CN116003151A - Carbon-carbon composite material crucible and preparation method thereof - Google Patents
Carbon-carbon composite material crucible and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 125
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 296
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 234
- 239000004917 carbon fiber Substances 0.000 claims abstract description 234
- 239000004744 fabric Substances 0.000 claims abstract description 50
- 238000010306 acid treatment Methods 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 36
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000280 densification Methods 0.000 claims abstract description 24
- 238000007740 vapor deposition Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 10
- 150000001721 carbon Chemical class 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 107
- 229920005989 resin Polymers 0.000 claims description 107
- 239000003292 glue Substances 0.000 claims description 55
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000005470 impregnation Methods 0.000 claims description 23
- 239000007791 liquid phase Substances 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- WIEXMPDBTYDSQF-UHFFFAOYSA-N 1,3-bis(furan-2-yl)propan-2-one Chemical compound C=1C=COC=1CC(=O)CC1=CC=CO1 WIEXMPDBTYDSQF-UHFFFAOYSA-N 0.000 claims description 15
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 128
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 34
- 239000002202 Polyethylene glycol Substances 0.000 description 32
- 229920001223 polyethylene glycol Polymers 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 30
- 238000005452 bending Methods 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 28
- 239000012159 carrier gas Substances 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 22
- 238000001816 cooling Methods 0.000 description 22
- 238000009960 carding Methods 0.000 description 20
- USRJNCZFXRJTNN-UHFFFAOYSA-N 1-(furan-2-yl)propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)CC1=CC=CO1 USRJNCZFXRJTNN-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000009941 weaving Methods 0.000 description 8
- 238000005491 wire drawing Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010000 carbonizing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
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Images
Classifications
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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
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62886—Coating the powders or the macroscopic reinforcing agents by wet chemical techniques
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5252—Fibers having a specific pre-form
- C04B2235/5256—Two-dimensional, e.g. woven structures
-
- 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 invention discloses a carbon-carbon composite material crucible and a preparation method thereof, belongs to the technical field of carbon-carbon composite material crucibles, and particularly relates to a preparation method of a pretreated carbon fiber chopped strand by cutting a carbon fiber precursor into carbon fiber chopped strands and performing pretreatment; in the pretreatment, an acid treatment liquid is used for carrying out short shredding treatment on the carbon fiber; adding the pretreated carbon fiber chopped filaments into a modification solution to carry out modification treatment to obtain modified carbon fiber chopped filaments; the modified solution contains amyl alcohol and propyl lactate; preparing a carbon fiber net tire by chopping modified carbon fibers, and preparing unidirectional cloth from the carbon fiber net tire and carbon fiber precursors; preparing a crucible preform by arranging a carbon fiber net tire, unidirectional cloth and bidirectional cloth on a model; and (5) carrying out frequent pressure gum dipping carbonization and vapor deposition densification on the crucible preform to obtain the carbon-carbon composite material crucible. The carbon-carbon composite material crucible prepared by the invention has good thermal conductivity and small thermal expansion coefficient.
Description
Technical Field
The invention belongs to the technical field of carbon-carbon composite material crucibles, and particularly relates to a carbon-carbon composite material crucible and a preparation method thereof.
Background
The carbon-carbon composite material is a material compounded by taking carbon or graphite fiber as a reinforcement and taking carbon or graphite as a matrix. The composite material has a series of advantages of high strength, high modulus, high dimensional stability, low density, small thermal expansion coefficient, thermal shock resistance, ablation resistance and the like, and can be rapidly developed as a novel high-temperature-resistant structural function integrated material. In recent years, carbon/carbon composite materials have been flushed out of the fields of military missiles and aerospace plane heat protection materials, and by virtue of the excellent performance and comprehensive cost performance advantages, the application space in other civil industrial fields is gradually developed. Wherein, the preform is used as a framework supporting material in the carbon/carbon composite material, and the preparation process is one of key core technologies of the carbon/carbon composite material.
Compared with a graphite crucible, the carbon-carbon composite material crucible has the advantages of remarkable structural strength and service life, and meanwhile, due to the large-size graphite crucible, the carbon/carbon composite material crucible is adopted to replace the graphite crucible, so that the cost can be effectively reduced. Meanwhile, because the isostatic pressing high-quality high-purity graphite of the graphite crucible produced in China almost completely depends on import, the development of the carbon-carbon composite material crucible has important significance for improving the technical development of the industry.
The carbon fiber has the characteristics of high rigidity, good bundling property, poor toughness and the like, and can cause poor carding effect, uneven carding and the like due to easy breakage in the carding process. The invention aims to provide a carbon-carbon composite material crucible prepared from carbon fiber precursors.
Disclosure of Invention
The invention aims to provide a carbon-carbon composite material with good tensile strength and bending strength and a method for preparing the carbon-carbon composite material crucible by using the carbon-carbon composite material, and the obtained carbon-carbon composite material crucible has good thermal conductivity and small thermal expansion coefficient.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a preparation method of a carbon-carbon composite crucible comprises the following steps:
cutting the carbon fiber precursor into carbon fiber chopped filaments, and preparing the pretreated carbon fiber chopped filaments through pretreatment; in the pretreatment, an acid treatment liquid is used for carrying out short shredding treatment on the carbon fiber;
adding the pretreated carbon fiber chopped filaments into a modification solution to carry out modification treatment to obtain modified carbon fiber chopped filaments; the modified solution contains amyl alcohol and propyl lactate;
preparing a crucible preform by arranging a carbon fiber net tire and two directions on a model;
and carrying out vapor deposition, liquid phase impregnation densification, carbonization and post-treatment on the crucible preform to obtain the carbon-carbon composite material crucible. When the crucible is prepared, the carbon fiber precursor is cut and pretreated to prepare the carbon fiber net tire which is not subjected to modification treatment on the carbon fiber chopped strands, and then the carbon fiber net tire is subjected to vapor deposition, liquid phase impregnation densification, carbonization and post treatment to obtain the carbon-carbon composite material crucible.
Preferably, the acid treatment solution is obtained by mixing potassium dichromate, concentrated sulfuric acid and deionized water.
Preferably, the modified liquid contains concentrated sulfuric acid as a catalyst.
Preferably, the modified solution contains 10-30wt% propyl lactate.
Preferably, the pretreated carbon fiber chopped strands are used in an amount of 20-60wt% of the modifying solution.
Preferably, the resin glue solution in the normal pressure gum dipping contains furfuryl ketone resin and p-chlorobenzenesulfonic acid.
Preferably, the density of the crucible preform is 0.30 to 0.70g/cm 3 。
Preferably, in the pretreatment of the carbon fiber, the carbon fiber precursor is cut into carbon fiber chopped filaments, then the carbon fiber chopped filaments are placed in ethanol, ultrasonically cleaned, taken out after the cleaning is finished, added into an acid treatment solution, treated for 3-10 hours at the temperature of 20-40 ℃, taken out, cleaned and dried, and the pretreated carbon fiber chopped filaments are obtained.
More preferably, in the pretreatment of the carbon fiber, the chopped carbon fiber filaments are used in an amount of 10 to 40wt% of ethanol.
More preferably, in the pretreatment of the carbon fiber, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 1-5wt% of potassium dichromate, and the acid treatment liquid contains 80-90wt% of concentrated sulfuric acid.
More preferably, in the pretreatment of the carbon fiber, the short cut carbon fiber is used in an amount of 10 to 25wt% of the acid treatment liquid.
More preferably, in the pretreatment of the carbon fiber, the length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preferably, in the preparation of the modified carbon fiber chopped strands, the pretreated carbon fiber chopped strands are added into a modified solution, a catalyst is added, the reaction is carried out for 2-6 hours at the temperature of 100-140 ℃, the carbon fiber chopped strands are taken out, washed to be neutral, added into a polyethylene glycol solution, treated for 2-8 hours at the temperature of 20-40 ℃, and dried, so that the modified carbon fiber chopped strands are obtained.
More preferably, in the preparation of the modified carbon fiber chopped filaments, the modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 10-30wt% of propyl lactate, and the use amount of the pretreated carbon fiber chopped filaments is 20-60wt% of the modified solution.
More preferably, in the preparation of the modified carbon fiber chopped filaments, the catalyst is concentrated sulfuric acid, and the use amount of the catalyst is 0.5-3wt% of the pretreated carbon fiber chopped filaments.
More preferably, in the preparation of the modified carbon fiber chopped strands, the polyethylene glycol solution contains 10-30wt% of polyethylene glycol, and the pretreatment carbon fiber chopped strands are used in an amount of 10-30wt% of the polyethylene glycol solution.
Preferably, in the preparation of the carbon fiber net tyre, the modified carbon fiber chopped filaments are carded, and after uniform carding, the carbon fiber net tyre is obtained. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g. In order to obtain the net tire with good uniformity, the carbon fiber before carding is modified, the modification effect is optimized by controlling different proportions and time, and the modifier does not pollute the environment in the later period. The modified carbon fiber has improved softness, better spinnability, difficult fracture in the carding process and capability of obtaining a net tire with good uniformity and fluffiness.
Preferably, in the preparation of the bidirectional cloth, weaving of carbon fiber precursors at 0-90 degrees is performed by a loom to obtain the bidirectional cloth (carbon cloth).
Preferably, in the preparation of the crucible preform, the carbon fiber net tyre is manufactured into a crucible shape on a mandrel, then the bidirectional cloth and the carbon fiber net tyre are alternately overlapped on the crucible shape, and the carbon fiber net tyre is arranged at the outermost layer, and the crucible preform is obtained by needling. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness.
More preferably, in the preparation of the crucible preform, the density of the crucible preform is 0.30 to 0.70g/cm 3 。
Preferably, in the preparation of the resin glue solution, the resin and the curing agent are added into ethanol and stirred and mixed to obtain the resin glue solution.
More preferably, in the preparation of the resin glue solution, the resin is furfuryl ketone resin and the curing agent is p-chlorobenzenesulfonic acid.
More preferably, in the preparation of the resin glue solution, the resin glue solution contains 15-25wt% of furfuryl ketone resin, and the usage amount of the curing agent in the resin glue solution is 2-5wt% of the resin.
More preferably, 3- (2-furyl) -2-propyl acrylate may be added to the resin dope, and the 3- (2-furyl) -2-propyl acrylate may be used in an amount of 0.6 to 3wt% of the furfuryl resin in the resin dope. After 3- (2-furyl) -2-propyl acrylate is added into the resin glue solution, the carbon fiber net tyre made of the modified carbon fiber chopped filaments is immersed into the resin glue solution, and the 3- (2-furyl) -2-propyl acrylate interacts with the carbon fiber chopped filament surface in the carbon fiber net tyre and amyl alcohol interacts with propyl lactate, so that the performance of the carbon-carbon composite material crucible obtained by subsequent carbonization treatment and vapor deposition is improved, the tensile strength and the bending strength are both improved, and the change of the thermal expansion coefficient is not great.
Preferably, in the preparation of the crucible, the crucible preform is subjected to vapor deposition, liquid phase impregnation densification, carbonization for 4-24 hours at the temperature of 600-1000 ℃ and post treatment to obtain the carbon-carbon composite material crucible.
In the post-treatment, the carbonized material is cooled, the temperature is increased from 0 ℃ to 2300 ℃ in 35-40h, then the heat is preserved for 2-6h at 2300 ℃, and then the carbonized material is discharged after natural cooling.
More preferably, in the preparation of the crucible, the density of the finally prepared carbon-carbon composite crucible is 1.30-1.70g/cm 3 。
Preferably, in the vapor deposition, methane or propylene gas or natural gas is used as raw material, the pressure of methane or propylene is 0.2-1MPa, and the flow rate of methane or propylene is 0.01-0.10m 3 ·h -1 The deposition temperature is 800-1250 ℃, the carrier gas is hydrogen or nitrogen, the atmosphere pressure of the carrier gas is 0.2-1MPa, and the flow rate of the carrier gas is 0.05-0.15 m 3 ·h -1 The deposition time is 50-150h; the pressure of the natural gas is 0.1-0.5MPa, and the flow rate of the natural gas is 0.3-6m 3 ·h -1 The deposition temperature is 800-1250 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 1-3MPa, and the flow rate of the carrier gas is 0.1-0.4. 0.4 m 3 ·h -1 The deposition time is 100-300h.
Preferably, in the liquid phase impregnation densification, the resin glue solution is adopted, the impregnation temperature is 0-300 ℃, and the impregnation time is 7-24 hours.
The invention discloses a carbon-carbon composite material crucible prepared by the method.
The invention discloses application of the modified carbon fiber chopped filaments in preparing a carbon-carbon composite material or a carbon fiber material.
The invention adopts the modified solution of amyl alcohol and propyl lactate to modify the carbon fiber chopped filaments, the obtained modified carbon fiber chopped filaments are made into carbon fiber net tyres, then the carbon fiber net tyres and the bidirectional cloth are used for preparing crucible prefabricated bodies, and the crucible bodies are subjected to gum dipping carbonization and vapor deposition densification to obtain the carbon-carbon composite material crucible, so that the carbon-carbon composite material crucible has the following beneficial effects: the carbon-carbon composite material has good tensile strength and bending strength, the tensile strength is 150-163MPa, and the bending strength is 168-176MPa; the obtained carbon-carbon composite material crucible has good heat conduction performance, small thermal expansion coefficient and good thermal stability. Therefore, the invention relates to a carbon-carbon composite material with good tensile strength and bending strength and a method for preparing the carbon-carbon composite material crucible by using the carbon-carbon composite material.
Drawings
FIG. 1 is an infrared view of a chopped strand of modified carbon fiber;
FIG. 2 is a graph of tensile strength of a carbon-carbon composite;
FIG. 3 is a graph of flexural strength of a carbon-carbon composite material;
FIG. 4 is a graph of the thermal expansion coefficient of a carbon-carbon composite crucible.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
example 1:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 13wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin and the curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl ketone resin, and the use amount of the curing agent in the resin glue solution is 3wt% of furfuryl ketone resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, propylene is used as a raw material, the pressure of the propylene is 0.5MPa, and the flow rate of the propylene is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 2:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin and the curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl ketone resin, and the use amount of the curing agent in the resin glue solution is 3wt% of furfuryl ketone resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, propylene is used asThe pressure of the raw material, propylene, is 0.5MPa, and the flow rate of the propylene is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 3:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin, 3- (2-furyl) -2-propyl acrylate and a curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl resin, the using amount of 3- (2-furyl) -2-propyl acrylate in the resin glue solution is 1.2wt% of the furfuryl resin, and the using amount of the curing agent in the resin glue solution is 3wt% of the furfuryl resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, propylene is used as a raw material, the pressure of the propylene is 0.5MPa, and the flow rate of the propylene is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 4:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin, 3- (2-furyl) -2-propyl acrylate and a curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl resin, the using amount of 3- (2-furyl) -2-propyl acrylate in the resin glue solution is 2.6wt% of the furfuryl resin, and the using amount of the curing agent in the resin glue solution is 3wt% of the furfuryl resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, propylene is used as a raw material, the pressure of the propylene is 0.5MPa, and the flow rate of the propylene is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 5:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: the carbon fiber net tire is manufactured into a crucible shape on a mandrel, then the two-way cloth and the carbon fiber net tire are alternately overlapped on the crucible shape, and the most isThe outer layer is a carbon fiber net tyre, and the crucible preform is obtained by needling. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin, 3- (2-furyl) -2-propyl acrylate and a curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl resin, the using amount of 3- (2-furyl) -2-propyl acrylate in the resin glue solution is 2.6wt% of the furfuryl resin, and the using amount of the curing agent in the resin glue solution is 3wt% of the furfuryl resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, methane is used as raw material, the pressure of the methane is 0.5MPa, and the flow rate of the methane is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 6:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin, 3- (2-furyl) -2-propyl acrylate and a curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl resin, the using amount of 3- (2-furyl) -2-propyl acrylate in the resin glue solution is 2.6wt% of the furfuryl resin, and the using amount of the curing agent in the resin glue solution is 3wt% of the furfuryl resin.
Preparation of a crucible: and (3) carrying out vapor deposition, liquid phase impregnation densification on the crucible preform, carbonizing at 800 ℃ for 12 hours, cooling, heating the crucible preform to 2300 ℃ from 0 ℃ within 38.5 hours, preserving the heat at 2300 ℃ for 4 hours, and naturally cooling to about 80 ℃ to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, methane is used as raw material, the pressure of the methane is 0.5MPa, and the flow rate of the methane is 0.05m 3 ·h -1 The deposition temperature is 1000 ℃, the carrier gas is hydrogen, the atmosphere pressure of the carrier gas is 0.5MPa, and the flow rate of the carrier gas is 0.09m 3 ·h -1 The deposition time was 100h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Example 7:
a preparation method of a carbon-carbon composite material crucible,
pretreatment of carbon fibers: cutting carbon fiber precursor into carbon fiber chopped filaments, then placing the carbon fiber chopped filaments in ethanol, ultrasonically cleaning, taking out, adding the carbon fiber chopped filaments into an acid treatment solution, treating for 6 hours at the temperature of 30 ℃, taking out, cleaning, and drying to obtain pretreated carbon fiber chopped filaments. The usage amount of the carbon fiber chopped filaments is 30wt% of ethanol, the acid treatment liquid is a mixed liquid of potassium dichromate, concentrated sulfuric acid and deionized water, the acid treatment liquid contains 3wt% of potassium dichromate, the acid treatment liquid contains 90wt% of concentrated sulfuric acid, and the usage amount of the carbon fiber chopped filaments is 20wt% of the acid treatment liquid. The length of the chopped carbon fiber is controlled to be 5+/-1 cm, and the cut surface is free from wiredrawing.
Preparing modified carbon fiber chopped filaments: adding the pretreated carbon fiber chopped filaments into a modified solution, adding a catalyst, reacting for 4 hours at the temperature of 120 ℃, taking out, cleaning to be neutral, adding the pretreated carbon fiber chopped filaments into a polyethylene glycol solution, treating for 4 hours at the temperature of 30 ℃, and drying to obtain the modified carbon fiber chopped filaments. The modified solution is a mixed solution of amyl alcohol and propyl lactate, the modified solution contains 25wt% of propyl lactate, the use amount of the pretreated carbon fiber chopped filaments is 40wt% of the modified solution, the catalyst is concentrated sulfuric acid, the use amount of the catalyst is 1.5wt% of the pretreated carbon fiber chopped filaments, the polyethylene glycol solution contains 20wt% of polyethylene glycol, and the use amount of the pretreated carbon fiber chopped filaments is 20wt% of the polyethylene glycol solution.
Preparing a carbon fiber net tire: carding the chopped modified carbon fiber, and after carding uniformly, obtaining the carbon fiber net tyre. The carbon wires are uniformly carded, the thickness is uniform, and the gram weight deviation is within the range of 10 g.
Preparation of bidirectional cloth: weaving the carbon fiber precursor at 0-90 degrees by a loom to obtain the bidirectional cloth (carbon cloth).
Preparation of crucible preform: and (3) manufacturing the carbon fiber net tire on a mandrel into a crucible shape, then alternately superposing the bidirectional cloth and the carbon fiber net tire on the mandrel, and needling to obtain a crucible preform, wherein the outermost layer is the carbon fiber net tire. The number of layers of the carbon fiber net tire and the bidirectional cloth depends on the required thickness. The density of the crucible preform is 0.50g/cm 3 。
Preparation of resin glue solution: adding the resin, 3- (2-furyl) -2-propyl acrylate and a curing agent into ethanol, and stirring and mixing to obtain resin glue solution. The resin is furfuryl ketone resin, the curing agent is p-chlorobenzenesulfonic acid, the resin glue solution contains 20wt% of furfuryl resin, the using amount of 3- (2-furyl) -2-propyl acrylate in the resin glue solution is 2.6wt% of the furfuryl resin, and the using amount of the curing agent in the resin glue solution is 3wt% of the furfuryl resin.
Preparation of a crucible: vapor deposition of crucible preform to obtain liquidPhase impregnation densification, carbonization for 12 hours at 800 ℃, cooling, heating the temperature from 0 ℃ to 2300 ℃ in 38.5 hours, then preserving heat for 4 hours at 2300 ℃, and naturally cooling to about 80 ℃ and discharging to obtain the carbon-carbon composite material crucible. The density of the finally prepared carbon-carbon composite material crucible is 1.50g/cm 3 。
In vapor deposition, natural gas is used as raw material, the pressure of the natural gas is 0.25MPa, the deposition temperature is 1000 ℃, the carrier gas is nitrogen, the atmosphere pressure of the carrier gas is 2MPa, and the flow rate of the carrier gas is 0.1-0.4 m 3 ·h -1 Initial flow of natural gas of 0.5 m 3 ·h -1 The deposition time was 1h, then the natural gas flow was adjusted to 4 m 3 ·h -1 The deposition time was 250h.
In the liquid phase impregnation densification, the resin glue solution is adopted, the temperature is raised from 0 ℃ to 75 ℃ for 60 minutes, and the temperature is kept at 75 ℃ for 60 minutes; the second stage temperature is raised from 75 ℃ to 120 ℃ and needs 60 minutes of heating time, and the temperature is kept at 120 ℃ for 160 minutes; the three-stage temperature is increased from 120 ℃ to 160 ℃ and needs 60 minutes of heating time, and the temperature is kept at 160 ℃ for 180 minutes; the four-stage temperature is raised from 160 ℃ to 200 ℃ and needs 60 minutes of heating time, and the temperature is kept at 200 ℃ for 180 minutes. Then cooling to 80 ℃ for a certain time and discharging.
Comparative example 1:
a preparation method of a carbon-carbon composite material crucible,
this comparative example differs from example 2 only in that in the preparation of the chopped strands of modified carbon fiber, the modified solution contained 5wt% of propyl lactate.
Comparative example 2:
a preparation method of a carbon-carbon composite material crucible,
This comparative example differs from example 2 only in that in the preparation of the chopped strands of modified carbon fiber, the modified solution contained 35% by weight of propyl lactate.
Comparative example 3:
a preparation method of a carbon-carbon composite material crucible,
the comparative example differs from example 2 only in that the chopped carbon fiber strands were not modified, and propyl lactate was not contained in the modified solution.
Test example:
1. characterization by Infrared Spectroscopy
Test sample: the modified carbon fiber chopped filaments prepared in example 1 were chopped into chopped carbon fibers before modification.
The infrared spectrum is shown in figure 1, wherein a is carbon fiber chopped yarn before modification, b is modified carbon fiber chopped yarn, and by comparison, the carbon fiber chopped yarn before modification is subjected to acid treatment and then is subjected to acid treatment at 3456cm -1 The absorption peak at 1678cm indicates the presence of a large number of hydroxyl groups -1 The presence of absorption peak indicates that there is carbon-oxygen double bond, indicates that the surface of the acid-treated carbon fiber chopped filament has carboxylic acid group, and the absorption peak of hydroxyl is reduced to 2800-3000cm after modification treatment -1 Obvious methyl and methylene absorption peaks appear at the positions, and the absorption peaks of the carbon-oxygen double bonds are enhanced, which indicates that the modified carbon fiber chopped filaments are successfully obtained.
2. Tensile Property test
Test sample: the carbon-carbon composite materials prepared in each of examples and comparative examples were cut into dimensions of 100mm×10 mm.
The tensile properties of the above samples were tested using an electronic universal tester.
The tensile strength is calculated as follows:
tensile strength = P/a; p is the maximum tensile load and A is the cross-sectional area of the sample.
The tensile properties of the carbon-carbon composite material prepared according to the present invention are shown in fig. 2, wherein a is example 1, b is example 2, c is example 3, d is example 4, e is example 5, f is example 6, g is example, H is comparative example 1, i is comparative example 2, j is comparative example 3, the tensile strength of the carbon-carbon composite material prepared in example 1 is 154.32MPa, the tensile strength of the carbon-carbon composite material prepared in example 2 is 156.48MPa, the tensile strength of the carbon-carbon composite material prepared in comparative example 3 is 148.52MPa, and comparison of example 2 with comparative example 3 shows that when the carbon-carbon composite material is prepared according to the method of the present invention, after the carbon fiber chopped filaments are modified, a crucible shape is made of a carbon fiber net tire and two-way cloth, a carbon composite material is obtained through vapor deposition and liquid phase impregnation densification, and finally a crucible is obtained through carbonization, wherein the modification of the carbon fiber chopped filaments improves the tensile strength of the carbon composite material obtained after carbonization, and compared with comparative example 3, the tensile strength of the carbon composite material obtained in example 2 is improved by 5.36%, which indicates that the carbon fiber net tire and resin adhesive made of the modified carbon fiber chopped filaments have better bonding effect, so that the tensile strength of the carbon composite material is improved; the tensile strength of the carbon-carbon composite material prepared in comparative example 1 is 148.73MPa, the tensile strength of the carbon-carbon composite material prepared in comparative example 2 is 149.06MPa, and comparative examples 1-2 are compared with comparative example 3, which shows that the higher the amount of propyl lactate used is, the better the modifying the chopped carbon fibers is, and the lower the amount of propyl lactate used is, the less the tensile strength of the carbon-carbon composite material prepared in the step is affected, and the higher the amount of propyl lactate used, the tensile strength of the obtained carbon-carbon composite material is lowered, so that the amount of propyl lactate used needs to be in a proper range; the tensile strength of the carbon-carbon composite material prepared in example 3 was 159.36MPa, the tensile strength of the carbon-carbon composite material prepared in example 4 was 161.74MPa, and example 4 compared with example 2 shows that when the carbon-carbon composite material of the previous step of preparing a crucible according to the method of example 2 was used, the tensile strength of the carbon-carbon composite material obtained after using 3- (2-furyl) -2-propyl acrylate in the resin glue solution was improved, and that the 3- (2-furyl) -2-propyl acrylate interacted with the chopped filaments of the modified carbon fibers in the carbon fiber web in the resin glue solution had the effect of improving the tensile strength of the carbon-carbon composite material. The tensile strength of the carbon-carbon composite material prepared in example 5 was 160.86MPa, the tensile strength of the carbon-carbon composite material prepared in example 6 was 161.56MPa, and the tensile strength of the carbon-carbon composite material prepared in example 7 was 161.71MPa.
The tensile strength of the carbon-carbon composite material obtained by the invention is 150-163MPa.
3. Bending performance test
Test sample: the carbon-carbon composite materials prepared in each of examples and comparative examples were cut into 55mm×10mm sizes.
The bending performance of the test sample is tested by a universal testing machine in a three-point bending mode, the span is 45mm, the radius of the pressure head and the support is 5mm, and the loading speed is 0.5mm/min.
The bending strength is calculated as follows:
flexural Strength=3PL/(2 bh) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the P is the maximum load, L is the span, h is the sample height, and b is the sample width.
The results of the bending property test of the carbon-carbon composite material prepared by the present invention are shown in fig. 3, wherein a is example 1, b is example 2, c is example 3, d is example 4, e is example 5, f is example 6, g is example, H is comparative example 1, i is comparative example 2, j is comparative example 3, the bending strength of the carbon-carbon composite material prepared by example 1 is 169.41MPa, the bending strength of the carbon-carbon composite material prepared by example 2 is 170.63MPa, the bending strength of the carbon-carbon composite material prepared by comparative example 3 is 162.48MPa, the comparison of example 2 with comparative example 3 shows that when the carbon-carbon composite material is prepared by the method of the present invention, after the carbon-fiber chopped fibers are modified, the modified carbon fiber chopped filaments are used for preparing a carbon fiber net tire, the carbon fiber net tire and the bidirectional cloth are prepared into a crucible shape, the carbon fiber net tire and the bidirectional cloth are subjected to vapor deposition and liquid phase impregnation densification to obtain a carbon-carbon composite material, and finally the crucible is obtained through carbonization, so that the bending strength of the carbon-carbon composite material obtained after carbonization is improved, and compared with comparative example 3, the bending strength of the carbon-carbon composite material prepared in example 2 is improved by 5.02%, which indicates that the carbon fiber net tire prepared by the modified carbon fiber chopped filaments has better bonding effect with the resin adhesive, so that the bending strength of the carbon-carbon composite material is improved; the bending strength of the carbon-carbon composite material prepared in comparative example 1 is 162.81MPa, the bending strength of the carbon-carbon composite material prepared in comparative example 2 is 163.78MPa, and comparative examples 1-2 are compared with comparative example 3, which shows that the higher the amount of propyl lactate used is, the better the modifying the chopped carbon fibers is, and the lower the amount of propyl lactate used is, the less influence on the bending strength of the carbon-carbon composite material prepared in the step is, and the higher the amount of propyl lactate used is, the bending strength of the obtained carbon-carbon composite material is reduced, so that the amount of propyl lactate used needs to be in a proper range; the bending strength of the carbon-carbon composite material prepared in example 3 was 173.39MPa, the bending strength of the carbon-carbon composite material prepared in example 4 was 174.54MPa, and example 4 compared with example 2 shows that when the carbon-carbon composite material of the previous step of preparing a crucible according to the method of example 2 was used, the bending strength of the carbon-carbon composite material obtained after using 3- (2-furyl) -2-propyl acrylate in a resin glue solution was improved, and that the 3- (2-furyl) -2-propyl acrylate interacted with the chopped filaments of the modified carbon fibers in the carbon fiber mesh in the resin glue solution, the effect of improving the bending strength of the carbon-carbon composite material was obtained, and the bending strength of the carbon-carbon composite material prepared in example 4 was improved by 7.42% compared with that of comparative example 3. The bending strength of the carbon-carbon composite material prepared in example 5 was 173.64MPa, the bending strength of the carbon-carbon composite material prepared in example 6 was 173.95MPa, and the bending strength of the carbon-carbon composite material prepared in example 7 was 174.35MPa.
The carbon-carbon composite material obtained by the invention has good bending strength, and the bending strength is 168-176MPa.
4. Thermal expansion test
Test sample: the carbon-carbon composite material crucibles prepared in each example and comparative example.
The coefficient of thermal expansion meter tests the coefficient of thermal expansion of the above samples.
The results of the thermal expansion test of the carbon-carbon composite material prepared by the present invention are shown in FIG. 4, wherein A is example 1, B is example 2, C is example 3, D is example 4, E is example 5, F is example 6, G is example, H is comparative example 1, I is comparative example 2, J is comparative example 3, and the numerical units thereof are 10 -6 And/k, which shows that the thermal expansion coefficient is very small, and the thermal expansion coefficient value of the carbon-carbon composite material crucible prepared by each example and the comparative example is between 1.4 and 1.7, which shows that the obtained carbon-carbon composite material crucible has good thermal stability.
The crucible of the carbon-carbon composite material obtained by the invention has the advantages of small thermal expansion coefficient and good thermal stability.
The above embodiments are merely for illustrating the present invention and not for limiting the same, and various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.
Claims (9)
1. A preparation method of a carbon-carbon composite crucible comprises the following steps:
cutting the carbon fiber precursor into carbon fiber chopped filaments, and preparing the pretreated carbon fiber chopped filaments through pretreatment; in the pretreatment, acid treatment liquid is used for carrying out short shredding treatment on the carbon fiber;
adding the pretreated carbon fiber chopped filaments into a modification solution to carry out modification treatment to obtain modified carbon fiber chopped filaments; the modified solution contains amyl alcohol and propyl lactate;
preparing a carbon fiber net tire by chopping modified carbon fibers, and preparing unidirectional cloth from the carbon fiber net tire and carbon fiber precursors;
preparing a crucible preform by arranging a carbon fiber net tire, unidirectional cloth and bidirectional cloth on a model;
and carrying out vapor deposition, liquid phase impregnation densification, carbonization and post-treatment on the crucible preform to obtain the carbon-carbon composite material crucible.
2. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: the acid treatment liquid is obtained by mixing potassium dichromate, concentrated sulfuric acid and deionized water.
3. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: catalyst concentrated sulfuric acid is added in the modification treatment.
4. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: the modified solution contains 10-30wt% of propyl lactate.
5. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: the usage amount of the pretreated carbon fiber chopped filaments is 20-60wt% of the modified solution.
6. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: the resin glue solution used in the liquid phase deposition densification contains furfuryl ketone resin and p-chlorobenzenesulfonic acid.
7. The method for preparing the carbon-carbon composite crucible according to claim 1, wherein: the density of the crucible preform is 0.30-0.70g/cm 3 。
8. A carbon-carbon composite crucible prepared by the method of any one of claims 1 to 7.
9. Use of the modified carbon fiber chopped strand according to claim 1 for preparing a carbon-carbon composite material or a carbon fiber material.
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