CN114315420A - Method for preparing carbon/carbon composite material high-temperature oxidation-resistant coating through in-situ reaction - Google Patents
Method for preparing carbon/carbon composite material high-temperature oxidation-resistant coating through in-situ reaction Download PDFInfo
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Abstract
The invention discloses a method for preparing a carbon/carbon composite material high-temperature oxidation-resistant coating through in-situ reaction, and belongs to the technical field of material preparation. The method comprises the steps of raw material composition design, powder mixing ball milling, drying, carbon/carbon composite material substrate cleaning and ultrahigh-speed laser cladding in-situ reaction to prepare the MAX-phase high-temperature antioxidant coating, so as to prepare the carbon/carbon composite material high-temperature antioxidant coating. The method adopts raw material powder to react in situ on the surface of the carbon/carbon composite material by utilizing the ultra-high-speed laser cladding technology to form an interface MAX phase layer. By means of the toughness of the MAX phase, the problems of cracking and peeling of the coating at high temperature are solved, meanwhile, the matrix carbon participates in the in-situ reaction of the surface, the coating and the matrix are chemically combined, and the binding force of the coating and the matrix is enhanced.
Description
Technical Field
The invention discloses a method for preparing a carbon/carbon composite material high-temperature oxidation-resistant coating through in-situ reaction, and belongs to the technical field of material preparation.
Background
The carbon/carbon composite material is widely used as aerospace and aviation materials due to excellent thermal and mechanical properties, but the application of the carbon/carbon composite material in the high-temperature field is influenced by the defect that the carbon/carbon composite material is easy to oxidize in an aerobic environment at the temperature higher than 450 ℃. Therefore, the integral oxidation resistance and ablation resistance of the composite material can be realized through the surface coating modification technology, sudden performance failure caused by coating falling is effectively avoided, and the reliability is improved. The hypersonic flight technology is regarded as a core technology in the aerospace field, and is increasingly paid more attention by various aerospace major countries. When the aircraft moves at a high speed, the temperature of the nose cone, the front edge stagnation point and other parts on the surface of the aircraft can reach thousands of even thousands of degrees centigrade. Under these harsh conditions, the composite materials such as carbon/carbon composite materials and carbon fiber reinforced ceramic matrix composite materials are difficult to meet the use requirements, and a high-temperature oxidation-resistant coating needs to be coated on the surface of the composite materials. The existing antioxidant coating for the composite material generally has the problems of high porosity, low bonding strength, poor high-temperature oxidation resistance and the like, and cannot meet the requirement of long-time use of the composite material in a high-temperature environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention adopts raw material powder to react in situ on the surface of the carbon/carbon composite material by utilizing the ultra-high-speed laser cladding technology to form an interface MAX phase layer. By means of the toughness of the MAX phase, the problems of cracking and peeling of the coating at high temperature are solved, meanwhile, the matrix carbon participates in the in-situ reaction of the surface, the coating and the matrix are chemically combined, and the binding force of the coating and the matrix is enhanced.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a carbon/carbon composite material high-temperature oxidation-resistant coating by in-situ reaction is characterized by comprising the following steps:
the method comprises the following steps: and ball-milling one of Ti powder, Si powder and Al powder and graphite powder in a ball mill, and drying to obtain mixed powder.
Step two: cleaning the surface of the carbon/carbon composite material substrate by adopting alcohol, and baking in an oven.
Step three: and (3) mixing the mixed powder dried in the step one with resin, and brushing the mixture on the surface of the carbon/carbon composite material substrate in the step two.
Step four: and (3) placing the carbon/carbon composite material substrate coated in the third step on a worktable of an ultra-high-speed laser cladding machine for fixing, and turning on an equipment switch for coating treatment to obtain the carbon/carbon composite material high-temperature antioxidant coating.
The preparation method of the carbon/carbon composite material high-temperature antioxidant coating is characterized in that the mixing weight ratio of the Ti powder, the Si powder or the Al powder and the graphite powder in the step one is that the Ti powder accounts for 40-60 wt.%, the Si powder or the Al powder accounts for 10-30 wt.%, and the graphite powder accounts for 30-50 wt.%.
The preparation method of the carbon/carbon composite material high-temperature oxidation-resistant coating is characterized in that the mixed powder in the step one is subjected to ball milling, and the particle size is 10-80 microns.
The preparation method of the carbon/carbon composite material high-temperature oxidation-resistant coating is characterized in that the drying temperature in the step one is 80-200 ℃, and the drying time is 1.0-6.0 h.
The preparation method of the carbon/carbon composite material high-temperature oxidation resistant coating is characterized in that the baking temperature in the step two is 60-180 ℃, and the baking time is 3-6 h.
The preparation method of the carbon/carbon composite material high-temperature oxidation-resistant coating is characterized in that the weight mixing ratio of the mixed powder to the resin in the step three is 2-10: 1; the coating thickness is 20-120 μm.
The preparation method of the carbon/carbon composite material high-temperature antioxidant coating is characterized in that in the fourth step, a cladding head of an ultra-high-speed laser cladding machine is protected by argon, the laser cladding power is 30W-220W, the moving speed of the cladding head is 2mm/s-18mm/s, the lap joint rate is 40% -60%, and after in-situ reaction, a MAX phase and ceramic mixed antioxidant coating is formed on the surface of the carbon/carbon composite material.
Compared with the prior art, the invention has the following advantages:
1. the method is characterized in that raw material powder is adopted to react in situ on the surface of a carbon/carbon composite material by utilizing an ultrahigh-speed laser cladding technology to form an interface MAX phase layer. By means of the toughness of the MAX phase, the problems of cracking and peeling of the coating at high temperature are solved, meanwhile, the matrix carbon participates in the in-situ reaction of the surface, the coating and the matrix are chemically combined, and the binding force of the coating and the matrix is enhanced.
2. The MAX phase coating is prepared on the surface of the carbon/carbon composite material by adopting an ultra-high-speed laser cladding method, so that the process not only enhances the interface bonding strength of the coating and the matrix, but also can locally repair the coating on the surface of the matrix at any time; on the other hand, the preparation period of the process method is short, and the process method has high working efficiency compared with the traditional process means such as magnetron sputtering and high-temperature sintering of coatings.
Drawings
FIG. 1 is a block diagram of the process flow for preparing a carbon/carbon composite high-temperature oxidation-resistant coating according to the present invention;
FIG. 2 is an XRD analysis of the coating of example 1 of the present invention;
FIG. 3 is an XRD analysis of the coating of example 2 of the present invention;
figure 4 is an XRD analysis pattern of the coating of example 3 of the present invention.
Detailed Description
Example 1
The method comprises the following steps: ti powder, Si powder and graphite powder are used as main raw materials, wherein the Ti powder accounts for 40 wt.%, the Si powder accounts for 30 wt.%, and the graphite powder accounts for 30 wt.%.
Step two: and (3) ball-milling the raw material powder in the step one in a ball mill to obtain mixed powder with the particle size of 10 microns.
Step three: and (5) drying the mixed powder subjected to ball milling in the step two in a drying oven at the drying temperature of 80 ℃ for 6.0 h.
Step four: the surface of the carbon/carbon composite material nozzle tube substrate with the density of 1.70g/cm3 is cleaned by alcohol and baked for 3 hours in an oven at 180 ℃.
Step five: mixing the mixed powder dried in the third step with phenolic resin, wherein the weight mixing ratio of the mixed powder to the phenolic resin is 2: and 1, brushing the mixture on the surface of the carbon/carbon composite material substrate in the step four, wherein the brushing thickness is 20 mu m.
Step six: and C, placing the carbon/carbon composite material substrate coated in the step five on a worktable of an ultra-high speed laser cladding machine for fixing, opening a switch of equipment for coating treatment, wherein a cladding head of the ultra-high speed laser cladding machine is protected by argon gas, the laser cladding power is 30W, the moving speed of the cladding head is 2mm/s, and the lap joint rate is 40%, so that the carbon/carbon composite material high-temperature oxidation-resistant coating is prepared.
The prepared coating has the following properties: the aperture ratio is less than or equal to 2.0 percent, the strength grade of the coating tested by a scratch method is more than or equal to 2 grade, the coating has no defects of cracking, bulging and the like, and the weight loss ratio in an aerobic atmosphere at 1500 ℃ for 1 hour is less than or equal to 1.5 percent.
As can be seen from the XRD analysis of FIG. 2, Ti was formed in the coating3SiC2The TiC and SiC ceramics also have oxidation resistance, so the overall oxidation resistance of the coating is not influenced by the impurities.
Example 2
The method comprises the following steps: ti powder, Si powder and graphite powder are used as main raw materials, wherein the Ti powder accounts for 60 wt.%, the Si powder accounts for 20 wt.%, and the graphite powder accounts for 20 wt.%.
Step two: and (3) ball-milling the raw material powder in the step (I) in a ball mill to obtain mixed powder with the particle size of 40 um.
Step three: and (5) drying the mixed powder subjected to ball milling in the step two in a drying oven at the drying temperature of 150 ℃ for 3.0 h.
Step four: the surface of the throat liner substrate made of the carbon/carbon composite material with the density of 1.80g/cm3 is cleaned by alcohol and baked for 5 hours in an oven at 80 ℃.
Step five: mixing the mixed powder dried in the step three with epoxy resin, wherein the weight mixing ratio of the powder to the epoxy resin is 5: and 1, brushing the mixture on the surface of the carbon/carbon composite material substrate in the step four, wherein the brushing thickness is 80 mu m.
Step six: and C, placing the carbon/carbon composite material substrate coated in the step five on a worktable of an ultra-high speed laser cladding machine for fixing, opening a switch of equipment for coating treatment, wherein a cladding head of the ultra-high speed laser cladding machine is protected by argon gas, the laser cladding power is 110W, the moving speed of the cladding head is 10mm/s, and the lap joint rate is 50%, so that the carbon/carbon composite material high-temperature oxidation-resistant coating is prepared.
The prepared coating has the following properties: the aperture ratio is less than or equal to 1.8 percent, the strength grade of the coating tested by a scratch method is more than or equal to grade 2, the coating has no defects of cracking, bulging and the like, and the weight loss ratio in an aerobic atmosphere at 1500 ℃ for 1 hour is less than or equal to 1.2 percent.
As can be seen from the XRD analysis chart of FIG. 3, the MAX phase material of Ti3SiC2 and TiC impure phase are generated in the coating, and the TiC ceramic also has oxidation resistance, so that the overall oxidation resistance of the coating is not influenced by the impure phase.
Example 3
The method comprises the following steps: ti powder, Al powder and graphite powder are used as main raw materials, wherein the Ti powder accounts for 50 wt.%, the Al powder accounts for 20 wt.%, and the graphite powder accounts for 30 wt.%.
Step two: and (3) ball-milling the raw material powder in the step one in a ball mill to obtain mixed powder with the particle size of 80 microns.
Step three: and (5) drying the mixed powder subjected to ball milling in the step two in a drying oven at the drying temperature of 200 ℃ for 1.0 h.
Step four: the surface of the throat liner substrate made of the carbon/carbon composite material with the density of 1.85g/cm3 is cleaned by alcohol and baked for 6 hours in an oven at 60 ℃.
Step five: mixing the powder dried in the third step with phenolic resin, wherein the weight mixing ratio of the powder to the phenolic resin is 10: and 1, coating the mixture on the surface of the carbon/carbon composite material substrate in the fourth step, wherein the coating thickness is 120 mu m.
Step six: and C, placing the carbon/carbon composite material substrate coated in the step five on a worktable of an ultra-high speed laser cladding machine for fixing, opening a switch of equipment for coating treatment, wherein a cladding head of the ultra-high speed laser cladding machine is protected by argon gas, the laser cladding power is 220W, the moving speed of the cladding head is 18mm/s, and the lap joint rate is 60%, so that the carbon/carbon composite material high-temperature oxidation-resistant coating is prepared.
The prepared coating has the following properties: the aperture ratio is less than or equal to 1.8 percent, the strength grade of the coating tested by a scratch method is more than or equal to grade 2, the coating has no defects of cracking, bulging and the like, and the weight loss ratio in an aerobic atmosphere at 1500 ℃ for 1 hour is less than or equal to 1.0 percent.
From the XRD analysis of fig. 4, it can be seen that MAX phase material of Ti3AlC2 is generated in the coating, and Ti3AlC2 has good oxidation resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A method for preparing a carbon/carbon composite material high-temperature oxidation-resistant coating by in-situ reaction is characterized by comprising the following steps:
the method comprises the following steps: placing one of Ti powder, Si powder and Al powder and graphite powder in a ball mill for ball milling and drying to obtain mixed powder;
step two: cleaning the surface of the carbon/carbon composite material substrate by adopting alcohol, and baking in an oven;
step three: mixing the mixed powder dried in the step one with resin, and brushing the mixture on the surface of the carbon/carbon composite material substrate in the step two;
step four: and (3) placing the carbon/carbon composite material substrate coated in the third step on a worktable of an ultra-high-speed laser cladding machine for fixing, and turning on an equipment switch for coating treatment to obtain the carbon/carbon composite material high-temperature antioxidant coating.
2. The method for preparing a carbon/carbon composite high-temperature oxidation-resistant coating through in-situ reaction as claimed in claim 1, wherein in the first step, the weight ratio of the Ti powder, the Si powder or the Al powder and the graphite powder is 40 wt.% to 60 wt.%, 10 wt.% to 30 wt.% and 30 wt.% to 50 wt.% respectively.
3. The method for preparing a carbon/carbon composite high-temperature oxidation-resistant coating through in-situ reaction as claimed in claim 1, wherein in the step one, the mixed powder has a particle size of 10 μm to 80 μm after ball milling.
4. The method for preparing a carbon/carbon composite material high-temperature oxidation-resistant coating through in-situ reaction as claimed in claim 1, wherein in the step one, the drying temperature is 80-200 ℃, and the drying time is 1.0-6.0 h.
5. The method for preparing a carbon/carbon composite material high-temperature oxidation resistant coating through in-situ reaction as claimed in claim 1, wherein in the second step, the baking temperature is 60-180 ℃, and the baking time is 3-6 h.
6. The method for preparing the carbon/carbon composite material high-temperature oxidation-resistant coating through the in-situ reaction in the claim 1, wherein in the third step, the mixing ratio of the mixed powder to the resin is 2-10: 1; the coating thickness is 20-120 μm.
7. The method for preparing the carbon/carbon composite material high-temperature oxidation resistant coating through the in-situ reaction as claimed in claim 1, wherein in the fourth step, the ultra-high speed laser cladding machine cladding head has argon protection, the laser cladding power is 30W-220W, the moving speed of the cladding head is 2mm/s-18mm/s, the lap joint rate is 40% -60%, and after the in-situ reaction, a MAX phase and ceramic mixed oxidation resistant coating is formed on the surface of the carbon/carbon composite material.
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| CN113526983A (en) * | 2020-04-16 | 2021-10-22 | 清华大学 | Composite high-temperature oxidation-resistant coating of graphite material for nuclear reactor and preparation method thereof |
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2021
- 2021-12-28 CN CN202111626459.9A patent/CN114315420A/en not_active Withdrawn
Patent Citations (7)
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| US20070172659A1 (en) * | 2006-01-26 | 2007-07-26 | Shao Richard L | Anti-oxidation coating for carbon composites |
| CN104018155A (en) * | 2014-06-06 | 2014-09-03 | 江苏大学 | Method for preparing Ti-Si-C coating on surface of titanium metal |
| CN105036801A (en) * | 2015-07-17 | 2015-11-11 | 常州大学 | Carbon/carbon composite material surface high temperature oxidation resistant coating and preparation method thereof |
| CN111455375A (en) * | 2020-04-08 | 2020-07-28 | 西北工业大学 | Method for repairing SiC coating of carbon/carbon composite material |
| CN113526983A (en) * | 2020-04-16 | 2021-10-22 | 清华大学 | Composite high-temperature oxidation-resistant coating of graphite material for nuclear reactor and preparation method thereof |
| CN112608168A (en) * | 2020-12-18 | 2021-04-06 | 江西信达航科新材料科技有限公司 | High-temperature-resistant and oxidation-resistant ceramic coating and preparation method thereof |
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Non-Patent Citations (1)
| Title |
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| H YANG ET AL.: "Ti3SiC2-TiC-Si Antioxidant Coating Prepared on SiC coated MG Spheres of HTR Fuel Element by Molten Salt Technique", 《INTERNATIONAL CONFERENCE ON HIGH TEMPERATURE REACTOR TECHNOLOGY》 * |
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Application publication date: 20220412 |