CN102718539A - Carbon/carbon/silicon carbide composite material thermal-insulation barrel and preparation method - Google Patents
Carbon/carbon/silicon carbide composite material thermal-insulation barrel and preparation method Download PDFInfo
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- CN102718539A CN102718539A CN2012102306775A CN201210230677A CN102718539A CN 102718539 A CN102718539 A CN 102718539A CN 2012102306775 A CN2012102306775 A CN 2012102306775A CN 201210230677 A CN201210230677 A CN 201210230677A CN 102718539 A CN102718539 A CN 102718539A
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Abstract
The invention discloses a carbon/carbon/silicon carbide composite material thermal-insulation barrel with a simple preparation technology and silicon steam corrosion resistance, and a preparation method. The carbon/carbon/silicon carbide composite material thermal-insulation barrel is characterized by being prepared by a process that a carbon fiber prefabricated body of the thermal-insulation barrel is machined and purified after being subjected to pyrolytic carbon and silicon carbide alternating densification or pyrolytic carbon and silicon carbide mixing densification with a chemical vapor infiltration method. The density of the carbon/carbon/silicon carbide composite material thermal-insulation barrel is 1.3-2.5g.cm<3>, the flexural strength is more than or equal to 300MPa, and the fracture toughness is more than or equal to 15MPa.m<1/2>. According to the carbon/carbon/silicon carbide composite material thermal-insulation barrel disclosed by the invention, corrosion on the core part carbon fiber of the carbon/carbon/silicon carbide composite material by silicon steam can be effectively inhibited. The flexural strength of the prepared carbon/carbon/silicon carbide composite material is more than 300MPa which is 2-5 times of that of carbon/carbon composite material, the fracture toughness is more than or equal to 15MPa.m<1/2>, the silicon steam corrosion resistance capability is improved by 5-10 times in comparison with that of the carbon/carbon composite material, and the service life of the thermal-insulation barrel is drastically prolonged. Meanwhile, the higher strength of the carbon/carbon/silicon carbide composite material thermal-insulation barrel is favorable for improving the safety of a 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 heat-preservation cylinder and preparation method.
Background technology
Premium propertiess such as carbon/carbon compound material is one of advanced composite material of present widespread use, and it is to strengthen the formed matrix material of carbon base body by thomel or various carbon fabric, and it is low to have density, and specific tenacity is high, and is wear-resistant, high temperature resistant, that thermal expansivity is little.The net tire that this material is usually earlier processed with thomel and net tire or carbon cloth and carbon cloth or net tire and carbon cloth is combined into the prefabricated carbon fiber body through alternative stacked acupuncture; Then precast body is put into the chemical gas phase reaction stove; The RESEARCH OF PYROCARBON of utilizing carbon-source gas cracking under the 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 become one of the important foundation material in fields such as aerospace, metallurgy, new forms of energy at present, is the ideal substitute of graphite product and high temperature steel.
At present, carbon/carbon compound material has been widely used in being used for making the thermal field part like high temperature fields such as single crystal growing furnace, polycrystalline furnaces, like 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 made the pre-test of silicon crystal growth crucible; charcoal is plain, 2004 (2): P3～P7 " discloses a kind of trial-production has carried out type approval test, and the result shows that C/C matrix material machinery intensity height, thermal shock resistance and chemicalstability are good; Be higher than the high purity graphite crucible its work-ing life; Yet test-results has also been found the defective of C/C composite material crucible pot, oxidative attack (SiO
2And Si) influence in work-ing life to the C/C composite material crucible pot is very big.
The applicant is in order to solve the influence of high temperature silicon steam to C/C matrix material use properties; C/C composite material crucible pot after the use of silicon single-crystal manufacturer has been carried out analyzing experiment; And adopted the mechanical property of material mechanics tester (American I nstron3369 material mechanics tester) test sample; ESEM (SEM, the microtexture of analysis of material of JSM～6360LV), X-ray energy spectrometer (EDS; EDX～GENESIS 60S type) the analytical sample surface-element distributes, and the result sees Fig. 1, Fig. 2, Fig. 3, Fig. 4.Can find out that from Fig. 1, Fig. 2 silicon steam corrodes sample inside, back and generated a lot of other materials; Can learn that from Fig. 3, Fig. 4 other material that is generated is silit (the perhaps mixture of silicon and silit); Simultaneously its Mechanics Performance Testing result is shown that without erosive sample bending strength be 105MPa; Be merely 24.5MPa by serious erosive sample bending strength; Close with the intensity of graphite, explain 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 influence of high temperature silicon steam to C/C matrix material use properties, with regard to present technology, the most frequently used method is made top coat exactly, mainly is that the silicon based ceramic coating is (like SiC or MoSi
2Deng).
It is matrix with the C/C matrix material that document 2 " in-situ growing carbon nano tube to the influence of CVD SiC coating, China YouSe Acta Metallurgica Sinica, 2011; (2): P418～P424 " has been introduced a kind of, adopts chemical Vapor deposition process to prepare the SiC coating at composite material surface, and the result shows: through (1100 ℃; 3min) (room temperature; 3min) after the thermal cycling 15 times, SiC coating rate of weight loss is 33.17%, and the subregion coating shedding is the weightless major cause of coating sample in the thermal shock process.It is thus clear that because thermal expansivity does not match between C/C matrices of composite material and the SiC coating, the associativity of the coating of preparation and C/C matrices of composite material is relatively poor, in the rapid heat cycle process, comes off easily, can not protect the C/C matrix material not to be etched for a long time.
To ceramic base coating and the unmatched defective of C/C matrix material thermal expansivity; Best solution is penetrated into the C/C composite inner to SiC through 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 present condition for application; charcoal is plain; 2008 (2): P29～P35 " has been introduced the preparation method of C/C-SiC matrix material; Analyzed various preparing methods' relative merits, the CVI+PIP hybrid technique that especially PIP method commonly used and new development is 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; Though 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 thomel, causes the damage of wild phase thomel; Cause carbon fiber-reinforced strengthening action to reduce; Thereby the over-all properties of material is descended, and particularly mechanical strength significantly reduces, and causes the calamitous fracture of material.Simultaneously, its technical process is complicated, needs repeatedly dipping repeatedly.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is simple, the steam of anti-silicon erosive carbon/carbon/composite material of silicon carbide heat-preservation cylinder 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 heat-preservation cylinder; It carries out after RESEARCH OF PYROCARBON and silit replaces density or RESEARCH OF PYROCARBON and silit caballing it through the prefabricated carbon fiber body of heat-preservation cylinder being adopted chemical vapor infiltration; Behind 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 that further increases carbon/carbon/composite material of silicon carbide heat-preservation cylinder, is provided with coat of silicon carbide on carbon/carbon/composite material of silicon carbide heat-preservation cylinder surface.
The preparation method of a kind of carbon/carbon/composite material of silicon carbide heat-preservation cylinder, it may further comprise the steps:
⑴ prefabricated carbon fiber system is equipped with: with the prefabricated carbon fiber body that thomel is processed desired structure and shape by the shape and the performance requriements of heat-preservation cylinder, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3
⑵ density: the prefabricated carbon fiber body that step ⑴ makes is put into the chemical gas phase reaction stove, and adopting chemical vapor infiltration that it is carried out RESEARCH OF PYROCARBON and silit, to replace density or RESEARCH OF PYROCARBON and silit caballing be 1.3g/ ㎝ until making density
3～2.5g/ ㎝
3Carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate;
⑶ machining: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods that the carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate of step ⑵ gained are processed into desired shape and size by product requirement;
⑷ purifying: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods of step ⑶ preparation are put into the high temperature purification stove carry out purifying, 1600 ℃～2800 ℃ of cleansing temps, purifying time 1h～10h promptly gets carbon/carbon/composite material of silicon carbide heat-preservation cylinder finished product.
The present invention is in step ⑵; The processing condition that described RESEARCH OF PYROCARBON and silit replace density do; Carbon-source gas is introduced 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 reaction gas pressure is 2kPa～12kPa; Close carbon-source gas then; As carrier gas, as diluents, trichloromethyl silane is introduced chemical vapor infiltration silit in the chemical gas phase reaction stove with hydrogen with Bubbling method with hydrogen or argon gas; The throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 in the reactant gases; Reaction gas pressure is 2kPa～12kPa, and the container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder base substrate.
The present invention is the resistance to corrosion that further improves material; In step ⑵; Described RESEARCH OF PYROCARBON and silit replace density and are chemical vapor infiltration silit at first, and then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silit, last chemical vapor infiltration silit.
The present invention is in step ⑵, and the processing condition of described RESEARCH OF PYROCARBON and silit caballing are simultaneously carbon-source gas and trichloromethyl silane to be introduced chemical vapor infiltration RESEARCH OF PYROCARBON and silit in the chemical gas phase reaction stove; The carbon-source gas flow is 1L/min～100 L/min, and trichloromethyl silane is introduced with Bubbling method, with hydrogen as carrier gas; With hydrogen or argon gas as diluents; Siliciumatom is 1:1～5 with the number ratio of carbon atom in the reactant gases, and the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, and reaction gas pressure is 2kPa～12kPa; The container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder base substrate.
The present invention is the anti-silicon steam corrosion ability that further increases carbon/carbon/composite material of silicon carbide heat-preservation cylinder; Carbon/the carbon that makes behind the step ⑶/composite material of silicon carbide heat-preservation cylinder goods are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
The processing condition of coat of silicon carbide according to the invention preparation are: with hydrogen as carrier gas; With hydrogen or argon gas is diluents; With Bubbling method trichloromethyl silane is introduced chemical vapor deposition of silicon carbide in the chemical gas phase reaction stove, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 in the reactant gases, and reaction gas pressure is 2kPa～12kPa; The container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder product surface.
Owing to adopt technique scheme; The present invention has realized goal of the invention preferably, and its technology is simple, and it is convenient to implement; Can effectively suppress of the erosion of silicon steam to carbon/carbon/composite material of silicon carbide core thomel; Carbon/carbon/composite material of silicon carbide the flexural strength of preparation is 2～5 times of carbon/carbon compound material greater than 300MPa, fracture toughness property>=15MPam
1/2, anti-silicon steam corrosion ability force rate carbon/carbon compound material is compared and has been improved 5～10 times, has increased substantially the work-ing life of heat-preservation cylinder, and simultaneously, its higher intensity also helps improving the security of thermal field.
Description of drawings
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 of carbon/carbon compound material sample before silicon steam corrodes;
Fig. 4 is the surface-element analysis of carbon/carbon compound material sample after silicon steam corrodes;
Fig. 5 is the cross section back scattering picture of the embodiment of the invention 1 said carbon/carbon/composite material of silicon carbide; The density of carbon/carbon among the figure/composite material of silicon carbide is 1.65g/ ㎝
3, wherein white portion is a silit, and central black is a thomel, and thomel outside surface black part is divided into RESEARCH OF PYROCARBON, adopts RESEARCH OF PYROCARBON and silit to replace density, and the temperature during the RESEARCH OF PYROCARBON density is 1100 ℃, the chemical vapor infiltration time is 80h; Temperature during the silit density is 1100 ℃, and the chemical vapor infiltration time is 50h;
Fig. 6 is RESEARCH OF PYROCARBON and silit when replacing density and RESEARCH OF PYROCARBON and silit caballing, the three-point bending resistance intensity-displacement curve figure of carbon/carbon/composite material of silicon carbide sampling and testing; Curve A is RESEARCH OF PYROCARBON and silit when replacing density among the figure, the three-point bending resistance intensity-displacement curve figure of sample; When curve B is RESEARCH OF PYROCARBON and silit caballing, the three-point bending resistance intensity-displacement curve figure of sample.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Can find out that from Fig. 1, Fig. 2 the carbon/carbon compound material sample is after silicon steam corrodes, sample inside has generated a lot of other materials; Can learn that from Fig. 3, Fig. 4 other material that is generated is silit (the perhaps mixture of silicon and silit); Simultaneously; The sample Mechanics Performance Testing is the result show, is 105MPa without erosive sample bending strength, is merely 24.5MPa by serious erosive sample bending strength; Close with the intensity of graphite, explain 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 heat-preservation cylinder; It carries out after RESEARCH OF PYROCARBON and silit replaces density or RESEARCH OF PYROCARBON and silit caballing (present embodiment is to replace density) it through the prefabricated carbon fiber body of heat-preservation cylinder being adopted chemical vapor infiltration; Behind machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3(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 heat-preservation cylinder, it may further comprise the steps:
⑴ prefabricated carbon fiber system is equipped with: with the prefabricated carbon fiber body that thomel is processed desired structure and shape by the shape and the performance requriements of heat-preservation cylinder, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3(present embodiment is 0.50g/ ㎝
3);
During preparation prefabricated carbon fiber body, can the net tire that thomel is processed be combined into the prefabricated carbon fiber body with netting tire or carbon cloth and carbon cloth or net tire and carbon cloth through alternative stacked acupuncture, also can adopt weave to be woven into the prefabricated carbon fiber body on thomel; Present embodiment adopts net tire and carbon cloth to be combined into the prefabricated carbon fiber body through alternative stacked acupuncture.
⑵ density: the prefabricated carbon fiber body that step ⑴ makes is put into the chemical gas phase reaction stove, adopt chemical vapor infiltration it to be carried out RESEARCH OF PYROCARBON replaces density with silit or RESEARCH OF PYROCARBON is 1.3g/ ㎝ with silit caballing (present embodiment is to replace density) until making density
3～2.5g/ ㎝
3(present embodiment is 1.65g/ ㎝
3) carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate;
In step ⑵, the processing condition that described RESEARCH OF PYROCARBON and silit replace density are the chemical gas phase reaction stove to be warming up to 900 ℃～1400 ℃ (present embodiment is 1100 ℃), insulation 1h～6h (present embodiment is 1h).Carbon-source gas (present embodiment is a methane) is introduced chemical vapor infiltration RESEARCH OF PYROCARBON in the chemical gas phase reaction stove; The chemical vapor infiltration time is 1h～600h (present embodiment is 80h); The carbon-source gas flow is 1L/min～100 L/min (present embodiment is 28L/min), and reaction gas pressure is 2kPa～12kPa (present embodiment is 5kPa); Close carbon-source gas then; With hydrogen as carrier gas; With hydrogen or argon gas (present embodiment is a hydrogen) as diluents; With Bubbling method trichloromethyl silane is introduced chemical vapor infiltration silit in the chemical gas phase reaction stove, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 (present embodiment is 1:5) in the reactant gases, and reaction gas pressure is 2kPa～12kPa (present embodiment is 3.5kPa); The container bottle of splendid attire trichloromethyl silane places water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures (present embodiment is 35 ℃), and the chemical vapor infiltration time is 1h～600h (present embodiment is 50h), so alternately to make density be 1.3g/ ㎝ in density
3～2.5g/ ㎝
3(present embodiment is 1.65g/ ㎝
3) carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate;
Present embodiment is chemical vapor infiltration RESEARCH OF PYROCARBON at first, chemical vapor infiltration silit then, and only alternately once, chemical vapor infiltration total time is 130 hours.
⑶ machining: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods that the carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate of step ⑵ gained are processed on request required shape and size;
⑷ high temperature purification: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods of step ⑶ preparation are put into the high temperature purification stove carry out purifying; 1600 ℃～2800 ℃ of cleansing temps (present embodiment is 2000 ℃); Purifying time 1h～10h (present embodiment is 2h) promptly gets carbon/carbon/composite material of silicon carbide heat-preservation cylinder finished product.
Can know by Fig. 5; White portion is a silit among the figure; Central black is a thomel, and thomel outside surface black part is divided into RESEARCH OF PYROCARBON, and the RESEARCH OF PYROCARBON of this explanation infiltration earlier is around carbon fibre growth; The silit of back infiltration coats RESEARCH OF PYROCARBON and thomel, can effectively stop the erosion of silicon steam to thomel and RESEARCH OF PYROCARBON.
Can be known that by Fig. 6 the bending strength of the carbon/carbon/composite material of silicon carbide sample testing of the present invention preparation is 325MPa (seeing curve A among the figure), be 3～4 times with the density carbon/carbon compound material, fracture toughness property>=15MPam
1/2, and broken curve shows tangible pseudo-plasticity, explains that the safety in utilization of carbon/carbon/composite material of silicon carbide heat-preservation cylinder is higher; Owing to contain a large amount of silicon carbide substrates in carbon/carbon/composite material of silicon carbide, the anti-silicon steam corrosion ability 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 heat-preservation cylinder is owing to adopt RESEARCH OF PYROCARBON and silit to replace the method preparation of density; Make full use of the characteristics that excellent bonding performance and silit intensity are high, resistance to corrosion is strong between RESEARCH OF PYROCARBON and the thomel; Make silit penetrate into carbon fiber substrate fully; Guarantee the high bond strength of silit 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 thomel; Protection carbon/carbon/composite material of silicon carbide heat-preservation cylinder is not corroded by silicon steam for a long time; Increased substantially the work-ing life of heat-preservation cylinder, simultaneously, its higher intensity also helps improving the security of thermal field.
Embodiment 2:
The present invention in step ⑵, chemical vapor infiltration RESEARCH OF PYROCARBON at first, penetration time 20 hours; Chemical vapor infiltration silit then, penetration time 20 hours, alternately 5 times; Last chemical vapor infiltration silit, chemical vapor infiltration total time is 200 hours, making density is 1.92g/ ㎝
3Carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate.
Surplus with embodiment 1.
The present invention adopts RESEARCH OF PYROCARBON and silit to replace the method for density, can make the higher carbon/carbon of density/composite material of silicon carbide in the short period of time.Simultaneously; Owing to when density of material is lower, just carry out chemical vapor infiltration silit; Make silit can penetrate into carbon fiber substrate fully, guarantee the high bond strength of silit and carbon fiber substrate, can effectively suppress of the erosion of silicon steam the core thomel; Protection carbon/carbon/composite material of silicon carbide heat-preservation cylinder is not corroded by silicon steam for a long time, has increased substantially the work-ing life of heat-preservation cylinder.And the repeatedly alternately strike of RESEARCH OF PYROCARBON and silit helps alleviating two kinds of unmatched problems of matrix thermal property, improves the overall performance of carbon/carbon/composite material of silicon carbide heat-preservation cylinder.
Embodiment 3:
The present invention is the resistance to corrosion that further improves carbon/carbon/composite material of silicon carbide; In step ⑵; Described RESEARCH OF PYROCARBON and silit replace density and are chemical vapor infiltration silit at first, earlier at carbon fiber surface parcel one deck silit, and then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silit; Last chemical vapor infiltration silit, so the resistance to corrosion of the carbon/carbon/composite material of silicon carbide heat-preservation cylinder of preparation is best.
Surplus with embodiment 2.
Embodiment 4:
The present invention is the anti-silicon steam corrosion ability that further increases carbon/carbon/composite material of silicon carbide heat-preservation cylinder, is provided with coat of silicon carbide on carbon/carbon/composite material of silicon carbide heat-preservation cylinder surface.Carbon/carbon/composite material of silicon carbide heat-preservation cylinder the goods that are about to make behind the step ⑶ are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
The processing condition of coat of silicon carbide according to the invention preparation are: with hydrogen as carrier gas; With hydrogen or argon gas (present embodiment is a hydrogen) is diluents; With Bubbling method trichloromethyl silane is introduced in the cvd furnace; The throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 (present embodiment is 1:10) in the reactant gases, and reaction gas pressure is 2kPa～12kPa (present embodiment is 5kPa); The container bottle of splendid attire trichloromethyl silane places water bath with thermostatic control; 18 ℃～45 ℃ of bath temperatures (present embodiment is 35 ℃); Depositing time is 1h～100h (present embodiment is 10h), can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide heat-preservation cylinder product surface.
Surplus with embodiment 1.
Owing to contain a large amount of silicon carbide substrates in the carbon/carbon/composite material of silicon carbide of preparation; Therefore; The carbon/carbon/dense silicon carbide coating layer of composite material of silicon carbide heat-preservation cylinder surface preparation and the hot matching of matrix in the present invention's preparation are good, and bonding strength is higher than direct coat of silicon carbide in the carbon/carbon compound material surface preparation.
Embodiment 5:
A kind of carbon/carbon/composite material of silicon carbide heat-preservation cylinder; It carries out after RESEARCH OF PYROCARBON and silit replaces density or RESEARCH OF PYROCARBON and silit caballing (present embodiment is caballing) it through the prefabricated carbon fiber body being adopted chemical vapor infiltration; Behind machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3(present embodiment is 1.7g/ ㎝
3), flexural strength>=300MPa, fracture toughness property>=15MPam
1/2
In step ⑵; The processing condition of described RESEARCH OF PYROCARBON and silit caballing do; Simultaneously carbon-source gas and trichloromethyl silane are introduced chemical vapor infiltration RESEARCH OF PYROCARBON and silit in the chemical gas phase reaction stove; The carbon-source gas flow is 1L/min～100 L/min (present embodiment is 18L/min), and trichloromethyl silane is introduced with Bubbling method, with hydrogen as carrier gas; With hydrogen or argon gas (present embodiment is a hydrogen) as diluents; Siliciumatom is 1:1～5 (present embodiment is 1:3) with the number ratio of carbon atom in the reactant gases, and the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 (present embodiment is 1:5), and reaction gas pressure is 2kPa～12kPa (present embodiment is 5kPa); The container bottle of splendid attire trichloromethyl silane places water bath with thermostatic control, 18 ℃～45 ℃ of bath temperatures (present embodiment is 35 ℃), and the chemical vapor infiltration time is 1h～600h (present embodiment is 100h), it is 1.3g/ ㎝ that caballing like this makes density
3～2.5g/ ㎝
3(present embodiment is 1.7g/ ㎝
3) carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate.
Can be known that by Fig. 6 the bending strength of the carbon/carbon/composite material of silicon carbide sample testing of the present invention preparation is 355MPa (seeing curve B among the figure), be 3～4 times with the density carbon/carbon compound material, fracture toughness property>=15MPam
1/2, and broken curve shows tangible pseudo-plasticity, explains that the safety in utilization of carbon/carbon/composite material of silicon carbide heat-preservation cylinder is higher; Owing to contain a large amount of silicon carbide substrates in carbon/carbon/composite material of silicon carbide, the anti-silicon steam corrosion ability force rate carbon/carbon compound material of carbon/carbon/composite material of silicon carbide is compared and has been improved 5～10 times.
Surplus with embodiment 1.
Embodiment 6:
The present invention is the anti-silicon steam corrosion ability that further increases carbon/carbon/composite material of silicon carbide heat-preservation cylinder, is provided with coat of silicon carbide on carbon/carbon/composite material of silicon carbide heat-preservation cylinder surface.Carbon/carbon/composite material of silicon carbide heat-preservation cylinder the goods that are about to make behind the step ⑶ are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
The processing condition of coat of silicon carbide according to the invention preparation are: with hydrogen as carrier gas; With hydrogen or argon gas (present embodiment is a hydrogen) is diluents; With Bubbling method trichloromethyl silane is introduced in the cvd furnace; The throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 (present embodiment is 1:10) in the reactant gases, and reaction gas pressure is 2kPa～12kPa (present embodiment is 5kPa); The container bottle of splendid attire trichloromethyl silane places water bath with thermostatic control; 18 ℃～45 ℃ of bath temperatures (present embodiment is 35 ℃); Depositing time is 1h～100h (present embodiment is 10h), can make fine and close coat of silicon carbide at carbon/carbon/composite material of silicon carbide heat-preservation cylinder product surface.
Surplus with embodiment 5.
Claims (9)
1. carbon/carbon/composite material of silicon carbide heat-preservation cylinder; It is characterized in that it carries out after RESEARCH OF PYROCARBON and silit replaces density or RESEARCH OF PYROCARBON and silit caballing it through the prefabricated carbon fiber body of heat-preservation cylinder being adopted chemical vapor infiltration; Behind machining, purifying, be prepared from, its density is 1.3g/ ㎝ again
3～2.5g/ ㎝
3, flexural strength>=300MPa, fracture toughness property>=15MPam
1/2
2. carbon/carbon according to claim 1/composite material of silicon carbide heat-preservation cylinder is characterized in that being provided with coat of silicon carbide on carbon/carbon/composite material of silicon carbide heat-preservation cylinder surface.
3. the preparation method of carbon/carbon/composite material of silicon carbide heat-preservation cylinder is characterized in that it may further comprise the steps:
⑴ prefabricated carbon fiber system is equipped with: with the prefabricated carbon fiber body that thomel is processed desired structure and shape by the shape and the performance requriements of heat-preservation cylinder, its density is 0.2g/ ㎝
3～1.0g/ ㎝
3
⑵ density: the prefabricated carbon fiber body that step ⑴ makes is put into the chemical gas phase reaction stove, and adopting chemical vapor infiltration that it is carried out RESEARCH OF PYROCARBON and silit, to replace density or RESEARCH OF PYROCARBON and silit caballing be 1.3g/ ㎝ until making density
3～2.5g/ ㎝
3Carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate;
⑶ machining: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods that the carbon/carbon/composite material of silicon carbide heat-preservation cylinder base substrate of step ⑵ gained are processed into desired shape and size by product requirement;
⑷ purifying: the carbon/carbon/composite material of silicon carbide heat-preservation cylinder goods of step ⑶ preparation are put into the high temperature purification stove carry out purifying, 1600 ℃～2800 ℃ of cleansing temps, purifying time 1h～10h promptly gets carbon/carbon/composite material of silicon carbide heat-preservation cylinder finished product.
4. according to the preparation method of the said carbon/carbon of claim 3/composite material of silicon carbide heat-preservation cylinder; It is characterized in that in step ⑵; The processing condition that described RESEARCH OF PYROCARBON and silit replace density do, carbon-source gas is introduced chemical vapor infiltration RESEARCH OF PYROCARBON in the chemical gas phase reaction stove, and the chemical vapor infiltration time is 1h～600h; The carbon-source gas flow is 1L/min～100 L/min, and reaction gas pressure is 2kPa～12kPa; Close carbon-source gas then; As carrier gas, as diluents, trichloromethyl silane is introduced chemical vapor infiltration silit in the chemical gas phase reaction stove with hydrogen with Bubbling method with hydrogen or argon gas; The throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 in the reactant gases; Reaction gas pressure is 2kPa～12kPa, and the container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder base substrate.
5. according to the preparation method of the said carbon/carbon of claim 3/composite material of silicon carbide heat-preservation cylinder; It is characterized in that in step ⑵; Described RESEARCH OF PYROCARBON and silit replace density and are chemical vapor infiltration silit at first; And then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silit, last chemical vapor infiltration silit.
6. according to the preparation method of the said carbon/carbon of claim 4/composite material of silicon carbide heat-preservation cylinder; It is characterized in that in step ⑵; Described RESEARCH OF PYROCARBON and silit replace density and are chemical vapor infiltration silit at first; And then alternately chemical vapor infiltration RESEARCH OF PYROCARBON and silit, last chemical vapor infiltration silit.
7. according to the preparation method of the said carbon/carbon of claim 3/composite material of silicon carbide heat-preservation cylinder, it is characterized in that in step ⑵ that the processing condition of described RESEARCH OF PYROCARBON and silit caballing do; Simultaneously carbon-source gas and trichloromethyl silane are introduced chemical vapor infiltration RESEARCH OF PYROCARBON and silit in the chemical gas phase reaction stove; The carbon-source gas flow is 1L/min～100 L/min, and trichloromethyl silane is introduced with Bubbling method, with hydrogen as carrier gas; With hydrogen or argon gas as diluents; Siliciumatom is 1:1～5 with the number ratio of carbon atom in the reactant gases, and the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20, and reaction gas pressure is 2kPa～12kPa; The container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder base substrate.
8. according to the preparation method of claim 3 or 4 or 5 or 6 or 7 said carbon/carbon/composite material of silicon carbide heat-preservation cylinders; It is characterized in that the carbon/carbon that makes behind the step ⑶/composite material of silicon carbide heat-preservation cylinder goods are put into the chemical gas phase reaction stove, adopt chemical Vapor deposition process to prepare coat of silicon carbide.
9. the preparation method of said according to Claim 8 carbon/carbon/composite material of silicon carbide heat-preservation cylinder; The processing condition that it is characterized in that the preparation of said coat of silicon carbide are: with hydrogen as carrier gas; With hydrogen or argon gas is diluents; With Bubbling method trichloromethyl silane is introduced chemical vapor deposition of silicon carbide in the chemical gas phase reaction stove, the throughput ratio of trichloromethyl silane and hydrogen is 1:5～20 in the reactant gases, and reaction gas pressure is 2kPa～12kPa; The container bottle of splendid attire trichloromethyl silane places 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 heat-preservation cylinder 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. |