CN102674893B - Ultrahigh-temperature antioxidant coating for carbon/carbon composite material and preparation method of ultrahigh-temperature antioxidant coating - Google Patents
Ultrahigh-temperature antioxidant coating for carbon/carbon composite material and preparation method of ultrahigh-temperature antioxidant coating Download PDFInfo
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- CN102674893B CN102674893B CN201210176569.4A CN201210176569A CN102674893B CN 102674893 B CN102674893 B CN 102674893B CN 201210176569 A CN201210176569 A CN 201210176569A CN 102674893 B CN102674893 B CN 102674893B
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Abstract
The invention discloses an ultrahigh-temperature antioxidant coating for a carbon/carbon composite material. The ultrahigh-temperature antioxidant coating consists of ZrB2, MoSi2, TiB2 and LuB6 in certain percent by volume. The invention additionally provides a preparation method of the coating. The preparation method comprises the following steps that: the carbon/carbon composite material is ground, polished, cleaned and dried; the ZrB2, MoSi2, TiB2, LuB6 and the carbon/carbon composite material are put in an electron beam physical vapor deposition furnace; the carbon/carbon composite material is heated by electron beams; the ZrB2, MoSi2, TiB2 and LuB6 are evaporated by the electron beams; and gas molecules are deposited on the surface of the carbon/carbon composite materials to form a ZrB2-MoSi2-TiB2-LuB6 coating for the carbon/carbon composite material. The coating which is prepared by adopting the method has the advantages that the coating is compact and even, the mechanical performance is good, the bonding strength with a carbon/carbon composite material substrate is high and the ultrahigh-temperature antioxidant performance of the carbon/carbon composite material can be effectively improved.
Description
Technical field
The invention belongs to anti-oxidant technical field of inorganic material, be specifically related to a kind of material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material 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.After yet this coating is oxidized under ultra-high temperature condition, there are the problems such as viscosity is low, vaporator rate is fast, diffusion coefficient is high in its oxidation products, causes ZrB
2rate of oxidation too fast, can not effectively stop carbon/carbon compound material generation oxidizing reaction.
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) adopt ceramic precursor infiltration pyrolysis method and document 2 (Niu Yaran, Zheng Xuebin, Ding Chuanxian. the preparation of plasma spraying high temperature material ultrahigh temperature oxidation resistant coating and sign. hot-spraying techniques, 2011, 3 (3): 1-10) adopt vacuum plasma spray coating method to prepare binary ZrB
2-SiC material ultrahigh temperature oxidation resistant coating.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) adopt pressureless sintering method to prepare binary ZrB
2-MoSi
2block ceramic.Yet under ultra-high temperature condition, adopt the ZrB of document 1,2 or 3 preparations
2-SiC and ZrB
2-MoSi
2, there is the defects such as viscosity is low, vaporator rate is fast, diffusion coefficient is high in its oxidation products, causes ZrB
2-SiC and ZrB
2-MoSi
2rate of oxidation too fast.
In addition, when described in adopting document 1, method is prepared the multi-element coating that contains anti-oxidant wild phase, because ceramic precursor cracking generally occurs in 1100 ℃, ZrB
2the bonding strength of-SiC and anti-oxidant wild phase is low, and under hyperthermal environments, 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, while forming coating, anti-oxidant wild phase, ZrB
2, SiC is coagulation phase, coating is stratiform and vesicular structure, the bonding strength of coating and matrix is low, density is low, coating ultrahigh-temperature antioxidant property is poor.When described in adopting document 3, method is prepared with the multi-element coating of anti-oxidant wild phase, pressureless sintering is difficult to realize the densification of material ultrahigh temperature oxidation resistant coating.
Document 4 (Han Jiecai, Hu Ping, Zhang Xinghong etc. LaB
6interpolation to ZrB
2the impact of-SiC based ultra-high temperature stupalith oxidation susceptibility. the academic conference 2007 of The Chinese Society of Theoretical and Applied Mechanics) studied ternary ZrB
2-SiC-LaB
6superhigh temperature ceramics.Document 5 (Li Xueying, Zhang Xinghong, Han Jiecai etc. Y
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) studied ternary ZrB
2-SiC-Y
2o
3superhigh temperature ceramics.Add LaB
6or Y
2o
3after, although improved the viscosity of oxidation products, reduce the vaporator rate of oxidation products, but still had the problems such as diffusion coefficient height.Therefore, ternary ZrB
2-SiC-LaB
6and ZrB
2-SiC-Y
2o
3the rate of oxidation of pottery is too fast.
Document 6 (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) studied ternary ZrB
2-SiC-HfB
2pottery.Due to HfB
2with ZrB
2oxidation products all there is the problems such as viscosity is low, vaporator rate is fast, diffusion coefficient is high, so ternary ZrB
2-SiC-HfB
2the rate of oxidation of pottery is too fast.
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) studied ternary ZrB
2-SiC-ZrC pottery.Because the CO gas producing after ZrC oxidation causes disadvantageous effect to the integrity of coating oxidation product and continuity.
In addition, when adopting the hot-pressing sintering method described in document 4, document 5, document 6 or document 7 to prepare ternary coating, the high pressure in sintering process will damage carbon/carbon composite material base body.
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 material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material is provided.This coating is fine and close evenly, mechanical property is good, high with the bonding strength of carbon/carbon composite material base body, 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 material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material, it is characterized in that, and by the one-tenth of following volume percent, be grouped into: ZrB
265%～80%, MoSi
210%～15%, TiB
25%～10%, LuB
65%～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.
The above-mentioned material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material, is grouped into by the one-tenth of following volume percent: ZrB
268%～76%, MoSi
212%～14%, TiB
26%～9%, LuB
66%～9%.
The above-mentioned material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material, is grouped into by the one-tenth of following volume percent: ZrB
272%, MoSi
213%, TiB
27%, LuB
68%.
In addition, the present invention also provides a kind of method of preparing the above-mentioned material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material, it is characterized in that, the method comprises the following steps:
Step 1, by carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, is placed on the middle part of electro beam physics vapour deposition stove vacuum chamber after oven dry;
Step 2, by target ZrB
2, MoSi
2, TiB
2and LuB
6be placed in proportion the bottom of vacuum chamber described in step 1;
Step 3, employing electron beam are heated to 1650 ℃～1800 ℃ by the carbon/carbon compound material at vacuum chamber middle part in step 1; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6surface of carbon/carbon composite after molecule heats in step 3 with the deposited at rates of 4 μ m/min～10 μ m/min, forms carbon/carbon compound material ZrB
2-MoSi
2-TiB
2-LuB
6coating; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa, described target ZrB
2, MoSi
2, TiB
2and LuB
6water surface of evaporation to the distance of carbon/carbon compound material deposition surface be 200mm～350mm.
Above-mentioned method, 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.
Above-mentioned method, medium described in step 1 is acetone, dehydrated alcohol or deionized water.
Above-mentioned method, the processing parameter heating described in step 3 is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 0.9A～1A, and the heating power of electron beam is 17.1kW～21kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
Above-mentioned method, the processing parameter of heating evaporation described in step 4 is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 1.5A～3A, and the heating power of electron beam is 28.5kW～63kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
Above-mentioned method, the ZrB of carbon/carbon compound material described in step 4
2-MoSi
2-TiB
2-LuB
6the thickness of coating is 150 μ m～1000 μ m.
The present invention compared with prior art has the following advantages:
(1) the present invention by adding TiB in component
2and LuB
6, 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
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 adopts electron beam by ZrB
2, MoSi
2, TiB
2and LuB
6flash to gaseous state, be then deposited on the high temperature surface of carbon/carbon compound material, under the bombardment effect and High temperature diffusion driving effect of electron beam, ZrB
2, SiC, TiB
2and LuB
6between each component and between each component and carbon/carbon compound material, spread, thus 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) ZrB for carbon/carbon compound material that adopts the present invention to prepare
2-MoSi
2-TiB
2-LuB
6the ultrahigh-temperature oxidation-resistance of coating is good, is placed in after the oxy-acetylene flame oxidation ablation 600s of 2200 ℃, and the linear ablative rate of coating is only 0.23 μ m/s～0.33 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 material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the embodiment of the present invention 1 preparation.
Fig. 2 is that the material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the embodiment of the present invention 1 preparation is placed in the ablation center microstructure photo after the oxy-acetylene flame oxidation ablation 600s of 2200 ℃.
Embodiment
Embodiment 1
The material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
280%, MoSi
210%, TiB
25%, LuB
65%.
The preparation method of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is:
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, put into after baking oven oven dry, be placed on the work rest at electro beam physics vapour deposition stove vacuum chamber middle part;
Step 2, by ZrB
2target, MoSi
2target, TiB
2target and LuB
6target is put into the water jacketed copper crucible of the stove of electro beam physics vapour deposition described in step 1 vacuum chamber bottom in proportion;
Step 3, employing electron beam are heated to 1800 ℃ by the carbon/carbon compound material in the movements and postures of actors of vacuum chamber described in step 1; 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 1A, and the heating power of electron beam is 20kW, and the beam spot diameter, of electron beam is Ф 30mm;
Step 4, employing electron beam be ZrB2 molecule, MoSi2 molecule, TiB2 molecule and the LuB6 molecule with formation gaseous state by target ZrB2, MoSi2, TiB2 and the LuB6 heating evaporation of vacuum chamber bottom in step 2, gaseous state ZrB
2, MoSi
2, TiB
2and LuB
6molecule is with the deposited at rates of 4 μ m/min in the surface of carbon/carbon compound material described in step 3, and forming thickness is the carbon/carbon compound material ZrB of 150 μ m
2-MoSi
2-TiB
2-LuB
6coating; Described each target water surface of evaporation is 200mm to the distance of carbon/carbon compound material deposition surface, and the pressure of described vacuum chamber is 2.0 * 10
-2pa, the design parameter of described each target of electron beam evaporation is: evaporation MoSi
2target and LuB
6the acceleration voltage of the electron beam of target is 20kV, and the heating current of electron beam is 1.5A, and the heating power of electron beam is 30kW, and the beam spot diameter, of electron beam is Ф 15mm; Evaporation TiB
2the acceleration voltage of the electron beam of target is 20kV, and the heating current of electron beam is 2A, and the heating power of electron beam is 40kW, and the beam spot diameter, of electron beam is Ф 15mm; Evaporation ZrB
2the acceleration voltage of the electron beam of target 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 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6as 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-MoSi
2-TiB
2-LuB
6painting is placed in 2200 ℃ of oxy-acetylene flames the ablation center microstructure photo after oxidation ablation 600s as shown in Figure 2; the ablation center thick coating of 150 μ m is not ablated off by complete oxidation; coating oxidation Product Films 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 oxidation-resistance of carbon/carbon compound material.Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6the linear ablative rate of coating is only 0.23 μ m/s.
Embodiment 2
The material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
276%, MoSi
212%, TiB
26%, LuB
66%.
The preparation method of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is:
Step 1, carbon/carbon compound material 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, and put into after baking oven oven dry, be placed on the work rest at electro beam physics vapour deposition stove vacuum chamber middle part;
Step 2, by ZrB
2target, MoSi
2target, TiB
2target and LuB
6target is put into the water jacketed copper crucible of the stove of electro beam physics vapour deposition described in step 1 vacuum chamber bottom;
Step 3, employing electron beam are heated to 1750 ℃ by carbon/carbon compound material described in step 1; The pressure of described vacuum chamber is 1.9 * 10
-2pa, the acceleration voltage of described electron beam is 19kV, and the heating current of electron beam is 0.9A, and the heating power of electron beam is 17.1kW, and the beam spot diameter, of electron beam is Ф 15mm;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule is with the deposited at rates of 6 μ m/min in the surface of carbon/carbon compound material described in step 3, and forming thickness is the carbon/carbon compound material ZrB of 450 μ m
2-MoSi
2-TiB
2-LuB
6coating; Described each target water surface of evaporation is 250mm to the distance of carbon/carbon compound material deposition surface, and the pressure of described vacuum chamber is 1.9 * 10
-2pa, the design parameter of described each target of electron beam evaporation is: evaporation MoSi
2target and LuB
6the acceleration voltage of the electron beam of target is 19kV, and the heating current of electron beam is 2.2A, and the heating power of electron beam is 41.8kW, and the beam spot diameter, of electron beam is Ф 30mm; Evaporation TiB
2the acceleration voltage of the electron beam of target is 19kV, and the heating current of electron beam is 2.2A, and the heating power of electron beam is 41.8kW, and the beam spot diameter, of electron beam is Ф 20mm; Evaporation ZrB
2the acceleration voltage of the electron beam of target 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 18mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6coating 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 600s 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 0.27 μ m/s.
Embodiment 3
The material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
272%, MoSi
213%, TiB
27%, LuB
68%.
The preparation method of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is:
Step 1, carbon/carbon compound material 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, put into after baking oven oven dry, be placed on the work rest at electro beam physics vapour deposition stove vacuum chamber middle part;
Step 2, by ZrB
2target, MoSi
2target, TiB
2target and LuB
6target is put into the water jacketed copper crucible of the stove of electro beam physics vapour deposition described in step 1 vacuum chamber bottom;
Step 3, employing electron beam are heated to 1730 ℃ by carbon/carbon compound material described in step 1; 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 0.95A, and the heating power of electron beam is 19kW, and the beam spot diameter, of electron beam is Ф 30mm;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule is with the deposited at rates of 8 μ m/min in the surface of carbon/carbon compound material described in step 3, and forming thickness is the carbon/carbon compound material ZrB of 600 μ m
2-MoSi
2-TiB
2-LuB
6coating; Described each target water surface of evaporation is 300mm to the distance of carbon/carbon compound material deposition surface, and the pressure of described vacuum chamber is 1.8 * 10
-2pa, the design parameter of described each target of electron beam evaporation is: evaporation MoSi
2target, LuB
6target, TiB
2the acceleration voltage of the electron beam of target is 20kV, and the heating current of electron beam is 1.5A, and the heating power of electron beam is 30kW, and the beam spot diameter, of electron beam is Ф 15mm; Evaporation ZrB
2the acceleration voltage of the electron beam of target 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 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6coating 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 600s 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 0.30 μ m/s.
Embodiment 4
The material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
268%, MoSi
214%, TiB
29%, LuB
69%.
The preparation method of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is:
Step 1, carbon/carbon compound material 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, put into after baking oven oven dry, be placed on the work rest at electro beam physics vapour deposition stove vacuum chamber middle part;
Step 2, by ZrB
2target, MoSi
2target, TiB
2target and LuB
6target is put into the water jacketed copper crucible of the stove of electro beam physics vapour deposition described in step 1 vacuum chamber bottom;
Step 3, employing electron beam are heated to 1680 ℃ by carbon/carbon compound material described in step 1; 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 vacuum chamber is 1A, and the heating power of vacuum chamber is 21kW, and the beam spot diameter, of vacuum chamber is Ф 20mm;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule is with the deposited at rates of 10 μ m/min in the surface of carbon/carbon compound material described in step 3, and forming thickness is the carbon/carbon compound material ZrB of 800 μ m
2-MoSi
2-TiB
2-LuB
6coating; Described each target water surface of evaporation is 320mm to the distance of carbon/carbon compound material deposition surface, and the pressure of described vacuum chamber is 1.7 * 10
-2pa, the design parameter of described each target of electron beam evaporation is: evaporation MoSi
2target and LuB
6the acceleration voltage of the electron beam of target is 19kV, and the heating current of electron beam is 1.5A, and the heating power of electron beam is 28.5kW, and the beam spot diameter, of electron beam is Ф 20mm; Evaporation TiB
2the acceleration voltage of the electron beam of target 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 20mm; Evaporation ZrB
2the acceleration voltage 21kV of the electron beam of target, the heating current of electron beam is 2.5A, and the heating power of electron beam is 52.5kW, and the beam spot diameter, of electron beam is Ф 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6coating 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 600s 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 0.31 μ m/s.
Embodiment 5
The material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material of the present embodiment is grouped into by the one-tenth of following volume percent: ZrB
265%, MoSi
215%, TiB
210%, LuB
610%.
The preparation method of the carbon/carbon compound material material ultrahigh temperature oxidation resistant coating of the present embodiment is:
Step 1, carbon/carbon compound material 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, put into after baking oven oven dry, be placed on the work rest at electro beam physics vapour deposition stove vacuum chamber middle part;
Step 2, by ZrB
2target, MoSi
2target, TiB
2target and LuB
6target is put into the water jacketed copper crucible of the stove of electro beam physics vapour deposition described in step 1 vacuum chamber bottom;
Step 3, employing electron beam are heated to 1650 ℃ by carbon/carbon compound material described in step 1; The pressure of described vacuum chamber is 1.6 * 10
-2pa, the acceleration voltage of described electron beam is 20kV, and the heating current of electron beam is 0.9A, and the heating power of electron beam is 18kW, and the beam spot diameter, of electron beam is Ф 30mm;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule is with the deposited at rates of 10 μ m/min in the surface of carbon/carbon compound material described in step 3, and forming thickness is the carbon/carbon compound material ZrB of 1000 μ m
2-MoSi
2-TiB
2-LuB
6coating; Described each target water surface of evaporation is 350mm to the distance of carbon/carbon compound material deposition surface, and the pressure of described vacuum chamber is 1.6 * 10
-2pa, the design parameter of described each target of electron beam evaporation is: evaporation MoSi
2target, LuB
6the acceleration voltage of the electron beam of target is 20kV, and the heating current of electron beam is 1.5A, and the heating power of electron beam is 30kW, and the beam spot diameter, of electron beam is Ф 15mm; Evaporation TiB
2the acceleration voltage of the electron beam of target is 20kV, and the heating current of electron beam is 2.6A, and the heating power of electron beam is 52kW, and the beam spot diameter, of electron beam is Ф 30mm; Evaporation ZrB
2the beam voltage 20kV of target, 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 15mm.
Carbon/carbon compound material ZrB prepared by the present embodiment
2-MoSi
2-TiB
2-LuB
6coating 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 600s 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 0.33 μ m/s.
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 (8)
1. for a material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material, it is characterized in that, by the one-tenth of following volume percent, be grouped into: ZrB
268%～76%, MoSi
212%～14%, TiB
26%～9%, LuB
66%～9%; The described material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material 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 the described material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material comprises the following steps:
Step 1, by carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, is placed on the middle part of electro beam physics vapour deposition stove vacuum chamber after oven dry;
Step 2, by target ZrB
2, MoSi
2, TiB
2and LuB
6be placed in proportion the bottom of vacuum chamber described in step 1;
Step 3, employing electron beam are heated to 1650 ℃～1800 ℃ by the carbon/carbon compound material at vacuum chamber middle part in step 1; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6surface of carbon/carbon composite after molecule heats in step 3 with the deposited at rates of 4 μ m/min～10 μ m/min, forms carbon/carbon compound material ZrB
2-MoSi
2-TiB
2-LuB
6coating; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa, described target ZrB
2, MoSi
2, TiB
2and LuB
6water surface of evaporation to the distance of carbon/carbon compound material deposition surface be 200mm～350mm.
2. the material ultrahigh temperature oxidation resistant coating for carbon/carbon compound material according to claim 1, is characterized in that, is grouped into: ZrB by the one-tenth of following volume percent
272%, MoSi
213%, TiB
27%, LuB
68%.
3. prepare as claimed in claim 1 or 2 the method for the material ultrahigh temperature oxidation resistant coating of carbon/carbon compound material, it is characterized in that, the method comprises the following steps:
Step 1, by carbon/carbon compound material sanding and polishing, in medium, ultrasonic cleaning is clean, is placed on the middle part of electro beam physics vapour deposition stove vacuum chamber after oven dry;
Step 2, by target ZrB
2, MoSi
2, TiB
2and LuB
6be placed in proportion the bottom of vacuum chamber described in step 1;
Step 3, employing electron beam are heated to 1650 ℃～1800 ℃ by the carbon/carbon compound material at vacuum chamber middle part in step 1; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa;
Step 4, employing electron beam are by the target ZrB of vacuum chamber bottom in step 2
2, MoSi
2, TiB
2and LuB
6heating evaporation is to form the ZrB of gaseous state
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6molecule, described gaseous state ZrB
2molecule, MoSi
2molecule, TiB
2molecule and LuB
6surface of carbon/carbon composite after molecule heats in step 3 with the deposited at rates of 4 μ m/min～10 μ m/min, forms carbon/carbon compound material ZrB
2-MoSi
2-TiB
2-LuB
6coating; The pressure of described vacuum chamber is 1.6 * 10
-2pa～2.0 * 10
-2pa, described target ZrB
2, MoSi
2, TiB
2and LuB
6water surface of evaporation to the distance of carbon/carbon compound material deposition surface be 200mm～350mm.
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, it is characterized in that, the processing parameter heating described in step 3 is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 0.9A～1A, the heating power of electron beam is 17.1kW～21kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
7. method according to claim 3, it is characterized in that, the processing parameter of heating evaporation described in step 4 is: the acceleration voltage of electron beam is 19kV～21kV, the heating current of electron beam is 1.5A～3A, the heating power of electron beam is 28.5kW～63kW, and the beam spot diameter, of electron beam is Ф 15mm～Ф 30mm.
8. method according to claim 3, is characterized in that, the ZrB of carbon/carbon compound material described in step 4
2-MoSi
2-TiB
2-LuB
6the thickness of coating is 150 μ m～1000 μ m.
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| CN105695917A (en) * | 2016-03-24 | 2016-06-22 | 中国科学院上海硅酸盐研究所 | High-temperature and ablation resistance TiB2-MoSi2 composite coating and preparation method thereof |
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