EP0630425A1 - Verfahren zum beschichten von kohlenstoffaserverstärktem kohlenstoff und danach hergestelltes produkt - Google Patents
Verfahren zum beschichten von kohlenstoffaserverstärktem kohlenstoff und danach hergestelltes produktInfo
- Publication number
- EP0630425A1 EP0630425A1 EP93906488A EP93906488A EP0630425A1 EP 0630425 A1 EP0630425 A1 EP 0630425A1 EP 93906488 A EP93906488 A EP 93906488A EP 93906488 A EP93906488 A EP 93906488A EP 0630425 A1 EP0630425 A1 EP 0630425A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon
- layer
- protective layer
- reinforced carbon
- crystalline
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims description 5
- 238000000576 coating method Methods 0.000 title claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 15
- 239000004917 carbon fiber Substances 0.000 claims abstract description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000011241 protective layer Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- -1 argon ions Chemical class 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims 1
- 229910004205 SiNX Inorganic materials 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- 239000002318 adhesion promoter Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000005513 bias potential Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Classifications
-
- 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
- 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
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
- 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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
- C04B41/526—Multiple coating or impregnation with materials having the same composition but different characteristics
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/902—High modulus filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49229—Prime mover or fluid pump making
- Y10T29/4927—Cylinder, cylinder head or engine valve sleeve making
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49229—Prime mover or fluid pump making
- Y10T29/4927—Cylinder, cylinder head or engine valve sleeve making
- Y10T29/49272—Cylinder, cylinder head or engine valve sleeve making with liner, coating, or sleeve
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the invention relates to a method for coating carbon fiber reinforced carbon (CFC) with at least one layer.
- CFC carbon fiber reinforced carbon
- Carbon fiber reinforced carbon is characterized by high strength and very good toughness. A wide use of this material is, however, currently severely restricted due to a lack of oxidation resistance. In particular, use above 400'C without protective gas is hardly possible.
- the present invention addresses the problem of providing a method for the coating of carbon fiber reinforced carbon having at least one layer so as to provide that a high oxidation resistance is also possible at higher temperatures, ie above 400 * C, but especially about 1.500'C .
- the problem is solved according to the invention in that an adhesive layer made of amorphous SiN x is applied to the carbon fiber-reinforced carbon (CFC), to which in turn the layer resistant to oxidation at a temperature T OO'C is applied as a protective layer made of silicon compounds.
- Crystalline S ' ⁇ N can be applied as a protective layer.
- amorphous SiN or SiO 2 or a combination of these with kri ⁇ stallinem Si3N4 can be applied advantageously, so that by the inventive method, a carbon-fiber-Ko len ⁇ material is provided, which even at high temperatures, about 1500 * C, even over 1700 ' C is resistant to oxidation, ie it is suitable to be used in particular in aerospace technology. Consequently, components such as outlet cone in turbines, turbine housings, hot gas guide parts, combustion chambers, guide vanes or others can be produced from the carbon fiber-reinforced carbon refined according to the invention.
- Amorphous silicon nitride is deposited as the adhesive layer in order to advantageously adapt the different coefficients of expansion of the carbon fiber-reinforced carbon and the protective layer to one another, since their coefficients of expansion have deviations that are too great from one another, so that there is otherwise the risk of cracks or flaking of the protective layer.
- a micro-multipolar plasma such as DECR plasma (D stributed electron cyclotron resonance) can be used to deposit the adhesive layer made of amorphous SiN x .
- the carbon fiber reinforced carbon is cleaned before the adhesive layer is applied. This can be done by bombardment by noble gas ions such as argon ions of a plasma preferably at a temperature above 200 * C and preferably at a pressure lower
- the application of the adhesive layer is facilitated by cleaning.
- a microwave-excited plasma is preferably used for cleaning.
- the carbon fiber-reinforced carbon should have an electrical potential (BIAS) of at least 20 V, preferably from 60 V to 150 V.
- the protective layer containing silicon nitride should be applied under or essentially avoiding stable diimides.
- dichlorosilane and ammonia in a ratio of 1: 2 to 1: 8, 20, preferably 1: 5, are used as process gases, hydrogen being used as the carrier gas.
- the crystalline silicon nitride layer is deposited at a pressure of less than 5 hPa and 25, preferably at a temperature between 1000'C and 1100'C.
- the invention relates to a carbon fiber reinforced carbon, in particular determined as a material for use in aerospace engineering, the carbon fiber reinforced carbon being distinguished in that the carbon fiber reinforced carbon has an outer protective layer which has a high resistance to oxidation is coated from crystalline silicon nitride, an adhesive layer being arranged between the protective layer and the carbon fiber reinforced carbon, the expansion coefficient of which lies between that of the protective layer and that of the carbon fiber reinforced carbon.
- An outlet cone of a turbine made of carbon-fiber-reinforced carbon (CFC) was introduced into a plant for plasma-assisted chemical vapor deposition (PECVD plant), in which the workpiece was a multi-multipolar-distributed plasma at a pressure of 5 x 10 'hPa exposed to a temperature of 500 * C to be shot with argon ions over a period of 10 minutes.
- the workpiece was at a BIAS potential of 60 V. The workpiece was cleaned by this process step.
- the workpiece provided with the adhesion promoter layer was then introduced into a CVD system in order to apply a crystalline Si3N4 protective layer.
- SiH2Cl2 and NH3 were also used as process gases. Since in the reaction of dichlorosilane and ammonia, diimide, Si (NH) 2 »is initially formed, from which silicon nitride is formed in two further stages by the release of ammonia, care must be taken to ensure that the reaction is complete in preferably -S ⁇ 3N4 and not diimides be deposited.
- the adhesion promoters is introduced mediate layer having workpiece into the reaction chamber, in order then in the CVD process at a temperature of 1050 * C and a process pressure of 2.5 hPa, the process gases of dichlorosilane and ammonia in a ratio of 1: 5 to introduce. H2 used as carrier gas. With these parameters, a deposition rate of 1 ⁇ m min "can be achieved.
- the workpiece is then exposed to the process gases for the deposition of the silicon nitride protective layer in the reaction space for 60 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4207380 | 1992-03-09 | ||
DE4207380 | 1992-03-09 | ||
PCT/EP1993/000508 WO1993018203A1 (de) | 1992-03-09 | 1993-03-06 | Verfahren zum beschichten von kohlenstoffaserverstärktem kohlenstoff |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0630425A1 true EP0630425A1 (de) | 1994-12-28 |
Family
ID=6453558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93906488A Withdrawn EP0630425A1 (de) | 1992-03-09 | 1993-03-06 | Verfahren zum beschichten von kohlenstoffaserverstärktem kohlenstoff und danach hergestelltes produkt |
Country Status (4)
Country | Link |
---|---|
US (1) | US5489422A (ja) |
EP (1) | EP0630425A1 (ja) |
JP (1) | JPH07504713A (ja) |
WO (1) | WO1993018203A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5682676A (en) * | 1994-09-22 | 1997-11-04 | Yamaha Hatsudoki Kabushiki Kaisha | Method for surface treatment of work having plural cylinders with different axial alignments |
DE102017204258B4 (de) | 2017-03-14 | 2023-08-17 | Schunk Kohlenstofftechnik Gmbh | Verfahren zur Herstellung eines porösen Körpers |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58161981A (ja) * | 1982-03-17 | 1983-09-26 | 株式会社東芝 | 窒化珪素被覆セラミツクス基材の製造方法 |
US4515860A (en) * | 1982-09-10 | 1985-05-07 | Dart Industries Inc. | Self protecting carbon bodies and method for making same |
US4534842A (en) * | 1983-06-15 | 1985-08-13 | Centre National De La Recherche Scientifique (Cnrs) | Process and device for producing a homogeneous large-volume plasma of high density and of low electronic temperature |
JPS6333575A (ja) * | 1986-07-28 | 1988-02-13 | Nippon Soken Inc | 電子サイクロトロンプラズマcvd装置 |
ES2006119A6 (es) * | 1988-03-24 | 1989-04-01 | Union Explosivos Rio Tinto | Procedimiento de obtencion de nitruro de silicio. |
DE3920450A1 (de) * | 1989-06-22 | 1991-01-10 | Schunk Kohlenstofftechnik Gmbh | Gegen oxidation geschuetzte kohlenstoffkoerper und verfahren zum herstellen des oxidationsschutzes |
US5254397A (en) * | 1989-12-27 | 1993-10-19 | Sumitomo Electric Industries, Ltd. | Carbon fiber-reinforced composite material having a gradient carbide coating |
-
1993
- 1993-03-06 EP EP93906488A patent/EP0630425A1/de not_active Withdrawn
- 1993-03-06 JP JP5515328A patent/JPH07504713A/ja active Pending
- 1993-03-06 US US08/302,736 patent/US5489422A/en not_active Expired - Fee Related
- 1993-03-06 WO PCT/EP1993/000508 patent/WO1993018203A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9318203A1 * |
Also Published As
Publication number | Publication date |
---|---|
US5489422A (en) | 1996-02-06 |
WO1993018203A1 (de) | 1993-09-16 |
JPH07504713A (ja) | 1995-05-25 |
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