CN103224688A - Ablation resistant composite material - Google Patents
Ablation resistant composite material Download PDFInfo
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- CN103224688A CN103224688A CN2013101309959A CN201310130995A CN103224688A CN 103224688 A CN103224688 A CN 103224688A CN 2013101309959 A CN2013101309959 A CN 2013101309959A CN 201310130995 A CN201310130995 A CN 201310130995A CN 103224688 A CN103224688 A CN 103224688A
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Abstract
Belonging to the technical field of fiber reinforced resin matrix composite materials, the invention relates to an ablation resistant composite material. Phenolic resin with excellent heat resistance is adopted as the matrix, carbon fibers are taken as a reinforcing material, and zirconium boride and POSS are employed as antioxidant additives to prepare the composite material through hot pressing. The ablation resistant composite material involved in the invention at least consists of, by mass: 100 parts of phenolic resin, 6-18 parts of zirconium boride, 90-110 parts of carbon fibers, and 1-8 parts of POSS. The composite material has the functional characteristics of light weight, heat resistance, corrosion resistance and the like, and has a simple preparation process. In an oxidation environment of 2000-3000DEG C, a dense ceramic layer can be formed so as to effectively prevent oxidative damage of the oxidizing atmosphere on the carbon layer and the carbon fibers. While maintaining proper mechanical properties and a low density, the composite material also realizes the purposes of resisting high temperature oxidation and high temperature particle flow scour ablation. The ablation resistant composite material is suitable for the working conditions of high temperature, high speed particle flow scour and oxidative damage.
Description
Technical field
The invention belongs to the fiber-reinforced resin matrix compound material technical field, relate to resistance to high temperature oxidation and particle erosion ablator technology, particularly resistance to high temperature oxidation and particle erosion ablative composite material.
Background technology
Polymer matrix composites are firm with height ratio, intensity is used widely, and the polymer matrix composites with anti-ablation function have also had certain development and the application of succeeing in recent years.Generally speaking, anti-oxidant and anti-ablation has complementary effect, by add antioxidant addn in the resin matrix of matrix material, makes matrix material also have good ablation resistance when having the good oxidation resistance energy.But under 2000 ℃～3000 ℃, general antioxidant addn lost efficacy, the polymer matrix composites antioxidant property sharply descends, and carbon-coating generation oxidation that resin matrix forms under hot environment destroys, and causes the ablation resistance of matrix material and performance that anti-high-velocity particles stream washes away sharply to descend.
Zhen Qiang etc. have delivered " ZrB on the fifth phase in 2010 " aerospace material technology "
2The microtexture of/C matrix material and high temperature oxidation mechanism " introduced a kind of C/C matrix material, by in the C/C matrix material, adding ZrB
2Additive improves the anti-ablation property and the antioxidant property of C/C matrix material.But B under the hot environment
2O
3Volatilization is at ZrO
2Ceramic surface forms a large amount of micropores, thereby has reduced ZrO
2The effect of pottery isolation oxidation atmosphere.
The people such as J.D.KOO of the upright university of Texas, USA Austin branch school Mechanical Academy have studied the influence of polyhedral oligomeric silsesquioxane (POSS) to the anti-ablation property of resol, and the result shows that POSS under the hot environment can improve the anti-ablation property of resol by the mode that pyrolytic decomposition is taken away a large amount of heat energy.But do not mention other performance of POSS.
Summary of the invention
The present invention aims to provide a kind ofly has the good resistance high temperature oxidation resistance and particle flux washes away the fiber-reinforced resin matrix compound material of ablation property.
The object of the present invention is achieved like this, adopts the resol with superior heat resistance performance as matrix, and as strongthener, as antioxidant addn, hot pressing is prepared into matrix material with zirconium boride 99.5004323A8ure and POSS with carbon fiber.Utilize zirconium boride 99.5004323A8ure and POSS additive that pyrolytic decomposition and oxidation take place in high temperature oxidation atmosphere, take away a large amount of heat energy and form fine and close refractory ceramics layer, increase substantially anti-ablation of matrix material and antioxidant property.
The anti-ablative composite material that the present invention relates to is formed and to be comprised resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, and dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 6 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 8 mass parts.
The anti-ablative composite material that the present invention relates to is formed and to be comprised resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, and dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 6 mass parts.
The anti-ablative composite material that the present invention relates to is formed and to be comprised resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, and dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 16 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 3 ~ 6 mass parts.
The anti-ablative composite material that the present invention relates to, described resol are selected from a kind of or wherein several mixed system that can mate use in phenol-formaldehyde, cresols-formaldehyde, Resorcinol-formaldehyde, the dihydroxyphenyl propane-formaldehyde.
The anti-ablative composite material that the present invention relates to, described carbon fiber can be a kind of in 3K carbon fiber, 6K carbon fiber, the 12 K carbon fibers or their compound system.
The anti-ablative composite material that the present invention relates to, described carbon fiber can be a kind of in fiber, cloth, felt, the three-dimensional fibrous braid.
The anti-ablative composite material that the present invention relates to, described zirconium boride 99.5004323A8ure are varigrained mixed system.
The anti-ablative composite material that the present invention relates to has light weight, functional performance such as heat-resisting, corrosion-resistant, preparation technology is simple, under 2000 ℃～3000 ℃ well-oxygenated environments, form fine and close ceramic layer and effectively stop the oxidation destruction of oxidizing atmosphere carbon-coating and carbon fiber, when keeping suitable mechanical property and lower density, realize that resistance to high temperature oxidation and high temperature particle flux wash away the purpose of ablation.Be applicable to that high temperature, high-velocity particles stream wash away and oxidation destructive operating mode.
Four, embodiment
Below in conjunction with embodiment the scheme that the present invention proposes is further specified, but not as the restriction to technical scheme.Anyly can realize that technological method of the present invention all constitutes a part that the present invention relates to technical scheme.
Embodiment one
With 8 parts of zirconium boride 99.5004323A8ure (0. 7um, gold grinds novel material Science and Technology Ltd. in Beijing) to add net content be 100 parts S-157 heat-reactive phenolic resin (phenol-formaldehyde resin, five or three productions) and in the mixture system of 1 part of three silicon phenyl POSS, ultrasonic dispersing 1 hour, soak into 100 parts of 12k carbon fibers (Tianniao High and New Technology Co., Ltd., Yixing City) with the glue after disperseing, make prepreg.Under 10MPa～15MPa, 160 ℃ solidify down and be prepared into matrix material in 30 minutes, oxygen/acetylene flame mass ablative rate is 0.0228g/s, linear ablative rate is-0.015mm/s that density is 1.61 g/cm
3
Embodiment two
With 10 parts of zirconium boride 99.5004323A8ure (50nm, paddy field, Shanghai material Science and Technology Ltd.) be 2126 phenol Cresol Formaldehyde Resin and 3 part of three silicon phenyl POSS(U.S. Hybrid Plastics company of 100 parts with net content) mixture system in, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 90 parts of 3k carbon cloths (Tianniao High and New Technology Co., Ltd., Yixing City), make prepreg.Utilize thermocompressor in 160 ℃, curing molding under the environment of 5MPa, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0220g/s, linear ablative rate is-0.013mm/s that density is 1.63 g/cm
3
Embodiment three
With 12 parts of zirconium boride 99.5004323A8ure (0. 7um, gold grinds novel material Science and Technology Ltd. in Beijing) be that the mixed solution of 100 parts of Resorcinol-formaldehyde resins (Xinhua Resin Factory, Shanghai) and 5 part of three silicon phenyl POSS mixes with net content, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 120 parts of 6k carbon fiber felts (Tianniao High and New Technology Co., Ltd., Yixing City), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0220g/s, linear ablative rate is-0.013mm/s that density is 1.63 g/cm
3
Embodiment four
With 8 parts of zirconium boride 99.5004323A8ure (0. 17um, gold grinds novel material Science and Technology Ltd. in Beijing) and 6 parts of zirconium boride 99.5004323A8ure (50nm, paddy field, Shanghai material Science and Technology Ltd.) be s-157 resol and 4 part of three silicon phenyl POSS of 100 parts with net content, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 110 parts of 3k carbon fiber puncture fabrics (Tianniao High and New Technology Co., Ltd., Yixing City), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0230g/s, linear ablative rate is-0.017mm/s that density is 1.65 g/cm
3
Embodiment five
With 16 parts of zirconium boride 99.5004323A8ure (0. 7um, gold grinds novel material Science and Technology Ltd. in Beijing) be that 100 parts dihydroxyphenyl propane-formaldehyde resin (Xinhua Resin Factory, Shanghai) and the mixed solution of 6 part of three silicon phenyl POSS mix with net content, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 100 part of 2.5 dimension 3k carbon fibre fabric (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0210g/s, linear ablative rate is-0.013mm/s that density is 1.67 g/cm
3
Embodiment six
With 10 parts of zirconium boride 99.5004323A8ure (0. 7um, gold grinds novel material Science and Technology Ltd. in Beijing) and 8 parts of zirconium boride 99.5004323A8ure (0. 17um, gold grinds novel material Science and Technology Ltd. in Beijing) be that 100 parts SL-1068 resol and the mixed solution of 8 part of three silicon phenyl POSS mix with net content, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 95 parts of three-dimensionals five to 6k carbon fibre fabric (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0200g/s, linear ablative rate is-0.013mm/s that density is 1.67 g/cm
3
Embodiment seven
With 6 parts of zirconium boride 99.5004323A8ure (0. 7um, gold grinds novel material Science and Technology Ltd. in Beijing) with 6 parts of zirconium boride 99.5004323A8ure 50nm, (paddy field, Shanghai material Science and Technology Ltd.) is that 100 parts SL-1069 resol and the mixed solution of 2 part of three silicon phenyl POSS mix with net content, ultrasonic dispersing 1.5 hours, glue after disperseing is soaked into 100 parts of 12k carbon fibers (Tuozhan Fiber Co., Ltd., Weihai), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its oxygen/acetylene flame mass ablative rate is 0.0205g/s, linear ablative rate is-0.014mm/s that density is 1.67 g/cm
3
Claims (7)
1. anti-ablative composite material is formed and is comprised resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, and dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 6 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 8 mass parts.
2. according to the anti-ablative composite material of claim 1, form and comprise resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 6 mass parts.
3. according to the anti-ablative composite material of claim 2, form and comprise resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS at least, dispersion by zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber preimpregnation, curing molding obtain, and its composition comprises at least:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 16 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 3 ~ 6 mass parts.
4. according to the arbitrary anti-ablative composite material of claim 1 ~ 3, described resol is selected from a kind of or wherein several mixed system that can mate use in phenol-formaldehyde, cresols-formaldehyde, Resorcinol-formaldehyde, the dihydroxyphenyl propane-formaldehyde.
5. according to the arbitrary anti-ablative composite material of claim 1 ~ 3, described carbon fiber can be a kind of in 3K carbon fiber, 6K carbon fiber, the 12 K carbon fibers or their compound system.
6. according to the anti-ablative composite material of claim 5, described carbon fiber can be a kind of in fiber, cloth, felt, the three-dimensional fibrous braid.
7. according to the arbitrary anti-ablative composite material of claim 1 ~ 3, described zirconium boride 99.5004323A8ure is varigrained mixed system.
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| CN201310130995.9A CN103224688B (en) | 2013-04-16 | 2013-04-16 | Ablation resistant composite material |
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| CN201310130995.9A CN103224688B (en) | 2013-04-16 | 2013-04-16 | Ablation resistant composite material |
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Cited By (11)
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| CN104803698A (en) * | 2015-04-13 | 2015-07-29 | 安徽省含山瓷业股份有限公司 | High-strength carbon fiber enhanced zirconium boride ceramic matrix composite and preparation method thereof |
| CN106700407A (en) * | 2016-11-14 | 2017-05-24 | 山东非金属材料研究所 | High-temperature ceramic resin based composite material |
| CN106867007A (en) * | 2017-03-13 | 2017-06-20 | 北京交通大学 | A kind of preparation method of resin impregnating glass fiber compound material |
| CN106947098A (en) * | 2017-03-13 | 2017-07-14 | 北京交通大学 | A kind of preparation method for becoming gradient phenolic impregnated carbon fiber ablative composite material |
| CN108395668A (en) * | 2018-02-11 | 2018-08-14 | 航天材料及工艺研究所 | A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified |
| CN109437942A (en) * | 2018-11-19 | 2019-03-08 | 北京交通大学 | A kind of light pyrolysis adaptively ties up the efficient heat insulation material of shape |
| CN110028754A (en) * | 2019-04-02 | 2019-07-19 | 航天特种材料及工艺技术研究所 | A kind of micro-ablation lightweight phenolic resin and preparation method thereof |
| CN110183815A (en) * | 2019-07-04 | 2019-08-30 | 北京理工大学 | A kind of phenol-formaldehyde resin modified and resistance to ablative composite material and preparation method thereof |
| CN110514066A (en) * | 2019-08-20 | 2019-11-29 | 湖北三江航天江北机械工程有限公司 | A kind of manufacturing method of the pressing device of resistance to ablation and pressure plate |
| CN112175335A (en) * | 2020-10-29 | 2021-01-05 | 吉林化工学院 | Ablation-resistant aerospace material and preparation method thereof |
| CN116444284A (en) * | 2023-04-13 | 2023-07-18 | 武汉理工大学 | Antioxidant composite material screening preparation method based on thermodynamic calculation |
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| US20030012938A1 (en) * | 2001-07-11 | 2003-01-16 | Moritz Bauer | Multilayer ceramic composite and process for forming the composite |
| CN102492260A (en) * | 2011-11-29 | 2012-06-13 | 广东榕泰实业股份有限公司 | Ablation-resisting composite material resin composition and preparation method of ablation-resisting composite material |
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| US20030012938A1 (en) * | 2001-07-11 | 2003-01-16 | Moritz Bauer | Multilayer ceramic composite and process for forming the composite |
| CN102492260A (en) * | 2011-11-29 | 2012-06-13 | 广东榕泰实业股份有限公司 | Ablation-resisting composite material resin composition and preparation method of ablation-resisting composite material |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803698A (en) * | 2015-04-13 | 2015-07-29 | 安徽省含山瓷业股份有限公司 | High-strength carbon fiber enhanced zirconium boride ceramic matrix composite and preparation method thereof |
| CN106700407A (en) * | 2016-11-14 | 2017-05-24 | 山东非金属材料研究所 | High-temperature ceramic resin based composite material |
| CN106700407B (en) * | 2016-11-14 | 2019-05-24 | 山东非金属材料研究所 | A kind of refractory ceramics polymer matrix composites |
| CN106947098A (en) * | 2017-03-13 | 2017-07-14 | 北京交通大学 | A kind of preparation method for becoming gradient phenolic impregnated carbon fiber ablative composite material |
| CN106867007A (en) * | 2017-03-13 | 2017-06-20 | 北京交通大学 | A kind of preparation method of resin impregnating glass fiber compound material |
| CN108395668A (en) * | 2018-02-11 | 2018-08-14 | 航天材料及工艺研究所 | A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified |
| CN109437942A (en) * | 2018-11-19 | 2019-03-08 | 北京交通大学 | A kind of light pyrolysis adaptively ties up the efficient heat insulation material of shape |
| CN110028754A (en) * | 2019-04-02 | 2019-07-19 | 航天特种材料及工艺技术研究所 | A kind of micro-ablation lightweight phenolic resin and preparation method thereof |
| CN110183815A (en) * | 2019-07-04 | 2019-08-30 | 北京理工大学 | A kind of phenol-formaldehyde resin modified and resistance to ablative composite material and preparation method thereof |
| CN110514066A (en) * | 2019-08-20 | 2019-11-29 | 湖北三江航天江北机械工程有限公司 | A kind of manufacturing method of the pressing device of resistance to ablation and pressure plate |
| CN110514066B (en) * | 2019-08-20 | 2021-12-07 | 湖北三江航天江北机械工程有限公司 | Ablation-resistant pressing device and manufacturing method of pressing plate |
| CN112175335A (en) * | 2020-10-29 | 2021-01-05 | 吉林化工学院 | Ablation-resistant aerospace material and preparation method thereof |
| CN112175335B (en) * | 2020-10-29 | 2021-04-20 | 吉林化工学院 | Ablation-resistant aerospace material and preparation method thereof |
| CN116444284A (en) * | 2023-04-13 | 2023-07-18 | 武汉理工大学 | Antioxidant composite material screening preparation method based on thermodynamic calculation |
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