EP1148962B1 - Metal-ceramic laminar-band composite - Google Patents

Metal-ceramic laminar-band composite Download PDF

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Publication number
EP1148962B1
EP1148962B1 EP99900123A EP99900123A EP1148962B1 EP 1148962 B1 EP1148962 B1 EP 1148962B1 EP 99900123 A EP99900123 A EP 99900123A EP 99900123 A EP99900123 A EP 99900123A EP 1148962 B1 EP1148962 B1 EP 1148962B1
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EP
European Patent Office
Prior art keywords
component
composite
composite according
multilayer
oxide
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Expired - Lifetime
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EP99900123A
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German (de)
English (en)
French (fr)
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EP1148962A1 (en
Inventor
Samuel Katz
Michael Katz
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Ceracom Inc
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CERACOM Inc
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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:
  • 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 interlayer 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.
  • 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 1c), 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 1c randomly interlaced multilayer curved band-like chips
  • the composite consists of the following components:
  • 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:
  • 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 Al 2 O 3 , SiO 2 , Y 2 O 3 , fully stabilized ZrO 2 , which sintering temperature do not exceed 1400 ⁇ 1600°C, for example, it can be such a compound as 3Al 2 O 3 ⁇ 2SiO 2 (mullite), or a different compounds in such systems as Al 2 O 3 -TiO 2 , or ZrO 2 -Y 2 O 3 -Al 2 O 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.
  • 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 Mullite/Chromium composite.
  • 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: Al 2 O 3 , Y 2 O 3 , fully stabilized ZrO 2 or HfO 2 and others.
  • 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(Al 2 O 3 +TiO 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 ZrO 2 , HfO 2 , ThO 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 ZrO 2 , HfO 2 , ThO 2 .
  • 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 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 ThO 2 ; 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 essence of the novel method consists in operations sequence, which insure production of composite with above-described laminar-band structure.
  • 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.
  • an article of desired shape and dimensions (taking into consideration shrinkage during sintering) is formed from the multilayer chips in a press die at a pressure in the range of 50 ⁇ 1000 MPa.
  • 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.
  • 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 Pressing in a graphite mold at a pressure in the range of 5 ⁇ 100 MPa and at a temperature in the range of 1400 ⁇ 2000°C, in vacuum or in an inert gas, in a resistively heating furnace or in an inductively heating furnace, for a period of time that is sufficient to reach practically the theoretical density.
  • Articles with more complicated and, especially, with thin-walled shape can be densified up to a practically pore-less condition by the use of Hot Isostatic Pressing (HIP) in inert gas under a pressure in the range of 100 ⁇ 300 MPa and at a temperature in the range of 1400 ⁇ 2000°C, also for a period of time that is sufficient for reaching practically the theoretical density.
  • HIP Hot Isostatic Pressing
  • Tables 2 5 are represented physical-mechanical properties of some typical composites: Table 2 for Group 2 Composites nY 2 O 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.
  • the composites with V ox :V met ⁇ 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 Y 2 O 3 .
  • Figure 6 are shown the concentration dependencies of bending strength and thermal shock resistance at multiple water quenches of the composite nY 2 O 3 /Mo.
  • 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 a jar 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.
  • oxide powders are dried at 400 ⁇ 800°C during 2 5 hours
  • metallic and carbide powders are dried at 250 ⁇ 3500C 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.
  • Casting of the organo-ceramic films can be carried out on any of conventional industrial machines, which are used for ceramic film casting by the "doctor blade” method.
  • 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 3Y/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 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).
  • Some products from the novel composites in particular nozzles and combustion chambers ( Figure 5), can have comparatively thin walls, which does not allow the use of a conventional press die.
  • the billet is formed in a steel press die under a moderate pressure, and then the billet is subjected to quasi-isostatic pressing.
  • 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.
  • 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.
  • 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 Y 2 O 3 powder or by another oxide.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Powder Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Laminated Bodies (AREA)
EP99900123A 1999-01-06 1999-01-06 Metal-ceramic laminar-band composite Expired - Lifetime EP1148962B1 (en)

Applications Claiming Priority (1)

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PCT/IL1999/000010 WO2000040359A1 (en) 1999-01-06 1999-01-06 Metal-ceramic laminar-band composite

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EP1148962A1 EP1148962A1 (en) 2001-10-31
EP1148962B1 true EP1148962B1 (en) 2002-11-06

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EP (1) EP1148962B1 (ja)
JP (1) JP2002534345A (ja)
CN (1) CN1334759A (ja)
AT (1) ATE227183T1 (ja)
AU (1) AU1781399A (ja)
CA (1) CA2357713A1 (ja)
DE (1) DE69903858T2 (ja)
WO (1) WO2000040359A1 (ja)

Cited By (1)

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RU2632078C1 (ru) * 2016-05-19 2017-10-02 Акционерное общество "Поликор" Алюмооксидная композиция и способ получения керамического материала для производства подложек

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US20050153160A1 (en) * 2004-01-12 2005-07-14 Yourong Liu Durable thermal barrier coating having low thermal conductivity
DE102004057268A1 (de) * 2004-11-26 2006-06-08 Webasto Ag Heizgerät und Verfahren zur Herstellung desselben
CN100396647C (zh) * 2005-08-16 2008-06-25 科发伦材料株式会社 氧化钇烧结体及其制造方法
EP1922427A4 (en) * 2005-08-19 2009-03-18 Genius Metal Inc MATERIALS BASED ON HARD METALS FOR HIGH TEMPERATURE APPLICATIONS
DE102012217191A1 (de) * 2012-09-24 2014-03-27 Siemens Aktiengesellschaft Herstellen eines Refraktärmetall-Bauteils
CN104195402B (zh) * 2014-04-18 2018-11-30 宁夏东方钽业股份有限公司 一种高温抗氧化紧固件的制备方法及抗氧化材料
DE102015218408A1 (de) 2015-09-24 2017-03-30 Siemens Aktiengesellschaft Bauteil und/oder Oberfläche aus einem Refraktärmetall oder einer Refraktärmetalllegierung für thermozyklische Belastungen und Herstellungsverfahren dazu
EP3514126A1 (de) * 2018-01-17 2019-07-24 Siemens Aktiengesellschaft Keramischer werkstoffverbund mit einer verbindungsschicht aus einem molybdän-titancarbid-kompositwerkstoff, bauteil, gasturbine, sowie verfahren
CN109898055A (zh) * 2019-03-27 2019-06-18 中国航发北京航空材料研究院 一种用于纤维增强镍基复合材料界面纳米多层扩散障涂层的制备方法
CN110193601B (zh) * 2019-06-13 2021-10-15 金堆城钼业股份有限公司 一种双层或多层难熔金属复合管材的制备方法
CN111285691B (zh) * 2020-02-13 2021-03-30 中南大学 一种钨网增韧碳氮化铪基金属陶瓷及其制备方法
CN111451501B (zh) * 2020-04-03 2021-12-21 季华实验室 一种基于共晶反应的激光增材制造钨零件的制备方法
CN113061793A (zh) * 2021-02-26 2021-07-02 成都虹波实业股份有限公司 一种难熔金属基高体积比陶瓷材料及其制备工艺
CN113395855B (zh) * 2021-06-08 2022-12-13 Oppo广东移动通信有限公司 壳体及其制备方法和电子设备
CN114042912B (zh) * 2021-11-12 2022-07-29 哈尔滨工业大学 一种通过粉末粒径精细化控制NiAl基复合材料力学性能的方法
CN115287574B (zh) * 2022-08-25 2023-06-16 航天特种材料及工艺技术研究所 一种高韧性抗烧蚀涂层及其制备方法

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Publication number Priority date Publication date Assignee Title
RU2632078C1 (ru) * 2016-05-19 2017-10-02 Акционерное общество "Поликор" Алюмооксидная композиция и способ получения керамического материала для производства подложек

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WO2000040359A1 (en) 2000-07-13
ATE227183T1 (de) 2002-11-15
DE69903858D1 (de) 2002-12-12
JP2002534345A (ja) 2002-10-15
EP1148962A1 (en) 2001-10-31
AU1781399A (en) 2000-07-24
CN1334759A (zh) 2002-02-06
CA2357713A1 (en) 2000-07-13
DE69903858T2 (de) 2003-07-17

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