USH1643H - Ductile metal ligament fiber coatings for ceramic composites - Google Patents
Ductile metal ligament fiber coatings for ceramic composites Download PDFInfo
- Publication number
- USH1643H USH1643H US08/637,338 US63733896A USH1643H US H1643 H USH1643 H US H1643H US 63733896 A US63733896 A US 63733896A US H1643 H USH1643 H US H1643H
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- Prior art keywords
- fiber
- matrix
- metal
- composite
- coating
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- 239000000835 fiber Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title claims abstract description 17
- 239000000919 ceramic Substances 0.000 title claims abstract description 16
- 210000003041 ligament Anatomy 0.000 title description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000012783 reinforcing fiber Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000001010 compromised effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 229910002614 GdAlO3 Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000008646 thermal stress Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62876—Coating fibres with metals
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62897—Coatings characterised by their thickness
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
- C04B2235/663—Oxidative annealing
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/762—Cubic symmetry, e.g. beta-SiC
- C04B2235/764—Garnet structure A3B2(CO4)3
Definitions
- This invention relates to a ceramic composite material composed of a refractory fiber reinforcement and a ceramic matrix.
- ceramics have superior high-temperature strength and modulus, lower density, and lower thermal conductivity than metallic materials.
- the principal disadvantages of ceramics as structural materials are their relatively low failure strain, low fracture toughness and catastrophic brittle failure characteristics. Because of these intrinsic limitations, monolithic ceramics lack the properties of reliability and durability that are necessary for structural design acceptance.
- high strength/high toughness composites can be obtained.
- Successfully tailored ceramic-matrix composites exhibit highly non-linear stress-strain behavior with ultimate strengths, failure strains and fracture toughnesses substantially greater than that of the unreinforced matrix.
- fiber coatings must be oxidation resistant, stable with the fiber and matrix, and function over a wide temperature range.
- oxidation-resistant fiber coatings have been proposed as alternatives to carbon and boron nitride.
- Fugitive coatings involving application of graphite or a refractory metal that forms a volatile oxide, such as molybdenum or tungsten, are one such proposal.
- the composites are densified in a reducing atmosphere and then heat-treated in an oxidizing atmosphere, leaving void space where there once was coating.
- Ductile coatings of a refractory noble metal have been proposed.
- Cleavable coatings of a refractory oxide such as beta-alumina are under consideration. Residual thermal stress and stress developed by reactions are also considerations.
- a reinforcing fiber suitable for high temperature use must also be creep resistant.
- anisotropic, single crystal alumina is currently the most creep resistant oxide fiber commercially available. Ceramic composites made with these single crystal fibers and yttrium-aluminum garnet (Y 3 Al 5 O 12 , YAG) matrices have been shown to be chemically stable. The CTE mismatch between these phases is small, but the anisotropy of thermal expansion in alumina causes residual stress of about 150 MPa (compressive) and about 60 MPa (tensile) to develop in the radial and axial directions, respectively, for c-axis alumina fibers in a YAG matrix.
- an improved method for fabricating ceramic composites particularly single crystal alumina fiber and yttrium-aluminum garnet (YAG) matrix composites.
- the method of this invention comprises the steps of (a) coating the fiber with a metal which is stable under oxidizing conditions, (b) coating the metal-coated fiber with a fugitive phase, (c) incorporating the coated fiber into a matrix material and (d) densifying the fiber-matrix into a composite.
- the ceramic reinforcing fibers employed herein may be single crystal alumina fiber (sapphire), polycrystalline alumina fiber, yttrium-aluminum garnet (YAG) fiber, polycrystalline YAG or directionally solidified YAG/alumina eutectic fibers.
- the ceramic matrix comprises material selected from the group consisting of Al 2 O 3 , beta-aluminas, magnetoplumbites, yttrium-aluminum garnet (Y 3 Al 5 O 12 , YAG), MgAl 2 O 4 , Ca/ZrO 2 , GdAlO 3 and Gd 3 Al 5 O 12 .
- Metals suitable for use in the present invention include palladium, platinum, rhodium or any other metal which is stable under oxidizing conditions from room temperature or below to the maximum use temperature of the densified composite, i.e., up to about 1800° C.
- the metal can be used alone or alloyed with other metals, such as nickel, aluminum, chromium, iron or the like, so long as oxidation resistance is not severely compromised.
- the fugitive phase can be any such fugitive phase known in the art, such as carbon or molybdenum.
- the fiber/matrix composite can be fabricated using techniques known in the art.
- a composite preform can be prepared by alternately layering a plurality of layers of fiber and matrix powder.
- the preform can then be pressureless-sintered at about 1700° C., and then hot-isostatically pressed at about 1700° C. with about 200 MPa applied pressure.
- the fiber, coated with the metal and the fugitive phase be incorporated with a suitable matrix into a composite under conditions that preserve the fugitive phase, such as reducing or inert gas conditions.
- the fugitive phase is removed by heat treatment in an atmosphere that causes the fugitive phase to volatilize, usually by forming a volatile oxide.
- Ligaments of the metal occupy the void space remaining.
- the ligaments should have a thickness ( ⁇ ), volume-percent metal, and metal composition such that the ductility of the metal ligaments relieves any compressive residual stress, and such that the toughness and strain to failure of the composite is optimized by promotion of crack deflection and fiber pullout along the metal ligament interface.
- Crack deflection and fiber pullout are usually associated with an interface that is weaker than the fiber or matrix by a factor of at least four.
- palladium is the most ductile, platinum intermediate, and rhodium has very little ductility at room temperature.
- a desired ductility over a given temperature range can be achieved by forming alloys of these metals, and other metals, such as nickel, aluminum, chromium and iron, so long as oxidation resistance is not severely compromised.
- the ligament volume percent and thickness can be controlled to further optimize the mechanical properties of the fiber-matrix interface.
- Fiber coating solutions were prepared by dissolving PdCl 2 in distilled water (90 g/l) and Mo powder in aqua regia (75 g/l). These solutions were mixed to provide a Pd:Mo mole ratio of 40:60. The mixed solutions was applied to Saphikon® continuous single crystal alumina fiber using a vertical continuous fiber coater, such as that disclosed by Hay et al, U.S. Pat. No. 5,217,533.
- the fibers were coated five times with the 40:60 mixture in air at 1100° C. at 10 cm/s.
- the coated fibers were laid up into tapes and vacuum hot pressed with 1 ⁇ m Ceralox® YAG powder in a 11/4-inch square graphite die at 1600°-1700° C. and 25 MPa.
- the fiber volume fraction was about 5 volume percent. Higher densities were achieved when the composite was cold pressed at 20 MPa and held at that pressure to about 1000° C. No pressure was applied during rapid heat up (5 min) between 1000° and 1500° C. 25 MPa pressure was re-applied at 1500° C. up to final temperature.
- the fiber-matrix interface in the hot pressed composites was observed by SEM and analytical TEM. Separate Mo and Pd grains were found in a continuous interlayer 0.5-2.0 ⁇ m thick along the fiber-matrix interface. No evidence of alloying was found.
- the samples were heat-treated in air between 1400° and 1600° C. for up to 100 hours, then characterized by optical microscopy, SEM and analytical TEM. In all cases, the Mo had been oxidized away, leaving isolated Pd grains and void space behind.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
An improved method for fabricating ceramic composites, particularly single crystal alumina fiber and yttrium-aluminum garnet (YAG) matrix composites. The method of this invention comprises the steps of (a) coating the fiber with a metal which is stable under oxidizing conditions, such as Pd, (b) coating the metal-coated fiber with a fugitive phase, such as Mo, (c) incorporating the coated fiber into a matrix material, (d) densifying the fiber-matrix into a composite and (e) heat treating the composite under oxidizing conditions to remove the fugitive phase.
Description
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
This invention relates to a ceramic composite material composed of a refractory fiber reinforcement and a ceramic matrix.
In general, ceramics have superior high-temperature strength and modulus, lower density, and lower thermal conductivity than metallic materials. The principal disadvantages of ceramics as structural materials are their relatively low failure strain, low fracture toughness and catastrophic brittle failure characteristics. Because of these intrinsic limitations, monolithic ceramics lack the properties of reliability and durability that are necessary for structural design acceptance. However, by incorporating high strength, relatively high modulus fibers into brittle ceramic matrices, high strength/high toughness composites can be obtained. Successfully tailored ceramic-matrix composites exhibit highly non-linear stress-strain behavior with ultimate strengths, failure strains and fracture toughnesses substantially greater than that of the unreinforced matrix.
It is well known that in order to exploit the benefits of fiber-reinforced ceramic-matrix composites, a relatively weak fiber/matrix interfacial bond strength is necessary to prevent catastrophic failure from propagating matrix cracks. The interface must provide sufficient fiber/matrix bonding for effective load transfer, but must be weak enough to debond and slip in the wake of matrix cracking while leaving the fibers to bridge the cracks and support the far-field applied load. Currently available fiber coatings such as carbon and boron nitride have demonstrated the desired mechanical characteristics necessary to enhance the composite strength and toughness, however the utility of these composites are severely limited by their susceptibility to oxidation embrittlement and strength degradation when stressed at or beyond the matrix cracking stress point and subsequently exposed to high-temperature oxidation. This fundamental limitation is due to the accelerated environmental degradation of the fiber coating at elevated temperatures in air following the onset of matrix cracking.
For air-breathing engines, fiber coatings must be oxidation resistant, stable with the fiber and matrix, and function over a wide temperature range. Several oxidation-resistant fiber coatings have been proposed as alternatives to carbon and boron nitride. Fugitive coatings involving application of graphite or a refractory metal that forms a volatile oxide, such as molybdenum or tungsten, are one such proposal. The composites are densified in a reducing atmosphere and then heat-treated in an oxidizing atmosphere, leaving void space where there once was coating. Ductile coatings of a refractory noble metal have been proposed. Cleavable coatings of a refractory oxide such as beta-alumina are under consideration. Residual thermal stress and stress developed by reactions are also considerations.
A reinforcing fiber suitable for high temperature use must also be creep resistant. Although anisotropic, single crystal alumina is currently the most creep resistant oxide fiber commercially available. Ceramic composites made with these single crystal fibers and yttrium-aluminum garnet (Y3 Al5 O12, YAG) matrices have been shown to be chemically stable. The CTE mismatch between these phases is small, but the anisotropy of thermal expansion in alumina causes residual stress of about 150 MPa (compressive) and about 60 MPa (tensile) to develop in the radial and axial directions, respectively, for c-axis alumina fibers in a YAG matrix.
I have found that single crystal alumina fiber and yttrium-aluminum garnet (YAG) matrix composites are improved by coating the fiber with a metal and a fugitive phase, prior to incorporating the fiber in the matrix.
Accordingly, it is an object of the present invention to provide an improved method for fabricating ceramic composites.
Other objects and advantages of the present invention will be apparent to those skilled in the art.
In accordance with the present invention there is provided an improved method for fabricating ceramic composites, particularly single crystal alumina fiber and yttrium-aluminum garnet (YAG) matrix composites. The method of this invention comprises the steps of (a) coating the fiber with a metal which is stable under oxidizing conditions, (b) coating the metal-coated fiber with a fugitive phase, (c) incorporating the coated fiber into a matrix material and (d) densifying the fiber-matrix into a composite.
The ceramic reinforcing fibers employed herein may be single crystal alumina fiber (sapphire), polycrystalline alumina fiber, yttrium-aluminum garnet (YAG) fiber, polycrystalline YAG or directionally solidified YAG/alumina eutectic fibers.
The ceramic matrix comprises material selected from the group consisting of Al2 O3, beta-aluminas, magnetoplumbites, yttrium-aluminum garnet (Y3 Al5 O12, YAG), MgAl2 O4, Ca/ZrO2, GdAlO3 and Gd3 Al5 O12.
Metals suitable for use in the present invention include palladium, platinum, rhodium or any other metal which is stable under oxidizing conditions from room temperature or below to the maximum use temperature of the densified composite, i.e., up to about 1800° C. The metal can be used alone or alloyed with other metals, such as nickel, aluminum, chromium, iron or the like, so long as oxidation resistance is not severely compromised.
The fugitive phase can be any such fugitive phase known in the art, such as carbon or molybdenum.
The fiber/matrix composite can be fabricated using techniques known in the art. For example, a composite preform can be prepared by alternately layering a plurality of layers of fiber and matrix powder. The preform can then be pressureless-sintered at about 1700° C., and then hot-isostatically pressed at about 1700° C. with about 200 MPa applied pressure.
It is necessary that the fiber, coated with the metal and the fugitive phase, be incorporated with a suitable matrix into a composite under conditions that preserve the fugitive phase, such as reducing or inert gas conditions. After the composite is densified, the fugitive phase is removed by heat treatment in an atmosphere that causes the fugitive phase to volatilize, usually by forming a volatile oxide. Ligaments of the metal occupy the void space remaining. The ligaments should have a thickness (δ), volume-percent metal, and metal composition such that the ductility of the metal ligaments relieves any compressive residual stress, and such that the toughness and strain to failure of the composite is optimized by promotion of crack deflection and fiber pullout along the metal ligament interface. Crack deflection and fiber pullout are usually associated with an interface that is weaker than the fiber or matrix by a factor of at least four. For example, of the refractory noble metals, palladium is the most ductile, platinum intermediate, and rhodium has very little ductility at room temperature. A desired ductility over a given temperature range can be achieved by forming alloys of these metals, and other metals, such as nickel, aluminum, chromium and iron, so long as oxidation resistance is not severely compromised. For a given metal composition, the ligament volume percent and thickness can be controlled to further optimize the mechanical properties of the fiber-matrix interface.
The following example illustrates the invention:
Fiber coating solutions were prepared by dissolving PdCl2 in distilled water (90 g/l) and Mo powder in aqua regia (75 g/l). These solutions were mixed to provide a Pd:Mo mole ratio of 40:60. The mixed solutions was applied to Saphikon® continuous single crystal alumina fiber using a vertical continuous fiber coater, such as that disclosed by Hay et al, U.S. Pat. No. 5,217,533.
The fibers were coated five times with the 40:60 mixture in air at 1100° C. at 10 cm/s. The coated fibers were laid up into tapes and vacuum hot pressed with 1 μm Ceralox® YAG powder in a 11/4-inch square graphite die at 1600°-1700° C. and 25 MPa. The fiber volume fraction was about 5 volume percent. Higher densities were achieved when the composite was cold pressed at 20 MPa and held at that pressure to about 1000° C. No pressure was applied during rapid heat up (5 min) between 1000° and 1500° C. 25 MPa pressure was re-applied at 1500° C. up to final temperature.
The fiber-matrix interface in the hot pressed composites was observed by SEM and analytical TEM. Separate Mo and Pd grains were found in a continuous interlayer 0.5-2.0 μm thick along the fiber-matrix interface. No evidence of alloying was found. The samples were heat-treated in air between 1400° and 1600° C. for up to 100 hours, then characterized by optical microscopy, SEM and analytical TEM. In all cases, the Mo had been oxidized away, leaving isolated Pd grains and void space behind.
Various modifications may be made in the instant invention without departing from the spirit and scope of the appended claims.
Claims (5)
1. An improved method for fabricating ceramic composites of ceramic reinforcing fiber and ceramic matrix, which comprises the steps of (a) coating the fiber with a metal which is stable under oxidizing conditions from about room temperature to about 1800° C., (b) coating the metal-coated fiber with a fugitive phase, (c) incorporating the coated fiber into a matrix material, (d) densifying the fiber-matrix into a composite and (e) heat treating the composite under oxidizing conditions to remove the fugitive phase.
2. The method of claim 1 wherein said metal is selected from the group consisting of palladium, platinum and rhodium.
3. The method of claim 1 wherein said fugitive phase is carbon or molybdenum.
4. The method of claim 1 wherein said fiber is continuous single crystal alumina fiber.
5. The method of claim 1 wherein said matrix is yttrium-aluminum garnet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/637,338 USH1643H (en) | 1996-04-10 | 1996-04-10 | Ductile metal ligament fiber coatings for ceramic composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/637,338 USH1643H (en) | 1996-04-10 | 1996-04-10 | Ductile metal ligament fiber coatings for ceramic composites |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH1643H true USH1643H (en) | 1997-04-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/637,338 Abandoned USH1643H (en) | 1996-04-10 | 1996-04-10 | Ductile metal ligament fiber coatings for ceramic composites |
Country Status (1)
| Country | Link |
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| US (1) | USH1643H (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8298286B2 (en) | 2006-12-19 | 2012-10-30 | Warsaw Orthopedic, Inc. | Non-linear vertebral mesh |
| CN105350080A (en) * | 2015-11-23 | 2016-02-24 | 东莞华晶粉末冶金有限公司 | A kind of silicon carbide composite whisker and its preparation method, composite material |
| CN105418165B (en) * | 2015-11-09 | 2018-08-31 | 东莞华晶粉末冶金有限公司 | Aluminum oxide composite whisker, preparation method thereof and composite material |
-
1996
- 1996-04-10 US US08/637,338 patent/USH1643H/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8298286B2 (en) | 2006-12-19 | 2012-10-30 | Warsaw Orthopedic, Inc. | Non-linear vertebral mesh |
| CN105418165B (en) * | 2015-11-09 | 2018-08-31 | 东莞华晶粉末冶金有限公司 | Aluminum oxide composite whisker, preparation method thereof and composite material |
| CN105350080A (en) * | 2015-11-23 | 2016-02-24 | 东莞华晶粉末冶金有限公司 | A kind of silicon carbide composite whisker and its preparation method, composite material |
| CN105350080B (en) * | 2015-11-23 | 2017-10-13 | 东莞华晶粉末冶金有限公司 | A kind of silicon carbide compound whisker and preparation method thereof, composite |
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