CN114874028A - Long-time oxidation-resistant ablation HfB of C/C composite material 2 -SiC-TaSi 2 Method for producing a coating - Google Patents
Long-time oxidation-resistant ablation HfB of C/C composite material 2 -SiC-TaSi 2 Method for producing a coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002679 ablation Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000005475 siliconizing Methods 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 230000007774 longterm Effects 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 38
- 239000005011 phenolic resin Substances 0.000 claims description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
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- 238000000034 method Methods 0.000 abstract description 19
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000001000 micrograph Methods 0.000 description 2
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- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
The invention relates to a long-time oxidation-resistant ablation HfB of a C/C composite material 2 ‑SiC‑TaSi 2 The preparation method of the coating comprises the step of preparing HfB on the surface of the C/C composite material by a slurry coating auxiliary high-temperature gas phase siliconizing method 2 ‑SiC‑TaSi 2 And (4) coating. The specific process is as follows: cleaning the C/C composite material and drying for later use; preparation of resin-SiC inner precoat and resin-HfB by slurry coating on C/C composite material surface 2 ‑SiC‑TaSi 2 An outer precoat layer; HfB obtained by high-temperature carbonization-gas phase siliconizing method 2 ‑SiC‑TaSi 2 And (4) coating. In HfB 2 Adding a proper amount of TaSi into the-SiC coating 2 Increase the coating heightThe oxygen resistance and stability of the glass phase generated on the warm surface enable the coating to have good long-term ablation resistance. The slurry coating is combined with the high-temperature gas-phase siliconizing method, and the thermal expansion mismatching of the coating and the C/C matrix is relieved and HfB is realized through the reasonable control of the components, the content and the thickness of the precoating layer 2 、TaSi 2 And (4) controlling the content. The slurry coating and high-temperature gas phase siliconizing method improves the compactness of the coating and the binding property with the C/C matrix by regulating and controlling the particle size and the resin content.
Description
Technical Field
The invention belongs to the technical field of C/C composite material coatings, and relates to a long-time oxidation-resistant ablation HfB of a C/C composite material 2 -SiC-TaSi 2 A method for preparing the coating.
Background
Carbon/carbon (C/C) composite materials are composite materials prepared by taking carbon fibers and fabrics thereof as reinforcing materials and carbon (or graphite) as a matrix through densification and graphitization treatment, and are widely applied to the field of aerospace due to low density, low thermal expansion coefficient and excellent high-temperature performance. But it is very easy to be oxidized in high temperature aerobic environment, and this oxidation sensitivity severely limits its application range. The high-temperature coating technology is an effective method for improving the oxidation resistance of the C/C composite material.
In recent years, the high-temperature coating on the surface of the C/C composite material is mainly ceramic coating, and the SiC can generate compact SiO under high temperature because of the similar thermal expansion coefficient of the SiC and the C/C composite material 2 And a glass layer for protecting the substrate from oxidation and becoming the main coating material. But when the temperature exceeds 1500 ℃, SiO 2 The stability of the glass layer is reduced and the oxidation resistance of the SiC coating is limited.
HfB 2 The high-temperature protective coating has excellent comprehensive properties such as high melting point, high strength and high hardness, and the introduction of the high-temperature protective coating into the SiC coating is an effective method for improving the high-temperature thermal protection stability of the SiC coating. Article "Wang P, Li H, Jia Y, et al. approximation resistance of HfB 2 -SiC coating prepared by in-situ reaction method for SiC coated C/C composites[J]Ceramics International,2017,43(15):12005-12012. "preparation of HfB on the surface of C/C composite material by embedding method 2 -a SiC coating having a heat flux density of 2400kW/m 2 The coating C/C composite material is formed after the material is ablated for 60s in oxyacetylene flameThe quantitative and linear ablation rates were 0.147mg/s and 0.267 μm/s, which were reduced by 21.8% and 60.0%, respectively, compared to the SiC coating. But HfB 2 The long-term ablation resistance of the SiC coating is weak, the effective protection time of the coating is short in an oxyacetylene flame ablation environment, the uniformity and the component content of the coating generated by the embedding reaction are difficult to control, and the performance stability of the material is easily influenced. Document two "Feng G, Li H, Yao X, et al. approximation resistance of TaC-modified HfC coating prepared by super sonic plasma spraying for SiC-coated carbon/carbon composites [ J]Ceramics International,2019,45(14):17936-17945. "preparation of HfC-TaC coating on the surface of SiC-embedded C/C composite by plasma spraying method at heat flux density of 2.38MW/m 2 The mass and the line ablation rate of the material ablated for 60s under oxyacetylene flame are respectively-0.35 mg/s and-1.05 mu m/s. Ta oxide and HfO in high temperature environment 2 Reaction to form Hf 6 Ta 2 O 17 The phase not only has relatively high melting point, but also can reduce damage caused by phase change, which shows that the protective effect of the coating can be improved by adding a proper amount of tantalum-based compound into the coating. However, the porosity of the coating prepared by the plasma spraying method is high, and the binding capacity with the matrix needs to be improved.
For the problems of coating compactness and binding with the matrix, the document three "Jiang Y, Liu T, Ru H, et al 2 -SiC-Si/SiC-Si coating for graphite materials[J]Journal of Alloys and Compounds,2019,782:761- 2 SiC coating which bonds well to the substrate and has a heat flow density of 2.38MW/m 2 After ablation for 90s under oxyacetylene flame, the mass of the coating sample and the linear ablation rate were 0.36mg/s and-0.31 μm/s, respectively. The effective control of the high-temperature stability of the Hf oxidation product is realized, and the key is to further improve the long-term ablation performance of the coating. In addition, because the texture structure of the graphite material is relatively uniform, the microstructure of the C/C composite material is complex, carbon fibers, carbon matrixes, fiber/matrix interfaces and the like exist, and the combination is high if slurry coating is adoptedThe oxidation-resistant coating is prepared on the surface of the C/C by warm gas phase siliconizing, and the problem of matching and compatibility of the physical and chemical properties of the coating and a matrix needs to be effectively solved.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a long-time oxidation-resistant ablative HfB of a C/C composite material 2 -SiC-TaSi 2 The preparation method of the coating is used for improving the oxidation resistance and ablation resistance of the C/C composite material.
Technical scheme
Long-time oxidation-resistant ablation HfB of C/C composite material 2 -SiC-TaSi 2 The preparation method of the coating is characterized by comprising the following steps:
step 1: ultrasonically cleaning the C/C composite material by using absolute ethyl alcohol, and drying the C/C composite material for 2-4 hours in an electrothermal blowing dry box at the temperature of 60-100 ℃;
step 2: mixing 20-40 wt.% of SiC, 55-75 wt.% of absolute ethyl alcohol and 5-12 wt.% of phenolic resin to prepare SiC-phenolic resin slurry, and mixing 8-20 wt.% of SiC and 23-38 wt.% of HfB 2 4-10 wt.% of TaSi 2 42-62 wt.% of absolute ethyl alcohol and 4-10 wt.% of phenolic resin are mixed to prepare HfB 2 -SiC-TaSi 2 The prepared slurry is fully stirred and subjected to ultrasonic treatment until no obvious agglomerated particles exist in the slurry, and then the SiC-phenolic resin slurry and HfB are mixed 2 -SiC-TaSi 2 -completion of phenolic resin slurry preparation;
and step 3: in order to relieve the physical and chemical property difference and the thermal expansion coefficient mismatching between the C/C matrix and the outer coating, firstly, preparing a SiC inner coating on the surface of the C/C composite material in advance; soaking the C/C composite material into the SiC-phenolic resin slurry and then drying to obtain an internal SiC coating;
then, the C/C composite with SiC precoat was dipped into HfB 2 -SiC-TaSi 2 Phenolic resin slurry to obtain external HfB 2 -SiC-TaSi 2 Coating;
then, curing the coated C/C composite material for 2-5 h at 180-300 ℃, and then carrying out Ar gasCarbonizing at 900-1200 ℃ for 2-5 h in an atmosphere to obtain the resin carbon-HfB 2 -SiC-TaSi 2 Pre-coating;
and 4, step 4: will have resin carbon-HfB 2 -SiC-TaSi 2 Putting the pre-coated C/C composite material into a graphite crucible with a silicon block at the bottom for siliconizing treatment, heating at the speed of 5-10 ℃/min in Ar atmosphere, preserving the temperature at 1800-1900 ℃ for 10-40 min, and finally obtaining the material with HfB 2 -SiC-TaSi 2 Coated C/C composite materials.
The C/C composite material is prepared by adopting a density of 1.7-1.75 g/cm 3 2.5D-C/C composite material.
And (3) drying the soaked SiC-phenolic resin slurry in the step (3) in an oven at the temperature of 60-100 ℃.
Advantageous effects
The invention provides a long-time oxidation-resistant ablation HfB of a C/C composite material 2 -SiC-TaSi 2 The preparation method of the coating comprises the step of preparing HfB on the surface of the C/C composite material by a slurry coating auxiliary high-temperature gas phase siliconizing method 2 -SiC-TaSi 2 And (4) coating. The specific process is as follows: cleaning the C/C composite material and drying for later use; preparation of resin-SiC inner precoat and resin-HfB by slurry coating on C/C composite material surface 2 -SiC-TaSi 2 An outer precoat layer; HfB obtained by high-temperature carbonization-gas phase siliconizing method 2 -SiC-TaSi 2 And (4) coating.
1. In HfB 2 Adding a proper amount of TaSi into the-SiC coating 2 The oxygen resistance and stability of the glass phase generated on the high-temperature surface of the coating can be improved, so that the coating has good long-term ablation resistance.
2. Preparation of HfB by slurry coating and high-temperature gas-phase siliconizing 2 -SiC-TaSi 2 The coating can effectively relieve the thermal expansion mismatch between the coating and the C/C matrix and realize HfB through reasonable control of the components, content and thickness of the precoating 2 、TaSi 2 And (4) effectively controlling the content.
3. Preparation of HfB by slurry coating combined with high-temperature gas-phase siliconizing method 2 -SiC-TaSi 2 During the coating process, HfB can be regulated and controlled 2 、TaSi 2 SiC particlesSize and resin content, a reasonable precoating pore structure is obtained, so that gas-phase Si can permeate and react in situ conveniently, and the compactness of the coating and the binding property of the coating and a C/C matrix are improved.
Drawings
FIG. 1 is a process flow diagram of the present invention
FIG. 2 shows the resin carbon-HfB after high temperature carbonization 2 -SiC-TaSi 2 Micrographs of precoat
FIG. 3 shows HfB after Si infiltration 2 -SiC-TaSi 2 Micrographs of the coating
FIG. 4 shows HfB 2 -SiC-TaSi 2 XRD pattern of coating
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example one
Step 1, using a density of 1.75g/cm 3 The 2.5D-C/C composite material is processed into a test sample with the size of 10mm multiplied by 10mm, and in order to prevent the edge of the test sample from peeling off due to stress concentration at the corner of the test sample, the edge of the test sample needs to be subjected to pre-chamfering treatment by using 400-mesh SiC sand paper. Ultrasonically cleaning the polished C/C composite material by absolute ethyl alcohol, and drying for 2 hours in an electrothermal blowing dry box at the temperature of 70 ℃.
Step 3, to mitigate the physicochemical property differences and coefficient of thermal expansion mismatch between the C/C substrate and the overcoat, the C/C substrate was first immersed in a SiC-phenolic resin slurry and dried in an oven at 70 ℃ to obtain a resin-SiC inner precoat. Then, the resin is added-SiC inter precoated C/C composite impregnated HfB 2 -SiC-TaSi 2 Phenol-formaldehyde resin slurries to obtain resin-HfB 2 -SiC-TaSi 2 An outer precoat layer. Thereafter, the coated sample was cured at 300 ℃ for 5h and then carbonized at 900 ℃ for 2h in an Ar gas atmosphere to obtain resin carbon-HfB 2 -SiC-TaSi 2 And (4) precoating.
Step 4, carrying resin carbon-HfB 2 -SiC-TaSi 2 Putting the pre-coated C/C composite material into a graphite crucible with a silicon block at the bottom for siliconizing treatment, heating at the speed of 5 ℃/min in Ar atmosphere, and preserving the temperature at 1800 ℃ for 30min to finally obtain the material with HfB 2 -SiC-TaSi 2 Coated C/C composite materials.
HfB obtained in this example 2 -SiC-TaSi 2 After static oxidation of the coating at 1700 ℃ for 262h, the weight loss is only 0.56%. And HfB prepared by embedding method 2 The mass loss of the-SiC coating reaches 2.53 percent after the-SiC coating is oxidized for 48 hours at 1700 ℃, and the HfB prepared by the slurry coating auxiliary embedding method 2 The mass loss of the-SiC coating after the oxidation at 1700 ℃ for 156h is 1.65%. [ ZHou L, ZHang J, Hu D, et al. high temperature oxidation and inhibition viruses of HfB 2 -SiC/SiC coatings for carbon/carbon composites fabricated by dipping-carbonization assisted pack cementation[J].Journal of Materials Science&Technology,2022,111:88-98.]。
Example two
Step 1, using a density of 1.75g/cm 3 The 2.5D-C/C composite material is processed into a cylindrical sample with the size of phi 30mm multiplied by 5mm, is ultrasonically cleaned by absolute ethyl alcohol and is dried for 4 hours in an electrothermal blowing dry box with the temperature of 100 ℃.
And 3, firstly, preparing a SiC inner coating on the surface of the C/C composite material in advance in order to relieve the difference of physical and chemical properties and the mismatch of thermal expansion coefficients between the C/C matrix and the outer coating. The C/C matrix was immersed in a SiC-phenolic resin slurry and dried in an oven at 70 ℃ to obtain a resin-SiC inner precoat. Then, the composite material is dipped into HfB 2 -SiC-TaSi 2 Obtaining resin-HfB from phenol-formaldehyde resin slurry 2 -SiC-TaSi 2 An outer precoat layer. Thereafter, the coated sample was cured at 180 ℃ for 3h and then carbonized at 900 ℃ for 5h in an Ar gas atmosphere to obtain resin carbon-HfB 2 -SiC-TaSi 2 And (4) precoating.
Step 4, the resin carbon-HfB is added 2 -SiC-TaSi 2 Putting the pre-coated C/C composite material into a graphite crucible with a silicon block at the bottom for siliconizing treatment, heating at the speed of 5 ℃/min in Ar atmosphere, and preserving the temperature at 1900 ℃ for 15min to finally obtain the material with HfB 2 -SiC-TaSi 2 Coated C/C composite materials.
At a heat flux density of 2.38MW/m 2 By ablation of 360s, HfB under oxyacetylene flame 2 -SiC-TaSi 2 The line ablation rate and the mass ablation rate of the coating are respectively-0.550 mu m/s and-0.012 mg/s, HfB 2 The line ablation rate and the mass ablation rate of the SiC coating are-0.889 μm/s and-0.01 mg/s, respectively, HfB 2 -SiC-TaSi 2 Coating is HfB 2 The line ablation rate of the SiC coating is improved by 61.636%, and the mass ablation rate is improved by 16.667%.
EXAMPLE III
Step 1, use the density of 1.7g/cm 3 The 2.5D-C/C composite material of (1) was processed into a test piece having a size of φ 30mm × 5mm, and in order to prevent the peeling of the coating due to stress concentration at the corners of the test piece, it was necessary to pre-chamfer the edges of the test piece with 400 mesh SiC paper. Ultrasonically cleaning the polished C/C composite material by absolute ethyl alcohol, and drying for 4 hours in an electrothermal blowing dry box at the temperature of 60 ℃.
Step 3, to mitigate the physicochemical property difference and thermal expansion coefficient mismatch between the C/C substrate and the overcoat, the C/C substrate was first immersed in a SiC-phenolic resin slurry and dried in an oven at 60 ℃ to obtain a resin-SiC inner precoat. Then, the C/C composite with the resin-SiC internal precoat was dipped into HfB 2 -SiC-TaSi 2 Phenol-formaldehyde resin slurries to obtain resin-HfB 2 -SiC-TaSi 2 An outer precoat layer. Thereafter, the coated sample was cured at 200 ℃ for 3h and then carbonized at 1200 ℃ for 3h in an Ar gas atmosphere to obtain resin carbon-HfB 2 -SiC-TaSi 2 And (4) precoating.
Step 4, carrying resin carbon-HfB 2 -SiC-TaSi 2 Putting the pre-coated C/C composite material into a graphite crucible with a silicon block at the bottom for siliconizing treatment, heating at the speed of 10 ℃/min in Ar atmosphere, and preserving the temperature at 1900 ℃ for 15min to finally obtain the material with HfB 2 -SiC-TaSi 2 Coated C/C composite materials.
At a heat flux density of 2.38MW/m 2 The sample was ablated in oxyacetylene flame for 90 s.times.4 times, and the linear and mass ablation rates were-0.564 μm/s and 0.0025mg/s, respectively.
Claims (3)
1. Long-time oxidation ablation resistant HfB of C/C composite material 2 -SiC-TaSi 2 The preparation method of the coating is characterized by comprising the following steps:
step 1: ultrasonically cleaning the C/C composite material by using absolute ethyl alcohol, and drying the C/C composite material for 2-4 hours in an electrothermal blowing dry box at the temperature of 60-100 ℃;
step 2: 20-40wt.% SiC, 55-75 wt.% of absolute ethyl alcohol and 5-12 wt.% of phenolic resin are mixed to prepare SiC-phenolic resin slurry, 8-20 wt.% of SiC and 23-38 wt.% of HfB 2 4-10 wt.% of TaSi 2 42-62 wt.% of absolute ethyl alcohol and 4-10 wt.% of phenolic resin are mixed to prepare HfB 2 -SiC-TaSi 2 The prepared slurry is fully stirred and subjected to ultrasonic treatment until no obvious agglomerated particles exist in the slurry, and then the SiC-phenolic resin slurry and the HfB are mixed 2 -SiC-TaSi 2 -completion of phenolic resin slurry preparation;
and step 3: in order to relieve the physical and chemical property difference and the thermal expansion coefficient mismatching between the C/C matrix and the outer coating, firstly, preparing a SiC inner coating on the surface of the C/C composite material in advance; soaking the C/C composite material into the SiC-phenolic resin slurry and then drying to obtain an internal SiC coating;
then, the C/C composite with SiC precoat is dipped into HfB 2 -SiC-TaSi 2 Phenolic resin slurry to obtain external HfB 2 -SiC-TaSi 2 Coating;
then, curing the coated C/C composite material at 180-300 ℃ for 2-5 h, and then carbonizing the composite material at 900-1200 ℃ for 2-5 h in Ar atmosphere to obtain resin carbon-HfB 2 -SiC-TaSi 2 Pre-coating;
and 4, step 4: will have resin carbon-HfB 2 -SiC-TaSi 2 Putting the pre-coated C/C composite material into a graphite crucible with a silicon block at the bottom for siliconizing treatment, heating at the speed of 5-10 ℃/min in Ar atmosphere, preserving the temperature at 1800-1900 ℃ for 10-40 min, and finally obtaining the material with HfB 2 -SiC-TaSi 2 Coated C/C composite materials.
2. The C/C composite of claim 1 long term ablation HfB oxidation resistance 2 -SiC-TaSi 2 The preparation method of the coating is characterized by comprising the following steps: the C/C composite material is prepared by adopting a density of 1.7-1.75 g/cm 3 2.5D-C/C composite material.
3. The C/C composite of claim 1 resistant to long term burnoutEtched HfB 2 -SiC-TaSi 2 The preparation method of the coating is characterized by comprising the following steps: and (4) drying the SiC-phenolic resin slurry immersed in the step (3) in a drying oven at the temperature of 60-100 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818426A (en) * | 2019-12-18 | 2020-02-21 | 中国矿业大学 | HfB on surface of carbon material2-TaSi2Preparation method of-SiC oxidation resistant coating |
| CN112409025A (en) * | 2020-11-25 | 2021-02-26 | 西北工业大学 | Has SiC-HfB2Preparation method of carbon/carbon composite material of-Si single-layer composite coating |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818426A (en) * | 2019-12-18 | 2020-02-21 | 中国矿业大学 | HfB on surface of carbon material2-TaSi2Preparation method of-SiC oxidation resistant coating |
| CN112409025A (en) * | 2020-11-25 | 2021-02-26 | 西北工业大学 | Has SiC-HfB2Preparation method of carbon/carbon composite material of-Si single-layer composite coating |
Non-Patent Citations (7)
| Title |
|---|
| LEI ZHOU等: "A dense ZrB2-SiC-Si/SiC-Si coating to protect carbon/carbon composites against oxidation at 1773 K and 1973 K", pages 2 * |
| LEI ZHOU等: "Investigation on the oxidation and ablation behaviors of HfB2-SiC-Si/SiC-Si coatings for carbon/carbon composites", pages 2 * |
| MENGLIN ZHANG等: "Oxidation inhibition behaviors of the HfB2-SiC-TaSi2 coating for carbon structural materials at 1700℃", pages 1 * |
| 付前刚等: "C/C复合材料表面耐高温抗氧化硅基陶瓷涂层研究进展" * |
| 向秋玲;汤振霄;彭可;易茂中;: "HfB_2-ZrB_2-SiC改性C/C复合材料的制备及性能", no. 02 * |
| 成来飞等: "《复合材料原理及工艺》", 西北工业大学出版社, pages: 172 - 173 * |
| 李淑萍;李克智;郭领军;: "碳/碳复合材料SiCHfSi_2TaSi_2抗烧蚀复合涂层", no. 05 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286402A (en) * | 2022-07-12 | 2022-11-04 | 中国科学院上海硅酸盐研究所 | High-temperature-resistant ablation-resistant composite coating and preparation method thereof |
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