CN1683284A - Method for quick preparing fiber reinforced ceramic base composite material or carbon/carbon composite material - Google Patents
Method for quick preparing fiber reinforced ceramic base composite material or carbon/carbon composite material Download PDFInfo
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- CN1683284A CN1683284A CN 200410031147 CN200410031147A CN1683284A CN 1683284 A CN1683284 A CN 1683284A CN 200410031147 CN200410031147 CN 200410031147 CN 200410031147 A CN200410031147 A CN 200410031147A CN 1683284 A CN1683284 A CN 1683284A
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Abstract
The present invention provides method of quick preparing fiber reinforced ceramic base composite material or carbon/carbon composite material, and belongs to the field of composite material preparing technology. The present invention features that the orientation of the product under deposition is several horizontally and rotated for homogeneous deposition; and that during the deposition, the pressure of work area, the width of the deposition area and the deposition sped are regulated form many times so as to obtain homogeneous base structure in the composite material and high performance. The present invention aims at producing material and product with high quality and performance and low cost.
Description
The invention provides a kind of quick method for preparing FRCMC or carbon/carbon composite, belong to the technology of preparing of matrix material.
Multiple excellent properties such as that FRCMC and carbon/carbon composite have is high temperature resistant, high specific strength, high ratio modulus obtain than widespread use at industrial circles such as aerospace.Chemical vapour deposition (or chemical vapor infiltration) technology (CVD or CVI) and liquid impregnation cracking technology are two kinds of preparation technologies that generally adopt at present, or with above both mix use; Its development is comparatively ripe, can realize producing in batches, can satisfy the requirement in existing use field substantially.But its complex process, the cycle is long, utilization rate of raw materials is low, energy consumption is big, cost is high, has limited this type of excellent material in the more application of broad range.
Therefore countries in the world, reduce cost to scheme the shortening manufacturing cycle all in the exploitation of carrying out new quick preparation technology, enlarge its application at industrial circles such as aviation, physical culture, medical treatment, machineries.The improvement technology of chemical vapour depositions such as at present existing forced-flow thermal gradient technology, pulse CV D technology, plasma enhanced CVD technology, directly-heated technology, chemical liquids gas-phase deposition, induction heating thermal gradient technology; The high-pressure impregnation cracking technology; And wrap innovative technologies such as yarn forming method in advance.Each novel process has had than much progress than traditional technology at different aspect, and also there is reduction in various degree the manufacturing cycle, and wherein several technologies have the industrial circle of particular requirement to use at some.But each novel process makes little progress aspect cost degradation, even cost also increases to some extent.Every technology is owing to all have certain shortcoming, up to the present still do not have to enter industrial circle on a large scale, the sign of replacement traditional technology.
The relative conventional gas-phase depositing operation of chemical liquids gas-phase deposition that wherein French nuclear power association proposes has been made great change and (has been called as CLVD, CLVI or RDT technology, its patent No. is: US4472454, US5547717, US5397595, US5389152 belong to the France and the man mechanism of number of the U.S. respectively).Its principle is: with the fiber preform with open pore structure be submerged in liquefied compound as matrix precursor (the deposit carbon matrix can use hexanaphthene, benzene, various liquid hydrocarbon with and composition thereof, deposition SiC matrix can use organosilanes such as trichloromethyl silane, deposition Si
3N
4Can use the mixture of various organosilanes and ammoniacal liquor, and the derivative deposition BN or the B that use boron
4C matrix or the like) in, method by heating element heating, straight-through electrically heated or induction heating heats up fiber preform, liquid matrix precursor close or the immersion fiber preform is heated to boiling gradually, heat up inner continuation of fiber preform with gaseous state, behind its cracking temperature, make product be deposited on fiber surface by reaction, and byproduct gas is discharged outside the precast body.In deposition process, because liquid matrix precursor intensive boiling heat transfer effect, make the extremely steep thermograde of the inside and outside generation of fiber preform (product), temperature is outwards reduced gradually by the precast body center, carry out along with sedimentary, the high-temperature zone expands outwardly gradually, and the deposition leading edge constantly advances to outside surface, make matrix layer by layer deposition in fiber preform, the final integral densification is finished.
The more traditional gas-phase deposition of the process cycle of this prepared material has shortened hundreds of times, and the U.S. reaches the special company of letter and uses the C/C brake flange densification with diameter 330mm in 8 hours of this technology, and density reaches 1.85g/cm
3, and each several part density is even, has improved two orders of magnitude than traditional chemical vapor deposition method densification speed, is that densification is fastest in the fast densified metallization processes that develops at present.Simplification, the shortening of manufacturing cycle, raw material availability owing to technological process significantly rises simultaneously, its densification process cost has deposited great reduction than conventional gas-phase, the cost of finished material also has bigger decline, makes the possible range of application of such material that bigger expansion arranged.Domestic also have three tame units to do this type of CLVD experimental study, comprise: Northwestern Polytechnical University, East China University of Science, Shaanxi non-metallic material technical study institute, wherein Northwestern Polytechnical University proposes and has used straight-through electrical heating method (Chinese patent first, application number: 00113762.X), and technology and method that external proposition has only simply reappeared in other two families, and the product properties of preparation is lower.
Yet this technology has some significant disadvantages:
1, because whole group goods all is submerged in the liquid precursor, different goods be in the different position of liquid level distance on, the gap of the pressure that liquid precursors produces and the gap of heat-sinking capability cause goods to produce the density gradient of (high-temperature zone-cold zone) from the inside to the outside, and the respective change of weave construction, also there are tangible density and weave construction gap between same group of a plurality of goods with the stove preparation, and this gap is bigger, can't satisfy the requirement of suitability for industrialized production to quality product and quality stability.
2, the increase of such equipment capacity also is restricted owing to previous reasons, because the increase of goods packet size can make the performance gap between goods become bigger.
3, the article shape that can prepare is single, and the technology of France and U.S.'s development can only prepare annular or tubular article, and the technology of domestic Northwestern Polytechnical University development can only prepare the long strip shape goods.
Above reason has all limited this kind Industrial Application of Technology, though reaching the special company of letter, the U.S. announces promptly that in middle nineteen nineties in last century they can be with the high performance goods of this prepared, but the report that does not still have its this technology of large-scale application is so far believed the influence that above reason is also arranged.
The objective of the invention is under the constant substantially prerequisite of increase technology within reason and equipment complexity and manufacturing cost, overcome the above problems, design a kind of suitability for industrialized production, outstanding, reliable Technology of steady quality of product performance of being suitable for, make this series products can be widely used in various demands field, promote the development of this industry.
On the basis of existing chemical liquids gas-phase deposition, technical solution of the present invention is as follows:
1, precast body or precast body group (goods or goods group) are horizontally placed.Can go here and there and outside a central shaft, (be suitable for hollow products such as ring-type, tubular), or place that (the solid product that is suitable for different shape is as flat board, rod, piece etc. in the outer skeleton.So-called outer skeleton is that an energy is under the prerequisite that does not influence deposition and heating, can be with precast body or precast body group hollow clamping body at the inside chucking, precast body or precast body group can fully be contacted) with the surrounding liquid presoma, and make its around central shaft or outside the axial rotation of skeleton, this central shaft or outer skeleton axially parallel with horizontal plane or approaching parallel, rotating speed can be adjusted between 0.01-1000r/min.Can add the material or the spare and accessory parts of insulation effect in goods group two ends, so that whole goods group trends towards identical towards the heat radiation of the outside surface of liquid precursors, the same deposition regional work temperature of different goods is also basic identical, reduces the difference of matrices of composite material weave construction.
2, sealing entire equipment, all protective gas, waste gas and unreacted gaseous precursor are all discharged by pressure regulation limit arranging device.In deposition is carried out, repeatedly adjust the limit arranging device operating pressure is changed within the specific limits, about between 1-6 normal atmosphere, adjust greatly (about 0.1-0.6Mpa).The variation of operating pressure can be adjusted width, the sedimentation velocity of deposition region and the matrices of composite material weave construction trend unanimity that makes the different depositional phases by the gradual change of operating pressure.In addition, the raising of operating pressure has the condensation of the unreacted gaseous state matrix precursor of promotion, the effect that improves the matrix precursor utilization ratio to a certain extent.In addition, the waste gas that deposition produces partly or entirely is inflammable gas, can be as the fuel of gas electricity generator after processing, and this electric energy can be used for other purposes.Waste gas also can be directly used in other purposes.
3, the huge power consumption of CLVD technology mainly consumes in the evaporation of matrix precursor, in the sedimentary later stage, because the violent boiling of liquid matrix precursor, with the strengthening effect of porous surface to boiling heat transfer, make the presoma steam output considerably beyond the deposition required, this situation is not obvious at the sedimentary commitment of large size goods.The maximum power requirement of depositing system equipment occurs during at certain certain value in the temperature difference between goods and liquid matrix precursor, the cylindrical place of precast body or precast body group (goods or goods group) can be wrapped that one deck is high temperature resistant, insulation, cheap felted fabric as far as possible, one or many uses, can make the peak power of the deposition demand suitable amplitude that descends, energy consumption, liquid matrix precursor consumption are descended, bring remarkable economic efficiency.
When 4, mentioning with kerosene as the presoma of deposit carbon matrix in the document, soot formation is arranged, and matrix precursor viscosity increases after 2-3 hour, character changes to some extent, believes it is that it is in the cause under the high temperature for a long time.And production practical application in industry goods required time is between 0-20 hour, so the recycle system of a matrix precursor is arranged in the design of depositing device, outside body of heater to matrix precursor cool off, filtration and sedimentation, flow back to cvd furnace then, to reduce the time that matrix precursor stops in the high-temperature zone, reduce the rotten probability of matrix precursor; To reduce consumption, reduce cost.The instant matrix precursor that adds also can be realized in this system in the deposition.
Action principle of the present invention is as follows:
The mode of deposition (influencing the principal element of matrix structure and bulk material properties) that the dispersed big major cause of existing chemical liquids gas-phase deposition quality product performance is exactly the deposition region all changes with the variation of space and time, and this is the shortcoming that can't eliminate in existing chemical liquids gas-phase deposition.The goods group is horizontal to make the mode of deposition between many goods approach unanimity and the present invention adopts, make the mode of deposition of the deposition region of same goods in the identical time approach unanimity by rotation, and the adjusting by pressure and power input, and some other control measures, make the interior different positions mode of deposition in whole deposition process of goods approach unanimity.By the combined action of above three aspects, make the capability and performance that adopts Technology of the present invention to make FRCMC and carbon/carbon compound material very even, can satisfy service requirements fully.
Advantage of the present invention:
1, the most essential characteristics and the advantage of the present invention is can be with the extremely short time, deposition prepare density and weave construction evenly, quality and stable outstanding FRCMC or carbon/carbon composite, compare with existing chemical liquids gas-phase deposition, quality, performance are better, product performance are more stable, and when pressure boost with under normal pressure, carry out CLVD and compare and can obviously reduce depositing time.
2, technology of the present invention is under the prerequisite of quality and performance raising, really can realize large-scale industrialization production, be designed for the equipment of suitability for industrialized production, its production capacity can reach 1000kg/ heat or higher, compare (design such as the Qiao Sheng of Northwestern Polytechnical University scholar, Shu WuBing and the equipment that uses) with the level of equipment tens kg/ heats with domestic existing chemical liquids gas phase deposition technology, be greatly improved, cost has decline by a relatively large margin, makes it to be applicable to more wide scope.
Claims (11)
1, a kind of quick method for preparing FRCMC or carbon/carbon compound material is used the ultimate principle identical with the chemical liquids vapour deposition.It is characterized in that: (1) is gone here and there single or multiple fiber preforms (or being called goods or goods group) and (be suitable for hollow pieces such as ring-type, tubular) outside a central shaft, or place in the outer skeleton that (solid article that is suitable for different shape is as flat board, rod, piece etc.So-called outer skeleton is that an energy is under the prerequisite that does not influence deposition and heating, can be with precast body or precast body group hollow clamping body at the inside chucking, precast body or precast body group can fully be contacted) with the surrounding liquid presoma, and make its around central shaft or outside the axial rotation of skeleton, this central shaft or outer skeleton axially parallel or approaching parallel with horizontal plane.(2) in deposition is carried out preceding or is carried out, the adjustable in pressure of work area.
2, before implementing according to claim 1 method, afterwards or middle, all can use other deposition method or dipping method to introduce the matrix or the additive of material identical or inequality, structure at fiber preform, in goods or finished product, or play the coating of various effects in the outside deposition of its any component; All can comprise the various processing of thermal treatment to fiber preform, at goods or finished product.
3, the fiber preform described in claim 1, it can be charcoal fiber, various ceramic fiber, various refractory metal fiber, alloy fiber, intermetallic fibres, or wherein several are mixed and made into arbitrarily; Wherein can add various additives such as whisker, particle, powder, carbon nanotube, additive can directly add or be generated by chemical reaction; Fiber volume fraction is between 5-70%; Wherein can add or not add the composition that resin, pitch, various silane, borine etc. play the caking agent effect; Can through or without the various processing that comprise thermal treatment.Its structure can be the felted thing that staple fibre constitutes, felted thing through acupuncture, (fabric is a plain to fabric laminate, drills, satin, no latitude cloth, the net tire, felt, acupuncture mat etc. or its arbitrary combination, behind its lamination can through or without acupuncture), various dimensions cloth (2.5 dimensions, three-dimensional, four-dimensional, five dimensions, 7 degree of freedom, ten one dimensions etc., or title 2.5D, 3D, 4D, 5D, 7D, 11D etc.), the whole felt of acupuncture, winding arrangement is (by fabric or band, perhaps fibrous bundle directly is entwined) etc., or form by above any two kinds or several textural associations.
When 4, the presoma described in claim 1 is worked is liquid state in depositing device, is evaporated to the reaction between gaseous state and intensification generation scission reaction, building-up reactions or multi-phase components (comprising single or multiple liquid, solute, suspended substance and gas) in the deposition region.It can be single liquid, or two kinds to multiple mixtures of liquids; In liquid, can dissolve other material that one or more work in deposition, in liquid, can be suspended with other solid phase additive; Also can in presoma, feed the gas that participates in reaction or do not participate in reacting in the course of the work.The presoma composition is formed in can change in the deposition process or not change all can.
5, the scope of working temperature in the deposition region described in claim 1, the material of difference, deposition matrix of looking presoma is not with to form weave constructions requirements different, the deposition matrix equal, between 500-2000 ℃.And can be in same goods or goods group preparation process variation by power or other parameter, temperature is adjusted, or is not adjusted and all can.
6, central shaft described in claim 1 or outer backbone winding axially rotate, and its speed range is between 0.01-1000r/min.
7, the variation of work area pressure described in claim 1 in deposition one heat (preparing one group of goods) process, can not adjusted or repeatedly adjust.The change of its force value within the specific limits, greatly between 1-6 normal atmosphere (about 0.1-0.6Mpa).
8, according to claim 1 in the method, the cylindrical place of precast body or precast body group (goods or goods group) can be wrapped that one deck is high temperature resistant, insulation, cheap felted fabric as far as possible, one or many uses.It can be charcoal fibrefelt, polypropylene cyanogen pre-oxygen silk felt or other any felted fabric that satisfies above requirement.
9, according to claim 1 in the method, can increase the recycle system of or several matrix precursors.Outside body of heater to matrix precursor cool off, filtration and sedimentation, flow back to cvd furnace then, the instant matrix precursor that adds also can be realized in this system in the deposition.More than several functions can be separately or arbitrary combination use, can be separately or in the recycle system of or several matrix precursors, realize jointly.
10,, can use or not use protective gas (protective gas comprises rare gas element and any gas that does not participate in the deposition process reaction) for implementing method according to claim 1.Implementing the waste gas that present method produces partly or entirely be inflammable gas, can increase by one and reclaim assembly or system, and it is recycled, and utilizes its generating or be used as other purposes of acting as a fuel.
11, for implementing the equipment that method is according to claim 1 used.It must comprise feature according to claim 1; It can have independent cooling, condenser system, or all can not; It uses operation material described in claim 3,4; Its processing parameter is in as in the scope as described in the claim 5,6,7; And can arbitrary combination comprise or not comprise as desired right in the claim 8,9,10.
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| CN 200410031147 CN1683284A (en) | 2004-04-13 | 2004-04-13 | Method for quick preparing fiber reinforced ceramic base composite material or carbon/carbon composite material |
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| CN 200410031147 CN1683284A (en) | 2004-04-13 | 2004-04-13 | Method for quick preparing fiber reinforced ceramic base composite material or carbon/carbon composite material |
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|---|---|---|---|---|
| CN102173853A (en) * | 2011-02-16 | 2011-09-07 | 北京科技大学 | Method for preparing highly-oriented perforated porous SiC ceramic material |
| CN102746015A (en) * | 2012-07-17 | 2012-10-24 | 山东宝纳新材料有限公司 | Reactively sintered carbon/carbon-silicon carbide-boron nitride composite friction material and method for preparing same |
| CN101386547B (en) * | 2008-08-21 | 2012-11-14 | 湖南金博复合材料科技有限公司 | Carbon/carbon compound material heating element and production technology thereof |
| CN103061004A (en) * | 2012-12-29 | 2013-04-24 | 中材科技股份有限公司 | Novel structure three-dimensional fabric and weaving method thereof |
| CN103061003A (en) * | 2012-12-29 | 2013-04-24 | 中材科技股份有限公司 | Novel structure three-dimensional woolen fabric and weaving method thereof |
| CN103058696A (en) * | 2012-12-14 | 2013-04-24 | 西北工业大学 | Preparation method for silicon nitride matrix |
| CN104387113A (en) * | 2014-11-17 | 2015-03-04 | 苏州博清高新材料有限公司 | Fiber-reinforced ceramic filter element and preparation method thereof |
| CN104446589A (en) * | 2014-12-24 | 2015-03-25 | 中南大学 | Method for preparing whisker modified carbon/carbon composite material |
| CN102099313B (en) * | 2008-07-17 | 2016-05-04 | 赫拉克勒斯公司 | The manufacture method of the nozzle of being made by composite or divergent nozzle element |
| CN114644528A (en) * | 2022-03-30 | 2022-06-21 | 江苏东润安全科技有限公司 | Hard material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102099313B (en) * | 2008-07-17 | 2016-05-04 | 赫拉克勒斯公司 | The manufacture method of the nozzle of being made by composite or divergent nozzle element |
| CN101386547B (en) * | 2008-08-21 | 2012-11-14 | 湖南金博复合材料科技有限公司 | Carbon/carbon compound material heating element and production technology thereof |
| CN102173853A (en) * | 2011-02-16 | 2011-09-07 | 北京科技大学 | Method for preparing highly-oriented perforated porous SiC ceramic material |
| CN102746015A (en) * | 2012-07-17 | 2012-10-24 | 山东宝纳新材料有限公司 | Reactively sintered carbon/carbon-silicon carbide-boron nitride composite friction material and method for preparing same |
| CN103058696A (en) * | 2012-12-14 | 2013-04-24 | 西北工业大学 | Preparation method for silicon nitride matrix |
| CN103061004B (en) * | 2012-12-29 | 2014-07-30 | 中材科技股份有限公司 | Novel structure three-dimensional fabric and weaving method thereof |
| CN103061003A (en) * | 2012-12-29 | 2013-04-24 | 中材科技股份有限公司 | Novel structure three-dimensional woolen fabric and weaving method thereof |
| CN103061003B (en) * | 2012-12-29 | 2014-09-03 | 中材科技股份有限公司 | Novel structure three-dimensional woolen fabric and weaving method thereof |
| CN103061004A (en) * | 2012-12-29 | 2013-04-24 | 中材科技股份有限公司 | Novel structure three-dimensional fabric and weaving method thereof |
| CN104387113A (en) * | 2014-11-17 | 2015-03-04 | 苏州博清高新材料有限公司 | Fiber-reinforced ceramic filter element and preparation method thereof |
| CN104446589A (en) * | 2014-12-24 | 2015-03-25 | 中南大学 | Method for preparing whisker modified carbon/carbon composite material |
| CN104446589B (en) * | 2014-12-24 | 2016-05-18 | 中南大学 | A kind of preparation method of whisker modified carbon/carbon compound material |
| CN114644528A (en) * | 2022-03-30 | 2022-06-21 | 江苏东润安全科技有限公司 | Hard material and preparation method and application thereof |
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