WO2000040359A1 - Metal-ceramic laminar-band composite - Google Patents
Metal-ceramic laminar-band composite Download PDFInfo
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- WO2000040359A1 WO2000040359A1 PCT/IL1999/000010 IL9900010W WO0040359A1 WO 2000040359 A1 WO2000040359 A1 WO 2000040359A1 IL 9900010 W IL9900010 W IL 9900010W WO 0040359 A1 WO0040359 A1 WO 0040359A1
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- component
- composite
- composite according
- multilayer
- chips
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Classifications
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- 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
- B22F3/002—Manufacture of articles essentially made from metallic fibres
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/062—Fibrous particles
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention relates to powder metallurgy and, in particular, to laminated metal-ceramic composite materials, which can be used for manufacture of some engineering parts of a high-temperature apparatus, specifically for thermal-protection linings, nozzles, combustion chambers, turbine blades and guide vanes of jet engines, crucibles, protection tubes of immersion thermometers for molten metals.
- the composites can be subdivided into the following groups: ⁇ Group 1 : Composites, keeping for a long time in oxidizing media at a temperature up to 1500 ⁇ 1800°C an enough strength, impact resistance, hardness.
- the most important applications of the composites include turbine blades, guide vanes and combustion chamber lining of jet engines;
- E Group 2 Composites, working at temperatures up to 2000°C and in a conditions of large thermal shocks, but are not exposed to serious mechanical loads.
- the most important applications of the composites include crucibles for high-temperature metals casting, protection tubes of immersion thermometers for molten metals;
- ⁇ Group 3 Composites, working at a temperature up to 2500 ⁇ 2800°C in abrasive and oxidative high-speed gas fluxes, at moderate mechanical loads, but in conditions of large heat flows and thermal shocks.
- the most important applications of the composites include nozzles, combustion chambers, turbopump parts, thermal protection plates.
- metal-ceramic composites which comprise a ceramic matrix and a powder or fibrous metallic inclusions.
- Thermal and crack endurance, fracture toughness of a such dispersion- or fibrous reinforced composites are insufficient for a majority of the above mentioned applications.
- the characteristic feature of the laminated composites is the braking of cracks on ceramic-metal interfaces: a crack, arising in ceramic layer, canceling at approach to metallic layer mainly because of the layer larger ductility.
- Composites of the subgroup have usually a good thermal shock resistance, high heat-insulating properties, but at the same time they have a number of typical drawbacks: limited interlay er adhesion and, as a consequence, lower mechanical properties, poor abrasion and wear resistance, and, as it must be especially noted, with such composites there is a problem of complex shape forming.
- this subgroup of metal-ceramic composites with a laminated structure are known also composites with so called laminar-granular structure, comprising randomly arranged cube-like multilayer granules (Figure lb) (for example: The composite HfC>2/Mo, J. Space/Aeron., 1965, v.43, No. 4, p.54).
- Substantially more complex parts can be manufactured from such composites, than from above mentioned multilayer composites, but there are a lot of different imperfections at interfaces of the multilayer granules, that results in reduction of strength, abrasion resistance and other mechanical properties
- the object of the present invention is to provide an isotropic metal- ceramic multi matrix composite, built from randomly interlaced multilayer curved band-like chips (Figure lc), with a high strength, thermal-shock and abrasion resistance and with other high physico-mechanical properties, which can be used at a temperature of 1500-2800°C, and the simple and available method of its manufacture, which allows the production of complicated shape articles.
- Figure lc randomly interlaced multilayer curved band-like chips
- the composite consists of the following components:
- ⁇ refractory oxide for example, such as alumina, yttria, zirconia or haf ia. This component is not obligatory for all versions of the composite;
- ⁇ an oxygen devoid compound, possessing increased high-temperature creep resistance, for example, zirconium carbide or hafnium carbide.
- This component is not obligatory for all versions of the composite; a ductile component of refractory metal, for example, molybdenum or tungsten metal.
- Every component of the novel composite is in the form of curved tapes with a thickness in the range of 5 ⁇ 200 microns, with a length in the range 25 150 thickness of the tape and with a width that is in the range of 5 50 thickness of the tape.
- the tapes form multilayer curved band-shaped chips, which are randomly interlaced, that provide the isotropic properties of the composite.
- the laminar-band structure has amongst others advantages, such as:
- the metallic tapes create, because of their plasticity, like in other multilayer structures with a metallic component, numerous barriers against cracks spreading and development, that provides a dramatic increase of a thermo- and crack-endurance;
- the novel composite has increased, as compared with other laminated composites of equal chemical composition, strength, fracture toughness, wear resistance, erosion resistance and oxidation resistance;
- novel composites are applicable in the three groups. In many situations the novel composites are probably the only solution of the problem of new high-temperature composites.
- the articles of Group 1 (see classification in the "Background of the Invention” section), such as nozzle guide vanes and turbine blades of gas turbine engines ( Figure 2), must keep for a long time a high strength, fracture toughness, chemical erosion resistance, thermal shock and oxidizing resistance, fatigue and creep resistance at a temperature up to 1300 ⁇ 1500°C.
- Group 1 composites can serve the novel composites, in which as an oxide component are used, for example, some compounds in the systems on the basis of AI2O3, Si ⁇ 2, Y2 ⁇ 3 > folty stabilized ZrC>2, which sintering temperature do not exceed 1400 ⁇ 1600°C, for example, it can be such a compound as 3Al2 ⁇ 3- 2Si ⁇ 2 (mullite), or a different compounds in such systems as Al2C>3-Ti ⁇ 2, or Zr ⁇ 2-Y2 ⁇ 3-Al2 ⁇ 3.
- an oxide component for example, some compounds in the systems on the basis of AI2O3, Si ⁇ 2, Y2 ⁇ 3 > folty stabilized ZrC>2, which sintering temperature do not exceed 1400 ⁇ 1600°C, for example, it can be such a compound as 3Al2 ⁇ 3- 2Si ⁇ 2 (mullite), or a different compounds in such systems as Al2C>3-Ti ⁇ 2, or Zr ⁇ 2-Y2 ⁇ 3-Al2 ⁇ 3.
- a ductile component of the Group 1 composites are used alloys, possessing a prolonged oxidizing resistance at a temperature of 1300 ⁇ 1500°C and compatibility with the oxide component as concern the sintering temperature.
- alloys possessing a prolonged oxidizing resistance at a temperature of 1300 ⁇ 1500°C and compatibility with the oxide component as concern the sintering temperature.
- Cr metal and its alloys there can be used Cr metal and its alloys, and also such alloy as NiAl-Cr and some other alloys on their basis.
- a very good example of the Group 1 composite is a
- the articles of Group 2 intended for work at temperatures up to 2000°C and at severe thermal shocks, but not at too large tensions (for example, such parts, as crucibles (figure 4), protection tubes of immersion thermometers (figure 3), heat resistant linings), can be manufactured from the novel composites, which contain as a metal component the refractory metals Nb, Mo, W and others, and as oxide component they contain the following refractory oxides: AI2O3, Y2C>3 > fully stabilized Zr ⁇ 2 or H1O2 and others.
- the novel composites are shown in Table 3 and Table 4.
- the Group 2 composites can serve protection tubes of immersion thermometers for liquid steel and its alloys, liquid copper and brass, and many other metals and their alloys, made from n(Al2 ⁇ 3+Ti ⁇ 2)/Mo the novel composites (figure 3).
- the protection tubes possess a very high resistance against erosion in slag, thermal shock resistance, small inertness, life time in liquid steel more than 3 ⁇ 5 hours, and provide continuous and precise temperature measurement.
- Such protection tube wall thickness can be, for example, from 2 to 5 mm.
- the articles of Group 3 must work at a temperatures up to 2500 2800°C in aggressive gas jets at large heat fluxes and thermal shocks (nozzles, combustion chambers (figure 5), etc.), must keep at the ultra high temperatures an enough strength, hardness and other mechanical properties, and simultaneously they must possess a high oxidizing and abrasion resistance.
- thermochemical influence of such aggressive gas jets must not cause appreciable mass loss, erosion, within a work time of 10 to 5000 seconds. These articles must withstand a large number of thermal shocks and be light weight because of their most frequent applications in a sufficiently light weight apparatus.
- Group 3 composites can serve the novel composites where as metallic component use refractory metals, for example, W, Mo, Ta and their alloys, melting temperatures of which are over 2500 3000°C, and as an oxide component are used the oxides with the highest refractoriness, in the first place fully stabilized Zr ⁇ 2, HfC » 2, Th ⁇ 2-
- metallic component use refractory metals, for example, W, Mo, Ta and their alloys, melting temperatures of which are over 2500 3000°C, and as an oxide component are used the oxides with the highest refractoriness, in the first place fully stabilized Zr ⁇ 2, HfC » 2, Th ⁇ 2-
- NbC, HfC, TaC NbC, HfC, TaC. These carbides and some compounds on their basis (see
- Table 5 are the only substances which keep strength and creep-resistance up to about 2500 3000°C. But since the carbides don't possess any plasticity and oxidizing resistance, their volume contents in the novel composites must be no more than 20 to 30%.
- the novel composites can be made jet engine nozzles, mainly non cooled, with a throat diameter of 1 to 200 mm which are of the most practical importance.
- Nozzles with a bigger throat diameter for instance, up to 500 to 800 mm, can be manufactured with use of a multi-part design approach only. It must be specially noted that such a multi-part design provides a substantial increase of a nozzle thermal endurance.
- the wall thickness of the nozzle throat inserts must not exceed 3 6 mm.
- the novel composites of the Group 3 are probably the only materials which possess simultaneously all of the characteristics.
- the Group 3 novel composites have an adjustable in a very wide range thermal conductivity, which is chosen according to permitted temperature on the internal (hot) and external surfaces of nozzle, and also depends on the needed local heat flux through the nozzle wall.
- the maximum work temperature on the internal (hot) surface of rocket nozzle can be reached by use of the novel composites, which comprise as a compound devoid of oxygen component post eutectic carbide-graphites in the systems ZrC-C, TaC-C, NbC-C or HfC-C and as metallic component the W with addition of up to 2 wt.% of TI1O2; for instance, the novel composites n(HfC-C)/W can be used. Beside of a very high work temperature and erosion resistance such composite possesses a high thermal endurance, that is typical for the post eutectic carbide-graphites.
- the invention can't be realized by using known methods of laminar and multilayer composite manufacture.
- the method of the novel composite article forming comprises the steps of providing oxide, metal and carbide powders possessing an average particle size 0.5 2.0 microns and a maximum agglomerated particles size of 10 microns. Then, by mixing of oxide, carbide and metallic powders with a corresponding film-forming binder is prepared a slurry from which are cast films with thickness 20+-300 microns.
- a film-forming binder it is preferable to use synthetic carboxilated butadiene-nitrile rubber. The synthetic rubber is added in slurry as a 5 16% solution in the benzine-acetone (1:1) mixture, in quantity 1 5 mas.% (in account on dry weight of the system: rubber + component of the composite).
- the cast films are cut to fixed length pieces, which then are collected into 2 5 mm thickness packets, consisting of alternatively ordered metal, carbide and oxide based films.
- the quantity of the same type films in every layer depend upon the films thickness and upon the desirable composition of the composite.
- the layers must have a minimum thickness to obtain the best quantity of interfaces.
- the film packets are subjected subsequently to densification in a roll mill, resulting in the reduction of their thickness to about 0.5 1 mm. This is done to reduce porosity, which take place in the ex-casted films.
- the films, which constitute these multilayer packets may have a thickness, after rolling, in the range of 5 50 microns.
- the film packets that were densified by the roll mill treatment, are packed, for instance, in spiral shape, into a steel cylindrical press die to form a multilayer cylindrical billet by uniaxial compaction.
- the compacted article is then heated in a vacuum or in an inert gas for removal of binder, in the temperature range from RT to 500°C with a temperature growth rate of l ⁇ lO °C/hour.
- the "brown" article is subjected to a preliminary sintering at a temperature in the range of 1150 ⁇ 1450°C until an article is reached of approximately 50+75% of theoretical density.
- the pre-sintered porous article is then densified to approximately
- a composite body of a comparatively simple shape, practically devoid of pores, can be produced by a Hot Pressing operation after the above described pressureless sintering.
- the ceramic article is subjected to Hot
- Tables 2 5 are represented physical-mechanical properties of some typical composites: Table 2 for Group 2 Composites nY2 ⁇ 3/Mo, Table 3 for some composites of Group 1 and Group 2, Table 4 and Table 5 for some composites of the Group 3.
- N Number of cold quenches 1000°C->20°C (water), until destruction.
- Table 2 are represented results of measurements of bending strength, heat conductivity, resistance to multiple quenching and oxidizing resistance for some variants of nY2 ⁇ 3/Mo composites.
- the composites with V ox :V me t ⁇ 1 do not possess a good high-temperature oxidizing resistance because of a considerable content of the metallic component.
- composite Y/2M and composite Y/3M already at heating in air up to 1400 ⁇ 1700°C occurs a degradation of surface within 1+2 hours, but they have a considerably increased abrasive resistance as compared with pure molybdenum.
- the composites of the type with a low metal content for instance the composite 7Y/M and composite 9Y/M have a low thermal endurance and thermal-shock resistance, that does not differ from the corresponding properties of pure Y2O3.
- the technology of the novel composite articles starts with the preparation of oxide, metal and carbide powders with an average particle size of 1 to 2 microns and a maximum agglomerated particle size of 10 microns.
- a grinding media which don't create a danger of powder contamination.
- a polyurethane or a rubber lined milling jar and grinding bodies from zirconia or yttria can be used.
- a contamination of the powder, in the process of its grinding, with traces of Fe, Ni and other elements, which are ground out from ajar wall material, are also permissible, because these elements, in most cases, are not high-melting and are easily evaporated during sintering.
- an average particle size has not to be less than 0.5 1 micron, as powder with elevated specific surface area requires a rise of quantity of binder for ensuring a necessary viscosity and cast properties of the slurry, that lead, ultimately, to an undesirably high shrinkage at sintering.
- the sintering conditions get worse, dwell temperature and/or dwell time, necessary for porosity reduction, are increased.
- oxide powders are dried at 400 ⁇ -800°C during 2 5 hours
- metallic and carbide powders are dried at 250 ⁇ 350°C during 2 5 hours.
- the powder After milling and drying, the powder is passed through a 400 mesh sieve to remove large agglomerates.
- an organic binder is added to the dry and de-agglomerated powders.
- a film forming binder can be used as many different substances.
- suitable synthetic butadiene-nitrile rubber The rubber is added in slip as the 5 16% solution (mas.%) of it in benzine-acetone (which are mixed in proportion from 1:1 to 4:3 volume parts) mixture in quantity 1 5 mas.% ( in account on dry weight of the system: rubber+powder).
- Such rubber binder has a number of advantages compared with well known binders (acrylic polymer, hydroxyethyl cellulose, polyurethane, polyvinyl butyral, etc.), and, in particular, has a good ductility that is necessary for making the, so called, complex-mass.
- a binder such as polyvinyl butyral permits to cast films of 20+40 microns thickness even more easily than the butadiene-nitrile rubber binder, but the polyvinyl butyral binder is uncomfortable for the laminated chips making by lathe machining: multilayer billets consisting of films, which were cast using polyvinyl butyral, show ease of cracking at lathe machining at room temperature and for prevention of the cracking it needs heating during the machining.
- Films with a thickness of less than 20 microns are difficult to make by usual methods of ceramic tape casting.
- films which were cast with a thickness of 50+100 microns.
- a thickness of the films are reducing usually in a 3 8 times ⁇ up to 15 20 microns.
- the film pieces were collected in 3 ⁇ 5 mm thickness packets, consisting of alternatively ordered oxide and metal films, with thickness ratio of oxide to metal films 5:1 (0.6 and 0.12 mm) in 5Y/M, 3:1 (0.36 and 0.12 mm) in 3 Y/M and 1 :1 (0.12 and 0.12 mm) in Y/M.
- These packets were rolled out to 0.7 ⁇ 1 mm thickness; thanks to rolling process a thickness of the constituent films were reduced in 2.5+4 times.
- the densified film packets are then laid as spiral into a cylindrical press die and subjected to uniaxial pressing with the purpose of cylindrical multilayer billet manufacture.
- the width of the chip must be no more than 5 7 mm, that is no more than 15 25 thicknesses of the chip, and no less then 5 10 thicknesses of the chip.
- the length of the multilayer chip must be no less then 25 50 thicknesses of the chip.
- the chips with such dimensions can be manufactured by other methods, for example by mechanical treatment of a multilayer plate on a planer, but in the variant of technological process it is need to use sufficiently large multilayer plates, which are usually difficult for manufacture.
- the multilayer chips are put into the press die for cold pressing.
- the shape of the article shaping can be carried out by the use of uniaxial pressing in a "usual" metallic press die or by the use of cold isostatic or quasi-isostatic pressing, usually under a pressure in the range of 100 ⁇ 500 MPa, preferably 150+250 MPa.
- the press die that is intended for cold quasi-isostatic pressing can contains, for example, a TEFLON-coated steel mandrel, which forms the internal surface of the article to be formed, and a rubber sleeve, which forms the external surface of the article (Figure 9).
- the billet is formed in a steel press die under a moderate pressure, and then the billet is subjected to quasi-isostatic pressing. After the article has been removed from the mold it is subjected to a thermal treatment.
- the thermal treatment in a vacuum tungsten furnace is started from the stage of the binder (and it's solvents) removal and preliminary sintering at a temperature in the range of 1100 ⁇ 1400°C during span, which is necessary to reach the article density, which is approximately 50 75% of theoretical density.
- the shrinkage usually is in the range from 3 to 12%.
- a tungsten furnace is used, because in graphite furnace can take place a reduction of the novel composite oxide component and a carbidization of it's metallic component, as result of a chemical interaction with such a reducing agent as carbon, which presents in atmosphere of the graphite furnaces.
- the rate of a temperature rise must be in the range of 1 10°C/hour up to the temperature of a total binder burnout, which for most binders is about 500°C.
- the firm enough but quite porous yet article is sintered in a vacuum furnace at a temperature in the range of 1300 ⁇ 2000°C up to required density, which consists 85 95% of theoretical density.
- a following densification of the simple shape articles up to a density of 97 100% of theoretical density can be carried out by Hot Pressing at a temperature in the range of 1300 ⁇ 2000°C and under a pressure of 20+100 MPa.
- Final densification of articles with more complicated shape, especially those having thin walls and which are uncomfortable for hot pressing is carried out in a two-step process: the step of high-temperature vacuum sintering and the step of Hot Isostatic Pressing.
- the article of such type is pressureless sintered up to approximately 95 98% of theoretical density, that is up to a state with a very large fraction of closed porosity.
- the high-temperature "dwell" span of the corresponding firing profile usually is 1 to 2 hours.
- the pressureless sintered article is densified up to practically 100%) of theoretical density by Hot Isostatic Pressing at a temperature in the range of 1300 ⁇ 2000°C and in an inert gas pressure of 150+200 MPa. If the HIP plant is equipped with a graphite furnace the article can be shielded from interaction with carbon by Y2O3 powder or by another oxide. While we have described our invention in detail it will of course be understood that we have done so for the purpose of illustration only and not for the purpose of limitation.
- Figure 1 Metal-ceramic laminated composites with different structures: a - multilayer composite; b - laminar-granular composite; c - laminar-band composite.
- Figure 4 Crucibles of the novel composites for molten metals and salts.
- Figure 5 Combustion chambers and nozzles with application of the novel composites of the Group 3: a — Liquid Propelled Combustion Chamber:
- Figure 7 ⁇ Y2Q /M0 composites strength degradation after a single quench in water from different temperatures of heating up.
- Figure 8 Scheme of laminated metal-ceramic chips manufacture: 1 ⁇ multilayer cylinder billet; 2 ⁇ mandrel; 3 - cutting tool
- Figure 9 Mold for quasi-isostatic forming of thin wall articles from the novel composite
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT99900123T ATE227183T1 (en) | 1999-01-06 | 1999-01-06 | METAL-CERAMIC LAYER COMPOSITE |
CA002357713A CA2357713A1 (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
EP99900123A EP1148962B1 (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
AU17813/99A AU1781399A (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
DE69903858T DE69903858T2 (en) | 1999-01-06 | 1999-01-06 | METAL-CERAMIC LAYER COMPOSITE |
PCT/IL1999/000010 WO2000040359A1 (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
CN99816218A CN1334759A (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
JP2000592097A JP2002534345A (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic thin band composite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IL1999/000010 WO2000040359A1 (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
Publications (1)
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WO2000040359A1 true WO2000040359A1 (en) | 2000-07-13 |
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ID=11062691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/IL1999/000010 WO2000040359A1 (en) | 1999-01-06 | 1999-01-06 | Metal-ceramic laminar-band composite |
Country Status (8)
Country | Link |
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EP (1) | EP1148962B1 (en) |
JP (1) | JP2002534345A (en) |
CN (1) | CN1334759A (en) |
AT (1) | ATE227183T1 (en) |
AU (1) | AU1781399A (en) |
CA (1) | CA2357713A1 (en) |
DE (1) | DE69903858T2 (en) |
WO (1) | WO2000040359A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20150224576A1 (en) * | 2012-09-24 | 2015-08-13 | Siemens Aktiengesellschaft | Production of a Refractory Metal Component |
US20200354279A1 (en) * | 2018-01-17 | 2020-11-12 | Siemens Aktiengesellschaft | Ceramic material composite comprising a bonding layer of a molybdenum-titanium carbide composite material, component, gas turbine, and method |
CN114042912A (en) * | 2021-11-12 | 2022-02-15 | 哈尔滨工业大学 | Method for finely controlling mechanical properties of NiAl-based composite material through powder particle size |
CN115287574A (en) * | 2022-08-25 | 2022-11-04 | 航天特种材料及工艺技术研究所 | High-toughness anti-ablation coating and preparation method thereof |
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US20050153160A1 (en) * | 2004-01-12 | 2005-07-14 | Yourong Liu | Durable thermal barrier coating having low thermal conductivity |
DE102004057268A1 (en) * | 2004-11-26 | 2006-06-08 | Webasto Ag | Heater and method of making the same |
CN100396647C (en) * | 2005-08-16 | 2008-06-25 | 科发伦材料株式会社 | Yttria sintered body and manufacturing method therefor |
EP1922427A4 (en) * | 2005-08-19 | 2009-03-18 | Genius Metal Inc | Hardmetal materials for high-temperature applications |
CN104195402B (en) * | 2014-04-18 | 2018-11-30 | 宁夏东方钽业股份有限公司 | A kind of preparation method and oxidation-resistant material of high-temperature oxidation resistant fastener |
DE102015218408A1 (en) | 2015-09-24 | 2017-03-30 | Siemens Aktiengesellschaft | Component and / or surface of a refractory metal or a refractory metal alloy for thermocyclic loads and manufacturing method thereto |
RU2632078C1 (en) * | 2016-05-19 | 2017-10-02 | Акционерное общество "Поликор" | Aluminoxide composition and method of producing ceramic material for production of substrates |
CN109898055A (en) * | 2019-03-27 | 2019-06-18 | 中国航发北京航空材料研究院 | A kind of preparation method for fiber reinforcement nickel-base composite material interface nanometer multilayer diffusion barrier coating |
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CN111285691B (en) * | 2020-02-13 | 2021-03-30 | 中南大学 | Tungsten mesh toughened hafnium carbonitride based metal ceramic and preparation method thereof |
CN111451501B (en) * | 2020-04-03 | 2021-12-21 | 季华实验室 | Preparation method for laser additive manufacturing of tungsten part based on eutectic reaction |
CN113061793A (en) * | 2021-02-26 | 2021-07-02 | 成都虹波实业股份有限公司 | Refractory metal-based high-volume-ratio ceramic material and preparation process thereof |
CN113395855B (en) * | 2021-06-08 | 2022-12-13 | Oppo广东移动通信有限公司 | Shell, preparation method thereof and electronic equipment |
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- 1999-01-06 WO PCT/IL1999/000010 patent/WO2000040359A1/en active IP Right Grant
- 1999-01-06 CN CN99816218A patent/CN1334759A/en active Pending
- 1999-01-06 DE DE69903858T patent/DE69903858T2/en not_active Expired - Fee Related
- 1999-01-06 AT AT99900123T patent/ATE227183T1/en not_active IP Right Cessation
- 1999-01-06 JP JP2000592097A patent/JP2002534345A/en active Pending
- 1999-01-06 EP EP99900123A patent/EP1148962B1/en not_active Expired - Lifetime
- 1999-01-06 AU AU17813/99A patent/AU1781399A/en not_active Abandoned
- 1999-01-06 CA CA002357713A patent/CA2357713A1/en not_active Abandoned
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PATENT ABSTRACTS OF JAPAN vol. 017, no. 307 (E - 1379) 11 June 1993 (1993-06-11) * |
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US9950368B2 (en) * | 2012-09-24 | 2018-04-24 | Siemens Aktiengesellschaft | Production of a refractory metal component |
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CN114042912A (en) * | 2021-11-12 | 2022-02-15 | 哈尔滨工业大学 | Method for finely controlling mechanical properties of NiAl-based composite material through powder particle size |
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Also Published As
Publication number | Publication date |
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CA2357713A1 (en) | 2000-07-13 |
AU1781399A (en) | 2000-07-24 |
EP1148962B1 (en) | 2002-11-06 |
EP1148962A1 (en) | 2001-10-31 |
ATE227183T1 (en) | 2002-11-15 |
CN1334759A (en) | 2002-02-06 |
DE69903858T2 (en) | 2003-07-17 |
DE69903858D1 (en) | 2002-12-12 |
JP2002534345A (en) | 2002-10-15 |
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