CN107814591A - A kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating - Google Patents

A kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating Download PDF

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CN107814591A
CN107814591A CN201711103758.8A CN201711103758A CN107814591A CN 107814591 A CN107814591 A CN 107814591A CN 201711103758 A CN201711103758 A CN 201711103758A CN 107814591 A CN107814591 A CN 107814591A
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coating
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CN107814591B (en
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任宣儒
李贺军
冯培忠
郭立童
张平
沈承金
鞠治成
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China University of Mining and Technology CUMT
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

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Abstract

A kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating, belongs to the preparation method of carbon material surface high-temperature oxidation resistant coating.The preparation method of antioxidant coating, the controllable boride MB of content is configured first2Slurry, wherein MB2In M=Zr, Ta or Hf, with the internally coated carbon material matrix surface brushings of SiC, dip-coating or spraying MB2The initialization layer of slurry, after obtaining initialization layer, then it is heat-treated by superhigh temperature and sinters synthetic coating.The present invention can control MB by the regulation and control and design that are matched to composite ceramics slurry powder2The constituent content of SiC (M=Zr, Ta or Hf) coating；Pass through brushing, dip-coating or the control for spraying number, it is possible to achieve to MB2The control of SiC (M=Zr, Ta or Hf) coating layer thickness.The initialization layer later stage is heat-treated by super high sintering temperature, can improve the consistency of coating and the bond strength at undercoating interface again.Preparation technology of the present invention is simple, and coating dense uniform, production cost is relatively low, suitable for the carbon material part of shape, different sizes.

Description

A kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating
Technical field
The present invention relates to a kind of preparation method of carbon material surface high-temperature oxidation resistant coating, particularly a kind of carbon material surface Boride MB2The preparation method of (M=Zr, Ta or Hf) modified silicon substrate antioxidant coating.
Background technology
Carbon material (graphite, C/C composites) is a kind of advanced engineering material for possessing excellent high temperature performance, has resistance to height The advantages that warm, small proportion, high intensity, high-modulus, high heat conductance, low-expansion coefficient and heat shock resistance, it can bear superhigh temperature Influence of the high rate of heat addition of environment to its performance, and as the gradual increase of temperature, its intensity show gradual increasing The trend added, and can more than 2000 DEG C at a high temperature of keep, become one of preferred material of high-temperature structural material, quilt It is widely used in field of aerospace.
Carbon material is full carbonaceous material, although it has excellent mechanical property in high temperature.But it but have one it is fatal Weakness, i.e., begin to aoxidize under 400 DEG C of air atmosphere, significantly limit its as high-temperature structural material should With.Therefore, the anti-oxidation key as carbon material application.At present, antioxidant coating method be acknowledged as one kind can be effective The method for improving carbon material anti oxidation ability, i.e., the coating of high temperature oxidation resisting material is prepared on the surface of carbon material, so as to effectively Contact of the oxygen with carbon material is prevented, realizes the protection to carbon material.
Among antioxidant coating, superhigh temperature ceramics MB2- SiC coatings present preferable potentiality, MB2M in-SiC is Magnesium-yttrium-transition metal M=Zr, Ta or Hf.SiC coatings can form one layer in (1400-1600 DEG C) oxidation of high temperature and can effectively protect The silicate glass layer of matrix, so as to show good antioxygenic property, but it is in medium temperature (700-1200 DEG C) and superhigh temperature Under aerobic environment (>1600 DEG C) it is difficult to effective protection to carbon material.By MB2(M=Zr, Ta or Hf) is modified, can With by MB2The liquid B generated after (M=Zr, Ta or Hf) oxidation2O3Strengthen oxidation of the coating to carbon material under medium temperature environment Protection；And under hyperthermic temperature, magnesium-yttrium-transition metal M (M=Zr, Ta or Hf) oxide again can be with magma cell interaction With formation M-Si-O (M=Zr, Ta or Hf) complex phase glassy layer, the stability of reinforcing glass layer.
" I.G.Talmy, J.A.Zaykoski, M.M.Opeka.High-temperature the chemistry and of document 1 oxidation of ZrB2ceramics containing SiC,Si3N4,Ta5Si3,and TaSi2[J].Journal of the American Cerimic Society,2008,91(7):2250-7 " reports Ta oxides in silicate glass In the presence of the stability of glass being favorably improved, so as to improve the high-temperature oxydation resistance of ceramics.
" Xuanru Ren, Hejun Li, Qiangang Fu, Yanhui Chu, the Kezhi Li.TaB of document 22-SiC-Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites.Journal of the European Ceramic Society,2013,33[15-16]:2953-2959 " report and be prepared for TaB in C/C composite material surfaces using two step investments2- SiC-Si antioxidant coatings, in pure SiC coatings Protection under, sample after 1773K is only aoxidized 11 hours quality weightlessness just reached 1.66 × 10-2g2/cm2, and pass through TaB2Modified, sample weightlessness of quality after 1773K oxidations are up to 300 hours is only 0.26 × 10-2g2/cm2。
" Xuanru Ren, Hejun Li, Yanhui Chu, Qiangang Fu, the Kezhi Li.Ultra-high of document 3 temperature ceramic HfB2-SiC coating for oxidation protection of SiC-coated carbon/carbon composites.International Journal of Applied Ceramic Technology.2015,12(3):560-567 " reports are known clearly to be prepared for using in-situ reaction in C/C composite material surfaces HfB2- SiC/SiC antioxidant coatings, under effective protection of coating, sample 1773K aoxidize 265 hours after mass loss only For 0.41 × 10-2g2/cm2。
" Xuanru Ren, Hejun Li, Qiangang Fu, Yanhui Chu, the Kezhi Li.Preparation of document 4 of oxidation protective ZrB2-SiC coating by in-situ reaction method on SiC- coated carbon/carbon composites.Surface & Coatings Technology,2014,247:61-67” Report is known clearly is prepared for ZrB using in-situ reaction in C/C composite material surfaces2- SiC/SiC antioxidant coatings, in coating Effectively under protection, sample mass loss after 1773K is aoxidized 550 hours is only 0.22%.
In view of modified phase MB2(M=Zr, Ta or Hf) to the excellent modified effect of silicon substrate coating, its content in the coating To MB2The oxidation protection effect of-SiC (M=Zr, Ta or Hf) coating plays the influence of key, affects coating in superhigh temperature oxygen Change the preventing mechanism and protection effect under environment, therefore control MB in coating2The content of (M=Zr, Ta or Hf) and coating Thickness plays vital effect to the structure and antioxygenic property that optimize coating.
At present, MB is prepared in carbon material surface2The method of-SiC (M=Zr, Ta or Hf) coating is mainly investment, original position Reaction method and plasma spraying method.Although plasma spraying method is easily controlled MB in the thickness and coating of coating2(M=Zr, Ta Or Hf) content, but need expensive Preparation equipment, cost is higher, and the porosity of coating is higher, bond strength compared with Difference；And although investment and in-situ reaction are with cost is relatively low, simple and easy, synthesis is mutually uniformly distributed and matrix compatibility Preferably, the advantages that interface bond strength is higher, but MB in more difficult control coating2The content and coating of (M=Zr, Ta or Hf) Thickness.
The content of the invention
The preparation method of silicon substrate antioxidant coating is modified the invention aims to provide a kind of carbon material surface boride, Solve existing carbon material surface and prepare MB2Phase component and coating layer thickness be not easily-controllable in the method for-SiC (M=Zr, Ta or Hf) coating The problem of processed.
The object of the present invention is achieved like this：The preparation method of antioxidant coating, the controllable boronation of content is configured first Thing MB2Slurry, wherein MB2In M=Zr, Ta or Hf, with the internally coated carbon material matrix surface brushings of SiC, dip-coating or Spray MB2The initialization layer of slurry, after obtaining initialization layer, then it is heat-treated by superhigh temperature and sinters synthetic coating.
Concretely comprise the following steps：
Step 1：Carbon material after the polishing of different roughness sand paper is cleaned by ultrasonic and dried, described carbon material is Graphite or C/C composites；
Step 2：Prepare SiC undercoating：After Si powder and 10-30% C powder that mass fraction is 70-90% are uniformly mixed Drying, the carbon material treated by step 1 is then put into graphite crucible and wrapped up with the powder after drying, then powder will be carried The graphite crucible of material and carbon material is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and heat up with 3~20 DEG C/min Superhigh temperature heat-treatment furnace is warming up to 2000~2300 DEG C by speed, is incubated 2~5h, SiC undercoating is obtained in carbon material surface；
Step 3：Prepare MB2- SiC external coatings, wherein M=Zr, Ta or Hf；By MB2Powder, SiC powder, Si powder and C powder uniformly mix Dried after conjunction, then add Ludox and be placed in being well mixed in ball mill, obtain composite ceramics slurry；
Wherein, MB2Powder is 10%-90wt.%, and SiC powder is 5%-80wt.%, and Si powder is 5%-30wt.%, and C powder is 5%-30wt.%；
The volume of described Ludox and the ratio of mixed powder quality are 0.5-3ml/g；
Step 4：By the composite ceramics slurry of preparation with the internally coated carbon material surfaces of SiC to brush, dip-coating or The mode of spraying prepares initialization layer, and the number of brushing, dip-coating or spraying is 2-10 times；
Brush every time, sample is put into 70-120 DEG C of baking oven after dip-coating or spraying and fully dries 1-10h, drying terminates Brushed next time again afterwards, dip-coating or spraying；
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through Argon gas atmosphere is protected, and superhigh temperature heat-treatment furnace is warming up into 2000~2300 DEG C with 3~10 DEG C/min heating rates, insulation 2 ~5h, MB is obtained in carbon material surface2- SiC external coatings.
The MB that carbon material surface obtains2- SiC external coatings are ZrB2- SiC, TaB2- SiC or HfB2-SiC。
Beneficial effect and advantage：As a result of such scheme, prepared on carbon material (graphite, C/C composites) surface MB2- SiC (M=Zr, Ta or Hf) antioxidant coating, it is pre- by the regulation and control and design matched to composite ceramics slurry powder, control Put MB in layer2The content of (M=Zr, Ta or Hf), and then realize to MB2The control of-SiC (M=Zr, Ta or Hf) coating ingredients content System.By brushing, dip-coating or the control for spraying number, realize to MB2The control of-SiC (M=Zr, Ta or Hf) coating layer thickness. The initialization layer later stage is heat-treated by super high sintering temperature, improves the consistency of coating and the bond strength of coating interface.Pass through the work Skill prepares MB2- SiC (M=Zr, Ta or Hf) coating, by the adjustment of technique, is realized to coating quality, thickness and MB2(M=Zr, Ta or Hf) content control, effectively overcome investment and in-situ reaction to prepare MB2- SiC (M=Zr, Ta or Hf) coating lacks Point, give full play to the superiority of the two technique.
In view of investment and the excellent properties of in-situ reaction prepares coating, can deeply optimize MB using the program2- The structure and superhigh temperature oxidation protection ability of SiC (M=Zr, Ta or Hf) coating, give full play to investment and reaction in-situ legal system Standby MB2- SiC (M=Zr, Ta or Hf) coating possessed advantage, effectively overcomes existing process phase component and coating layer thickness to be not easy The shortcomings that control, expand MB2The application prospect of-SiC (M=Zr, Ta or Hf) coating.Moreover, the present invention need not be expensive The equipment such as plasma spraying, magnetron sputtering or chemical vapor deposition, technique is simple, and manufacturing cost is relatively low, suitable for shape, The carbon material part of different sizes.
Solve existing carbon material surface and prepare MB2Phase component and coating in the method for-SiC (M=Zr, Ta or Hf) coating The problem of thickness is difficult to control, has reached the purpose of the present invention.
Brief description of the drawings：
Fig. 1 is the TaB prepared using the present invention2Mass fraction is 80% TaB2The XRD diffraction patterns of-SiC coatings.
Fig. 2 is the TaB prepared using the present invention2Mass fraction is 80% TaB2The SEM photograph of-SiC coatings.
Fig. 3 is the HfB prepared using the present invention2Mass fraction is 60% HfB2The XRD diffraction patterns of-SiC coatings.
Fig. 4 is the HfB prepared using the present invention2Mass fraction is 60% HfB2The SEM photograph of-SiC coatings.
Fig. 5 is the ZrB prepared using the present invention2Mass fraction is 20% ZrB2The XRD diffraction patterns of-SiC coatings.
Fig. 6 is the ZrB prepared using the present invention2Mass fraction is 20% ZrB2The SEM photograph of-SiC coatings.
Embodiment
The preparation method of antioxidant coating, the controllable MB of content is configured first2Slurry, wherein MB2In M=Zr, Ta or Hf, with the internally coated carbon material matrix surface brushings of SiC, dip-coating or spraying MB2The initialization layer of slurry, obtain initialization layer Afterwards, then by superhigh temperature it is heat-treated sintering synthetic coating.
Concretely comprise the following steps：
Step 1：Carbon material after the polishing of different roughness sand paper is cleaned by ultrasonic and dried, described carbon material is Graphite or C/C composites；
Step 2：Prepare SiC undercoating：After Si powder and 10-30% C powder that mass fraction is 70-90% are uniformly mixed Drying, the carbon material treated by step 1 is then put into graphite crucible and wrapped up with the powder after drying, then powder will be carried The graphite crucible of material and carbon material is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and heat up with 3~20 DEG C/min Superhigh temperature heat-treatment furnace is warming up to 2000~2300 DEG C by speed, is incubated 2~5h, SiC undercoating is obtained in carbon material surface；
Step 3：Prepare MB2- SiC external coatings, wherein M=Zr, Ta or Hf；By MB2Powder, SiC powder, Si powder and C powder uniformly mix Dried after conjunction, then add Ludox and be placed in being well mixed in ball mill, obtain composite ceramics slurry；
Wherein, MB2Powder is 10%-90wt.%, and SiC powder is 5%-80wt.%, and Si powder is 5%-30wt.%, and C powder is 5%-30wt.%；
The volume of described Ludox and the ratio of mixed powder quality are 0.5-3ml/g；
Step 4：By the composite ceramics slurry of preparation with the internally coated carbon material surfaces of SiC to brush, dip-coating or The mode of spraying prepares initialization layer, and the number of brushing, dip-coating or spraying is 2-10 times；
Brush every time, sample is put into 70-120 DEG C of baking oven after dip-coating or spraying and fully dries 1-10h, drying terminates Brushed next time again afterwards, dip-coating or spraying；
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through Argon gas atmosphere is protected, and superhigh temperature heat-treatment furnace is warming up into 2000~2300 DEG C with 3~10 DEG C/min heating rates, insulation 2 ~5h, MB is obtained in carbon material surface2- SiC external coatings；
The MB that carbon material surface obtains2- SiC external coatings are ZrB2- SiC, TaB2- SiC or HfB2-SiC。
The present invention is described in further detail with reference to the accompanying drawings and examples
Embodiment 1：
Step 1：Graphite after the polishing of different roughness sand paper is cleaned by ultrasonic and dried.
Step 2：Prepare SiC undercoating：By mass fraction to be dried after 85% Si powder and the uniform mixing of 15% C powder, Then the graphite treated by step 1 is put into graphite crucible and wrapped up with the powder after drying, then powder and stone will be carried The graphite crucible of ink is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and with 10 DEG C/min heating rates by superelevation Warm treatment furnace is warming up to 2150 DEG C, is incubated 2h, SiC undercoating is obtained in graphite surface.
Step 3：Prepare TaB2- SiC external coatings：By TaB2Powder (80wt.%), SiC powder (5wt.%), Si powder (10wt.%) Dried with after C powder (5wt.%) uniformly mixing, then add a certain amount of Ludox (volume of Ludox and mixed powder quality Ratio be 2.5ml/g) be placed in ball mill be well mixed, obtain composite ceramics slurry.
Step 4：The composite ceramics slurry of preparation is prepared with the internally coated carbon material surfaces of SiC in a manner of dip-coating Initialization layer, the number of dip-coating is 10 times, and sample is put into 90 DEG C of baking ovens after each dip-coating and fully dries 3h, is dried after terminating again Carry out dip-coating next time.
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through Argon gas atmosphere is protected, and superhigh temperature heat-treatment furnace is warming up into 2200 DEG C with 10 DEG C/min heating rates, 4h is incubated, in graphite table Face obtains TaB2- SiC external coatings；Its material phase analysis is as shown in figure 1, its surface topography is as shown in Figure 2.
Embodiment 2：
Step 1：Graphite after the polishing of different roughness sand paper is cleaned by ultrasonic and dried.
Step 2：Prepare SiC undercoating：By mass fraction to be dried after 75% Si powder and the uniform mixing of 25% C powder, Then the graphite treated by step 1 is put into graphite crucible and wrapped up with the powder after drying, then powder and stone will be carried The graphite crucible of ink is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and with 15 DEG C/min heating rates by superelevation Warm treatment furnace is warming up to 2050 DEG C, is incubated 4h, SiC undercoating is obtained in graphite surface.
Step 3：Prepare HfB2- SiC external coatings：By HfB2Powder (60wt.%), SiC powder (10wt.%), Si powder (20wt.%) and C powder (10wt.%) are dried after uniformly mixing, and then adding a certain amount of Ludox, (volume of Ludox is with mixing The ratio for closing powder quality is 2ml/g) it is placed in being well mixed in ball mill, obtain composite ceramics slurry.
Step 4：The composite ceramics slurry of preparation is prepared with the internally coated carbon material surfaces of SiC in a manner of brushing Initialization layer, the number of dip-coating is 3 times, and sample is put into 90 DEG C of baking ovens after brushing every time and fully dries 2h, is dried after terminating again Brushed next time.
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through Argon gas atmosphere is protected, and superhigh temperature heat-treatment furnace is warming up into 2100 DEG C with 10 DEG C/min heating rates, 3h is incubated, in graphite table Face obtains HfB2- SiC external coatings；Its surface topography is as shown in Figure 4；Its material phase analysis is as shown in figure 3, its surface topography such as Fig. 4 It is shown.
Embodiment 3：
Step 1：Graphite after the polishing of different roughness sand paper is cleaned by ultrasonic and dried.
Step 2：Prepare SiC undercoating：By mass fraction to be dried after 80% Si powder and the uniform mixing of 20% C powder, Then the graphite treated by step 1 is put into graphite crucible and wrapped up with the powder after drying, then powder and stone will be carried The graphite crucible of ink is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and with 5 DEG C/min heating rates by superhigh temperature Heat-treatment furnace is warming up to 2200 DEG C, is incubated 2h, SiC undercoating is obtained in graphite surface.
Step 3：Prepare ZrB2- SiC external coatings：By ZrB2Powder (20wt.%), SiC powder (60wt.%), Si powder (15wt.%) and C powder (5wt.%) are dried after uniformly mixing, and then adding a certain amount of Ludox, (volume of Ludox is with mixing The ratio for closing powder quality is 1.5ml/g) it is placed in being well mixed in ball mill, obtain composite ceramics slurry.
Step 4：The composite ceramics slurry of preparation is prepared with the internally coated carbon material surfaces of SiC in a manner of dip-coating Initialization layer, the number of dip-coating is 5 times, and sample is put into 80 DEG C of baking ovens after each dip-coating and fully dries 5h, is dried after terminating again Carry out dip-coating next time.
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through Argon gas atmosphere is protected, and superhigh temperature heat-treatment furnace is warming up into 2200 DEG C with 5 DEG C/min heating rates, 2h is incubated, in graphite table Face obtains ZrB2- SiC external coatings；Its material phase analysis is as shown in figure 5, its surface topography is as shown in Figure 6.
It is described above, it is only the preferable embodiment of the present invention, therefore the scope that the present invention is implemented can not be implemented according to more than Example is defined, and the equivalent modification carried out according to the scope of the claims of the present invention and description and change, is still contained for the present invention The scope of lid.

Claims (6)

1. a kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating, it is characterised in that：Antioxidant coating Preparation method, configure the controllable boride MB of content first2Slurry, wherein MB2In M=Zr, Ta or Hf, in SiC The brushing of carbon material matrix surface, dip-coating or the spraying MB of coating2The initialization layer of slurry, after obtaining initialization layer, then by superelevation Warm processing sintering synthetic coating.
2. a kind of carbon material surface boride according to claim 1 is modified the preparation method of silicon substrate antioxidant coating, its It is characterised by concretely comprising the following steps：
Step 1：Carbon material after the polishing of different roughness sand paper is cleaned by ultrasonic and dried, described carbon material is graphite Or C/C composites；
Step 2：Prepare SiC undercoating：Dried after Si powder and 10-30% C powder that mass fraction is 70-90% are uniformly mixed, Then will by step 1 treat carbon material be put into graphite crucible and with drying after powder wrap up, then will carry powder with The graphite crucible of carbon material is put into superhigh temperature heat-treatment furnace, is passed through argon gas atmosphere protection, and with 3 ~ 20 DEG C/min heating rates Superhigh temperature heat-treatment furnace is warming up to 2000 ~ 2300 DEG C, 2 ~ 5h is incubated, SiC undercoating is obtained in carbon material surface；
Step 3：Prepare MB2- SiC external coatings, wherein M=Zr, Ta or Hf；By MB2Powder, SiC powder, Si powder and C powder are uniformly after mixing Drying, then add Ludox and be placed in being well mixed in ball mill, obtain composite ceramics slurry；
Step 4：By the composite ceramics slurry of preparation with the internally coated carbon material surfaces of SiC to brush, dip-coating or spraying Mode prepare initialization layer, brush, the number of dip-coating or spraying is 2-10 times；
Step 5：After prepared by initialization layer, the carbon material with initialization layer is placed in superhigh temperature heat-treatment furnace, is passed through argon gas Atmosphere protection, and superhigh temperature heat-treatment furnace is warming up to 2000 ~ 2300 DEG C with 3 ~ 10 DEG C/min heating rates, 2 ~ 5h is incubated, Carbon material surface obtains MB2- SiC external coatings.
3. a kind of carbon material surface boride according to claim 2 is modified the preparation method of silicon substrate antioxidant coating, its It is characterised by：In step 3, MB2Powder is 10%-90wt.%, and SiC powder is that 5%-80 wt.%, Si powder are that 5%-30 wt.%, C powder is 5%-30 wt.%。
4. a kind of carbon material surface boride according to claim 2 is modified the preparation method of silicon substrate antioxidant coating, its It is characterised by：In step 3, the volume of described Ludox and the ratio of mixed powder quality are 0.5-3ml/g.
5. a kind of carbon material surface boride according to claim 2 is modified the preparation method of silicon substrate antioxidant coating, its It is characterised by：In step 4, brush every time, sample is put into 70-120 DEG C of baking oven after dip-coating or spraying and fully dries 1- 10h, dry brushed next time again after terminating, dip-coating or spraying, brush, the number of dip-coating or spraying is 2-10 times.
6. a kind of carbon material surface boride according to claim 2 is modified the preparation method of silicon substrate antioxidant coating, its It is characterised by：In step 5, MB that carbon material surface obtains2- SiC external coatings are ZrB2- SiC, TaB2- SiC or HfB2-SiC。
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