WO2007062094A2 - Refractory composite - Google Patents
Refractory composite Download PDFInfo
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- WO2007062094A2 WO2007062094A2 PCT/US2006/045152 US2006045152W WO2007062094A2 WO 2007062094 A2 WO2007062094 A2 WO 2007062094A2 US 2006045152 W US2006045152 W US 2006045152W WO 2007062094 A2 WO2007062094 A2 WO 2007062094A2
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- Prior art keywords
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- 239000000835 fiber Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001764 infiltration Methods 0.000 claims abstract description 8
- 230000008595 infiltration Effects 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000000280 densification Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 4
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000007799 cork Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003870 refractory metal Substances 0.000 claims description 4
- ZRBFEDMQRDRUDG-UHFFFAOYSA-N silicon hexaboride Chemical compound B12B3[Si]45B3B2B4B51 ZRBFEDMQRDRUDG-UHFFFAOYSA-N 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- NUSDCJCJVURPFV-UHFFFAOYSA-N silicon tetraboride Chemical compound B12B3B4[Si]32B41 NUSDCJCJVURPFV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 21
- 150000001721 carbon Chemical class 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 208000021017 Weight Gain Diseases 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000011184 SiC–SiC matrix composite Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009734 composite fabrication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011174 green composite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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Definitions
- SiC silicon carbide
- carbon matrix Composites of silicon carbide (SiC) fibers in a carbon matrix have been manufactured and used successfully for aircraft flaps and seals on afterburners. These composites utilize amorphous silicon carbide fibers that contain some oxygen, commercially available as ceramic grade Nicalon ® fiber from Nippon Carbon. Composites of this type are disclosed in United States Patent No. 5,759,688, which is incorporated by reference as if fully written out below.
- these composites Because of the limited heat resistance of the amorphous reinforcing fibers, these composites have a maximum service temperature of 1371 0 C (2500 0 F). To operate at these temperatures, the composite is generally chemical vapor deposition CVD/SiC coated and may be glazed with an external sealant. Tests indicate that due to the nature of the interface bond between the CVD coating and the amorphous silicon carbide fiber reinforced carbon composite, spallation of the coating may occur under extended heat cycling, and/or salt fog exposure.
- a refractory composite article having oxidation resistance greater than inhibited carbon/carbon composite materials, comprising a composite of continuous, polycrystalline stoichiometric SiC reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, the composite having a SiC pack cementation coating.
- a refractory composite article comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix, wherein the carbon matrix comprises an organic resin containing an oxidation inhibitor compound and wherein the organic resin has been subjected to carbonization and thereafter to densification by chemical vapor infiltration of at least carbon to form a silicon carbide fiber reinforced carbon composite, wherein the silicon carbide fiber reinforced carbon composite is coated with a SiC pack cementation coating to form the refractory composite.
- a net shaped composite material for structural applications having oxidation resistance greater than inhibited carbon/carbon composite materials, comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, formed by impregnating the fibers with an organic resin and staging to form a " prepreg, shaping and curing the prepreg to form a laminate, carbonizing the shaped laminate to form a carbonized part and densifying the carbonized part by chemical vapor infiltration to form a component, wherein prior to the carbonizing, the organic resin contains the oxygen inhibitor compound; and wherein the component is coated with a SiC pack cementation coating.
- the Figure is a photomicrograph of a sectioned SiC fiber reinforced carbon matrix composite coupon having a pack cementation coating.
- the reactive pack coated substrate showed a very slight weight gain (about 1 g/m 2 ) in 8 hours of exposure at any of 538°C (1000 0 F), 816 0 C (1500 0 F), or 1093 0 C (2000 0 F).
- the reactive pack coated composite showed only small weight gains (about 14 g/m 2 ) in 60 hours (3 cycles), and demonstrated the suitability of this coated composite for hypersonic vehicle applications.
- the reactive pack-coated, polycrystalline stoichiometric SiC fiber-reinforced carbon matrix composite system enjoys a performance advantage because of the thermal compatibility of its constituent elements, and its simplicity.
- the reactive pack coating converts the surface matrix carbon, and thus has good adhesion to the substrate. With a substantially crack-free surface, no external sealant is required, and less inhibitor in the substrate matrix can be used. Glass formation is expected to be minimal. AU of these factors contribute to a reduction in the occurrence of coating spallation.
- Lightweight, strong, tough, and oxidation-resistant composites are provided, which maintain their properties even after prolonged high-temperature exposure.
- the polycrystalline, stoichiometric SiC fiber reinforced carbon composites, having a pack cementation coating, are particularly useful in those applications which require materials capable of withstanding high temperature spikes up to 1760 0 C (3200°F).
- the net shape fabricability and the ability of the composites to be processed unrestrained permits the production of parts with a wide variety of sizes, shapes and configurations.
- Examples of utility for such reactive pack coated, polycrystalline stoichiometric SiC fiber reinforced carbon composites are structural components for aero engines such as flaps, seals, flame holders and liners; turbine rotors and structural parts for hypersonic vehicles such as bolts, fasteners, skins and leading edges. These composites may also be used as thermal protection materials, such as thermal protection anchorage panels.
- the process for manufacturing these SiC/C composites includes the following.
- Continuous, polycrystalline stoichiometric SiC fibers are impregnated with a thermosetting resin containing fillers.
- the fibers may then be staged in an oven at about 38 0 C to about 104°C (about 100°F to about 22O 0 F) to remove solvents and partially cure the resin.
- the staged fibers are cut, laid-up as desired, and prepared for molding.
- the fibers can be molded in a hydraulic press or in an autoclave by conventional procedures for curing phenolic or epoxy laminates.
- the molded part is then heat-treated at temperatures from about 538 0 C to about 1760 0 C (about 1000 0 F to about 3200 0 F) in an inert environment to convert the organic matrix to carbon.
- the carbonized part is then subjected to a carbon chemical vapor impregnation (CVI) for densification.
- CVI carbon chemical vapor impregnation
- SiC fibers usable in this composite article include, but are not limited to, Ube Industries' TyrannoTM series of continuous, polycrystalline stoichiometric SiC fibers, such as TyrannoTM SA-3, Nippon Carbon's Hi-NicalonTM Type S fiber, and Dow Coming's SylramicTM fiber.
- the most suitable polycrystalline, stoichiometric SiC fibers may contain about 0.3% to about 0.8% oxygen by weight, or less.
- Polycrystalline stoichiometric SiC fibers containing up to about 1% oxygen by weight may be used in the subject composite.
- ceramic grade, amorphous SiC fibers may contain about 10% oxygen by weight, or more.
- the fibers may take the form of fabric, chopped fabric, yarn, chopped yarn, and tape. SiC yarns may be woven into net shapes by braiding or by multidirectional weaving.
- Impregnation of the fibers can take place before or after weaving.
- the yarn, fabric, and/or tape may be laid flat on a tool and stacked to form a layered reinforcement with the fibers aligned in one or in several directions in the lamina plane.
- the yam, fabric, and/or tape may be wrapped or wound around a mandrel to form a variety of shape and reinforcement orientations.
- Fiber volumes in the laminate can range from about 25 to about 60%.
- the slurries used to impregnate the fibers may comprise phenolic, epoxy, or furan resins containing dispersed f ⁇ ller(s).
- Representative phenolics include, but are not limited to, those supplied under the trademark Durite ® SC 1008 by Borden
- epoxies include, but are not limited to, those supplied by Resolution Performance Products under the trademarks Epon 828 and Epon 1031.
- Representative furans include, but are not limited to, those supplied by Dynachem, Inc., under the trademarks PhenAlloy
- the filler(s) used may include, but are not limited to, carbon, boron, boron carbide, boron nitride, silicon, silicon carbide, silicon nitride, silicon tetraboride, silicon hexaboride, titanium diboride, and zirconium diboride, either alone or in combination. Filler volumes in the matrix can range from about 2% to about 25%.
- the carbon matrices of the SiC fiber reinforced composites may contain fillers that act as oxidation inhibitors in an amount effective to improve oxidation resistance. These include silicon, boron and the boron containing fillers mentioned above, as well as other boron containing compounds such as refractory metal borides, including those of hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.
- oxidation inhibitors may be present in the matrix in volumes up to about 25%. In some embodiments, the volume of inhibitor in the matrix may range from about 2% to about 25%. hi particular embodiments, the volume of inhibitor in the matrix may range from about 5% to about 15%.
- the heat-treatment schedule used to carbonize the organic resin should be slow enough so as not to generate volatiles within the part too quickly, which could cause delaminations.
- the temperature is to be sufficiently high to convert the resin to predominantly carbon without thermally degrading the reinforcing fibers.
- molded parts are brought from ambient to about 538°C to about 176O 0 C (about 1000°F to about 3200°F) in about 50 to about 250 hours.
- Chemical vapor infiltration (CVI) is conducted after the composites undergo carbonization, or pyrolysis. One or more infiltrations are required for optimum strength and oxidation resistance.
- the first CVI is preferably with carbon; subsequent CVI's can be carried out with carbon or SiC.
- At least one CVI is carried out with carbon.
- Carbon CVI may be conducted with low molecular weight alkanes or allcenes such as methane, ethane, propane, propene, or mixtures thereof such as natural gas at about 816 0 C to about 1204°C (about 1500 0 F to about 2200 0 F) and a pressure of about 670 Pa to 6.67 IdPa (about 5 to 50 ton).
- SiC CVI may be conducted with methane and silane such as silicon tetrachloride, or with an organosilane such as methyltrichlorosilane, dimethyldichlorosilane, methyldichlorosilane or their mixtures at about 871°C to about 1204 0 C (about 1600 0 F to about 2200°F) and a pressure of about 267 Pa to about 26.7 IcPa (about 2 to about 200 ton).
- silane such as silicon tetrachloride
- organosilane such as methyltrichlorosilane, dimethyldichlorosilane, methyldichlorosilane or their mixtures
- Carbon, boron nitride, or other coatings can be applied to the fibers to improve the composite's strength and toughness.
- the coatings should be of a low modulus material layer that can interrupt crack propagation from the matrix into the fiber.
- Fiber coatings can be applied by chemical vapor deposition, electrochemical, wet chemical, or slurry methods. The fiber coating may be applied directly to the yam and/or fabric before it is impregnated or in situ after the composite has been heat treated (carbonized).
- the present polycrystalline, stoichiometric SiC fiber reinforced carbon composites are particularly suited, because of better thermal stability and higher coefficient of thermal expansion (CTE) of the polycrystalline SiC reinforcing fibers, to the use of reactive pack coating for the SiC fiber reinforced carbon matrix substrate.
- Reactive pack cementation coatings of carbonaceous substrates, such as carbon/carbon composites are known.
- the phrase "pack cementation” as used herein refers to the heat driven conversion of outer surface carbon in a carbon matrix composite to primarily silicon carbide by the infiltration of and reaction with silicon liquid and/or SiO gas supplied by the reactive pack mixture which surrounds the carbonaceous article.
- a reactive pack mixture composition useful for the formation of a SiC pack cementation coating for protecting the carbonaceous substrate from degradation at temperatures above about 427 0 C (80O 0 F) 5 that is, the carbon matrix of the composite comprises in one embodiment, silicon from about 15% to about 50% by weight of the total coating composition; boron from 0% to about 25% by weight of the total coating composition when present; SiO 2 from about 0.01% to about 3% by weight of the total coating composition; and SiC from about 40% to about 85% by weight of the total coating composition.
- Such coatings may be applied to the SiC/C composites by preparing a reactive pack mixture composition of from about 15% to about 50% silicon, up to about 25% boron if present (B from 0% up to about 25%), from about 0.01% to about 3% SiO 2 and from about 40% to about 85% SiC, all by weight of the total pack mixture composition; coating the SiC/C composite carbonaceous substrate with a release agent; surrounding the release agent-coated carbonaceous substrate with the pack mixture composition; and firing the carbonaceous substrate for a period of time sufficient to effectuate the formation of a protective SiC pack cementation coating on the carbonaceous substrate.
- a suitable release agent is cork, for providing the clean release of spent pack composition from the carbonaceous substrate, although other release agents may be used.
- Elemental silicon can be purchased from Elkem Materials, Inc., as 0.045 mm (-325 mesh) powder; the boron, in amorphous form, may be purchased from Tronox, Inc., as TronaTM elemental boron powder; the SiO 2 may be purchased from Atlantic Equipment Engineers as a 0.045 mm or finer (-325 mesh) powder, and the SiC (green) may be purchased from Atlantic Equipment Engineers as a 0.009 mm (1200 grit) powder.
- Cork may be purchased with a 0.074 mm or finer (-200 mesh) particle size and a density of between 128 to 160 kg/m 3 (between 8 to 10 lbs/ft 3 ), from the Maryland Cork Co., Inc.
- the powdered cork may be mixed with a liquid carrier, such as 0.4% aqueous solution of xanthan gum.
- a liquid carrier such as 0.4% aqueous solution of xanthan gum.
- the xanthan gum may be purchased from CP Kelco as KelzanTM-S powder.
- the carbonaceous substrate may be placed in a non-reactive retort, surrounded by pack mixture on all sides.
- the pack-coated substrate may be placed directly into a furnace without first encasing it in a retort.
- the packed retort, or the pack-coated substrate without the retort is placed in a furnace, which is heated to a temperature ranging between about 1593 0 C to about 1760 0 C (about 2900 0 F and about
- This temperature may then be held for a period of about 2 to about 16 hours, depending on the reactivity of the substrate and the amount of coating pick-up desired. Firing of the substrate may take place in an inert atmosphere, such as argon, in one embodiment at slightly above atmospheric pressure of about 101.3 kPa.
- the pack mixture composition reacts with the carbonaceous substrate upon firing to convert a portion of the substrate surface into SiC, which protects against the oxidation of the substrate at elevated temperatures, and thus allows the SiC/C composite substrate to maintain its mechanical integrity for longer periods of time.
- Continuous, polycrystalline stoichiometric SiC fiber reinforced inhibited carbon composites have significant advantages over conventional ceramic composites. Utilization of an inhibited carbon matrix provides all of the advantages that carbon has over ceramic matrices, such as thermal stability, elasticity and fabricability, while overcoming carbon's disadvantage of poor oxidation resistance. Notched izod impact strengths, which are commonly used to gauge toughness, indicate that SiC fiber reinforced carbon composites are 10 to 100 times more resistant to catastrophic failure than monolithic ceramics.
- the SiC fiber reinforced carbon composites can be fabricated into large, complex shapes, and demonstrate mechanical properties suitable for structural applications. Green composite fabrication can be carried out by traditional glass/epoxy molding techniques well known to the aerospace industry. Although carbon/carbon (C/C) composites can be manufactured in a similar manner, they do not offer the high degree of oxidation resistance displayed by the inhibited SiC/C materials, and are subject to catastrophic failure when the coatings are breached.
- continuous, polycrystalline stoichiometric SiC fiber reinforced carbon composites are more compatible with reactive pack coatings than C/C composites or even amorphous SiC fiber reinforced carbon composites of similar strength, and have greater compressive and interlaminar properties than C/C composites, and greater tensile modulus than amorphous SiC fiber reinforced carbon composites.
- the oxidation resistance of the SiC fiber reinforced carbon composites is significantly greater than the best inhibited C/C or C/SiC materials, and in many instances better than SiC/SiC composites having fibers with carbon coatings.
- Temperature resistance of reactive pack coated continuous, polycrystalline stoichiometric SiC fiber reinforced inhibited carbon composites is higher than coated C/C composites or amorphous SiC fiber reinforced inhibited carbon composites.
- the staged sheet was cut into 10 rectangular patterns 19.7 cm (7.75-inches) wide by 21.0 cm (8.25- inches) long and stacked with the warp fibers aligned.
- the stacked plies were sandwiched between two metal plates and sealed in a plastic bag with an exhaust outlet.
- the bagged part was placed in an autoclave and the exhaust outlet was connected to a vacuum.
- the autoclave was pressurized to 1.03 MPa (150 psig), brought up to 154 0 C (310 0 F) in 4 hours and held at 154°C (31O 0 F) for 3 hours.
- the autoclave was then cooled and the consolidated plies were removed.
- the cured composite was placed in a furnace and brought to 816°C (1500°F) in 80 hours in nitrogen.
- the part was transferred to a vacuum furnace and brought to 1760°C (3200°F) in 22 hours in argon.
- the pyrolized part was then infiltrated two times with pyrolytic carbon via a CVI process.
- the infiltrated composite had a density of 2230 kg/m 3 (2.23 g/cc), a fiber volume of about 47%, and an inhibitor volume of about 11.5%.
- the resulting inhibited SiC/C composite was mechanically tested, and had a tensile strength of 248 MPa (36 ksi), a compressive strength of 331 MPa (48 ksi), a fiexural strength of 296 MPa (43 ksi), a tensile modulus of 103 GPa (15 msi), an interlaminar shear strength of 30.3 MPa (4400 psi), and an interlaminar tensile strength of 15.9 MPa (2300 psi).
- One of the failed flex coupons was sectioned and examined under high magnification.
- the coating 12 thickness averaged 0.127 mm (5 mils). The differences between the two types of coated composites are profound.
- the polycrystalline stoichiometric SiC fiber has greater heat resistance, higher thermal expansion and higher modulus.
- the polycrystalline stoichiometric SiC fiber reinforced carbon composite can be protected with a reactive pack derived SiC (pack cementation) coating, improving the adhesion between the substrate and coating, and minimizing coating spallation.
- the stoichiometric fibers have a coefficient of thermal expansion (CTE) that is a perfect match for the SiC pack cementation coating, resulting in nominally crack free coatings, and minimizing glass formation in SiC coated inhibited carbon matrix composites. Additionally, a 65% improvement in the composite tensile modulus was shown for the composite comprising polycrystalline, stoichiometric SiC fibers in a carbon matrix having the reactive pack derived pack cementation coating.
- CTE coefficient of thermal expansion
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Abstract
A refractory composite article (10) includes a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix (11); the carbon matrix is an organic resin containing an inhibitor compound that has been subjected to carbonization and thereafter to densification by chemical vapor infiltration of at least carbon to form a silicon carbide fiber reinforced carbon composite; and the silicon carbide fiber reinforced carbon composite is coated with a SiC pack cementation coating (12) to form the refractory composite. The pack cementation coating (12) is prepared by providing a pack mixture composition; coating the composite with a release agent; surrounding the release agent-coated composite with the pack mixture composition; and firing the composite to form a protective SiC pack cementation coating (12) on the composite (10).
Description
REFRACTORY COMPOSITE
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the filing date of United States
Provisional Application Serial No. 60/739,192, filed on November 23, 2005, which is hereby incorporated in its entirety.
BACKGROUND
Composites of silicon carbide (SiC) fibers in a carbon matrix have been manufactured and used successfully for aircraft flaps and seals on afterburners. These composites utilize amorphous silicon carbide fibers that contain some oxygen, commercially available as ceramic grade Nicalon® fiber from Nippon Carbon. Composites of this type are disclosed in United States Patent No. 5,759,688, which is incorporated by reference as if fully written out below.
Because of the limited heat resistance of the amorphous reinforcing fibers, these composites have a maximum service temperature of 13710C (25000F). To operate at these temperatures, the composite is generally chemical vapor deposition CVD/SiC coated and may be glazed with an external sealant. Tests indicate that due to the nature of the interface bond between the CVD coating and the amorphous silicon carbide fiber reinforced carbon composite, spallation of the coating may occur under extended heat cycling, and/or salt fog exposure.
SUMMARY
A refractory composite article is provided having oxidation resistance greater than inhibited carbon/carbon composite materials, comprising a composite of continuous, polycrystalline stoichiometric SiC reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, the composite having a SiC pack cementation coating.
A refractory composite article is provided comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix, wherein the carbon matrix comprises an organic resin containing an oxidation inhibitor compound and wherein the organic resin has been subjected to carbonization and thereafter to densification by chemical vapor infiltration of at least carbon to form a silicon carbide fiber reinforced carbon composite, wherein the silicon carbide fiber reinforced carbon composite is coated with a SiC pack cementation coating to form the refractory composite.
A net shaped composite material for structural applications is provided, having oxidation resistance greater than inhibited carbon/carbon composite materials, comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, formed by impregnating the fibers with an organic resin and staging to form a " prepreg, shaping and curing the prepreg to form a laminate, carbonizing the shaped laminate to form a carbonized part and densifying the carbonized part by chemical vapor infiltration to form a component, wherein prior to the carbonizing, the organic resin contains the oxygen inhibitor compound; and wherein the component is coated with a SiC pack cementation coating.
BRIEF DESCRIPTION OF THE DRAWING
The Figure is a photomicrograph of a sectioned SiC fiber reinforced carbon matrix composite coupon having a pack cementation coating.
DETAILED DESCRIPTION
It has now been found that the use of polycrystalline, stoichiometric SiC fibers, with the same or a similar carbon matrix will extended the maximum service temperature of the refractory composite to over 16490C (3000°F), while maintaining most of its mechanical properties. The better thermal stability of these polycrystalline SiC reinforcing fibers allow the application of SiC coatings through a reactive pack, (i.e. pack cementation coatings) thus improving the interface bond and resisting
coating spallation. The higher coefficient of thermal expansion (CTE) of these polycrystalline SiC fibers are a better match to the CTE of the reactive pack derived pack cementation coatings, and serve to reduce the formation of cooldown cracks in the coatings.
hi static oxidation testing, the reactive pack coated substrate showed a very slight weight gain (about 1 g/m2) in 8 hours of exposure at any of 538°C (10000F), 8160C (15000F), or 10930C (20000F). In 1649°C (30000F) downcycle testing, the reactive pack coated composite showed only small weight gains (about 14 g/m2) in 60 hours (3 cycles), and demonstrated the suitability of this coated composite for hypersonic vehicle applications.
The reactive pack-coated, polycrystalline stoichiometric SiC fiber-reinforced carbon matrix composite system enjoys a performance advantage because of the thermal compatibility of its constituent elements, and its simplicity. The reactive pack coating converts the surface matrix carbon, and thus has good adhesion to the substrate. With a substantially crack-free surface, no external sealant is required, and less inhibitor in the substrate matrix can be used. Glass formation is expected to be minimal. AU of these factors contribute to a reduction in the occurrence of coating spallation.
Lightweight, strong, tough, and oxidation-resistant composites are provided, which maintain their properties even after prolonged high-temperature exposure. The polycrystalline, stoichiometric SiC fiber reinforced carbon composites, having a pack cementation coating, are particularly useful in those applications which require materials capable of withstanding high temperature spikes up to 17600C (3200°F). The net shape fabricability and the ability of the composites to be processed unrestrained permits the production of parts with a wide variety of sizes, shapes and configurations.
Examples of utility for such reactive pack coated, polycrystalline stoichiometric SiC fiber reinforced carbon composites, are structural components for aero engines such as flaps, seals, flame holders and liners; turbine rotors and
structural parts for hypersonic vehicles such as bolts, fasteners, skins and leading edges. These composites may also be used as thermal protection materials, such as thermal protection anchorage panels.
The process for manufacturing these SiC/C composites includes the following.
Continuous, polycrystalline stoichiometric SiC fibers are impregnated with a thermosetting resin containing fillers. The fibers may then be staged in an oven at about 380C to about 104°C (about 100°F to about 22O0F) to remove solvents and partially cure the resin. The staged fibers are cut, laid-up as desired, and prepared for molding. The fibers can be molded in a hydraulic press or in an autoclave by conventional procedures for curing phenolic or epoxy laminates. The molded part is then heat-treated at temperatures from about 5380C to about 17600C (about 10000F to about 32000F) in an inert environment to convert the organic matrix to carbon. The carbonized part is then subjected to a carbon chemical vapor impregnation (CVI) for densification.
SiC fibers usable in this composite article include, but are not limited to, Ube Industries' Tyranno™ series of continuous, polycrystalline stoichiometric SiC fibers, such as Tyranno™ SA-3, Nippon Carbon's Hi-Nicalon™ Type S fiber, and Dow Coming's Sylramic™ fiber. The most suitable polycrystalline, stoichiometric SiC fibers may contain about 0.3% to about 0.8% oxygen by weight, or less. Polycrystalline stoichiometric SiC fibers containing up to about 1% oxygen by weight may be used in the subject composite. In comparison, ceramic grade, amorphous SiC fibers may contain about 10% oxygen by weight, or more. The fibers may take the form of fabric, chopped fabric, yarn, chopped yarn, and tape. SiC yarns may be woven into net shapes by braiding or by multidirectional weaving.
Impregnation of the fibers can take place before or after weaving. The yarn, fabric, and/or tape may be laid flat on a tool and stacked to form a layered reinforcement with the fibers aligned in one or in several directions in the lamina plane. The yam, fabric, and/or tape may be wrapped or wound around a mandrel to form a variety of shape and reinforcement orientations. Fiber volumes in the laminate can range from about 25 to about 60%. By utilizing impregnated fabrics and the like,
it is possible to produce structures of complex shapes with a very high degree of fiber orientation and alignment.
The slurries used to impregnate the fibers may comprise phenolic, epoxy, or furan resins containing dispersed fϊller(s). Representative phenolics include, but are not limited to, those supplied under the trademark Durite® SC 1008 by Borden
Chemical, Inc. and Arofene™ 134A by Ashland Chemical. Representative epoxies include, but are not limited to, those supplied by Resolution Performance Products under the trademarks Epon 828 and Epon 1031. Representative furans include, but are not limited to, those supplied by Dynachem, Inc., under the trademarks PhenAlloy
440 and PhenAlloy 2160.
The filler(s) used may include, but are not limited to, carbon, boron, boron carbide, boron nitride, silicon, silicon carbide, silicon nitride, silicon tetraboride, silicon hexaboride, titanium diboride, and zirconium diboride, either alone or in combination. Filler volumes in the matrix can range from about 2% to about 25%.
The carbon matrices of the SiC fiber reinforced composites may contain fillers that act as oxidation inhibitors in an amount effective to improve oxidation resistance. These include silicon, boron and the boron containing fillers mentioned above, as well as other boron containing compounds such as refractory metal borides, including those of hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. In certain embodiments, oxidation inhibitors may be present in the matrix in volumes up to about 25%. In some embodiments, the volume of inhibitor in the matrix may range from about 2% to about 25%. hi particular embodiments, the volume of inhibitor in the matrix may range from about 5% to about 15%.
The heat-treatment schedule used to carbonize the organic resin should be slow enough so as not to generate volatiles within the part too quickly, which could cause delaminations. The temperature is to be sufficiently high to convert the resin to predominantly carbon without thermally degrading the reinforcing fibers. In certain embodiments, molded parts are brought from ambient to about 538°C to about 176O0C (about 1000°F to about 3200°F) in about 50 to about 250 hours.
Chemical vapor infiltration (CVI) is conducted after the composites undergo carbonization, or pyrolysis. One or more infiltrations are required for optimum strength and oxidation resistance. The first CVI is preferably with carbon; subsequent CVI's can be carried out with carbon or SiC. In certain embodiments, at least one CVI is carried out with carbon. Carbon CVI may be conducted with low molecular weight alkanes or allcenes such as methane, ethane, propane, propene, or mixtures thereof such as natural gas at about 8160C to about 1204°C (about 15000F to about 22000F) and a pressure of about 670 Pa to 6.67 IdPa (about 5 to 50 ton). SiC CVI may be conducted with methane and silane such as silicon tetrachloride, or with an organosilane such as methyltrichlorosilane, dimethyldichlorosilane, methyldichlorosilane or their mixtures at about 871°C to about 12040C (about 16000F to about 2200°F) and a pressure of about 267 Pa to about 26.7 IcPa (about 2 to about 200 ton).
Carbon, boron nitride, or other coatings can be applied to the fibers to improve the composite's strength and toughness. The coatings should be of a low modulus material layer that can interrupt crack propagation from the matrix into the fiber. Fiber coatings can be applied by chemical vapor deposition, electrochemical, wet chemical, or slurry methods. The fiber coating may be applied directly to the yam and/or fabric before it is impregnated or in situ after the composite has been heat treated (carbonized).
The present polycrystalline, stoichiometric SiC fiber reinforced carbon composites are particularly suited, because of better thermal stability and higher coefficient of thermal expansion (CTE) of the polycrystalline SiC reinforcing fibers, to the use of reactive pack coating for the SiC fiber reinforced carbon matrix substrate. Reactive pack cementation coatings of carbonaceous substrates, such as carbon/carbon composites, are known. The phrase "pack cementation" as used herein refers to the heat driven conversion of outer surface carbon in a carbon matrix composite to primarily silicon carbide by the infiltration of and reaction with silicon liquid and/or SiO gas supplied by the reactive pack mixture which surrounds the carbonaceous article.
A reactive pack mixture composition useful for the formation of a SiC pack cementation coating for protecting the carbonaceous substrate from degradation at temperatures above about 4270C (80O0F)5 that is, the carbon matrix of the composite, comprises in one embodiment, silicon from about 15% to about 50% by weight of the total coating composition; boron from 0% to about 25% by weight of the total coating composition when present; SiO2 from about 0.01% to about 3% by weight of the total coating composition; and SiC from about 40% to about 85% by weight of the total coating composition.
Such coatings may be applied to the SiC/C composites by preparing a reactive pack mixture composition of from about 15% to about 50% silicon, up to about 25% boron if present (B from 0% up to about 25%), from about 0.01% to about 3% SiO2 and from about 40% to about 85% SiC, all by weight of the total pack mixture composition; coating the SiC/C composite carbonaceous substrate with a release agent; surrounding the release agent-coated carbonaceous substrate with the pack mixture composition; and firing the carbonaceous substrate for a period of time sufficient to effectuate the formation of a protective SiC pack cementation coating on the carbonaceous substrate. A suitable release agent is cork, for providing the clean release of spent pack composition from the carbonaceous substrate, although other release agents may be used.
Elemental silicon can be purchased from Elkem Materials, Inc., as 0.045 mm (-325 mesh) powder; the boron, in amorphous form, may be purchased from Tronox, Inc., as Trona™ elemental boron powder; the SiO2 may be purchased from Atlantic Equipment Engineers as a 0.045 mm or finer (-325 mesh) powder, and the SiC (green) may be purchased from Atlantic Equipment Engineers as a 0.009 mm (1200 grit) powder. Cork may be purchased with a 0.074 mm or finer (-200 mesh) particle size and a density of between 128 to 160 kg/m3 (between 8 to 10 lbs/ft3), from the Maryland Cork Co., Inc. However, a variety of particle sizes and densities will be effective for the purpose stated herein. For ease of application, in certain embodiments, the powdered cork may be mixed with a liquid carrier, such as 0.4%
aqueous solution of xanthan gum. The xanthan gum may be purchased from CP Kelco as Kelzan™-S powder.
The carbonaceous substrate may be placed in a non-reactive retort, surrounded by pack mixture on all sides. Alternatively, the pack-coated substrate may be placed directly into a furnace without first encasing it in a retort. The packed retort, or the pack-coated substrate without the retort, is placed in a furnace, which is heated to a temperature ranging between about 15930C to about 17600C (about 29000F and about
32000F). This temperature may then be held for a period of about 2 to about 16 hours, depending on the reactivity of the substrate and the amount of coating pick-up desired. Firing of the substrate may take place in an inert atmosphere, such as argon, in one embodiment at slightly above atmospheric pressure of about 101.3 kPa.
The pack mixture composition reacts with the carbonaceous substrate upon firing to convert a portion of the substrate surface into SiC, which protects against the oxidation of the substrate at elevated temperatures, and thus allows the SiC/C composite substrate to maintain its mechanical integrity for longer periods of time.
Reactive pack cementation coatings are discussed further in U.S. Letters Patent No. 5,275,983, which is incorporated by reference as if fully written out below.
Continuous, polycrystalline stoichiometric SiC fiber reinforced inhibited carbon composites have significant advantages over conventional ceramic composites. Utilization of an inhibited carbon matrix provides all of the advantages that carbon has over ceramic matrices, such as thermal stability, elasticity and fabricability, while overcoming carbon's disadvantage of poor oxidation resistance. Notched izod impact strengths, which are commonly used to gauge toughness, indicate that SiC fiber reinforced carbon composites are 10 to 100 times more resistant to catastrophic failure than monolithic ceramics.
The SiC fiber reinforced carbon composites can be fabricated into large, complex shapes, and demonstrate mechanical properties suitable for structural applications. Green composite fabrication can be carried out by traditional
glass/epoxy molding techniques well known to the aerospace industry. Although carbon/carbon (C/C) composites can be manufactured in a similar manner, they do not offer the high degree of oxidation resistance displayed by the inhibited SiC/C materials, and are subject to catastrophic failure when the coatings are breached.
Additionally, continuous, polycrystalline stoichiometric SiC fiber reinforced carbon composites are more compatible with reactive pack coatings than C/C composites or even amorphous SiC fiber reinforced carbon composites of similar strength, and have greater compressive and interlaminar properties than C/C composites, and greater tensile modulus than amorphous SiC fiber reinforced carbon composites. The oxidation resistance of the SiC fiber reinforced carbon composites is significantly greater than the best inhibited C/C or C/SiC materials, and in many instances better than SiC/SiC composites having fibers with carbon coatings. Temperature resistance of reactive pack coated continuous, polycrystalline stoichiometric SiC fiber reinforced inhibited carbon composites is higher than coated C/C composites or amorphous SiC fiber reinforced inhibited carbon composites.
Example 1
One sheet of 40.6 cm (16-inch) wide by 105 cm (41.5-inch) long 8-harness satin Tyranno™ SA-3 fabric (comprising polycrystalline, stoichiometric silicon carbide fibers) was impregnated with 158 grams of a slurry consisting of 18% boron carbide powder, 52% Ashland Arofene™ 134A (phenolic resin), and 30% isopropyl alcohol (percentages by weight). The molded (phenolic) composite comprised 58.3% fiber, 29.2% resin, and 12.5% boron carbide by weight. The coated sheet was placed in a circulating oven and staged for 30 minutes at 88 0C (19O0F). The staged sheet was cut into 10 rectangular patterns 19.7 cm (7.75-inches) wide by 21.0 cm (8.25- inches) long and stacked with the warp fibers aligned. The stacked plies were sandwiched between two metal plates and sealed in a plastic bag with an exhaust outlet. The bagged part was placed in an autoclave and the exhaust outlet was connected to a vacuum. The autoclave was pressurized to 1.03 MPa (150 psig), brought up to 1540C (3100F) in 4 hours and held at 154°C (31O0F) for 3 hours. The autoclave was then cooled and the consolidated plies were removed. The cured
composite was placed in a furnace and brought to 816°C (1500°F) in 80 hours in nitrogen. After cool down the part was transferred to a vacuum furnace and brought to 1760°C (3200°F) in 22 hours in argon. The pyrolized part was then infiltrated two times with pyrolytic carbon via a CVI process. The infiltrated composite had a density of 2230 kg/m3 (2.23 g/cc), a fiber volume of about 47%, and an inhibitor volume of about 11.5%.
The resulting inhibited SiC/C composite was mechanically tested, and had a tensile strength of 248 MPa (36 ksi), a compressive strength of 331 MPa (48 ksi), a fiexural strength of 296 MPa (43 ksi), a tensile modulus of 103 GPa (15 msi), an interlaminar shear strength of 30.3 MPa (4400 psi), and an interlaminar tensile strength of 15.9 MPa (2300 psi).
Seven additional fiexural coupons were coated with a release agent and packed in a reactive mixture of 59.5% silicon carbide powder, 35% metallic silicon powder, 5% amorphous boron powder, and 0.5% silicon dioxide powder, in a graphite retort (percentages by weight). The retort was placed in a vacuum furnace, brought up to 15100C (27500F) in 19 hours and held for one hour, then up to 1760°C (3200°F) in 3 hours and held for 8 hours, in argon.
After cool-down, the coupons were extracted. One coupon was tested in flexure, and then sectioned for optical examination. It was found to have a continuous SiC coating averaging 0.127 mm (5 mils) in thickness. The fiexural strength, calculated with the coating thickness subtracted from the coupon thickness, was unchanged from that of an uncoated coupon. Static oxidation testing in air at 5380C (10000F), 8160C (15000F), and 10930C (20000F) for 8 hours showed only minor weight changes. Two hours exposure at 16490C (30000F) resulted in a weight gain of 8 g/m2. Downcycle testing was conducted where a coupon was subjected to 2 hours exposure at 16490C (30000F) followed by 18 hours at 6490C (12000F) then 16 hours in a humidity chamber set at 350C (95°F) and 95% relative humidity. The cumulative weight gains were 9 g/m2 after the first cycle, 12 g/m2 after the second cycle, and 14 g/m2 after the third cycle.
Example 2
Composites of amorphous silicon carbide fibers in a carbon matrix coated by CVD and of polycrystalline, stoichiometric SiC fibers in a carbon matrix having a reactive pack coating were prepared and tested. A comparison of the properties of the two types of composites, using coated flex coupons, is shown in the table below.
A reduction of 22% was observed in the flex strength using the entire coupon thickness in the calculations, but when the coating was subtracted out, there was no change in the flex strength. One of the failed flex coupons was sectioned and examined under high magnification. A micrograph of a flex coupon, comprising a SiC reactive pack-coated polycrystalline, stoichiometric SiC fiber reinforced carbon composite 10, is shown in the Figure. The composite article 11, made of stacked plies, had a SiC pack cementation coating 12. The surfaces are rather irregular. The coating 12 thickness averaged 0.127 mm (5 mils).
The differences between the two types of coated composites are profound. The polycrystalline stoichiometric SiC fiber has greater heat resistance, higher thermal expansion and higher modulus. This results in a stiffer composite that can be used at much higher temperatures, such as 1371°C (2500°F) long term, and 1760°C (3200°F) short term. More importantly, the polycrystalline stoichiometric SiC fiber reinforced carbon composite can be protected with a reactive pack derived SiC (pack cementation) coating, improving the adhesion between the substrate and coating, and minimizing coating spallation.
The stoichiometric fibers have a coefficient of thermal expansion (CTE) that is a perfect match for the SiC pack cementation coating, resulting in nominally crack free coatings, and minimizing glass formation in SiC coated inhibited carbon matrix composites. Additionally, a 65% improvement in the composite tensile modulus was shown for the composite comprising polycrystalline, stoichiometric SiC fibers in a carbon matrix having the reactive pack derived pack cementation coating.
Although the refractory composite has been described in detail through the above detailed description and the preceding examples, these examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art without departing from the spirit and the scope of the invention. It should be understood that the embodiments described above are not only in the alternative, but can be combined.
Claims
1. A refractory composite article having oxidation resistance greater than inhibited carbon/carbon composite materials, comprising a composite of continuous, polycrystalline stoichiometric SiC reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, the composite having a SiC pack cementation coating.
2. The article of claim 1, wherein the inhibited carbon matrix contains the oxidation inhibitor from an effective amount to provide oxidation resistance up to about 25 volume percent, the oxidation inhibitor comprising at least one of boron, boron carbide, boron nitride, silicon tetraboride, silicon hexaboride, or zirconium diboride; or refractory metal borides of at least one of hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten; or mixtures thereof; optionally wherein the inhibited carbon matrix additionally contains a filler comprising at least one of carbon, silicon carbide, silicon nitride, or mixtures thereof.
3. The article of claim 1, wherein the pack cementation coating is derived from a reactive pack mixture composition comprising: a) Si from about 15% to about 50% by total weight of the pack mixture composition; b) B from 0% up to about 25% by total weight of the pack mixture composition; c) SiO2 from about 0.01% to about 3% by total weight of the pack mixture composition; and d) SiC from about 40% to about 85% by total weight of the pack mixture composition.
4. The article of claim 2, wherein the pack cementation coating is derived from a reactive pack mixture composition comprising: a) Si from about 15% to about 50% by total weight of the pack mixture composition; b) B from 0% up to about 25% by total weight of the pack mixture composition; c) SiO2 from about 0.01% to about 3% by total weight of the pack mixture composition; and d) SiC from about 40% to about 85% by total weight of the pack mixture composition.
5. The article of claim 1, wherein the fibers comprise fabric, chopped fabric, yarn, chopped yarn, or tape.
6. The article of claim 1, wherein the fiber comprises Tyranno™ SA-3 fiber.
7. The article as in claim 3 or 4, wherein the reactive pack mixture composition comprises: a) from about 25% to about 40% Si by total weight of the pack mixture composition;
. b) from about 0% to about 15% B by total weight of the pack mixture composition; c) from about 0.01% to about 1% SiO2 by total weight of the pack mixture composition; and d) from about 44% to about 75% SiC by total weight of the pack mixture composition.
8. The article of any of claims 1-5, wherein the pack cementation coating is prepared by a) providing a reactive pack mixture composition of from about 15% to about 50% Si, 0% up to about 25% B, from about 0.01% to about 3% SiO2 and from about 40% to about 85% SiC, all by total weight of the pack mixture composition; b) coating the composite with a release agent; c) surrounding the release agent-coated composite with the pack mixture composition; and d) firing the composite for a period of time sufficient to effectuate the formation of a protective SiC pack cementation coating on the composite.
9. The article as in claim 8, wherein the release agent is a slurry comprising cork suspended in a binder-containing liquid carrier, optionally wherein the binder- containing liquid carrier is an aqueous solution of xanthan gum.
10. A refractory composite article comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix, wherein the carbon matrix comprises an organic resin containing an oxidation inhibitor compound and wherein the organic resin has been subjected to carbonization and thereafter to densification by chemical vapor infiltration of at least carbon to form a silicon carbide fiber reinforced carbon composite, wherein the silicon carbide fiber reinforced carbon composite is coated with a SiC pack cementation coating to form the refractory composite.
11. The article of claim 10, wherein the inhibited carbon matrix contains the oxidation inhibitor from an effective amount to provide oxidation resistance up to about 25 volume percent, the inhibitor comprising at least one of boron, boron carbide, boron nitride, silicon tetraboride, silicon hexaboride, or zirconium diboride; or refractory metal borides of at least one of hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten; or mixtures thereof; optionally wherein the inhibited carbon matrix additionally contains a filler comprising at least one of carbon, silicon carbide, silicon nitride, or mixtures thereof.
12. A net shaped composite material for structural applications having oxidation resistance greater than inhibited carbon/carbon composite materials comprising a plurality of continuous, polycrystalline stoichiometric silicon carbide reinforcing fibers in an inhibited carbon matrix containing an oxidation inhibitor, formed by impregnating the fibers with an organic resin and staging to form a prepreg, shaping and curing the prepreg to form a laminate, carbonizing the shaped laminate to form a carbonized part and densifying the carbonized part by chemical vapor infiltration to form a component, wherein prior to the carbonizing, the organic resin contains the oxidation inhibitor; and wherein the component is coated with a SiC pack cementation coating.
13. The shaped material of claim 12, wherein the organic resin comprises at least one of phenolic, epoxy, and furan.
14. The shaped material of claim 12, wherein the oxidation inhibitor comprises at least one of boron, boron carbide, boron nitride, silicon tetraboride, silicon hexaboride, or zirconium diboride; or refractory metal borides of at least one of hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten; or mixtures thereof; optionally wherein the organic resin additionally contains a filler comprising at least one of carbon, silicon carbide, silicon nitride, or mixtures thereof.
15. The shaped material of claim 12, wherein the fibers comprise fabric, chopped fabric, yarn, chopped yarn, or tape.
16. The shaped material of claim 12, wherein the fibers comprise Tyranno™ SA-3 fiber.
17. A component for an aero engine comprising the refractory composite article of any of claims 1-6.
18. The component of claim 17, comprising at least one of flaps, seals, liners or flame holders.
19. A structural part for a hypersonic vehicle comprising the refractory composite article of any of claims 1-6.
20. The structural part of claim 19 wherein the structural part comprises at least one of bolts, fasteners, skins or leading edges.
21. A thermal protection material comprising the refractory composite article of any of claims 1-6.
22. A component for an aero engine comprising the shaped material of any of claims 12-16.
23. The component of claim 22, comprising at least one of flaps, seals, liners or flame holders.
24. A structural part for a hypersonic vehicle comprising the shaped material of any of claims 12-16.
25. The structural part of claim 24 wherein the structural part comprises at least one of bolts, fasteners, skins or leading edges.
26. A thermal protection material comprising the shaped material of any of claims 12-16.
27. A turbine rotor comprising the refractory composite article of any of claims 1- 6.
28. A turbine rotor comprising the shaped material of any of claims 12-16.
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CN109420737B (en) * | 2017-08-31 | 2020-11-10 | 沈阳汇亚通铸造材料有限责任公司 | Water-based release agent and preparation method thereof |
US20190376389A1 (en) * | 2018-06-08 | 2019-12-12 | General Electric Company | Composite Component Modifications |
DE102022102373A1 (en) * | 2022-02-01 | 2023-08-03 | The Yellow SiC Holding GmbH | Process and device for the production of a workpiece containing silicon carbide |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3672936A (en) * | 1968-04-18 | 1972-06-27 | Carborundum Co | Reinforced carbon and graphite articles |
US4830919A (en) * | 1981-04-07 | 1989-05-16 | Ltv Aerospace & Defense Company | Composition for forming a protective coating on carbon-carbon substrates and article |
US4585675A (en) * | 1981-04-07 | 1986-04-29 | Ltv Aerospace And Defense Company | Alumina silicon carbide, and silicon primary protective coatings for carbon-carbon substrates |
US4465777A (en) * | 1981-04-08 | 1984-08-14 | Vought Corporation | Composition and method for forming a protective coating on carbon-carbon substrates |
US4472476A (en) * | 1982-06-24 | 1984-09-18 | United Technologies Corporation | Composite silicon carbide/silicon nitride coatings for carbon-carbon materials |
US4544412A (en) * | 1982-06-24 | 1985-10-01 | United Technologies Corporation | Deposition of improved SiC coatings on carbon-base materials |
US4476164A (en) * | 1982-06-24 | 1984-10-09 | United Technologies Corporation | Deposition of improved SiC coatings on carbon-base materials |
US4476178A (en) * | 1982-06-24 | 1984-10-09 | United Technologies Corporation | Composite silicon carbide coatings for carbon-carbon materials |
US4425407A (en) * | 1982-06-24 | 1984-01-10 | United Technologies Corporation | CVD SiC pretreatment for carbon-carbon composites |
FR2544661A1 (en) * | 1983-04-19 | 1984-10-26 | Europ Propulsion | COMPOSITE MATERIALS CONSISTING OF A RESIN CARBON COKE MATRIX, REINFORCED BY REFRACTORY FIBERS COATED WITH PYROLYTIC CARBON, AND PROCESS FOR OBTAINING THEM |
US4559270A (en) * | 1983-07-28 | 1985-12-17 | Union Carbide Corporation | Oxidation prohibitive coatings for carbonaceous articles |
JPS60226462A (en) * | 1984-04-24 | 1985-11-11 | 宇部興産株式会社 | Inorganic fiber reinforced heat-resistant ceramic composite material |
US4892790A (en) * | 1984-11-30 | 1990-01-09 | General Atomics | Oxidation-inhibited carbonous materials |
JPS61247663A (en) * | 1985-04-22 | 1986-11-04 | 工業技術院長 | Manufacture of carbon continuous fiber reinforced sic composite body |
US5362567A (en) * | 1986-02-06 | 1994-11-08 | Aerotherm Corporation | Carbon-carbon composite and method of preparation |
US5284685A (en) * | 1988-08-31 | 1994-02-08 | Aerospatiale Societe Nationale Industrielle | Composite material with carbon reinforced fibers and its production |
US5209950A (en) * | 1989-06-19 | 1993-05-11 | Bp Chemicals (Hitco) Inc. | Composition for sic pack cementation coating of carbonaceous substrates |
EP0495570B1 (en) * | 1991-01-16 | 1999-04-28 | Sgl Carbon Composites, Inc. | Silicon carbide fiber reinforced carbon composites |
US5354527A (en) * | 1992-02-21 | 1994-10-11 | The Carborundum Company | Process for making silicon carbide ceramic fibers |
DE10204860A1 (en) * | 2002-02-06 | 2003-08-14 | Man Technologie Gmbh | Fiber composite ceramic material, used e.g. for heat engine, heat exchanger, hot gas pipe or nozzle or plasma containing vessel, has heat-conducting three-dimensional fabric with silicon carbide matrix produced in three stages |
-
2006
- 2006-11-21 CN CNA2006800424799A patent/CN101309881A/en active Pending
- 2006-11-21 KR KR1020087012426A patent/KR20080068096A/en not_active Application Discontinuation
- 2006-11-21 US US11/602,570 patent/US20070128421A1/en not_active Abandoned
- 2006-11-21 EP EP06838239A patent/EP1951639A4/en not_active Withdrawn
- 2006-11-21 WO PCT/US2006/045152 patent/WO2007062094A2/en active Application Filing
- 2006-11-21 JP JP2008542426A patent/JP2009517313A/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of EP1951639A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102225868A (en) * | 2011-04-13 | 2011-10-26 | 中材高新材料股份有限公司 | Preparation of zirconium diboride-silicon carbide ultrahigh-temperature ceramic by slip-casting molding non-pressurized sintering method |
JP2013210372A (en) * | 2013-04-26 | 2013-10-10 | Ibiden Co Ltd | Nuclear fuel cladding and method for manufacturing the same |
CN104003746A (en) * | 2014-05-14 | 2014-08-27 | 西北工业大学 | Preparation method of fiber enhanced ceramics base composite material sharp leading edge |
CN109982986A (en) * | 2016-09-16 | 2019-07-05 | 通用电气公司 | Silicon composition of boracic and forming method thereof |
Also Published As
Publication number | Publication date |
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EP1951639A2 (en) | 2008-08-06 |
US20070128421A1 (en) | 2007-06-07 |
CN101309881A (en) | 2008-11-19 |
EP1951639A4 (en) | 2009-12-09 |
KR20080068096A (en) | 2008-07-22 |
WO2007062094A3 (en) | 2007-10-04 |
JP2009517313A (en) | 2009-04-30 |
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