US3298826A - Embrittlement-resistant iron-chromium-aluminum-yttrium alloys - Google Patents

Embrittlement-resistant iron-chromium-aluminum-yttrium alloys Download PDF

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US3298826A
US3298826A US357845A US35784564A US3298826A US 3298826 A US3298826 A US 3298826A US 357845 A US357845 A US 357845A US 35784564 A US35784564 A US 35784564A US 3298826 A US3298826 A US 3298826A
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium

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  • This invention relates to oxidation-resistant all-oys and more particularly to alloys of iron, chromium, aluminum and yttrium.
  • Another object is to provide an iron-chromium-aluminum-yttrium alloy which is resistant to embrittlement at temperatures 0f 650 to 1300 F.
  • Another object is to provide an embrittlement-resistant ironchromium-aluminum-yttrium alloy which retains a high degree of resistance to -oxidation and corrosion.
  • a novel alloy having the following composition is provided: 0 to 20 weight percent chromium, 0.5 to 12 weight percent aluminum, 0.1 to 3.0 weight percent yttrium and the balance iron.
  • This alloy is less susceptible to embrittlement than previously known iron-chromium-aluminum-yttrium alloys, but it exhibits substantially the same superior resistance to oxidation and corrosion.
  • embrittlement of iron-chromiumaluminum-yttrium .alloys is avoided by reducing the chromium content of a level below the previous minimum.
  • my invention is not to be understood as limited to 4a particular theory, it is postulated that embrittlement below 550 C. is caused by precipitation of a chromiumrich ferrite phase and above 550 C. by precipitation of an iron-chromium sigma phase and that precipitation of these phases is significantly lessened in the temperature range of interest at chromium levels below 20 weight percent.
  • yttrium renders ironchromium-.aluminum alloys resistant to oxidation over a wider range of compositions than was previously believed effective. Oxidation resistance is maintained at low levels of chromium, and even in chromium-free alloys.
  • Chromium is provided in the alloy .at a level of 0 to 20 weight percent. At higher levels the alloy is subject to embrittlement as described above. An intermediate level of 5 to 15 weight percent chromium is preferred in order to retain to the maximum extent the favorable properties of the previous iron-chromium-aluminum-yttrium alloys, while avoiding embrittlement.
  • An aluminum content of at least 0.5 weight percent is required for oxidation resistance, and above 12 weight percent aluminum the alloy becomes embrittled.
  • an aluminum content of 4 to 6 weight percent is preferred for maximum workability and oxidation resistance.
  • an aluminum content of 5 to 7.5 weight percent is preferred.
  • the yttrium content of the alloy may be varied from 0.1 to 3.0 weight percent. At lower levels the alloy loses its oxidation resistance and at higher levels an excessive amount of second phase limits fabricability. About 1 weight percent is preferred.
  • alloy composition disclosed and claimed herein may be fabricated into usable shapes by means of conventional -techniques such as extrusion, rolling and drawing.
  • Example I Alloy specimens of the weight composition iron-25 percent chromium-4 percent aluminum-1 percent yttrium and iron-15 percent chromium-4 percent aluminum-1 percent yttrium were prepared in 6.3 millimeter diameter rod form by swaging of extruded rods. The specimens were heated in air at a temperature of 450 C. for a period of over 200 hours. Hardness of the specimens was measured periodically throughout the heating period. The results obtained may be seen by reference to the accompanying figure wherein hardness is plotted as a function of time at temperature. The hardness of the 25 percent chromium specimen showed a significant increase while the 15 ipercent chromium specimen was increased only slightly.
  • Example Il Alloy specimens of the composition given in Example I were tested by'exposure to superheated steam :at 730 C. and 1150 C. The results obtained may be seen by reference to the following table.
  • the superheatedsteam corrosion resistance of the percent chromium alloy is similar to the resistance of the percent chromium alloy.
  • Example III Alloy specimens of the composition iron-15 weight percent chromium-4 weight percent aluminum-1 Weight percent yttrium .and the balance iron were prepared by induction melting, extruding at 1000" C. into rods, hotpress-forging the rods into sheet, hot-rolling, and cold rolling the sheet to a thickness of 0.76 millimeter. Specimens were tested for oxidation resistance by heating in air at temperatures of 450, 650, 750, 900, 1100, and 1300o C. for 1000 hours. One set of specimens was tested in the cold-rolled condition and another set was annealed at 1000 C. prior to testing. All of the specimens maintained their integrity in these tests, with an adherent oxide coating being formed on the surface.
  • Example IV TABLE II.-OXIDATION TESTING OF ALLOY SPECIMENS Centuneter Alloy Composition (weight percent) Test Temperature, Test Temperature,
  • An alloy of iron, chromium, .aluminum and yttrium which consists of 0 to 15 Weight percent chromium, 0.5 to 12 weight percent aluminum, 0.1 to 3 percent yttrium and the balance iron.
  • An alloy of iron, chromium, aluminum and yttrium which Iconsists of 5 to 15 weight percent chromium, 0.5 to 12 Weight percent aluminum, 0.1 to 3 percent yttrium and the balance iron.
  • An alloy consisting of 0.5 to 12 weight ⁇ percent aluminum, 0.1 to 3.0 Weight percent yttrium and the balance iron.

Description

Jan. 17, 1967 c. s.wuKUslcK 3,298,826
EMBRITTLEMENT-RES ISTANT IRON- GHROMIUM-ALUMINUM-YTTRIUM ALLOYS Filed April 6, 1964 lCarl S. Wukusick ATTORNEY.
United States Patent O Atomic Energy Commission Filed Apr. 6, 1964, Ser. No. 357,845 4 Claims. (Cl. 75--124) This invention relates to oxidation-resistant all-oys and more particularly to alloys of iron, chromium, aluminum and yttrium.
Alloys of iron, chromium, aluminum and yttrium were originally developed for their oxidation resistance in air at temperatures over 2000 F. As described in U.S. Patent 3,027,252, issued March 27, 1962, to James A. McGurty and lohn F. Collins, the useful range of compositions for these alloys was as follows: 20.0 to 95.0 weight percent chromium, 0.5 to 4.0 weight percent aluminum, 0.5 to 3.0 weight percent yttrium and the balance iron.
These alloys have also been found highly resistant to oxidation :and corrosion by superheated steam and thus potentially useful in solving a critical problem in nuclear reactor technol-ogy. One of the most 4promising approaches for obtaining increased efficiency in the generation of power by nuclear reactors is the use of a superheated steam system wherein superheating is effected by direct passage of steam through the reactor core. Development of this type reactor has been hampered by the lack of suitable fuel-element cladding and structural materials. Stainless steels and other metals which have been employed for conventional superheated-steam equipment such as turbines are unsatisfactory for prolonged use in a nuclear reactor superheated steam environment. Oxidation and corrosion of these metals are accelerated by the presence of free oxygen produced by radiolytic decomposition of water. In addition, neutron economy imposes a severe limitation on cladding thickness so that better resistance is required than for conventional applications.
While satisfactory with regar-d t-o oxidation and corrosion by superheated steam, the above-described ironchromium-aluminum-yttrium alloys are defective in that their mechanical properties are adversely affected by holding .at the temperatures encountered in superheated-steam react-or service. These alloys become severely hardened and embrittled within several hours at` temperatures of about 650 to 1000 F., and prolonged holding at temperatures from 1000 to 1300 F. may also result in embrittlement. Typical superheated steam nuclear reactor systems require :an operating steam temperature of about 900 to 1050 F. an-d a fuel element temperature up to about 125 0 F. The high probability of embrittlement and mechanical failure thus precludes use of existing ironchromium-aluminum-yttrium alloys in such systems. It is desired to eliminate or minimize the embrittlement characteristic of these alloys while retaining their resistance to oxidation and corrosion.
It is therefore an object of my invention t provide an alloy suitable for use in contact with superheated-steam in nuclear reactors.
Another object is to provide an iron-chromium-aluminum-yttrium alloy which is resistant to embrittlement at temperatures 0f 650 to 1300 F.
Another object is to provide an embrittlement-resistant ironchromium-aluminum-yttrium alloy which retains a high degree of resistance to -oxidation and corrosion.
Other objects and advantages of my invention will be apparent from the following detailed description and claims.
"ice
In accordance with my invention a novel alloy having the following composition is provided: 0 to 20 weight percent chromium, 0.5 to 12 weight percent aluminum, 0.1 to 3.0 weight percent yttrium and the balance iron. This alloy is less susceptible to embrittlement than previously known iron-chromium-aluminum-yttrium alloys, but it exhibits substantially the same superior resistance to oxidation and corrosion.
I have found that embrittlement of iron-chromiumaluminum-yttrium .alloys is avoided by reducing the chromium content of a level below the previous minimum. Although my invention is not to be understood as limited to 4a particular theory, it is postulated that embrittlement below 550 C. is caused by precipitation of a chromiumrich ferrite phase and above 550 C. by precipitation of an iron-chromium sigma phase and that precipitation of these phases is significantly lessened in the temperature range of interest at chromium levels below 20 weight percent. l have also found that yttrium renders ironchromium-.aluminum alloys resistant to oxidation over a wider range of compositions than was previously believed effective. Oxidation resistance is maintained at low levels of chromium, and even in chromium-free alloys.
Chromium is provided in the alloy .at a level of 0 to 20 weight percent. At higher levels the alloy is subject to embrittlement as described above. An intermediate level of 5 to 15 weight percent chromium is preferred in order to retain to the maximum extent the favorable properties of the previous iron-chromium-aluminum-yttrium alloys, while avoiding embrittlement.
An aluminum content of at least 0.5 weight percent is required for oxidation resistance, and above 12 weight percent aluminum the alloy becomes embrittled. At the preferred chromium content an aluminum content of 4 to 6 weight percent is preferred for maximum workability and oxidation resistance. For chromium-free alloys an aluminum content of 5 to 7.5 weight percent is preferred.
The yttrium content of the alloy may be varied from 0.1 to 3.0 weight percent. At lower levels the alloy loses its oxidation resistance and at higher levels an excessive amount of second phase limits fabricability. About 1 weight percent is preferred.
The alloy composition disclosed and claimed herein may be fabricated into usable shapes by means of conventional -techniques such as extrusion, rolling and drawing.
My invention is further illustrated by the following examples.
Example I Alloy specimens of the weight composition iron-25 percent chromium-4 percent aluminum-1 percent yttrium and iron-15 percent chromium-4 percent aluminum-1 percent yttrium were prepared in 6.3 millimeter diameter rod form by swaging of extruded rods. The specimens were heated in air at a temperature of 450 C. for a period of over 200 hours. Hardness of the specimens was measured periodically throughout the heating period. The results obtained may be seen by reference to the accompanying figure wherein hardness is plotted as a function of time at temperature. The hardness of the 25 percent chromium specimen showed a significant increase while the 15 ipercent chromium specimen was increased only slightly.
Example Il Alloy specimens of the composition given in Example I were tested by'exposure to superheated steam :at 730 C. and 1150 C. The results obtained may be seen by reference to the following table.
It may be seen from the above that the superheatedsteam corrosion resistance of the percent chromium alloy is similar to the resistance of the percent chromium alloy.
Example III Alloy specimens of the composition iron-15 weight percent chromium-4 weight percent aluminum-1 Weight percent yttrium .and the balance iron were prepared by induction melting, extruding at 1000" C. into rods, hotpress-forging the rods into sheet, hot-rolling, and cold rolling the sheet to a thickness of 0.76 millimeter. Specimens were tested for oxidation resistance by heating in air at temperatures of 450, 650, 750, 900, 1100, and 1300o C. for 1000 hours. One set of specimens was tested in the cold-rolled condition and another set was annealed at 1000 C. prior to testing. All of the specimens maintained their integrity in these tests, with an adherent oxide coating being formed on the surface.
Example IV TABLE II.-OXIDATION TESTING OF ALLOY SPECIMENS Centuneter Alloy Composition (weight percent) Test Temperature, Test Temperature,
C, 200 hours C, 500 hours Fe-l() Cr-4 Al 09 0 .11 .15 (l) (2) 11e-10 Cr-4 Al-l Y 18 0 03 13 96 (3) Fe-5 Cr-6 .Al-1 Y 1l 02 09 15 93 4. 5 Fe-7.5 Al-l Y. 07 .21 05 .30 98 4. 9 1re-25 (Jr-4 Ar-i Y .01 01 .01 .1G 1. 5 3. 7 50 It may be seen from the above that a range of alloy compositions exhibit excellent oxidation resistance when stabilized by the presence of yttrium. The specimen without yttrium failed at 1100 C. and above. Substantially the same results were -obtained for the chromium-free alloy as for the chromium-containing alloys, thus demonstrating that chromium is not critical to oxidation resistance.
The above examples are merely illustrative and are not to be understood as limiting the scope of my invention, which is limited only as indicated by the appended claims.
Having thus described my invention, I claim:
1. An alloy of iron, chromium, .aluminum and yttrium which consists of 0 to 15 Weight percent chromium, 0.5 to 12 weight percent aluminum, 0.1 to 3 percent yttrium and the balance iron.
2. An alloy of iron, chromium, aluminum and yttrium which Iconsists of 5 to 15 weight percent chromium, 0.5 to 12 Weight percent aluminum, 0.1 to 3 percent yttrium and the balance iron.
3. An alloy resistant to embrittlement in service at a temperature of 650 F. to 1300 F., said .alloy consisting of 5 to 15 Weight percent chromium, 4 to 6 weight percent aluminum, 0.1 to 3 Weight percent yttrium and the balance iron.
4. An alloy consisting of 0.5 to 12 weight `percent aluminum, 0.1 to 3.0 Weight percent yttrium and the balance iron.
References Cited by the Examiner UNITED STATES PATENTS 2,043,631 6/1936 Scheil 75--124 2,061,370 11/1936 Rohn 75-124 2,105,283 l/1938 Godecke --124 2,190,486 2/ 1940 Schafmeister 75-128 2,191,790 2/1940 Franks 75-124 X 3,027,252 3/1962 McGurty 75-126 DAVID L. RECK, Primary Examiner.
P. WEINSTEIN, Assistant Examinez'.

Claims (1)

1. AN ALLOY OF IRON, CHROMIUM, ALUMINUM AND YTTRIUM WHICH CONSISTS OF 0 TO 15 WEIGHT PRCENT CHROMIUM, 0.5 TO 12 WEIGHT PERCENT ALUMINUM, 0.1 TO 3 PERCENT YTTRIUM AND THE BALANCE IRON.
US357845A 1964-04-06 1964-04-06 Embrittlement-resistant iron-chromium-aluminum-yttrium alloys Expired - Lifetime US3298826A (en)

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US357845A US3298826A (en) 1964-04-06 1964-04-06 Embrittlement-resistant iron-chromium-aluminum-yttrium alloys
GB5802/65A GB1045993A (en) 1964-04-06 1965-02-10 Embrittlement-resistant iron-aluminum-yttrium alloys
DE19651558670 DE1558670A1 (en) 1964-04-06 1965-03-17 Corrosion and rust-resistant alloy
DEU11533A DE1258110B (en) 1964-04-06 1965-03-17 Use of an oxidation-resistant, non-brittle iron alloy as a material for components in superheated steam systems
FR11947A FR1429100A (en) 1964-04-06 1965-04-05 Brittle resistant iron-chromium-aluminum-yttrium alloys
BE662120D BE662120A (en) 1964-04-06 1965-04-06

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419705A (en) * 1966-10-07 1968-12-31 Gen Electric Heater filament for an electrical cigarette lighter
US3542530A (en) * 1968-05-23 1970-11-24 United Aircraft Corp Nickel or cobalt base with a coating containing iron chromium and aluminum
US3800631A (en) * 1972-05-11 1974-04-02 Gen Electric Fe Al Cr Y Co ALLOY
DE2829373A1 (en) * 1977-07-05 1979-01-18 Johnson Matthey Co Ltd OXIDATION RESISTANT ALLOY AND METHOD FOR PRODUCING IT
US4230489A (en) * 1978-04-28 1980-10-28 United Kingdom Atomic Energy Authority Alloys of Fe, Cr, Si, Y and Al
US4277374A (en) * 1980-01-28 1981-07-07 Allegheny Ludlum Steel Corporation Ferritic stainless steel substrate for catalytic system
EP0033203A2 (en) * 1980-01-28 1981-08-05 Allegheny Ludlum Steel Corporation Substrate for catalytic system and ferritic stainless steel from which it is formed
EP0034133A1 (en) * 1980-02-06 1981-08-19 Bulten-Kanthal AB Electrical heating element
EP0036938A2 (en) * 1980-03-21 1981-10-07 Hoechst Aktiengesellschaft Process for the preparation and use of a catalyst carrier
US4334923A (en) * 1980-02-20 1982-06-15 Ford Motor Company Oxidation resistant steel alloy
US4414023A (en) * 1982-04-12 1983-11-08 Allegheny Ludlum Steel Corporation Iron-chromium-aluminum alloy and article and method therefor
US4661169A (en) * 1982-04-12 1987-04-28 Allegheny Ludlum Corporation Producing an iron-chromium-aluminum alloy with an adherent textured aluminum oxide surface
EP0236823A2 (en) * 1986-03-01 1987-09-16 Thyssen Aktiengesellschaft vorm. August Thyssen-Hütte Metallic semi-finished product, process for its manufacture and uses of the semi-finished product
US4870046A (en) * 1987-04-24 1989-09-26 Nippon Steel Corporation Rolled high aluminum stainless steel foil for use as a substrate for a catalyst carrier
US4999158A (en) * 1986-12-03 1991-03-12 Chrysler Corporation Oxidation resistant iron base alloy compositions
US5578265A (en) * 1992-09-08 1996-11-26 Sandvik Ab Ferritic stainless steel alloy for use as catalytic converter material
US6436163B1 (en) * 1994-05-23 2002-08-20 Pall Corporation Metal filter for high temperature applications
US6607576B1 (en) * 1994-12-29 2003-08-19 Chrysalis Technologies Incorporated Oxidation, carburization and/or sulfidation resistant iron aluminide alloy
CN102693793A (en) * 2012-06-04 2012-09-26 惠州市富济电子材料有限公司 Heating resistant material, ceramic heating component provided with same, and preparing and application

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2082631A (en) * 1980-02-28 1982-03-10 Firth Brown Ltd Ferritic iron-aluminium-chromium alloys
DE19753876A1 (en) * 1997-12-05 1999-06-10 Asea Brown Boveri Iron aluminide coating and method of applying an iron aluminide coating

Citations (6)

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US2043631A (en) * 1930-11-29 1936-06-09 Vereinigte Stahlwerke Ag Chromium-aluminium steel adapted to be used for articles exposed to high temperatures
US2061370A (en) * 1934-01-18 1936-11-17 Rohn Wilhelm Heat resisting article
US2105283A (en) * 1935-08-09 1938-01-11 Degea Ag Heat resistant alloys
US2190486A (en) * 1930-07-21 1940-02-13 Krupp Nirosta Co Inc Austenitic chromium nickel steel alloy
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
US3027252A (en) * 1959-09-29 1962-03-27 Gen Electric Oxidation resistant iron-chromium alloy

Family Cites Families (2)

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US3017265A (en) * 1959-09-25 1962-01-16 Gen Electric Oxidation resistant iron-chromium alloy
US3031297A (en) * 1959-11-03 1962-04-24 Gen Electric Oxidation resistant alloy

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2190486A (en) * 1930-07-21 1940-02-13 Krupp Nirosta Co Inc Austenitic chromium nickel steel alloy
US2043631A (en) * 1930-11-29 1936-06-09 Vereinigte Stahlwerke Ag Chromium-aluminium steel adapted to be used for articles exposed to high temperatures
US2061370A (en) * 1934-01-18 1936-11-17 Rohn Wilhelm Heat resisting article
US2105283A (en) * 1935-08-09 1938-01-11 Degea Ag Heat resistant alloys
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
US3027252A (en) * 1959-09-29 1962-03-27 Gen Electric Oxidation resistant iron-chromium alloy

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419705A (en) * 1966-10-07 1968-12-31 Gen Electric Heater filament for an electrical cigarette lighter
US3542530A (en) * 1968-05-23 1970-11-24 United Aircraft Corp Nickel or cobalt base with a coating containing iron chromium and aluminum
US3800631A (en) * 1972-05-11 1974-04-02 Gen Electric Fe Al Cr Y Co ALLOY
DE2829373A1 (en) * 1977-07-05 1979-01-18 Johnson Matthey Co Ltd OXIDATION RESISTANT ALLOY AND METHOD FOR PRODUCING IT
US4230489A (en) * 1978-04-28 1980-10-28 United Kingdom Atomic Energy Authority Alloys of Fe, Cr, Si, Y and Al
US4277374A (en) * 1980-01-28 1981-07-07 Allegheny Ludlum Steel Corporation Ferritic stainless steel substrate for catalytic system
EP0033203A2 (en) * 1980-01-28 1981-08-05 Allegheny Ludlum Steel Corporation Substrate for catalytic system and ferritic stainless steel from which it is formed
EP0033203A3 (en) * 1980-01-28 1981-08-26 Allegheny Ludlum Steel Corporation Substrate for catalytic system and ferritic stainless steel from which it is formed
US4376245A (en) * 1980-02-06 1983-03-08 Bulten-Kanthal Ab Electrical heating element
EP0034133A1 (en) * 1980-02-06 1981-08-19 Bulten-Kanthal AB Electrical heating element
US4334923A (en) * 1980-02-20 1982-06-15 Ford Motor Company Oxidation resistant steel alloy
EP0036938B1 (en) * 1980-03-21 1983-06-29 Hoechst Aktiengesellschaft Process for the preparation and use of a catalyst carrier
EP0036938A2 (en) * 1980-03-21 1981-10-07 Hoechst Aktiengesellschaft Process for the preparation and use of a catalyst carrier
US4414023A (en) * 1982-04-12 1983-11-08 Allegheny Ludlum Steel Corporation Iron-chromium-aluminum alloy and article and method therefor
US4661169A (en) * 1982-04-12 1987-04-28 Allegheny Ludlum Corporation Producing an iron-chromium-aluminum alloy with an adherent textured aluminum oxide surface
EP0236823A2 (en) * 1986-03-01 1987-09-16 Thyssen Aktiengesellschaft vorm. August Thyssen-Hütte Metallic semi-finished product, process for its manufacture and uses of the semi-finished product
EP0236823A3 (en) * 1986-03-01 1988-05-25 Thyssen Aktiengesellschaft Vorm. August Thyssen-Hutte Metallic semi-finished product, process for its manufacture and uses of the semi-finished product
US4999158A (en) * 1986-12-03 1991-03-12 Chrysler Corporation Oxidation resistant iron base alloy compositions
US4870046A (en) * 1987-04-24 1989-09-26 Nippon Steel Corporation Rolled high aluminum stainless steel foil for use as a substrate for a catalyst carrier
US5578265A (en) * 1992-09-08 1996-11-26 Sandvik Ab Ferritic stainless steel alloy for use as catalytic converter material
US6436163B1 (en) * 1994-05-23 2002-08-20 Pall Corporation Metal filter for high temperature applications
US6607576B1 (en) * 1994-12-29 2003-08-19 Chrysalis Technologies Incorporated Oxidation, carburization and/or sulfidation resistant iron aluminide alloy
CN102693793A (en) * 2012-06-04 2012-09-26 惠州市富济电子材料有限公司 Heating resistant material, ceramic heating component provided with same, and preparing and application
CN102693793B (en) * 2012-06-04 2014-11-19 惠州市富济电子材料有限公司 Heating resistant material, ceramic heating component provided with same, and preparing and application

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DE1258110B (en) 1968-01-04
DE1558670A1 (en) 1970-04-23
BE662120A (en) 1965-08-02

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