US3807996A - Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide - Google Patents
Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide Download PDFInfo
- Publication number
- US3807996A US3807996A US00270260A US27026072A US3807996A US 3807996 A US3807996 A US 3807996A US 00270260 A US00270260 A US 00270260A US 27026072 A US27026072 A US 27026072A US 3807996 A US3807996 A US 3807996A
- Authority
- US
- United States
- Prior art keywords
- carbide
- metal
- nickel
- fibers
- forming metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 118
- 239000002184 metal Substances 0.000 title claims abstract description 118
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title abstract description 49
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract description 36
- 239000004917 carbon fiber Substances 0.000 title abstract description 36
- 239000011159 matrix material Substances 0.000 title abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000007731 hot pressing Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000011651 chromium Substances 0.000 claims description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052804 chromium Inorganic materials 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000835 fiber Substances 0.000 abstract description 74
- 239000010410 layer Substances 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 239000010953 base metal Substances 0.000 abstract description 9
- 238000005382 thermal cycling Methods 0.000 abstract description 9
- 230000009977 dual effect Effects 0.000 abstract description 6
- 239000002344 surface layer Substances 0.000 abstract description 5
- 238000007747 plating Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 241000581364 Clinitrachus argentatus Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49801—Shaping fiber or fibered material
Definitions
- ABSTRACT Composite articles having a nickel base metal matrix reinforced with a plurality of high strength, high modulus carbon fibers having a thin, intermediate layer of a metal carbide disposed upon at least a portion of the fiber surfaces.
- Such composites are characterized by improved thermal cycling characteristics and are produced by coating a plurality of carbon fibers first with a thin, continuous layer of nickel, and then with a second thin, continuous overcoating of a metal capable of diffusing through the nickel coating and reacting with carbon to form a metal carbide; and then hot pressing the dual-coated fibers for a time and at a temperature and pressure sufficient to bond them together and diffuse at least a portion of the carbide-forming metal surface layer through the nickel undercoating and effect reaction between said carbide-forming metal and said carbon fibers to produce a metal carbide coating on at least a portion of the surface of the fibers.
- the interfacial bond strength between the carbon fibers and the nickel matrix also increases while, at the same time, the nickel matrix expands at a greater rate than do the fibers.
- Full expansion of the matrix at the fiber interface is constrained, however, by the interfacial bond strength of these materials. This causes a compressive stress to be exerted on the matrix and a tensile stress to be exerted on the fibers.
- the compressive stress on the matrix is relieved by plastic flow of the matrix in a direction perpendicular to the fiber axis, resulting in distortion of the composite dimensions.
- the stresses exerted on the matrix and fibers are reversed, i.e., the fibers are subjected to a compressive stress and a tensile stress is exerted on the matrix as it attempts to contract at a faster rate than the interfacial bond strength with the fiber will allow.
- the interfacial bond strength of the fibers and matrix is gradually reduced by the cooling and, eventually, declines to a point where it is exceeded by the tensile stress exerted on the matrix. This causes slippage of the matrix and a permanent weakening of the bonding between the fibers and the matrix, which seriously degrades the mechanical properties of the composite.
- the interfacial bonding characteristics of carbon fiber-nickel base metal matrix composites can be substantially improved by providing a thin, intermediate layer of a metal carbide over at least a portion of the interface between the surface of the fibers and the nickel base matrix.
- the composites are characterized by improved thermal cycling characteristics and may be repeatedly cycled over a wide range of temperatures without undergoing the ratcheting effect and mechanical property degradation heretofore characteristic of carbon fibernickel matrix composites.
- Any metal carbide which can be formed by the reaction of carbon and a metal capable of reacting with carbon to produce a metal carbide can be employed to improve the interfacial bonding characteristics of carbon fiber-nickel base metal matrix composites.
- Coatings of this type are provided at the interface between the surface of the carbon fibers and the nickel base metal matrix according to the invention by coating a plurality of carbon fibers first with a thin, continuous layer of nickel, and then with a second thin, continuous overcoating of a metal capable of diffusing through the nickel coating and reacting with carbon to form a metal carbide; and then hot pressing the dual-coated fibers for a time and at a temperature and pressure sufficient to bond them together and diffuse at least a portion of the carbide-forming metal surface layer through the nickel undercoating and effect reaction between said carbide-forming metal and said carbon fibers to produce a metal carbide coating on at least a portion of the surface of the fibers.
- a thin, continuous coating of nickel can be applied to the carbon fibers by a variety of known techniques, including electrodeposition from an aqueous salt bath, electro-less deposition, thermal decomposition of an appropriate metal carbonyl or halide, and sputtering. Electrodeposition from an aqueous salt bath provides a uniform, tenaciously bonded coating and is the preferred means of applying nickel to the fibers according to the present invention. In order to allow for subsequent diffusion of the exterior coating through the nickel coating, the nickel coating should not be applied in a thickness in excess of bout 5 microns. Most preferably, it is applied in a thickness of from about 1 micron to about 3 microns.
- the carbon fibers After the carbon fibers have been coated with nickel, they are coated with a second thin, continuous layer of a metal capable of diffusing through the nickel coating and reacting with carbon to form a metal carbide.
- the second coating is applied to the nickel coating by the same techniques employed to deposit the nickel coating, e.g., electrodeposition from an aqueous salt bath, electroless deposition, thermal decomposition of an appropriate metal carbonyl or halide, and sputtering. While the nickle coating should be applied in a thickness of at least about 1 micron, the carbide-forming metal may be applied in somewhat thinner coats, e.g., up to about 5,000 A.
- the carbideforming metal In order to ensure that sufficient carbide-forming metal is present to diffuse through the nickel coating and react with the carbon fibers to form an amount of metal carbide which will effectively bond the metal matrix to the carbon fibers, the carbideforming metal should be applied in a thickness of at least 50 A. However, in order to prevent excessive degradation of the carbon fibers, the thickness of the carbide-forming metal coating should not exceed 5,000 A. Preferably, the carbide-forming metal is present in a thickness of from about 500 A to about 2,000 A.
- metals capable of diffusing through nickel and reacting with carbon to form a metal carbide which can be employed to improve the interfacial bonding characteristics and thermal cycling characteristics of carbon fiber-nickel metal matrix composites according to the present invention are such metals as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and iron.
- the most preferred metals are chromium and iron.
- the dualcoated fibers are hot pressed, preferably in side-by-side or parallel manner, for a time and at a temperature and pressure sufficient to bond them together and diffuse at least a portion of the carbide-forming metal surface layer through the nickel undercoating and effect reaction between said carbide-forming metal and said carbon fibers to produce a metal carbide coating on at least a portion of the surface of the fibers.
- Hot pressing is conducted in a non-oxidizing atmosphere, e.g., in an inert atmosphere or under vacuum.
- an inert atmosphere is meant an atmosphere which does not react with nickel or the carbide-forming metal under the reaction conditions employed during hot pressing such as nitrogen, argon, xenon, helium and the like.
- the temperature at which hot pressing is effected will depend upon the sintering temperature of the carbideforming metal employed, and the temperature at which such metal reacts with carbon to form a metal carbide.
- the pressure required will, of course, depend upon the temperature employed, with higher pressures being required at lower temperatures.
- hot pressing can be readily effected at temperatures of from about 700 C. to about 1,300 C., preferably from about 800 C. to about l,l00 C. Pressures in excess of 500 psi. are usually employed, with pressures of from about 1,500 psi. to about 2,500 psi. being preferred. To avoid fiber rupture during hot pressing, it is preferred not to use pressures in excess of 4,500 psi.
- Hot pressing should be continued for a time sufficient to diffuse the carbide-forming metal through the nickel undercoating, effect reaction between the carbideforming metal which diffuses through the nickel and the carbon fibers, and effectively bond the coated fibers and attain maximum densification.
- the time required to accomplish this for any given metal will depend, of course, upon the temperature and pressure employed. Under most conditions, hot pressing can be completed within from about 2 minutes to about minutes, usually within from about 30 minutes to about 60 minutes.
- the metal carbide coating which forms at the interface between the surface of the carbon fibers and the nickel base matrix according to the present invention serves to improve the interfacial bonding characteristics and thermal cycling characteristics of the resulting composite. Because this metal carbide layer is formed at relatively low temperatures in the presence of an intermediate nickel layer which serves as a diluent for the reaction between the carbide-forming metal and the carbon fibers, excessive degradation of the fibers is thereby avoided.
- High modulus, high strength carbon fibers suitable for use in the instant invention can be prepared as described in U.S. Pat. No. 3,503,708 and 3,412,062.
- carbon as used throughout this specification includes all forms of the material, both graphitic and non-graphitic.
- nickel base metal matrix includes matrices containing at least 50 percent by weight of nickel.
- EXAMPLE 1 A two ply graphite yarn having 720 filaments per ply wherein the filaments are characterized by an average Youngs modulus of 75 X psi. and an average tensile strength of 335 X 10 psi. was electroplated with nickel using a standard Watts plating solution. The fibers were passed between copper rollers which were positioned about two inches before a plating bath and connected to an electrical source whereby electrical contact was made with the fibers. The fibers were then passed into the plating bath where nickel was deposited on the fibers from a nickel anode.
- the aqueous electroplating solution employed contained 200 grams of Ni- SOhd 4 -6H O, 50 grams of NiCl 6H O and 30 grams of H 80 per liter of water.
- the solution temperature was maintained at 50 C., and a plating current of 2.5 amperes was employed.
- the residence time of the fibers in the bath was 14 minutes.
- the yarn was washed by passing it through hot water, dried at 200 C., and stored on take-up spools.
- Metallographic examination of the resultant nickel coated fibers showed that all monofilaments had a coating of nickel thereon, and that the coating thickness ranged from i to 3 microns.
- the nickel clad fibers produced in this manner were than heated at a temperature of 800 C. in an atmosphere containing 85 volume percent argon and 15 volume percent hydrogen in order to clean the fibers and reduce any nickel oxide present.
- a second layer of chromium was then applied to the fibers in a manner similar to that described above using a lead anode and an aqueous plating bath containing 250 grams of H CrO and 2.5 grams of (SO per liter of water.
- the (80 was partially provided by Cr (SO,,) and partially by H 80
- the plating solution was maintained at room temperature and a plating current of 7.5 amperes was employed.
- the residence time of the fibers in the bath was 1 1 minutes.
- the yarn After passing through the electroplating solution, the yarn was washed in hot water, dried at 200 C., and stored on take-up spools.
- Metallographic examination of the resultant chromium coated fibers showed that all monofilaments had a coating of chromium thereon and that the coating thickness ranged from 2,000 A to 4,000 A.
- the total weight of chromium deposited was about weight percent of the nickel coating.
- the dual-coated fibers produced in this manner were then cut into approximately 1 inch lengths, aligned in a parallel manner in a graphite mold and hot pressed under vacuum (about 20 microns of mercury pressure) for 1 hour at a temperature of 1,050" C. and a pressure of about 3,000 psi. to form solid bars approximately one-inch long, one-eighth-inch wide, and onesixteenth-inch thick.
- Each specimen contained about coated fiber plys, or about 50 volume percent fibers and 50 volume percent metal.
- a portion of the chromium overlayer diffused through the nickel undercoating during the hot pressing and reacted with the carbon fibers to produce acoatin'g of chromium carbide at the interface between the fibers and the nickel matrix.
- a number of the composites produced in this manner were treated with a 50 volume percent solution of hydrochloric acid in water to dissolve the nickel and unreacted chromium present on the fibers.
- Metallographic examination of the recovered fibers showed the presence of undulations on the surface of the fibers caused by the reaction of the fibers with the chromium to form chromium carbide.
- Nickel coated fibers produced and heat-treated as described in Example 1 were cut into approximately 5 inch lengths, clamped to an electrical lead and immersed in a plating bath where iron was deposited on the fibers from an iron node.
- the aqueous electroplating solution employed contained 350 grams of Fe(NH $0., per liter of water.
- the plating solution was maintained at room temperature and a plating current of 5 amperes was employed.
- the residence time of the fibers in the bath was 17 seconds. At the end of this time, the yarn was then removed from the bath, washed in hot water and dried at 200 C.
- Metallographic examination of the resultant iron coated fibers showed that all monofilaments had a coating of iron thereon, and that the coating thickness ranged from 2,000 A to 4,000 A.
- the total weight of iron deposited was about 20 weight percent of the nickel coating.
- the dual-coated fibers were then formed into composites of the same size and shape as described in EX- ample l by employing the same procedure described therein.
- a portion of the o'verlayer, in this case iron diffused through the nickel undercoating during hot pressing and reacted with the carbon fibers to produce a coating of iron carbide at the interface between the fibers and the nickel matrix.
- Example 2 As in Example 1, a number of composites produced in this manner were treated with a 50 volume percent solution of hydrochloric acid in water to dissolve the unreacted metals present on the fibers. Again, metallographic examination of the recovered fibers showed the presence of undulations on the surface of the fibers, in this case caused by the reaction of the fibers with the iron to form iron carbide.
- Example 2 The remaining composites were then thermally cycled in the same manner as the composites in Example 1. As in the composites produced in accordance with Example 1, no dimensional change was found to occur as a result of the thermal cycling. Again, metallographic examination of the composites showed the matrix was still uniformly clad around the filaments.
- Composites produced in the above manner are extremely useful as materials of construction for subsonic and supersonic aricraft, space system components and various propulsion devices.
- the composite articles of the instant invention may be fabricated to meet various design requirements as to size, shape, stress relationships, and the like.
- any shape in which the metallized carbon fibers are wound or stacked in parallel relationship can be provided.
- such fibers can be wound on a mandrel and hot pressed to produce a coiled composite, or laid out in parallel manner and compressed to produce plates of various sizes and shapes.
- laminates can be prepared in which the metallized fibers are arranged in layers wherein the fibers of each layer remain in parallel relationship but are in non-parallel relationship to the fibers of the adjacent layer.
- a process for producing a composite article having a nickel base metal matrix reinforced with a plurality of high strength, high modulus carbon fibers having a thin, intermediate layer of a metal carbide disposed upon at least a portion of the fiber surfaces which comprises coating a plurality of carbon fibers first with a thin, continuous layer of nickel, and then with a second thin, continuous overcoating of a metal capable of diffusing through the nickel coating and reacting with carbon to form a metal carbide; and then, hot pressing the dual-coated fibers in a non-oxidizing atmosphere for a time and at a temperature and pressure sufficient to bond them together and diffuse at least a portion of the carbide-forming metal surface layer through the nickel undercoating and effect reaction between said carbideforming metal and said carbon fibers to produce a metal carbide coating on at least a portion of the surface of the fibers.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Electroplating Methods And Accessories (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00270260A US3807996A (en) | 1972-07-10 | 1972-07-10 | Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide |
DE19732334218 DE2334218C3 (de) | 1972-07-10 | 1973-07-05 | Verfahren zur Herstellung von Verbundmaterial aus einer mit Kohlenstoffasern verstärkten Nickelmatrix |
IT51319/73A IT989794B (it) | 1972-07-10 | 1973-07-09 | Procedimento per produrre oggetti compositi a matrice metallica rinforzata con fibre |
JP48076669A JPS5224501B2 (pt) | 1972-07-10 | 1973-07-09 | |
FR7325063A FR2192193B1 (pt) | 1972-07-10 | 1973-07-09 | |
GB3270573A GB1371889A (en) | 1972-07-10 | 1973-07-09 | Carbon fibre reinforced nickel matrix composite having an intermediate layer of metal carbide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00270260A US3807996A (en) | 1972-07-10 | 1972-07-10 | Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide |
Publications (1)
Publication Number | Publication Date |
---|---|
US3807996A true US3807996A (en) | 1974-04-30 |
Family
ID=23030579
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00270260A Expired - Lifetime US3807996A (en) | 1972-07-10 | 1972-07-10 | Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide |
Country Status (5)
Country | Link |
---|---|
US (1) | US3807996A (pt) |
JP (1) | JPS5224501B2 (pt) |
FR (1) | FR2192193B1 (pt) |
GB (1) | GB1371889A (pt) |
IT (1) | IT989794B (pt) |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3888661A (en) * | 1972-08-04 | 1975-06-10 | Us Army | Production of graphite fiber reinforced metal matrix composites |
US3918141A (en) * | 1974-04-12 | 1975-11-11 | Fiber Materials | Method of producing a graphite-fiber-reinforced metal composite |
US4083719A (en) * | 1975-10-29 | 1978-04-11 | Hitachi, Ltd. | Copper-carbon fiber composites and process for preparation thereof |
US4252856A (en) * | 1973-03-12 | 1981-02-24 | Union Carbide Corporation | Chemically bonded aluminum coated carbon via monocarbides |
US4440571A (en) * | 1981-07-10 | 1984-04-03 | Nippon Carbon Co., Ltd. | Process for the surface treatment of inorganic fibers for reinforcing titanium or nickel and product |
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 |
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 |
US4680100A (en) * | 1982-03-16 | 1987-07-14 | American Cyanamid Company | Electrochemical cells and electrodes therefor |
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US11097511B2 (en) | 2014-11-18 | 2021-08-24 | Baker Hughes, A Ge Company, Llc | Methods of forming polymer coatings on metallic substrates |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07818B2 (ja) * | 1985-11-20 | 1995-01-11 | 株式会社日立製作所 | 金属マトリツクス−繊維複合材の製造方法 |
GB2219006A (en) * | 1988-05-26 | 1989-11-29 | Rolls Royce Plc | Coated fibre for use in a metal matrix |
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US3888661A (en) * | 1972-08-04 | 1975-06-10 | Us Army | Production of graphite fiber reinforced metal matrix composites |
US4252856A (en) * | 1973-03-12 | 1981-02-24 | Union Carbide Corporation | Chemically bonded aluminum coated carbon via monocarbides |
US3918141A (en) * | 1974-04-12 | 1975-11-11 | Fiber Materials | Method of producing a graphite-fiber-reinforced metal composite |
US4083719A (en) * | 1975-10-29 | 1978-04-11 | Hitachi, Ltd. | Copper-carbon fiber composites and process for preparation thereof |
US4440571A (en) * | 1981-07-10 | 1984-04-03 | Nippon Carbon Co., Ltd. | Process for the surface treatment of inorganic fibers for reinforcing titanium or nickel and product |
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 |
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 |
US4680100A (en) * | 1982-03-16 | 1987-07-14 | American Cyanamid Company | Electrochemical cells and electrodes therefor |
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 |
US4624751A (en) * | 1983-06-24 | 1986-11-25 | American Cyanamid Company | Process for fiber plating and apparatus with special tensioning mechanism |
US4911797A (en) * | 1983-06-24 | 1990-03-27 | American Cyanamid Company | Contact roller mounting assembly and tensioning mechanism for electroplating fiber |
US5622751A (en) * | 1991-12-30 | 1997-04-22 | Societe Europeenne De Propulsion | Method of protecting products of composite material against oxidizing and products protected thereby |
US20050181209A1 (en) * | 1999-08-20 | 2005-08-18 | Karandikar Prashant G. | Nanotube-containing composite bodies, and methods for making same |
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 |
US6355340B1 (en) | 1999-08-20 | 2002-03-12 | M Cubed Technologies, Inc. | Low expansion metal matrix composites |
US20060062985A1 (en) * | 2004-04-26 | 2006-03-23 | Karandikar Prashant G | Nanotube-containing composite bodies, and methods for making same |
US20100092751A1 (en) * | 2007-01-24 | 2010-04-15 | Airbus Sas | Fiber composite comprising a metallic matrix, and method for the production thereof |
US9963395B2 (en) | 2013-12-11 | 2018-05-08 | Baker Hughes, A Ge Company, Llc | Methods of making carbon composites |
US10202310B2 (en) | 2014-09-17 | 2019-02-12 | Baker Hughes, A Ge Company, Llc | Carbon composites |
US10501323B2 (en) | 2014-09-29 | 2019-12-10 | Baker Hughes, A Ge Company, Llc | Carbon composites and methods of manufacture |
US10315922B2 (en) | 2014-09-29 | 2019-06-11 | Baker Hughes, A Ge Company, Llc | Carbon composites and methods of manufacture |
US10480288B2 (en) | 2014-10-15 | 2019-11-19 | Baker Hughes, A Ge Company, Llc | Articles containing carbon composites and methods of manufacture |
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 |
US20160136923A1 (en) * | 2014-11-13 | 2016-05-19 | Baker Hughes Incorporated | Reinforced composites, methods of manufacture, and articles therefrom |
US11148950B2 (en) | 2014-11-13 | 2021-10-19 | Baker Hughes, A Ge Company, Llc | Reinforced composites, methods of manufacture, and articles therefrom |
US9962903B2 (en) * | 2014-11-13 | 2018-05-08 | Baker Hughes, A Ge Company, Llc | Reinforced composites, methods of manufacture, and articles therefrom |
US10119011B2 (en) | 2014-11-17 | 2018-11-06 | Baker Hughes, A Ge Company, Llc | Swellable compositions, articles formed therefrom, and methods of manufacture thereof |
US11097511B2 (en) | 2014-11-18 | 2021-08-24 | Baker Hughes, A Ge Company, Llc | Methods of forming polymer coatings on metallic substrates |
US10300627B2 (en) | 2014-11-25 | 2019-05-28 | Baker Hughes, A Ge Company, Llc | Method of forming a flexible carbon composite self-lubricating seal |
CN104674327A (zh) * | 2015-03-03 | 2015-06-03 | 北京汽车股份有限公司 | 复合镀层的制备方法及复合镀层 |
CN104674327B (zh) * | 2015-03-03 | 2017-07-28 | 北京汽车股份有限公司 | 复合镀层的制备方法及复合镀层 |
US9840887B2 (en) | 2015-05-13 | 2017-12-12 | Baker Hughes Incorporated | Wear-resistant and self-lubricant bore receptacle packoff tool |
US10125274B2 (en) | 2016-05-03 | 2018-11-13 | Baker Hughes, A Ge Company, Llc | Coatings containing carbon composite fillers and methods of manufacture |
US10344559B2 (en) | 2016-05-26 | 2019-07-09 | Baker Hughes, A Ge Company, Llc | High temperature high pressure seal for downhole chemical injection applications |
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CN111360269A (zh) * | 2020-04-03 | 2020-07-03 | 南京环达新材料有限公司 | 一种多级纳米结构增强的叠层状镍基复合材料及其制备方法 |
CN111360269B (zh) * | 2020-04-03 | 2022-05-06 | 浙江蓝天知识产权运营管理有限公司 | 一种多级纳米结构增强的叠层状镍基复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
FR2192193A1 (pt) | 1974-02-08 |
JPS4953119A (pt) | 1974-05-23 |
FR2192193B1 (pt) | 1976-06-18 |
DE2334218B2 (de) | 1976-04-08 |
JPS5224501B2 (pt) | 1977-07-01 |
IT989794B (it) | 1975-06-10 |
GB1371889A (en) | 1974-10-30 |
DE2334218A1 (de) | 1974-01-31 |
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Owner name: AMOCO CORPORATION, A CORP. OF INDIANA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE CORPORATION;REEL/FRAME:004634/0001 Effective date: 19860620 |