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Publication numberUS3550247 A
Publication typeGrant
Publication dateDec 29, 1970
Filing dateJan 31, 1968
Priority dateFeb 2, 1967
Also published asDE1696487A1
Publication numberUS 3550247 A, US 3550247A, US-A-3550247, US3550247 A, US3550247A
InventorsLee Stanley Evans, Peter Ernest Morgan
Original AssigneeCourtaulds Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method for producing a metal composite
US 3550247 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

United States Patent US. Cl. 29-419 8 Claims ABSTRACT OF THE DISCLOSURE Carbon filaments are coated with a metal by electrodeposition, electroless plating or chemical plating. Preferably the carbon filaments are subjected to an oxidising treatment under strong oxidising conditions before being coated with the metal. Metal coated filaments are incorporated in the metal matrix by electroforming, powder technology techniques, casting or by subjecting the coated filaments to a combination of heat and pressure to coalesce them into a composite material.

This invention relates to the reinforcement of metals and is particularly concerned with the use of carbon filaments as the reinforcement.

Carbon filaments are not normally wetted by molten metals, and the reinforcing capacity of such filaments cannot be fully developed merely by casting a metal round a mat of filaments. We have now found that this difiiculty may be overcome by forming a metal coating on carbon filaments by electrodeposition, electroless plating or by chemical plating, and it is an object of this invention to provide a process for the deposition of such a metal coating.

According to the invention, a process for forming a metal coating on carbon filaments comprises depositing a metal coating on the carbon filaments by electrodeposition, electroless plating or chemical plating.

The invention also includes metal coated carbon filaments and carbon filaments so coated and incorporated in a metal matrix, when produced by the respective processes of the present invention.

The carbon filaments may be, for example, in the form of a tow, or they may be staple fibre yarn, or cohesive structures made from these, for example woven or knitted fabrics. A carbon filament may be produced by subjecting a filament having a carbon to carbon backbone to a series of heat treatments designed to reduce the filament essentially to that carbon backbone. In general, the heat. treatment involves at least two and preferably three stages. The first is a pre-oxidation stage carried out at comparatively mild temperatures, for example about 200 C. to 300 C. in an oxygen containing atmosphere such as air. Secondly a carbonisation stage is carried out in a substantially inert atmosphere at a temperature of the order of 1000 C. or more and finally there may be a further and stronger heat treatment, sometimes referred to as a graphitisation treatment, at a still higher temperature and also in an inert atmosphere. The stages are not necessarily distinct and some over lapping may take place.

Carbon filaments having properties which make them suitable for reinforcing metals have been produced from various filaments having a carbon to carbon backbone including filaments of viscose rayon, polyamides and polymers or copolymers of acrylonitrile which are known as the acrylics. Carbon filaments of particularly good strength properties, especially in respect of their Youngs modulus of elasticity, have been obtained from ice acrylic filaments, particularly when the third stage in the heat treatment is carried out to produce graphitised filaments. These properties are enhanced when the filaments have a high tenacity as is described in the specification of U8. patent application Ser. No. 689,801, dated Dec. 12, 1967 and assigned to the assignees of this present application. Graphitised filaments are especially suitable for use in the process of this invention, although those which have not received the final high temperature treatment may also be employed.

In a preferred form of the invention the carbon filaments are subjected to an oxidising treatment under strong oxidising conditions before they are coated with the required metal. Preferred aqueous oxidising agents include concentrated nitric acid, and solutions containing chromic acid as commonly used in the laboratory as oxidising agents. These reagents may be used either hot or cold, although more rapid reaction may be expected at elevated temperatures. Exposure of the carbon filaments to the oxidising agents for quite a short time is sufficient, and good results have been obtained, for example, using concentrated nitric acid with only five to ten minutes reaction time. When the filaments have been treated in this manner, and if necessary, washed free of the oxidising agent, it is found that the processes of chemical plating, electroless plating and and electroplating may all be carried out with particular ease, and that a large bundle of filaments may be coated with metal substantially uniformly.

By chemical plating is meant a process whereby metal ions are deposited from solution onto the article to be plated by a reduction reaction. The article to be plated may or may not be a catalyst for the reduction reaction.

The chemical plating process in which the article being plated or a preformed coating thereon acts as a catalyst to the reduction is known as electroless plating.

process known as the liquid infiltration of molten metal.

When the initial metal coating is formed by electrodeposition then this may be continued until the complete metal matrix is formed; the whole metal coating process could then be said to be an electroforming process. If

the metal matrix is produced by electroforming alone, it

is necessary first to form the carbon filaments into a construction which will produce an article of the desired shape after electroforming.

Another method by which the metal coated filaments may be made into a matrix is by hot pressing. In this process the filaments suitably coated with metal are laid together. While it may be possible to obtain useful composite material by laying together metal coated filaments in random orientation the strength of the composite is in general improved by the use of substantially parallel reinforcing filaments. It is thus preferred that the filaments should be laid together substantially parallel with one another. If desired layers of substantially parallel filaments may be laid at right angles to one another to provide reinforcement in two directions. Packing filaments together at the maximum packing density theoret' ically possible will give a proportion of the filamentary material in the mass of approximately percent by volume and it may be possible to approach this density reasonably closely in a composite. In general the best results so far as strength of the composite are concerned are obtained by using the highest practicable percentage of reinforcement. Since no additional matrix material is employed the amount of reinforcement will be dependent upon the mean thickness of the metal coating and the mean diameter of the filaments. Thus a 50 percent reinforcement by volume could be obtained by using metal coated filaments in which the ratio of the diameters of the carbon or graphite filaments and the metal coated carbon or graphite filaments is about l: /2.

When the metal coated fibres have been laid together in the required form they are heated to a temperature which is dependent on the fusion point of the metal. While it is possible to operate at a temperature at which fusion actually occurs or above this temperature, this may in some cases lead to a reduction of the strength of the composite. It is therefore preferred to use temperatures which are somewhat below the temperature of fusion. The heating may be carried out in a press which is designed to compress the fibres together to cause them to coalesce into a unitary mass. In any case the atmosphere in which the heating takes place will require to be controlled except possibly when certain noble metals are being used. Thus for example it may be desired to exclude oxygen from the atmosphere and indeed it may sometimes be desirable to carry out the process in vacuo. Pressure is applied to the mass of filaments at the temperature desired whereupon coalescence of the filaments takes place to yield a composite material comprising carbon filaments in a metal matrix. Considerable pressures may require to be employed, which may, for example, be of the order of 5000 lbs. per square inch. (350 kg./cm.

The metal which is used to form the initial coating on the carbon filaments may be the same as or different from that of the metal in which the carbon filaments are to be embedded, but of course it must be capable of being applied by electrodeposition, electroless plating or by chemical plating. If the coating metal is different from that of the matrix then a good bond should be obtained and maintained between them. Also, the coating metal should be capable of withstanding the conditions employed in embedding the coated filaments in a metal matrix and the conditions which the reinforced metal article will meet in use. For example, the coating metal should have a melting point sufficiently high that it does not melt either when the reinforced article becomes hot in use or when the coated filaments are embedded in molten metal. The precious metals, for example, platinum, rhodium, ruthenium and palladium, are useful as the coating metal in this respect because of their high melting points.

Nickel, chromium, aluminium, copper and lead are examples of metals which can benefit from reinforcement with carbon filaments in certain uses. Thus, the strength of components made of nickel or chromium or their alloys which are subject to high temperatures, for example turbine blades, may be improved by the incorporation of carbon filaments. Also the creep properties of nickel, which are comparatively poor, are greatly improved. Aluminum cables are commonly made thicker than necessary for the current to be carried for reasons of strength and the incorporation of carbon filaments can give equivalent strength to thinner cables without greatly affecting the current-carrying capacity of the cables. Lead sheet commonly is used to line vessels such as acid tanks and in such use, particularly when lining a vertical wall, is liable to extensive creep. This creep can be greatly reduced by uSing lead sheet reinforced with carbon filaments. Again the grids for battery plates for lead/acid batteries can be made from lead reinforced with carbon filaments.

The electroless plating process is the preferred process because the thickness of the deposited coating can be increased with time, unlike uncontrolled processes like the well-known silver mirror process, and it is especially preferred to use electroless plating since this has the advantage of markedly improved throwing compared with other plating processes such as electroplating. The elec troless nickel process is the one which has been most used and can be used in the process of this invention provided that the carbon filaments, which are not a catalyst to the reaction, are first sensitised. This may be achieved, for example, by first forming a thin coating of palladium on the filaments by dipping them in a solution containing palladium ions, for example palladium chloride, and then reducing those ions to the metal. The reduction may be carried out, for example, by immersing the dipped carbon filaments in the electroless nickel plating solution which contains a reducing agent, for example sodium hypophosphite. Alternatively, the filaments can be treated with, for example, stannous chloride solution, and subsequently with palladium chloride solution, under which circumstances the palladium salt is reduced to the metal on the filaments. A coating of electroless nickel, which is very hard, can then be formed on the palladium sensitised carbon filaments.

Copper, cobalt, palladium and gold are further examples of metals which can be deposited by electroless plating.

The coating of the carbon filaments may be operated batch-wise or continuously depending on the article being made. Thus, a batch-wise process for making an aero plane nose-cone from nickel reinforced with carbon filaments may comprise depositing a layer of nickel onto a mandrel, laying a carbon fabric over the coated layer and then continuing deposition by the process of the invention until the nose-cone is fully formed, when the carbon filaments will be completely embedded in the nickel and strongly bonded thereto. The nose-cone can then be stripped off the mandrel.

We claim:

1. A process for the production of a metal composite which comprises subjecting carbon filaments to an oxidizing treatment under strong oxidizing conditions, depositing a metal coating on the carbon filaments by e1ec trodeposition, electroless plating or chemical plating and building up a metal matrix around the metal-coated filaments to form a composite material.

2. The process claimed in claim 1 and comprising graphitizing the carbon filaments before coating them with metal.

3. The process claimed in claim 1 in which the carbon filaments are arranged in parallel formation in the composite.

4. The process claimed in claim 1 in which the metal matrix is built up around the carbon filaments by electroforming.

5. The process claimed in claim 1 in which the metal matrix is built up around the coated filaments by powder technology techniques or casting.

6. The process claimed in claim 1 in which the metal matrix is produced by forming a suflicient metal coating on the filaments and combining them together under the application of heat and pressure. p

7. The process claimed in claim 1 in which the composite contains at least 50 percent of carbon filament reinforcement.

8. The process claimed in claim 1 in which the metal used for coating the filaments is selected from the group consisting of nickel, chromium, copper, lead, cobalt, palladium, platinum, gold, ruthenium and rhodium.

References Cited UNITED STATES PATENTS 1,137,373 4/1915 Aylsworth 264109X 3,071,637 1/1963 Horn et al. 29-419UX 3,084,421 4/1963 McDanels et al. 29-420.5X 3,098,723 7/1963 Micks 29419UX 3,310,387 3/1967 Sump et al. 29-419UX 3,404,061 10/1968 Shane et a1. 264--l09X JOHN F. CAMPBELL, Primary Examiner D. C. REILEY, Assistant Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3660140 *Jun 18, 1970May 2, 1972United Aircraft CorpTreatment of carbon fibers
US3769086 *Nov 8, 1971Oct 30, 1973Schladitz Whiskers AgPorous, electrically conductive member
US3807996 *Jul 10, 1972Apr 30, 1974Union Carbide CorpCarbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US3818588 *Mar 29, 1973Jun 25, 1974Nat Res DevElectrical brushes
US3827129 *Jan 6, 1972Aug 6, 1974British Railways BoardMethods of producing a metal and carbon fibre composite
US3904405 *Feb 2, 1973Sep 9, 1975Ametek IncSliding seal parts and process of making
US3918141 *Apr 12, 1974Nov 11, 1975Fiber MaterialsMethod of producing a graphite-fiber-reinforced metal composite
US4254548 *May 8, 1979Mar 10, 1981Hitachi, Ltd.Method of fabricating electrode plate for supporting semiconductor device
US4311406 *Jun 25, 1979Jan 19, 1982Exxon Research & Engineering Co.Hybrid piston pin
US4468272 *Aug 24, 1983Aug 28, 1984Toyota Jidosha Kabushiki KaishaComposite material manufacturing method exothermically reducing metallic oxide in binder by element in matrix metal
US4481249 *Jun 24, 1983Nov 6, 1984Bayer AktiengesellschaftMetallized carbon fibres and composite materials containing these fibres
US4609449 *Feb 28, 1984Sep 2, 1986American Cyanamid CompanyApparatus for the production of continuous yarns or tows comprising high strength metal coated fibers
US4661403 *Sep 12, 1984Apr 28, 1987American Cyanamid CompanyYarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US4680093 *Jun 24, 1983Jul 14, 1987American Cyanamid CompanyMetal bonded composites and process
US4808481 *Oct 31, 1986Feb 28, 1989American Cyanamid CompanyInjection molding granules comprising copper coated fibers
US4831707 *Jan 13, 1984May 23, 1989Fiber Materials, Inc.Method of preparing metal matrix composite materials using metallo-organic solutions for fiber pre-treatment
US4904351 *Jul 13, 1988Feb 27, 1990American Cyanamid CompanyProcess for continuously plating fiber
US4909910 *Jul 7, 1988Mar 20, 1990American CyanamidYarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US6112395 *Nov 12, 1998Sep 5, 2000Usf Filtration And Separations Group, Inc.Process of making fine and ultra fine metallic fibers
US6497029Sep 5, 2000Dec 24, 2002Pall Filtration And Separations Group Inc.Process for making fine and ultra fine metallic fibers
US7293403 *Nov 21, 2003Nov 13, 2007Astrium GmbhCombustion chamber with internal jacket made of a ceramic composite material and process for manufacture
US7393473Jul 5, 2006Jul 1, 2008Dowa Mining Co., Ltd.Method for producing a composite plated product
US7514022Jun 21, 2005Apr 7, 2009Dowa Mining Co., Ltd.Composite plated product and method for producing same
US8109130Aug 7, 2009Feb 7, 2012Advanced Technology Materials, Inc.Apparatus and process for sensing fluoro species in semiconductor processing systems
US20100092751 *Jan 12, 2008Apr 15, 2010Airbus SasFiber composite comprising a metallic matrix, and method for the production thereof
US20100163782 *Sep 3, 2009Jul 1, 2010Industrial Technology Research InstituteCarbon-Containing Metal-Based Composite Material and Manufacturing Method Thereof
US20100330365 *Feb 24, 2009Dec 30, 2010Hassel JoergStrand-like material composite with cnt yarns and method for the manufacture thereof
US20110033692 *Apr 1, 2009Feb 10, 2011Siemens AktiengesellschaftComposite material composed of a metal matrix in which cnt filaments are distributed, and method for the production of such a composite material
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EP1609888A2 *Jun 21, 2005Dec 28, 2005Dowa Mining Co., Ltd.Composite plated product and method for producing same
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U.S. Classification29/419.1, 205/159, 205/142, 427/304, 427/305, 205/76, 205/138, 264/109, 264/DIG.190
International ClassificationC04B41/88, C23C18/18, D06Q1/04, C25D1/00, C04B41/51, D01F11/12, C22C49/14
Cooperative ClassificationC25D1/00, C04B41/009, D01F11/127, C04B41/51, C04B41/88, C23C18/1851, D06Q1/04, Y10S264/19, C22C49/14
European ClassificationC04B41/00V, C23C18/18B, D01F11/12H, C04B41/88, C25D1/00, C04B41/51, C22C49/14, D06Q1/04
Legal Events
Jun 14, 1985AS01Change of name
Effective date: 19820520
Jun 14, 1985ASAssignment
Effective date: 19820520