US3860443A - Graphite composite - Google Patents

Graphite composite Download PDF

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US3860443A
US3860443A US34365073A US3860443A US 3860443 A US3860443 A US 3860443A US 34365073 A US34365073 A US 34365073A US 3860443 A US3860443 A US 3860443A
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titanium
fibers
method
defined
metal
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Walter L Lachman
Robert A Penty
Apul F Jahn
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Fiber Materials Inc
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Fiber Materials Inc
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062Borides, Nitrides or Silicides
    • C04B41/507Borides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/87Ceramics
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/38Borides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56After-treatment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12465All metal or with adjacent metals having magnetic properties, or preformed fiber orientation coordinate with shape
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12486Laterally noncoextensive components [e.g., embedded, etc.]

Abstract

A novel graphite fiber/metal composite material, the graphite fibers having a coat of titanium boride which may be mixed with titanium carbide. The coat, which promotes wetting by metals such as aluminum, copper and lead, is formed by an intermediate temperature vapor deposition technique involving the reduction with zinc vapor of a mixture of gaseous titanium and boron halides.

Description

United States Patent [191 Lachman et al.

[111 3,860,443 [4 1" Jan. 14,1975

[ GRAPHITE COMPOSITE [75] Inventors: Walter L. Lachman, Concord,

Mass.; Robert A. Penty, Kennebunk, Maine; Apul F. Jahn, Chelmsford, Mass.

[73] Assignee: Fiber Materials, Inc., Graniteville,

Mass.

[22] Filed: Mar. 22, 1973 [21] Appl. No.1 343,650

[52] U.S. Cl 117/106, 29/1912, 117/228,

1l7/DIG. 10, l17/DIG. 11, 423/47 [51] Int. Cl C23c 1l/00 [58] Field of Search 117/106 R, 228, DIG. 10,

[56] References Cited UNITED STATES PATENTS 2,978,358 4/1961 Campbell 117/106 C Micks .Q. 29/1835 Van Amstel ll7/l06 R Primary ExaminerWilliam E. Schulz Attorney, Agent, or FirmSchiller and Pandiscio [57] ABSTRACT 10 Claims, 1 Drawing Figure GRAPHITE COMPOSITE The present invention relates to composite materials, and more specifically to composites of carbon fibers embedded in a metallic matrix, and the method of making same.

High strength, low weight structures can be formed of composites of filaments embedded or bound in a matrix. Particularly, carbon fibers have high tensile strength and a high modulus of elasticity, so that composites formed of a metal matrix containing such fibers aligned in the direction of maximum expected stress can be readily used for components requiring high strength-to-density anad high modulus-to-density ratios over a wide range of temperatures. Metal-graphite composites also combine the lubricating properties of graphite with the toughness of the metal to provide a material with a low coefficient of friction and wear resistance. Composites of graphite with materials such as aluminum and copper, exhibit great strength and high electrical conductivity.

A number of metals in molten form, such as aluminum and the like, do not readily wet graphite. It has been suggested that the graphite can be wetted by molten aluminum if a layer of aluminum carbide is first provided at the interface between the metal and fiber, but that such aluminum carbide phase cannot be tolerated due to its thermochemical and mechanical instability. In U.S. Pat. No. 3,553,820 issued to R. V. Sara, it is taught that aluminum graphite fiber composites can be formed by first coating the fibers with a tantalum film by electrodeposition from a fused salt bath, outgassing the fibers by pumping them down to a very low pressure and submerging the outgassed fibers into a pressurized molten aluminum bath to fill the interstices of the fibers. A similar process is described in U.S. Pat. No. 3,571,901 issued to R. V. Sara, in which the carbon fibers are first coated with silver or a silver aluminum alloy by electrodeposition from the plating solution, then the fibers are contacted with aluminum foil and the combined foil-fiber is heated while under pressure to the solidus temperature of the foil. In both of these systems, it is also suggested that the metal coating can be applied by sputtering or by reduction of salts of the metal. Whether using silver or tantalum, it is difficult to obtain uniform thin coatings on the fibers, and in any event, the resulting composites contain substantial amounts of expensive, heavy material such as silver and tantalum.

Electrodeposition and chemical deposition techniques have also been used to deposit the matrix material directly around graphite fibers, the coated fibers being subsequently hot-pressed to form composites. The major disadvantage of forming composites with such deposition techniques is that for the most part, the matrix material is usually limited to a rather pure metal, which for many purposes has markedly inferior properties compared to alloys.

A principal object of the present invention is therefore to provide a simple, unique process for forming metal/graphite fiber composites without resort to high pressures or temperatures. Another object of the present invention is to provide a unique metal/graphite composite in which the composition of the matrix material may be varied over a wide margin. Yet other objects of the present invention will in part appear obvious and will in part appear hereinafter.

The invention accordingly comprises the process and the several steps and the relation of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and relation of elements which are exemplified in the following detailed disclosureand the scope of the invention all of which will be indicated in the claims.

Generally to effect the foregoing and other objects the present invention involves a thin, substantially uniform coating of a wetting agent on carbon fibers, the wetting agent being titanium boride, titanium carbide or a mixture of both, the interstices between the coated fibers being filled with a metal infiltrated initially as a liquid under ambient pressure. Because it is not considered possible to account for the formulae generally of borides in terms of ordinary conceptions of valency, the term boride as used herein is not to be considered limited to any particular stoichiometric relation unless specifically indicated.

For a fuller understanding of the nature and objects of the present invention, reference should be had to the following detailed description taken in connection with the accompanying drawing wherein there is shown a diagramatic illustration, in cross-section, of a carbonfiber metal composite produced according to the teachings of the invention.

Although graphite fibers are preferred in the practice of the instant invention it is intended that the term carbon fibers should include both graphitic and nongraphitic carbon fibers. The carbon fibers used in the invention may be made from any of a large number of precursors such as pitch, rayon, polyacrylonitrile or the like in the form of yarn, tow, webs which are woven, knitted, felted, and the like. In a preferred form, the fibers are graphite derived from rayon in uniaxial yarn form, of seven micron average fiber diameter, containing approximately 11,000 fibers in the yarn. Such carbon fibers and textiles are well known and available commercially, and the method of producing same is well known in the art.

The composite of the invention comprises, as shown in the drawing, a plurality of graphite fibers 20 each having a substantially continuous surface coating 21 of a wetting agent which is titanium boride, titanium carbide or a mixture of both. Typically, the fiber diameter is about seven microns and the coating thickness is as thin as A, so that for the sake of clarity the relative thickness of the coating in the drawing has been exagerated. The fibers are embedded in a solid metallic matrix 22 which may be aluminum, magnesium, copper, lead, zinc, tin and various alloys of these metals such as aluminum/silicon and the like.

In order for infiltration or investment of a bundle of fibers to occur on immersion in a liquid, the liquid must wet the fiber surfaces. As previously noted, molten metals such as aluminum and copper do not readily wet graphite. Consequently, the present invention provides on the surfaces of the graphite fibers a coating of a wetting agent. This coating is a substantially uniform layer, preferably in the range between 100 to 10,000 A in thickness, of titanium boride, titanium carbide, or a mixture thereof. While there are many techniques for coating fibers, the preferred method in the present invention involves a vapor phase deposition whereby the material of the coatings is deposited as a consequence of the simultaneous reduction of a mixture of a gaseous compound of titanium and a gaseous compound of boron. Vapor deposition techniques to form coatings are well known in the art and usually are carried out at temperatures between about 900 to 1,400C. For example, it is known that intermetallic compounds, such as hafnium boride, can be deposited as a coating from a mixture of gaseous hafnium chloride and boron trichloride reduced by hydrogen gas.

In the process of the present invention, the preferred vapor deposition process involves a comparatively low temperature reduction of a mixture of titanium tetrachloride and boron trichloride with zinc metal vapor as the reducing agent. It is postulated that the use of the zinc metal which serves as a slow reducing agent permits a wide variety of reactions to occur whereby better control will be obtained over the process.

For example, if the relative weight ratio of boron trichloride to titanium tetrachloride of the mixture thereof is low (i.e., less than about one-third) the coating on the fiber will constitute a mixture of titanium carbide and a boride which has an approximate composition expressed substantially as TiB. At higher weight ratios the composition of the deposited coat approaches TiB The foregoing can be explained on the basis of the following series of postulated reactions that are believed to occur in the gas phase and at the graphite fiber surfaces during the deposition process. It is believed that the first two equations express the reduction processes which are occurring.

TiCl Zn TiCl ZnCl 2BCl 3Zn 2B 3ZnCl It is believed then that the boron thus produced and the carbon of the fibers react with the titanium dichloride somewhat as follows:

2TiCl XB TiB TiCL,

2TiCl C TiC TiCL,

From equation (3), it appears that if there is enough of the boron halide to provide a relative excess of boron so that X in equation (3) is around the value of 2, the form of titanium boride formed will closely approximate TiB This latter consideration can be important because to achieve a satisfactory composite, it is not only desirable that the fiber coat promote wetting by the matrix metal, but that it also provides a chemically stable interface between the fiber and the metal of the matrix. For example, if the metal of the matrix is copper, a coating which is a mixture of TiC and TiB is satisfactory. On the other hand, if the metal of the matrix is aluminum or an alloy with a high percentage of aluminum, it has been found that the coating composition should be substantially TiB Fibers with the requisite coat are then drawn through 6 cess can be carried out at ambient pressure preferably under an inert atmosphere such as argon or the like. The metal-fiber mass is then allowed to cool below the solidus temperature of the metal, thereby forming a solid composite. The composites, which can be originally made in the form of wires, rods, tapes or sheets, can be pressed together at a temperature above the melting point of the matrix to give bulk composites of various shapes such as bars, angle sections and panels. If desired, during the pressing of such shapes, any ex cess metal may be expressed from the composite in order to increase the volume percentage of the fibers.

The following examples illustrate more clearly the manner in which carbon fiber composites are produced according to the invention. The invention however should not be construed as being limited to the particular embodiments set forth in the examples.

EXAMPLE I Graphite yarn containing approximately 1 1,000 individual fibers of 50 X 10 modulus was exposed to a vapor reaction mixture formed of 0.38% TiCl 0.21% BCl and 0.80% Zn, the balance being argon (all percentages being by weight). The gas mixture was maintained at a temperature of 650C for 30 minutes to provide a coating of about 200 A, believed to be substantially TiB- on the yarn'fibers. The coated fibers were transferred under argon to a molten bath containing 13% by weight of silicon-aluminum alloy and kept immersed in the bath at 650C for 2. minutes. The resulting metal-fiber composite was removed from the bath and then allowed to cool below the solidus temperature of the alloy. A section taken across the long axis of the fibers through the composite appears substantially as shown in the drawing.

A number of sections of the composite described in this Example I were hot pressed in a graphite die under vacuum at 600C for 5 minutes to form a composite plate 6 inches long by 0.5 inches wide by 0.05 inches thick.

EXAMPLE II The graphite yarn similar to that used in Example I was exposed to a similar gas mixture in which however the composition was as follows: 0.38 wt.% TiCl 0.14 wt.% BCl and 0.80 wt.% Zn, the balance being argon. The fibers were exposed to that gasmixture at 650C for 30 minutes and transferred under argon to a molten bath containing a bronze alloy of about wt.% Cu and 10 wt.% Sn at about 980C for one minute. The composite was removed from the bath and allowed to cool to form a solid article.

EXAMPLE lll Coated graphite fibers were prepared as in Example I, and tansferred under argon to a molten bath containing a lead alloy (0.4% Ca, 99.6% Pb) held at about 550C. The fibers were kept in the bath for ten minutes, and the composite was then removed and allowed to cool below the solidus temperature of the alloy. The resulting composite could be hot pressed to form bearmgs.

Since certain changes may be made in the above process and product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted in an illustrative and not in a limiting sense.

What is claimed is: 1. Method of forming a fiber-metal composite, comprising the steps of:

forming a coating of material selected from the group consisting of titanium boride, and a mixture of titanium boride and titanium carbide on a plurality of carbon fibers; v

immersing the coated fibers into a body of molten metal selected from the group consisting of magnesium, lead, zinc, copper, aluminum, tin and alloys of said metals until said metal substantially fills the interstices between'said fibers; and

cooling the metal body with said coated fibers embedded therein to a temperature at which said metal solidifies.

2. Method as defined in claim 1 wherein said coated fibers are immersed in said body of molten metal at ambient atmospheric pressure.

3. Method as defined in claim 1 wherein the step of coating includes the reduction of a gaseous compound of titanium in the presence of said fibers whereby said titanium boride or mixture of titanium boride and titanium carbide is produced.

coating is effected by reducing with zinc vapor a gase- 6 Y Y ous compound; of titanium in the presence of said fibers.

a 5. Method asdefined in claim 3 wherein the step of coating is effected by reducing a gaseous compound of boron and a gaseous compound of titanium in the presence of said fibers.

6. Method as defined in claim 3 wherein the step of coating is effected by reducing with zinc vapor a gaseous compound of boron and a gaseous compound of titanium in the presence of said fibers.

7. Method as defined in claim 1 wherein said metal is aluminum.

8. Method as defined in claim 5 wherein said step of coating is effected for a time sufficient to deposit on each of said fibers a layer having a thickness in the range between about to l0,000 A.

9. Method as defined in claim 5 wherein the relative proportion of said compound of boron to said compound of titanium is suffici'ently large so that the titanium boride form'ed in said layer upon reduction of said compounds is substantially TiB,.

10. Method as defined in claim 5 wherein the relative proportion of said compoundof boron to said comride formed in said layer upon reduction of pounds is substantially TiB.

i l =k Notice of Adverse Decision in Interference In Interference N 0. 99,222, involving Patent N 0. 3,860,443, W.

[Oficial Gazette August 2, 1977.]

L. Dachj udgment Disclaimer 3,860,443.-Walter L. Lachman, Concord, Mess, Robert A. Penty, Kennebunk, Maine, and Paul F. Jaim, Chelmsford, Mass. GRAPHITE COM- POSITE. Patent dated J an. 14, 1974. Disclaimer filed June 24, 1977, by the assignee, Fiber Materials, I no. Hereby enters this disclaimer to all claims of said patent.

[Ofliez'al Gazette November 15, 1977.]

Claims (10)

1. METHOD OF FORMING A FIBER-METAL COMPOSITE, COMPRISING THE STEPS OF: FORMING A COATING OF MATERIAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM BORIDE, AND A MIXTURE OF TITANIUM BORIDE AND TITANIUM CARBIDE ON A PLURALITY OF CARBON FIBERS; IMMERSING THE COATED FIBERS INTO A BODY OF MOLTEN METAL SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM, LEAD, ZINC, COPPER, ALUMINUM, TIN AND ALLOYS OF SAID METALS UNTIL SAID METAL SUBSTANTIALLY FILLS THE INTERSTICES BETWEEN SAID FIBERS; AND COOLING THE METAL BODY WITH SAID COATED FIBERS EMBEDDED THEREIN TO A TEMPERATURE AT WHICH SAID METAL SOLIDIFIES.
2. Method as defined in claim 1 wherein said coated fibers are immersed in said body of molten metal at ambient atmospheric pressure.
3. Method as defined in claim 1 wherein the step of coating includes the reduction of a gaseous compound of titanium in the presence of said fibers whereby said titanium boride or mixture of titanium boride and titanium carbide is produced.
4. Method as defined in claim 3 wherein the step of coating is effected by reducing with zinc vapor a gaseous compound of titanium in the presence of said fibers.
5. Method as defined in claim 3 wherein the step of coating is effected by reducing a gaseous compound of boron and a gaseous compound of titanium in the presence of said fibers.
6. Method as defined in claim 3 wherein the step of coating is effected by reducing with zinc vapor a gaseous compound of boron and a gaseous compound of titanium in tHe presence of said fibers.
7. Method as defined in claim 1 wherein said metal is aluminum.
8. Method as defined in claim 5 wherein said step of coating is effected for a time sufficient to deposit on each of said fibers a layer having a thickness in the range between about 100 to 10, 000 A.
9. Method as defined in claim 5 wherein the relative proportion of said compound of boron to said compound of titanium is sufficiently large so that the titanium boride formed in said layer upon reduction of said compounds is substantially TiB2.
10. Method as defined in claim 5 wherein the relative proportion of said compound of boron to said compound of titanium is small enough that the titanium boride formed in said layer upon reduction of said compounds is substantially TiB.
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Cited By (32)

* Cited by examiner, † Cited by third party
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US4082864A (en) * 1974-06-17 1978-04-04 Fiber Materials, Inc. Reinforced metal matrix composite
US4132828A (en) * 1976-11-26 1979-01-02 Toho Beslon Co., Ltd. Assembly of metal-coated carbon fibers, process for production thereof, and method for use thereof
US4169739A (en) * 1978-04-12 1979-10-02 Semix, Incorporated Method of making silicon-impregnated foraminous sheet by partial immersion and capillary action
US4171991A (en) * 1978-04-12 1979-10-23 Semix, Incorporated Method of forming silicon impregnated foraminous sheet by immersion
US4174234A (en) * 1978-04-12 1979-11-13 Semix, Incorporated Silicon-impregnated foraminous sheet
US4215764A (en) * 1976-07-01 1980-08-05 Fiber Materials, Inc. Acoustic filter
US4223075A (en) * 1977-01-21 1980-09-16 The Aerospace Corporation Graphite fiber, metal matrix composite
US4287259A (en) * 1979-12-05 1981-09-01 The United States Of America As Represented By The United States Department Of Energy Preparation and uses of amorphous boron carbide coated substrates
US4358506A (en) * 1980-06-09 1982-11-09 Josef Intrater Metal and carbon composites thereof
EP0067252A1 (en) * 1981-06-08 1982-12-22 Advanced Technology Inc. Metal, carbon, carbide and other compositions thereof, alloys and methods for preparing same
US4374903A (en) * 1980-06-09 1983-02-22 Advanced Technology, Inc. Metal coatings or metal sandwiches with boron nitride or titanium diboride substrates
US4376804A (en) * 1981-08-26 1983-03-15 The Aerospace Corporation Pyrolyzed pitch coatings for carbon fiber
US4376803A (en) * 1981-08-26 1983-03-15 The Aerospace Corporation Carbon-reinforced metal-matrix composites
US4396677A (en) * 1980-10-24 1983-08-02 Josef Intrater Metal, carbon, carbide and other composites thereof
US4461689A (en) * 1977-06-20 1984-07-24 Siemens Aktiengesellschaft Method and apparatus for coating a graphite member
US4578287A (en) * 1984-10-09 1986-03-25 The United States Of America As Represented By The Secretary Of The Navy Process for producing graphite fiber/aluminum-magnesium matrix composites
US4731298A (en) * 1984-09-14 1988-03-15 Agency Of Industrial Science & Technology Carbon fiber-reinforced light metal composites
US4847167A (en) * 1987-07-15 1989-07-11 Sumitomo Chemical Company, Limited Fiber-reinforced metallic composite material
US4859503A (en) * 1986-12-04 1989-08-22 Central National De La Recherche Scientifique (Cnrs) Process for coating carbon fibers with a carbide, and carbon fibers thus coated
US4873149A (en) * 1986-06-20 1989-10-10 Nisshin Steel Co., Ltd. Vibration-damper metal sheets
US4873121A (en) * 1986-04-09 1989-10-10 Kernforschungsaniage Julich Gmbh Cathode/membrane assembly and method of making same
US5049419A (en) * 1989-05-18 1991-09-17 Toray Industries, Inc. Method for manufacturing a precursor wire for a carbon-fiber-reinforced metal composite material
US5089356A (en) * 1990-09-17 1992-02-18 The Research Foundation Of State Univ. Of New York Carbon fiber reinforced tin-lead alloy as a low thermal expansion solder preform
US5205970A (en) * 1992-04-03 1993-04-27 General Electric Company Method of infiltration forming a silicon carbide body with improved surface finish
US5227249A (en) * 1991-10-03 1993-07-13 Standard Oil Company Boride coatings for SiC reinforced Ti composites
US5244748A (en) * 1989-01-27 1993-09-14 Technical Research Associates, Inc. Metal matrix coated fiber composites and the methods of manufacturing such composites
US5294489A (en) * 1992-04-02 1994-03-15 General Electric Company Protective coating with reactive interlayer on reinforcement in silicon carbide composite
US5316851A (en) * 1991-06-12 1994-05-31 General Electric Company Silicon carbide composite with metal boride coated fiber reinforcement
EP1168438A2 (en) * 2000-06-23 2002-01-02 Sumitomo Electric Industries, Ltd. High thermal conductivity composite material, and method for producing the same
US20030164206A1 (en) * 2001-05-15 2003-09-04 Cornie James A. Discontinuous carbon fiber reinforced metal matrix composite
US20100264266A1 (en) * 2009-04-15 2010-10-21 The Boeing Company Metal-coated fabrics for fiber-metal laminates
CN107675108A (en) * 2017-09-05 2018-02-09 巩义市泛锐熠辉复合材料有限公司 Preparation method for carbon-copper composite

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US4082864A (en) * 1974-06-17 1978-04-04 Fiber Materials, Inc. Reinforced metal matrix composite
US4215764A (en) * 1976-07-01 1980-08-05 Fiber Materials, Inc. Acoustic filter
US4132828A (en) * 1976-11-26 1979-01-02 Toho Beslon Co., Ltd. Assembly of metal-coated carbon fibers, process for production thereof, and method for use thereof
US4223075A (en) * 1977-01-21 1980-09-16 The Aerospace Corporation Graphite fiber, metal matrix composite
US4461689A (en) * 1977-06-20 1984-07-24 Siemens Aktiengesellschaft Method and apparatus for coating a graphite member
US4174234A (en) * 1978-04-12 1979-11-13 Semix, Incorporated Silicon-impregnated foraminous sheet
US4169739A (en) * 1978-04-12 1979-10-02 Semix, Incorporated Method of making silicon-impregnated foraminous sheet by partial immersion and capillary action
US4171991A (en) * 1978-04-12 1979-10-23 Semix, Incorporated Method of forming silicon impregnated foraminous sheet by immersion
US4287259A (en) * 1979-12-05 1981-09-01 The United States Of America As Represented By The United States Department Of Energy Preparation and uses of amorphous boron carbide coated substrates
US4374903A (en) * 1980-06-09 1983-02-22 Advanced Technology, Inc. Metal coatings or metal sandwiches with boron nitride or titanium diboride substrates
US4358506A (en) * 1980-06-09 1982-11-09 Josef Intrater Metal and carbon composites thereof
US4396677A (en) * 1980-10-24 1983-08-02 Josef Intrater Metal, carbon, carbide and other composites thereof
EP0067252A1 (en) * 1981-06-08 1982-12-22 Advanced Technology Inc. Metal, carbon, carbide and other compositions thereof, alloys and methods for preparing same
US4376804A (en) * 1981-08-26 1983-03-15 The Aerospace Corporation Pyrolyzed pitch coatings for carbon fiber
US4376803A (en) * 1981-08-26 1983-03-15 The Aerospace Corporation Carbon-reinforced metal-matrix composites
US4731298A (en) * 1984-09-14 1988-03-15 Agency Of Industrial Science & Technology Carbon fiber-reinforced light metal composites
US4578287A (en) * 1984-10-09 1986-03-25 The United States Of America As Represented By The Secretary Of The Navy Process for producing graphite fiber/aluminum-magnesium matrix composites
US4873121A (en) * 1986-04-09 1989-10-10 Kernforschungsaniage Julich Gmbh Cathode/membrane assembly and method of making same
US4873149A (en) * 1986-06-20 1989-10-10 Nisshin Steel Co., Ltd. Vibration-damper metal sheets
US4859503A (en) * 1986-12-04 1989-08-22 Central National De La Recherche Scientifique (Cnrs) Process for coating carbon fibers with a carbide, and carbon fibers thus coated
US4921725A (en) * 1986-12-04 1990-05-01 Centre National De La Recherche Scientifique (Cnrs) Process for coating carbon fibers with a carbide
US4847167A (en) * 1987-07-15 1989-07-11 Sumitomo Chemical Company, Limited Fiber-reinforced metallic composite material
US5244748A (en) * 1989-01-27 1993-09-14 Technical Research Associates, Inc. Metal matrix coated fiber composites and the methods of manufacturing such composites
US5049419A (en) * 1989-05-18 1991-09-17 Toray Industries, Inc. Method for manufacturing a precursor wire for a carbon-fiber-reinforced metal composite material
US5089356A (en) * 1990-09-17 1992-02-18 The Research Foundation Of State Univ. Of New York Carbon fiber reinforced tin-lead alloy as a low thermal expansion solder preform
US5316851A (en) * 1991-06-12 1994-05-31 General Electric Company Silicon carbide composite with metal boride coated fiber reinforcement
US5227249A (en) * 1991-10-03 1993-07-13 Standard Oil Company Boride coatings for SiC reinforced Ti composites
US5294489A (en) * 1992-04-02 1994-03-15 General Electric Company Protective coating with reactive interlayer on reinforcement in silicon carbide composite
US5205970A (en) * 1992-04-03 1993-04-27 General Electric Company Method of infiltration forming a silicon carbide body with improved surface finish
EP1168438A2 (en) * 2000-06-23 2002-01-02 Sumitomo Electric Industries, Ltd. High thermal conductivity composite material, and method for producing the same
EP1168438A3 (en) * 2000-06-23 2004-11-10 Sumitomo Electric Industries, Ltd. High thermal conductivity composite material, and method for producing the same
US20030164206A1 (en) * 2001-05-15 2003-09-04 Cornie James A. Discontinuous carbon fiber reinforced metal matrix composite
US20100264266A1 (en) * 2009-04-15 2010-10-21 The Boeing Company Metal-coated fabrics for fiber-metal laminates
CN107675108A (en) * 2017-09-05 2018-02-09 巩义市泛锐熠辉复合材料有限公司 Preparation method for carbon-copper composite

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