EP0724021B1 - Verfahren zur Herstellung eines elektrisch leitenden Cermets - Google Patents
Verfahren zur Herstellung eines elektrisch leitenden Cermets Download PDFInfo
- Publication number
- EP0724021B1 EP0724021B1 EP95113512A EP95113512A EP0724021B1 EP 0724021 B1 EP0724021 B1 EP 0724021B1 EP 95113512 A EP95113512 A EP 95113512A EP 95113512 A EP95113512 A EP 95113512A EP 0724021 B1 EP0724021 B1 EP 0724021B1
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- EP
- European Patent Office
- Prior art keywords
- powder
- volume
- noble metal
- ceramic
- decrease
- 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.)
- Expired - Lifetime
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the 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
- 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
-
- 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
- B22F1/12—Metallic powder containing non-metallic particles
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- 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
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
Definitions
- the present invention relates to a method for producing an electrically conductive Cermets with a precious metal content of less than 35% by volume by mixing powders a high temperature resistant ceramic and a noble metal, forming a green body the powder mixture and sintering of the green body to form a dense ceramic phase and a contiguous network of metallic phase having cermets.
- precious metal here are gold, silver, and the group The platinum metals platinum, palladium, rhodium, iridium, osmium and ruthenium meant.
- Cermets are intimate mixtures of ceramic and metallic components designated. They combine the corrosion resistance and the hardness of ceramic with the electrical conductivity and the strength of metals. They are used for example for electrical feedthroughs for discharge lamps, in spark plugs or for the manufacture used by sensor elements in electrical Massen shedflußmessem.
- a generic method for producing such a cermet is known from DE-A1 26 58 647 known. Therein it is proposed, first a dispersion of alumina powder with the addition of chromium nitrate, which is a bonding agent between the ceramic phase and the metal phase to produce. After evaporation of the Dispersion are the individual particles produced with a coating of precious metal, For example, provide platinum by adding a solution of chloroplatinic acid or tetramine-platinum chloride be exposed under the presence of a reducing agent, from which then Platinum on the The green body at approx. 1400 ° C becomes a cermet with good electrical conductivity receive. The electrical conductivity is based on the generated, cohesive, skeletal structure of the metallic phase. The volume fraction of platinum metal is at the known cermet, for example, about 12.5%.
- the present invention is therefore based on the object to provide a method which the production of cermets based on high temperature resistant materials with good electrical properties Conductivity and high density with low precious metal content allows.
- a noble metal powder which at sintering temperature to form the metallic phase an increase in volume, a decrease in volume or no change in volume that a ceramic powder is used, which at sintering temperature to form the ceramic Phase has a volume decrease, and that in the case that the noble metal powder has a volume decrease, the decrease in volume of the ceramic powder is greater than the decrease in volume of the noble metal powder.
- the term "precious metal” is understood to mean gold, silver, ruthenium, rhodium, palladium, osmium, iridium or platinum.
- the reduction in the sintering activity of the noble metal is accomplished by a variety of known means, such as crystal growth inhibiting additives, a narrow particle size distribution of the noble metal powder, a morphology of the individual grains of the powder, which involves low surface energy, or a low specific surface area of the powder as a whole , to reach.
- the ceramic powder used has a high sintering activity.
- the volume decrease of the powder used for the formation of the green body is determined by means of dilatometer measurements determined.
- appropriate dilatometer samples are obtained by cold pressing made of precious metal and ceramic powder. These measurements will be under certain In the case of the precious metal powder, an increase in volume on heating has even been observed.
- the volume increase can be, for example, by relaxation processes of the pre-consolidated Explain samples. In this regard, under the main claim as "small" designated Volume decrease during sintering of the precious metal powder also increases the volume understand.
- the noble metal powder has a lower sintering activity than the ceramic powder.
- the comparison The sintering activities of precious metal powder and ceramic powder is carried out by heating cold pre-pressed samples of the respective powder while observing the grain growth. the one Powder has the higher sintering activity at which grain growth occurs at the lower temperature starts.
- the sintering activity is particularly low due to the low surface energy. Structures and networks in the green body produced with such a powder therefore also remain during sintering at temperatures above 1500 ° C.
- noble metal powder of which 50% by weight. a grain size of less than 20 microns, preferably less than 15 microns, and of the 10 wt .-% have a particle size of at least 2 microns, preferably at least 4 microns.
- Such a powder has a relatively narrow particle size distribution and one for a slow one Sintering cheap average grain size.
- Very small grains are avoided as possible due to their small radii they have a high surface energy and thus a high sintering activity exhibit.
- Very large starting grains besides smaller grains can be a fortified Grain growth, a so-called giant grain growth, experienced in which the areas around the Impoverish "giant grains” of precious metal. This precious metal depletion can lead to separations in lead the filigree, metallic network structure.
- a narrow particle size distribution is reduced the sintering speed in addition.
- the specific Surface measured by the BET method, is larger by at least a factor of 20 as the specific surface of the noble metal powder.
- the specific surface is a measure of the sintering activity. For a ceramic powder with a relatively large specific surface area in comparison to the noble metal powder, a higher sintering activity is expected. This is an early one Volume decrease of the ceramic phase ensured.
- a ceramic powder with a medium Grain size which is at least ten times smaller than that of the noble metal powder use, wherein at least 90 wt .-% of the ceramic powder has a grain size of not more than 5 have ⁇ m.
- noble metal powder has proven to be particularly favorable, in which the volume decrease the metallic phase in the densification of the green body by at least 5%, preferably 10% less than that of the ceramic phase. As it is only on the difference the specific volume shrinkage arrives, the selection of suitable starting materials be turned off on the ceramic powder instead of the precious metal powder. As at the beginning already explained, under some circumstances, the observed with the noble metal powder Volume shrinkage will be zero or even negative.
- a ceramic powder is used, in which the volume decrease of the ceramic Phase at a lower temperature than the volume decrease in the metallic Phase. This ensures that the metallic phase at any time during dense sintering, a relative volume within the green body is available is greater than its relative initial volume. The tearing of fine ramifications the metallic phase is thus prevented.
- the cermet according to the prior art according to FIG. 1 contains about 40% by volume of platinum.
- the ceramic phase consists essentially of Al 2 O 3 and is densely sintered.
- the sintering temperature of this cermet should therefore have been above 1650 ° C.
- a striking feature of the microsection is the broad size distribution of the cut surfaces of the metallic one Phase.
- some very large areas can be seen. These big contiguous Areas of metallic phase have very many pores.
- the individual areas of metallic phase with a plurality of sharp edges, or very small radii are provided.
- the high sintering activity could for example, to the concentration of metallic phase in the mentioned very large Areas.
- These areas contribute to the electrical conductivity of the cermet not essential. On the contrary, they degrade the given platinum content Conductivity, because in them, the conductive material is concentrated and accordingly to others Job is missing.
- the uneven distribution of the apparent from FIG metallic phase because of differences in the thermal expansion coefficient of Ceramic and metal also stress within the cermet and therefore leads to a Strength reduction.
- the cermet the micrograph of which is shown in binary form in Figure 2 , has a platinum content of 30% by volume; the remainder consists essentially of alumina.
- the green body mixed and molded from the starting powders was densely sintered at 1700 ° C.
- the binary image of FIG. 2 shows the more uniform distribution of the metallic phase in the ceramic phase.
- the cut surfaces of the metallic phase as shown in the micrograph of Figure 2, an area of at most 1000 .mu.m 2 , preferably less than 800 .mu.m 2 and if the curve of Area distribution drops very steeply from its maximum to larger values.
- Such a narrow size distribution of the cut surfaces of metallic areas in the sectional image is an indication of a homogeneous distribution and a finely branched structure of the metallic areas in the cermet.
- FIG. 3 shows the result of a statistical image analysis on the distribution of the metallic phase of the micrograph shown in FIG. 2 on the basis of a histogram.
- the Y axis denotes the absolute frequency of the respective length classes.
- the maximum of the frequency is at a circumferential length of about 16 microns, the frequency distribution decreases slightly slower in the direction of the smaller lengths and slightly slower in the direction of the longer lengths. Overall, however, the frequency distribution is relatively narrow.
- the mean value of the frequency curve is 32 ⁇ m. From the information below the diagram shown, the frequencies in the respective length classes are listed in detail.
- FIG. 4 also shows, in the form of a histogram, the area fraction of metallic phase in a total of 9 statistically selected image sections.
- the histogram illustrates impressively that in all selected image sections the area covered by the metallic phase is almost constant at 29%. This too is an indication of the uniform distribution of the metallic phase.
- a further frequency distribution likewise in the form of a histogram, is shown.
- the X-axis denotes the distance of adjacent areas with metallic phase in ⁇ m and the Y-axis the absolute frequency of the respective distance classes.
- the maximum frequency for a distance class is in the range from 289 to 394 ⁇ m.
- the mean distance is given as 260 ⁇ m.
- the frequency distribution drops steeply at greater distances and flatter at shorter intervals. Overall, however, the frequency distribution is very narrow.
- the statistical image analyzes shown in FIGS. 3 to 5 prove the uniform distribution of the metallic phase in the cermet according to the invention.
- FIG. 6 shows the result of a dilatometric measurement of Al 2 O 3 powder and platinum powder used to produce a cermet according to the invention.
- compacts were produced from the powders by cold pressing.
- the length of the Al 2 O 3 powder compact was 39.31 mm, that of the platinum powder compact 23.48 mm.
- the time in minutes is plotted on the x-axis of the diagram shown in FIG. 6, the temperature in ° C. on the left y-axis, and the length changes measured on the compacts on the right-hand y-axis.
- a first rapid heating phase with phase 1 a subsequent slower heating phase with phase 2 and a constant high temperature region at about 1600 ° C. are designated phase 3.
- the corresponding temperature profile is indicated by the reference numeral 4 in the diagram.
- the extension trace 5 of the platinum powder compact shows no decrease in length increasing temperature. On the contrary, it became around 1580 despite high temperature sintering ° C detected an irreversible increase in length of about 6%. It follows that also at the maximum temperature of the dilatometer measurement in the platinum powder used no sintering has, as in this case a length decrease of the sample should have been observed.
- a platinum starting powder was used, which had a BET surface area of 0.06 m 2 / g. Its average grain size was 10 microns. About 80% by weight of the platinum powder was in the particle size range between 4 ⁇ m and 20 ⁇ m. Overall, the platinum powder is characterized by a very low sintering activity. The structure obtained with it once in the green body therefore essentially remains even when sintered at 1700 ° C.
- the Al 2 O 3 starting powder used had an average particle size of about 1 ⁇ m. 90% by weight of the starting Al 2 O 3 powder had a particle size of less than 3 ⁇ m. Its BET surface area is 4 m 2 / g.
- the Al 2 O 3 starting powder is characterized by a significantly higher sintering activity compared to platinum powder. It has also been found that during dense sintering, the ceramic phase formed from the Al 2 O 3 starting powder experiences a substantially greater volume decrease than the metallic phase formed from the platinum powder. In this case, a noticeable decrease in volume occurs at the ceramic phase at a temperature of about 1400 ° C, while no change in volume is observed in the metallic phase.
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Description
Unter dem Begriff "Edelmetall" werden dabei Gold, Silber, Ruthenium, Rhodium, Palladium, Osmium, Iridium oder Platin verstanden.
Eine mögliche Erklärung für die Abnahme der elektrischen Leitfähigkeit beim Sintern von Grünkörpem mit geringem Edelmetallgehalt bei hohen Temperaturen wäre, daß die metallische Phase sich beim Erhitzen unter Verkleinerung ihrer Oberfläche und Verringerung der Oberflächenenergie zusammenzieht. Dadurch können beispielsweise feine Verästelungen des zusammenhängenden metallischen Gefüges getrennt werden. Als Folge davon nimmt die Leitfähigkeit des Cermets ab. Dies wird vermieden, indem für die Bildung des Grünkörpers ein Edelmetallpulver mit geringer Sinteraktivität eingesetzt wird. Die das Sintern der metallischen Phase bewirkenden Transportvorgänge, die unter Abrundung kleiner Radien zu einer Oberflächenverkleinerung der metallischen Phase führen, laufen dadurch nicht oder nur in geringem Umfang ab. Im Grünkörper realisierte feine Strukturen des Edelmetalls bleiben auch nach dem Sintern bei hohen Temperaturen erhalten; feine Verästelungen der metallischen Phase werden nicht unterbrochen. Die Verringerung der Sinteraktivität des Edelmetalls ist über eine Vielzahl bekannter Maßnahmen, wie beispielsweise durch kristallwachstumshemmende Zusätze, durch eine enge Korngrößenverteilung des Edelmetallpulvers, durch eine Morphologie der einzelnen Körner des Pulvers, die eine geringe Oberflächenenergie beinhaltet, oder durch eine geringe spezifische Oberfläche des Pulvers insgesamt, zu erreichen. Vorteilhafterweise weist das eingesetzte keramische Pulver eine hohe Sinteraktivität auf.
- Figur 1
- ein Binärbild eines Schliffes von einem handelsüblichen Cermet,
- Figur 2
- ein Binärbild eines Schliffes von einem nach dem erfindungsgemäßen Verfahren hergestellten Cermets,
- Figur 3
- eine statistische Auswertung des in Figur 2 dargestellten Schliffbildes,
- Figur 4
- eine weitere statistische Auswertung des in Figur 2 dargestellten Schliffbildes,
- Figur 5
- ein weitere statistische Auswertung des in Figur 2 dargestellten Schliffbildes und
- Figur 6
- das Ergebnis einer dilatometrischen Messung bei einem für die Herstellung des erfindungsgemäßen Cermets eingesetzten Keramik-Pulver und bei einem Edelmetall-Pulver.
Claims (8)
- Verfahren zur Herstellung eines elektrisch leitenden Cermets mit einem Edelmetallanteil von weniger als 35 Vol.-% durch Mischen von Pulvem einer hochtemperaturfesten Keramik und eines Edelmetalls, Formen eines Grünkörpers aus dem Pulvergemisch und Sintern des Grünkörpers unter Bildung eines eine dichte keramische Phase und ein zusammenhängendes Netzwerk aus metallischer Phase aufweisenden Cermets, wobei ein Edelmetallpulver eingesetzt wird, das beim Sintern eine geringere Sinteraktivität als das Keramikpulver aufweist und unter Bildung der metallischen Phase eine Volumenzunahme, eine Volumenabnahme oder keine Volumenänderung aufweist, und wobei ein Keramikpulver eingesetzt wird, das beim Sintern unter Bildung der keramischen Phase eine Volumenabnahme aufweist, und dass in dem Fall, dass das Edelmetallpulver eine Volumenabnahme aufweist, die Volumenabnahme des Keramikpulvers größer ist als die Volumenabnahme des Edelmetallpulvers.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein Edelmetallpulver mit einer spezifischen Oberfläche, gemessen nach dem BET-Verfahren, von weniger als 1 m2/g, vorzugsweise von weniger als 0,1 m2/g, eingesetzt wird.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass Edelmetallpulver eingesetzt wird, mit einer mittleren Korngröße von mindestens 10 µm, vorzugsweise mindestens 20 µm, wobei maximal 10 Gew.-% des Edelmetallpulvers eine Korngröße von weniger als 2 µm aufweist.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Keramikpulver eingesetzt wird, dessen spezifische Oberfläche, gemessen nach dem BET-Verfahren, um mindestens den Faktor 20 größer ist als die spezifische Oberfläche des Edelmetallpulvers.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Keramikpulver eingesetzt wird, mit einer mittleren Korngröße, die um mindestens das zehnfache kleiner ist als diejenige des Edelmetallpulvers, wobei mindestens 90 Gew.-% des Keramikpulvers eine Korngröße von maximal 5 µm aufweisen.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Edelmetallpulver eingesetzt wird, bei dem die Volumenabnahme beim Sintern um mindestens 5%, vorzugsweise um mindestens 10% geringer ist als die entsprechende Volumenabnahme des Keramikpulvers bei der Bildung der keramischen Phase.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Keramikpulver eingesetzt wird, bei dem die Volumenabnahme bei einer niedrigeren Temperatur einsetzt als die Volumenabnahme des Edelmetallpulvers.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass als Edelmetallpulver Platinpulver eingesetzt wird, dass die hochtemperaturfeste Keramik Aluminiumoxid enthält, und dass bei Temperaturen zwischen 1500 °C und 1750 °C, vorzugsweise knapp unterhalb des Schmelzpunktes von Platin gesintert wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19502129A DE19502129C2 (de) | 1995-01-25 | 1995-01-25 | Verfahren zur Herstellung eines elektrisch leitenden Cermets |
DE19502129 | 1995-01-25 |
Publications (2)
Publication Number | Publication Date |
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EP0724021A1 EP0724021A1 (de) | 1996-07-31 |
EP0724021B1 true EP0724021B1 (de) | 2005-03-30 |
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Application Number | Title | Priority Date | Filing Date |
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EP95113512A Expired - Lifetime EP0724021B1 (de) | 1995-01-25 | 1995-08-29 | Verfahren zur Herstellung eines elektrisch leitenden Cermets |
Country Status (4)
Country | Link |
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US (1) | US5796019A (de) |
EP (1) | EP0724021B1 (de) |
JP (1) | JPH08269592A (de) |
DE (2) | DE19502129C2 (de) |
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CN113814395B (zh) * | 2021-10-08 | 2023-05-23 | 中南大学湘雅医院 | 金属锡强化纳米TiO2光固化3D打印陶瓷浆料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3901717A (en) * | 1971-12-10 | 1975-08-26 | Far Fab Assortiments Reunies | Hard precious material |
US4183746A (en) * | 1975-12-24 | 1980-01-15 | Johnson, Matthey & Co., Limited | Cermets |
US4234338A (en) * | 1978-12-28 | 1980-11-18 | The United States Of America As Represented By The United States Department Of Energy | Thermal shock resistance ceramic insulator |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB981792A (en) * | 1962-05-07 | 1965-01-27 | Mond Nickel Co Ltd | Improvements relating to precious metals and alloys thereof |
US3208848A (en) * | 1964-02-25 | 1965-09-28 | Jr Ralph P Levey | Alumina-cobalt-gold composition |
US3623849A (en) * | 1969-08-25 | 1971-11-30 | Int Nickel Co | Sintered refractory articles of manufacture |
WO1989001706A1 (en) * | 1987-08-14 | 1989-02-23 | The Ohio State University | Machine workable, thermally conductive, high strength, ceramic superconducting composite |
DE4029066A1 (de) * | 1990-09-13 | 1992-03-19 | Friedrichsfeld Ag | Keramischer formkoerper |
WO1993017969A1 (en) * | 1992-03-02 | 1993-09-16 | The University Of Kansas | Superconductors having continuous ceramic and elemental metal matrices |
DE4335697C2 (de) * | 1993-10-20 | 1997-04-30 | Friatec Keramik Kunststoff | Verfahren zur Herstellung einer hochvakuumdichten, aber spannungsarmen Fügestelle |
-
1995
- 1995-01-25 DE DE19502129A patent/DE19502129C2/de not_active Expired - Fee Related
- 1995-08-29 DE DE59510995T patent/DE59510995D1/de not_active Expired - Lifetime
- 1995-08-29 EP EP95113512A patent/EP0724021B1/de not_active Expired - Lifetime
-
1996
- 1996-01-05 US US08/583,516 patent/US5796019A/en not_active Expired - Lifetime
- 1996-01-24 JP JP8028726A patent/JPH08269592A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3901717A (en) * | 1971-12-10 | 1975-08-26 | Far Fab Assortiments Reunies | Hard precious material |
US4183746A (en) * | 1975-12-24 | 1980-01-15 | Johnson, Matthey & Co., Limited | Cermets |
US4234338A (en) * | 1978-12-28 | 1980-11-18 | The United States Of America As Represented By The United States Department Of Energy | Thermal shock resistance ceramic insulator |
Also Published As
Publication number | Publication date |
---|---|
DE19502129A1 (de) | 1996-08-01 |
DE19502129C2 (de) | 2003-03-20 |
EP0724021A1 (de) | 1996-07-31 |
DE59510995D1 (de) | 2005-05-04 |
JPH08269592A (ja) | 1996-10-15 |
US5796019A (en) | 1998-08-18 |
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