DE3744250C1 - Process for improving the wettability of the surfaces of SiC ceramic by metal - Google Patents

Process for improving the wettability of the surfaces of SiC ceramic by metal

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Publication number
DE3744250C1
DE3744250C1 DE19873744250 DE3744250A DE3744250C1 DE 3744250 C1 DE3744250 C1 DE 3744250C1 DE 19873744250 DE19873744250 DE 19873744250 DE 3744250 A DE3744250 A DE 3744250A DE 3744250 C1 DE3744250 C1 DE 3744250C1
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Germany
Prior art keywords
ceramic
metal
wettability
sic
improving
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Expired
Application number
DE19873744250
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German (de)
Inventor
Bernd Gottselig
Ernoe Gyarmati
Aristides Naoumidis
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Forschungszentrum Juelich GmbH
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Kernforschungsanlage Juelich GmbH
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Application filed by Kernforschungsanlage Juelich GmbH filed Critical Kernforschungsanlage Juelich GmbH
Priority to DE19873744250 priority Critical patent/DE3744250C1/en
Priority to US07/287,342 priority patent/US4961529A/en
Priority to EP88121379A priority patent/EP0322732B1/en
Priority to DE88121379T priority patent/DE3887747D1/en
Priority to AT88121379T priority patent/ATE101385T1/en
Priority to JP63323807A priority patent/JPH01197374A/en
Application granted granted Critical
Publication of DE3744250C1 publication Critical patent/DE3744250C1/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/025—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of glass or ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/08—Non-oxidic interlayers
    • C04B2237/083—Carbide interlayers, e.g. silicon carbide interlayers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2237/36—Non-oxidic
    • C04B2237/365—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • C04B2237/406—Iron, e.g. steel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

To improve the wettability of the surfaces of SiC ceramic by metal, a 1-3 mu m thick titanium layer is applied, preferably by sputtering, to the polished ceramic surface, preferably cleaned by means of Ar<+> etching. The ceramic is then maintained at a temperature in the range of 1200-1550@C, preferably at 1450@C, for at least 0.5 hour, in particular for 1-2 hours, under protective gas (preferably argon freed of oxidising residues). The heating rate is here preferably about 20-60@C/min. In this way there is formed on the ceramic surface a titanium carbosilicide layer (Ti3SiC2) which is outstandingly suitable, for example, for soldered and diffusion-welded bonds to metals.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Verbesserung der Benetzbarkeit der Oberflächen von SiC-Keramik mit Metall.The invention relates to a method for Improving the wettability of the surfaces of SiC ceramic with metal.

Die Einführung von keramischen Komponenten, wie SiC-Bauteilen, hängt im starken Maße davon ab, inwieweit es gelingt, sie mit metallischen Werkstoffen zu verbinden.The introduction of ceramic components, like SiC components, depends heavily on it to what extent they succeed with metallic To connect materials.

Für solche Verbindungen muß insbesondere auch eine Einsatzmöglichkeit bei hohen Temperaturen (ca. 1000°C) gegeben sein. Es werden daher soge­ nannte stoffschlüssige Verbindungen angestrebt, die einen guten Übergang von einem Partner auf den anderen gewährleisten.For such connections in particular also an application at high temperatures (approx. 1000 ° C). So-called called cohesive connections, making a good transition from partner to partner guarantee the other.

Grundsätzlich bestehen zwei Wege, um Metall/ Keramik-Verbindungen mit den angesprochenen Merkmalen herzustellen, und zwar:There are basically two ways to Ceramic connections with the addressed Manufacture characteristics, namely:

  • 1. Durch Lötverbindung:
    Löten ist ein klassisches Verfahren der Ver­ bindungstechnik. Leider konnten die Erfahrungen aus dem metallischen Bereich nur eingeschränkt übernommen werden, da aufgrund der hohen Oberflächenspannung der keramischen Oberfläche keine Benetzung dieses Fügepartners stattfindet.     1. By solder connection:
    Soldering is a classic connection technology process. Unfortunately, the experience from the metallic area could only be taken over to a limited extent, since due to the high surface tension of the ceramic surface there is no wetting of this joining partner.
  • Um eine Benetzung zu erreichen, ist es nötig, die Keramik zu metallisieren. Die metalli­ sierte Keramik wird dann von Loten benetzt und die Verbindung kann hergestellt werden. To achieve wetting, it is necessary to metallize the ceramic. The metalli Ceramic is then wetted by solders and the connection can be made.
  • 2. Durch Diffusionsschweißen:
    Dieses Verfahren beruht darauf, daß sich an der Kontaktstelle zweier Materialien eine Reaktionsschicht ausbildet, die einen Übergang zwischen den zu verbindenden Werkstoffe erzeugt.    2. By diffusion welding:
    This method is based on the fact that a reaction layer forms at the contact point of two materials, which creates a transition between the materials to be joined.
  • So hergestellte Verbindungen zwischen technisch interessanten Legierungen und SiC-Keramiken erwiesen sich als wenig belastbar, was auf die Entstehung von Reaktionsprodukten in der Übergangszone der beiden zu fügenden Partner, insbesondere auf die Bildung spröder Metallcarbide, zurückzuführen ist.Connections made in this way between technical interesting alloys and SiC ceramics proved to be little resilient to what the formation of reaction products in the transition zone of the two to be joined Partners, especially on brittle education Metal carbides.

Diese Probleme können durch eine Metallisierung der Keramik umgangen werden, welche die Benetzbar­ keit durch Metall verbessert und Störreaktionen im Fügebereich mindert.These problems can be caused by a metallization the ceramics are bypassed, which the wettable speed improved by metal and interference reactions diminishes in the joining area.

Ziel der Erfindung ist daher ein Verfahren, mit dem eine solche Metalli­ sierung erreicht werden kann.The aim of the invention is hence a process with which such a metalli can be achieved.

Das zu diesem Zweck entwickelte erfindungsgemäße Verfahren ist gemäß Anspruch 1 dadurch gekennzeichnet, daß auf die polierte Oberfläche eine 1 bis 3 µm dicke Titanschicht aufgebracht und dann die Keramik zumindest für 0,5 h unter Schutzgas bei einer Temperatur im Bereich von 1200 bis 1550°C gehalten wird.The invented for this purpose developed The method according to claim 1 is characterized in that on the polished surface a 1 to 3 µm thick titanium layer applied and then the ceramic for at least 0.5 h under protective gas at a temperature in the range of 1200 to 1550 ° C is maintained.

Vorteilhafte Ausbildungen des Verfahrens nach Anspruch 1 sind in den Ansprüchen 2 bis 7 beschrieben.Advantageous training of the method according to claim 1 are described in claims 2 to 7.

Durch eine solche Behandlung erhält die Silicium­ carbidoberfläche eine im wesentlichen aus Ti3SiC2 bestehende Schicht, die zum einen am Übergang von Keramik zum Metall für eine gute Haftung sorgt und zum anderen die Ausbildung von störenden Reaktionsprodukten am Übergang zum Metall weit­ gehend verhindert.Such a treatment gives the silicon carbide surface a layer consisting essentially of Ti 3 SiC 2 , which ensures good adhesion on the one hand at the transition from ceramic to metal and on the other hand largely prevents the formation of disruptive reaction products at the transition to the metal.

Das erfindungsgemäße Verfahren wird anhand der nachfolgenden Ausführungen näher erläutert. Es kann folgende Schritte umfassen:The method according to the invention is illustrated in the following Explanations explained. It can include the following steps:

  • - Polieren der SiC-Keramikoberfläche auf Rauhig­ keiten zwischen Ra = 0,01 bis 0,1 µm.- Polishing the SiC ceramic surface to rough between Ra = 0.01 to 0.1 µm.
  • - Aufbringen einer 1 bis 3 µm dicken Titanschicht auf die polierte Oberfläche, insbesondere durch Aufsputtern von Titan. Die polierte SiC-Fläche kann vorher durch Ar⁺-Ätzen von an der Keramikoberfläche haftenden Verunreinigungen befreit werden.- Application of a 1 to 3 µm thick titanium layer on the polished surface, in particular by sputtering titanium. The polished SiC surface can be cleaned beforehand Ar⁺ etching of those adhering to the ceramic surface Impurities are freed.
  • - Glühen der titanbeschichteten Keramikoberfläche zur Umwandlung der Oberflächenschicht in Titan­ carbosilicid (Ti3SiC2) bei Temperaturen von 1200 bis 1550°C unter Schutzgas, wobei insbe­ sondere wie folgt verfahren wird:- Annealing the titanium-coated ceramic surface to convert the surface layer into titanium carbosilicide (Ti 3 SiC 2 ) at temperatures from 1200 to 1550 ° C under a protective gas, in particular as follows:
  • Das Werkstück mit titanbeschichteter Oberfläche wird in einen Ofen gebracht, der auf 1 Pa evakuiert wird. Danach wird eine Schutzgasspülung (Ar von 99,9997%iger Reinheit) zugeschaltet. Das zuströmende Gas wird dabei zunächst durch Überleiten über P2O5 getrocknet und üer Titanschwamm geleitet, um oxidierende Reste zu beseitigen. Sodann wird das Werkstück bzw. die beschichtete Oberfläche für zumindest 0,5 h auf die genannte Glühtemperatur aufgeheizt, insbesondere auf 1450°C. Die Aufheizrate kann dabei insbe­ sondere zwischen 20 und 60°C/min liegen.The workpiece with the titanium-coated surface is placed in an oven, which is evacuated to 1 Pa. A protective gas purge (Ar of 99.9997% purity) is then switched on. The inflowing gas is first dried by passing it over P 2 O 5 and passed over a titanium sponge in order to remove oxidizing residues. The workpiece or the coated surface is then heated to the stated annealing temperature, in particular to 1450 ° C., for at least 0.5 h. The heating rate can be between 20 and 60 ° C / min in particular.
  • Die Behandlungsdauer bei Glühtemperatur hängt von der Schichtdicke des Titans ab und beträgt insbesondere 1 bis 2 h. So wird beispiels­ weise ein mit 3,0 µm Ti beschichtetes Material 2 h lang bei 1450°C gehalten.The treatment time at the annealing temperature depends on the layer thickness of the titanium and is especially 1 to 2 hours. For example a material coated with 3.0 µm Ti Maintained at 1450 ° C for 2 hours.
  • Die Abkühlung erfolgt im Ofen, aus dem dann das beschichtete Werkstück entnommen wird.The cooling takes place in the oven, from which then the coated workpiece is removed.

Die auf diese Weise behandelte Keramikoberfläche weist eine zu 95% aus Titancarbosilicid (Ti3TiC2) mit Spuren von TiSi2 und TiC bestehende Oberflächenschicht auf, die fest mit der Keramik verzahnt ist und für Löt- und Diffusionsschweißver­ bindungen mit Metallen, wie insbesondere mit Stahl oder Nickelbasierlegierungen hervorragend geeignet ist, die, wie nachfolgend beschrieben, gebildet werden.:The ceramic surface treated in this way has a surface layer consisting of 95% titanium carbosilicide (Ti 3 TiC 2 ) with traces of TiSi 2 and TiC, which is firmly interlocked with the ceramic and for soldering and diffusion welding connections with metals, in particular with Steel or nickel-based alloys, which are formed as described below:

  • 1. Herstellung einer Lötverbindung:
    Bei Löttemperaturen bis zu 1200°C und üblicher­ weise von 900 bis 1100°C lassen sich mit einer so behandelten Oberfläche unter Anwendung üblicher Lote, feste Lötverbindungen mit Metallteilen schaffen, die aus gebräuchlichen Legierungen bestehen, aber keine Reaktivmetalle, wie Ti oder Zr enthalten dürfen.    1. Making a solder joint:
    At soldering temperatures up to 1200 ° C and usually from 900 to 1100 ° C, a surface treated in this way can be used to create solid solder connections with metal parts made of common alloys, but not containing reactive metals such as Ti or Zr .
  • 2. Erzeugung einer Diffusionsschweißverbindung:
    Diffusionsschweißverbindungen mit Stahl- oder Nickelbasislegierungsteilen werden mit so beschichteten SiC-Oberflächen in der Heißpresse erzeugt. Dazu wird der Fügeraum zunächst evakuiert und dann mit Schutzgas (z. B. Ar/4% H2) gespült. Die Fügetempera­ turen liegen bei maximal 1200°C, insbesondere im Bereich von 900 bis 1200°C. Die Aufheiz­ rate beträgt 150 bis 300°C/min und die Glühdauer beträgt bis zu 1 h, insbesondere 15 bis 30 min. Abgekühlt wird durch Konvektion.    2. Generation of a diffusion weld joint:
    Diffusion welded joints with steel or nickel-based alloy parts are produced with SiC surfaces coated in this way in the hot press. For this purpose, the joining room is first evacuated and then flushed with protective gas (e.g. Ar / 4% H 2 ). The joining temperatures are at a maximum of 1200 ° C, in particular in the range from 900 to 1200 ° C. The heating rate is 150 to 300 ° C / min and the annealing time is up to 1 h, in particular 15 to 30 min. It is cooled by convection.

Der metallische Fügepartner sollte jeweils vor der Fügung geschliffen und poliert werden, wobei die Endrauhigkeit der Kontaktfläche Ra = 0,01 bis 0,1 µm betragen sollte.The metallic joining partner should always be in front the joint can be ground and polished, whereby the final roughness of the contact surface Ra = 0.01 should be up to 0.1 µm.

Claims (7)

1. Verfahren zur Verbesserung der Benetzbarkeit der Oberflächen von SiC-Keramik mit Metall, dadurch gekennzeichnet, daß auf die polierte Oberfläche eine 1 bis 3 µm dicke Titanschicht aufgebracht und dann die Keramik zumindest für 0,5 h unter Schutzgas bei einer Temperatur im Bereich von 1200 bis 1550°C gehalten wird.1. A method for improving the wettability of the surfaces of SiC ceramic with metal, characterized in that a 1 to 3 µm thick titanium layer is applied to the polished surface and then the ceramic at least for 0.5 h under protective gas at a temperature in the range 1200 to 1550 ° C is maintained. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Oberfläche durch Ar⁺-Ätzen gereinigt wird.2. The method according to claim 1, characterized, that the surface is cleaned by Ar⁺ etching becomes. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Titanschicht aufgesputtert wird.3. The method according to claim 1 or 2, characterized, that the titanium layer is sputtered on. 4. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Keramik 1 bis 2 h lang erhitzt wird.4. Method according to one of the preceding Expectations, characterized, that the ceramic is heated for 1 to 2 hours. 5. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Keramik auf eine Temperatur von 1450°C erhitzt wird.5. Method according to one of the preceding Expectations, characterized, that the ceramic to a temperature of 1450 ° C. is heated. 6. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Keramik in Schutzgas, insbesondere in von oxidierenden Resten befreitem Argon aufge­ heizt wird.6. Method according to one of the preceding Expectations,  characterized, that the ceramic in protective gas, especially in Argon freed from oxidizing residues is heated. 7. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Keramik mit einer Geschwindigkeit von 20 bis 60°C/min aufgeheizt wird.7. Method according to one of the preceding Expectations, characterized, that the ceramic at a speed of 20 to 60 ° C / min is heated.
DE19873744250 1987-12-24 1987-12-24 Process for improving the wettability of the surfaces of SiC ceramic by metal Expired DE3744250C1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE19873744250 DE3744250C1 (en) 1987-12-24 1987-12-24 Process for improving the wettability of the surfaces of SiC ceramic by metal
US07/287,342 US4961529A (en) 1987-12-24 1988-12-20 Method and components for bonding a silicon carbide molded part to another such part or to a metallic part
EP88121379A EP0322732B1 (en) 1987-12-24 1988-12-21 Method of joining an article of silicon carbide to another article of silicon carbide or metal
DE88121379T DE3887747D1 (en) 1987-12-24 1988-12-21 Method for connecting a silicon carbide molded part to a further molded part made of silicon carbide or metal.
AT88121379T ATE101385T1 (en) 1987-12-24 1988-12-21 METHOD OF JOINING A SILICON CARBIDE PART WITH ANOTHER SILICON CARBIDE OR METAL PART.
JP63323807A JPH01197374A (en) 1987-12-24 1988-12-23 Method for bonding silicon carbide molded body to silicon carbide or metal molded body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19873744250 DE3744250C1 (en) 1987-12-24 1987-12-24 Process for improving the wettability of the surfaces of SiC ceramic by metal

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DE3744250C1 true DE3744250C1 (en) 1989-08-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4125469A1 (en) * 1990-08-03 1992-02-06 Ngk Spark Plug Co Combined metal and ceramic rotor blade - has treated surfaces near end of bonding zone and untreated contact surfaces away from end
WO2001046083A1 (en) * 1999-12-22 2001-06-28 Drexel University Process for forming 312 phase materials and process for sintering the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NICHTS ERMITTELT *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4125469A1 (en) * 1990-08-03 1992-02-06 Ngk Spark Plug Co Combined metal and ceramic rotor blade - has treated surfaces near end of bonding zone and untreated contact surfaces away from end
WO2001046083A1 (en) * 1999-12-22 2001-06-28 Drexel University Process for forming 312 phase materials and process for sintering the same
US6461989B1 (en) 1999-12-22 2002-10-08 Drexel University Process for forming 312 phase materials and process for sintering the same
CN1293019C (en) * 1999-12-22 2007-01-03 德崇大学 Process for forming 312 phase materials and process for sintering the same

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