CN101153384B - Method for manufacturing unit doublet carbide codeposition fibre-reinforced composite - Google Patents
Method for manufacturing unit doublet carbide codeposition fibre-reinforced composite Download PDFInfo
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- CN101153384B CN101153384B CN2006100323361A CN200610032336A CN101153384B CN 101153384 B CN101153384 B CN 101153384B CN 2006100323361 A CN2006100323361 A CN 2006100323361A CN 200610032336 A CN200610032336 A CN 200610032336A CN 101153384 B CN101153384 B CN 101153384B
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Abstract
The invention relates to a preparation method for making unit doublet carbide codeposition fiber reinforcement composite material through chemical gas phase permeation/deposition process, wherein, codeposition unit doublet carbide is obtained inside a preformed billet body made of C fiber, boron fiber, ceramic fiber and metal fiber, etc. by use of the designability of chemical gas phase permeation/deposition process to make fiber-reinforcement unit doublet carbide composite material; the carbide is the combination of any two sorts of carbide of HfC, TaC, ZrC, NbC, WC, TiC, B4C, VC, AlC and SiC, etc. The material made through the method is characterized by high temperature resistance, wear resistance, anti scour, antioxidation, ablation resistance and excellent thermal shock resistance.
Description
Technical field:
Technical field: the present invention relates to a kind of chemical vapor infiltration/depositing operation and make the unit doublet carbide codeposition fibre-reinforced composite method, be mainly used in high temperature, high hard, anti-oxidant, the anti-functional structure parts of ablating etc. and to require.
Background technology:
Background technology: chemical vapour deposition is a chemical synthetic material on atom, molecular level, thereby can carry out the design and the preparation of material at the nanometer level; Preparation technology can guarantee The Nomenclature Composition and Structure of Complexes controllability circulation ratio; Material preparation and element manufacturing have consistence; Equipment is simple, operation is simple and easy, be easy to realize automatic control.Another advantage for preparing material with chemical gaseous phase depositing process is to be prepared under the temperature more much lower than material melting point.As 3890 ℃ of the fusing points of TaC, but can under 800～1400 ℃ of temperature, deposit.Simultaneously, chemical vapor infiltration/deposition also is the important method of FRCMC, and can utilize the designability of chemical vapor deposition method, prepares the matrix material of various structures and performance.
At present, tend on the C/C matrix material, apply refractory carbides (as HfC, TaC) coating in the world as engine jet pipe, and best with the coating performance of chemical vapour deposition, but still have very big difficulty.As: coating is too thin, is washed away by high velocity air very soon, does not have anti-purpose of ablating, and coating is too thick, shows as the character of pottery, then is subjected to thermal shocking easily and degrades.
Summary of the invention:
Summary of the invention: for further improving mechanical behavior under high temperature, antioxidant property, the thermal shock resistance of fiber reinforcement carbide matrix material, the present invention utilizes the self-organization style structure of unit doublet carbide codeposition matrix material, proposes a kind of chemical vapor infiltration/depositing operation and makes the unit doublet carbide codeposition fibre-reinforced composite method.
The manufacture method of unit doublet carbide codeposition fibre-reinforced composite comprises the preparation, the deposition that deposit base substrate, and concrete processing parameter is as follows:
The deposition base substrate is fiber establishment body or fibrefelt body, and fiber is C fiber, boron fibre, ceramic fiber or refractory metal fiber;
The deposition base substrate is gone into stove: with the base substrate chemical vapor infiltration/cvd furnace of packing into, cvd furnace is vacuumized and remains on below the 100Pa, be warming up to 700～1600 ℃ of depositing temperatures;
The base substrate codeposition: cvd furnace feeds the M of carbon source gas, two kinds of carbide simultaneously
1, M
2Source gas, hydrogen and diluent gas Ar gas carry out M
1C and M
2The codeposition of C, codeposition pressure 50～10000Pa; Carbon source gas is gaseous hydrocarbon, comprises CH
4, C
2H
6, C
3H
8, C
3H
6, C
2H
4Or C
2H
2The hydrocarbon polymer of maybe can vaporizing comprises liquefied gas, Sweet natural gas, hexanaphthene or C
6H
6The fusing point of described carbide comprises HfC, TaC, ZrC, NbC, WC, TiC, SiC, B more than 2000 ℃
4C, VC or AlC; Described M
1, M
2Source gas is halogenide or the organic compound that gaseous state maybe can heat vaporization, comprises MF
5, MCl
5, MBr
5, MI
5, MCl
4, MF
4, MBr
4, MI
4, MCl
3, MF
3, MBr
3, MI
3, HMCl
3, H
2MCl
2, H
3MCl, M (OC
2H
5)
5, M (OC
2H
5)
4, M (OC
2H
5)
3, CH
3MCl
3, (CH
3)
2MCl
2, (CH
3)
3MCl, MH
4Or MH
3
Off-response gas, logical diluent gas Ar, cooling, the deposition goods are come out of the stove, and cut the fine and close carbide skinning of product surface, ultrasonic cleaning, drying;
Repeat said process, till deposition extrudate density index reaches service requirements.
The present invention is according to the additivity of matrix material and anti-thermal shock, the oxidation-resistance of codeposition unit doublet carbide material, and the designability principle of chemical vapor deposited coatings, adopt the equipment and the preparation technology of chemical vapour deposition, preparation prepares the codeposition unit doublet carbide that the coefficient of expansion and Young's modulus have certain variable densification in the fiber base substrate, can on filamentary material, deposit the coefficient of expansion and differ bigger flawless refractory carbides, its technical process is simple, and control is convenient; The matrix material that utilizes this method to make, flawless, internal stress is little, and the hot strength height has good thermal shock resistance, the antioxidant property excellence.Have better mechanical property and simple carbide material incomparable thermostability and reliability, thus wider than simple carbide ceramic applications, longer service life.Be mainly used in high temperature, high hard, anti-oxidant, the anti-functional structure parts of ablating etc. and to require.
Description of drawings:
Fig. 1: the manufacturing process skeleton diagram of unit doublet carbide codeposition fibre-reinforced composite;
Fig. 2: TaC-SiC codeposition matrix material SEM photo.
Embodiment:
Now in conjunction with the accompanying drawings the present invention is described further:
Embodiment 1: referring to accompanying drawing 1, Fig. 2, get the C fiber establishment body of 3D establishment, cut into the ring specimen of Φ (70-100) * 65mm, behind the weighing, put into chemical vapor deposition stove; Be evacuated down to below the 50Pa, be warmed to 1100 ℃, carry out the deposition of CVD-C earlier, feed Ar and C with 3: 1 ratios
3H
6Carry out the deposition of CVD-C, keep furnace pressure 1000～2000Pa deposition 20hr; Carry out the TaC-SiC codeposition then, do carrier gas with TaCl with Ar
5Introduce in the stove, add C simultaneously
3H
6With reducing gas H
2, use H
2Do carrier gas with CH
3SiCl
3(MTS) bring cvd furnace into by another road pipeline, Ar makes diluent gas, H
2With the ratio of Ar be 1: (1～5), H
2: MTS 〉=10 keep furnace pressure 500～1000Pa deposition 60hr; Stop deposition; Continue logical Ar insulation 30min, vacuumize cooling; Blow-on sampling weighing, detection to the room temperature.Car removes diameter inner and outer surface layers carbide skinning, and ultrasonic cleaning, drying are put into cvd furnace and continued deposition, carry out the TaC-SiC codeposition repeatedly repeatedly.
Sample with the cold edge of resin, grinds, throws with bortz powder, cream after cutting, observes pattern such as Fig. 2 of coating under scanning electron microscope.From Fig. 2 can the clear TaC of finding out and SiC codeposition matrix material be component gradient alternately change pattern, rather than uniformly; Grey is the high soft district of SiC ratio, and white is the high high rigidity district of TaC ratio.This periodically variable pattern, just TaC and SiC codeposition the competition the result, because the difference of lattice parameter and can not form sosoloid, when causing a kind of coating deposition, repel the deposition of another kind of coating, descend more up to a kind of degree of supersaturation that is deposited to that is coated with, and the degree of supersaturation of another kind of coating is higher, and the activation energy of system is higher, just causes the transformation of coating deposition kind, by lattice distortion, carry out heteroepitaxial growth, reach the purpose that reduces system capacity.So circulation has just formed composition and hardness fluctuations multilayer depositional texture, is broken up to system.
Ablation test shows that this self-organization style has excellent thermal shock resistance and antioxidant property, thereby probably becomes the anti-ablator of high-performance of new generation.
Embodiment 2: referring to accompanying drawing 1, get the SiC fiber establishment body of 4D establishment, cut into the ring specimen of Φ (70-100) * 65mm, behind the weighing, put into chemical vapor deposition stove; Be evacuated down to below the 50Pa, be warmed to 1300 ℃, carry out the TaC-HfC codeposition, do carrier gas with TaCl with Ar
5Introduce in the stove, add CH simultaneously
4With reducing gas H
2, do carrier gas with HfCl with Ar
4Go into cvd furnace by another pass, add CH simultaneously
4With reducing gas H
2, Ar makes diluent gas, keeps furnace pressure 500～1000Pa deposition 60hr; Stop deposition; Continue logical Ar insulation 30min, vacuumize cooling; Blow-on sampling weighing, detection to the room temperature.Car removes diameter inner and outer surface layers carbide skinning, and ultrasonic cleaning, drying are put into cvd furnace and continued deposition, carry out the TaC-HfC codeposition repeatedly repeatedly.Can make the fibre-reinforced TaC-HfC codeposition of the SiC matrix material of compact structure.
Embodiment 3: referring to accompanying drawing 1, get boron fiber (or tungsten W silk) the establishment body of 4D establishment, cut into the ring specimen of Φ (70-100) * 65mm, behind the weighing, put into chemical vapor deposition stove; Other technology can make B fiber (or tungsten W silk) the enhanced TaC-HfC codeposition matrix material of compact structure with embodiment 2.
Claims (1)
1. the manufacture method of unit doublet carbide codeposition fibre-reinforced composite comprises it is characterized in that preparation, the deposition of base substrate:
Described base substrate is fiber establishment body or fibrefelt body, and fiber is C fiber, boron fibre, ceramic fiber or refractory metal fiber;
Base substrate is gone into stove: with base substrate pack into chemical vapor infiltration poke or cvd furnace, infiltration stove or cvd furnace are vacuumized and remain on below the 100Pa, be warming up to 700～1600 ℃ of depositing temperatures;
The base substrate codeposition: infiltration stove or cvd furnace feed the M of carbon source gas, two kinds of carbide simultaneously
1, M
2Source gas, hydrogen and diluent gas Ar gas carry out M
1C and M
2The codeposition of C, codeposition pressure 50～10000Pa;
Described carbon source gas is gaseous hydrocarbon, and gaseous hydrocarbon is CH
4, C
2H
6, C
3H
8, C
3H
6, C
2H
4Or C
2H
2, the hydrocarbon polymer of maybe can vaporizing, the hydrocarbon polymer of can vaporizing is liquefied gas, Sweet natural gas, hexanaphthene or C
6H
6
The fusing point of described carbide is HfC, TaC, ZrC, NbC, WC, TiC, SiC, B more than 2000 ℃
4C, VC or AlC;
Described M
1, M
2Source gas is halogenide or the organic compound that gaseous state maybe can heat vaporization, is MF
5, MCl
5, MBr
5, MI
5, MCl
4, MF
4, MBr
4, MI
4, MCl
3, MF
3, MBr
3, MI
3, HMCl
3, H
2MCl
2, H
3MCl, M (OC
2H
5)
5, M (OC
2H
5)
4, M (OC
2H
5)
3, CH
3MCl
3, (CH
3)
2MCl
2, (CH
3)
3MCl, MH
4Or MH
3
Off-response gas, logical diluent gas Ar, cooling, goods are come out of the stove, and cut the fine and close carbide skinning of product surface, ultrasonic cleaning, drying;
Repeat said process, till the extrudate density index reaches service requirements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100323361A CN101153384B (en) | 2006-09-28 | 2006-09-28 | Method for manufacturing unit doublet carbide codeposition fibre-reinforced composite |
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|---|---|---|---|
| CN2006100323361A CN101153384B (en) | 2006-09-28 | 2006-09-28 | Method for manufacturing unit doublet carbide codeposition fibre-reinforced composite |
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|---|---|
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| CN101153384B true CN101153384B (en) | 2010-11-10 |
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| CN101486588B (en) * | 2009-03-04 | 2013-03-20 | 中南大学 | Preparation of carbon fiber reinforced carbon-silicon carbide double matrix friction material |
| CN103922797B (en) * | 2009-12-28 | 2016-03-16 | 东洋炭素株式会社 | Tantalum carbide-covered carbon material and manufacture method thereof |
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| CN102965638B (en) * | 2012-11-19 | 2014-11-05 | 西北工业大学 | Method for preparing C-coated HfC (hybrid fiber coaxial) whiskers |
| CN103951453B (en) * | 2013-07-23 | 2016-05-04 | 太仓派欧技术咨询服务有限公司 | A kind of at 2000 DEG C of following long-term metal ceramic-based composite materials that use |
| CN103724028B (en) * | 2013-07-23 | 2016-05-04 | 苏州宏久航空防热材料科技有限公司 | A kind of at 1600 DEG C of following long-term metal ceramic-based composite materials that use |
| CN103910533B (en) * | 2013-11-25 | 2016-03-30 | 中航复合材料有限责任公司 | The preparation method of the ceramic modified carbon/carbon composite of a kind of double elements |
| CN103936464A (en) * | 2014-03-27 | 2014-07-23 | 西北工业大学 | Preparation method of HfC-SiC modified carbon/carbon composite material |
| CN104150938B (en) * | 2014-08-06 | 2015-11-18 | 西北工业大学 | The preparation method of one dimension hafnium carbide HfC material modification carbon/carbon composite |
| CN105418112B (en) * | 2016-01-11 | 2018-03-23 | 山东理工大学 | Ethanol disperses the preparation method of tungsten carbide carbon SiClx carbon fiber friction material |
| CN105439598B (en) * | 2016-01-11 | 2018-05-22 | 山东理工大学 | Ethyl alcohol disperses the preparation method of niobium carbide silicon carbide―carbon fiber friction material |
| CN105439597B (en) * | 2016-01-11 | 2018-05-22 | 山东理工大学 | Ethyl alcohol disperses the preparation method of titanium-carbon boride SiClx-carbon fiber friction material |
| CN108440010B (en) * | 2018-04-28 | 2020-05-12 | 航天材料及工艺研究所 | Hybrid fiber reinforced ultrahigh-temperature ablation-resistant composite material and preparation method thereof |
| CN109399625B (en) * | 2018-11-21 | 2021-10-01 | 华侨大学 | Preparation method of boron-doped semiconductor graphene |
| CN112899650B (en) * | 2019-03-28 | 2023-02-03 | 中国兵器工业第五九研究所 | Preparation method of (Ta, hf, zr) C composite coating with excellent stability |
| CN111133614B (en) * | 2019-12-30 | 2024-02-23 | 上海杉杉科技有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN111571123A (en) * | 2020-04-25 | 2020-08-25 | 南通洪源地质工程材料有限公司 | Processing technology of seamless drill pipe |
| CN113800933B (en) * | 2021-09-30 | 2022-06-28 | 西北工业大学 | Carbon fiber reinforced ceramic matrix composite material and preparation method thereof |
| CN113816755B (en) * | 2021-10-14 | 2023-09-01 | 西安鑫垚陶瓷复合材料有限公司 | Two-dimensional silicon carbide/silicon carbide composite bar and preparation method of connecting piece |
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