CN102674892B - Carbon/carbon composite ultrahigh temperature anti-oxidation coating and preparation process thereof - Google Patents
Carbon/carbon composite ultrahigh temperature anti-oxidation coating and preparation process thereof Download PDFInfo
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- CN102674892B CN102674892B CN201210176551.4A CN201210176551A CN102674892B CN 102674892 B CN102674892 B CN 102674892B CN 201210176551 A CN201210176551 A CN 201210176551A CN 102674892 B CN102674892 B CN 102674892B
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Abstract
The invention provides a carbon/carbon composite ultrahigh temperature anti-oxidation coating which is composed of ZrB2, HfC, SiC, TiB2 and Sc2O3 in a certain volume percentage. In addition, the invention also provides a preparation process of the carbon/carbon composite ultrahigh temperature anti-oxidation coating. The process comprises the steps of 1, conducting grinding, polishing, washing and drying on a carbon/carbon composite; 2, conducting ball milling on the ZrB2, the HfC, the SiC, the TiB2, the Sc2O3 and an organic solvent to obtain slurry; 3, coating the slurry on the surface of the carbon/carbon composite to obtain a slurry coating; and 4, sintering the carbon/carbon composite with the slurry coating on the surface by an electron beam, and obtaining the carbon/carbon composite ZrB2-HfC-SiC-TiB2-Sc2O3 coating. The coating prepared according to the process is compact, uniform, good in mechanical property, high in binding strength with a carbon/carbon composite substrate and capable of effectively improving the ultrahigh temperature anti-oxidation performance of the carbon/carbon composite.
Description
Technical field
The invention belongs to anti-oxidant technical field of inorganic material, be specifically related to a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating and preparation method thereof.
Background technology
Carbon/carbon compound material has the high special performance going up not down with the rising of temperature than the performance of strong, Gao Bimo, low density, low thermal coefficient of expansion, heat shock resistance and mechanical strength, is at present uniquely can under temperature is the ultra-high temperature condition of 1800 ℃～2500 ℃, keep higher force to learn the material of performance.Yet although carbon/carbon compound material has many good performances under ultra-high temperature condition, it oxidizing reaction very easily occurs in temperature in higher than the aerobic environment of 400 ℃, cause the over-all properties of carbon/carbon compound material to decline.
Material ultrahigh temperature oxidation resistant coating is the important channel of improving carbon/carbon compound material ultrahigh-temperature antioxidant property.ZrB
2fusing point up to 3245 ℃, be the desirable material ultrahigh temperature oxidation resistant coating material of carbon/carbon compound material.
Document 1 (E. L. Corral, R. E. Loehman. Ultra-high-temperature ceramic coatings for oxidation protection of Carbon – Carbon composites.Journal of American Ceramic Society, 2008,91 (5): 1495-1502) with document 2 (Niu Yaran, Zheng Xuebin, Ding Chuanxian. the preparation of plasma spraying high-temperature oxidation resistant coating and sign. hot-spraying techniques, 2011,3 (3): 1-10) all by adding SiC to improve ZrB
2antioxidant property.Document 3 (D. Sciti, F. Monteverde, S. Guicciardi et al.Microstructure and mechanical properties of ZrB
2-MoSi
2ceramic composites produced by different sintering techniques.Materials Science and Engineering A, 2006,434:303-309) by adding MoSi
2improve ZrB
2antioxidant property.Yet under ultra-high temperature condition, ZrB
2-SiC and ZrB
2-MoSi
2oxidation products all there is the defects such as viscosity is low, vaporator rate is fast, diffusion coefficient is high, cause ZrB
2-SiC and ZrB
2-MoSi
2rate of oxidation too fast.
Document 4 (Han Jiecai, Hu Ping, the .LaB such as Zhang Xinghong
6interpolation to ZrB
2the impact of-SiC based ultra-high temperature stupalith oxidation susceptibility. the academic conference of The Chinese Society of Theoretical and Applied Mechanics, 2007) by adding SiC, LaB
6improve ZrB
2antioxidant property.Document 5 (Li Xueying, Zhang Xinghong, the .Y such as Han Jiecai
2o
3doping ZrB
2the Burning corrosion resistance energy of-SiC based ultra-high temperature pottery. Rare Metals Materials and engineering, 2011,40 (5): 820-823) by adding SiC, Y
2o
3improve ZrB
2antioxidant property.Document 6 (Zhang Weigang. the wide temperature range self-healing anti-oxidation of carbon/carbon compound material. Chinese material progress, 2011,30 (11): 25-31) with document 7 (V. Medri, F. Monteverde, A. Balbo, et al.Comparison of ZrB
2-ZrC-SiC composites fabricated by spark plasma sintering and hot-pressing.Advanced Engineering Materials, 2005,7 (3): 159-163) by adding SiC, ZrC to improve ZrB
2antioxidant property.Document 8 (F. Monteverde, A. Bellosi, L. Scatteia. Processing and properties of ultra-high temperature ceramics for space applications.Materials Science and Engineering A, 2008,485:415-421) by adding SiC, HfB
2improve ZrB
2antioxidant property.Although document 4 to 8 has improved the viscosity of oxidation products, has reduced the vaporator rate of oxidation products, but still there is the defects such as diffusion coefficient height of oxidation products, cause coating to lose efficacy because of too fast oxidation.
In addition, when the ceramic precursor cleavage method described in adopting document 1 or document 6 is prepared the multi-element coating that contains anti-oxidant wild phase, because ceramic precursor cracking generally occurs in 1100 ℃～1500 ℃, ZrB
2-SiC or ZrB
2the bonding strength of-ZrC-SiC and anti-oxidant wild phase is low, and the easy unsticking of anti-oxidant wild phase lost efficacy.
When described in adopting document 2, method is prepared the multi-element coating that contains anti-oxidant wild phase, because the spray distance of traditional plasma spraying technology is far away, anti-oxidant wild phase, ZrB
2be coagulation phase with SiC, manufactured coating is stratiform and vesicular structure, and the bonding strength of coating and matrix is low, and the density of coating is low, and ultrahigh-temperature antioxidant property is poor.
When described in adopting document 3, method is prepared the multi-element coating that contains anti-oxidant wild phase, pressureless sintering is difficult to realize the densification of material ultrahigh temperature oxidation resistant coating.
When the hot-pressing sintering method described in adopting document 4, document 5, document 7 and document 8 is prepared ternary coating, the high pressure in sintering process will damage carbon/carbon compound material.
Document 9 (Li Jun, Luo Ruiying, Zhang Renqin. solid state diffusion+EB-PVD legal system is studied for carbon/carbon compound material multilayer oxidation protection coating. charcoal element technology, 2007,26 (3): 1-5) adopt electro beam physics vapour deposition method to prepare Y
2o
3-Al
2o
3-SiC coating.The method is because to matrix, thereby heating does not make the coating of preparation be columnar crystal structure, and columnar grain, in the densification of ultrahigh-temperature generation recrystallize, causes coating to occur hole, during with other phase mixed deposit, is difficult to prepare the Carbide Phases of stoichiometric ratio.The ultrahigh-temperature antioxidant property of the multi-element coating that therefore, prepared by employing the method is poor.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating is provided.This coating is fine and close, evenly, mechanical property is good, high with the bonding strength of carbon/carbon compound material, can effectively improve the ultrahigh-temperature antioxidant property of carbon/carbon compound material.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, it is characterized in that, and by the one-tenth of following volume percent, be grouped into: ZrB
255%～70%, HfC 5%～10%, and SiC 10%～15%, TiB
27%～10%, Sc
2o
38%～10%; Described carbon/carbon compound material material ultrahigh temperature oxidation resistant coating refers to that this coating take carbon/carbon compound material as matrix, is to have oxidation-resistance under the condition of 1800 ℃～2500 ℃ in temperature.
Above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, is grouped into by the one-tenth of following volume percent: ZrB
257%～67%, HfC 6%～9%, and SiC 11%～14%, TiB
28%～10%, Sc
2o
38%～10%.
Above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, is grouped into by the one-tenth of following volume percent: ZrB
263%, HfC 7%, and SiC 12%, TiB
29%, Sc
2o
39%.
In addition, the present invention also provides a kind of method of preparing above-mentioned carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, it is characterized in that, the method comprises the following steps:
Step 1, by after carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder and Sc
2o
3powder by volume after percentage mix, is put into ball grinder ball milling 48h～72h with polyvinylpyrrolidone-ethanolic soln 1: 2 in mass ratio～5, obtains slip;
Step 3, slip described in step 2 is brushed equably or is sprayed in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 300 μ m～1000 μ m, is then placed in baking oven and dries;
Step 4, the vacuum chamber of electron beam furnace is put into in the surface after drying in step 3 with the carbon/carbon compound material of slurry coating, electron beam in vacuum chamber is heated to 2500～2700 ℃ by surface with the carbon/carbon compound material of slurry coating, keep naturally cooling to 25 ℃ of room temperatures after 0.5h～1h, obtaining thickness is the carbon/carbon compound material ZrB of 220 μ m～840 μ m
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa～2.0 * 10
-2pa.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, the process of sanding and polishing described in step 1 is: use successively the silicon carbide paper of No. 400, No. 600, No. 800 and No. 1200 by carbon/carbon compound material sanding and polishing.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, medium described in step 1 is acetone, dehydrated alcohol or deionized water.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, in step 2, the median size of each powder is respectively: ZrB
2the median size of powder is 1 μ m～2 μ m, and the median size of HfC powder is 1 μ m～2 μ m, and the median size of SiC powder is 0.05 μ m～1 μ m, TiB
2the median size of powder is 1 μ m～3 μ m, Sc
2o
3the median size of powder is 1 μ m～3 μ m.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, in step 2, the quality purity of each powder all >=99.6%.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, described in step 2, in polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 20%～40%.
The preparation method of above-mentioned a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, the processing parameter of the heating of electron beam described in step 4 carbon/carbon compound material is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 2A～3A, the heating power of electron beam is 38kW～63kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
The present invention compared with prior art has the following advantages:
(1) the present invention by adding TiB in component
2and Sc
2o
3, Melting point elevation, vaporator rate reduction, viscosity rising, the diffusion coefficient of outer oxide product borosilicate glass are reduced, make internal layer oxidation products ZrO
2and HfO
2melting point elevation, diffusion coefficient reduce, stable mutually, therefore can effectively improve the ultrahigh-temperature oxidation-resistance of carbon/carbon compound material.
(2) the present invention is first by ZrB
2, HfC, SiC, TiB
2, Sc
2o
3obtain slurry coating with the surface that sprays to carbon/carbon compound material after organic solvent mixing and ball milling, then adopt electron beam that surface is heated to high temperature with the carbon/carbon compound material of slurry coating, rely on bombardment effect, High temperature diffusion driving effect and the Sc of electron beam
2o
3shortly ooze effect, between each component of slurry coating and between slurry coating and carbon/carbon compound material, there is diffusion-sintering, the pinning effect of HfC phase, SiC phase can suppress again the overgrowth of crystal grain in sintering process simultaneously, therefore manufactured coating is fine and close evenly, mechanical property is good, high with the bonding strength of carbon/carbon compound material, preparation technology is to carbon/carbon composite material base body not damaged.
(3) the carbon/carbon compound material ZrB that adopts the present invention to prepare
2-HfC-SiC-TiB
2-Sc
2o
3the ultrahigh-temperature oxidation-resistance of coating is good, is placed in after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃, and linear ablative rate is only 0.16 μ m/s～0.25 μ m/s.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the profile scanning electromicroscopic photograph of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the embodiment of the present invention 1 preparation.
Fig. 2 is that the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the embodiment of the present invention 1 preparation is placed in the ablation center microstructure photo after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃.
Embodiment
Embodiment 1
The carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
270%, HfC 5%, and SiC 10%, TiB
27%, Sc
2o
38%.
The preparation method of the present embodiment is as follows:
Step 1, carbon/carbon compound material is used successively after the silicon carbide paper sanding and polishing of No. 400, No. 600, No. 800 and No. 1200, in dehydrated alcohol, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder, Sc
2o
3powder by volume after percentage mix, is put into ball grinder with polyvinylpyrrolidone-ethanolic soln in mass ratio at 1: 2, and ball milling 48h, obtains slip; In described polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 20%; In described, the median size size of each powder is respectively: ZrB
22 μ m, HfC 2 μ m, SiC 1 μ m, TiB
23 μ m, Sc
2o
33 μ m, quality purity is respectively ZrB
299.7%, HfC 99.7%, and SiC 99.9%, TiB
299.7%, Sc
2o
399.7%.
Step 3, slip described in step 2 is evenly painted in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 300 μ m, is then positioned in baking oven and dries;
Step 4, the vacuum chamber of electron beam furnace is put into the carbon/carbon compound material of slurry coating in surface in step 3, adopt electron beam that surface is heated to 2700 ℃ with the carbon/carbon compound material of slurry coating, insulation 0.5h, forms the carbon/carbon compound material ZrB that thickness is 220 μ m after naturally cooling to 25 ℃ of room temperatures
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 2.0 * 10
-2pa, the acceleration voltage of described electron beam is 21kV, and the heating current of electron beam is 2A, and the heating power of electron beam is 42kW, and the beam spot diameter, of electron beam is Ф 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3as shown in Figure 1, coating is fine and close, evenly and be combined well with carbon/carbon composite material base body for the profile scanning electromicroscopic photograph of coating.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3painting is placed in 2200 ℃ of oxy-acetylene flames the ablation center microstructure photo after oxidation ablation 300s as shown in Figure 2; the ablation center thick coating of 220 μ m is not ablated off by complete oxidation; the oxidation products film of coating solidifies the fine and close protective membrane of rear formation; be attached to the surface of carbon/carbon compound material, effectively improved the ultrahigh-temperature antioxidant property of carbon/carbon composite material base body.Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3the linear ablative rate of coating is only 0.16 μ m/s.
Embodiment 2
The carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
267%, HfC 6%, and SiC 11%, TiB
28%, Sc
2o
38%.
The preparation method of the present embodiment is as follows:
Step 1, carbon/carbon compound material is used successively after the silicon carbide paper sanding and polishing of No. 400, No. 600, No. 800 and No. 1200, in acetone, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder, Sc
2o
3powder by volume after percentage mix, is put into ball grinder ball milling 64h with polyvinylpyrrolidone-ethanolic soln in mass ratio at 1: 5, obtains slip; In described polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 24%; The median size of described each powder is respectively: ZrB
21 μ m, HfC 1 μ m, SiC 0.05 μ m, TiB
21 μ m, Sc
2o
31 μ m, quality purity is respectively ZrB
299.6%, HfC 99.6%, and SiC 99.6%, TiB
299.6%, Sc
2o
399.6%;
Step 3, slip described in step 2 is evenly sprayed in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 550 μ m, is then positioned in baking oven and dries;
Step 4, there is the carbon/carbon compound material of slurry coating to put into the vacuum chamber of electron beam furnace on surface in step 3, adopt electron beam that surface is heated to 2650 ℃ with the carbon/carbon compound material of slurry coating, insulation 1h, obtains the carbon/carbon compound material ZrB that thickness is 450 μ m after naturally cooling to 25 ℃ of room temperatures
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa, the acceleration voltage of described electron beam is 21kV, and the heating current of electron beam is 3A, and the heating power of electron beam is 63kW, and the beam spot diameter, of electron beam is Ф 20mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3coating is fine and close, even, is combined well with carbon/carbon composite material base body; Be placed in after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃, coating oxidation ablation is not obvious, and oxidation products film solidifies the fine and close protective membrane of rear formation, and the linear ablative rate of coating is only 0.19 μ m/s.
Embodiment 3
The carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
263%, HfC 7%, and SiC 12%, TiB
29%, Sc
2o
39%.
The preparation method of the present embodiment is as follows:
Step 1, carbon/carbon compound material is used successively after the silicon carbide paper sanding and polishing of No. 400, No. 600, No. 800 and No. 1200, at deionized water for ultrasonic ripple, clean up, then put into baking oven and dry;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder, Sc
2o
3powder by volume after percentage mix, is put into ball grinder with polyvinylpyrrolidone-ethanolic soln in mass ratio at 1: 3, and ball milling 48h, obtains slip; In described polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 20%; The median size size of described each powder is respectively: ZrB
22 μ m, HfC 2 μ m, SiC 0.5 μ m, TiB
22 μ m, Sc
2o
32 μ m, quality purity is respectively ZrB
299.8%, HfC 99.7%, and SiC 99.6%, TiB
299.8%, Sc
2o
399.7%;
Step 3, slip described in step 2 is evenly painted in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 700 μ m, is then positioned in baking oven and dries;
Step 4, there is the carbon/carbon compound material of slurry coating to put into the vacuum chamber of electron beam furnace on surface in step 3, adopt electron beam to have the carbon/carbon compound material of slurry coating to be heated to 2600 ℃ on surface, insulation 0.5h, forms the carbon/carbon compound material ZrB that thickness is 610 μ m after naturally cooling to 25 ℃ of room temperatures
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 2.0 * 10
-2pa, the acceleration voltage of described electron beam is 20kV, and the heating current of electron beam is 2.5A, and the heating power of electron beam is 50kW, and the beam spot diameter, of electron beam is Ф 30mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3coating is fine and close, even, is combined well with carbon/carbon composite material base body; Be placed in after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃, coating oxidation ablation is not obvious, and oxidation products film solidifies the fine and close protective membrane of rear formation, and the linear ablative rate of coating is only 0.21 μ m/s.
Embodiment 4
The carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
257%, HfC 9%, and SiC 14%, TiB
210%, Sc
2o
310%.
The preparation method of the present embodiment is as follows:
Step 1, carbon/carbon compound material is used successively after the silicon carbide paper sanding and polishing of No. 400, No. 600, No. 800 and No. 1200, in dehydrated alcohol, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder and Sc
2o
3powder by volume after percentage mix, is put into ball grinder ball milling 64h with polyvinylpyrrolidone-ethanolic soln in mass ratio at 1: 2, obtains slip; In described polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 40%; The median size of described each powder is respectively: ZrB
21 μ m, HfC 1 μ m, SiC 0.05 μ m, TiB
22 μ m, Sc
2o
32 μ m, quality purity is respectively ZrB
299.9%, HfC 99.7%, and SiC 99.8%, TiB
299.9%, Sc
2o
399.8%;
Step 3, slip described in step 2 is evenly painted in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 850 μ m, is then positioned in baking oven and dries;
Step 4, the vacuum chamber of electron beam furnace is put into the carbon/carbon compound material of slurry coating in surface in step 3, adopt electron beam to have the carbon/carbon compound material of slurry coating to be heated to 2550 ℃ on surface, insulation 1h, obtains the carbon/carbon compound material ZrB that thickness is 720 μ m after naturally cooling to 25 ℃ of room temperatures
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa, the acceleration voltage of described electron beam is 19kV, and the heating current of electron beam is 2A, and the heating power of electron beam is 38kW, and the beam spot diameter, of electron beam is Ф 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3coating is fine and close, even, is combined well with carbon/carbon composite material base body; Be placed in after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃, coating oxidation ablation is not obvious, and oxidation products film solidifies the fine and close protective membrane of rear formation, and the linear ablative rate of coating is only 0.23 μ m/s.
Embodiment 5
The carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
255%, HfC 10%, and SiC 15%, TiB
210%, Sc
2o
310%.
The preparation method of the present embodiment is as follows:
Step 1, carbon/carbon compound material is used successively after the silicon carbide paper sanding and polishing of No. 400, No. 600, No. 800 and No. 1200, at deionized water for ultrasonic ripple, clean up, then put into baking oven and dry;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder and Sc
2o
3powder by volume after percentage mix, is put into ball grinder with polyvinylpyrrolidone-ethanolic soln in mass ratio at 1: 4, and ball milling 72h, obtains slip; In described polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 30%; The median size of described each powder is respectively: ZrB
21 μ m, HfC 1 μ m, SiC 1 μ m, TiB
21 μ m, Sc
2o
31 μ m, quality purity is respectively ZrB
299.6%, HfC 99.7%, and SiC 99.6%, TiB
299.9%, Sc
2o
399.9%;
Step 3, slip described in step 2 is evenly sprayed in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 1000 μ m, is then positioned in baking oven and dries;
Step 4, there is the carbon/carbon compound material of slurry coating to put into the vacuum chamber of electron beam furnace on surface in step 3, adopt electron beam that surface is heated to 2500 ℃ with the carbon/carbon compound material of slurry coating, insulation 0.5h, forms the carbon/carbon compound material ZrB that thickness is 840 μ m after naturally cooling to 25 ℃ of room temperatures
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa, the acceleration voltage of described electron beam is 20kV, and the heating current of electron beam is 3A, and the heating power of electron beam is 60kW, and the beam spot diameter, of electron beam is Ф 30mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-HfC-SiC-TiB
2-Sc
2o
3coating is fine and close, even, is combined well with carbon/carbon composite material base body; Be placed in after the oxy-acetylene flame oxidation ablation 300s of 2200 ℃, coating oxidation ablation is not obvious, and oxidation products film solidifies the fine and close protective membrane of rear formation, and the linear ablative rate of coating is only 0.25 μ m/s.
The electron beam furnace that the embodiment of the present invention adopts is the L8 type electron beam furnace that Ukraine power technology machine science production company manufactures.
The above, be only preferred embodiment of the present invention, not the present invention imposed any restrictions.Every any simple modification of above embodiment being done according to invention technical spirit, change and equivalence change, and all still belong in the protection domain of technical solution of the present invention.
Claims (9)
1. a carbon/carbon compound material material ultrahigh temperature oxidation resistant coating, is characterized in that, is grouped into: ZrB by the one-tenth of following volume percent
257%～67%, HfC6%～9%, SiC11%～14%, TiB
28%～10%, Sc
2o
38%～10%; Described carbon/carbon compound material material ultrahigh temperature oxidation resistant coating refers to that this coating take carbon/carbon compound material as matrix, in temperature, be to have oxidation-resistance under the condition of 1800 ℃～2500 ℃, the preparation method of described carbon/carbon compound material material ultrahigh temperature oxidation resistant coating comprises the following steps:
Step 1, by after carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder and Sc
2o
3powder by volume after percentage mix, is put into ball grinder ball milling 48h～72h with polyvinylpyrrolidone-ethanolic soln 1: 2 in mass ratio～5, obtains slip;
Step 3, slip described in step 2 is brushed equably or is sprayed in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 300 μ m～1000 μ m, is then placed in baking oven and dries;
Step 4, the vacuum chamber of electron beam furnace is put into in the surface after drying in step 3 with the carbon/carbon compound material of slurry coating, electron beam in vacuum chamber is heated to 2500～2700 ℃ by surface with the carbon/carbon compound material of slurry coating, keep naturally cooling to 25 ℃ of room temperatures after 0.5h～1h, obtaining thickness is the carbon/carbon compound material ZrB of 220 μ m～840 μ m
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa～2.0 * 10
-2pa.
2. a kind of carbon/carbon compound material material ultrahigh temperature oxidation resistant coating according to claim 1, is characterized in that, is grouped into: ZrB by the one-tenth of following volume percent
263%, HfC7%, SiC12%, TiB
29%, Sc
2o
39%.
3. prepare a method for carbon/carbon compound material material ultrahigh temperature oxidation resistant coating as claimed in claim 1 or 2, it is characterized in that, the method comprises the following steps:
Step 1, by after carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, then puts into baking oven and dries;
Step 2, by ZrB
2powder, HfC powder, SiC powder, TiB
2powder and Sc
2o
3powder by volume after percentage mix, is put into ball grinder ball milling 48h～72h with polyvinylpyrrolidone-ethanolic soln 1: 2 in mass ratio～5, obtains slip;
Step 3, slip described in step 2 is brushed equably or is sprayed in step 1 to the surface of carbon/carbon composite after drying, forming thickness is the slurry coating of 300 μ m～1000 μ m, is then placed in baking oven and dries;
Step 4, the vacuum chamber of electron beam furnace is put into in the surface after drying in step 3 with the carbon/carbon compound material of slurry coating, electron beam in vacuum chamber is heated to 2500～2700 ℃ by surface with the carbon/carbon compound material of slurry coating, keep naturally cooling to 25 ℃ of room temperatures after 0.5h～1h, obtaining thickness is the carbon/carbon compound material ZrB of 220 μ m～840 μ m
2-HfC-SiC-TiB
2-Sc
2o
3coating; The pressure of described vacuum chamber is 1.8 * 10
-2pa～2.0 * 10
-2pa.
4. method according to claim 3, is characterized in that, the process of sanding and polishing described in step 1 is: use successively the silicon carbide paper of No. 400, No. 600, No. 800 and No. 1200 by carbon/carbon compound material sanding and polishing.
5. method according to claim 3, is characterized in that, medium described in step 1 is acetone, dehydrated alcohol or deionized water.
6. method according to claim 3, is characterized in that, in step 2, the median size of each powder is respectively: ZrB
2the median size of powder is 1 μ m～2 μ m, and the median size of HfC powder is 1 μ m～2 μ m, and the median size of SiC powder is 0.05 μ m～1 μ m, TiB
2the median size of powder is 1 μ m～3 μ m, Sc
2o
3the median size of powder is 1 μ m～3 μ m.
7. method according to claim 3, is characterized in that, in step 2, the quality purity of each powder all >=99.6%.
8. method according to claim 3, is characterized in that, described in step 2, in polyvinylpyrrolidone-ethanolic soln, the massfraction of polyvinylpyrrolidone is 20%～40%.
9. method according to claim 3, it is characterized in that, the processing parameter of the heating of electron beam described in step 4 carbon/carbon compound material is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 2A～3A, the heating power of electron beam is 38kW～63kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
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| CN103819227B (en) * | 2014-01-02 | 2015-05-13 | 哈尔滨工业大学 | Preparation method of ZrB2-SiC/SiC ceramic coating |
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| CN109735789B (en) * | 2019-01-25 | 2021-04-13 | 航天材料及工艺研究所 | Multi-element Zr/Hf-based ultrahigh-melting-point carbide oxidation-resistant coating and preparation method thereof |
| CN109608218B (en) * | 2019-01-28 | 2021-09-24 | 中国人民解放军国防科技大学 | Self-healing ceramic matrix composite and low-temperature rapid preparation method thereof |
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