CN105924199B - A kind of fast preparation method of low cost carbon/carbon compound material - Google Patents

A kind of fast preparation method of low cost carbon/carbon compound material Download PDF

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CN105924199B
CN105924199B CN201610267194.0A CN201610267194A CN105924199B CN 105924199 B CN105924199 B CN 105924199B CN 201610267194 A CN201610267194 A CN 201610267194A CN 105924199 B CN105924199 B CN 105924199B
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carbon
compound material
carbon compound
density
pressure
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CN105924199A (en
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李同起
张中伟
梅敏
冯志海
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China Academy of Launch Vehicle Technology CALT
Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/424—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Abstract

The present invention relates to a kind of fast preparation methods of inexpensive carbon/carbon compound material, belong to field of compound material, are mainly used for reducing the manufacturing cycle and cost of high-compactness carbon/carbon compound material.By carrying out being compounded to form low-density carbon/carbon compound material in fibre bundle to the carbon fibre fabric after sizing, then by filling carbon particle between carbon fiber bundle, hole become larger as micropore, then it is carbonized by low pressure liquid impregnation or chemical vapor infiltration, joint high-temperature heat treatment obtains high density carbon/carbon compound material.The method that the present invention prepares carbon/carbon compound material is compared with the traditional method, and substantially reducing for high-compactness carbon/carbon compound material manufacturing cycle and being greatly reduced for manufacturing cost may be implemented.

Description

A kind of fast preparation method of low cost carbon/carbon compound material
Technical field
The present invention relates to a kind of fast preparation methods of inexpensive carbon/carbon compound material, belong to field of compound material.
Background technique
Carbon/carbon compound material due to have high temperature resistant, mechanical behavior under high temperature are excellent, Temperature Size stablize many advantages, such as and It is widely used in the high-temperature component of aerospace craft, such as engine larynx lining, jet pipe, aircraft end ablation component.Tradition Carbon/carbon compound material can be prepared by liquid phase or gas phase process, wherein liquid phase process mainly uses pitch or resin for before Body is driven by processes such as impregnating by pressure, carbonization and high-temperature heat treatments repeatedly to prepare, and gas phase process is then mainly passing through Learning gas-phase permeation (CVI) technology will deposit in carbon fibre fabric after hydro carbons organic gas high temperature pyrolysis.Usual liquid phase method can be with The carbon/carbon compound material of higher density is obtained, (pressure densifies its density up to 2.0g/ up to 50MPa or more) by high pressure cm3More than；And the carbon/carbon compound material density that simple CVI method is formed is lower, usually less than 1.6g/cm3.In conjunction with liquid phase side Method continues with high pressure densification process and carries out density to carbon/carbon compound material prepared by CVI method, it is also possible to obtain density is high In 1.8g/cm3Above carbon/carbon compound material.In the forming process of traditional high-compactness carbon/carbon compound material, high pressure Densification process is the key that realize macropore filling in material.Just because of using multiple low pressure liquid phase of densification or long-time CVI technique and subsequent multiple phase autoclave densification process, cause high-compactness (1.8g/cm3More than) carbon/carbon composite wood The manufacturing cycle of material is very long, will not usually be less than 5 months, and due to using high pressure, even super-pressure densification facility, material The manufacturing cost of material is very high.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming existing high-compactness carbon/carbon compound material long preparation period, cost high temperature Problem provides a kind of fast preparation method of inexpensive carbon/carbon compound material, realizes the fast of high-compactness carbon/carbon compound material Speed, low cost preparation.
The technology of the present invention solution: in advance carrying out shaping carbon fibre fabric, is then carbonized or is changed using liquid impregnation It learns vapor deposition (CVI) method to be filled carbon fiber bundle inner pore, then fiber interfascicular is filled by carbon particle, Interfascicular macropore is divided into micropore, high-compactness is then formed by liquid phase low pressure impregnation carbonization and high-temperature heat treatment method Carbon/carbon compound material, specific as follows:
(1) using normal pressure impregnating resin or pitch and solidify, carbonization treatment or carry out short time chemical vapor infiltration (CVI) Densify the sizing to realize carbon fibre fabric；Its shape is kept by profiling fixture in fabric type-approval process, prevents fabric from becoming Shape；Sizing carbon fibre fabric is obtained after the completion；
(2) carbonization treatment is carried out by sizing carbon fibre fabric using low pressure impregnating resin or pitch and after solidifying, or will determined Type carbon fibre fabric carries out chemical vapor infiltration (CVI) density for a long time, fibre bundle inner pore is substantially filled with, then carry out high temperature Heat treatment obtains low-density carbon/carbon compound material；
(3) granularity is less than the carbonaceous particle of pore-size between carbon fiber bundle by mixing with liquid phase carrier, then vacuum- Impregnating by pressure in the hole of fiber interfascicular, forms carbon particle and fills carbon/carbon compound material into low-density carbon/carbon compound material；
(4) carbon particle filling carbon/carbon compound material is continued to carry out carbon using low pressure impregnating resin or pitch and after solidifying Change processing, or long-time chemical vapor infiltration (CVI) densification and high temperature are continued to carbon particle filling carbon/carbon compound material Heat treatment forms high-compactness carbon/carbon compound material.
Step (1), step (2) and step (4) resin be after high temperature pyrolysis with carbon remain based on resin, including Phenolic resin, furfural acetone resin；The pitch is dipping agent bitumen, can for one of coal base, petroleum base and synthetic asphalts or It is a variety of.
Normal pressure dipping process described in step (1), for by the fixed carbon fibre fabric of setting tooling under normal pressure in liquid phase The process impregnated in resin or the pitch of melting；Resin dipping carries out at normal temperature, and the mobility of resin can be added by solvent Amount number control；Bituminizing then needs to carry out in the bituminous liquids being thermally formed.
Step (1) profiling fixture is fixed fabric shape, has the characteristics that mold, the clamping plate of opening character, material is stone Ink material, carbon/carbon compound material or metal, wherein graphite material and carbon/carbon compound material profiling fixture can further apply Carbonization treatment and high-temperature heat treatment process, and metal tooling is only capable of being further used for carbonization treatment.
Short time described in step (1) carries out chemical vapor infiltration (CVI) densification and refers to propane, propylene, methane gas Phase pyrolytic deposition forms the process of thin layer pyrocarbon matrix to carbon fiber surface, wherein the densification time is shorter, is no more than 100h； Optimization sedimentation time is 10h~50h.
Low pressure dipping process described in step (2) is to carry out the carbon fibre fabric after sizing under lower pressurized condition The process of liquid-phase resin or pitch is impregnated, wherein moulding pressure is 0.1~3MPa.
When step (2) and step (4) long-time carry out chemical vapor infiltration (CVI) density process as than step (1) Between longer gas phase density process, sedimentation time be 100h~500h.
Step (2) the low pressure dipping process or CVI process can repeat 1~2 time, until low density carbon/carbon is multiple The density ratio carbon fibre fabric of condensation material increases by 20%~50%.
Step (3) described carbon particle is with carbon solid powder as main component, including graphite powder, carbon black, carbon fiber powder End.
Liquid phase carrier described in step (3) is the liquid-phase system that can be uniformly dispersed therein carbonaceous particle, including alcohol One or more of class, ketone, benzene homologues, resin.
Vacuum described in step (3)-impregnating by pressure process is first to vacuumize to low-density carbon/carbon compound material, so The process of impregnating by pressure, moulding pressure after afterwards being submerged low-density carbon/carbon compound material with the liquid phase carrier containing carbonaceous particle For 0.1~5MPa；Vacuum-dipping process can be repeated to improve the compactedness of carbon particle；By liquid phase after the completion of dipping Carrier is by dry removal or by being heating and curing.
The heat treatment process that high-temperature heat treatment process described in step (2) and step (4) is not more than 2000 DEG C.
Resin described in step (4) or bituminizing, solidification, carbonization and high-temperature heat treatment process can be repeated, directly Density to carbon/carbon compound material reaches predetermined density or reaches high-compactness 1.8g/cm3More than；Wherein last time high temperature Heat treatment temperature is no more than 1500 DEG C, to keep the higher mechanical property of carbon/carbon compound material.
Impregnation pressure described in step (4) is within the scope of 1~5MPa.
The present invention has the beneficial effect that compared with prior art
(1) this technology method substantially increases efficiency of densification by introducing carbon particulate matter, make to prepare high-compactness carbon/ 30% or more the cycle time of carbon composite, manufacturing cost reduce by 40% or more.
(2) this technology method is by being pre-formed matrix carbon in fabric fibre beam, it is ensured that sufficiently filling out in fibre bundle It fills and interface cohesion；It can effectively be kept by control maximum heat treatment temperature and last time high-temperature heat treatment temperature simultaneously The mechanical property of carbon/carbon compound material is not greatly reduced because quickly preparing.
(3) this technology method can be realized by low pressure impregnation carbonization or/and chemical vapor infiltration, and abandon preparation High pressure densification process needed for high densification material makes high-compactness so as to avoid high pressure, super-pressure densification facility While carbon/carbon compound material cost reduces, process safety is also greatly improved.
Specific embodiment
Embodiment 1:
1) use density for 0.6g/cm3Needled carbon fiber plate fabric, with a thickness of 30mm.Utilize the graphite with sieve pore Plate is fixed as profiling fixture by graphite bolt.It is then placed in progress normal pressure leaching in the ethanol solution of phenolic resin Stain.Excess surface resin is removed after taking out after the completion of dipping, is then heating and curing.To cured dipping fabric at 900 DEG C Lower carbonization 1h, the carbon fibre fabric being formed.
2) carbon fibre fabric being formed is immersed in phenolic resin and then is forced into 1MPa and carry out pressurization liquid impregnation, taken Excess surface resin is removed after out, is then heating and curing.It is carbonized at 900 DEG C 2h to cured dipping fabric, then exists 2000 DEG C of high-temperature heat treatment 2h are carried out, low-density carbon/carbon compound material has been obtained, density is about 0.85g/cm3。
3) using the graphite powder that granularity is 5 microns as filling carbon particle, its is fully dispersed into ethyl alcohol, form concentration about The suspension of 50g/100g, then pressure be 3MPa in the case where carry out impregnating by pressure, by graphite powder be filled into low density carbon/ In carbon composite, then pass through heating volatilization removal alcohol solvent.Be repeated once filling process, obtain carbon particle filling carbon/ Carbon composite.
4) carbon particle filling carbon/carbon compound material is placed in melting medium temperature coal pitch, liquid is carried out under the pressure of 3MPa It mutually impregnates, after 900 DEG C of carbonizations and 1800 DEG C of high-temperature heat treatments, then the liquid phase bituminizing under 4MPa pressure is carried out, through 900 DEG C After carbonization and 1800 DEG C of high-temperature heat treatments, then the liquid phase bituminizing under 5MPa pressure is carried out, through 900 DEG C of carbonizations and 1500 DEG C of height Density 1.85g/cm is obtained after warm processing3Carbon/carbon compound material.
Comparative example: fabric identical with the present embodiment is obtained into low density carbon/carbon composite wood behind above-mentioned (1) and (2) Then material carries out high pressure densification and high-temperature heat treatment using conventional method using medium temperature coal pitch as impregnating agent, is repeated three Density about 1.85g/cm is obtained after secondary3Carbon/carbon compound material.
After tested, this technology method prepare the high-compactness carbon/carbon compound material period be 3 months.With tradition in comparative example The carbon/carbon compound material that method obtains is compared, and manufacturing cycle and cost reduce by 38% and 50% or more respectively, and mechanical property is basic Quite, it is not decreased obviously.
Embodiment 2:
1) use density for 0.9g/cm3Suture carbon fiber plate fabric, with a thickness of 15mm.Utilize the graphite with sieve pore Plate is fixed as profiling fixture by graphite bolt.Then it is carried out shaping using chemical vapor deposition process.With propane For presoma, 30h is densified at 1000 DEG C, the carbon fibre fabric being formed.
2) after the carbon fibre fabric being formed being removed profiling fixture, continue chemical vapor deposition density.With propane For presoma, 1800 DEG C of high-temperature heat treatments are carried out after 300h is densified at 1000 DEG C, have obtained low density carbon/carbon composite wood Material, density is about 1.1g/cm3。
3) using carbon black as filling carbon particle, its is fully dispersed to in ethyl alcohol dilute resin solution, form concentration Then the about suspension of 30g/100g carries out impregnating by pressure in the case where pressure is 5MPa, arrive low-density for carbon black-filled In carbon/carbon compound material, then pass through heating volatilization removal alcohol solvent and solidified resin.It is repeated once filling process, is obtained Carbon particle fills carbon/carbon compound material.
4) carbon particle filling carbon/carbon compound material is placed in phenolic resin, liquid impregnation is carried out under the pressure of 3MPa, After 900 DEG C of carbonizations and 1800 DEG C of high-temperature heat treatments, then the resin dipping under 4MPa pressure is carried out, through 900 DEG C of carbonizations and 2000 After DEG C high-temperature heat treatment, then the resin dipping under 5MPa pressure is carried out, is obtained after 900 DEG C of carbonizations and 1500 DEG C of high-temperature heat treatments Density is 1.89g/cm3Carbon/carbon compound material.
Comparative example: fabric identical with the present embodiment is obtained into low density carbon/carbon composite wood behind above-mentioned (1) and (2) Then material carries out high pressure densification and high-temperature heat treatment using conventional method using medium temperature coal pitch as impregnating agent, is repeated three Density about 1.90g/cm is obtained after secondary3Carbon/carbon compound material.
After tested, this technology method prepare the high-compactness carbon/carbon compound material period be 2.5 months.It is passed with comparative example The carbon/carbon compound material that system method obtains is compared, and manufacturing cycle and cost reduce by 45% and 45% or more respectively, mechanical property base This quite, is not decreased obviously.
Embodiment 3:
1) use density for 1.1g/cm3Three-dimensional carbon fiber block fabric, with a thickness of 50mm.Using wall surface with sieve pore Metallic channel is as profiling fixture, without obvious gap between fabric and tooling.It is then placed in the ethanol solution of phenolic resin and carries out Normal pressure dipping.Removal excess surface resin is taken out after the completion of dipping, is then heating and curing.Exist to cured dipping fabric Be carbonized 3h at 900 DEG C, the carbon fibre fabric being formed.
2) after the carbon fibre fabric being formed being removed profiling fixture, continue chemical vapor deposition density.With propylene For presomas, 1800 DEG C of high-temperature heat treatments are carried out after 50h is densified at 1000 DEG C, have obtained low-density carbon/carbon compound material, Its density is about 1.31g/cm3。
3) to grind the carbon fiber powder (about 10 microns of granularity) obtained as filling carbon particle, its is fully dispersed to use In toluene, the suspension that concentration is about 25g/100g is formed, then impregnating by pressure is carried out in the case where pressure is 5MPa, by carbon Fiber grain is filled into low-density carbon/carbon compound material, then passes through heating volatilization removal toluene solvant.It is repeated once filling Process obtains carbon particle and fills carbon/carbon compound material.
4) carbon particle filling carbon/carbon compound material is placed in melting medium temperature asphalt, is carried out under the pressure of 3MPa Liquid impregnation after 900 DEG C of carbonizations and 2000 DEG C of high-temperature heat treatments, then carries out the bituminizing under 4MPa pressure, through 900 DEG C of carbon After change and 2000 DEG C of high-temperature heat treatments, then the bituminizing under 5MPa pressure is carried out, at 900 DEG C of carbonizations and 1500 DEG C of high warms Density 1.89g/cm is obtained after reason3Carbon/carbon compound material.
Comparative example: fabric identical with the present embodiment is obtained into low density carbon/carbon composite wood behind above-mentioned (1) and (2) Then material carries out high pressure densification and high-temperature heat treatment using conventional method using medium temperature coal pitch as impregnating agent, is repeated four Density about 1.95g/cm is obtained after secondary3Carbon/carbon compound material.
After tested, this technology method prepare the high-compactness carbon/carbon compound material period be 3 months.With tradition in comparative example The carbon/carbon compound material that method obtains is compared, and manufacturing cycle and cost reduce by 45% and 60% or more respectively, mechanical properties decrease No more than 5%, it is not decreased obviously.
Embodiment 4:
1) use density for 0.9g/cm3Suture carbon fiber plate fabric, with a thickness of 15mm.Utilize carbon/carbon with sieve pore Composite material flat plate is fixed as profiling fixture by carbon/carbon compound material bolt.It is then placed in the mid temperature pitch of melting Middle progress normal pressure dipping.Removal excess surface pitch is taken out after the completion of dipping, be carbonized 2h at 900 DEG C, the carbon being formed Fabric.
2) after the carbon fibre fabric being formed being removed profiling fixture, continue chemical vapor deposition density.With methane For presomas, 2000 DEG C of high-temperature heat treatments are carried out after 50h is densified at 1000 DEG C, have obtained low-density carbon/carbon compound material, Its density is about 1.18g/cm3。
It is 3) using about 5 microns of granularity of graphous graphite powder as filling carbon particle, its is fully dispersed to in phenolic resin, The suspension that concentration is about 30g/100g is formed, in the case where pressure is 5MPa to low-density after regulating and controlling its mobility with ethyl alcohol Carbon/carbon compound material carries out impregnating by pressure, and carbon particle is filled into low-density carbon/carbon compound material fiber interfascicular, is then passed through Heating volatilization removal ethyl alcohol, and solidified resin.It is repeated once filling process, carbon particle is obtained and fills carbon/carbon compound material.
4) carbon particle filling carbon/carbon compound material is placed in phenolic resin, liquid impregnation is carried out under the pressure of 3MPa, After 900 DEG C of carbonizations and 1800 DEG C of high-temperature heat treatments, then the resin dipping under 4MPa pressure is carried out, through 900 DEG C of carbonizations and 2000 After DEG C high-temperature heat treatment, then the resin dipping under 5MPa pressure is carried out, after 900 DEG C of carbonizations and 1800 DEG C of high-temperature heat treatments, then Resin dipping, 900 DEG C of carbonizations and the 1500 DEG C of high-temperature heat treatments under a 5MPa pressure are carried out, acquisition density is 1.92g/cm3 Carbon/carbon compound material.
Comparative example: fabric identical with the present embodiment is obtained into low density carbon/carbon composite wood behind above-mentioned (1) and (2) Then material carries out high pressure densification and high-temperature heat treatment using conventional method using medium temperature coal pitch as impregnating agent, is repeated four Density about 1.96g/cm is obtained after secondary3Carbon/carbon compound material.
After tested, this technology method prepare the high-compactness carbon/carbon compound material period be 3.3 months.It is passed with comparative example The carbon/carbon compound material that system method obtains is compared, and manufacturing cycle and cost reduce by 42% and 55% or more respectively, mechanical property base This quite, is not decreased obviously.
Embodiment 5:
1) use density for 0.6g/cm3Needled carbon fiber plate fabric, with a thickness of 30mm.Utilize the graphite with sieve pore Material plates are fixed as profiling fixture by graphite material bolt.It is then placed in the mid temperature pitch of melting and carries out often Pressure dipping.Removal excess surface pitch is taken out after the completion of dipping, be carbonized 2h at 900 DEG C, the carbon fibre fabric being formed.
2) after the carbon fibre fabric being formed being removed profiling fixture, continue chemical vapor deposition density.With methane For presomas, 1800 DEG C of high-temperature heat treatments are carried out after 80h is densified at 1000 DEG C, have obtained low-density carbon/carbon compound material, Its density is about 0.86g/cm3。
3) using granularity in 3 microns~20 microns of carbon fiber powder as filling carbon particle, its is fully dispersed to using phenol In the ethanol solution of urea formaldehyde, the suspension that concentration is about 30g/100g is formed, then in the case where pressure is 5MPa to low Density carbon/carbon compound material carries out impregnating by pressure, carbon particle is filled into low-density carbon/carbon compound material fiber interfascicular, then It is volatilized by heating and removes ethyl alcohol, and solidified resin.It is repeated twice filling process, carbon particle is obtained and fills carbon/carbon compound material.
4) carbon particle filling carbon/carbon compound material is placed in melting mid temperature pitch, liquid phase is carried out under the pressure of 3MPa Dipping after 900 DEG C of carbonizations, then carries out the resin dipping under 4MPa pressure, through 900 DEG C of carbonizations and 2000 DEG C of high-temperature heat treatments Afterwards, then resin dipping under 5MPa pressure is carried out, after 900 DEG C of carbonizations and 1800 DEG C of high-temperature heat treatments, then carries out a 5MPa Resin dipping, 900 DEG C of carbonizations and 1500 DEG C of high-temperature heat treatments under pressure, acquisition density are 1.83g/cm3Carbon/carbon composite wood Material.
Comparative example: fabric identical with the present embodiment is obtained into low density carbon/carbon composite wood behind above-mentioned (1) and (2) Then material carries out high pressure densification and high-temperature heat treatment using conventional method using medium temperature coal pitch as impregnating agent, is repeated four Density about 1.86g/cm is obtained after secondary3Carbon/carbon compound material.
After tested, this method prepare the high-compactness carbon/carbon compound material period be 3.5 months.With tradition side in comparative example The carbon/carbon compound material that method obtains is compared, and manufacturing cycle and cost reduce by 40% and 52% or more respectively, the basic phase of mechanical property When not being decreased obviously.

Claims (11)

1. a kind of fast preparation method of low cost carbon/carbon compound material, it is characterised in that step includes:
(1) using normal pressure impregnating resin or pitch and solidify, carbonization treatment or to carry out short time chemical vapor infiltration (CVI) fine and close Change the sizing to realize carbon fibre fabric；Its shape is kept by profiling fixture in fabric type-approval process, prevents fabric distortion；It is complete At rear acquisition sizing carbon fibre fabric；Wherein, the short time is no more than 100h；
(2) carbonization treatment is carried out by sizing carbon fibre fabric using low pressure impregnating resin or pitch and after solidifying, or the carbon that will be formed Fabric carries out chemical vapor infiltration (CVI) density for a long time, and fibre bundle inner pore is substantially filled with, then carries out at high warm Reason obtains low-density carbon/carbon compound material；Wherein, low pressure dipping process described in step (2) is to knit the carbon fiber after sizing Object carries out the process of dipping liquid-phase resin or pitch under lower pressurized condition, and wherein moulding pressure is 0.1~3MPa；
(3) carbonaceous particle by granularity less than pore-size between carbon fiber bundle with liquid phase carrier by mixing, then vacuum-pressurization It is impregnated into low-density carbon/carbon compound material in the hole of fiber interfascicular, forms carbon particle and fill carbon/carbon compound material；Wherein, Moulding pressure is 0.1~5MPa；
(4) carbon particle filling carbon/carbon compound material is continued to carry out at carbonization using low pressure impregnating resin or pitch and after solidifying Reason, or carbon particle filling carbon/carbon compound material is continued at long-time chemical vapor infiltration (CVI) densification and high warm Reason forms high-compactness carbon/carbon compound material；Wherein, the pressure of low pressure dipping is within the scope of 1~5MPa；
Wherein, when step (2) and step (4) long-time carry out chemical vapor infiltration (CVI) density process as than step (1) Between longer gas phase density process, sedimentation time be 100h~500h.
2. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly (1), step (2) and step (4) resin be after high temperature pyrolysis with carbon remain based on resin；The pitch is coal One of base, petroleum base and synthetic asphalts are a variety of.
3. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly normal pressure dipping process described in (1), for by the fixed carbon fibre fabric of profiling fixture under normal pressure in liquid-phase resin or melting Pitch in the process that impregnates；Resin dipping carries out at normal temperature, the mobility of resin by solvent adding amount number control System；Bituminizing then needs to carry out in the bituminous liquids being thermally formed.
4. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly (1) described profiling fixture is fixed fabric shape, has the characteristics that mold, the clamping plate of opening character, material be graphite material, carbon/ Carbon composite or metal, wherein graphite material and carbon/carbon compound material profiling fixture can further apply carbonization treatment and High-temperature heat treatment process, and metal tooling is only capable of being further used for carbonization treatment.
5. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly the progress of short time described in (1) chemical vapor infiltration (CVI) densification refers to propane, propylene, methane gas phase pyrolytic deposition The process of thin layer pyrocarbon matrix is formed to carbon fiber surface, wherein the densification time is shorter, is no more than 100h.
6. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly (2) described low pressure dipping process or CVI process repeat 1~2 time, until the density ratio of low-density carbon/carbon compound material Carbon fibre fabric increases by 20%~50%.
7. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly (3) described carbon particle is with carbon solid powder as main component.
8. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly liquid phase carrier described in (3) is the liquid-phase system that can be uniformly dispersed therein carbonaceous particle.
9. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly vacuum described in (3)-impregnating by pressure process is first to vacuumize to low-density carbon/carbon compound material, then with containing carbon The liquid phase carrier of matter particle by low-density carbon/carbon compound material submerge after impregnating by pressure process, moulding pressure be 0.1~ 5MPa；Vacuum-dipping process is repeated to improve the compactedness of carbon particle；Liquid phase carrier is passed through into drying after the completion of dipping It removes or by being heating and curing.
10. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly the heat treatment process that high-temperature heat treatment process described in (2) and step (4) is not more than 2000 DEG C.
11. a kind of fast preparation method of inexpensive carbon/carbon compound material according to claim 1, it is characterised in that: step Suddenly resin or bituminizing, solidification, carbonization and high-temperature heat treatment process described in (4) are repeated, until carbon/carbon compound material Density reach predetermined density or reach high-compactness 1.8g/cm3More than；Wherein last time high-temperature heat treatment temperature is no more than 1500 DEG C, to keep the higher mechanical property of carbon/carbon compound material.
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