DE239520T1 - Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse. - Google Patents

Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse.

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Publication number
DE239520T1
DE239520T1 DE198787630032T DE87630032T DE239520T1 DE 239520 T1 DE239520 T1 DE 239520T1 DE 198787630032 T DE198787630032 T DE 198787630032T DE 87630032 T DE87630032 T DE 87630032T DE 239520 T1 DE239520 T1 DE 239520T1
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Prior art keywords
metal
boron source
parent metal
mass
boron
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Pending
Application number
DE198787630032T
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English (en)
Inventor
Michael K. Newark Delaware 19711 Aghajanian
Marc S. Newkirk
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Lanxide Technology Co LP
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Lanxide Technology Co LP
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Publication of DE239520T1 publication Critical patent/DE239520T1/de
Pending legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/10Isostatic pressing, i.e. using non-rigid pressure-exerting members against rigid parts or dies
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/5156Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on rare earth compounds
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58071Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on titanium borides
    • CCHEMISTRY; METALLURGY
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/636Polysaccharides or derivatives thereof
    • C04B35/6365Cellulose or derivatives thereof
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • C04B35/65Reaction sintering of free metal- or free silicon-containing compositions
    • C04B35/652Directional oxidation or solidification, e.g. Lanxide process
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653Processes involving a melting step
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1057Reactive infiltration
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/14Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Cephalosporin Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Moulding By Coating Moulds (AREA)
  • Glass Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Reinforced Plastic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Pinball Game Machines (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Packages (AREA)
  • Supports For Pipes And Cables (AREA)
  • Electrostatic, Electromagnetic, Magneto- Strictive, And Variable-Resistance Transducers (AREA)
  • Gloves (AREA)
  • Road Signs Or Road Markings (AREA)
  • Materials For Medical Uses (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Paper (AREA)

Claims (14)

EP 87630032.8 Lanxide Technology Companyf LP Patentansprüche
1. Verfahren zur Herstellung eines freitragenden Körpers, das umfaßt:
(a) Auswählen eines Grundmetails,
(b) Erhitzen dieses Grundmetalls in einer im wesentlichen inerten Atmosphäre auf eine Temperatur über seinem Schmelzpunkt, um einen Körper aus dem geschmolzenen Metall zu erzeugen, sowie Inkontaktbringen dieses Körpers aus dem geschmolzenen Grundmetall mit einer Masse, die eine Borquelle enthält,
(c) Aufrechterhalten der genannten Temperatur für einen Zeitraum, der ausreicht, eine Infiltration des geschmolzenen Grundmetalls in die genannte Masse und die Umsetzung des geschmolzenen Grundmetalls mit der genannten Borquelle unter Bildung eines Grundmetallborids zu gestatten und
(d) Fortsetzen dieser Infiltration und Umsetzung für einen Zeitraum, der ausreicht, den freitragenden Körper, der eine metallische Phase und ein Grundmetallborid enthält, herzustellen.
2. Verfahren nach Anspruch 1, das das Ausbilden der genannten Masse durch Vermischen der Borquelle mit einem inerten Füllstoff, Ablaufenlassen der Infiltration und Umsetzung in die gebildete Masse, um den Füllstoff einzubetten, und Herstellen eines Verbundmaterials in Form eines freitragenden Körpers, der eine den Füllstoff einbettende Matrix aufweist, wobei die Matrix eine Metallphase und ein Grundmetallborid enthält, umfaßt.
3. Verfahren nach Anspruch 1 oder 2, bei dem die Borquelle in wenigstens stöchiometrischer Menge vorhanden ist und die
Infiltration und Umsetzung für einen Zeitraum fortgesetzt wird, der ausreicht, im wesentlichen das gesamte Grundmetall zu verbrauchen.
4. Verfahren nach Anspruch 3, bei dem die Infiltration und Umsetzung für einen Zeitraum fortgesetzt wird, der ausreicht, einen porösen Körper herzustellen.
5. Verfahren nach irgendeinem der Ansprüche 1, 2 oder 3, bei dem das Grundmetall aus einer Gruppe ausgewählt ist, die aus Aluminium, Titan, Zirkonium, Silicium, Hafnium, Lanthan, Eisen, Calcium, Vanadium, Niob, Magnesium und Beryllium besteht.
6. Verfahren nach irgendeinem der vorausgehenden Ansprüche, bei dem das Grundmetall Aluminium ist, die Borquelle elementares Bor ist und der freitragende Körper Aluminium und Aluminiumborid enthält.
7. Verfahren nach Anspruch 1, bei dem die Masse eine niedrige Dichte der genannten Borquelle enthält, wodurch ein freitragender Körper gebildet wird, der Eigenschaften aufweist, die von den Eigenschaften der metallischen Phase dominiert werden.
8. Verfahren nach Anspruch 2, bei dem die Masse eine niedrige Dichte der Borquelle in Zwischenräumen zwischen den Bestandteilen des Füllstoffs enthält, wodurch die resultierende Matrix Eigenschaften aufweist, die von der metallischen Phase dominiert werden.
9· Verfahren nach irgendeinem der Ansprüche 7 oder 8, bei dem die Borquelle elementares Bor ist.
10. Verfahren nach Anspruch 1, bei dem die genannte Masse eine hohe Dichte der Borquelle enthält, wodurch ein freitragender Körper gebildet wird, der Eigenschaften aufweist, die von dem Grundmetallborid dominiert werden.
11. Verfahren nach Anspruch 2, bei dem die genannte Masse eine
hohe Dichte der genannten Borquelle in den Zwischenräumen zwischen den Bestandteilen des Füllstoffs aufweist, wodurch die resultierende Matrix Eigenschaften aufweist, die von dem Grundmetallborid dominiert werden.
12. Verfahren nach Anspruch 10 oder 11, bei dem die genannte Borquelle elementares Bor ist.
13. Verfahren nach Anspruch 2 oder 6, bei dem die genannte Masse wenigstens etwa 50 Gew.-% der genannten Borquelle enthält und das genannte Grundmetallborid in wenigstens einer Dimension zu einem wesentlichen Grad miteinander in Verbindung steht.
14. Verfahren nach irgendeinem der vorausgehenden Ansprüche, bei dem die genannte Masse ein durch das Grundmetall reduzierbares Metallborid enthält und die metallische Phase ein Metall aus dem genannten Metallborid enthält.
15· Verfahren nach Anspruch 14, bei dem das genannte Grundmetall Titan ist und das genannte reduzierbare Metallborid Aluminiumdodecaborid ist.
DE198787630032T 1986-03-07 1987-03-05 Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse. Pending DE239520T1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/837,448 US4777014A (en) 1986-03-07 1986-03-07 Process for preparing self-supporting bodies and products made thereby

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Publication Number Publication Date
DE239520T1 true DE239520T1 (de) 1988-05-19

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DE8787630032T Expired - Fee Related DE3769682D1 (de) 1986-03-07 1987-03-05 Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse.
DE198787630032T Pending DE239520T1 (de) 1986-03-07 1987-03-05 Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse.

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DE8787630032T Expired - Fee Related DE3769682D1 (de) 1986-03-07 1987-03-05 Verfahren zum herstellen von selbsttragenden formkoerpern und nach ihm hergestellte erzeugnisse.

Country Status (29)

Country Link
US (1) US4777014A (de)
EP (1) EP0239520B1 (de)
JP (2) JPS62220266A (de)
KR (1) KR950002915B1 (de)
CN (1) CN1016620B (de)
AT (1) ATE63141T1 (de)
BG (1) BG60109B2 (de)
BR (1) BR8701042A (de)
CA (1) CA1329875C (de)
CS (1) CS277413B6 (de)
DD (1) DD256871A5 (de)
DE (2) DE3769682D1 (de)
DK (1) DK169411B1 (de)
ES (1) ES2000417B3 (de)
FI (1) FI88019C (de)
GR (1) GR3002397T3 (de)
HU (1) HU203710B (de)
IE (1) IE59796B1 (de)
IL (1) IL82060A (de)
IN (1) IN166061B (de)
MX (1) MX168883B (de)
NO (1) NO169972C (de)
NZ (1) NZ219533A (de)
PL (1) PL154577B1 (de)
PT (1) PT84422B (de)
RU (1) RU2022948C1 (de)
TR (1) TR23190A (de)
YU (1) YU46532B (de)
ZA (1) ZA871656B (de)

Families Citing this family (77)

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US4960736A (en) * 1986-09-16 1990-10-02 Lanxide Technology Company, Lp Surface bonding of ceramic bodies
US5015610A (en) * 1986-09-16 1991-05-14 Lanxide Technology Company, Lp Porous ceramic composite with dense surface
US5238886A (en) * 1986-09-16 1993-08-24 Lanxide Technology Company, Lp Surface bonding of ceramic bodies
US5139977A (en) * 1986-09-16 1992-08-18 Lanxide Technology Company, Lp Porous ceramic composite with dense surface
US5104835A (en) * 1986-09-16 1992-04-14 Lanxide Technology Company, Lp Surface bonding of ceramic bodies
US5254509A (en) * 1987-01-13 1993-10-19 Lanxide Technology Company, Lp Production of metal carbide articles
US4891338A (en) * 1987-01-13 1990-01-02 Lanxide Technology Company, Lp Production of metal carbide articles
US5082807A (en) * 1987-01-13 1992-01-21 Lanxide Technology Company, Lp Production of metal carbide articles
US5401694A (en) * 1987-01-13 1995-03-28 Lanxide Technology Company, Lp Production of metal carbide articles
US4828008A (en) * 1987-05-13 1989-05-09 Lanxide Technology Company, Lp Metal matrix composites
US5202059A (en) * 1987-06-12 1993-04-13 Lanxide Technology Company, Lp Coated ceramic filler materials
US5296417A (en) * 1987-07-15 1994-03-22 Lanxide Technology Company, Lp Self-supporting bodies
US4940679A (en) * 1987-07-15 1990-07-10 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products made thereby
US4885130A (en) * 1987-07-15 1989-12-05 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products produced thereby
US5180697A (en) * 1987-07-15 1993-01-19 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products produced thereby
US5017334A (en) * 1987-07-15 1991-05-21 Lanxide Technology Company, Lp Process for preparing self-supporting bodies and products produced thereby
IL86947A (en) * 1987-07-15 1992-08-18 Lanxide Technology Co Ltd Process for preparing self-supporting bodies and products made thereby
AU620360B2 (en) * 1987-12-23 1992-02-20 Lanxide Corporation A method of producing and modifying the properties of ceramic composite bodies
US5298051A (en) * 1987-12-23 1994-03-29 Lanxide Technology Company, Lp Method of modifying ceramic composite bodies by a post-treatment process and articles produced thereby
US4915736A (en) * 1987-12-23 1990-04-10 Lanxide Technology Company, Lp Method of modifying ceramic composite bodies by carburization process and articles produced thereby
US5162098A (en) * 1987-12-23 1992-11-10 Lanxide Technology Company, Lp Method of modifying ceramic composite bodies by a post-treatment process and articles produced thereby
US5143870A (en) * 1987-12-23 1992-09-01 Lanxide Technology Company, Lp Method of modifying ceramic composite bodies by a post-treatment process and articles produced thereby
US4935055A (en) * 1988-01-07 1990-06-19 Lanxide Technology Company, Lp Method of making metal matrix composite with the use of a barrier
US5143540A (en) * 1988-01-13 1992-09-01 The Dow Chemical Company Densification of ceramic-metal composites
US4834938A (en) * 1988-04-25 1989-05-30 The Dow Chemical Company Method for making composite articles that include complex internal geometry
CA1338006C (en) * 1988-06-17 1996-01-30 James A. Cornie Composites and method therefor
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KR950002915B1 (ko) 1995-03-28
IN166061B (de) 1990-03-10
ATE63141T1 (de) 1991-05-15
IE870573L (en) 1987-09-05
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CS277413B6 (en) 1993-03-17
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NO169972B (no) 1992-05-18
CN87101720A (zh) 1988-08-31
YU46532B (sh) 1993-11-16
CZ151487A3 (en) 1993-02-17
NZ219533A (en) 1990-02-26
IL82060A0 (en) 1987-10-20
TR23190A (tr) 1989-06-06
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PL264412A1 (en) 1988-04-28
FI88019B (fi) 1992-12-15
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PT84422A (en) 1987-04-01
CA1329875C (en) 1994-05-31
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AU6988287A (en) 1987-09-10
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DK115887D0 (da) 1987-03-06
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FI88019C (fi) 1993-03-25
US4777014A (en) 1988-10-11
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