EP0277450A1 - Process for preparing metal-ceramic composite materials by using surface-active metals at the ceramic-metal interfaces - Google Patents
Process for preparing metal-ceramic composite materials by using surface-active metals at the ceramic-metal interfaces Download PDFInfo
- Publication number
- EP0277450A1 EP0277450A1 EP19870420356 EP87420356A EP0277450A1 EP 0277450 A1 EP0277450 A1 EP 0277450A1 EP 19870420356 EP19870420356 EP 19870420356 EP 87420356 A EP87420356 A EP 87420356A EP 0277450 A1 EP0277450 A1 EP 0277450A1
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- EP
- European Patent Office
- Prior art keywords
- metal
- ceramic
- phase
- powder
- manufacturing
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000002131 composite material Substances 0.000 title description 14
- 150000002739 metals Chemical class 0.000 title description 10
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002905 metal composite material Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000654 additive Substances 0.000 claims abstract 2
- 230000000996 additive effect Effects 0.000 claims abstract 2
- 230000001427 coherent effect Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910033181 TiB2 Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004663 powder metallurgy Methods 0.000 claims description 4
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- -1 titanium hydride Chemical compound 0.000 claims description 3
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 3
- 229910000753 refractory alloy Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000005501 phase interface Effects 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052706 scandium Inorganic materials 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 229910001374 Invar Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- BNCWKBNJIUQMOF-UHFFFAOYSA-N [O-2].[Ti+4].[Ni+2].[Al+3].[Al+3].[O-2].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Ni+2].[Al+3].[Al+3].[O-2].[O-2].[O-2].[O-2].[O-2] BNCWKBNJIUQMOF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- 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
Definitions
- the present invention relates to ceramic-metal composites and their production methods. It makes it possible to produce, by the methods of powder metallurgy and / or ceramic, a set of homogeneous polyphase materials, which have at least one ceramic phase and one metal phase.
- Powder metallurgy technologies are now well known. They derive from ceramic art. Details of these can be found, in particular, in French patent 2,057,562.
- the constituents of the materials to be formed are used in the form of powders, some of which may be pre-alloyed beforehand.
- the rest of the process is conditioned by the type of shaping used to make the desired article. among the different possible types, it should be mentioned, although this is not limiting: - pouring into a porous mold, - spreading in thin sheet, - extrusion, - thermoplastic injection, - pressing, - electrophoresis, etc ...
- a temporary binder is generally added to the composition, in the form of an organic polymer. Its role is to gather the grains of powder into small quasi-spherical granules of similar size and provided with plasticity.
- the pressing dies are fed with this granule. It allows a reproducible filling.
- a pressure close to 1 T / cm2 by means of two punches, in the case of biaxial pressing. Under the effect of the pressure, the granules deform until they become practically contiguous while expelling residual air from the matrix. Compacts are thus obtained, the density of which can be greater than 70% of the theoretical density.
- the compacts are then transferred to ovens to be densified by the sintering operation, after purification of the organic binders.
- This sintering can be carried out with or without pressure at a sufficient temperature, in the vast majority of cases, to achieve volume diffusion of the elements.
- the compacts evolve towards greater stability, on the one hand, by reducing their surface energy by elimination of the pores and crystal growth and, on the other hand, by forming the stable phases at the considered temperatures.
- the binding phase has a continuity character: it coats the grains of the dispersed phase or phases, but generally remains a minority in volume; by way of example, it can be said that the binding phase occupies 30% + or - 10% of the volume. It is under these conditions that, in general, the best properties are obtained, without this is an absolute rule.
- heterogeneities encountered in these systems, at the end of the production processes, such as sintering or infiltration, are of two types: - Porosity, - Poor phase dispersion.
- the role of the surfactants will be to serve as an intermediary between the dispersed and metal phases, and to lower the energy of GIBBS of the whole. It has been found that certain metals which have a certain affinity for the metal phase and an affinity for the ceramic phase, particularly by forming compounds, of very negative free enthalpy, could play this role. This is particularly the case when the surfactant element has an isotype (or even isomorphic) compound, or a structure close to that of the ceramic phase.
- These surface-active elements are particularly reactive, and especially with respect to oxygen; this is the reason why, rather than using them directly in metal form, one will preferably use one of their compounds, easily decomposable to heat, such as hydrides.
- These compounds, generators of surface-active elements are introduced in pulverulent form, before mixing-grinding of the other constituents, with a suitable particle size, so as to obtain an intimate mixture and of uniform particle size of the whole.
- the systems which are the subject of the invention contain a metallic part, which is a minority in volume, ie from 50% to 5%, and a ceramic part, ie from 50% to 95%; this metallic part, contains, in addition, the surface-active metals, which ensure the connection and the transition between the metallic and ceramic phases, possibly by the formation of compounds, during the sintering process.
- the ceramic material is chosen from the following compounds: - corundum type compounds: Al203, Cr203, Ti203 Y203, etc ..., - silicon nitride, titanium nitride, boron nitride, - titanium diboride, - silicon carbide, boron carbide, titanium carbide,
- the metal part is chosen from the metals and alloys below: - nickel, - alloys refractory to Ni, Cr, Co, Fe (type the product known under the brand name Refractaloy) - controlled expansion alloys based on iron and nickel, known under the brand names Invar, ADR, N42, N56, Dilver, or Platinite - aluminum, - alloy used in friction such as lead bronze, tin, aluminum, silicon.
- ceramics, metals, compounds generating surface-active metals are used in the form of powders. These powders are used by the methods of powder metallurgy (or ceramic), methods well known to those skilled in the art, for the production of objects, obtained in the green state, in an intermediate stage. These objects are then densified in a secondary vacuum oven preferably working under load (although the load is not necessary).
- the sintering temperature is located near the melting temperature of the metal alloy used (for example more or less 100 ° C). During the heat treatment, the surface-active metal or metals diffuse and ensure the bonding at the interfaces, with possible formation of compounds or alloys.
- an argon sweep is carried out, with a flow rate of 1 l / min. approximately, for 2 min., in order to expel most of the air. Then we close the jar quickly.
- the jar is placed on a jar turner, speed of the order of 90 revolutions per minute, and it is rotated for approximately 8 hours. The purpose of this operation is to homogenize and grind the different constituents.
- the suspension of beads is separated, then it is dried with stirring to avoid demixing of the constituents, optionally under reduced pressure, preferably in a granulator.
- the powder is then compacted in the press in the form of test tubes, and the residual camphor is sublimed.
- the test pieces are then treated in a sintering oven under load, working under secondary vacuum.
- One operates under a vacuum of 10 ⁇ 5 torre and under a load corresponding to a pressure of 10 MPa.
- the heat treatment comprises a level of decomposition of hydrides between 300 ° C and 500 ° C and a level of sintering 30 min. at 1200 ° C, the temperature rise being carried out in 2 hours.
- a pellet of density 6.02 is obtained.
- the duration and the temperature of the sintering stage depend on the pressure exerted: without pressure they can be brought to 2 hours and 1450 ° C, respectively.
- Ceramic-metal composites are thus obtained, corresponding to the invention.
- Sintering is carried out under the following conditions: Temperature rise of 1000 ° C, linearly in 75 min. , under vacuum of 10 ⁇ 5 torre without pressure; progressive loading up to a pressure of 10 MPa reached in 15 min. and maintaining the pressure until the end of the heat treatment; rise to 1350 ° C in 1 hour and step of 40 min. at this temperature.
- a composite pellet of density 5.15 is obtained.
- Example 2 The procedure is as in Example 1, with a heat treatment of 1 hour at 1360 ° C, according to the following formula: - 438 g of chromium oxide - 236 g of MCrA1Y alloy.
- the composition of MCrA1Y is in percentage: Ni 10, Co 52, Cr 25, Al 7, Ti 5, YO, 75; Its average particle size is around 25 microns.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
Description
La présente invention concerne des composites céramique-métal et leurs procédés de production . Elle permet de produire , par les méthodes de la métallurgie des poudres et/ou céramique , un ensemble de matériaux polyphasés homogènes , qui présentent au moins une phase céramique et une phase métal .The present invention relates to ceramic-metal composites and their production methods. It makes it possible to produce, by the methods of powder metallurgy and / or ceramic, a set of homogeneous polyphase materials, which have at least one ceramic phase and one metal phase.
Les technologies de la métallurgie des poudres sont maintenant bien connues . Elles dérivent de l'art céramique . Des précisions sur celles-ci peuvent être trouvées , en particulier , dans le brevet français 2.057.562 . Les constituants du matériaux à former sont utilisés sous forme de poudres , certaines d'entre elles pouvant au préalable être préalliées .Powder metallurgy technologies are now well known. They derive from ceramic art. Details of these can be found, in particular, in French patent 2,057,562. The constituents of the materials to be formed are used in the form of powders, some of which may be pre-alloyed beforehand.
Ces poudres sont mélangées et broyées ensemble , en milieu liquide , ou à sec . Cette étape de mélange-broyage est déterminante pour le reste du procédé . C'est d'elle , en effet , que dépend l'homogénéité , d'où les caractéristiques du produit final . On la conduit dans des broyeurs munis de média de broyage . Ces média de broyage sont variés , de par leur natures , pierres naturelles , céramiques , alliages , cermets , etc.., et de par leur formes , billes , galets , cylindres , etc...Le choix de ces média , où les considérations économiques ne sont pas absentes , est fondé sur les risques de pollution , et la recherche du type de granulométrie envisagée .These powders are mixed and ground together, in a liquid medium, or dry. This mixing-grinding step is decisive for the rest of the process. It is on it, in fact, that homogeneity depends, hence the characteristics of the final product. It is carried out in grinders provided with grinding media. These grinding media are varied, by their nature, natural stones, ceramics, alloys, cermets, etc., and by their shapes, balls, rollers, cylinders, etc. The choice of these media, where the considerations economic are not absent, is based on the risks of pollution, and the search for the type of particle size envisaged.
La suite du procédé est conditionnée par le type de mise en forme retenue pour confectionner l'article désiré. parmi les différents types possibles , il y a lieu de citer , bien que cela ne soit pas limitatif :
- le coulage en moule poreux ,
- l'épandage en feuille mince,
- l'extrusion ,
- l'injection thermoplastique ,
- le pressage ,
- l'électrophorèse ,
etc ...The rest of the process is conditioned by the type of shaping used to make the desired article. among the different possible types, it should be mentioned, although this is not limiting:
- pouring into a porous mold,
- spreading in thin sheet,
- extrusion,
- thermoplastic injection,
- pressing,
- electrophoresis,
etc ...
Toutes ces méthodes de mises en formes peuvent être appliquées dans le cadre de l'invention , sans sortir de l'invention . L'homme de l'art comprendra qu'il est , ici inutile de les détailler toutes . Dans les exemples qui suivent , pour ne pas alourdir inutilement , la description du procédé , objet de l'invention , on s'est limité au pressage .All these shaping methods can be applied within the framework of the invention, without departing from the invention. Those skilled in the art will understand that it is unnecessary to detail them all here. In the examples which follow, in order not to unnecessarily burden the description of the process which is the subject of the invention, we have limited ourselves to pressing.
Pour cette mise en forme , on procède , le plus souvent à la granulation du mélange , à la suite du traitement de mélange-broyage . A cet effet , on ajoute généralement un liant temporaire dans la composition , sous forme d'un polymère organique . Son rôle est de rassembler les grains de poudre en petites granules quasi-sphériques de taille voisine et pourvues de plasticité . On alimente avec ce granulé les matrices de pressage . Il en permet un remplissage reproductible . On applique ensuite sur le moule , une pression voisine de 1 T/cm2 , par l'intermédiaire de deux poinçons , dans le cas du pressage biaxial . Sous l'effet de la pression , les granules se déforment jusqu'à devenir pratiquement jointives tout en chassant l'air résiduel de la matrice . On obtient ainsi des compacts dont la densité peut être supérieure à 70 % de la densité théorique . Les compacts sont ensuite transférés dans des fours pour être densifiés par l'opération de frittage , après épuration des liants organiques. Ce frittage peut être réalisé avec ou sans pression à une température suffisante , dans la grande majorité des cas , pour atteindre la diffusion en volume des éléments . Durant ce traitement thermique , les compacts évoluent vers une plus grande stabilité , d'une part , en réduisant leur énergie superficielle par élimination des pores et croissance cristalline et , d'autre part , en formant les phases stables aux températures considérées .For this shaping, the granulation of the mixture is most often carried out, following the mixture-grinding treatment. To this end, a temporary binder is generally added to the composition, in the form of an organic polymer. Its role is to gather the grains of powder into small quasi-spherical granules of similar size and provided with plasticity. The pressing dies are fed with this granule. It allows a reproducible filling. We apply then on the mold, a pressure close to 1 T / cm2, by means of two punches, in the case of biaxial pressing. Under the effect of the pressure, the granules deform until they become practically contiguous while expelling residual air from the matrix. Compacts are thus obtained, the density of which can be greater than 70% of the theoretical density. The compacts are then transferred to ovens to be densified by the sintering operation, after purification of the organic binders. This sintering can be carried out with or without pressure at a sufficient temperature, in the vast majority of cases, to achieve volume diffusion of the elements. During this heat treatment, the compacts evolve towards greater stability, on the one hand, by reducing their surface energy by elimination of the pores and crystal growth and, on the other hand, by forming the stable phases at the considered temperatures.
C'est par cette technologie que sont fabriquées , de plus en plus , les pièces industrielles de grandes séries , et certains alliages spéciaux , en particulier ceux décrits dans les brevets français 1 473 618 , 2 223 473 , 2 095 826 . Ces brevets concernent des alliages à dispersoïdes céramiques. La matière céramique en teneur généralement inférieure à 10 % , n'y intervient pas pour ses qualités mécaniques intrinsèques , mais en tant que sites d'ancrage des disclocations et sites de blocage de propagation des disclocations . On s'est , en effet , aperçu , que des dispersions de fines particules , préférentiellement sous forme d'oxydes , de dimensions inférieures ou voisines du millier d'Angströms accroissaient la dureté et la résistance au fluage de telles compositions . La prédominance de la masse métallique , et les propriétés restent cependant telles que la dénominations d'alliages convient mieux à ces compositions que le terme de composites.It is by this technology that more and more industrial parts are produced in large series, and certain special alloys, in particular those described in French patents 1,473,618, 2,223,473, 2,095,826. These patents relate to alloys with ceramic dispersoids. The ceramic material, generally less than 10%, does not intervene there for its intrinsic mechanical qualities, but as sites for anchoring disclocations and sites for blocking the propagation of disclocations. It has been found, in fact, that dispersions of fine particles, preferably in the form of oxides, of dimensions less than or close to a thousand Angstroms increased the hardness and the creep resistance of such compositions. The predominance of metallic mass, and the properties remain however such that the designation of alloys is better suited to these compositions than the term composites.
Dans les composites , objet de la présente invention , on cherche à avoir le maximum de phases céramiques en volume de façon à pouvoir profiter le plus possible des propriétés intrinsèques des céramiques , telles que la stabilité chimique et dimensionnelle , en milieu agressif . On limite , volontairement , le métal aux joints de grains . On sait , en effet , que dans les céramiques , c'est le joint de joint qui est fragile , et limite la résistance des céramiques à des valeurs très inférieures ( environ un facteur 10 ) à leur résistances théoriques .In the composites which are the subject of the present invention, it is sought to have the maximum of ceramic phases by volume so as to be able to benefit as much as possible from the intrinsic properties of ceramics, such as chemical and dimensional stability, in an aggressive medium. The metal is deliberately limited to the grain boundaries. We know, in fact, that in ceramics, it is the gasket that is fragile, and limits the resistance of ceramics to values much lower (about a factor of 10) than their theoretical resistances.
Dans de tels composites , on cherche, généralement, à former une phase liante métallique , et une , voire plusieurs phases dispersées de type céramique . La phase liante présente un caractère de continuité : elle enrobe les grains de la ou des phases dispersées , mais reste , généralement , minoritaire en volume ; à titre d'exemple , on peut dire , que la phase liante occupe 30 % + ou - 10% du volume. C'est dans ces conditions que , d'une façon générale , on obtient les meilleures propriétés , sans que cela soit une règle absolue.In such composites, it is generally sought to form a metallic binder phase, and one, or even several dispersed phases of the ceramic type. The binding phase has a continuity character: it coats the grains of the dispersed phase or phases, but generally remains a minority in volume; by way of example, it can be said that the binding phase occupies 30% + or - 10% of the volume. It is under these conditions that, in general, the best properties are obtained, without this is an absolute rule.
La réalisation de tels matériaux se heurtait , jusqu'à ce jour , à une difficulté majeure : le bon mouillage des deux phases . De nombreux systèmes ont été étudiés ;nous citerons , ici , pour illustrer ce propos , le système nickel-alumine , le système cuivre-alumine, sur lesquels il existe des publications relativement récentes.Until now, the production of such materials has encountered a major difficulty: the proper wetting of the two phases. Many systems have been studied; we will cite, here, to illustrate this point, the nickel-alumina system, the copper-alumina system, on which there are relatively recent publications.
Les hétérogénéités que l'on rencontre dans ces systèmes , à l'issue des procédés d'élaboration , tels que le frittage ou l'infiltration , sont de deux types:
- Porosité ,
- Mauvaise dispersion des phases .The heterogeneities encountered in these systems, at the end of the production processes, such as sintering or infiltration, are of two types:
- Porosity,
- Poor phase dispersion.
Il en résulte les inconvénients majeurs suivants :
- Nécessité d'accroître le pourcentage de phase liante pour obtenir une phase continue ,
- Affaiblissement de la majorité des caractéristiques ,
- Mauvaise reproductibilité dans l'élaboration du matériaux et principalement de l'opération de frittage ou d'infiltration .The following major drawbacks result:
- Need to increase the percentage of binding phase to obtain a continuous phase,
- Weakening of the majority of the characteristics,
- Poor reproducibility in the development of materials and mainly of the sintering or infiltration operation.
La présence de ces deux défauts est due au manque d'"attraction", on pourrait dire aussi d'"affinité" , de la phase liante avec le ou les phases dispersées . Cela correspond sur le plan chimique , à l'absence ou à la rareté et/ou la faiblesse des liaisons des atomes en présence . Il en résulte que , dans les traitements d'élaboration du matériaux , l'évolution du système se traduit par une trop faible variation d'énergie de Gibbs , pour obtenir un enrobage des grains de la phase dispersée; dans certains cas , il y aurait même accroissement de cette énergie.The presence of these two defects is due to the lack of "attraction", one could also say of "affinity", of the binding phase with the dispersed phase or phases. This corresponds chemically to the absence or scarcity and / or weakness of the bonds of the atoms present. It follows that, in the processing of the materials, the evolution of the system results in too low a variation of Gibbs energy, to obtain a coating of the grains of the dispersed phase; in some cases, there would even be an increase in this energy.
L'emploi de certains éléments d'addition, que nous appellerons métaux tensio-actifs , permet de résoudre cette difficulté . Le choix de ces éléments n'est pas quelconque , mais dépend des caractéristiques physico-chimiques du système , et , en particulier du métal de la phase liante et de la nature de la phase dispersée ; on peut citer à ce propos :
- la cristallographie des phases en présence ,
- le rayon atomique des cations de la phase dispersée ,
- l'électronégativité telle que l'a définie L.PAULING , des éléments de la phase dispersée.The use of certain addition elements, which we will call surface-active metals, makes it possible to resolve this difficulty. The choice of these elements is not arbitrary, but depends on the physico-chemical characteristics of the system, and, in particular on the metal of the binder phase and on the nature of the dispersed phase; we can quote on this subject:
- the crystallography of the phases present,
- the atomic radius of the cations of the dispersed phase,
- electronegativity as defined by L. PAULING, elements of the dispersed phase.
Pour une meilleure compréhension de ce qui suit,nous rappellerons brièvement, de façon très schématique, quelques notions de chimie et de cristallographie.For a better understanding of what follows, we will briefly recall, very schematically, some notions of chemistry and crystallography.
La nature des liaisons chimiques dans les cristaux constituant les matériaux céramique est , principalement, de type ionique et/ou covalent ; dans un grand nombre de cas , il y a hybridation de ces deux types de liaison : on peut citer comme exemple l'oxyde de chrome Cr203 , l'alumine A1203 . Dans de tels réseaux , on a l'habitude de considérer que les anions (les O-- , dans les exemples ci-dessus) , forment un empilage défini , généralement tridimensionnel , assez souvent de type compact , comme cela est le cas avec Cr203 et Al203 . Dans les trous de cet édifice , se répartissent les cations ( Al 3+ , ou Cr 3+ , dans les exemples ci-dessus). Dans les réseaux dont la covalence est plus marquée , par exemple le Nitrure de Silicium Si3N4 , l'édifice cristallin est construit en fonction de la répartition spatiale des liaisons chimiques . Il s'ensuit que les atomes de même nature ne sont pas forcément équivalents , c'est ainsi que dans Si3N4 on distingue deux types de sites azote.The nature of the chemical bonds in the crystals constituting the ceramic materials is mainly of the ionic and / or covalent type; in a large number of cases, these two types of bond are hybridized: chromium oxide Cr203, alumina A1203 may be cited as an example. In such networks, it is customary to consider that the anions (the O--, in the examples above), form a defined stacking, generally three-dimensional, quite often of compact type, as is the case with Cr203 and Al203. In the holes of this building, the cations are distributed (Al 3+, or Cr 3+, in the examples above). In networks with more marked covalence, for example Silicon Nitride Si3N4, the crystal structure is constructed as a function of the spatial distribution of the chemical bonds. It follows that atoms of the same kind are not necessarily equivalent, this is how in Si3N4 we distinguish two types of nitrogen sites.
Dans les deux cas , liaisons ioniques ou liaisons covalentes, il y a insaturation des atomes superficiels . Il résulte de cette insaturation que, dans l'expression donnant l'énergie de GIBBS du composé considéré , il conviendrait de rajouter un terme pour tenir compte des phénomènes superficiels . Les cristaux , quant à eux , dans le milieu où il sont placés , modifieront leurs structures externes , par exemple en adsorbant des espèces chimiques , pour atteindre un niveau de stabilité plus grande, lequel correspond à une énergie de GIBBS plus faible. Dans le cas des oxydes cités plus haut , il a été mis en évidence par certains chercheurs la présence de groupements -OH superficiels , résultant de la capture de protons.In both cases, ionic bonds or covalent bonds, there is unsaturation of the surface atoms. It follows from this unsaturation that, in the expression giving the energy of GIBBS of the compound considered, a term should be added to take account of surface phenomena. As for the crystals, in the medium in which they are placed, they will modify their external structures, for example by adsorbing chemical species, to reach a higher level of stability, which corresponds to a lower GIBBS energy. In the case of the oxides mentioned above, it has been demonstrated by certain researchers the presence of superficial -OH groups, resulting from the capture of protons.
Les liaisons entre atomes, dans les phases métalliques sont différentes : certains électrons périphériques des atomes sont délocalisés dans les zones de Brillouin ; si bien qu'on peut schématiser une phase métal par un empilement défini tridimensionnel de cations dans un nuage d'électrons . En réalité , pour expliquer l'ensemble des caractéristiques physiques et particulièrement dans le cas des métaux de transition réfractaires, il faut concevoir un modèle plus complexe , où interviennent des hybridations entre atomes, des orbitales électroniques externes , (Cela est particulièrement marqué pour la colonne VIB de la classification pérodique) . A cette liaison métallique il peut , donc , se superposer une liaison à caractère covalent partiel .The bonds between atoms in the metallic phases are different: certain peripheral electrons of the atoms are delocalized in the Brillouin zones; so that one can schematize a metal phase by a defined three-dimensional stack of cations in an electron cloud. In reality, to explain all of the physical characteristics and particularly in the case of refractory transition metals, it is necessary to design a more complex model, in which hybridizations between atoms take place, external electronic orbitals, (This is particularly marked for the column VIB of the periodic classification). It can therefore be superimposed on this metal bond a partial covalent bond.
On conçoit , d'après ce qui précède , qu'il soit difficile de lier ensemble une phase céramique et une phase métal , la nature des forces entre faces opposées étant plutôt de nature répulsive . La modification des films superficiels des grains entraîne , généralement , un accroissement de l'énergie de GIBBS.It is understood, from the above, that it is difficult to link together a ceramic phase and a metal phase, the nature of the forces between opposite faces being rather repulsive in nature. The modification of the surface films of the grains generally results in an increase in the energy of GIBBS.
Le rôle des tensio-actifs sera de servir d'intermédiaire entre les phases dispersées et métal, et d'abaisser l'énergie de GIBBS de l'ensemble . On a constaté que , certains métaux qui présentent une certaine affinité pour la phase métal et une affinité pour la phase céramique , particulièrement en formant des composée , d'enthalpie libre très négative , pouvaient jouer ce rôle . C'est particulièrement le cas quand l'élément tensio-actif présente un composé isotype (ou même isomorphe), ou de structure voisine de celui de la phase céramique .The role of the surfactants will be to serve as an intermediary between the dispersed and metal phases, and to lower the energy of GIBBS of the whole. It has been found that certain metals which have a certain affinity for the metal phase and an affinity for the ceramic phase, particularly by forming compounds, of very negative free enthalpy, could play this role. This is particularly the case when the surfactant element has an isotype (or even isomorphic) compound, or a structure close to that of the ceramic phase.
Parmi les éléments susceptibles d'être utilisés comme tensio-actifs , nous avons trouvé que les éléments suivants étaient particulièrement efficaces :
- Ti , V , So
- Zr , Y , Nb
- Hf , La et Terres rares, TaAmong the elements that could be used as surfactants, we found that the following elements were particularly effective:
- Ti, V, So
- Zr, Y, Nb
- Hf, La and Rare earths, Ta
Ces éléments tensio-actifs sont particulièrement réactifs, et tout spécialement vis-à-vis de l'oxygène ; c'est la raison pour laquelle, plutôt que de les utiliser directement sous forme métal , on emploiera , de préférence , un de leurs composés , facilement décomposables à la chaleur , tels que des hydrures . Ces composés , générateurs d'éléments tensio-actifs , sont introduits sous forme pulvérulente , avant le mélangeage-broyage des autres constituants , avec une granulométrie convenable , de façon à obtenir un mélange intime et de granulométrie homogène de l'ensemble .These surface-active elements are particularly reactive, and especially with respect to oxygen; this is the reason why, rather than using them directly in metal form, one will preferably use one of their compounds, easily decomposable to heat, such as hydrides. These compounds, generators of surface-active elements, are introduced in pulverulent form, before mixing-grinding of the other constituents, with a suitable particle size, so as to obtain an intimate mixture and of uniform particle size of the whole.
Les systèmes , objet de l'invention , contiennent une partie métallique , minoritaire en volume , soit de 50 % à 5 % , et une partie céramique, soit de 50 % à 95 %; cette partie métallique , contient , en outre , les métaux tensio-actifs , qui assurent la liaison et la transition entre les phases métalliques et céramiques , éventuellement par la formation de composés , lors du processus de frittage .The systems which are the subject of the invention contain a metallic part, which is a minority in volume, ie from 50% to 5%, and a ceramic part, ie from 50% to 95%; this metallic part, contains, in addition, the surface-active metals, which ensure the connection and the transition between the metallic and ceramic phases, possibly by the formation of compounds, during the sintering process.
Pour la fabrication de tels composites , on choisit la matière céramique parmi les composés qui suivent :
- composés de type corindon : Al203 , Cr203 , Ti203 Y203 ,etc...,
- nitrure de silicium , nitrure de titane , nitrure de bore ,
- diborure de titane ,
- carbure de silicium , carbure de bore , carbure de titane ,For the manufacture of such composites, the ceramic material is chosen from the following compounds:
- corundum type compounds: Al203, Cr203, Ti203 Y203, etc ...,
- silicon nitride, titanium nitride, boron nitride,
- titanium diboride,
- silicon carbide, boron carbide, titanium carbide,
La partie métallique est choisie parmi les métaux et alliages ci-dessous :
- nickel ,
- alliages réfractaires au Ni , Cr , Co , Fe ( type le produit connu sous le nom de marque Refractaloy )
- alliages à dilatation controlée à base de fer et de nickel , connus sous les noms de marque Invar , ADR , N42 , N56 , Dilver , ou Platinite
- aluminium ,
- alliage utilisé en frottement tel que le bronze au plomb , à l'étain , à l'aluminium , au silicium .The metal part is chosen from the metals and alloys below:
- nickel,
- alloys refractory to Ni, Cr, Co, Fe (type the product known under the brand name Refractaloy)
- controlled expansion alloys based on iron and nickel, known under the brand names Invar, ADR, N42, N56, Dilver, or Platinite
- aluminum,
- alloy used in friction such as lead bronze, tin, aluminum, silicon.
L'ensemble des constituants : céramiques , métalliques, composés générateurs de métaux tensio-actifs, sont utilisés sous forme de poudres . Ces poudres sont mis en oeuvre par les méthodes de la métallurgie des poudres ( ou céramique ), méthodes bien connues de l'homme de l'art, pour la production d'objets , obtenus à l'état vert , dans un stade intermédiaire . Ces objets sont ensuite densifiés dans un four sous vide secondaire travaillant de préférence sous charge ( bien que la charge ne soit pas nécessaire ) . La température de frittage se situe au voisinage de la température de fusion de l'alliage métallique utilisé ( par exemple plus ou moins 100 °C ). Lors du traitement thermique , le ou les métaux tensio-actifs diffusent et assurent la liaison aux interfaces , avec formation éventuelle de composés ou alliages .All the constituents: ceramics, metals, compounds generating surface-active metals, are used in the form of powders. These powders are used by the methods of powder metallurgy (or ceramic), methods well known to those skilled in the art, for the production of objects, obtained in the green state, in an intermediate stage. These objects are then densified in a secondary vacuum oven preferably working under load (although the load is not necessary). The sintering temperature is located near the melting temperature of the metal alloy used (for example more or less 100 ° C). During the heat treatment, the surface-active metal or metals diffuse and ensure the bonding at the interfaces, with possible formation of compounds or alloys.
Les exemples ci-après permettront de mieux comprendre le procédé de fabrication de ces composites , objet de l'invention .The examples below will make it possible to better understand the process for manufacturing these composites, which are the subject of the invention.
On verse dans une jarre, récipient cylindrique, en acier inoxydable de capacité de 1 litre environ, contenant 2,5 kg de billes en acier inoxydable de diamètre de 1 cm environ :
- 312 g d'oxyde de chrome Cr203 en poudre (de surface spécifique, méthode Blaine, 25 000 cm2/g, par exemple sans que cela soit une nécessité.)
- 313 g de poudre de nickel (S.S. Blaine: 5 000 cm2/g, environ .)
- 50 g de poudre d'hydrure de titane S.S. Blaine: 3000 cm2/g environ.)
- 130 g de trifluorotrichoroéthane, type flugène 113 par exemple.
- 50 g de camphre.Poured into a jar, a cylindrical container, made of stainless steel with a capacity of approximately 1 liter, containing 2.5 kg of stainless steel balls with a diameter of approximately 1 cm:
- 312 g of chromium oxide Cr203 powder (specific surface area, Blaine method, 25,000 cm2 / g, for example without this being a necessity.)
- 313 g of nickel powder (SS Blaine: 5,000 cm2 / g, approx.)
- 50 g of SS Blaine titanium hydride powder: approximately 3000 cm2 / g.)
- 130 g of trifluorotrichoroethane, type flugene 113 for example.
- 50 g of camphor.
On effectue, ensuite , dans la jarre, un balayage d'argon, avec un débit de 1 l/min. environ, durant 2 min., afin de chasser la majorité de l'air. Puis on ferme la jarre rapidement . On place la jarre sur un tourne-jarre , vitesse de l'ordre de 90 tours par minutes , et on la met en rotation durant 8 heures environ . Cette opération a pour but d'homogénéiser et de broyer les différents constituants.Then, in the jar, an argon sweep is carried out, with a flow rate of 1 l / min. approximately, for 2 min., in order to expel most of the air. Then we close the jar quickly. The jar is placed on a jar turner, speed of the order of 90 revolutions per minute, and it is rotated for approximately 8 hours. The purpose of this operation is to homogenize and grind the different constituents.
A l'issue du traitement, on sépare la suspension des billes, puis on la sèche sous agitation pour éviter une démixion des constituants , éventuellement , sous pression réduite , de préférence dans un granulateur.At the end of the treatment, the suspension of beads is separated, then it is dried with stirring to avoid demixing of the constituents, optionally under reduced pressure, preferably in a granulator.
On compacte ensuite la poudre à la presse sous forme d'éprouvettes, puis on sublime le camphre résiduel . Les éprouvettes sont , ensuite , traitées dans un four de frittage sous charge , travaillant sous vide secondaire .
On opère sous un vide de 10⁻⁵ torre et sous une charge correspondant à une pression de 10 MPa . Le traitement thermique comporte un palier de décomposition des hydrures entre 300°C et 500°C et un palier de frittage de 30 min. à 1200 °C , la montée en température étant réalisée en 2 heures .The powder is then compacted in the press in the form of test tubes, and the residual camphor is sublimed. The test pieces are then treated in a sintering oven under load, working under secondary vacuum.
One operates under a vacuum of 10⁻⁵ torre and under a load corresponding to a pressure of 10 MPa. The heat treatment comprises a level of decomposition of hydrides between 300 ° C and 500 ° C and a level of sintering 30 min. at 1200 ° C, the temperature rise being carried out in 2 hours.
On obtient une pastille de densité 6,02 .A pellet of density 6.02 is obtained.
La durée et la température du palier de frittage sont fonction de la pression exercée : sans pression elles pourront être portées, respectivement, à 2 heures et 1450°C.The duration and the temperature of the sintering stage depend on the pressure exerted: without pressure they can be brought to 2 hours and 1450 ° C, respectively.
On obtient, ainsi des composites céramique-métal, répondant à l'invention.Ceramic-metal composites are thus obtained, corresponding to the invention.
On opère comme précédemment d'après la formule suivante :
- 362 g de poudre d'alumine alpha de surface spécifique , méthode Blaine , 5000 cm2/g .
- 86,5 g de poudre d'hydrure de titane .
- 70,2 g de poudre d'aluminium diamètre moyen des particules de l'ordre du micron .
- 153,7 g de poudre de nickel .We operate as before according to the following formula:
- 362 g of alpha alumina powder with a specific surface, Blaine method, 5000 cm2 / g.
- 86.5 g of titanium hydride powder.
- 70.2 g of aluminum powder with average particle diameter of the order of a micron.
- 153.7 g of nickel powder.
Le frittage est réalisé dans les conditions suivantes :
Montée en température de 1000 ° C , linéairement en
75 min. , sous vide de 10⁻⁵ torre sans pression ; mise sous charge progressive jusqu'à une pression de 10 MPa atteinte en 15 min. et maintien de la pression jusqu'à la fin du traitement thermique ; montée à 1350 ° C en 1 heure et palier de 40 min. à cette température .Sintering is carried out under the following conditions:
Temperature rise of 1000 ° C, linearly in
75 min. , under vacuum of 10⁻⁵ torre without pressure; progressive loading up to a pressure of 10 MPa reached in 15 min. and maintaining the pressure until the end of the heat treatment; rise to 1350 ° C in 1 hour and step of 40 min. at this temperature.
On obtient une pastille composite de densité 5,15 .A composite pellet of density 5.15 is obtained.
On opère comme dans l'exemple 1 , avec un traitement thermique de 1 heure à 1360 ° C , d'après la formule suivante :
- 438 g d'oxyde de chrome
- 236 g d'alliage MCrA1Y . La composition de MCrA1Y est en pourcentage : Ni 10 , Co 52 , Cr 25 , Al 7 , Ti 5 , Y O,75 ; Sa granulométrie moyenne est de l'ordre de 25 microns .The procedure is as in Example 1, with a heat treatment of 1 hour at 1360 ° C, according to the following formula:
- 438 g of chromium oxide
- 236 g of MCrA1Y alloy. The composition of MCrA1Y is in percentage: Ni 10, Co 52, Cr 25, Al 7, Ti 5, YO, 75; Its average particle size is around 25 microns.
A l'issue du traitement thermique , on obtient un composite de densité 5,45 .At the end of the heat treatment, a composite with a density of 5.45 is obtained.
- 41/ Dans les exemples ci-dessus on peut faire varier la proportion de phase métallique de 5 % à 50 % en volume.41 / In the above examples, the proportion of metallic phase can be varied from 5% to 50% by volume.
- 42/ Dans les exemples ci-dessus on modifie la teneur en métal tensio-actif, de façon à la faire varier de 2% à 50% atomique de la phase métal.42 / In the above examples, the content of surfactant metal is modified, so as to vary it from 2% to 50 atomic% of the metal phase.
- 43/ Dans les exemples ci-dessus, on remplace la poudre de nickel, par de la poudre d'alliage réfractaire au Ni, Cr, Co, Fe, type Refractaloy.43 / In the examples above, the nickel powder is replaced by powder of refractory alloy with Ni, Cr, Co, Fe, type Refractaloy.
- 44/ Dans les exemples ci-dessus, on remplace la poudre de nickel, par des alliages à dilatation déterminée, type Invar A D R, ou N42 ou N58 ou Dilver ou Platinite.44 / In the above examples, the nickel powder is replaced by alloys with determined expansion, type Invar A D R, or N42 or N58 or Dilver or Platinite.
- 45/ Dans les exemples ci-dessus, la poudre céramique est remplacée par de la poudre de nitrure de silicium, de carbure de silicium, de carbure de bore, de nitrure de bore ( HBN ou CBN )45 / In the above examples, the ceramic powder is replaced by powder of silicon nitride, silicon carbide, boron carbide, boron nitride (HBN or CBN)
- 46/ Dans les exemples ci-dessus,on utilise les autres métaux tensio-actifs énumérés plus haut.46 / In the examples above, the other surface-active metals listed above are used.
- 47/ On utilise comme poudre métallique de la poudre d'aluminium, comme poudre céramique de la poudre de diborure de titane TiB2 ( 60 % en volume ), avec un des métaux tensio-actifs mentionnés plus haut, et en particulier, le titane ( en raison de 25 % atomique par rapport à la masse métallique ). Après frittage sous charge correspondant à une pression de 10 MPa durant 1 heure à 1380 ° C , on obtient un composite de densité voisine de 4,05 .47 / Aluminum powder is used as metallic powder, as ceramic powder titanium diboride powder TiB2 (60% by volume), with one of the surfactant metals mentioned above, and in particular, titanium ( due to 25 atomic% relative to the metallic mass). After sintering under load corresponding to a pressure of 10 MPa for 1 hour at 1380 ° C., a composite with a density close to 4.05 is obtained.
- 48/ On utilise comme poudre métallique une poudre d'alliage de frottement tel qu'un bronze au plomb, à l'étain à l'aluminium, ou au silicium, et comme poudre céramique du nitrure de titane et/ou du nitrure de bore.48 / As a metallic powder, a friction alloy powder such as lead, tin, aluminum or silicon bronze is used, and as titanium powder titanium nitride and / or boron nitride .
Les applications de tels composites sont extrêmement nombreuses et dépendent bien sûr des composites fabriqués . On peut citer à ce propos :
- La réalisation de pièces de structure, et en particulier dans les machines thermiques.
- La réalisation de pièces de frottement.
- La réalisation de pièces de contact dans l'électrotechnique.
- La réalisation d'outils de coupe, de meule,d'organes soumis à l'abrasion et à la corrosion.
- La réalisation d'électrodes.
- La réalisation de prothèses médicales.The applications of such composites are extremely numerous and depend of course on the composites produced. We can cite in this regard:
- The production of structural parts, and in particular in thermal machines.
- The production of friction parts.
- The production of contact parts in electrical engineering.
- The production of cutting tools, grinding wheels, organs subject to abrasion and corrosion.
- The production of electrodes.
- The production of medical prostheses.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87420356T ATE90398T1 (en) | 1986-12-29 | 1987-12-29 | PROCESS FOR MAKING CERAMIC-METAL COMPOSITES USING TENSIOACTIVE METALS AT THE CERAMIC-METAL CONTACT SURFACES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8618479 | 1986-12-29 | ||
FR8618479A FR2608950B1 (en) | 1986-12-29 | 1986-12-29 | PROCESS FOR MANUFACTURING CERAMIC-METAL COMPOSITE MATERIALS USING SURFACTANT METALS AT CERAMIC-METAL INTERFACES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0277450A1 true EP0277450A1 (en) | 1988-08-10 |
EP0277450B1 EP0277450B1 (en) | 1993-06-09 |
Family
ID=9342523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87420356A Expired - Lifetime EP0277450B1 (en) | 1986-12-29 | 1987-12-29 | Process for preparing metal-ceramic composite materials by using surface-active metals at the ceramic-metal interfaces |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0277450B1 (en) |
AT (1) | ATE90398T1 (en) |
DE (1) | DE3786163T2 (en) |
ES (1) | ES2042597T3 (en) |
FR (1) | FR2608950B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5145513A (en) * | 1990-04-13 | 1992-09-08 | Centre National De Le Recherche Scientifique | Process for the preparing via the in situ reduction of their components and grinding oxide/metal composite materials |
WO2015139699A1 (en) * | 2014-03-20 | 2015-09-24 | Schaeffler Technologies AG & Co. KG | Bearing element for a sliding or rolling bearing |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007005211B4 (en) | 2007-01-30 | 2010-03-11 | Iav Gmbh Ingenieurgesellschaft Auto Und Verkehr | Method for producing a composite material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1473618A (en) * | 1966-03-30 | 1967-03-17 | Sherritt Gordon Mines Ltd | Manufacturing process of nickel and chromium alloys reinforced by a dispersion of refractory oxide |
FR2057562A5 (en) * | 1969-08-27 | 1971-05-21 | Int Nickel Ltd | |
FR2095826A5 (en) * | 1970-06-22 | 1972-02-11 | Sherritt Gordon Mines Ltd | |
FR2223473A1 (en) * | 1973-03-28 | 1974-10-25 | United Aircraft Corp |
-
1986
- 1986-12-29 FR FR8618479A patent/FR2608950B1/en not_active Expired - Lifetime
-
1987
- 1987-12-29 AT AT87420356T patent/ATE90398T1/en not_active IP Right Cessation
- 1987-12-29 DE DE87420356T patent/DE3786163T2/en not_active Expired - Fee Related
- 1987-12-29 ES ES87420356T patent/ES2042597T3/en not_active Expired - Lifetime
- 1987-12-29 EP EP87420356A patent/EP0277450B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1473618A (en) * | 1966-03-30 | 1967-03-17 | Sherritt Gordon Mines Ltd | Manufacturing process of nickel and chromium alloys reinforced by a dispersion of refractory oxide |
FR2057562A5 (en) * | 1969-08-27 | 1971-05-21 | Int Nickel Ltd | |
FR2095826A5 (en) * | 1970-06-22 | 1972-02-11 | Sherritt Gordon Mines Ltd | |
FR2223473A1 (en) * | 1973-03-28 | 1974-10-25 | United Aircraft Corp |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN, vol. 10, no. 17 (C-324)[2074], 23 janvier 1986; & JP-A-60 169 533 (TOSHIBA TUNGALOY K.K.) 03-09-1985 * |
PATENT ABSTRACTS OF JAPAN, vol. 5, no. 85 (C-57)[757], 3 juin 1981; & JP-A-56 029 650 (TOSHIBA TUNGALOY K.K.) 25-03-1981 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5145513A (en) * | 1990-04-13 | 1992-09-08 | Centre National De Le Recherche Scientifique | Process for the preparing via the in situ reduction of their components and grinding oxide/metal composite materials |
WO2015139699A1 (en) * | 2014-03-20 | 2015-09-24 | Schaeffler Technologies AG & Co. KG | Bearing element for a sliding or rolling bearing |
CN106415036A (en) * | 2014-03-20 | 2017-02-15 | 舍弗勒技术股份两合公司 | Bearing element for a sliding bearing or a rolling bearing |
Also Published As
Publication number | Publication date |
---|---|
DE3786163D1 (en) | 1993-07-15 |
ATE90398T1 (en) | 1993-06-15 |
ES2042597T3 (en) | 1993-12-16 |
FR2608950B1 (en) | 1991-10-18 |
DE3786163T2 (en) | 1994-01-27 |
FR2608950A1 (en) | 1988-07-01 |
EP0277450B1 (en) | 1993-06-09 |
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