CN103193497B - Sticky product with silicon erosion resistance of carbon/carbon composite material and preparation method thereof - Google Patents
Sticky product with silicon erosion resistance of carbon/carbon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sticky product with silicon erosion resistance of a carbon/carbon composite material and a preparation method thereof. The method comprises the steps of: putting a carbon fiber precast body into a reaction chamber of a vacuum high-temperature furnace; depositing an inner coating containing silicon carbide at the surface of a carbon fiber; depositing pyrolytic carbon at the surface of the carbon fiber to prepare a carbon/carbon composite material billet; putting into a vacuum autoclave and an atmospheric carbonization furnace, carrying out vacuum impregnation of resin, pressurized solidification, and normal-pressure carbonization; continuing to fill resin carbon in a residual hole inside the billet to obtain the compact carbon/carbon composite material billet; finally putting into a vacuum high-temperature furnace; and carrying out high-temperature graphite purification treatment and overall coating of an outer coating containing silicon carbide, so as to prepare the sticky product with silicon erosion resistance of the carbon/carbon composite material.
Description
Technical field
The present invention relates to a kind of anti-silicon and corrode carbon/carbon compound material goods of adhesion and preparation method thereof, belong to technical field of composite materials.
Technical background
Carbon graphite is the material being made up of carbon, has the characteristics such as good conduction, heat conduction, anticorrosive, radiation hardness, high-low temperature resistant, particularly has high temperature resistant, stable chemical nature, does not pollute the outstanding advantages such as high-purity semiconductor material.The application in semi-conductor industry of semi-conductive development and carbon graphite material is undivided.Enter 21 century, photovoltaic industry has obtained development rapidly, and the increase of advancing by leaps and bounds has all appearred in polycrystalline silicon used for solar battery ingot material on output and market, and this provides a new application that development prospect is wide also to graphite product in photovoltaic industry field.
Carbon-graphite product is applied with regard to the type with carbon graphite class material in semi-conductor, photovoltaic industry field, is divided into the type of three development.The first kind is the graphite product of mold pressing (or extruding or vibration) moulding process method.This class graphite product, in the carbon graphite material product group of semi-conductor, the application of photovoltaic industry field, occupies a very little part now.Second Type is the isotropy high purity graphite products of isostatic pressing process method.In current semi-conductor, photovoltaic industry field, it obtains applying the most widely.The more than 80% of graphite product amount of the whole semi-conductor in the Ta Zhan world, the application of photovoltaic industry field.The 3rd type is carbon/carbon-fibre composite.This is more novel material and goods that a class substitutes graphite material in semi-conductor, the application of photovoltaic industry field.
Carbon/carbon compound material is carbon fiber reinforced carbon matrix composite.It has the outstanding features such as quality is light, ablation resistance good, thermal-shock resistance is good, damage tolerance is high, hot strength is high, designability is strong, and therefore, it has application more widely in many fields such as space flight, aviation, nuclear power.And matrix material can be prepared and be met the desired performance of specific end use and shape by kind, structure, quantity and the matrix precursor of selection fiber and processing condition, and therefore its range of application is more and more extensive, is also more and more subject to people's attention.Carbon/carbon compound material intensity is far longer than graphite, and its good stability of the dimension, shock-resistant, thermal shock resistance good, and its comprehensive mechanical performance is better than graphite.This material can pass through purification process, and metals content impurity is controlled at below 5ppm.
The preparation process of carbon/carbon compound material comprises the selection of fortifying fibre and fabric thereof, the selection of matrix carbon precursor, moulding, the densification of carbon base body and the processing detection of the finished product etc. of C/C preform blank.The specific performance of C/C matrix material depends on a number of factors: kinds of fibers, fibre content, fibre array, body material, fibrolaminar formation, compactness extent, thermal treatment and improved properties etc.
As semi-conductor, photovoltaic industry carbon-carbon composite thermal field product, with the comparison of conventional graphite product, there is following outstanding advantages: ﹙ 1 ﹚ and can significantly extend product work-ing life, reduce the number of times of changing parts, thereby improve the utilization ratio of equipment, reduce maintenance cost; ﹙ 2 ﹚, compared with conventional graphite product, can do thinlyyer, thereby can utilize, existing installation production size is longer, the product of larger diameter, can save a large amount of new installation investment costs, also makes its temperature field more even; ﹙ 3 ﹚, due to its good thermal shock, are being difficult for cracking under the high warm condition of shaking repeatedly, thereby have avoided the variation in temperature field; ﹙ 4 ﹚ are drawing when large diameter product, and conventional graphite thermal field formed product difficulty, and because carbon/carbon compound material has excellent performance is external while drawing large diameter product at present, has more adopted carbon-carbon composite thermal field product.
Although the world and China substitute in semi-conductor, photovoltaic industry with obtaining no small progress on graphite product at carbon-carbon composite, but it generally also exists following problem: ﹙ 1 ﹚ manufacturing cost at present, Hen Gao ﹙ is generally a times of graphite product, even more Gao Xie ﹚.﹙ 2 ﹚ carbon/carbon-fibre composites in the mill the production cycle long, production efficiency is low.﹙ 3 ﹚ are because the history of manufacture semi-conductor, carbon-to-carbon fibre composite research and development for photovoltaic industry, production is also very short, inadequate in technologic maturity, therefore in some performance, still have much room for improvement.
Chinese patent literature CN 102660768A(application number 201210166266.4) preparation technology of a kind of monocrystaline silicon stove carbon/carbon composite material crucible disclosed, the method adopts the precast body of PAN-based carbon fiber establishment, with Sweet natural gas, propylene, the mixed gas of oil liquefied gas is carbon source, nitrogen or argon gas are carrier gas, in the samming thermal field forming at vertical tank type multiple cvd furnace, the upper air on timing for cutting replace tubes road and lower air inlet, utilize the pressure difference of the inside and outside gas of crucible, realize equal warm therapy, pressure differential method, forced draft method combines, realize the quick densifying of crucible base substrate entirety, crucible is after 300 to 350 hours, density reachable is to 1.6g/cm
3above.There is following shortcoming in this technical scheme: 1 Density inhomogeneity, and top layer density is high, and core density is low; 2 unprotect layers, not anti-silicon steam corrodes.
Chinese patent literature CN 102731119A(application number 201210230689.8) disclose that a kind of preparation technology is simple, carbon/carbon/composite material of silicon carbide crucible and preparation method that the steam of resistance to silicon corrodes, it is characterized in that it adopts chemical vapor infiltration to carry out RESEARCH OF PYROCARBON to it by the carbon fabric perform to crucible and silicon carbide replaces after density or RESEARCH OF PYROCARBON and silicon carbide caballing, after machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3, flexural strength>=300MPa, fracture toughness property>=15MPam
1/2.There is following shortcoming in this technical scheme: 1 Density inhomogeneity, and top layer density is high, and core density is low; 2 silicon carbide are not directly to protect carbon fiber or directly protect crucible at crucible surface at fiber surface, but are dispersed among matrix, and protection efficiency is not high; 3 preparation costs are high.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of anti-silicon to corrode carbon/carbon compound material goods of adhesion and preparation method thereof.
Term explanation
Carbon/carbon composite material crucible, be in the carbon fiber stereo fabric precast body hole by the moulding of crucible shape, adopt chemical vapour deposition (being CVD technique), liquid impregnation technique (being PIP technique) fill carbon base body and carbon fiber reinforced carbon matrix composite element.
Technical solution of the present invention is as follows:
Anti-silicon corrodes a preparation method for the carbon/carbon compound material goods of adhesion, and step is as follows:
(1) carbon fiber surface of carbon fabric perform is deposited to rich silicon carbide undercoat, then, at carbon fiber surface deposition RESEARCH OF PYROCARBON, the carbon/carbon compound material base substrate making;
(2) carbon/carbon compound material base substrate step (1) being made is placed in vacuum hotpressing impregnating autoclave, is under the condition of 20～120 ℃ of 200～2000Pa, temperature in vacuum tightness, insulation 10～120min; Then importing thermosetting resin, is 10～120min in air pressure 0.5～5.0MPa, soaking time; Then pass into nitrogen, under the condition of 80～240 ℃ of air pressure 0.5～5.0MPa, temperature, soaking time is 10～120min; Then under normal pressure (0.1MPa), 800～1200 ℃ of conditions of temperature, charing 10～120min;
Repeat above-mentioned steps 1～3 time, make fine and close carbon/carbon compound material base substrate;
(3) fine and close carbon/carbon compound material base substrate step (2) being made is placed in vacuum high-temperature and processes stove, passes into assisted Extraction scrubbed gas, under the condition of 1800～2500 ℃ of temperature, vacuum tightness 100～6000Pa, and insulation 10～300min; Then,, take nitrogen, hydrogen as dilution protection gas, pass into small molecule hydrocarbon and small molecules silicon chloride compound gas, the small molecules hydrocarbon gas: small molecules silicon chloride compound gas: N
2: H
2volume ratio be (0～50): (0～50): (10～100): (0～4) is that 900～1500 ℃, vacuum tightness are 100～6000Pa, N in temperature
2under the condition of airshed 100～2000ml/min, ventilatory response 20～300min, makes anti-silicon and corrodes the carbon/carbon compound material goods of adhesion.
Preferred according to the present invention, the carbon fabric perform in described step (1) is selected the arrange net carbon fiber stereo fabric of acupuncture or carbon fiber stereo weaving of carbon fiber winding, carbon cloth lamination, carbon fiber.
Preferred according to the present invention, the concrete steps in described step (1) are as follows:
First by carbon fabric perform under the condition of 900～1500 ℃ of temperature, vacuum tightness 100～6000Pa, preheating 5～30min; Then pass into gas mixture, carbon source gas in gas mixture: silicon source gas: N
2: H
2volume ratio be (0～50): (0～50): (10～100): (0～4), N
2airshed 100～2000ml/min, the ventilatory response time is 20～300min; Then by carbon source gas: N
2: H
2volume ratio be (10～40): (10～40): (1～4) passes into gas mixture, N
2airshed 100～2000ml/min, ventilatory response 24～240h.
Further preferred according to the present invention, carbon source gas in above-mentioned gas mixture: silicon source gas: N
2: H
2volume ratio be (0～40): (5～40): (10～40): (1～2).
Further preferred according to the present invention, above-mentioned carbon source gas is selected from a kind of or mixing in propylene, propane, methane, liquefied petroleum gas (LPG).
Further preferred according to the present invention, above-mentioned silicon source gas is selected from a kind of or mixing in tetrachloro silicane, trichlorosilane, METHYL TRICHLORO SILANE, dimethyl dichlorosilane (DMCS);
Each step of the present invention all can select the conventional equipments such as vacuum resistance High Temperature Furnaces Heating Apparatus, vacuum induction High Temperature Furnaces Heating Apparatus, vacuum hotpressing tank, normal pressure resistance furnace, normal pressure carbide furnace to complete.
Preferred according to the present invention, the thermosetting resin in described step (2) is selected from one of resol, furane resin, Ben Bing Evil piperazine resin.Above-mentioned resol, furane resin, benzoxazine colophony are the low viscous thermosetting resin of high carbon residue rate.
Preferred according to the present invention, in described step (3), assisted Extraction scrubbed gas is chlorine and/or freonll-11.
Preferred according to the present invention, described step (3) the small molecular hydrocarbon gas: small molecules silicon chloride compound gas: N
2: H
2volume ratio be (0～40): (5～40): (10～40): (1～2).
Preferred according to the present invention, described step (3) the small molecular hydrocarbon gas is selected from a kind of or mixing in propylene, propane, methane, liquefied petroleum gas (LPG).
Preferred according to the present invention, described step (3) small molecular silicon chloride compound gas is selected from a kind of or mixing in tetrachloro silicane, trichlorosilane, METHYL TRICHLORO SILANE, dimethyl dichlorosilane (DMCS).
Method of the present invention is particularly suitable for making the various carbon/carbon composite material crucibles that need to resist silicon steam to corrode that semicon industry is used, and other thermojunction member such as guide shell, cover plate, bolt, is also suitable for preparing oxidation resistant carbon/carbon compound material member.
A kind of anti-silicon corrodes the carbon/carbon compound material goods of adhesion, comprise carbon fabric perform, rich silicon carbide undercoat and silicon carbide outer coating, the rich silicon carbide undercoat of carbon fiber surface deposition 1～30 μ m of carbon fabric perform, internally coated outside deposition 10～300 μ m silicon carbide outer coatings of rich silicon carbide.
Beneficial effect
1, the silicon carbide outer coating in the carbon/carbon compound material goods of anti-silicon erosion adhesion of the present invention stops high temperature silicon material and carbon fabric perform body contact reacts, cause silicon material and carbon fabric perform adhesion, also reduced silicon steam simultaneously and infiltrated to carbon fabric perform is inner; The tight wrap carbon fiber precast body of rich silicon carbide undercoat, prevents that it from being corroded by ambiances such as silicon steam, keeps the enhancement of carbon fiber.Thereby make carbon fabric perform not easy to crack, improved work reliability and work-ing life, meanwhile,, with the adhesion of silicon material, do not reduced silicon material pollution loss and feeding labor capacity.
2, the operation of the rich silicon carbide undercoat of the direct protection carbon fiber in preparation method of the present invention and the silicon carbide outer coating of Global Macros crucible operates in the situation of not blowing out and has merged with deposition density operation, high temperature purification respectively; do not increasing under the extra prerequisite that takes on stove workload; adopt the first density measure of deposition, rear dipping; the synergy of accelerating density, makes small product size density reach 1.60～1.75g/cm
3, the process time is than adopting separately a kind of wherein method significantly to reduce, and the anti-silicon erosion of worth product adhesion, long service life, and feeding adhesion, has reduced cost.
Accompanying drawing explanation
Fig. 1 is the structural representation that anti-silicon corrodes the carbon/carbon composite material crucible of adhesion.
Wherein, 1, carbon fiber; 2, rich silicon carbide undercoat, 3, silicon carbide outer coating.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited to this.
Raw material sources
Carbon fiber arrange net acupuncture crucible precast body, carbon fiber knit crucible is prefabricated, carbon cloth lamination crucible precast body Jiangsu Tianniao High Technology Co., Ltd. is on sale;
Furane resin and resol, the bright Chemical Co., Ltd. in Wuxi is on sale;
Preparation draws the carbon/carbon composite material crucible of silicon single crystal material, crucible size Φ 500 × 450mm.
(1) coating in advance: the carbon fiber the having made acupuncture crucible precast body of arranging net is placed in the reaction chamber of chemical vapor deposition stove, under 1000 ℃ of high temperature, 3000Pa low-voltage vacuum condition, preheating 30min; Then take nitrogen, hydrogen as dilution protection gas, pass into by METHYL TRICHLORO SILANE: N
2: H
2volume ratio be 10:20:1 mix gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 1000ml/min; the ventilatory response time is 60min; obtain the rich silicon carbide undercoat of>=10 μ m; then deposit density; the carbon fiber crucible precast body of coating processing and frock are placed in the reaction chamber of chemical vapor deposition stove; under 1000 ℃ of high temperature, 3000Pa low-voltage vacuum condition, take nitrogen as dilution protection gas, by methane: N
2: H
2volume ratio be that 10:10:1 passes into gas mixture, infiltrate precast body inside, RESEARCH OF PYROCARBON is at coat carbon fiber surface deposition, filling carbon fiber crucible precast body internal void, N
2airshed 500ml/min, the ventilatory response time is 180h, obtains volume density>=1.35g/cm
3carbon/carbon compound material base substrate.
(2) dipping density: by volume density>=1.35g/cm
3carbon/carbon compound material base substrate be placed in vacuum hotpressing impregnating autoclave, at temperature 60 C, under vacuum tightness 2000Pa condition, adopt furane resin dippings carbon/carbon compound material base substrate, insulation 30min; ,, fill mesolow nitrogen, to 2.0MPa, resin liquid is squeezed into inside workpiece depths, insulation 30min thereafter; Again, keep 2.0MPa nitrogen pressure, be warming up to 120 ℃, soaking time 60min carries out thermofixation; Finally, proceed in normal pressure carbide furnace resin charing 120min under 800 ℃, 0.1MPa nitrogen protection;
Repeat above-mentioned steps 2 times, obtain volume density>=1.65g/cm
3fine and close carbon/carbon compound material base substrate;
(3) purification greying and external coating (EC): by volume density>=1.65g/cm
3fine and close carbon/carbon compound material base substrate be placed in vacuum high-temperature and process stove, under 2100 ℃ of high temperature, 3000Pa low-voltage vacuum condition, take chlorine and freonll-11 as assisted Extraction scrubbed gas, insulation 60min high temperature graphitization is purified; Then, be down under 1000 ℃ of high temperature, 1000Pa low-voltage vacuum condition, take nitrogen, hydrogen as dilution protection gas, by METHYL TRICHLORO SILANE: N
2: H
2volume ratio be that 10:10:1 passes into gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 1500ml/min, the ventilatory response time is 60min, forms the rich silicon carbide outer coating of>=50 μ m, makes anti-silicon and corrodes the carbon/carbon compound material goods of adhesion.
Make the carbon/carbon compound material article construction of anti-silicon erosion adhesion as shown in Figure 1, comprise carbon fiber 1, rich silicon carbide undercoat 2 and silicon carbide outer coating 3, the carbon fiber surface of carbon fiber 1 deposits the rich silicon carbide undercoat 2 of 10 μ m, the outside deposition 100 μ m silicon carbide outer coatings 3 of rich silicon carbide undercoat 2.
After testing, the carbon/carbon compound material goods that the anti-silicon making corrodes adhesion under 10h silicon vapor action material bending strength degradation 3%.
The carbon/carbon composite material crucible of preparation purification melting polysilicon, crucible size Φ 600 × 600mm.
(1) undercoat and deposition density: the carbon fiber knit crucible precast body having made is placed in the reaction chamber of chemical vapor deposition stove, under 900 ℃ of high temperature, 100Pa low-voltage vacuum condition, preheating 5min; Then prepare undercoat, take nitrogen, hydrogen as dilution protection gas, pass into by methane: tetrachloro silicane: N
2: H
2volume ratio be 10:10:10:1 mix gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 100ml/min, the ventilatory response time is 300min, obtains the rich silicon carbide undercoat of>=5 μ m.Then deposit density, the carbon fiber crucible precast body of coating processing and frock are placed in the reaction chamber of chemical vapor deposition stove, under 900 ℃ of high temperature, 100Pa low-voltage vacuum condition, take nitrogen as dilution protection gas, by propylene: N
2: H
2volume ratio be that 10:30:1 passes into gas mixture, infiltrate precast body inside, RESEARCH OF PYROCARBON is at coat carbon fiber surface deposition, filling carbon fiber crucible precast body internal void, N
2airshed 2000ml/min, the ventilatory response time is 240h, obtains volume density>=1.30g/cm
3carbon/carbon compound material base substrate.
(2) dipping density: by volume density>=1.35g/cm
3carbon/carbon compound material base substrate be placed in vacuum hotpressing impregnating autoclave, 120 ℃ of temperature, under vacuum tightness 200Pa condition, adopt resin impregnating carbon/carbon compound material base substrate, insulation 120min; ,, fill mesolow nitrogen, to 1.0MPa, resin liquid is squeezed into inside workpiece depths, insulation 30min thereafter; Again, keep 1.0MPa nitrogen pressure, be warming up to 240 ℃, soaking time 120min carries out thermofixation; Finally, proceed in normal pressure carbide furnace resin charing 120min under 1200 ℃ of temperature, 0.1MPa nitrogen protection;
Repeat above-mentioned steps 1 time, obtain volume density>=1.60g/cm
3carbon/carbon composite material crucible base substrate.
(3) purification greying and external coating (EC): by volume density>=1.60g/cm
3fine and close carbon/carbon compound material base substrate be placed in vacuum high-temperature and process stove, under 2200 ℃ of high temperature, 100Pa low-voltage vacuum condition, take chlorine and freonll-11 as assisted Extraction scrubbed gas, insulation 10min high temperature graphitization is purified; Then, be down under 900 ℃ of high temperature, 100Pa low-voltage vacuum condition, take nitrogen, hydrogen as dilution protection gas, by methane: tetrachloro silicane: N
2: H
2volume ratio be that 10:10:10:1 passes into gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 100ml/min, the ventilatory response time is 60min, forms the outer undercoat of the rich silicon carbide of>=30 μ m, makes anti-silicon and corrodes the carbon/carbon compound material goods of adhesion.
Make the carbon/carbon compound material goods that anti-silicon corrodes adhesion, comprise carbon fiber 1, rich silicon carbide undercoat 2 and silicon carbide outer coating 3, the carbon fiber surface of carbon fiber 1 deposits the rich silicon carbide undercoat 2 of 8 μ m, the outside deposition 90 μ m silicon carbide outer coatings 3 of rich silicon carbide undercoat 2.
After testing, the carbon/carbon compound material goods that the anti-silicon making corrodes adhesion under 10h silicon vapor action material bending strength degradation 4%.
Embodiment 3
Prepare the carbon/carbon composite material crucible of polycrystalline silicon ingot casting, crucible size 800 × 800 × 600mm.
(1) undercoat and deposition density: the carbon cloth lamination crucible precast body having made is placed in the reaction chamber of chemical vapor deposition stove, under 1500 ℃ of high temperature, 6000Pa low-voltage vacuum condition, preheating 15min; Then prepare undercoat, take nitrogen, hydrogen as dilution protection gas, pass into by METHYL TRICHLORO SILANE: N
2: H
2volume ratio be 10:10:1 mix gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 2000ml/min; the ventilatory response time is 100min; obtain the rich silicon carbide undercoat of>=20 μ m; then deposit density; the carbon fiber crucible precast body of coating processing and frock are placed in the reaction chamber of chemical vapor deposition stove; under 1500 ℃ of high temperature, 6000Pa low-voltage vacuum condition, take nitrogen as dilution protection gas, by methane: N
2: H
2volume ratio be that 10:10:1 passes into gas mixture, infiltrate precast body inside, RESEARCH OF PYROCARBON is at coat carbon fiber surface deposition, filling carbon fiber crucible precast body internal void, N
2airshed 1500ml/min, the ventilatory response time is 240h, obtains volume density>=1.40g/cm
3carbon/carbon compound material base substrate.
(2) dipping density: by volume density>=1.40g/cm
3carbon/carbon compound material base substrate be placed in vacuum hotpressing impregnating autoclave, 20 ℃ of temperature, under vacuum tightness 2000Pa condition, adopt furane resin dippings carbon/carbon compound material base substrate, insulation 120min; ,, fill mesolow nitrogen, to 5.0MPa, resin liquid is squeezed into inside workpiece depths, insulation 10min thereafter; Again, keep 5.0MPa nitrogen pressure, be warming up to 80 ℃, soaking time 10min carries out thermofixation; Finally, proceed in normal pressure carbide furnace resin charing 30min under 1000 ℃ of temperature, 0.1MPa nitrogen protection;
Aforesaid operations repeats 3 times, obtains volume density>=1.65g/cm
3carbon/carbon composite material crucible base substrate.
(3) purification greying and external coating (EC): by volume density>=1.65g/cm
3fine and close carbon/carbon compound material base substrate be placed in vacuum high-temperature and process stove, under 2500 ℃ of high temperature, 6000Pa low-voltage vacuum condition, take chlorine and freonll-11 as assisted Extraction scrubbed gas, insulation 300min high temperature graphitization is purified; Then, be down under 1500 ℃ of high temperature, 6000Pa low-voltage vacuum condition, take nitrogen, hydrogen as dilution protection gas, by METHYL TRICHLORO SILANE: N
2: H
2volume ratio be that 10:10:1 passes into gas mixture, infiltrate precast body inside, pyrolyzate deposits at carbon fiber surface, N
2airshed 2000ml/min, the ventilatory response time is 200min, forms the outer undercoat of the rich silicon carbide of>=100 μ m, makes anti-silicon and corrodes the carbon/carbon compound material goods of adhesion.
Make the carbon/carbon compound material goods that anti-silicon corrodes adhesion, comprise carbon fiber 1, rich silicon carbide undercoat 2 and silicon carbide outer coating 3, the carbon fiber surface of carbon fiber 1 deposits the rich silicon carbide undercoat 2 of 25 μ m, the outside deposition 150 μ m silicon carbide outer coatings 3 of rich silicon carbide undercoat 2.
After testing, the carbon/carbon compound material goods that the anti-silicon making corrodes adhesion under 10h silicon vapor action material bending strength degradation 2%.
Comparative example 1
According to Chinese patent literature CN 102660768A(application number 201210166266.4) product for preparing of the method recorded in embodiment, under 10h silicon vapor action material bending strength degradation 40%.
Comparative example 2
Please be with Chinese patent literature CN 102731119A(application number 201210230689.8) product for preparing of the method recorded in embodiment 1, under 10h silicon vapor action material bending strength degradation 7%.
Can be found by above-mentioned materials flexural strength data, silicon carbide outer coating in the carbon/carbon compound material goods of anti-silicon erosion adhesion of the present invention stops high temperature silicon material and carbon fabric perform body contact reacts, cause silicon material and carbon fabric perform adhesion, also reduced silicon steam simultaneously and infiltrated to carbon fabric perform is inner; The tight wrap carbon fiber precast body of rich silicon carbide undercoat, prevent that it from being corroded by ambiances such as silicon steam, keep the enhancement of carbon fiber, the flexural strength decline degree of carbon fiber is also not obvious, and prior art (comparative example 1 and comparative example 2) cannot reach this effect.
Claims (10)
1. anti-silicon corrodes a preparation method for the carbon/carbon compound material goods of adhesion, it is characterized in that, step is as follows:
(1) carbon fiber surface of carbon fabric perform is deposited to rich silicon carbide undercoat, then, in carbon fiber surface deposition RESEARCH OF PYROCARBON, the carbon/carbon compound material base substrate making, concrete steps are as follows:
First by carbon fabric perform under the condition of 900～1500 ℃ of temperature, vacuum tightness 100～6000Pa, preheating 5～30min; Then pass into gas mixture, carbon source gas in gas mixture: silicon source gas: N
2: H
2volume ratio be (0～50): (0～50): (10～100): (0～4), N
2airshed 100～2000ml/min, the ventilatory response time is 20～300min; Then by carbon source gas: N
2: H
2volume ratio be (10～40): (10～40): (1～4) passes into gas mixture, N
2airshed 100～2000ml/min, ventilatory response 24～240 h;
(2) carbon/carbon compound material base substrate step (1) being made is placed in vacuum hotpressing impregnating autoclave, is under the condition of 20～120 ℃ of 200～2000Pa, temperature in vacuum tightness, insulation 10～120min; Then importing thermosetting resin, is 10～120min in air pressure 0.5～5.0MPa, soaking time; Then pass into nitrogen, under the condition of 80～240 ℃ of air pressure 0.5～5.0MPa, temperature, soaking time is 10～120min; Then under normal pressure, 800～1200 ℃ of conditions of temperature, charing 10～120min;
Repeat above-mentioned steps 1～3 time, make fine and close carbon/carbon compound material base substrate;
(3) fine and close carbon/carbon compound material base substrate step (2) being made is placed in vacuum high-temperature and processes stove, passes into assisted Extraction scrubbed gas, under the condition of 1800～2500 ℃ of temperature, vacuum tightness 100～6000Pa, and insulation 10～300 min; Then,, take nitrogen, hydrogen as dilution protection gas, pass into small molecule hydrocarbon and small molecules silicon chloride compound gas, the small molecules hydrocarbon gas: small molecules silicon chloride compound gas: N
2: H
2volume ratio be (0～50): (0～50): (10～100): (0～4) is that 900～1500 ℃, vacuum tightness are 100～6000Pa, N in temperature
2under the condition of airshed 100～2000ml/min, ventilatory response 20～300min, makes anti-silicon and corrodes the carbon/carbon compound material goods of adhesion;
In described step (3), assisted Extraction scrubbed gas is chlorine and/or freonll-11.
2. preparation method as claimed in claim 1, is characterized in that, the carbon fabric perform in described step (1) is selected the arrange net carbon fiber stereo fabric of acupuncture or carbon fiber stereo weaving of carbon fiber winding, carbon cloth lamination, carbon fiber.
3. preparation method as claimed in claim 1, is characterized in that, carbon source gas in described gas mixture: silicon source gas: N
2: H
2volume ratio be (0～40): (5～40): (10～40): (1～2).
4. preparation method as claimed in claim 1, is characterized in that, described carbon source gas is selected from a kind of or mixing in propylene, propane, methane, liquefied petroleum gas (LPG).
5. preparation method as claimed in claim 1, is characterized in that, described silicon source gas is selected from a kind of or mixing in tetrachloro silicane, trichlorosilane, METHYL TRICHLORO SILANE, dimethyl dichlorosilane (DMCS).
6. preparation method as claimed in claim 1, is characterized in that, the thermosetting resin in described step (2) is selected from one of resol, furane resin, benzoxazine colophony.
7. preparation method as claimed in claim 1, is characterized in that, described step (3) the small molecular hydrocarbon gas: small molecules silicon chloride compound gas: N
2: H
2volume ratio be (0～40): (5～40): (10～40): (1～2).
8. preparation method as claimed in claim 1, is characterized in that, described step (3) the small molecular hydrocarbon gas is selected from a kind of or mixing in propylene, propane, methane, liquefied petroleum gas (LPG).
9. preparation method as claimed in claim 1, is characterized in that, described step (3) small molecular silicon chloride compound gas is selected from a kind of or mixing in tetrachloro silicane, trichlorosilane, METHYL TRICHLORO SILANE, dimethyl dichlorosilane (DMCS).
10. the anti-silicon that a claim 1 makes corrodes the carbon/carbon compound material goods of adhesion, it is characterized in that, comprise carbon fabric perform, rich silicon carbide undercoat and silicon carbide outer coating, the rich silicon carbide undercoat of carbon fiber surface deposition 1～30 μ m of carbon fabric perform, internally coated outside deposition 10～300 μ m silicon carbide outer coatings of rich silicon carbide.
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| CN111807853B (en) * | 2020-07-07 | 2021-05-28 | 湖南碳谷新材料有限公司 | Carbon-carbon composite material and preparation process and application thereof |
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| CN115180969B (en) * | 2022-07-15 | 2023-03-03 | 湖南东方辉陵碳素新材料有限公司 | High-thermal-conductivity carbon-carbon composite material and preparation method thereof |
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Effective date of registration: 20190124 Address after: No. 90 Nanhuan East Road, Yucheng National High-tech Industrial Development Zone, Dezhou City, Shandong Province, 251200 Patentee after: Shandong Daopuan Brake Material Co., Ltd. Address before: No. 88 Nanhuan Road, Yucheng City, Dezhou City, Shandong Province, 251200 Patentee before: Shandong Guojing New Materials Co., Ltd. |