US3622283A - Tin-carbon fiber composites - Google Patents

Tin-carbon fiber composites Download PDF

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US3622283A
US3622283A US639153A US3622283DA US3622283A US 3622283 A US3622283 A US 3622283A US 639153 A US639153 A US 639153A US 3622283D A US3622283D A US 3622283DA US 3622283 A US3622283 A US 3622283A
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tin
corrosion resistant
composite article
resistant composite
fibers
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Raymond V Sara
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BP Corp North America Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C1/06—Frames; Stringers; Longerons ; Fuselage sections
    • B64C1/12—Construction or attachment of skin panels
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C2001/0054—Fuselage structures substantially made from particular materials
    • B64C2001/0072—Fuselage structures substantially made from particular materials from composite materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64C—AEROPLANES; HELICOPTERS
    • B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
    • B64C2001/0054—Fuselage structures substantially made from particular materials
    • B64C2001/0081—Fuselage structures substantially made from particular materials from metallic materials
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/40—Weight reduction
    • 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
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12444—Embodying fibers interengaged or between layers [e.g., paper, etc.]
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12625—Free carbon containing component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2944—Free metal in coating
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • ABSTRACT Low-density, high-strength tin base composites are provided by coating carbon fibers with a metallic coupling agent and then bonding them together, preferably in a parallel or aligned manner, by means of a tin or tin base alloy matrix. Such composites are characterized by physical properties which are much superior to those evidenced by the matrix material alone and find utility in applications where the chemical properties of tin are desired but its use is prohibited or limited due to its poor physical properties.
  • the present invention relates to carbon fiber-tin composites made up of a plurality of carbon fibers coated with a metallic coupling agent and bonded together, preferably in a side-byside or parallel manner, by means of a tin base metal matrix.
  • Tin is an element which finds wide useage in industry. One of its most important uses is as a protective coating for stronger materials or substrates. The use of pure tin alone as a material of construction is limited by its inherently poor physical properties, such as low tensile strength and modulus of and/or antimony. However, weak.
  • the carbon fiber-tin composite of the invention comprises a plurality of carbon fibers each of which is coated with a thin layer of a coupling metal having a melting a thm but continuous film of a suitable metal, shaping an aggregate of the so-coated fibers into the desired form, infiltrating the voids between the individual fibers with molten tin or tin base alloy and cooling the resultant tin infiltrated aggregate to produce a composite article.
  • a graphite fiber-tin composite containing approximately 33.5 volume percent fibers, is characterized by a density a material of construction in apparatus which require strong, corrosion resistant parts or components.
  • FIGURE shown in the drawing presented herewith is a diagrammatical illustration of a rectangular section of a carbon fiber-metal matrix composite article produced according to the teachings of the instant invention.
  • a rectangular composite article 1 consisting of aligned graphite fibers 2 having disposed on their surface a continuous 2-micron thick coating of nickel 3. These socoated fibers are bonded together by a tin matrix 4.
  • the graphite fibers 2 are approximately 1 inch in length and disposed in the tin matrix 4 in a parallel or side-by-side manner.
  • length dimension of the fibers 2 is perpendicular to the surface of the drawing.
  • Carbon textiles in any form can be employed in the practice of the instant invention. However, it is preferred to employ carbon fibers in yarn or monofilament form. Carbon textiles are available commercially and are generally produced by the techniques described in US. Pat. Nos. 3,107,152 and 3,l 16,975, among others.
  • the coupling metal used can be any metal which has a melting point greater than the metal matrix which adheres to the carbon and is readily wetted by the matrix metal without forming low melting point alloys or brittle intermetallic phases.
  • Metals which are preferred as coupling agents are nickel, titanium and chromium.
  • the selected coupling metal can be deposited on the carbon fibers by a variety of methods. The techniques available for accomplishing this include electrodeposition from a suitable plating bath, thermal decomposition of the appropriate metal halide or sputtering. The exact deposition technique to be employed is dictated by a number of factors. Sputtering can be used on relatively complex shapes and results in a tenacious bond between the coupling metal and the carbon fiber substrate.
  • Such a bond is a highly desirable feature in carbon fiber-metal matrix composites.
  • Thermal decomposition of the appropriate halide requires a heating of the carbon fiber substrate and, accordingly, somewhat limits the type of shapes which can be coated in this manner.
  • Electrodeposition of a metal from a plating solution is an ideal way of coating carbon fibers with a thin metallic film and is the preferred coating technique.
  • tin base alloys of low melting point metals such as lead, antimony, and bismuth may also be employed in the practice of the instant invention.
  • a single ply of graphite yarn having an average filament diameter of 6.9 microns and consisting of 720 monofilaments per ply was cut into a plurality of 4-inch lengths. These 4 inch sections of graphite yarn were then predipped into acetone to facilitate their subsequent coating with nickel.
  • Nickel was so-treated graphite yarn by using a nickel anode and an electroplating plating solution prepared by dissolving 200 grams of NiSO '6H O and 22 grams of H BO in 500 ml. of distilled water. The plating solution temperature was maintained at approximately 52 C. The plating current varied between about 400 to about 1000 milliamperes.
  • a metallographic examination of the resultant fibers showed that all monofilaments had a coating of nickel thereon and that the average coating thickness ranged from 1 to 3 microns.
  • These nickel clad fibers were then cut in approximately l-inch lengths and placed in an aligned position (all parallel) in a cylindrical capillary tube measuring approximately 1 inch in length and having an internal diameter of about 0.135 inches which was provided with a top and bottom closure.
  • the surface of the cylinder was provided with 12 randomly placed holes or openings to facilitate the ingress of tin into the cylinder and hence into the voids between the aligned graphite fibers.
  • the cylinder containing the fibers was placed into an airtight chamber which also contained a vessel of tin.
  • the chamber was then evacuated to a pressure of approximately ZXlO-mm. of mercury to out gas the graphite fibers.
  • the chamber with the tin therein was heated to a temperature of approximately 300 C.
  • the cylinder containing the aligned fibers was then submerged below the surface of the molten tin.
  • the chamber was subsequently filled with argon gas to a pressure of about latmosphere to insure that molten tin filled essentially all the voids between the aligned graphite fibers.
  • the capsule was withdrawn from the molten tin, cooled, and removed from the chamber.
  • a metallographic examination of the resultant nickel coated graphite fiber-tin composite showed that the nickel coating was well bonded to the graphite fiber substrate; that the tin matrix material had uniformly and completely wetted the socoated fibers without disturbing the continuity of the nickel coating; and that no undesireable reaction zone was formed at the nickel-tin interface.
  • carbon is meant to include both the nongraphitic and graphitic forms of carbon.
  • a corrosion resistant composite article comprising a plurality of carbon fibers bonded together by a tin base metal matrix. said carbon fibers having a substantially continuous coating of a coupling metal having a higher melting point than said tin base metal matrix on their outer surface.
  • the corrosion resistant composite article of claim 3 wherein said coupling metal is selected from the group consisting of nickel, titanium and chromium.
  • the corrosion resistant composite article of claim 15 wherein the thickness of said nickel coupling metal is from I to 3 microns.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Aviation & Aerospace Engineering (AREA)
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  • Manufacture Of Alloys Or Alloy Compounds (AREA)
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Abstract

Low-density, high-strength tin base composites are provided by coating carbon fibers with a metallic coupling agent and then bonding them together, preferably in a parallel or aligned manner, by means of a tin or tin base alloy matrix. Such composites are characterized by physical properties which are much superior to those evidenced by the matrix material alone and find utility in applications where the chemical properties of tin are desired but its use is prohibited or limited due to its poor physical properties.

Description

waited States a ent [72] inventor Raymond V. Sara North Olmsted. Ohio [21] Appl No. 639.153 [22 Filed May 17, 1967 [45] Patented Nov. 23, 1971 [73] Assignee Union Carbide Corporation [54] TIN-CARBON FIBER COMPOSITES 16 Claims, 1 Drawing Fig.
[52] US. Cl 29/1835, 29/1912, 29/1914, 29/195 [51 1 int. Cl 13321) 15/02, B32b 15/04, B32b 15/14 [50] Field of Search 29/191.4,
[56] References Cited UNITED STATES PATENTS 3,047,383 7/1962 Slayter 29/180 3,098,723 7/1963 Wicks 29/1835 3,282,658 1/1966 Wainer 29/1835 3,352,650 1 1/1967 Goldstein et a1 29/191.4
Primary Examiner-Allen B. Curtis Assislan! Examiner-O. F. Crutchfield Attorneys-Paul A. Rose, Robert C. Cummings and Frederick J. McCarthy, .Ir.
ABSTRACT: Low-density, high-strength tin base composites are provided by coating carbon fibers with a metallic coupling agent and then bonding them together, preferably in a parallel or aligned manner, by means of a tin or tin base alloy matrix. Such composites are characterized by physical properties which are much superior to those evidenced by the matrix material alone and find utility in applications where the chemical properties of tin are desired but its use is prohibited or limited due to its poor physical properties.
PAIENTEuNnv 23 m1 INVENTOR WQND SARA BACKGROUND OF INVENTION 1. Field of the Invention The present invention relates to carbon fiber-tin composites made up of a plurality of carbon fibers coated with a metallic coupling agent and bonded together, preferably in a side-byside or parallel manner, by means of a tin base metal matrix.
2. Description of Prior Art Tin is an element which finds wide useage in industry. One of its most important uses is as a protective coating for stronger materials or substrates. The use of pure tin alone as a material of construction is limited by its inherently poor physical properties, such as low tensile strength and modulus of and/or antimony. However, weak.
It has been proposed to increase the tensile strength of tin by reinforcing it with an inert fibrous material. One of the most promising materials available today for this purpose is carbon textiles. However, it has been discovered that strong, nonporous carbon fiber-tin composites cannot be simply formed by bonding carbon fibers together by means of a tin matrix. This is believed to are not adequately wetted coated fibers are cooled dewets or separates from causes voids or weak spots posite article.
It was discovered that this problem can be overcome by first coating the carbon fibers with a thin but continuous metallic film or coupling agent which has a melting point greater than tin and is also readily wetted by tin. Carbon fiber-tin comby molten tin and that when the sothe tin thereon, at least in part, the carbon fibers and, accordingly to be present in the resultant com- SUMMARY Broadly stated, the carbon fiber-tin composite of the invention comprises a plurality of carbon fibers each of which is coated with a thin layer of a coupling metal having a melting a thm but continuous film of a suitable metal, shaping an aggregate of the so-coated fibers into the desired form, infiltrating the voids between the individual fibers with molten tin or tin base alloy and cooling the resultant tin infiltrated aggregate to produce a composite article.
A graphite fiber-tin composite, containing approximately 33.5 volume percent fibers, is characterized by a density a material of construction in apparatus which require strong, corrosion resistant parts or components.
DESCRIPTION OF THE DRAWING The sole FIGURE shown in the drawing presented herewith is a diagrammatical illustration of a rectangular section of a carbon fiber-metal matrix composite article produced according to the teachings of the instant invention.
Referring now in detail to the drawing, there is shown in cross section a rectangular composite article 1 consisting of aligned graphite fibers 2 having disposed on their surface a continuous 2-micron thick coating of nickel 3. These socoated fibers are bonded together by a tin matrix 4. The graphite fibers 2 are approximately 1 inch in length and disposed in the tin matrix 4 in a parallel or side-by-side manner. The
length dimension of the fibers 2 is perpendicular to the surface of the drawing.
Description of the Preferred Embodiment of the Invention Carbon textiles in any form can be employed in the practice of the instant invention. However, it is preferred to employ carbon fibers in yarn or monofilament form. Carbon textiles are available commercially and are generally produced by the techniques described in US. Pat. Nos. 3,107,152 and 3,l 16,975, among others.
The coupling metal used can be any metal which has a melting point greater than the metal matrix which adheres to the carbon and is readily wetted by the matrix metal without forming low melting point alloys or brittle intermetallic phases. Metals which are preferred as coupling agents are nickel, titanium and chromium. The selected coupling metal can be deposited on the carbon fibers by a variety of methods. The techniques available for accomplishing this include electrodeposition from a suitable plating bath, thermal decomposition of the appropriate metal halide or sputtering. The exact deposition technique to be employed is dictated by a number of factors. Sputtering can be used on relatively complex shapes and results in a tenacious bond between the coupling metal and the carbon fiber substrate. Such a bond is a highly desirable feature in carbon fiber-metal matrix composites. Thermal decomposition of the appropriate halide requires a heating of the carbon fiber substrate and, accordingly, somewhat limits the type of shapes which can be coated in this manner. Electrodeposition of a metal from a plating solution is an ideal way of coating carbon fibers with a thin metallic film and is the preferred coating technique.
While the preferred binder or matrix metal is tin, it will be readily appreciated by those skilled in the art that tin base alloys of low melting point metals such as lead, antimony, and bismuth may also be employed in the practice of the instant invention.
The following example illustrates in detail the practice of the instant invention.
A single ply of graphite yarn having an average filament diameter of 6.9 microns and consisting of 720 monofilaments per ply was cut into a plurality of 4-inch lengths. These 4 inch sections of graphite yarn were then predipped into acetone to facilitate their subsequent coating with nickel. Nickel was so-treated graphite yarn by using a nickel anode and an electroplating plating solution prepared by dissolving 200 grams of NiSO '6H O and 22 grams of H BO in 500 ml. of distilled water. The plating solution temperature was maintained at approximately 52 C. The plating current varied between about 400 to about 1000 milliamperes. A metallographic examination of the resultant fibers showed that all monofilaments had a coating of nickel thereon and that the average coating thickness ranged from 1 to 3 microns. These nickel clad fibers were then cut in approximately l-inch lengths and placed in an aligned position (all parallel) in a cylindrical capillary tube measuring approximately 1 inch in length and having an internal diameter of about 0.135 inches which was provided with a top and bottom closure. The surface of the cylinder was provided with 12 randomly placed holes or openings to facilitate the ingress of tin into the cylinder and hence into the voids between the aligned graphite fibers. The cylinder containing the fibers was placed into an airtight chamber which also contained a vessel of tin. The chamber was then evacuated to a pressure of approximately ZXlO-mm. of mercury to out gas the graphite fibers. The chamber with the tin therein was heated to a temperature of approximately 300 C. The cylinder containing the aligned fibers was then submerged below the surface of the molten tin. The chamber was subsequently filled with argon gas to a pressure of about latmosphere to insure that molten tin filled essentially all the voids between the aligned graphite fibers. After about 30 seconds of pressurizing the specimen, the capsule was withdrawn from the molten tin, cooled, and removed from the chamber.
A metallographic examination of the resultant nickel coated graphite fiber-tin composite showed that the nickel coating was well bonded to the graphite fiber substrate; that the tin matrix material had uniformly and completely wetted the socoated fibers without disturbing the continuity of the nickel coating; and that no undesireable reaction zone was formed at the nickel-tin interface.
The physical properties of a nickel clad graphite fiber-tin composite are listed below. For comparison, similar property data is also listed for pure tin.
Physical Properties of Tin and A Nickel Clad Graphite Fiber- Tin Composite Containing 33.5"lo Fibers graphite fihcrtin curnpusltL From the foregoing data, it is observed that a composite of the invention, containing approximately 33.5 volume percent graphite fibers, is characterized by a density percent less than tin, a modulus of elasticity twice as great as tin, and a tensile strength approximately 24 times greater than tin metal.
A composite so-produced, in addition to its utility as a chemical corrosion resistant material of construction, is extremely useful as a low density material of construction for subsonic and supersonic aircraft. space system components. and various nuclear devices.
While the foregoing example concerns a composite where the fibers are positioned in a side-by-side relationship. it is readily apparent to those skilled in the art that the graphite fibers may be randomly orientated in the tin matrix if more isotropic physical properties are desired without losing the benefits of the instant invention. In addition, it is obvious that the thickness of the metal coupling agent can be varied as desired. For example, a thickness ofonly 0.1 microns has been found to be effective. Likewise. it will be appreciated by those versed in the art that although graphite fibers and fabrics are preferred in the practice of the instant invention. nongraphitic carbon fibers and fabrics may also be employed. Also. other methods of infiltrating the metal clad carbon fibers with tin and tin base alloys will readily suggest themselves to the skilled artisan.
As used herein and in the appended claims the term carbon is meant to include both the nongraphitic and graphitic forms of carbon.
The foregoing example is presented for illustrative purposes only and is not intended to unduly limit the reasonable scope of the instant invention. The limitations of the invention are defined by the following claims.
What is claimed is:
l. A corrosion resistant composite article comprising a plurality of carbon fibers bonded together by a tin base metal matrix. said carbon fibers having a substantially continuous coating of a coupling metal having a higher melting point than said tin base metal matrix on their outer surface.
2. The corrosion resistant article of claim 1 wherein said tin base metal matrix is essentially tin.
3. The corrosion resistant composite article of claim 1 wherein said fibers are graphite.
4. The corrosion resistant composite article of claim 1 wherein said carbon fibers are in yarn form.
5. The corrosion resistant composite article of claim 1 wherein said carbon fibers are arranged in a side-by-side, parallel relationship.
6. The corrosion resistant composite article of claim I wherein said coupling metal is selected from the group consisting of nickel, titanium and chromium.
7. The corrosion resistant composite article of claim 1 wherein said coupling metalis nickel.
8. The corrosion resistant composite article of claim 7 wherein said coupling metal is from 1 to 3 microns thick.
9. The corrosion resistant composite article of claim 3 wherein said graphite fibers are in yarn form.
10. The corrosion resistant composite article of claim 3 wherein said graphite fibers are arranged in a side-by-side, parallel relationship.
11. The corrosion resistant composite article of claim 3 wherein said coupling metal is selected from the group consisting of nickel, titanium and chromium.
12. The corrosion resistant composite article of claim 3 wherein said coupling metal is nickel.
E3. The corrosion resistant composite article of claim 12 wherein said coupling metal is from I to 3 microns thick.
14. The corrosion resistant composite article of claim 2 wherein said fibers are graphite.
H5. The corrosion resistant composite article of claim 14 wherein said coupling metal is nickel.
H6. The corrosion resistant composite article of claim 15 wherein the thickness of said nickel coupling metal is from I to 3 microns.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION hunt ,283 November 23,1971
Inventofls) Raymond V Sara Issue Date It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 29, insert a comma after "aegordingly" Column 2, line 66, change "IO-mm." to read "10 mm." Column 3, line 12, change "33.5 r/o" to read "33.5 v/o".
Signed and sealed this 20th day of March 1973.
(SEAL) Attest:
EDWARD M.FLET( IHER,JR. ROBERT GOTTSCHALK Attestlng Offlcer Commissioner of Patents

Claims (15)

  1. 2. The corrosion resistant article of claim 1 wherein said tin base metal matrix is essentially tin.
  2. 3. The corrosion resistant composite article of claim 1 wherein said fibers are graphite.
  3. 4. The corrosion resistant composite article of claim 1 wherein said carbon fibers are in yarn form.
  4. 5. The corrosion resistant composite article of claim 1 wherein said carbon fibers are arranged in a side-by-side, parallel relationship.
  5. 6. The corrosion resistant composite article of claim 1 wherein said coupling metal is selected from the group consisting of nickel, titanium and chromium.
  6. 7. The corrosion resistant composite article of claim 1 wherein said coupling metal is nickel.
  7. 8. The corrosion resistant composite article of claim 7 wherein said coupling metal is from 1 to 3 microns thick.
  8. 9. The corrosion resistant composite article of claim 3 wherein said graphite fibers are in yarn form.
  9. 10. The corrosion resistant composite article of claim 3 wherein said graphite fibers are arranged in a side-by-side, parallel relationship.
  10. 11. The corrosion resistant composite article of claim 3 wherein said coupling metal is selected from the group consisting of nickel, titanium and chromium.
  11. 12. The corrosion resistant composite article of claim 3 wherein said coupling metal is nickel.
  12. 13. The corrosion resistant composite article of claim 12 wherein said coupling metal is from 1 to 3 microns thick.
  13. 14. The corrosion resistant composite article of claim 2 wherein said fibers are graphite.
  14. 15. The corrosion resistant composite article of claim 14 wherein said coupling metal is nickel.
  15. 16. The corrosion resistant composite article of claim 15 wherein the thickness of said nickel coupling metal is from 1 to 3 microns.
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US3720257A (en) * 1970-01-07 1973-03-13 Bbc Brown Boveri & Cie Method of producing carbon fiber-reinforced metal
US3807996A (en) * 1972-07-10 1974-04-30 Union Carbide Corp Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US3888661A (en) * 1972-08-04 1975-06-10 Us Army Production of graphite fiber reinforced metal matrix composites
US3894677A (en) * 1971-03-24 1975-07-15 Nasa Method of preparing graphite reinforced aluminum composite
US3938579A (en) * 1970-09-10 1976-02-17 United Kingdom Atomic Energy Authority Method of producing composite bearing materials
US4223075A (en) * 1977-01-21 1980-09-16 The Aerospace Corporation Graphite fiber, metal matrix composite
US4341823A (en) * 1981-01-14 1982-07-27 Material Concepts, Inc. Method of fabricating a fiber reinforced metal composite
US4609449A (en) * 1982-03-16 1986-09-02 American Cyanamid Company Apparatus for the production of continuous yarns or tows comprising high strength metal coated fibers
US4624751A (en) * 1983-06-24 1986-11-25 American Cyanamid Company Process for fiber plating and apparatus with special tensioning mechanism
US4648902A (en) * 1983-09-12 1987-03-10 American Cyanamid Company Reinforced metal substrate
US4661403A (en) * 1982-03-16 1987-04-28 American Cyanamid Company Yarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US4680093A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Metal bonded composites and process
US4680100A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Electrochemical cells and electrodes therefor
US4762603A (en) * 1983-06-24 1988-08-09 American Cyanamid Company Process for forming electrodes
US4831707A (en) * 1980-11-14 1989-05-23 Fiber Materials, Inc. Method of preparing metal matrix composite materials using metallo-organic solutions for fiber pre-treatment
US4837073A (en) * 1987-03-30 1989-06-06 Allied-Signal Inc. Barrier coating and penetrant providing oxidation protection for carbon-carbon materials
US4852453A (en) * 1982-03-16 1989-08-01 American Cyanamid Company Chaff comprising metal coated fibers
WO1989011551A1 (en) * 1988-05-23 1989-11-30 Yoon Technology Fabrication of fusible core alloy composites for plastics molding
US4904351A (en) * 1982-03-16 1990-02-27 American Cyanamid Company Process for continuously plating fiber
US4909910A (en) * 1982-03-16 1990-03-20 American Cyanamid Yarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US4911797A (en) * 1983-06-24 1990-03-27 American Cyanamid Company Contact roller mounting assembly and tensioning mechanism for electroplating fiber
US4942090A (en) * 1982-03-16 1990-07-17 American Cyanamid Chaff comprising metal coated fibers
US4976828A (en) * 1982-03-16 1990-12-11 American Cyanamid Company Chaff comprising metal coated fibers
US5066544A (en) * 1990-08-27 1991-11-19 U.S. Philips Corporation Dispersion strengthened lead-tin alloy solder
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
US5779872A (en) * 1992-03-13 1998-07-14 Toyota Jidosha Kabushiki Kaisha Composite material having anti-wear property and process for producing the same
EP1096032A2 (en) * 1999-11-01 2001-05-02 Ford Global Technologies, Inc. Fibre reinforced metal-matrix composite
US20050166386A1 (en) * 2003-11-20 2005-08-04 Twigg Edwin S. Method of manufacturing a fibre reinforced metal matrix composite article
US20050181209A1 (en) * 1999-08-20 2005-08-18 Karandikar Prashant G. Nanotube-containing composite bodies, and methods for making same
US20060062985A1 (en) * 2004-04-26 2006-03-23 Karandikar Prashant G Nanotube-containing composite bodies, and methods for making same
FR2876044A1 (en) * 2004-10-05 2006-04-07 Ensmse Deposition of metal particles on fibrous material filter, useful to e.g. eliminate pollutants in gas effluent, comprises contacting the material with aqueous solution, applying negative polarization and drying to form a uniform coating
US20060156662A1 (en) * 2004-12-01 2006-07-20 Airbus Deutschland Gmbh Structural element, method for manufacturing a structural element and use of a structural element for an aircraft hull
US7169465B1 (en) 1999-08-20 2007-01-30 Karandikar Prashant G Low expansion metal-ceramic composite bodies, and methods for making same
US7244034B1 (en) 1999-08-20 2007-07-17 M Cubed Technologies, Inc. Low CTE metal-ceramic composite articles, and methods for making same
EP2208706A1 (en) * 2007-09-18 2010-07-21 Shimane Prefectural Government Metal covered carbon material and carbon-metal composite material using the metal covered carbon material
US20120009110A1 (en) * 2010-02-04 2012-01-12 Third Millennium Metals, Llc Metal-Carbon Compositions
CN103194698A (en) * 2013-04-17 2013-07-10 中北大学 Carbon fiber reinforced tin-base composite material and preparation method thereof
US20170307454A1 (en) * 2014-10-20 2017-10-26 Bae Systems Plc Strain sensing in composite materials

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Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3720257A (en) * 1970-01-07 1973-03-13 Bbc Brown Boveri & Cie Method of producing carbon fiber-reinforced metal
US3938579A (en) * 1970-09-10 1976-02-17 United Kingdom Atomic Energy Authority Method of producing composite bearing materials
US3894677A (en) * 1971-03-24 1975-07-15 Nasa Method of preparing graphite reinforced aluminum composite
US3807996A (en) * 1972-07-10 1974-04-30 Union Carbide Corp Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US3888661A (en) * 1972-08-04 1975-06-10 Us Army Production of graphite fiber reinforced metal matrix composites
US4223075A (en) * 1977-01-21 1980-09-16 The Aerospace Corporation Graphite fiber, metal matrix composite
US4831707A (en) * 1980-11-14 1989-05-23 Fiber Materials, Inc. Method of preparing metal matrix composite materials using metallo-organic solutions for fiber pre-treatment
US4341823A (en) * 1981-01-14 1982-07-27 Material Concepts, Inc. Method of fabricating a fiber reinforced metal composite
US4680100A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Electrochemical cells and electrodes therefor
US4976828A (en) * 1982-03-16 1990-12-11 American Cyanamid Company Chaff comprising metal coated fibers
US4661403A (en) * 1982-03-16 1987-04-28 American Cyanamid Company Yarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US4680093A (en) * 1982-03-16 1987-07-14 American Cyanamid Company Metal bonded composites and process
US4942090A (en) * 1982-03-16 1990-07-17 American Cyanamid Chaff comprising metal coated fibers
US4909910A (en) * 1982-03-16 1990-03-20 American Cyanamid Yarns and tows comprising high strength metal coated fibers, process for their production, and articles made therefrom
US4609449A (en) * 1982-03-16 1986-09-02 American Cyanamid Company Apparatus for the production of continuous yarns or tows comprising high strength metal coated fibers
US4904351A (en) * 1982-03-16 1990-02-27 American Cyanamid Company Process for continuously plating fiber
US4852453A (en) * 1982-03-16 1989-08-01 American Cyanamid Company Chaff comprising metal coated fibers
US4624751A (en) * 1983-06-24 1986-11-25 American Cyanamid Company Process for fiber plating and apparatus with special tensioning mechanism
US4762603A (en) * 1983-06-24 1988-08-09 American Cyanamid Company Process for forming electrodes
US4911797A (en) * 1983-06-24 1990-03-27 American Cyanamid Company Contact roller mounting assembly and tensioning mechanism for electroplating fiber
US4648902A (en) * 1983-09-12 1987-03-10 American Cyanamid Company Reinforced metal substrate
US4837073A (en) * 1987-03-30 1989-06-06 Allied-Signal Inc. Barrier coating and penetrant providing oxidation protection for carbon-carbon materials
US4927712A (en) * 1988-04-27 1990-05-22 Yoon Technology Fusible core alloy composites for plastics molding
US4962003A (en) * 1988-04-27 1990-10-09 Lhymn Yoon O Development of fusible alloy composites
WO1989011551A1 (en) * 1988-05-23 1989-11-30 Yoon Technology Fabrication of fusible core alloy composites for plastics molding
US5066544A (en) * 1990-08-27 1991-11-19 U.S. Philips Corporation Dispersion strengthened lead-tin alloy solder
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
US5839496A (en) * 1992-03-13 1998-11-24 Toyota Jidosha Kabushiki Kaisha Composite material having anti-wear property and process for producing the same
US5861217A (en) * 1992-03-13 1999-01-19 Toyota Jidosha Kabushiki Kaisha Composite material having anti-wear property and process for producing the same
US5779872A (en) * 1992-03-13 1998-07-14 Toyota Jidosha Kabushiki Kaisha Composite material having anti-wear property and process for producing the same
US7169465B1 (en) 1999-08-20 2007-01-30 Karandikar Prashant G Low expansion metal-ceramic composite bodies, and methods for making same
US20050181209A1 (en) * 1999-08-20 2005-08-18 Karandikar Prashant G. Nanotube-containing composite bodies, and methods for making same
US7244034B1 (en) 1999-08-20 2007-07-17 M Cubed Technologies, Inc. Low CTE metal-ceramic composite articles, and methods for making same
EP1096032A2 (en) * 1999-11-01 2001-05-02 Ford Global Technologies, Inc. Fibre reinforced metal-matrix composite
US6376098B1 (en) * 1999-11-01 2002-04-23 Ford Global Technologies, Inc. Low-temperature, high-strength metal-matrix composite for rapid-prototyping and rapid-tooling
EP1096032A3 (en) * 1999-11-01 2004-01-21 Ford Global Technologies, Inc. Fibre reinforced metal-matrix composite
US20050166386A1 (en) * 2003-11-20 2005-08-04 Twigg Edwin S. Method of manufacturing a fibre reinforced metal matrix composite article
US7516548B2 (en) * 2003-11-20 2009-04-14 Rolls-Royce Plc Method of manufacturing a fibre reinforced metal matrix composite article
US20060062985A1 (en) * 2004-04-26 2006-03-23 Karandikar Prashant G Nanotube-containing composite bodies, and methods for making same
FR2876044A1 (en) * 2004-10-05 2006-04-07 Ensmse Deposition of metal particles on fibrous material filter, useful to e.g. eliminate pollutants in gas effluent, comprises contacting the material with aqueous solution, applying negative polarization and drying to form a uniform coating
US20060156662A1 (en) * 2004-12-01 2006-07-20 Airbus Deutschland Gmbh Structural element, method for manufacturing a structural element and use of a structural element for an aircraft hull
EP1666354B1 (en) * 2004-12-01 2010-09-29 Airbus Operations GmbH Structural component, process for manufacturing a structural component and use of a structural component for an aircraft skin
US7850118B2 (en) 2004-12-01 2010-12-14 Airbus Deutschland Gmbh Structural element, method for manufacturing a structural element and use of a structural element for an aircraft hull
EP2208706A1 (en) * 2007-09-18 2010-07-21 Shimane Prefectural Government Metal covered carbon material and carbon-metal composite material using the metal covered carbon material
EP2208706A4 (en) * 2007-09-18 2013-03-27 Shimane Prefectural Government Metal covered carbon material and carbon-metal composite material using the metal covered carbon material
US8349759B2 (en) * 2010-02-04 2013-01-08 Third Millennium Metals, Llc Metal-carbon compositions
US20120009110A1 (en) * 2010-02-04 2012-01-12 Third Millennium Metals, Llc Metal-Carbon Compositions
US8541335B2 (en) 2010-02-04 2013-09-24 Third Millennium Metals, Llc Metal-carbon compositions
US8541336B2 (en) 2010-02-04 2013-09-24 Third Millennium Metals, Llc Metal-carbon compositions
US8546292B2 (en) 2010-02-04 2013-10-01 Third Millennium Metals, Llc Metal-carbon compositions
US8551905B2 (en) 2010-02-04 2013-10-08 Third Millennium Metals, Llc Metal-carbon compositions
CN103194698A (en) * 2013-04-17 2013-07-10 中北大学 Carbon fiber reinforced tin-base composite material and preparation method thereof
US20170307454A1 (en) * 2014-10-20 2017-10-26 Bae Systems Plc Strain sensing in composite materials
US10444089B2 (en) * 2014-10-20 2019-10-15 Bae Systems Plc Strain sensing in composite materials

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FR1561254A (en) 1969-03-28
DE1558690A1 (en) 1971-10-07
DE1558690B2 (en) 1971-10-07

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