EP0570072A2 - Procédé d'obtention d'un alliage à base de chrome - Google Patents
Procédé d'obtention d'un alliage à base de chrome Download PDFInfo
- Publication number
- EP0570072A2 EP0570072A2 EP93201342A EP93201342A EP0570072A2 EP 0570072 A2 EP0570072 A2 EP 0570072A2 EP 93201342 A EP93201342 A EP 93201342A EP 93201342 A EP93201342 A EP 93201342A EP 0570072 A2 EP0570072 A2 EP 0570072A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- chromium
- based alloy
- alloy
- alloy according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
- B22F2201/013—Hydrogen
Definitions
- the invention relates to a chromium-based alloy.
- a major disadvantage of pure chromium is the brittleness of the material, which usually begins at around 400 ° C., depending on the shaping, so that the use of the material in practice is often only possible due to increased manufacturing and construction costs.
- DE-OS 16 08 116 describes a chromium alloy which contains up to 45% by weight of iron and / or nickel and / or cobalt and up to a total of 5% by weight of Al, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Y and rare earths and up to 1% by weight of C, N, B and Si.
- the alloying of iron in particular, but also of nickel and cobalt is said Oxidation and corrosion resistance increased and the deformability at low temperatures can be improved.
- the addition of Al, Ti, Zr, Hf, V, Nb, Ta as well as Y and rare earths is said to significantly reduce the ductile-brittle transition temperature. In fact, the transition temperature of this alloy is still too ductile-brittle, so that this alloy has no practical significance.
- DE-OS 21 05 750 relates to a cast body made of a chromium-based alloy, which consists of a single crystal or of directed crystals.
- the alloy preferably contains 5-50% by weight of iron and / or cobalt and / or nickel and 1-25% by weight of niobium and / or tantalum and / or molybdenum and / or tungsten and / or rhenium and up to 2% by weight.
- Y and / or rare earths and / or aluminum as well as up to 1% by weight boron and / or carbon and / or nitrogen and / or silicon in conjunction with additives on metals which form boride, carbide, nitride or silicide.
- This prior publication also describes that this alloy in the monocrystalline state enables a transition temperature which was at that time reduced by several 100 ° C. in a ductile, brittle manner and a relatively high impact strength at room temperature.
- this alloy no information can be found in the previous publication.
- the main disadvantage of this alloy is that it is no longer mechanically formable as a cast alloy, so that not all workpieces can be produced in any dimensions. In particular, the production of semi-finished products, such as sheets, rods and wire, is not possible.
- US 3 591 362, US 3 874 938 and DE-AS 23 03 802 generally describe dispersion-strengthened metal alloys which can contain up to 25% by volume of a dispersoid, including oxides of rare earth metals. Chromium contents of the alloy of up to 65% by weight are described in the claims. From the examples and the description, however, it appears that the invention is primarily based on alloys with a significantly lower chromium content, in particular is aimed at ODS superalloys with a chromium content between approximately 10 and 20% by weight. US 3 909 309 describes a method for improving the flexural strength in ODS superalloys. Chromium contents of up to 65% by weight are mentioned in a subclaim.
- ODS superalloys are primarily used in hot gas turbine construction, where good corrosion resistance to vanadium pentoxide is not so important.
- the dispersoids are primarily added to increase the strength properties of the alloy.
- US Pat. No. 3,841,847 shows a chromium-based alloy with at least 70% by weight of chromium, which in addition to yttrium, aluminum and silicon can also contain up to 18% by weight of yttrium oxide. With this alloy too, the transition temperature is ductile and brittle, so that the production of semi-finished products and parts by forming processes is problematic.
- the object of the present invention is to provide a chromium-based alloy which has good corrosion resistance, in particular to combustion gases and non-volatile combustion residues of fossil fuels, and which at the same time has a ductile-brittle transition temperature which is sufficiently low for forming processes and good heat resistance properties .
- a chromium-based alloy with a chromium content of more than 65% by weight which in addition to the usual impurities consists of 0.005-5% by weight of one or more rare earth oxides and 0.1 to 32% by weight of one or more Metals from the group iron, nickel and cobalt.
- rare earth oxides are known for various alloys to increase the heat resistance through dispersion strength.
- yttrium oxide and / or lanthanum oxide as oxides of the rare earths with a proportion of 0.5 to 2% by weight and of iron and nickel with a proportion of 5 to 25% by weight has proven particularly advantageous.
- the alloy according to the invention is particularly suitable as a material for stationary but also moving parts in all systems in which temperatures of about 800 to over 1200 o C occur and in which contact with gases and residues from the combustion, in particular fossil fuels and pure or polluted air.
- the alloy has a high heat resistance and a high recrystallization temperature as well as a coefficient of thermal expansion which, compared to known chrome alloys, is much better adapted to other high-temperature materials, such as ceramics, which further increases the area of application of the alloy according to the invention expanded.
- the optional addition of up to 30% by weight of one or more metals from the group aluminum, titanium, zirconium and hafnium primarily improves the oxidation resistance of the alloy.
- Aluminum and / or titanium and / or zircon with a proportion of 3 to 10% by weight have been found to be particularly suitable.
- the optional addition of up to 10% by weight of one or more metals from the group vanadium, niobium, molybdenum, tantalum, tungsten and rhenium increases the dimensional stability at high temperatures in components made from the alloy according to the invention, which is particularly long when it occurs Continuous stresses that act on the components is important.
- the light and ductile metals vanadium and niobium are preferred.
- the addition of the refractory metals tungsten and rhenium can reduce the oxidation resistance of the alloy, which is why they are advantageously used only in relatively small amounts.
- Vanadium, niobium and molybdenum individually or in combination with a total content of 3 to 8% by weight, have proven to be particularly advantageous.
- the mixture of the starting powder is pressed to a minimum compression density of 65% and the compact is sintered at a sintering temperature between 1500 and 1600 o C under an H2 atmosphere for 15-20 hours.
- the sintered plates were cut into steel sheet with a thickness of 2 mm on all sides.
- the forged plates were forged by 35% and cooled from the forging end temperature in the furnace to room temperature within 12 hours.
- the plates were rolled into sheets of 4.5 mm thickness and cooled from the final roll temperature in the furnace to room temperature within 12 hours.
- the sheets were heated to 1250 o C and rolled to a thickness of 2 mm and the edges trimmed.
- the sheets were again heated to 1250 ° C. and annealed at this temperature for one hour.
- the sheets were 1.3 mm thick finish rolled and then subjected to final annealing at 1600 o C for one hour.
- samples with the dimensions 100 mm ⁇ 100 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm.
- the alloys according to the invention have a corrosion resistance which is improved by a factor of 2 compared to pure chromium.
- samples with the dimensions 20 mm ⁇ 30 mm were cut from the sheets produced according to the production example. The samples were then ground on both sides to remove the surface steel layers to a final thickness of 1 mm. After weighing, the samples were oxidized in air once at a temperature of 1000 ° C. and once at a temperature of 1200 ° C. over a period of 7 days. At 1000 o C a well adhering oxide layer formed on the samples, so that the average Weight gain of the samples was used as a measure of the oxidation resistance.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Materials For Medical Uses (AREA)
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT981/92 | 1992-05-14 | ||
AT0098192A AT399165B (de) | 1992-05-14 | 1992-05-14 | Legierung auf chrombasis |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0570072A2 true EP0570072A2 (fr) | 1993-11-18 |
EP0570072A3 EP0570072A3 (fr) | 1994-01-12 |
EP0570072B1 EP0570072B1 (fr) | 1996-07-31 |
Family
ID=3504219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93201342A Expired - Lifetime EP0570072B1 (fr) | 1992-05-14 | 1993-05-10 | Procédé d'obtention d'un alliage à base de chrome |
Country Status (7)
Country | Link |
---|---|
US (1) | US5608174A (fr) |
EP (1) | EP0570072B1 (fr) |
JP (1) | JPH0633180A (fr) |
AT (2) | AT399165B (fr) |
AU (1) | AU681577B2 (fr) |
DE (1) | DE59303350D1 (fr) |
ES (1) | ES2090843T3 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19546614A1 (de) * | 1995-12-13 | 1997-06-19 | Forschungszentrum Juelich Gmbh | Oxidationsbeständige, chromoxidbildende Legierung |
DE10340132B4 (de) * | 2003-08-28 | 2010-07-29 | Eads Deutschland Gmbh | Oxidationsbeständige, duktile CrRe-Legierung, insbesondere für Hochtemperaturanwendungen, sowie entsprechender CrRe-Werkstoff |
EP2230707A1 (fr) | 2009-03-12 | 2010-09-22 | Plansee Se | Inter-connecteur d'une cellule de combustible à haute température dotée d'un électrolyte solide |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT4737U1 (de) * | 2001-01-15 | 2001-11-26 | Plansee Ag | Pulvermetallurgisches verfahren zur herstellung hochdichter formteile |
US6692586B2 (en) | 2001-05-23 | 2004-02-17 | Rolls-Royce Corporation | High temperature melting braze materials for bonding niobium based alloys |
US20090068055A1 (en) * | 2007-09-07 | 2009-03-12 | Bloom Energy Corporation | Processing of powders of a refractory metal based alloy for high densification |
DE102013214464A1 (de) * | 2013-07-24 | 2015-01-29 | Johannes Eyl | Verfahren zum Herstellen einer chromhaltigen Legierung und chromhaltige Legierung |
CN104419858A (zh) * | 2013-08-20 | 2015-03-18 | 东睦新材料集团股份有限公司 | 一种铬基合金及其制造方法 |
CN104419856A (zh) * | 2013-08-20 | 2015-03-18 | 东睦新材料集团股份有限公司 | 一种铬基合金及其制造方法 |
CN104419857A (zh) * | 2013-08-20 | 2015-03-18 | 东睦新材料集团股份有限公司 | 一种铬基合金及其制造方法 |
KR101691916B1 (ko) * | 2014-10-20 | 2017-01-04 | 한국원자력연구원 | 내식성이 우수한 크롬-알루미늄 이원계 합금 및 이의 제조방법 |
CN113430398B (zh) * | 2021-05-17 | 2022-11-01 | 攀钢集团攀枝花钢铁研究院有限公司 | 一种含有钒元素的JCr98级金属铬及其制备方法 |
CN114032349B (zh) * | 2021-11-17 | 2022-08-12 | 齐鲁工业大学 | 一种高铬铸铁用变质剂及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2105750C3 (de) * | 1971-02-08 | 1975-04-24 | Battelle-Institut E.V., 6000 Frankfurt | Verwendung einer Chrombasislegierung zur Herstellung von Feingußoder FormguBkörhern |
JPH02258946A (ja) * | 1989-03-30 | 1990-10-19 | Kubota Ltd | 複合焼結合金、耐熱部材および加熱炉内鋼材支持部材 |
EP0299027B1 (fr) * | 1987-01-28 | 1991-10-02 | Metallwerk Plansee Gesellschaft M.B.H. | Alliage de metaux refractaires resistant au fluage et son procede de production |
EP0510495A1 (fr) * | 1991-04-26 | 1992-10-28 | Kubota Corporation | Alliage fritté résistant à la chaleur, renforcé par dispersion d'oxydes |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3017265A (en) * | 1959-09-25 | 1962-01-16 | Gen Electric | Oxidation resistant iron-chromium alloy |
US3027252A (en) * | 1959-09-29 | 1962-03-27 | Gen Electric | Oxidation resistant iron-chromium alloy |
US3174853A (en) * | 1962-03-15 | 1965-03-23 | Gen Electric | Chromium base alloys |
US3138457A (en) * | 1963-02-11 | 1964-06-23 | Commw Of Australia | Chromium-tungsten-tantalum alloys |
US3227548A (en) * | 1963-02-18 | 1966-01-04 | Gen Electric | Chromium base alloy |
US3347667A (en) * | 1964-05-21 | 1967-10-17 | Gen Electric | Chromium base alloy |
DE1608116A1 (de) * | 1967-12-14 | 1970-12-10 | Schmid Geb Reiniger Dipl Ing S | Legierungen auf Chrombasis fuer Elektroden,insbesondere Zuendkerzenelektroden |
US3591362A (en) * | 1968-03-01 | 1971-07-06 | Int Nickel Co | Composite metal powder |
US3787202A (en) * | 1970-11-18 | 1974-01-22 | Cyclops Corp | High temperature chromium-nickel alloy |
US3874938A (en) * | 1971-04-06 | 1975-04-01 | Int Nickel Co | Hot working of dispersion-strengthened heat resistant alloys and the product thereof |
DE2221220C3 (de) * | 1971-05-12 | 1974-01-17 | Gebrueder Sulzer Ag, Winterthur (Schweiz) | Verwendung einer Chrom-Basis-Legierung als Kokillenwerkstoff |
BE794801A (fr) * | 1972-01-31 | 1973-07-31 | Int Nickel Ltd | Procede de recuit en zones d'alliages |
US3999985A (en) * | 1972-09-15 | 1976-12-28 | The British Non-Ferrous Metals Research Association | Chromium alloys |
US3841847A (en) * | 1972-09-15 | 1974-10-15 | British Non Ferrous Metals Res | Chromium alloys containing y{11 o{11 {11 and aluminium or silicon or both |
US3909309A (en) * | 1973-09-11 | 1975-09-30 | Int Nickel Co | Post working of mechanically alloyed products |
JPS5855502A (ja) * | 1981-09-28 | 1983-04-01 | Toyo Soda Mfg Co Ltd | 金属クロム板の製造法 |
US5126106A (en) * | 1990-05-22 | 1992-06-30 | Tosoh Corporation | Chromium-based weld material and rolled article and process for producing the rolled article |
-
1992
- 1992-05-14 AT AT0098192A patent/AT399165B/de not_active IP Right Cessation
-
1993
- 1993-05-10 AT AT93201342T patent/ATE140981T1/de active
- 1993-05-10 EP EP93201342A patent/EP0570072B1/fr not_active Expired - Lifetime
- 1993-05-10 ES ES93201342T patent/ES2090843T3/es not_active Expired - Lifetime
- 1993-05-10 DE DE59303350T patent/DE59303350D1/de not_active Expired - Lifetime
- 1993-05-12 JP JP5133829A patent/JPH0633180A/ja active Pending
- 1993-05-13 AU AU38643/93A patent/AU681577B2/en not_active Expired
-
1995
- 1995-05-15 US US08/440,693 patent/US5608174A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2105750C3 (de) * | 1971-02-08 | 1975-04-24 | Battelle-Institut E.V., 6000 Frankfurt | Verwendung einer Chrombasislegierung zur Herstellung von Feingußoder FormguBkörhern |
EP0299027B1 (fr) * | 1987-01-28 | 1991-10-02 | Metallwerk Plansee Gesellschaft M.B.H. | Alliage de metaux refractaires resistant au fluage et son procede de production |
JPH02258946A (ja) * | 1989-03-30 | 1990-10-19 | Kubota Ltd | 複合焼結合金、耐熱部材および加熱炉内鋼材支持部材 |
EP0510495A1 (fr) * | 1991-04-26 | 1992-10-28 | Kubota Corporation | Alliage fritté résistant à la chaleur, renforcé par dispersion d'oxydes |
Non-Patent Citations (2)
Title |
---|
Week 9048, Derwent Publications Ltd., London, GB; AN 90-358316 & JP-A-2 258 946 (KUBOTA CORPORATION) 19. Oktober 1990 * |
Week 9048, Derwent Publications Ltd., London, GB; AN 90-358316 & JP-A-2 258 946 (KUBOTA CORPORATION) 19.Oktober 1990 * Zusammenfassung* * Beispiel 2 * * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19546614A1 (de) * | 1995-12-13 | 1997-06-19 | Forschungszentrum Juelich Gmbh | Oxidationsbeständige, chromoxidbildende Legierung |
DE19546614C2 (de) * | 1995-12-13 | 1998-12-17 | Forschungszentrum Juelich Gmbh | Oxidationsbeständige, chromoxidbildende Legierung |
DE10340132B4 (de) * | 2003-08-28 | 2010-07-29 | Eads Deutschland Gmbh | Oxidationsbeständige, duktile CrRe-Legierung, insbesondere für Hochtemperaturanwendungen, sowie entsprechender CrRe-Werkstoff |
EP2230707A1 (fr) | 2009-03-12 | 2010-09-22 | Plansee Se | Inter-connecteur d'une cellule de combustible à haute température dotée d'un électrolyte solide |
US9029044B2 (en) | 2009-03-12 | 2015-05-12 | Plansee Se | Interconnector for a high-temperature solid electrolyte fuel cell, method of producing a fuel cell, and high-temperature solid electrolyte fuel cell |
Also Published As
Publication number | Publication date |
---|---|
EP0570072A3 (fr) | 1994-01-12 |
AU3864393A (en) | 1993-11-18 |
AU681577B2 (en) | 1997-09-04 |
JPH0633180A (ja) | 1994-02-08 |
EP0570072B1 (fr) | 1996-07-31 |
US5608174A (en) | 1997-03-04 |
ATE140981T1 (de) | 1996-08-15 |
ES2090843T3 (es) | 1996-10-16 |
ATA98192A (de) | 1994-08-15 |
AT399165B (de) | 1995-03-27 |
DE59303350D1 (de) | 1996-09-05 |
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