CN103224688B - Ablation resistant composite material - Google Patents
Ablation resistant composite material Download PDFInfo
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- CN103224688B CN103224688B CN201310130995.9A CN201310130995A CN103224688B CN 103224688 B CN103224688 B CN 103224688B CN 201310130995 A CN201310130995 A CN 201310130995A CN 103224688 B CN103224688 B CN 103224688B
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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 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 used widely than firm, intensity with height, and the polymer matrix composites with resistance to ablation function there has also been certain development and the application that succeeds in recent years.Generally, anti-oxidant and resistance to ablation has complementary effect, by adding antioxidant addn in the resin matrix of matrix material, makes matrix material also have good ablation resistance while having good oxidation resistance energy.But at 2000 DEG C ~ 3000 DEG C, general antioxidant addn lost efficacy, polymer matrix composites antioxidant property sharply declines, the carbon-coating generation Oxidative demage that resin matrix is formed in high temperature environments, and the performance causing the ablation resistance of matrix material and anti-high-velocity particles stream to wash away sharply declines.
Zhen Qiang etc. have delivered " ZrB on the fifth phase in 2010 " aerospace material technique "
2the microtexture of/C composite and high temperature oxidation mechanism " describe a kind of C/C matrix material, by adding ZrB in C/C matrix material
2additive improves anti-yaw damper performance and the antioxidant property of C/C matrix material.But B under hot environment
2o
3volatilization, at ZrO
2ceramic surface forms a large amount of micropores, thus reduces ZrO
2the effect of pottery isolation oxidation atmosphere.
Texas, USA stands the people such as the J.D.KOO of university's Austin Mechanical Academy and have studied polyhedral oligomeric silsesquioxane (POSS) to the impact of resol anti-yaw damper performance, and result shows that mode that POSS under hot environment can take away a large amount of heat energy by pyrolytic decomposition improves the anti-yaw damper performance of resol.But do not mention other performance of POSS.
Summary of the invention
The present invention aims to provide a kind ofly has the fiber-reinforced resin matrix compound material that good high temperature oxidation resistance and particle flux wash away ablation property.
The object of the present invention is achieved like this, adopts the resol with superior heat resistance performance as matrix, and using carbon fiber as strongthener, with zirconium boride 99.5004323A8ure and POSS as antioxidant addn, hot pressing becomes matrix material.Utilize zirconium boride 99.5004323A8ure and POSS additive that pyrolytic decomposition and oxidation occur in high temperature oxidative atmosphere, take away a large amount of heat energy and form fine and close refractory ceramics layer, increasing substantially matrix material anti-yaw damper and antioxidant property.
The resistance to ablative composite material that the present invention relates to, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 6 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 8 mass parts.
The resistance to ablative composite material that the present invention relates to, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 6 mass parts.
The resistance to ablative composite material that the present invention relates to, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 16 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 3 ~ 6 mass parts.
The resistance to ablative composite material that the present invention relates to, described resol is selected from a kind of in phenol-formaldehyde, cresols-formaldehyde, Resorcinol-formaldehyde, dihydroxyphenyl propane-formaldehyde or wherein several mixed system that can mate use.
The resistance to ablative composite material that the present invention relates to, described carbon fiber can be a kind of in 3K carbon fiber, 6K carbon fiber, 12 K carbon fibers or their compound system.
The resistance to ablative composite material that the present invention relates to, described carbon fiber can be the one in fiber, cloth, felt, dimensional fibre cloth.
The resistance to ablative composite material that the present invention relates to, described zirconium boride 99.5004323A8ure is varigrained mixed system.
The resistance to ablative composite material that the present invention relates to has light weight, the functional performance such as heat-resisting, corrosion-resistant, preparation technology is simple, under 2000 DEG C ~ 3000 DEG C well-oxygenated environments, forming fine and close ceramic layer effectively stops oxidizing atmosphere to the Oxidative demage of carbon-coating and carbon fiber, while keeping suitable mechanical property and lower density, realize the object that resistance to high temperature oxidation and high-temperature particle stream wash away ablation.Be applicable to high temperature, high-velocity particles stream washes away the operating mode with Oxidative demage.
four, embodiment
Below in conjunction with embodiment, the scheme that the present invention proposes is further described, but not as the restriction to technical scheme.Any one can realize technological method of the present invention and all form the part that the present invention relates to technical scheme.
Embodiment one
By 8 parts of zirconium boride 99.5004323A8ure (0. 7um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) add the S-157 heat-reactive phenolic resin (phenol-formaldehyde resin that net content is 100 parts, five or three produced) and 1 part of three silicon phenyl POSS mixture system in, ultrasonic wave disperses 1 hour, infiltrate 100 parts of 12k carbon fibers (Tianniao High and New Technology Co., Ltd., Yixing City) with the glue after dispersion, make prepreg.Under 10MPa ~ 15MPa, at 160 DEG C, solidification is prepared into matrix material in 30 minutes, and oxygen/acetylene flame mass ablative rate is 0.0228g/s, and linear ablative rate is-0.015mm/s, and density is 1.61 g/cm
3.
Embodiment two
By 10 parts of zirconium boride 99.5004323A8ure (50nm, paddy field, Shanghai material Science and Technology Ltd.) be 2126 phenol-cresol-formaldehyde resins and 3 part of three Hybrid Plastics company of the silicon phenyl POSS(U.S. of 100 parts with net content) mixture system in, ultrasonic wave disperses 1.5 hours, glue after dispersion is infiltrated 90 parts of 3k carbon cloths (Tianniao High and New Technology Co., Ltd., Yixing City), makes prepreg.Utilize thermocompressor in 160 DEG C, curing molding under the environment of 5MPa, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0220g/s, and linear ablative rate is-0.013mm/s, and density is 1.63 g/cm
3.
Embodiment three
By 12 parts of zirconium boride 99.5004323A8ure (0. 7um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) being 100 parts of Resorcinol-formaldehyde resins (Xinhua Resin Factory, Shanghai) and 5 part of three silicon phenyl POSS with net content, mixed solution mixes, ultrasonic wave disperses 1.5 hours, glue after dispersion is infiltrated 120 parts of 6k carbon fiber felts (Tianniao High and New Technology Co., Ltd., Yixing City), makes prepreg.Utilize thermocompressor curing molding, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0220g/s, and linear ablative rate is-0.013mm/s, and density is 1.63 g/cm
3.
Embodiment four
By 8 parts of zirconium boride 99.5004323A8ure (0. 17um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) 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 wave disperses 1.5 hours, glue after dispersion is infiltrated 110 parts of 3k Carbon fibre puncture fabrics (Tianniao High and New Technology Co., Ltd., Yixing City), makes prepreg.Utilize thermocompressor curing molding, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0230g/s, and linear ablative rate is-0.017mm/s, and density is 1.65 g/cm
3.
Embodiment five
By 16 parts of zirconium boride 99.5004323A8ure (0. 7um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) be that the dihydroxyphenyl propane-formaldehyde resin (Xinhua Resin Factory, Shanghai) of 100 parts and the mixed solution of 6 part of three silicon phenyl POSS mix with net content, ultrasonic wave disperses 1.5 hours, glue after dispersion is infiltrated 100 part of 2.5 dimension 3k carbon fibre fabric (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize thermocompressor curing molding, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0210g/s, and linear ablative rate is-0.013mm/s, and density is 1.67 g/cm
3.
Embodiment six
By 10 parts of zirconium boride 99.5004323A8ure (0. 7um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) and 8 parts of zirconium boride 99.5004323A8ure (0. 17um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) be that the SL-1068 resol of 100 parts and the mixed solution of 8 part of three silicon phenyl POSS mix with net content, ultrasonic wave disperses 1.5 hours, glue after dispersion is infiltrated 95 parts of three-dimensionals five to 6k carbon fibre fabric (Nanjing Glass Fibre Research and Design Institute), makes prepreg.Utilize thermocompressor curing molding, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0200g/s, and linear ablative rate is-0.013mm/s, and density is 1.67 g/cm
3.
Embodiment seven
By 6 parts of zirconium boride 99.5004323A8ure (0. 7um, Beijing Zhong Jinyan novel material Science and Technology Ltd.) by 6 parts of zirconium boride 99.5004323A8ure 50nm, (paddy field, Shanghai material Science and Technology Ltd.) and net content are that the SL-1069 resol of 100 parts and the mixed solution of 2 part of three silicon phenyl POSS mix, ultrasonic wave disperses 1.5 hours, glue after dispersion is infiltrated 100 parts of 12k carbon fibers (Tuozhan Fiber Co., Ltd., Weihai), makes prepreg.Utilize thermocompressor curing molding, the matrix material be prepared into, its oxygen/acetylene flame mass ablative rate is 0.0205g/s, and linear ablative rate is-0.014mm/s, and density is 1.67 g/cm
3.
Claims (7)
1. a resistance to ablative composite material, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 6 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 8 mass parts.
2. resistance to ablative composite material according to claim 1, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
Resol 100 mass parts
Zirconium boride 99.5004323A8ure 8 ~ 18 mass parts
Carbon fiber 90 ~ 110 mass parts
POSS 1 ~ 6 mass parts.
3. resistance to ablative composite material according to claim 2, composition at least comprises resol, carbon fiber, zirconium boride 99.5004323A8ure and three silicon phenyl POSS, and obtained by the dispersion of zirconium boride 99.5004323A8ure and POSS and glue preparation, fiber prepreg, curing molding, its composition at least comprises:
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 resistance to ablative composite material of claim 1 ~ 3, described resol is selected from a kind of in phenol-formaldehyde, cresols-formaldehyde, Resorcinol-formaldehyde, dihydroxyphenyl propane-formaldehyde or wherein several mixed system that can mate use.
5., according to the arbitrary resistance to ablative composite material of claim 1 ~ 3, described carbon fiber can be a kind of in 3K carbon fiber, 6K carbon fiber, 12 K carbon fibers or their compound system.
6. resistance to ablative composite material according to claim 5, described carbon fiber can be the one in fiber, cloth, felt, dimensional fibre cloth.
7., according to the arbitrary resistance to ablative composite material of claim 1 ~ 3, described zirconium boride 99.5004323A8ure is varigrained mixed system.
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Families Citing this family (11)
| 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 |
| 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 |
| CN109437942B (en) * | 2018-11-19 | 2020-10-20 | 北京交通大学 | Light pyrolysis self-adaptive dimensional efficient heat-proof material |
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| DE10133635A1 (en) * | 2001-07-11 | 2003-02-06 | Sgl Carbon Ag | Multi-layer ceramic composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Non-Patent Citations (1)
| Title |
|---|
| "Phenolic resin–trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: Structure and properties";Yudong Zhang et al;《Polymer》;20061231;第47卷;第2984-2996页 * |
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