exhaust gas catalyzer

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5386849U (https=) * 1976-12-20 1978-07-17
US4339509A (en) 1979-05-29 1982-07-13 Howmet Turbine Components Corporation Superalloy coating composition with oxidation and/or sulfidation resistance
RU2308535C1 (ru) * 2006-03-13 2007-10-20 Юлия Алексеевна Щепочкина Сталь

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859082A (en) * 1969-07-22 1975-01-07 Armco Steel Corp Wrought austenitic alloy products
US3833358A (en) * 1970-07-22 1974-09-03 Pompey Acieries Refractory iron-base alloy resisting to high temperatures
US3778256A (en) * 1970-12-28 1973-12-11 Hitachi Ltd Heat-resistant alloy for a combustion liner of a gas turbine
US3900316A (en) * 1972-08-01 1975-08-19 Int Nickel Co Castable nickel-chromium stainless steel
US4088478A (en) * 1974-04-24 1978-05-09 Carondelet Foundry Company Corrosion-resistant alloys
US3947266A (en) * 1974-05-17 1976-03-30 Carondelet Foundry Company Corrosion-resistant alloys
US4278465A (en) * 1979-11-02 1981-07-14 Carondelet Foundry Company Corrosion-resistant alloys
US4409025A (en) * 1981-01-12 1983-10-11 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4419129A (en) * 1981-01-12 1983-12-06 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4442068A (en) * 1981-10-12 1984-04-10 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4448749A (en) * 1981-10-12 1984-05-15 Kubota Ltd. Heat resistant cast iron-nickel-chromium alloy
US4560408A (en) * 1983-06-10 1985-12-24 Santrade Limited Method of using chromium-nickel-manganese-iron alloy with austenitic structure in sulphurous environment at high temperature
US5660938A (en) * 1993-08-19 1997-08-26 Hitachi Metals, Ltd., Fe-Ni-Cr-base superalloy, engine valve and knitted mesh supporter for exhaust gas catalyzer

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JPS4931848B1 (https=) 1974-08-26
FR1570154A (https=) 1969-06-06
SE345878B (https=) 1972-06-12
DE1758385B1 (de) 1971-09-23
GB1206666A (en) 1970-09-30

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