US3754898A - Austenitic iron alloys - Google Patents
Austenitic iron alloys Download PDFInfo
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- US3754898A US3754898A US00216297A US3754898DA US3754898A US 3754898 A US3754898 A US 3754898A US 00216297 A US00216297 A US 00216297A US 3754898D A US3754898D A US 3754898DA US 3754898 A US3754898 A US 3754898A
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- 229910000640 Fe alloy Inorganic materials 0.000 title claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011651 chromium Substances 0.000 claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000007792 addition Methods 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910001566 austenite Inorganic materials 0.000 claims description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910018138 Al-Y Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- -1 actinide metals Chemical class 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Definitions
- ABSTRACT ⁇ g z i Search Czzc The productlon of an austenmc 1ron base alloy wtth rel- 75/124 atively high aluminum and chromium content which forms an altlminutn oxide protective film in the pres- 56] (defences Cited ence of yttriu'm and/or rare earth elements and has high UNITED STATES PATENTS 3/1962 McGurty 75/124 temperature resistance.
- ferritic alloys are magnetic, have low thermal expansion properties, poor high temperature strength and fair workability.
- the austenitic alloys are non-magnetic, have high thermal expansion properties, good high temperature strength and excellent workability.
- F erritic alloys which are oxidation resistant and which contain chromium, aluminum and yttrium are useful but have poor structural strength at high temperature and are difficult to produce economically in sheet form.
- My invention of an austenitic alloy which readily forms an aluminum oxide film has greater strength at high temperature and is easily workable to produce standard products using conventional facilities presently employed in automotive and similar metal working shops.
- the nitrogen oxide contamination can be minimized by adjusting the engine combustion conditions to realize less oxidizing combustion conditions. This resolution of the nitrogen oxide problem results in an even greater emission of carbon monoxide and hydrocarbon contaminants.
- the combustion gases which exit from engines at temperatures of l,400F to l,700F are mixed with additional air in an automotive reactor connected to the engine exhaust ports, the carbon monoxide and hydrocarbon contaminants are oxidized to yield innocuous carbon dioxide and water vapor.
- the gas which exhausts from an engine equipped with an exhaust reactor and operated under proper conditions such as a rich mixture and a retarded spark contains insignificant amounts of the carbon monoxide, nitrogen oxide and hydrocarbon contaminants.
- High temperature technology is generally based on the use of metals which react with oxygen, nitrogen and/or other corrosive reactants at elevated temperatures to form a protective film which protects the base metal.
- iron, nickel and cobalt are useful as base metals for high temperature heat resistant alloys. Iron, nickel and cobalt react with oxygen at elevated temperatures and readily convert to the oxides. However, the oxides formed are chemically weak and are readily reduced by other high temperature metals. Thus when iron, nickel or cobalt alloys which contain other elements which are more reactive with oxygen are heated in an oxidizing atmosphere the addition elements when present in suitable concentration will preferentially oxidize at the surface of the metal. A barrier to further significant oxidation is obtained if the oxide film (of the additive metal) which forms is adherant and coherant.
- the aluminum oxide film especially that which forms on alloys which contain small amounts (0.1 to 5.0 w/o) of yttrium or rare earth elements is the more protective of the base metals.
- My invention consists of the production of an austenitic iron base alloy with high aluminum and chromium content so that in the presence of yttrium and/or rare earth elements an aluminum oxide protective film forms.
- Alloys which contain 4 w/o aluminum, 20 or 25 w/o nickel and 5, l0 and 15 w/o chromium plus 1 w/o yttrium were found to be austenitic and readily workable hot or cold.
- the oxide film formed on these austenitic alloys on exposure to air at elevated temperatures (l,800-2,300F) was a thin aluminum oxide film which is also protective of the ferritic Fe-Cr-ALY alloys.
- austenitic iron base alloys containing Ni, Cr, Al, and Y to have superior oxidation resistance due to the formation of a thin aluminum oxide film which is adherent, non-spalling and highly protective of the base metal.
- compositional limits for defining the range of alloys which possess the required austenite stability and aluminum oxide protective film oxidation resistance may generally be defined as having 16 to 45 w/o Ni, 4 to 25 w/o Cr, 3% w/o to 5% w/o aluminum and 0.1 to 5 w/o Y. i found the most useful composition to be the following: Fe-20 percent Ni-lO percent Cr-4 percent Al-l percent Y.
- the function of the alloying additions in the oxidation resistant alloys is as follows: The nickel with the help of chromium is added to the alloy to obtain the desired austenitic structure. The aluminum content with the help of the chromium and yttrium contents provides the superior oxidation resistance.
- useful alloys would fall within the following composition range Fe-IQ- to 45 w/o M4 to 25 w/o Cr-3 6 to 5% w/oAl-0.l to 5 w/oY, and contain 0- 20w/o Mn-O to 0.5 w/oC-O to 0.5 w/oN and/or 0 to lw/o Cu as a partial substitution of the austenite stabilizing nickel content.
- Table I illustrate the desirable strength advantage of the low nickel manganese containing alloy (Fe-10Cr-l5Ni-4Al-5Mn-lCu-1Y) as compared to the higher nickel non-manganese containing composition (Fe- 1 Cr-20Ni-4Al-1Y).
- oxidation resistance and high temperature strength useful alloys would fall within the following composition range Fe-8 to 45 w/o Ni-4 to 25 w/o Cr-3l to 5% w/o Al-0.l to 5 w/o Y and 0.5 to 20 w/o Mn-0.l to l w/o Cu 0.1 to w/o W and/or Mo-0.l to 2 percent Cb and/or Ta, Ti, Zr, or Hf and 0.05 to 0.5 w/o carbon and/or nitrogen.
- austenitic alloys containing iron, nickel, aluminum and yttrium have superior oxidation resistance because of the formation of an aluminum oxide protective film and are high temperature oxidation resistant, have good strength along with workability compared to oxidation resistant ferritic alloys.
- additions of manganese and/or copper, carbon and nitrogen provides austenitic alloys of lower nickel content and higher strength than the base Fe-Ni-Cr-Al-Y compositions. Further additions to the base Fe-Ni-Cr-Al-Y alloy of additions which are effective for improving the strength of stainless steel alloys such as molybdenum, tungsten, manganese, columbium, carbon and/or nitrogen are significantly advantageous for increasing the high temperature strength of the Fe-Ni-Cr-Al-Y alloys.
- the rare earth elements have an effect similar to yttrium for decisively improving the protective qualities of aluminum oxide protective films in terms of non-spalling properties and effectiveness as a nitrogen barrier.
- the most protective aluminum oxide films are formed on alloys which contain yttrium alone or in combination with small additions of the rare earth metals and/or actinide metals. It is recognized that the yttrium content of my alloys may be partially substituted or wholely replaced by rare earth metal or actinide metal additions without loss of excellent oxidation resistance.
- An austenitic alloy of iron, nickel, chromium, aluminum and yttrium consisting essentially of 20.0 weight percent of nickel, 10.0 weight percent chromium, 4.0 weight percent of aluminum and 1.0 weight percent yttrium and the balance consisting essentially of iron.
- An austenitic alloy of iron, nickel, chromium, aluminum, and yttrium consisting essentially of 16 to 45 weight percent of nickel, 4 to 25 weight percent of chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium and the balance consisting essentially of iron.
- An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, manganese, copper and yttrium which consists of 15.0 weight percent of nickel, 10.0 weight percent of chromium, 4.0 weight percent aluminum, 5.0 weight percent manganese, 1.0 weight percent copper, 1.0 weight percent yttrium and the balance consisting essentially of iron.
- An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, yttrium and containing additions of manganese, carbon, nitrogen and copper as a partial substitution of the austenite stabilizing nickel content within the following ranges, 10.0 to 45.0 weight percent nickel, 4 to 25.0 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5.0 weight percent yttrium and containing 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen and/or 0. to 1 weight percent copper with the balance iron.
- An austenitic iron base alloy as described in claim 4 having improved high temperature strength and including iron, 8 to 45 weight percent nickel, 4 to 25 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium, and contain 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen, 0 to 1 weight percent copper, and/or as a partial substitution of the austenite stabilizing nickel content and for increased high temperature strength 0.1 to 10 weight percent tungsten and/or molybdenum, and/or 0.1 to 2 weight percent columbium and/or tantalum, titanium,
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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)
Abstract
The production of an austenitic iron base alloy with relatively high aluminum and chromium content which forms an aluminum oxide protective film in the presence of yttrium and/or rare earth elements and has high temperature resistance.
Description
United States Patent 1 1111 3,754,898
McGurt v v Au 28 1973 [54] AUSTENITIC IRON ALLOYS 3,540,881 '11/1940 White 75/124 3,298,826 1/1967 Wukusick 75/124 [761 Invent g 1 3,113,991 12/1963 Kleber 75/126 0 ColomalDl 1193511118, 19607 2,879,194 3/1959 Eichelberger 7s/124- 221 Filed: Jan. 7, 1972 1 Primary Examiner-Hy1and Bizot [211 App]. No.. 216,297 Attorney Ed a d J [52] US. Cl. 75/122, 75/124, 75/125, 1
75/128 E I [57] ABSTRACT {g z i Search Czzc The productlon of an austenmc 1ron base alloy wtth rel- 75/124 atively high aluminum and chromium content which forms an altlminutn oxide protective film in the pres- 56] (defences Cited ence of yttriu'm and/or rare earth elements and has high UNITED STATES PATENTS 3/1962 McGurty 75/124 temperature resistance.
5 Claims, No Drawings AUSTENITIC IRON ALLOYS My invention relates to high temperature, oxidation resistant austenitic iron alloys and more particularly to alloys of iron, nickel, aluminum and yttrium which have oxidation resistance based on the formation of an aluminum oxide protective film.
Because of its allotropic properties iron forms, depending on the addition of other alloying elements, two series of alloys, the ferritic and the austenitic which differ significantly in properties. Generally, ferritic alloys are magnetic, have low thermal expansion properties, poor high temperature strength and fair workability. The austenitic alloys are non-magnetic, have high thermal expansion properties, good high temperature strength and excellent workability.
F erritic alloys which are oxidation resistant and which contain chromium, aluminum and yttrium are useful but have poor structural strength at high temperature and are difficult to produce economically in sheet form.
My invention of an austenitic alloy which readily forms an aluminum oxide film has greater strength at high temperature and is easily workable to produce standard products using conventional facilities presently employed in automotive and similar metal working shops.
In the ordinary automobile engine, exhaust gases which contain carbon monoxide, nitrogen oxides and hydrocarbon gas contaminants are present in harmful quantities.
The nitrogen oxide contamination can be minimized by adjusting the engine combustion conditions to realize less oxidizing combustion conditions. This resolution of the nitrogen oxide problem results in an even greater emission of carbon monoxide and hydrocarbon contaminants. However, if the combustion gases which exit from engines at temperatures of l,400F to l,700F are mixed with additional air in an automotive reactor connected to the engine exhaust ports, the carbon monoxide and hydrocarbon contaminants are oxidized to yield innocuous carbon dioxide and water vapor. Thus the gas which exhausts from an engine equipped with an exhaust reactor and operated under proper conditions such as a rich mixture and a retarded spark contains insignificant amounts of the carbon monoxide, nitrogen oxide and hydrocarbon contaminants.
The chemical reactions referenced above create increases in temperature to 1,700-2,000F and beyond. In my invention 1 have provided oxidation resistant alloys which are chemically stable at such temperatures, are workable, have strength and are economically feasible for high production.
High temperature technology is generally based on the use of metals which react with oxygen, nitrogen and/or other corrosive reactants at elevated temperatures to form a protective film which protects the base metal.
iron, nickel and cobalt are useful as base metals for high temperature heat resistant alloys. Iron, nickel and cobalt react with oxygen at elevated temperatures and readily convert to the oxides. However, the oxides formed are chemically weak and are readily reduced by other high temperature metals. Thus when iron, nickel or cobalt alloys which contain other elements which are more reactive with oxygen are heated in an oxidizing atmosphere the addition elements when present in suitable concentration will preferentially oxidize at the surface of the metal. A barrier to further significant oxidation is obtained if the oxide film (of the additive metal) which forms is adherant and coherant.
Present day high temperature technology is thus based on the use of iron, nickel and cobalt base alloys which contain chromium and/or aluminum and whose oxidation resistance is dependant on the formation of aluminum oxide or chromium oxide protective films.
The aluminum oxide film, especially that which forms on alloys which contain small amounts (0.1 to 5.0 w/o) of yttrium or rare earth elements is the more protective of the base metals.
My invention consists of the production of an austenitic iron base alloy with high aluminum and chromium content so that in the presence of yttrium and/or rare earth elements an aluminum oxide protective film forms.
Alloys which contain 4 w/o aluminum, 20 or 25 w/o nickel and 5, l0 and 15 w/o chromium plus 1 w/o yttrium were found to be austenitic and readily workable hot or cold. The oxide film formed on these austenitic alloys on exposure to air at elevated temperatures (l,800-2,300F) was a thin aluminum oxide film which is also protective of the ferritic Fe-Cr-ALY alloys. I found austenitic iron base alloys containing Ni, Cr, Al, and Y to have superior oxidation resistance due to the formation of a thin aluminum oxide film which is adherent, non-spalling and highly protective of the base metal.
The exact compositional limits for defining the range of alloys which possess the required austenite stability and aluminum oxide protective film oxidation resistance may generally be defined as having 16 to 45 w/o Ni, 4 to 25 w/o Cr, 3% w/o to 5% w/o aluminum and 0.1 to 5 w/o Y. i found the most useful composition to be the following: Fe-20 percent Ni-lO percent Cr-4 percent Al-l percent Y.
The function of the alloying additions in the oxidation resistant alloys is as follows: The nickel with the help of chromium is added to the alloy to obtain the desired austenitic structure. The aluminum content with the help of the chromium and yttrium contents provides the superior oxidation resistance.
For economic reasons it is desirable to limit the nickel content of commercial alloys.
It is well known that manganese, carbon, nitrogen and copper like nickel promote austenite stabilization. I have found that the content in my alloys of strategic and expensive nickel can be lowered to below 15 percent without loss of austenite stability by the addition to the alloy of manganese and copper. The Fe-l5w/o Ni- 1 0w/o-Cr-4w/oAl-5w/oMn- 1 w/oCu- 1 w/oY was found to possess the desired austenite stability and the excellent strength and oxidation resistance typical of the non-manganese and copper containing alloys.
I have found based on phase stability and oxidation resistance, useful alloys would fall within the following composition range Fe-IQ- to 45 w/o M4 to 25 w/o Cr-3 6 to 5% w/oAl-0.l to 5 w/oY, and contain 0- 20w/o Mn-O to 0.5 w/oC-O to 0.5 w/oN and/or 0 to lw/o Cu as a partial substitution of the austenite stabilizing nickel content.
It is well known in the art that carbon and nitrogen in small amounts (less than 0.4 w/o) and molybdenum, tungsten, columbium, tantalum, titanium, zirconium and hafnium in larger amounts added to austenitic iron base alloys such as the stainless steels improve the high temperature strength of the austenite structure. Evaluations were conducted to determine the effectiveness of such strengthening additions for improving the properties of these new austenitic alloys. In addition to high temperature strength the effects of the additions on austenite stability and oxidation resistance were also determined. Examples of the effectiveness of such strengthening additions are shown in Table I.
TABLE I Effects of Alloy Additions to FeCr-Ni-Al-Y ti Base Alloys on Stress Rupture Strength at 1800F Additions of molybdenum and tungsten alone and in combination are effective to improve the strength in this regard.
The data shown in Table I illustrate the desirable strength advantage of the low nickel manganese containing alloy (Fe-10Cr-l5Ni-4Al-5Mn-lCu-1Y) as compared to the higher nickel non-manganese containing composition (Fe- 1 Cr-20Ni-4Al-1Y).
Based on austenite phase stability, oxidation resistance and high temperature strength useful alloys would fall within the following composition range Fe-8 to 45 w/o Ni-4 to 25 w/o Cr-3l to 5% w/o Al-0.l to 5 w/o Y and 0.5 to 20 w/o Mn-0.l to l w/o Cu 0.1 to w/o W and/or Mo-0.l to 2 percent Cb and/or Ta, Ti, Zr, or Hf and 0.05 to 0.5 w/o carbon and/or nitrogen.
I have in my invention found that austenitic alloys containing iron, nickel, aluminum and yttrium have superior oxidation resistance because of the formation of an aluminum oxide protective film and are high temperature oxidation resistant, have good strength along with workability compared to oxidation resistant ferritic alloys.
I have found that additions of manganese and/or copper, carbon and nitrogen provides austenitic alloys of lower nickel content and higher strength than the base Fe-Ni-Cr-Al-Y compositions. Further additions to the base Fe-Ni-Cr-Al-Y alloy of additions which are effective for improving the strength of stainless steel alloys such as molybdenum, tungsten, manganese, columbium, carbon and/or nitrogen are significantly advantageous for increasing the high temperature strength of the Fe-Ni-Cr-Al-Y alloys.
It is well known that the rare earth elements have an effect similar to yttrium for decisively improving the protective qualities of aluminum oxide protective films in terms of non-spalling properties and effectiveness as a nitrogen barrier. However, the most protective aluminum oxide films are formed on alloys which contain yttrium alone or in combination with small additions of the rare earth metals and/or actinide metals. It is recognized that the yttrium content of my alloys may be partially substituted or wholely replaced by rare earth metal or actinide metal additions without loss of excellent oxidation resistance.
Although the present invention has been described in preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and appended Claims.
1 claim:
1. An austenitic alloy of iron, nickel, chromium, aluminum and yttrium consisting essentially of 20.0 weight percent of nickel, 10.0 weight percent chromium, 4.0 weight percent of aluminum and 1.0 weight percent yttrium and the balance consisting essentially of iron.
2. An austenitic alloy of iron, nickel, chromium, aluminum, and yttrium consisting essentially of 16 to 45 weight percent of nickel, 4 to 25 weight percent of chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium and the balance consisting essentially of iron.
3. An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, manganese, copper and yttrium which consists of 15.0 weight percent of nickel, 10.0 weight percent of chromium, 4.0 weight percent aluminum, 5.0 weight percent manganese, 1.0 weight percent copper, 1.0 weight percent yttrium and the balance consisting essentially of iron.
'4. An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, yttrium and containing additions of manganese, carbon, nitrogen and copper as a partial substitution of the austenite stabilizing nickel content within the following ranges, 10.0 to 45.0 weight percent nickel, 4 to 25.0 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5.0 weight percent yttrium and containing 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen and/or 0. to 1 weight percent copper with the balance iron.
5. An austenitic iron base alloy as described in claim 4 having improved high temperature strength and including iron, 8 to 45 weight percent nickel, 4 to 25 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium, and contain 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen, 0 to 1 weight percent copper, and/or as a partial substitution of the austenite stabilizing nickel content and for increased high temperature strength 0.1 to 10 weight percent tungsten and/or molybdenum, and/or 0.1 to 2 weight percent columbium and/or tantalum, titanium,
zirconium or hafnium.
Claims (4)
- 2. An austenitic alloy of iron, nickel, chromium, aluminum, and yttrium consisting essentially of 16 to 45 weight percent of nickel, 4 to 25 weight percent of chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium and the balance consisting essentially of iron.
- 3. An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, manganese, copper and yttrium which consists of 15.0 weight percent of nickel, 10.0 weight percent of chromium, 4.0 weight percent aluminum, 5.0 weight percent manganese, 1.0 weight percent copper, 1.0 weight percent yttrium and the balance consisting essentially of iron.
- 4. An austenitic alloy of iron consisting essentially of nickel, chromium, aluminum, yttrium and containing additions of manganese, carbon, nitrogen and copper as a partial substitution of the austenite stabilizing nickel content within the following ranges, 10.0 to 45.0 weight percent nickel, 4 to 25.0 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5.0 weight percent yttrium and containing 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen and/or 0. to 1 weight percent copper with the balance iron.
- 5. An austenitic iron base alloy as described in claim 4 having improved high temperature strength and including iron, 8 to 45 weight percent nickel, 4 to 25 weight percent chromium, 3.5 to 5.5 weight percent aluminum, 0.1 to 5 weight percent yttrium, and contain 0. to 20 weight percent manganese, 0. to 0.5 weight percent carbon, 0. to 0.5 weight percent nitrogen, 0 to 1 weight percent copper, and/or as a partial substitution of the austenite stabilizing nickel content and for increased high temperature strength 0.1 to 10 weight percent tungsten and/or molybdenum, and/or 0.1 to 2 weight percent columbium and/or tantalum, titanium, zirconium or hafnium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21629772A | 1972-01-07 | 1972-01-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3754898A true US3754898A (en) | 1973-08-28 |
Family
ID=22806514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00216297A Expired - Lifetime US3754898A (en) | 1972-01-07 | 1972-01-07 | Austenitic iron alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3754898A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989514A (en) * | 1974-07-25 | 1976-11-02 | Nisshin Steel Co., Ltd. | Heat-resisting austenitic stainless steel |
| DE2713721A1 (en) * | 1976-03-29 | 1977-10-06 | Brunswick Corp | IRON-NICKEL-CHROME-ALUMINUM-YTTRIUM ALLOY AND REMOVABLE SEALS MADE FROM THEM |
| US4086085A (en) * | 1976-11-02 | 1978-04-25 | Mcgurty James A | Austenitic iron alloys |
| US4144380A (en) * | 1976-06-03 | 1979-03-13 | General Electric Company | Claddings of high-temperature austenitic alloys for use in gas turbine buckets and vanes |
| US4204862A (en) * | 1975-10-29 | 1980-05-27 | Nippon Steel Corporation | Austenitic heat-resistant steel which forms Al2 O3 film in high-temperature oxidizing atmosphere |
| US4237193A (en) * | 1978-06-16 | 1980-12-02 | General Electric Company | Oxidation corrosion resistant superalloys and coatings |
| US4261767A (en) * | 1976-07-28 | 1981-04-14 | Creusot-Loire | Alloy resistant to high temperature oxidation |
| US4275124A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Carbon bearing MCrAlY coating |
| US4275090A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Process for carbon bearing MCrAlY coating |
| US4385934A (en) * | 1979-04-23 | 1983-05-31 | Mcgurty James A | Austenitic iron alloys having yttrium |
| US4398951A (en) * | 1981-04-22 | 1983-08-16 | Unisearch Limited | Fermalloy(Fe-Mn-Al stainless steel) |
| EP0093661A1 (en) * | 1982-04-29 | 1983-11-09 | Imphy S.A. | Iron-nickel-chromium-aluminium-rare earth metal type alloy |
| US4459043A (en) * | 1980-11-14 | 1984-07-10 | Smiths Industries Public Limited Company | Reflective elements and sensors including reflective elements |
| US4460542A (en) * | 1982-05-24 | 1984-07-17 | Cabot Corporation | Iron-bearing nickel-chromium-aluminum-yttrium alloy |
| FR2566803A1 (en) * | 1984-06-29 | 1986-01-03 | Manoir Fonderies Acieries | NOVEL AUSTENIALLY ALLOY CONTAINING ALUMINUM AND POSSIBLY YTTRIUM, FUEL OR COKING WORKING OVEN WORKING AT HIGH TEMPERATURE INCLUDING SUCH ALLOY AND USE OR APPLICATION OF SAID ALLOY OR FURNACE IN PROCESSING PROCESSES FUEL OR COKING, OR THE MANUFACTURE OF DRILLING CABLES OR TUBES |
| US4668585A (en) * | 1984-06-08 | 1987-05-26 | Osaka Prefecture, Horonobu Oonishi and Kyocera Corporation | Fe-Cr-Al type implant alloy composite for medical treatment |
| US4743318A (en) * | 1986-09-24 | 1988-05-10 | Inco Alloys International, Inc. | Carburization/oxidation resistant worked alloy |
| US4999158A (en) * | 1986-12-03 | 1991-03-12 | Chrysler Corporation | Oxidation resistant iron base alloy compositions |
| US5089223A (en) * | 1989-11-06 | 1992-02-18 | Matsushital Electric Works, Ltd. | Fe-cr-ni-al ferritic alloys |
| US20050011593A1 (en) * | 2003-07-15 | 2005-01-20 | General Electric Company | Process for a beta-phase nickel aluminide overlay coating |
| US8431072B2 (en) * | 2011-05-24 | 2013-04-30 | Ut-Battelle, Llc | Cast alumina forming austenitic stainless steels |
| US11193190B2 (en) | 2018-01-25 | 2021-12-07 | Ut-Battelle, Llc | Low-cost cast creep-resistant austenitic stainless steels that form alumina for high temperature oxidation resistance |
| US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
| US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
-
1972
- 1972-01-07 US US00216297A patent/US3754898A/en not_active Expired - Lifetime
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989514A (en) * | 1974-07-25 | 1976-11-02 | Nisshin Steel Co., Ltd. | Heat-resisting austenitic stainless steel |
| US4204862A (en) * | 1975-10-29 | 1980-05-27 | Nippon Steel Corporation | Austenitic heat-resistant steel which forms Al2 O3 film in high-temperature oxidizing atmosphere |
| DE2713721A1 (en) * | 1976-03-29 | 1977-10-06 | Brunswick Corp | IRON-NICKEL-CHROME-ALUMINUM-YTTRIUM ALLOY AND REMOVABLE SEALS MADE FROM THEM |
| US4144380A (en) * | 1976-06-03 | 1979-03-13 | General Electric Company | Claddings of high-temperature austenitic alloys for use in gas turbine buckets and vanes |
| US4261767A (en) * | 1976-07-28 | 1981-04-14 | Creusot-Loire | Alloy resistant to high temperature oxidation |
| US4086085A (en) * | 1976-11-02 | 1978-04-25 | Mcgurty James A | Austenitic iron alloys |
| US4237193A (en) * | 1978-06-16 | 1980-12-02 | General Electric Company | Oxidation corrosion resistant superalloys and coatings |
| US4275124A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Carbon bearing MCrAlY coating |
| US4275090A (en) * | 1978-10-10 | 1981-06-23 | United Technologies Corporation | Process for carbon bearing MCrAlY coating |
| US4385934A (en) * | 1979-04-23 | 1983-05-31 | Mcgurty James A | Austenitic iron alloys having yttrium |
| US4459043A (en) * | 1980-11-14 | 1984-07-10 | Smiths Industries Public Limited Company | Reflective elements and sensors including reflective elements |
| US4398951A (en) * | 1981-04-22 | 1983-08-16 | Unisearch Limited | Fermalloy(Fe-Mn-Al stainless steel) |
| EP0093661A1 (en) * | 1982-04-29 | 1983-11-09 | Imphy S.A. | Iron-nickel-chromium-aluminium-rare earth metal type alloy |
| US4460542A (en) * | 1982-05-24 | 1984-07-17 | Cabot Corporation | Iron-bearing nickel-chromium-aluminum-yttrium alloy |
| US4668585A (en) * | 1984-06-08 | 1987-05-26 | Osaka Prefecture, Horonobu Oonishi and Kyocera Corporation | Fe-Cr-Al type implant alloy composite for medical treatment |
| FR2566803A1 (en) * | 1984-06-29 | 1986-01-03 | Manoir Fonderies Acieries | NOVEL AUSTENIALLY ALLOY CONTAINING ALUMINUM AND POSSIBLY YTTRIUM, FUEL OR COKING WORKING OVEN WORKING AT HIGH TEMPERATURE INCLUDING SUCH ALLOY AND USE OR APPLICATION OF SAID ALLOY OR FURNACE IN PROCESSING PROCESSES FUEL OR COKING, OR THE MANUFACTURE OF DRILLING CABLES OR TUBES |
| EP0169119A1 (en) * | 1984-06-29 | 1986-01-22 | Manoir Industries | Austenitic phase alloy containing chromium and aluminium; use in cracking furnaces and drilling pipes or cables |
| US4743318A (en) * | 1986-09-24 | 1988-05-10 | Inco Alloys International, Inc. | Carburization/oxidation resistant worked alloy |
| US4999158A (en) * | 1986-12-03 | 1991-03-12 | Chrysler Corporation | Oxidation resistant iron base alloy compositions |
| US5089223A (en) * | 1989-11-06 | 1992-02-18 | Matsushital Electric Works, Ltd. | Fe-cr-ni-al ferritic alloys |
| US20050011593A1 (en) * | 2003-07-15 | 2005-01-20 | General Electric Company | Process for a beta-phase nickel aluminide overlay coating |
| US7244467B2 (en) * | 2003-07-15 | 2007-07-17 | General Electric Company | Process for a beta-phase nickel aluminide overlay coating |
| US8431072B2 (en) * | 2011-05-24 | 2013-04-30 | Ut-Battelle, Llc | Cast alumina forming austenitic stainless steels |
| US11193190B2 (en) | 2018-01-25 | 2021-12-07 | Ut-Battelle, Llc | Low-cost cast creep-resistant austenitic stainless steels that form alumina for high temperature oxidation resistance |
| US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
| US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
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