CN102731133B - Fastener using carbon/carbon/silicon carbide composite material and preparation method of fastener - Google Patents
Fastener using carbon/carbon/silicon carbide composite material and preparation method of fastener Download PDFInfo
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- CN102731133B CN102731133B CN 201210230680 CN201210230680A CN102731133B CN 102731133 B CN102731133 B CN 102731133B CN 201210230680 CN201210230680 CN 201210230680 CN 201210230680 A CN201210230680 A CN 201210230680A CN 102731133 B CN102731133 B CN 102731133B
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Abstract
The invention discloses a fastener using carbon/carbon/silicon carbide composite material, with a simple production process and resistance to erosion of silicon vapor, and a preparation method of the fastener. The preparation method of the fastener is characterized by comprising the steps of carrying out the chemical vapor infiltration on the carbon fibre preform of the fastener to to densify pyrolytic carbon and silicon carbide alternatively or perform caballing to the pyrolytic carbon and the silicon carbide, mechanically machining, and purifying to obtain the product. The density of the fastener is between 1.3g/ cm<3> and 2.5g/cm<3>; the flexural strength of the fastener is more than or equal to 300MPa; and the fracture toughness of the fastener is more than or equal to 15MPa.m<l/2>. According to the fastener and the preparation method provided by the invention, the erosion of the silicon vapor on the core carbon fibre of the carbon/carbon/silicon carbide composite material can be effectively inhibited. The flexural strength of the prepared carbon/carbon/silicon carbide composite material is more than 300MPa and is 2-5 times of that of the carbon/carbon composite material; the fracture toughness of the carbon/carbon/silicon carbide composite material is more than or equal to 15MPa.m<l/2>; the resistance of the carbon/carbon/silicon carbide composite material to the erosion of the silicon vapour is increased by 5-10 times compared with that of the carbon/carbon composite material; the service life of the fastener is greatly prolonged; and meanwhile, the higher strength of the fastener is beneficial to the improvement of the safety of the thermal field.
Description
Technical field
The present invention relates to a kind of high temperature furnace used thermal field part and preparation method, specifically a kind of carbon/carbon/composite material of silicon carbide fastening piece and preparation method.
Background technology
The premium propertiess such as carbon/carbon compound material is one of advanced composite material of current widespread use, and it is to strengthen the formed matrix material of carbon base body by carbon fiber or various carbon fabric, has density low, and specific tenacity is high, wear-resistant, and high temperature resistant, thermal expansivity is little.The net tire that this material is first made with carbon fiber usually and net tire or carbon cloth and carbon cloth or net tire and carbon cloth are combined into carbon fabric perform by alternative stacked acupuncture, then precast body is put into to the chemical gas phase reaction stove, the RESEARCH OF PYROCARBON of utilizing carbon-source gas cracking under high temperature to produce is carried out the chemical gas phase density to precast body, the prefabricated carbon fiber volume density is progressively increased and becomes carbon/carbon compound material.This material has now become one of the important foundation material in the fields such as aerospace, metallurgy, new forms of energy, is the ideal substitute of graphite product and high temperature steel.
At present, carbon/carbon compound material has been widely used in as high temperature fields such as single crystal growing furnace, polycrystalline furnaces, is used for making the thermal field part, as crucible, guide shell, heat-preservation cylinder, heating element, fastening piece etc.
Document 1: the C/C composite material crucible pot that " the C/C matrix material is manufactured the pre-test of silicon crystal growth crucible; charcoal element; 2004 (2): P3～P7 " discloses a kind of trial-production has carried out type approval test, result shows that C/C matrix material machinery intensity is high, thermal shock resistance and chemical stability good, its work-ing life is higher than the high purity graphite crucible, yet test-results has also been found the defect of C/C composite material crucible pot, oxidative attack (SiO
2and Si) very large on the impact in work-ing life of C/C composite material crucible pot.
The applicant is in order to solve the impact of high temperature silicon steam on C/C matrix material use properties, C/C composite material crucible pot after silicon single-crystal manufacturer is used has carried out analyzing experiment, and adopted the mechanical property of material mechanics tester (American I nstron3369 material mechanics tester) test sample, scanning electron microscope (SEM, JSM～6360LV) microtexture of analysis of material, X-ray energy spectrometer (EDS, EDX～GENESIS 60S type) the analytical sample surface-element distributes, and the results are shown in Figure 1, Fig. 2, Fig. 3, Fig. 4.Can find out that from Fig. 1, Fig. 2 silicon steam corrodes rear sample inside and generated a lot of other materials; From Fig. 3, Fig. 4, can learn, other material generated is silicon carbide (or mixture of silicon and silicon carbide); Its mechanical experimental results is shown to without the sample bending strength corroded be 105MPa simultaneously, by the sample bending strength of Eroded, be only 24.5MPa, close with the intensity of graphite, illustrate that it is the major cause that causes the C/C composite material crucible pot to lose efficacy that silicon steam corrodes.
In order to solve the impact of high temperature silicon steam on C/C matrix material use properties, with regard to current technology, the most frequently used method is made top coat exactly, is mainly that the silicon based ceramic coating is (as SiC or MoSi
2deng).
It is matrix that document 2 " impact of in-situ growing carbon nano tube on CVD SiC coating; China YouSe Acta Metallurgica Sinica; 2011; (2): P418～P424 " has been introduced a kind of C/C of take matrix material, adopt chemical Vapor deposition process to prepare the SiC coating at composite material surface, result shows: through (1100 ℃, 3min) (room temperature, 3min) after thermal cycling 15 times, SiC coating rate of weight loss is 33.17%, and in the thermal shock process, the subregion coating shedding is the major cause of coating sample weightlessness.Visible, because thermal expansivity between C/C matrices of composite material and SiC coating does not mate, the associativity of the coating of preparation and C/C matrices of composite material is poor, in the rapid heat cycle process, easily comes off, and can not protect for a long time the C/C matrix material not to be etched.
For ceramic base coating and the unmatched defect of C/C Thermal expansion coefficient of composites, best solution is penetrated into the C/C composite inner to SiC by chemical vapor infiltration (being called for short CVI) method exactly, thereby form C/SiC or C/C-SiC matrix material, method commonly used has chemical vapor infiltration, precursor to transform (being called for short PIP) method or CVI+PIP method.
Document 3 " C/C-SiC composite material and preparation method thereof and application present situation; charcoal element; 2008 (2): P29～P35 " has been introduced the preparation method of C/C-SiC matrix material, analyzed various preparation methods' relative merits, the CVI+PIP hybrid technique especially PIP method commonly used and new development got up introduces.Document points out to adopt single CVI method to be difficult to prepare highdensity C/SiC or C/C-SiC matrix material, although and adopt single PIP method or CVI+PIP method can prepare highdensity C/SiC or C/C-SiC matrix material, yet the residual a certain amount of Si of meeting in the PIP process, free Si unavoidably can react with carbon fiber, cause the damage of wild phase carbon fiber, cause carbon fiber-reinforced strengthening action to reduce, thereby the over-all properties of material is descended, particularly mechanical strength significantly reduces, and causes the calamitous fracture of material.Simultaneously, its technical process complexity, need to flood repeatedly repeatedly.
Summary of the invention
The purpose of this invention is to provide carbon/carbon that a kind of preparation technology is simple, the steam of anti-silicon corrodes/composite material of silicon carbide fastening piece and preparation method.
The present invention adopts following technical scheme to realize its goal of the invention, a kind of carbon/carbon/composite material of silicon carbide fastening piece, it adopts chemical vapor infiltration to carry out after RESEARCH OF PYROCARBON and silicon carbide replaces density or RESEARCH OF PYROCARBON and silicon carbide caballing it by the carbon fabric perform to fastening piece, 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.
The present invention is the anti-silicon steam corrosion ability of carbon/carbon/composite material of silicon carbide fastening piece that further increases, and at carbon/carbon/composite material of silicon carbide fastener surface, is provided with coat of silicon carbide.
The preparation method of a kind of carbon/carbon/composite material of silicon carbide fastening piece, it comprises the following steps:
(1) carbon fabric perform preparation: the carbon fabric perform that carbon fiber is made to desired structure and shape by shape and the performance requriements of fastening piece, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3;
(2) density: the carbon fabric perform that (1) step is made is put into the chemical gas phase reaction stove, adopts chemical vapor infiltration it to be carried out to RESEARCH OF PYROCARBON and silicon carbide replace density or RESEARCH OF PYROCARBON and silicon carbide caballing until to make density be 1.3g/ ㎝
3～2.5g/ ㎝
3carbon/carbon/composite material of silicon carbide fastening piece base substrate;
(3) machining: by step (2) carbon/the carbon of gained/composite material of silicon carbide fastening piece base substrate be processed into the carbon/carbon of desired shape and size/composite material of silicon carbide fastening piece goods by product requirement;
(4) purifying: carbon/carbon (3) prepared by step/composite material of silicon carbide fastening piece goods are put into the high temperature purification stove and are carried out purifying, 1600 ℃～2800 ℃ of cleansing temps, and purifying time 1h～10h, obtain carbon/carbon/composite material of silicon carbide fastening piece finished product.
The present invention step (2) in, the processing condition that described RESEARCH OF PYROCARBON and silicon carbide replace density are, carbon-source gas is introduced to chemical vapor infiltration RESEARCH OF PYROCARBON in the chemical gas phase reaction stove, the chemical vapor infiltration time is 1h～600h, the carbon-source gas flow is 1L/min～100 L/min, and the pressure of reactant gases is 2kPa～12kPa; Then close carbon-source gas, using hydrogen as carrier gas, using hydrogen or argon gas as diluent gas, by Bubbling method, trichloromethyl silane is introduced to chemical vapor infiltration silicon carbide in the chemical gas phase reaction stove, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapor infiltration time is 1h～600h, and so alternately density makes carbon/carbon/composite material of silicon carbide fastening piece base substrate.
The present invention further improves the resistance to corrosion of material, step (2) in, described RESEARCH OF PYROCARBON and silicon carbide replace density for chemical vapor infiltration silicon carbide at first, and then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide, last chemical vapor infiltration silicon carbide.
The present invention step (2) in, the processing condition of described RESEARCH OF PYROCARBON and silicon carbide caballing are, carbon-source gas and trichloromethyl silane are introduced to chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide in the chemical gas phase reaction stove simultaneously, the carbon-source gas flow is 1L/min～100 L/min, trichloromethyl silane is introduced by Bubbling method, using hydrogen as carrier gas, using hydrogen or argon gas as diluent gas, in reactant gases, Siliciumatom is 1:1～5 with the number ratio of carbon atom, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapor infiltration time is 1h～600h, so caballing makes carbon/carbon/composite material of silicon carbide fastening piece base substrate.
The present invention is the anti-silicon steam corrosion ability of carbon/carbon/composite material of silicon carbide fastening piece that further increases, carbon/carbon that (3) step is made afterwards/composite material of silicon carbide fastening piece goods are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
Processing condition prepared by coat of silicon carbide of the present invention are: using hydrogen as carrier gas, take hydrogen or argon gas as diluent gas, by Bubbling method, trichloromethyl silane is introduced to chemical vapor deposition of silicon carbide in the chemical gas phase reaction stove, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapour deposition time is 1h～100h, can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide fastening piece product surface.
Owing to adopting technique scheme, the present invention has realized goal of the invention preferably, its technique is simple, it is convenient to implement, can effectively suppress the erosion of silicon steam to carbon/carbon/composite material of silicon carbide core carbon fiber, the preparation carbon/carbon/the composite material of silicon carbide flexural strength is greater than 300MPa, is 2～5 times of carbon/carbon compound material, fracture toughness property>=15MPam
1/2, anti-silicon steam corrosion energy force rate carbon/carbon compound material is compared and has been improved 5～10 times, has increased substantially the work-ing life of fastening piece, and simultaneously, its higher intensity also is conducive to improve the security of thermal field.
The accompanying drawing explanation
Fig. 1 is the surface microscopic topographic figure of carbon/carbon compound material sample before silicon steam corrodes;
Fig. 2 is the surface microscopic topographic figure of carbon/carbon compound material sample after silicon steam corrodes;
Fig. 3 is the surface-element analysis chart of carbon/carbon compound material sample before silicon steam corrodes;
Fig. 4 is the surface-element analysis chart of carbon/carbon compound material sample after silicon steam corrodes;
Fig. 5 is the cross section back scattering picture of the described carbon/carbon of the embodiment of the present invention 1/composite material of silicon carbide; The density of carbon/carbon in figure/composite material of silicon carbide is 1.65g/ ㎝
3, wherein white portion is silicon carbide, and central black is carbon fiber, and carbon fiber outside surface black part is divided into RESEARCH OF PYROCARBON, adopts RESEARCH OF PYROCARBON and silicon carbide to replace density, and the temperature during RESEARCH OF PYROCARBON density is 1100 ℃, the chemical vapor infiltration time is 80h; Temperature during the silicon carbide density is 1100 ℃, and the chemical vapor infiltration time is 50h;
Fig. 6 is RESEARCH OF PYROCARBON and silicon carbide while replacing density and RESEARCH OF PYROCARBON and silicon carbide caballing, the three-point bending resistance intensity of carbon/carbon/composite material of silicon carbide sampling and testing-displacement curve figure; In figure, curve A is RESEARCH OF PYROCARBON and silicon carbide while replacing density, the three-point bending resistance intensity of sample-displacement curve figure; When curve B is RESEARCH OF PYROCARBON and silicon carbide caballing, the three-point bending resistance intensity of sample-displacement curve figure.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
From Fig. 1, Fig. 2, can find out, the carbon/carbon compound material sample is after silicon steam corrodes, and sample inside has generated a lot of other materials; From Fig. 3, Fig. 4, can learn, other material generated is silicon carbide (or mixture of silicon and silicon carbide); Simultaneously, the sample mechanical experimental results shows, without the sample bending strength corroded, is 105MPa, by the sample bending strength of Eroded, is only 24.5MPa, close with the intensity of graphite, illustrate that it is the major cause that causes carbon/carbon compound material to lose efficacy that silicon steam corrodes.
Embodiment 1:
A kind of carbon/carbon/composite material of silicon carbide fastening piece, it adopts chemical vapor infiltration to carry out after RESEARCH OF PYROCARBON and silicon carbide replaces density or RESEARCH OF PYROCARBON and silicon carbide caballing (the present embodiment is alternately density) it by the carbon fabric perform to fastening piece, after machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3(the present embodiment is 1.65g/ ㎝
3), flexural strength>=300MPa, fracture toughness property>=15MPam
1/2.
The preparation method of a kind of carbon/carbon/composite material of silicon carbide fastening piece, it comprises the following steps:
(1) carbon fabric perform preparation: the carbon fabric perform that carbon fiber is made to desired structure and shape by shape and the performance requriements of fastening piece, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3(the present embodiment is 0.50g/ ㎝
3);
While preparing carbon fabric perform, the net tire that carbon fiber can be made and net tire or carbon cloth and carbon cloth or net tire and carbon cloth are combined into carbon fabric perform by alternative stacked acupuncture, also can adopt weave to be woven into carbon fabric perform on carbon fiber; The present embodiment adopts net tire and carbon cloth to be combined into carbon fabric perform by alternative stacked acupuncture.
(2) density: the carbon fabric perform that (1) step is made is put into the chemical gas phase reaction stove, adopts chemical vapor infiltration it to be carried out to RESEARCH OF PYROCARBON and silicon carbide replace density or RESEARCH OF PYROCARBON and silicon carbide caballing (the present embodiment is alternately density) until to make density be 1.3g/ ㎝
3～2.5g/ ㎝
3(the present embodiment is 1.65g/ ㎝
3) carbon/carbon/composite material of silicon carbide fastening piece base substrate;
Step (2) in, the processing condition that described RESEARCH OF PYROCARBON and silicon carbide replace density are, the chemical gas phase reaction stove is warming up to 900 ℃～1400 ℃ (the present embodiment is 1100 ℃), insulation 1h～6h(the present embodiment is 1h).Carbon-source gas (the present embodiment is methane) is introduced to chemical vapor infiltration RESEARCH OF PYROCARBON in the chemical gas phase reaction stove, the chemical vapor infiltration time is that 1h～600h(the present embodiment is 80h), the carbon-source gas flow is that 1L/min～100 L/min(the present embodiment are 28L/min), the pressure of reactant gases is that 2kPa～12kPa(the present embodiment is 5kPa); Then close carbon-source gas, using hydrogen as carrier gas, using hydrogen or argon gas (the present embodiment is hydrogen) as diluent gas, by Bubbling method, trichloromethyl silane is introduced to chemical vapor infiltration silicon carbide in the chemical gas phase reaction stove, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is that 1:5～20(the present embodiment is 1:5), the pressure of reactant gases is that 2kPa～12kPa(the present embodiment is 3.5kPa); The container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, and 18 ℃～45 ℃ of bath temperatures (the present embodiment is 35 ℃), the chemical vapor infiltration time is that 1h～600h(the present embodiment is 50h), so alternately to make density be 1.3g/ ㎝ in density
3～2.5g/ ㎝
3(the present embodiment is 1.65g/ ㎝
3) carbon/carbon/composite material of silicon carbide fastening piece base substrate;
The present embodiment is chemical vapor infiltration RESEARCH OF PYROCARBON at first, chemical vapor infiltration silicon carbide then, and only alternately once, chemical vapor infiltration total time is 130 hours.
(3) machining: by step (2) carbon/the carbon of gained/composite material of silicon carbide fastening piece base substrate be processed on request the carbon/carbon of required shape and size/composite material of silicon carbide fastening piece goods;
(4) high temperature purification: carbon/carbon (3) prepared by step/composite material of silicon carbide fastening piece goods are put into the high temperature purification stove and are carried out purifying, 1600 ℃～2800 ℃ of cleansing temps (the present embodiment is 2000 ℃), purifying time 1h～10h(the present embodiment is 2h), obtain carbon/carbon/composite material of silicon carbide fastening piece finished product.
As shown in Figure 5, in figure, white portion is silicon carbide, central black is carbon fiber, carbon fiber outside surface black part is divided into RESEARCH OF PYROCARBON, the RESEARCH OF PYROCARBON of first infiltration of this explanation is around carbon fibre growth, the silicon carbide of rear infiltration coats RESEARCH OF PYROCARBON and carbon fiber, can effectively stop the erosion of silicon steam to carbon fiber and RESEARCH OF PYROCARBON.
As shown in Figure 6, the bending strength of carbon/carbon prepared by the present invention/composite material of silicon carbide sample testing is that 325MPa(is shown in curve A in figure), be 3～4 times of same density carbon/carbon compound material, fracture toughness property>=15MPam
1/2, and broken curve shows obvious pseudo-plasticity, illustrates that the safety in utilization of carbon/carbon/composite material of silicon carbide fastening piece is higher; Owing to containing a large amount of silicon carbide substrates in carbon/carbon/composite material of silicon carbide, the anti-silicon steam corrosion energy force rate carbon/carbon compound material of carbon/carbon/composite material of silicon carbide is compared and has been improved 5～10 times.
Carbon/carbon of the present invention/composite material of silicon carbide fastening piece is owing to adopting RESEARCH OF PYROCARBON and silicon carbide to replace the method preparation of density, the excellent bonding performance and the silicon carbide intensity that take full advantage of between RESEARCH OF PYROCARBON and carbon fiber are high, the characteristics that resistance to corrosion is strong, make silicon carbide penetrate into fully carbon fiber substrate, guarantee the high bond strength of silicon carbide and carbon fiber substrate, intensity is higher than carbon/carbon compound material, and can effectively suppress the erosion of silicon steam to carbon/carbon/composite material of silicon carbide core carbon fiber, protection carbon/carbon/composite material of silicon carbide fastening piece is not corroded by silicon steam for a long time, increased substantially the work-ing life of fastening piece, simultaneously, its higher intensity also is conducive to improve the security of thermal field.
Embodiment 2:
The present invention step (2) in, chemical vapor infiltration RESEARCH OF PYROCARBON at first, penetration time 20 hours, then chemical vapor infiltration silicon carbide, penetration time 20 hours, alternately 5 times, last chemical vapor infiltration silicon carbide, chemical vapor infiltration total time is 200 hours, making density is 1.92g/ ㎝
3carbon/carbon/composite material of silicon carbide fastening piece base substrate.
Remaining with embodiment 1.
The present invention adopts RESEARCH OF PYROCARBON and silicon carbide to replace the method for density, can make in the short period of time carbon/carbon that density is higher/composite material of silicon carbide.Simultaneously; owing to just carrying out chemical vapor infiltration silicon carbide when density of material is lower; make silicon carbide can penetrate into fully carbon fiber substrate; guarantee the high bond strength of silicon carbide and carbon fiber substrate; can effectively suppress the erosion of silicon steam to the core carbon fiber; protection carbon/carbon/composite material of silicon carbide fastening piece is not corroded by silicon steam for a long time, has increased substantially the work-ing life of fastening piece.And the repeatedly alternately strike of RESEARCH OF PYROCARBON and silicon carbide is conducive to alleviate two kinds of unmatched problems of matrix thermal characteristics, improve the overall performance of carbon/carbon/composite material of silicon carbide fastening piece.
Embodiment 3:
The present invention further improves the resistance to corrosion of carbon/carbon/composite material of silicon carbide, step (2) in, described RESEARCH OF PYROCARBON and silicon carbide replace density for chemical vapor infiltration silicon carbide at first, first at carbon fiber surface parcel one deck silicon carbide, and then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide, last chemical vapor infiltration silicon carbide, so the resistance to corrosion of the carbon/carbon of preparation/composite material of silicon carbide fastening piece is best.
Remaining with embodiment 2.
Embodiment 4:
The present invention is the anti-silicon steam corrosion ability of carbon/carbon/composite material of silicon carbide fastening piece that further increases, and at carbon/carbon/composite material of silicon carbide fastener surface, is provided with coat of silicon carbide.Carbon/carbon that soon (3) step will make afterwards/composite material of silicon carbide fastening piece goods are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
Processing condition prepared by coat of silicon carbide of the present invention are: using hydrogen as carrier gas, take hydrogen or argon gas (the present embodiment is hydrogen) is diluent gas, by Bubbling method, trichloromethyl silane is introduced in cvd furnace, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is that 1:5～20(the present embodiment is 1:10), the pressure of reactant gases is that 2kPa～12kPa(the present embodiment is 5kPa); The container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures (the present embodiment is 35 ℃), depositing time is that 1h～100h(the present embodiment is 10h), can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide fastening piece product surface.
Remaining with embodiment 1.
Owing in the carbon/carbon prepared/composite material of silicon carbide, containing a large amount of silicon carbide substrates, therefore, carbon/the carbon prepared in the present invention/dense silicon carbide coating layer prepared by the composite material of silicon carbide fastener surface and the thermal matching of matrix are good, and bonding strength is higher than the coat of silicon carbide directly prepared at surface of carbon/carbon composite.
Embodiment 5:
A kind of carbon/carbon/composite material of silicon carbide fastening piece, it is by adopting chemical vapor infiltration to carry out after RESEARCH OF PYROCARBON and silicon carbide replaces density or RESEARCH OF PYROCARBON and silicon carbide caballing (the present embodiment is caballing) it to carbon fabric perform, after machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3(the present embodiment is 1.7g/ ㎝
3), flexural strength>=300MPa, fracture toughness property>=15MPam
1/2.
Step (2) in, the processing condition of described RESEARCH OF PYROCARBON and silicon carbide caballing are, carbon-source gas and trichloromethyl silane are introduced to chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide in the chemical gas phase reaction stove simultaneously, the carbon-source gas flow is that 1L/min～100 L/min(the present embodiment are 18L/min), trichloromethyl silane is introduced by Bubbling method, using hydrogen as carrier gas, using hydrogen or argon gas (the present embodiment is hydrogen) as diluent gas, in reactant gases, Siliciumatom is 1:3 with the number ratio of carbon atom for 1:1～5(the present embodiment), the throughput ratio of trichloromethyl silane and hydrogen is that 1:5～20(the present embodiment is 1:5), the pressure of reactant gases is that 2kPa～12kPa(the present embodiment is 5kPa), the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures (the present embodiment is 35 ℃), the chemical vapor infiltration time is that 1h～600h(the present embodiment is 100h), it is 1.3g/ ㎝ that caballing like this makes density
3～2.5g/ ㎝
3(the present embodiment is 1.7g/ ㎝
3) carbon/carbon/composite material of silicon carbide fastening piece base substrate.
As shown in Figure 6, the bending strength of carbon/carbon prepared by the present invention/composite material of silicon carbide sample testing is that 355MPa(is shown in curve B in figure), be 3～4 times of same density carbon/carbon compound material, fracture toughness property>=15MPam
1/2, and broken curve shows obvious pseudo-plasticity, illustrates that the safety in utilization of carbon/carbon/composite material of silicon carbide fastening piece is higher; Owing to containing a large amount of silicon carbide substrates in carbon/carbon/composite material of silicon carbide, the anti-silicon steam corrosion energy force rate carbon/carbon compound material of carbon/carbon/composite material of silicon carbide is compared and has been improved 5～10 times.
Remaining with embodiment 1.
Embodiment 6:
The present invention is the anti-silicon steam corrosion ability of carbon/carbon/composite material of silicon carbide fastening piece that further increases, and at carbon/carbon/composite material of silicon carbide fastener surface, is provided with coat of silicon carbide.Carbon/carbon that soon (3) step will make afterwards/composite material of silicon carbide fastening piece goods are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
Processing condition prepared by coat of silicon carbide of the present invention are: using hydrogen as carrier gas, take hydrogen or argon gas (the present embodiment is hydrogen) is diluent gas, by Bubbling method, trichloromethyl silane is introduced in cvd furnace, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is that 1:5～20(the present embodiment is 1:10), the pressure of reactant gases is that 2kPa～12kPa(the present embodiment is 5kPa); The container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures (the present embodiment is 35 ℃), depositing time is that 1h～100h(the present embodiment is 10h), can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide fastening piece product surface.
Remaining with embodiment 5.
Claims (5)
1. the preparation method of carbon/carbon/composite material of silicon carbide fastening piece is characterized in that it comprises the following steps:
(1) carbon fabric perform preparation: the carbon fabric perform that carbon fiber is made to desired structure and shape by shape and the performance requriements of fastening piece, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3;
(2) density: the carbon fabric perform that (1) step is made is put into the chemical gas phase reaction stove, adopts chemical vapor infiltration it to be carried out to RESEARCH OF PYROCARBON and silicon carbide replace density until to make density be 1.3g/ ㎝
3～2.5g/ ㎝
3carbon/carbon/composite material of silicon carbide fastening piece base substrate;
The processing condition that described RESEARCH OF PYROCARBON and silicon carbide replace density are, carbon-source gas is introduced to chemical vapor infiltration RESEARCH OF PYROCARBON in the chemical gas phase reaction stove, the chemical vapor infiltration time is 1h～600h, and the carbon-source gas flow is 1L/min～100 L/min, and the pressure of reactant gases is 2kPa～12kPa; Then close carbon-source gas, using hydrogen as carrier gas, using hydrogen or argon gas as diluent gas, by Bubbling method, trichloromethyl silane is introduced to chemical vapor infiltration silicon carbide in the chemical gas phase reaction stove, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapor infiltration time is 1h～600h, and so alternately density makes carbon/carbon/composite material of silicon carbide fastening piece base substrate;
(3) machining: by step (2) carbon/the carbon of gained/composite material of silicon carbide fastening piece base substrate be processed into the carbon/carbon of desired shape and size/composite material of silicon carbide fastening piece goods by product requirement;
(4) purifying: carbon/carbon (3) prepared by step/composite material of silicon carbide fastening piece goods are put into the high temperature purification stove and are carried out purifying, 1600 ℃～2800 ℃ of cleansing temps, purifying time 1h～10h, obtain carbon/carbon/composite material of silicon carbide fastening piece finished product, and its density is 1.3g/ ㎝
3～2.5g/ ㎝
3, flexural strength>=300MPa, fracture toughness property>=15MPam
1/2.
2. the preparation method of carbon/carbon/composite material of silicon carbide fastening piece is characterized in that it comprises the following steps:
(1) carbon fabric perform preparation: the carbon fabric perform that carbon fiber is made to desired structure and shape by shape and the performance requriements of fastening piece, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3;
(2) density: the carbon fabric perform that (1) step is made is put into the chemical gas phase reaction stove, adopts chemical vapor infiltration to carry out RESEARCH OF PYROCARBON and silicon carbide caballing to it until to make density be 1.3g/ ㎝
3～2.5g/ ㎝
3carbon/carbon/composite material of silicon carbide fastening piece base substrate;
The processing condition of described RESEARCH OF PYROCARBON and silicon carbide caballing are, carbon-source gas and trichloromethyl silane are introduced to chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide in the chemical gas phase reaction stove simultaneously, the carbon-source gas flow is 1L/min～100 L/min, trichloromethyl silane is introduced by Bubbling method, using hydrogen as carrier gas, using hydrogen or argon gas as diluent gas, in reactant gases, Siliciumatom is 1:1～5 with the number ratio of carbon atom, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapor infiltration time is 1h～600h, so caballing makes carbon/carbon/composite material of silicon carbide fastening piece base substrate,
(3) machining: by step (2) carbon/the carbon of gained/composite material of silicon carbide fastening piece base substrate be processed into the carbon/carbon of desired shape and size/composite material of silicon carbide fastening piece goods by product requirement;
(4) purifying: carbon/carbon (3) prepared by step/composite material of silicon carbide fastening piece goods are put into the high temperature purification stove and are carried out purifying, 1600 ℃～2800 ℃ of cleansing temps, purifying time 1h～10h, obtain carbon/carbon/composite material of silicon carbide fastening piece finished product, and its density is 1.3g/ ㎝
3～2.5g/ ㎝
3, flexural strength>=300MPa, fracture toughness property>=15MPam
1/2.
3. the preparation method of carbon/carbon/composite material of silicon carbide fastening piece according to claim 1, it is characterized in that step (2) in, described RESEARCH OF PYROCARBON and silicon carbide replace density for chemical vapor infiltration silicon carbide at first, and then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silicon carbide, last chemical vapor infiltration silicon carbide.
4. according to the preparation method of claim 1 or 2 or 3 described carbon/carbon/composite material of silicon carbide fastening piece, it is characterized in that carbon/carbon that (3) step is made afterwards/composite material of silicon carbide fastening piece goods put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
5. the preparation method of carbon/carbon/composite material of silicon carbide fastening piece according to claim 4, it is characterized in that processing condition prepared by described coat of silicon carbide are: using hydrogen as carrier gas, take hydrogen or argon gas as diluent gas, by Bubbling method, trichloromethyl silane is introduced to chemical vapor deposition of silicon carbide in the chemical gas phase reaction stove, in reactant gases, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, the pressure of reactant gases is 2kPa～12kPa, the container bottle of splendid attire trichloromethyl silane is placed in water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures, the chemical vapour deposition time is 1h～100h, can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide fastening piece product surface.
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Address after: 413000 Hunan province Yiyang Yingbin Road No. 2 Patentee after: Hunan gold carbon Limited by Share Ltd Address before: 413000 Hunan province Yiyang Yingbin Road No. 2 Patentee before: Hunan KBCarbon Composite Science and Technology Co., Ltd. |