CS356590A3 - Ceramo-metallic sandwich material - Google Patents
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/345—Refractory metal oxides
- C04B2237/346—Titania or titanates
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/58—Forming a gradient in composition or in properties across the laminate or the joined articles
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- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
- C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
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Abstract
Description
-1--1-
Vynález se týká keramickokovového sendvičovéhomateriálu /CMC = Ceramic Metal Compoud/, sestavajícíhoz porézní keramiky infiltrované kovem* Z EB 0 155 331 / lanxide/ je znám keramicko kovo-vý materiál shora uvedeného druhu. Podle hodu 11 lanxi-dova patentu musí malé úhly hranice zrn ležet uvnitřurčité oblasti,aby se umožnila dobrá infiltrace kerami-ckého tělesa . Dále je z GB patentu 21 48 270 / British CeramicResearch Assoc./ ze 30, května 1985 známo, že se cer-mety vyrobí tak, že se porézní SiC-keramika s poro -žitou 39 infiltruje roztaveným hliníkem při 70C 0 Ca za tlaku 6,72 kpsi.BACKGROUND OF THE INVENTION The present invention relates to a ceramic-metal sandwich material (CMC = Ceramic Metal Compoud) consisting of a porous ceramic infiltrated with metal. According to the Thickness of Lanxi's patent, the small grain boundary angles must lie within a particular region to allow good infiltration of the ceramic body. Furthermore, GB Patent 21 48 270 (British Ceramic Research Assoc.) Of May 30, 1985 discloses that ceres are prepared by infiltrating molten aluminum at 70 ° C under a pressure of 6 with a porous SiC-ceramic having a pH of 39. , 72 kpsi.
Další cermety jsou popsány v CS patentu 20 61 32z 01. října 1983·Zde se vyrábí evakuací porézníhokeramického materiálu z 93 až 90 / A^O^,zbytek jeS1O2 a infiltrací hliníkem nebo sloučeninami hliníkupři teplotách 700 až 900 °C pod inertním plynem a za -2- tlaku více než 1 MTa. Keramické tvarové tělískc/mápřed infiltrací porozitu 41 lodle stavu techniky se tedy infiltruje vysoce-porézní keramický materiál roztaveným kovem, takžez tohoto vyrobený produkt vykazuje převážně kovovoustrukturu.Tato keramickékovový sendvičový materiál/CMC/ φέ vlastnosti odpovídající co nejvíce kovovépovaze,takže požadavky na tvrdost, odolnost vůči te-plotám a opotřebení se pohybují hluboko pod hodnotamičistě keramických materiálů» Ůlo hou předloženého vynálezu je zlepšit vlast -nosti keramických materiálů s ohledem na pevnost vohybu,houževnatost,modul E, tvrdost odolnost vůči opo-třebení při zachování popřípadě zlepšení převažujícíchvlastností jako je tvrdost,teplotní chování a odol -rošt vůči opotřebení ve srovnání s kovovými materiá-ly. Úloha je vyřešena znaky uvedenými v definici předmětu vynálezu.Ukázalo se,že při vícevrstvé výstavběkeramiky a celkové porozitě 5 až 30 0 umožní infiltra-ce taveninou kovu dosáhnout požadovanou kombinacivlastností.Celková porozita odpovídá při tom výchozí i porozitě keramiky před infiltrací taveninou kovu.koz- -3- hodující při tom je střední poloměr pórů 100 až 1000 nm,který se zjišťuje pomocí Carlo-Erbova rtuťového měřičepórovitosti.Other cermets are described in CS Patent 20 61 32, issued October 1, 1983, which is produced by evacuating porous ceramic material from 93 to 90% Al2 O3, the remainder being SiO2 and infiltrating aluminum or compounds at temperatures of 700 DEG to 900 DEG C. under inert gas -2- pressure more than 1 MTa. Thus, the ceramic molding prior to the infiltration of the prior art porosity 41 infiltrates the high-porous ceramic material with the molten metal, so that the product produced is predominantly of a metal structure. BACKGROUND OF THE INVENTION It is an object of the present invention to improve the properties of ceramic materials with respect to tensile strength, toughness, modulus E, hardness resistance to wear, while maintaining or improving the prevailing properties such as hardness. , thermal behavior and wear resistance compared to metal materials. The problem is solved by the features disclosed in the definition of the subject matter of the invention. It has been shown that in multilayer construction of a ceramic and a total porosity of 5 to 30, the infiltration by the metal melt can achieve the desired combination of properties. Preferred is a mean pore radius of 100 to 1000 nm, which is determined by Carlo-Erb mercury porosity.
Pomocí vícevrstvé výstavby se dosáhne sítovitéstruktury pórů keramického materiálu,který se dá ob -vzléstě příznivě infiltrovat taveninou kovu. Síiovitástruktura pórů je podle vynálezu ovladatelná pomocípoužitá velikosTi^ částic keramického materiálu jakoži rychlostí nanášení v plasmatickém paprsku stabilizo-vaném kapalinou.By multilayer construction, the porosity of the pores of the ceramic material is achieved, which can be advantageously infiltrated by the metal melt. According to the invention, the porous pore structure can be controlled by using the particle size of the ceramic material as well as the liquid-deposition rate in the plasma beam.
Na základě pokusů se ukázalo,že malé úhly hranicezrnuváděné v lanxidově patentu nejsou nezbytné,kdyžkeramika vykazuje sítcvitou strukturu pórů,které jevystavěna spolu spojenými póry a kanály pórů.Tatozvéštní strukrura existuje tehdy,když je keramika vy-stavěna z většího počtu tenkých vrstev,které opět jsouvytvořeny tak,že jejich porosita je nastavitelná.It has been shown by experiments that small angles bounded by the lanxide patent are not necessary, when the ceramic exhibits a mesh-like pore structure which is coupled with the interconnected pores and pores of the pores. they are designed so that their porosity is adjustable.
Pro určité případě použití, například spojovánís kovovými strukturami, jako například svařované ne-bo spájené keramicko/kovové konstrukce se ukázalo ja-ko prospěšné,když keramický materiál vykazuje směremzvnitřku ven se zvyšující porozitu a tím zvyšující sepodíl kovu.Takto vystavěná sítovina pórů se označujejako " gradientová struktura". Vlastnosti kovu převážu· -4- jí na zevní oblasti sendvičového materiálu, zatím couvnitř převládají vlastnosti keramiky.For certain applications, for example bonding with metal structures, such as welded or brazed ceramic / metal structures, it has been shown to be beneficial if the ceramic material exhibits porosity-enhancing porosity and thus increasing metal particle size. gradient structure ". The properties of the metal prevail on the outside of the sandwich material, while the ceramic properties prevail.
Tato gradientova struktura se docílí pomocí varia-ce velikosti částic při nastříkévání na základní tělesov plasmovém paprsku stabilizovaném kapalinou. Začíná senapříklad s velmi jemným práškem s 20 fum a velikostčástic se zvyšuje v zevních vrstvách keramického mate -riálu na hodnotu d^Q > 100/um. Je ale možné postupo-vat i obráceně,vždy podle toho .kde leží strana přivrá-cená kovové ploše.Podstatné je,aby plocha keramickéhosendvičového tělesa ležící nejblíže ke kovové konstruk-ci vykazovala strukturu,která byla vyrobena z práškus velkým průměrem částic. 3?ro zvyšování tvrdosti a odolnosti vůči opotřebe-ní se může s výhodou používat vícesložkový materiál nabázi oxidu v částečně zreagovaném stavu, lod pojmemvícesložkové materiály se rozumí směsi dvou nebo víceoxidokeramických materiálů,které se rozemelou na prá-šek a při slinovacích teplotách nechají částečně zrea-govat.Teprve potom následuje vnášení do reakční oblastiplasmatického hořáku. Dále je vynález blíže vysvětlen pomocí více pří-kladů provedení,přičemž keramicko- kovové sendvičovémateriály podle vynálezu byly vyrobeny stříkáním v plas-mě a potom se zpracují infiltrací kovem na CMC. Napro-ti tomu se staví obvyklé CMC- materiály popsané v lan- -5- xidově patentu.Iři tom se ukazuje,že vlastnosti mate-riálu CMC podle vynálezu doznávají ještě zřetelnějšízlepšení,když vykazují gradientovou strukturu popsanouv bodech 3 až 5 definice předmětu vynálezu.This gradient structure is achieved by a particle size variation when spraying onto the bodies with a liquid-stabilized plasma beam. For example, a very fine powder with 20 µm starts and the particle size increases in the outer layers of the ceramic material to a value of d ≥ Q / 100 µm. However, it is also possible to do the reverse, in each case where the metal-facing side is located. It is essential that the surface of the ceramic body which is closest to the metal structure exhibits a structure which has been made of powder with a large particle diameter. In order to increase the hardness and wear resistance, the multi-component material can be advantageously used in the partially reacted oxide, the vessel component materials being understood to be mixtures of two or more oxy-ceramic materials which are ground to a powder and partially leave off at sintering temperatures. Then, a plasma torch is introduced into the reaction zone. In the following, the invention is explained in more detail with the aid of several embodiments, whereby the ceramic-metal sandwich materials of the present invention were made by plasma spraying and then treated with metal infiltration on CMC. In addition, the conventional CMC materials described in the patent specification of the patent appear to be even more pronounced when they exhibit a gradient structure as described in points 3 to 5 of the invention.
Hodnoty hustoty a pórovitosti byly určeny podleDIN 51056, hod. oty tvrdosti podle Vickera podle DIN50133.Dejdříve se stříkáním v plasmě vyrobí z mate -riálu AlgO^ a AlgliO^ desky,přičemž velikost částic dj-θse pohybovala mezi 60 až 70 yum a rychlost nanášení přinastříjávání v plasmovém paprsku činila 300 m/s.Tloušť-ka jednotlivých nanášených vrstev činila 100 jum, do-sažená celková pórovitost se u oxidu hlinitého pohy-bovala okolo 18 °/s a u aluminiumtitanétu okolo 15 0.·Tvarový součinitel nastříkaných částic činil 1 : 5 až1 : 20 u oxidu hlinitého a 1 : 15 až 1 : 25 u alumini-umtitanátu. Z těchto desek se nastříhaly zkušební díly prozjištění charakteristických hodnot materiálu ,v roz -měrech 100 x 100 x 30 mm,předehřály se na teplotu1000 °C a infiltrovaly se při 750 °C tlakem p = 35 barůpo dobu 15 s kovovou taveninou ze slitiny AISilOMg.Rychlost ochlazování po infiltraci činila 200. 0 C zahodinu v programově řízené peci,takže se díly ochla-dily během 5 hodin na teplotu místnosti. lotom se zjišťoval objem zbytkových pórů a u alu- -6- miniumoxidové keramiky byla zjištěna hodnota 5 cí° ,vztaženo na výchozí pórovitost a u keramiky z alumi-niumtitanátu 7 ¢.Density and porosity values were determined according to DIN 51056, Vicker's hardness grade according to DIN50133. Initially, the plasma was produced from a AlgO2 and AlgliO2 matrix, with a particle size dj-θ of between 60 and 70 µm and a deposition rate the plasma spraying was 300 m / s. The thickness of the individual coatings was 100 µm, the total porosity achieved for alumina was about 18 ° / s and aluminum titanium was about 15%. 5 to 1: 20 for alumina and 1: 15 to 1: 25 for aluminum umitanate. The test pieces were cut from these plates to determine material characteristics, 100 x 100 x 30 mm, preheated to 1000 ° C and infiltrated at 750 ° C with a pressure of p = 35 bar for 15 seconds with a metal melt of AISilOMg alloy. The cooling rate after infiltration was 200 ° C per hour in a program controlled furnace so that the parts were cooled to room temperature over 5 hours. The volume of the residual pores was determined by the lot and the value of 5%, based on the initial porosity and the alumina titanate 7 ¢, was determined in the case of alumina-minium oxide ceramics.
Další zkušební tělísko se vyrobí s gradientovoustrukturou podle vynálezu.Výrobní podmínky jsou stej-né jako pádmíhky uvedené shora,přičemž se ale nanáše-ly dvě rozdílné velikosti částic s d^Q hodnotou 40popřípadě 100 yum pomocí dvou kanálů.Dři tom se proud-částic á hodnotou = 40 jum kontinuálně zvyšovalz 0 na 25 kg/h,zatím co proud částic s hodnotou = 100 um se v téže míře snižoval ze 25 fcg/h na 0.Přepnutí z jednoho kanálu na druhý kanál se provádě-lo v průběhu jedné hodiny.Při tom získané jednotli-vé tlouštky vrstev se pohybují mezi 80 až 100 jum,celková pórovitost okolo 12 $é. Po infiltraci slitinouAlSilCMg vykazovalo zkušební tělísko objem zbytko-vých pórů 0,6 5», vztaženo na výhozí pórovitost.The other test specimens are made with the gradient structure of the present invention. The production conditions are the same as those mentioned above, but two different particle sizes are applied with a value of 40 or 100 µm using two channels. = 40 µm continuously increasing 0 to 25 kg / h, while the particle stream with a value = 100 µm decreased to the same extent from 25 µg / h to 0. Switching from one channel to another channel was carried out within one hour. In this case, the individual layer thicknesses are between 80 and 100 [mu] m, the total porosity is about 12 [mu] m. After infiltration with AlSilCMg alloy, the test specimen had a residual pore volume of 0.65%, based on the ejection porosity.
Hodnoty naměřené na zkušebních tělesech jsoushrnuty v tabulce 1. Hodnoty pro pevnost v ohybu /4bodové ohýbací zařízení/ ,E-modúl a KIC se zjišto -vály standardními ohybovými zkoušekami na tyčíchs rozměry 3,5 x 4,5 x 45 mm. Pro srovnání jsou uve-dena data materiálu běžně vyráběného celokeramickéhotělesa,uváděného jako A^O^ / hodnoty z literatury/.Ukazuje se ,že sendvičový materiál keramicko-kovový,podle vynálezu vykazuje velmi dobré hodnoty pro pev- -7- nost v ohybu. ,odolnost proti vzniku trhlin /KIC/ a tvr-dost a tím představuje s ohledem na kombinaci cha-rakteristických hodnot materiálu jakož i s ohledem najednotlivé charakteristické hodnoty výrazné zlepšeníoproti běžným materiálům. ·—*>·.->'’ .»^..αϊ.ύ.·..ΛΑ.ί-. -·*-' .·..·. •-«.‘-i-.·—........... ' ’ ' ' 1 .· 1 - -8- T a bulka t materiály X A12O3 ai2o3 Al2TiO5 ai2o3 charakteristické sintrová- stříká- stř íká- stříká- ‘.odro ty no /99,8 c// no no no infil- trováno = CMC hustota g/cm3 >3,9 3,3 3,4 3,6 pevnost v MPa ohybu /4-bodové/ 300 25 45 510 + 50 modul E GPa 310 22 13 250 + 80 KIC 6 ·· - 10 - 12 tvrdost Vicker c. /EV200/20^ 2000 920 + 250 1120±200 1600 + 300 -9- pokr. tabulky 1 charakteristi-cké hodnoty materiály ai2tío5 stříkáno infiltrová- no = CMC Al20^ sgradiento-vou struk-turou stříkáno a infiltro-váno = CMC XX lanxide A hustota 3 g/cnr' 3,7 3,6 - 3,7 3,0 - 3,6 pevnost v oljbu MPa /4-bodové/ 490 + 80 550 + 40 50 - 350 modul E GPa 300 + 100 350 + 50 88 - 310 KIC MPaX" m 13 - 15 15 - 18 3 - 9,5 tvrdost Vicker /HV200/2q/ 1800 + 300 1750 + 300 500 - 1800 x Datenblatt Ceramíques Techniaues DesmarquestxxJ.Met.Sci. 24 / 1989/,658-670The values measured on the test specimens are summarized in Table 1. The values for flexural strength / 4-point bending device /, E-modul and KIC were determined by standard rod bending tests with dimensions of 3.5 x 4.5 x 45 mm. For comparison, the material data of a commercially available all-ceramic body, referred to as " AO " (literature values) is shown. The ceramic-metal sandwich material according to the invention has been shown to have very good flexural strength values. , crack resistance (KIC) and hardness, and thus, with respect to the combination of characteristic material values as well as with respect to the unique characteristic value, represent a significant improvement over conventional materials. · - *> · .-> ''. »^ .. αϊ.ύ. · ..ΛΑ.ί-. - · * - '. · .. ·. • - «.'- i-. · —........... '' '1. · 1 - -8- T a bullet t materials X A12O3 ai2o3 Al2TiO5 ai2o3 characteristic sinter-sprayer ká- ty / 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 300 25 45 510 + 50 module E GPa 310 22 13 250 + 80 KIC 6 ·· - 10 - 12 hardness Vicker c. / EV200 / 20 ^ 2000 920 + 250 1120 ± 200 1600 + 300 -9- cont. infiltration = CMC Al 2 O 3 sgraded structure sprayed and infiltrated = CMC XX lanxide A density 3 g / cnr 3.7 3.6 - 3.7 3.0 - 3 , 6 lead strength MPa / 4-point / 490 + 80 550 + 40 50 - 350 module E GPa 300 + 100 350 + 50 88 - 310 KIC MPaX "m 13 - 15 15 - 18 3 - 9,5 hardness Vicker / HV200 / 2q / 1800 + 300 1750 + 300 500 - 1800 x Datenblatt Ceramíques Techniaues DesmarquestxxJ.Met.Sci. 24/1989 /, 658-670
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Applications Claiming Priority (1)
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---|---|---|---|
DE3924268A DE3924268A1 (en) | 1989-07-22 | 1989-07-22 | CERAMIC METAL COMPOSITE |
Publications (1)
Publication Number | Publication Date |
---|---|
CS356590A3 true CS356590A3 (en) | 1992-01-15 |
Family
ID=6385594
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CS903565A CS356590A3 (en) | 1989-07-22 | 1990-07-18 | Ceramo-metallic sandwich material |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0410284B1 (en) |
JP (1) | JPH03141182A (en) |
KR (1) | KR910002737A (en) |
CN (1) | CN1049647A (en) |
AT (1) | ATE112249T1 (en) |
CA (1) | CA2021645A1 (en) |
CS (1) | CS356590A3 (en) |
DE (2) | DE3924268A1 (en) |
FI (1) | FI903677A0 (en) |
HU (1) | HU904567D0 (en) |
NO (1) | NO903034L (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ299845B6 (en) * | 1999-04-09 | 2008-12-10 | W. C. Heraeus Gmbh & Co. Kg | Precious metal glaze |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2287038A (en) * | 1993-09-30 | 1995-09-06 | Automotive Products Plc | Metal matrix composites |
GB9320150D0 (en) * | 1993-09-30 | 1993-11-17 | Automotive Products Plc | Metal matrix composite components |
GB2365875B (en) * | 1998-12-30 | 2003-03-26 | Intellikraft Ltd | Solid state material |
DE10113590A1 (en) * | 2001-03-20 | 2002-10-02 | Drm Druckgus Gmbh | Production of a casting mold comprises forming a porous precursor produced from a metal oxide ceramic material by sintering with the aid of local heating, and infiltrating with a metal melt made from aluminum and/or magnesium |
CN103072363A (en) * | 2012-12-12 | 2013-05-01 | 西北工业大学 | Preparation method of structure-designable high energy and secondary impact resistance metal/ceramic laminar composite material |
DE102016203030A1 (en) | 2016-02-26 | 2017-08-31 | Heraeus Deutschland GmbH & Co. KG | Copper-ceramic composite |
CN105734325A (en) * | 2016-03-17 | 2016-07-06 | 合肥晨煦信息科技有限公司 | Ceramic metal matrix composite and preparing method thereof |
CN108129169B (en) * | 2016-12-01 | 2021-01-19 | 比亚迪股份有限公司 | Metal ceramic product and preparation method thereof |
CN108745491B (en) * | 2018-06-21 | 2021-02-19 | 湖北秦鸿新材料股份有限公司 | High-wear-resistance roller sleeve of coal mill and preparation method thereof |
DE102021004325A1 (en) | 2021-08-24 | 2023-03-02 | HiPer Medical AG | Multiphase ceramic-ceramic composite and method of making same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ211405A (en) * | 1984-03-16 | 1988-03-30 | Lanxide Corp | Producing ceramic structures by oxidising liquid phase parent metal with vapour phase oxidising environment; certain structures |
DE3543342A1 (en) * | 1985-12-07 | 1987-06-11 | Bojak Kurt | Composite material having high wear resistance and dimensional stability, and process for its manufacture |
JPS62156938A (en) * | 1985-12-28 | 1987-07-11 | 航空宇宙技術研究所 | Manufacture of leaning-function material |
US4718941A (en) * | 1986-06-17 | 1988-01-12 | The Regents Of The University Of California | Infiltration processing of boron carbide-, boron-, and boride-reactive metal cermets |
DE3724995A1 (en) * | 1987-02-26 | 1988-09-08 | Radex Heraklith | Process for manufacturing a composite body and the composite body itself |
DE3914010C2 (en) * | 1989-04-26 | 1995-09-14 | Osaka Fuji Corp | Process for the production of metal-ceramic composites and use of the process for controlling the material properties of composites |
-
1989
- 1989-07-22 DE DE3924268A patent/DE3924268A1/en not_active Withdrawn
-
1990
- 1990-07-04 KR KR1019900010060A patent/KR910002737A/en not_active Application Discontinuation
- 1990-07-06 NO NO90903034A patent/NO903034L/en unknown
- 1990-07-18 CS CS903565A patent/CS356590A3/en unknown
- 1990-07-18 EP EP90113734A patent/EP0410284B1/en not_active Expired - Lifetime
- 1990-07-18 DE DE59007316T patent/DE59007316D1/en not_active Expired - Lifetime
- 1990-07-18 AT AT90113734T patent/ATE112249T1/en not_active IP Right Cessation
- 1990-07-20 FI FI903677A patent/FI903677A0/en not_active IP Right Cessation
- 1990-07-20 HU HU904567A patent/HU904567D0/en unknown
- 1990-07-20 CA CA002021645A patent/CA2021645A1/en not_active Abandoned
- 1990-07-21 CN CN90104772A patent/CN1049647A/en active Pending
- 1990-07-23 JP JP2193198A patent/JPH03141182A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ299845B6 (en) * | 1999-04-09 | 2008-12-10 | W. C. Heraeus Gmbh & Co. Kg | Precious metal glaze |
Also Published As
Publication number | Publication date |
---|---|
HU904567D0 (en) | 1990-12-28 |
EP0410284B1 (en) | 1994-09-28 |
NO903034D0 (en) | 1990-07-06 |
ATE112249T1 (en) | 1994-10-15 |
EP0410284A2 (en) | 1991-01-30 |
FI903677A0 (en) | 1990-07-20 |
DE3924268A1 (en) | 1991-01-31 |
EP0410284A3 (en) | 1991-03-20 |
JPH03141182A (en) | 1991-06-17 |
DE59007316D1 (en) | 1994-11-03 |
NO903034L (en) | 1991-01-23 |
KR910002737A (en) | 1991-02-26 |
CA2021645A1 (en) | 1991-01-23 |
CN1049647A (en) | 1991-03-06 |
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