CN1064031C - Method for preparing high temperature anti-oxidation carbon base composite material - Google Patents
Method for preparing high temperature anti-oxidation carbon base composite material Download PDFInfo
- Publication number
- CN1064031C CN1064031C CN98101476A CN98101476A CN1064031C CN 1064031 C CN1064031 C CN 1064031C CN 98101476 A CN98101476 A CN 98101476A CN 98101476 A CN98101476 A CN 98101476A CN 1064031 C CN1064031 C CN 1064031C
- Authority
- CN
- China
- Prior art keywords
- powder
- temperature
- graphite
- composite material
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- 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
- C04B41/5057—Carbides
- C04B41/5059—Silicon carbide
Abstract
The present invention relates to a preparation method of high-temperature anti-oxidation carbon base composite materials. In the method, calcined coke powder, asphalt powder, graphite powder and B4C powder are mixed according to a certain proportion and then treated by ball milling in a ball mill for certain time so that B4C particles are uniformly dispersed; the mixed powder is pressed into a B4C particle dispersed internal modified graphite material by the hot pressing technology; then the base material is put in a high-temperature vacuum resistance furnace and siliconized by SiO steam as a siliconizing steam source at the high temperature of 1500 to 1600 DEG C in vacuum, and a gradient SiC coating /B4C particle internal modified graphite matrix composite material is obtained. The method has the advantages of simple technological process, high repeatability, etc.; the prepared composite material has thermal-shock resistance and favorable high-temperature (1300 DEG C) oxidation resistance.
Description
The invention belongs to a preparation method of a composite material, and particularly relates to a preparation method of a high-temperature oxidation-resistant carbon-based composite material.
The carbon material has excellent electric and thermal conductivity, corrosion resistance and high-temperature stability, and is widely applied to the high-temperature field as a structural and engineering material. However, the carbon material begins to undergo an oxidation reaction in an oxidizing atmosphere of 400 ℃ or higher, so that various physical and mechanical properties thereof are rapidly deteriorated. Therefore, the oxidation protection treatment of the carbon material is a fundamental measure for prolonging the service life of the carbon material and improving the working stability and reliability of the carbon material.
The coating treatment of the carbon material is a main method for solving the problem of high-temperature (more than 1000 ℃) oxidation protection of the carbon material. The SiC coating has high thermal stability, good chemical compatibility with the carbon matrix and close thermal expansion coefficient. CVD SiC coating is the main ceramic coating material applied to carbon material oxidation protection at present. However, such coatings still have certain disadvantages in use: an obvious interface exists between the SiC coating and the carbon matrix, the CVD process is usually carried out at high temperature (more than 1000 ℃), in the process of cooling the deposition to room temperature, due to the difference of the thermal expansion coefficients between the coating and the carbon matrix, microcracks are caused by the concentration of thermal stress at the interface, and the microcracks gradually expand in the thermal cycle process to cause the peeling or even the falling off of the coating and the carbon matrix, so that the oxidation protection is failed; on the other hand, the bonding force between the CVD SiC coating and the matrix is weak, and the CVD SiC coating is easy to be wounded under the impact of external force.
To overcome the above-mentioned deficiencies of SiC coatings, Dengjingyi et al (carbon, 1995, (2): 4) deposited a gradient SiC coating on the surface of a carbon substrate by CVD. However, this process is complicated, requires continuous changes in the composition of the atmosphere, and makes it difficult to obtain a uniform and desirable coating for large or complex parts. Gee et al (Journal of Material Science, 1991,26(4): 1093) the SiC coating is coated with boric acid glass, and the boric acid glass has lower viscosity and fluidity at high temperature and can heal microcracks in the SiC coating. However, boric acid glass has high volatility at high temperature (>900 ℃) and low viscosity, which leads to high oxygen diffusion coefficient, so that the service life of the coating system is limited. Piquero et al (Carbon, 1995, 33 (4): 455) use B4The oxidation protection research of the C inner coating and SiC outer coating system is carried out, and the oxidation protection effect is not ideal because the mismatch of the thermal expansion coefficients between the ceramic coatings and the carbon substrate still exists in the coating system.
The invention aims to provide a preparation method of a high-temperature oxidation-resistant carbon-based composite material.
The object of the invention is achieved by first preparing B4And C particles are dispersed in the interior of the modified graphite base material. Mixing coke powder, asphalt powder, graphite powder and B4Mixing the C powder according to a certain proportion, and then mixing and ball-milling the mixture in a ball mill for a certain time to ensure that the B powder4And (3) uniformly dispersing the C particles. Pressing the mixed powder into B by a hot pressing process4And C, dispersing and modifying the graphite material. Then the substrate material is placed in a high-temperature vacuum resistance furnace, and SiO steam is used as a silicification steam source for high-temperature silicification treatment at 1500-1600 ℃ under the vacuum condition. By CVI (chemical vapor infiltration) diffusion of SiO vapor in the matrix materialA gradient SiC coating is generated on the surface of the bulk material, thereby obtaining a gradient SiC coating/B4C, modifying the graphite matrix composite material inside. The gradient distribution of the SiC coating promotes the chemical combination of the SiC coating and the carbon matrix on one hand, and avoids the SiC coating from being injured due to the impact of external force; on the other hand, the thermal stress between the coating and the carbon substrate can be redistributed instead of being concentrated on a distinct interface, thereby greatly reducing the possibility of microcracking. B dispersed in the matrix4The C particles can be converted into B by oxidation2O3And micropores generated by CVI diffusion of SiO steam in the SiC coating are filled, so that the composite material realizes self-healing oxidation resistance. The prepared composite material has the advantages of heat shock resistanceGood high-temperature (1300 ℃) oxidation resistance.
The preparation method of the invention is to prepare the gradient SiC coating on the surface of the graphite matrix material by adopting CVI diffusion of SiO steam, and is characterized in that the graphite matrix material is prepared from calcined coke powder, asphalt powder, graphite powder and B4C, mixing according to a certain proportion, ball-milling and hot-pressing to obtain the product.
The surface of the graphite base material adopts SiO and CVI diffusion to prepare a gradient SiC coating, and SiO is used for preparing the gradient SiC coating2And carbon powder or silicon powder as raw material according to SiO2C or Si = 1: 1 (weight ratio), siliconizing the graphite-based material under vacuum conditions at 1500-.
The graphite matrix material is prepared from calcined coke powder, asphalt powder, graphite powder and B4C, uniformly mixing the components in a weight ratio of (20-40) to (1-10) to (1-5), ball-milling the mixture for 0.5 to 2 hours, and then carrying out hot pressing on the mixture at the temperature of 2300 ℃ under the pressure of 20MPa to obtain the graphite matrix material.
Compared with the prior art, the invention has the following advantages:
1. the process is relatively simple and has good repeatability;
2. the gradient distribution of the SiC coating is realized by adopting a chemical vapor infiltration process, so that the chemical combination of the coating and the matrix material is promoted on the one hand; on the other hand, the occurrence of microcracks caused by the concentration of thermal stress is avoided;
3. b dispersed in the matrix4The C particles can be converted into B by oxidation2O3Filling micropores generated in the SiC coating due to chemical vapor diffusion of SiO steam, so that the composite material realizes self-healing oxidation resistance;
4. the composite material has good thermal shock resistance and high-temperature (1300 ℃) oxidation resistance.
The examples of the invention are as follows:
example 1
Mixing calcined coke powder, asphalt powder, graphite powder and B4Mixing the C powder according to the following ratio of 35: 10: 1: 2 (weight ratio), and then mixing and ball-milling for 1 hour in a ball mill to ensure that B powder4Uniform dispersion of C particles. The mixed powder is pressed into B by a hot pressing process (20MPa, 2000-4And C particles are dispersed in the modified graphite material. Then the matrix material is put in a graphite crucible, and the bottom of the graphite crucible is filled with mixed powder of quartz powder and carbon powder (the molar ratio is 1: 1). The graphite crucible is placed in a high-temperature vacuum resistance furnace, and SiO steam (from 1500 ℃ C.) is used at 1600 ℃ under the vacuum condition Reaction produced) as a source of silicidation vapor for high temperature silicidation. After siliconization for 1 hour, the gradient SiC coating/B4C particle internal modified graphite matrix composite material is obtained. The composite was at 1300 ℃. Constant temperature oxidation test was carried out in dry air of 2L/min. The weight change during oxidation is shown in figure 1.
Example 2
Mixing calcined coke powder, asphalt powder, graphite powder and B4The base material was prepared by mixing and ball-milling the powder C in the following ratio of 35: 10: 1: 2 (weight ratio), and the rest was the same as in example 1. The composite material was subjected to constant temperature oxidation test at 1300 ℃ in 2L/min dry air. The weight change during oxidation is shown in figure 2.
Example 3
Mixing calcined coke powder, asphalt powder, graphite powder and B4The base material was prepared by mixing and ball-milling the powder C in the following ratio 40: 10: 1: 3 (weight ratio), and the rest was the same as in example 1. The composite material was subjected to constant temperature oxidation test at 1300 ℃ in 2L/min dry air. The weight change during oxidation is shown in figure 3.
Example 4
Mixing calcined coke powder, asphalt powder, graphite powder and B4The base material was prepared by mixing and ball-milling the powder C in the following ratio of 30: 1: 2 (weight ratio), and the rest was the same as in example 1. The composite material was subjected to constant temperature oxidation test at 1300 ℃ in 2L/min dry air. The weight change during oxidation is shown in figure 4.
Example 5
Mixing calcined coke powder, asphalt powder, graphite powder and B4The base material was prepared by mixing and ball-milling the powder C in the following ratio of 30: 5: 1: 4 (weight ratio), and the rest was the same as in example 1. Prepared byThe composite sample was warmed to 1020 ℃ and then quickly dropped in room temperature (20 ℃) water after 10 thermal shocks (△ T =1000 ℃), a constant temperature oxidation test was performed at 1300 ℃, 2L/min dry air.
Example 6
The raw material for generating SiO vapor was composed of quartz powder and Si powder (molar ratio 1: 1), and the rest was the same as in example 1. The prepared composite material sample is subjected to constant temperature oxidation test at 1300 ℃ in 2L/min dry air. The weight change during oxidation is shown in figure 6.
Claims (1)
1. A preparation method of a high-temperature oxidation-resistant carbon-based composite material is characterized by comprising the following steps:
(1) mixing calcined coke powder, asphalt powder, graphite powder and B4C, uniformly mixing the raw materials according to the weight ratio of (20-40) to (1-10) to 1 to (1-5), ball-milling the mixture for 0.5 to 2 hours, and carrying out hot pressing on the mixture at the temperature of 2300 ℃ under the pressure of 20MPa and 2000-;
(2) adopting SiO to the surface of the graphite base material obtained in the step (1)2Chemical vapor infiltration diffusion of vapor to produce gradient SiC coatings with SiO2And carbon powder or silicon powder as raw material according to SiO2And the weight ratio of C or Si = 1: 1, siliconizing the graphite matrix material for 1 hour at 1500-1600 ℃ under the vacuum condition, and obtaining the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101476A CN1064031C (en) | 1998-05-19 | 1998-05-19 | Method for preparing high temperature anti-oxidation carbon base composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101476A CN1064031C (en) | 1998-05-19 | 1998-05-19 | Method for preparing high temperature anti-oxidation carbon base composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235941A CN1235941A (en) | 1999-11-24 |
| CN1064031C true CN1064031C (en) | 2001-04-04 |
Family
ID=5216722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98101476A Expired - Fee Related CN1064031C (en) | 1998-05-19 | 1998-05-19 | Method for preparing high temperature anti-oxidation carbon base composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1064031C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340791C (en) * | 2003-11-24 | 2007-10-03 | 西安超码科技有限公司 | Method for preventing oxidization of carbon-carbon composite material |
| CN1297515C (en) * | 2005-08-11 | 2007-01-31 | 中国科学院山西煤炭化学研究所 | Preparation method of charcoal material surface coating for resisting high temperature oxidation |
| CN101752547B (en) * | 2008-12-18 | 2012-05-30 | 中国电子科技集团公司第十八研究所 | Li-ion secondary battery cathode material preparation method with nuclear shell structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS648872A (en) * | 1986-07-08 | 1989-01-12 | Nippon Denso Co | Power source circuit for vehicle |
| JPH0826089A (en) * | 1994-07-19 | 1996-01-30 | Nippondenso Co Ltd | Antiskid controller |
| JPH0952777A (en) * | 1995-08-10 | 1997-02-25 | Tokai Carbon Co Ltd | Production of oxidation resistant c/c composite material |
-
1998
- 1998-05-19 CN CN98101476A patent/CN1064031C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS648872A (en) * | 1986-07-08 | 1989-01-12 | Nippon Denso Co | Power source circuit for vehicle |
| JPH0826089A (en) * | 1994-07-19 | 1996-01-30 | Nippondenso Co Ltd | Antiskid controller |
| JPH0952777A (en) * | 1995-08-10 | 1997-02-25 | Tokai Carbon Co Ltd | Production of oxidation resistant c/c composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1235941A (en) | 1999-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20130005690A (en) | Method for preparing high density fiber reinforced silicon carbide composite materials | |
| CN106673708B (en) | A kind of method that surface of carbon/carbon composite prepares silicon carbide nanometer line porous layer | |
| CN1821183A (en) | Method for preparing anti-oxidation multiple phase coating of carbon/carbon composite material surface | |
| CN114890820B (en) | Coating composition for improving surface compactness of carbon/carbon composite material, preparation method thereof and thermal field component | |
| CN111517797B (en) | Low-temperature normal-pressure sintering preparation method of high-purity SiC ceramic coating capable of being produced in mass | |
| CN115180981B (en) | Nano-wire cross-scale toughening complex-phase ceramic antioxidant coating and preparation method and application thereof | |
| CN114538964B (en) | MoSi 2-rich high-temperature oxidation resistant coating on surface of SiC-Si coated carbon/carbon composite material and preparation method thereof | |
| CN105218102A (en) | A kind of precursor process prepares the method for SiC/TiC composite ceramics | |
| CN114368981A (en) | Graphite material, workpiece oxidation resistance treatment technology and application | |
| CN112279685A (en) | MTaO with environmental thermal barrier coating4Graphite-based composite material and preparation method thereof | |
| Li et al. | Effect factors on thermal and mechanical properties of SiO2 and TiB2 modified SiBCN-based adhesives | |
| CN1064031C (en) | Method for preparing high temperature anti-oxidation carbon base composite material | |
| Zhang et al. | A thick SiC-Si coating prepared by one-step pack cementation for long-term protection of carbon/carbon composites against oxidation at 1773 K | |
| CN106631161A (en) | Method for preparing high-temperature oxidation resistant composite coating on surface of carbon-based material | |
| CN1762905A (en) | A kind of preparation method of charcoal material surface gradient coating for resisting oxidation | |
| CN1821175A (en) | Method for preparing silicon carbide whisker/aluminium oxide composite ceramic powder using natural kaolin | |
| CN1762904A (en) | A kind of preparation method of charcoal material surface coating for resisting high temperature oxidation | |
| CN114309583B (en) | Gradient ceramic coating for gradient mullite lap joint and preparation method thereof | |
| CN105669231A (en) | Preparation method of carbon fiber reinforced MoSi2-SiC ceramic matrix composite | |
| Zhu et al. | Fabricating 2.5 D SiCf/SiC composite using polycarbosilane/SiC/Al mixture for matrix derivation | |
| CN114478068A (en) | High-temperature oxidation-resistant graphite product and preparation method thereof | |
| JPH0848509A (en) | Production of carbonaceous porous body | |
| JP3966911B2 (en) | In-furnace members and jigs | |
| AU2004232516B2 (en) | Use of a silicon carbide-based ceramic material in aggressive environments | |
| KR102238819B1 (en) | Method for producing silicon carbide fiber and the silicon carbide fiber manufactured by using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |