CN117105684A - Method for preparing high-density high-strength carbon material based on waste carbon-carbon composite material - Google Patents
Method for preparing high-density high-strength carbon material based on waste carbon-carbon composite material Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 100
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 55
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 56
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000005011 phenolic resin Substances 0.000 claims abstract description 53
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 53
- 239000004005 microsphere Substances 0.000 claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 18
- 239000004917 carbon fiber Substances 0.000 claims abstract description 18
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000000280 densification Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000010786 composite waste Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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- 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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/62615—High energy or reactive ball milling
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Abstract
The invention discloses a method for preparing a high-density high-strength carbon material based on a waste carbon-carbon composite material, which comprises the following steps: 1) Taking waste carbon-carbon composite materials as raw materials, and mechanically crushing; 2) The crushed carbon-carbon waste is subjected to high-energy ball milling to obtain fine materials dissociated from carbon fiber and pyrolytic carbon interfaces; 3) Coating the waste carbon fine materials by using phenolic resin alcohol solution; 4) Fully mixing the mesophase carbon microspheres with the carbon waste coated by the resin, and performing cold molding and carbonization treatment to obtain the high-density high-strength carbon material. The invention solves the problem of tight combination of carbon fiber and pyrolytic carbon interface, and realizes nearly 100% recovery of waste carbon-carbon composite material. The carbon material prepared by the invention has high density and high strength, low production cost, short preparation period and low requirements on process operation and equipment.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, relates to a preparation method of a high-density high-strength carbon material, and in particular relates to a method for preparing a high-density high-strength carbon material based on a waste carbon-carbon composite material.
Background
The carbon-carbon composite material is a carbon-based composite material in which a carbon matrix (pyrolytic carbon, resin carbon, pitch carbon) is reinforced by carbon fibers or carbon fiber products. The composite material has the characteristics of low density, high heat conductivity, low thermal expansion coefficient, good high-temperature mechanical property and the like, and is widely applied to the fields of aerospace, photovoltaics and military industry. In recent years, with the tremendous development of aerospace and photovoltaic industries in China, the consumption of carbon-carbon composite materials is rising year by year. A new problem is the large amount of scrap, including cuttings and scraps, that is generated during the production and processing of carbon-carbon composites. How to recycle these wastes and reproduce products with high added value has become an unavoidable key problem.
The high-density carbon material has excellent mechanical property, ideal self-lubricating property and excellent heat conduction/electric conductivity, and is widely applied to the fields of electrolytic aluminum, aerospace, transportation and the like. The production of high-density carbon materials by using carbon-carbon composite waste as aggregate is a good choice for reproducing high-added-value products. Based on the above, the problem that the interface between the carbon fiber and the pyrolytic carbon in the carbon-carbon waste is tightly combined and difficult to disperse must be solved. Tightly combined carbon fibers/pyrolytic carbon can cause incomplete coating of the binder and oversized stacking pores between aggregates, thereby negatively affecting the product. The solutions currently in common use are sieving and oxidation treatments: on one hand, sieving reduces the recycling rate, and only large particles can be removed, so that the problem of interfacial dispersion of fine particles cannot be solved. On the other hand, the oxidation treatment reduces the strength of aggregate, and has high cost and long treatment time, which is not suitable for large-scale industrialization. Secondly, the problem that the density of the carbon material produced by taking the carbon-carbon waste as the aggregate is low must be solved. The carbon materials produced by using the carbon and carbon waste materials of CN108395268A and CN114773078A have the problem of lower density, and all the carbon materials need long-time chemical vapor deposition densification, and the density after densification is only 1.3g/cm 3 This clearly increases the production costs and the time costs. CN114276158A prepares a carbon material with higher density by taking carbon-carbon waste as a raw material, the cost is that the waste needs strong acid and alkali treatment, oxidation treatment and repeated three times of impregnation densification treatment,this process is also not suitable for practical industrial production.
Disclosure of Invention
The invention aims to provide a method for preparing a high-density high-strength carbon material based on recovery of a waste carbon-carbon composite material, which has the advantages of low cost, short period and convenience. The invention provides a preparation idea of realizing carbon fiber and pyrolytic carbon interface dissociation by mechanical shaping of carbon waste and realizing one-time carbonization densification by combining self-sintering with traditional sintering, thereby preparing the high-density high-strength carbon material.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the method for preparing the high-density high-strength carbon material based on the recovery of the waste carbon-carbon composite material provided by the invention comprises the following steps:
step one, mechanically crushing the waste carbon-carbon composite material to obtain waste carbon-carbon coarse material particles;
step two, using alcohol as a ball milling medium, performing high-energy ball milling on the waste carbon-carbon coarse material particles in the step one, and mechanically shaping to obtain waste carbon-carbon fine material particles dissociated from carbon fiber and pyrolytic carbon interfaces;
step three, adding the waste carbon fine material particles in the step two into phenolic resin alcohol solution, fully stirring, and then drying to obtain waste carbon coarse material particles coated by phenolic resin;
step four, ball milling, crushing and refining the phenolic resin coated waste carbon-carbon coarse material particles in the step three by taking water as a ball milling medium to obtain phenolic resin coated waste carbon-carbon fine material particles;
adding the intermediate phase carbon microspheres into waste carbon fine particles coated with phenolic resin according to a preset proportion, fully ball-milling, and drying moisture to obtain a refined mixture of the waste carbon particles coated with the phenolic resin and the intermediate phase carbon microspheres;
step six, carrying out cold molding on the mixed material obtained in the step five to obtain a green body;
and step seven, carbonizing the green body obtained in the step six under the protection of inert atmosphere to obtain the high-density high-strength carbon material taking the carbon-carbon waste as the aggregate.
Preferably, in the second step, the ball milling rotating speed is 800-1000r/min, and the ball milling time is 1-2h.
Preferably, in the third step, the mass ratio of the waste carbon fine particles to the phenolic resin is (11-14): 7, and the mass concentration of the phenolic resin in the phenolic resin alcoholic solution is 0.16g/ml.
Preferably, in the third step, the stirring speed is 600-800r/min, and the stirring time is 1-2h.
Preferably, in the fourth step, the ball milling rotating speed is 200-400r/min, and the ball milling time is 1-2h.
Preferably, in the fifth step, the mass of the mesophase carbon microsphere accounts for 25% -50% of the total mass of the mesophase carbon microsphere and the phenolic resin coated waste carbon fine particles.
Preferably, in the fifth step, the ball milling rotating speed is 100-200r/min, and the ball milling time is 1-2h.
Preferably, in the sixth step, the molding pressure of the cold molding is 2-10MPa, and the dwell time is 3min.
Preferably, in the seventh step, the process parameters of the carbonization treatment are specifically: RT-300 ℃ for 3 hours; 300-800 ℃ for 12 hours; 800-1000 ℃ for 2 hours; 1000-1000 ℃ for 1h;1000-600 ℃ for 6.5h; 600-RT, naturally cooling.
The principle and the beneficial effects of the invention are as follows:
the invention takes cutting materials and leftover materials in the production and processing of carbon-carbon composite materials as raw materials, obtains waste carbon-carbon coarse material particles after mechanical crushing, and then carries out high-energy ball milling on the waste carbon-carbon coarse material particles to obtain micron-sized particles dissociated at the interface of carbon fibers and pyrolytic carbon. This is advantageous for achieving 100% recycling of the carbon-carbon waste, complete coating of the carbon-carbon waste with the phenolic resin, and reduction of stacking porosity of the aggregate. The mechanical separation of carbon fiber and pyrolytic carbon interface inevitably causes the phenomenon of grain refinement. The increased specific surface area of the thinned particles leads to increased addition of the binder, thereby reducing the density of the final product. In order to eliminate negative effects caused by grain refinement and shorten the preparation period, the aim of preparing the high-density carbon material by primary carbonization is fulfilled, the self-sintering property of the mesocarbon microbeads is utilized to cooperate with the traditional sintering behavior of resin coated waste carbon, and the aim of preparing the high-density high-strength carbon material based on recovery of the waste carbon-carbon composite material is fulfilled.
The method has the characteristics of 100% of carbon-carbon waste utilization rate, low production cost, short preparation period and low requirements on process operation and equipment.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is a SEM secondary electron photograph of mechanically crushed carbon-carbon waste material of example 1;
FIG. 3 is a SEM secondary electron photograph of carbon-carbon waste material after high energy ball milling in example 1;
FIG. 4 is a SEM secondary electron photograph of the resin-coated carbon-carbon scrap of example 1;
FIG. 5 is a photograph of a high density high strength carbon material prepared in example 1;
fig. 6 is an SEM secondary electron photograph of the high-density high-strength carbon material prepared in example 1.
Detailed Description
The following examples are given to further illustrate the present invention, but are not intended to limit the scope thereof.
Example 1
Step 1: cutting the carbon-carbon composite leftover material into about 2X 2cm by a cutting machine 3 And collecting the cut material during the cutting process. Subsequently, the small blocks and the cutting materials are put into a mechanical crusher for crushing, and waste carbon-carbon coarse material particles are obtained.
Step 2: 200g of the waste carbon coarse material particles in the step 1 are weighed, divided into 4 parts equally, and respectively put into four zirconia ball milling tanks, and 60ml of alcohol is injected into each ball milling tank. The rotation speed of the ball mill is set to 1000r/min, and the ball mill is operated for 15min and is suspended for 5min for 2h. And then placing the waste carbon-carbon fine material subjected to ball milling in a 70 ℃ oven to be dried to constant weight, and obtaining waste carbon-carbon fine material particles with carbon fibers and pyrolytic carbon interface dissociation.
Step 3: 20g of the waste carbon fine particles were added to 67mL of a phenolic resin alcoholic solution having a mass concentration of 0.16g/mL in batches, with stirring. Subsequently, the mixture was stirred with a magnetic stirrer at a stirring speed of 800r/min for 2 hours. And (3) placing the stirred slurry in a 65 ℃ oven, and drying alcohol to obtain waste carbon coarse material particles coated by the phenolic resin.
Step 4: 30g of phenolic resin coated waste carbon coarse material particles are weighed, divided into 2 parts, respectively put into two corundum ball milling tanks, and 40ml of water is injected. Setting the rotating speed of a ball mill to 400r/min, and ball-milling for 2 hours to obtain waste carbon fine material particles coated by phenolic resin; then respectively adding 15g of mesophase carbon microspheres into each corundum ball milling tank, reducing the rotating speed of the ball mill to 100r/min, and ball milling for 2 hours. Placing the fully stirred phenolic resin coated waste carbon and the intermediate phase carbon microsphere in a 75 ℃ oven, and drying the water to obtain the refined phenolic resin coated waste carbon particle and the intermediate phase carbon microsphere mixed material.
Step 5: filling the mixed material obtained in the step 4 into a stainless steel die with the size of 40 multiplied by 60mm 2 The loading height was 40mm. Then the mixture is placed in a flat vulcanizing machine for cold compression molding, the molding pressure is 2-10MPa, and the pressure maintaining time is 3min. And after pressure relief, obtaining the high-density high-strength carbon material green body.
Step 6: and (5) placing the green body obtained in the step (5) into a high-temperature tube furnace, and washing the green body with inert gas for 15min. And (3) carbonizing under the protection of inert gas. The technological parameters of carbonization treatment are specifically as follows: RT-300 ℃ for 3 hours; 300-800 ℃ for 12 hours; 800-1000 ℃ for 2 hours; 1000-1000 ℃ for 1h;1000-600 ℃ for 6.5h; 600-RT, naturally cooling. Finally obtaining the high-density high-strength carbon material.
The SEM secondary electron photograph of the waste carbon-carbon coarse material particles obtained in step 1 of this example is shown in fig. 2. As can be seen from fig. 2, the carbon fibers in the waste carbon-carbon coarse material particles are tightly combined with pyrolytic carbon, and a large number of carbon fibers are in a bamboo raft shape under the influence of the pyrolytic carbon.
The SEM secondary electron photograph of the waste carbon-carbon fine particles obtained in step 2 of this example is shown in fig. 3. As can be seen from fig. 3, the pyrolytic carbon and carbon fiber have been completely separated after high-energy ball milling, and the particles become micron-sized.
The SEM secondary electron photograph of the phenolic resin coated waste carbon fine particles prepared in step 4 of this example is shown in fig. 4. As can be seen from fig. 4, the phenolic resin is able to completely encapsulate the dissociated carbon fibers with pyrolytic carbon, i.e., carbon-carbon waste.
A macroscopic photograph of the high density and high strength carbon material prepared in this example is shown in fig. 5. As can be seen from fig. 5, the sample of the high-density high-strength carbon material prepared based on the recovery of the waste carbon-carbon composite material is complete.
SEM secondary electron photographs of the microstructure of the high-density and high-strength carbon material prepared in this example are shown in fig. 6. As can be seen from fig. 6, the high-density high-strength carbon material prepared based on the recovery of the waste carbon-carbon composite material has a relatively dense structure.
The high-density and high-strength carbon material prepared in this example had a density of 1.50g/cm 3 The open porosity was 20.1%, the compressive strength was 122.24MPa, the electrical resistivity was 8.41mΩ & cm, and the electrical conductivity was 11890.61S/m.
Example 2
Step 1: step 1 is the same as in example 1.
Step 2: 200g of the waste carbon coarse material particles in the step 1 are weighed, divided into 4 parts equally, and respectively put into four zirconia ball milling tanks, and 60ml of alcohol is injected into each ball milling tank. The rotation speed of the ball mill is set to 900r/min, and the ball mill is operated for 15min and is suspended for 5min for 1.5h. And then placing the waste carbon-carbon fine material subjected to ball milling in a 70 ℃ oven to be dried to constant weight, and obtaining waste carbon-carbon fine material particles with carbon fibers and pyrolytic carbon interface dissociation.
Step 3: 26g of the waste carbon fine particles were added to 87.5mL of a phenolic resin alcoholic solution having a mass concentration of 0.16g/mL in portions with stirring. Subsequently, the mixture was stirred with a magnetic stirrer at a stirring speed of 700r/min for 1.5 hours. And (3) placing the stirred slurry in a 65 ℃ oven, and drying alcohol to obtain waste carbon coarse material particles coated by the phenolic resin.
Step 4: 39g of phenolic resin coated waste carbon coarse material particles are weighed, divided into 2 parts, respectively put into two corundum ball milling tanks, and 40ml of water is injected. Setting the rotating speed of a ball mill to 300r/min, and ball-milling for 1.5h to obtain waste carbon fine material particles coated by phenolic resin; then 10.5g of mesophase carbon microspheres are respectively added into each corundum ball milling tank, the rotating speed of the ball mill is reduced to 150r/min, and the ball milling is carried out for 1.5h. Placing the fully stirred phenolic resin coated waste carbon and the intermediate phase carbon microsphere in a 75 ℃ oven, and drying the water to obtain the refined phenolic resin coated waste carbon particle and the intermediate phase carbon microsphere mixed material.
Step 5: step 5 is the same as in example 1.
Step 6: step 6 is the same as in example 1.
The density of the high-density and high-strength carbon material prepared in this example was 1.42g/cm 3 The open porosity was 25.7%, the compressive strength was 109.74MPa, the electrical resistivity was 9.20mΩ & cm, and the electrical conductivity was 10869.56S/m.
Example 3
Step 1: step 1 is the same as in example 1.
Step 2: 200g of the waste carbon coarse material particles in the step 1 are weighed, divided into 4 parts equally, and respectively put into four zirconia ball milling tanks, and 60ml of alcohol is injected into each ball milling tank. The rotation speed of the ball mill is set to 800r/min, and the ball mill is operated for 15min and is suspended for 5min for 1h. And then placing the waste carbon-carbon fine material subjected to ball milling in a 70 ℃ oven to be dried to constant weight, and obtaining waste carbon-carbon fine material particles with carbon fibers and pyrolytic carbon interface dissociation.
Step 3: 30g of the waste carbon fine particles were added to 101mL of a phenolic resin alcoholic solution having a mass concentration of 0.16g/mL in batches, with stirring. Subsequently, the mixture was stirred with a magnetic stirrer at a stirring speed of 600r/min for 1 hour. And (3) placing the stirred slurry in a 65 ℃ oven, and drying alcohol to obtain waste carbon coarse material particles coated by the phenolic resin.
Step 4: 45g of phenolic resin coated waste carbon coarse material particles are weighed, divided into 2 parts, respectively put into two corundum ball milling tanks, and 40ml of water is injected. Setting the rotating speed of a ball mill to be 200r/min, and ball-milling for 1h to obtain waste carbon fine material particles coated by phenolic resin; and then adding 7.5g of mesophase carbon microspheres into each corundum ball milling tank, reducing the rotating speed of the ball mill to 100r/min, and ball milling for 1h. Placing the fully stirred phenolic resin coated waste carbon and the intermediate phase carbon microsphere in a 75 ℃ oven, and drying the water to obtain the refined phenolic resin coated waste carbon particle and the intermediate phase carbon microsphere mixed material.
Step 5: step 5 is the same as in example 1.
Step 6: step 6 is the same as in example 1.
The density of the high-density and high-strength carbon material prepared in this example was 1.37g/cm 3 The open porosity is 28.6%, the compressive strength is 98.07MPa, the resistivity is 9.94mΩ & cm, and the conductivity is 10060.36S/m.
Comparative example 1
Step 1: step 1 was performed as in example 3.
Step 2: this step is different from example 3, step 2 only in that the ball milling time is 1h, and the other conditions are the same.
Step 3: 38g of the waste carbon fine particles were added to 128mL of a phenolic resin alcoholic solution having a mass concentration of 0.16g/mL in batches, with stirring. Subsequently, the mixture was stirred with a magnetic stirrer at a stirring speed of 600r/min for 1 hour. And (3) placing the stirred slurry in a 65 ℃ oven, and drying alcohol to obtain waste carbon coarse material particles coated by the phenolic resin.
Step 4: 57g of phenolic resin coated waste carbon coarse material particles are weighed, divided into 2 parts, respectively put into two corundum ball milling tanks, and 40ml of water is injected. Setting the rotating speed of a ball mill to be 200r/min, and ball-milling for 1h to obtain waste carbon fine material particles coated by phenolic resin; and then adding 1.5g of mesophase carbon microspheres into each corundum ball milling tank, reducing the rotating speed of the ball mill to 100r/min, and ball milling for 1h. Placing the fully stirred phenolic resin coated waste carbon and the intermediate phase carbon microsphere in a 75 ℃ oven, and drying the water to obtain the refined phenolic resin coated waste carbon particle and the intermediate phase carbon microsphere mixed material.
Step 5: step 5 was performed as in example 3.
Step 6: step 6 was performed as in example 3.
The high density and high strength carbon material prepared in this comparative exampleDensity of 1.21g/cm 3 The open porosity was 36.7%, the compressive strength was 40.59MPa, the electrical resistivity was 13.33mΩ & cm, and the electrical conductivity was 7501.87S/m.
Comparative example 2
Step 1: step 1 was the same as in comparative example 1.
Step 2: step 2 was performed as in comparative example 1.
Step 3: 50g of the waste carbon fine particles were added to 168mL of a phenolic resin alcoholic solution with a mass concentration of 0.16g/mL in batches, and stirred while adding. Subsequently, the mixture was stirred with a magnetic stirrer at a stirring speed of 600r/min for 1 hour. And (3) placing the stirred slurry in a 65 ℃ oven, and drying alcohol to obtain waste carbon coarse material particles coated by the phenolic resin.
Step 4: 75g of phenolic resin coated waste carbon coarse material particles are weighed, divided into 2 parts, respectively put into two corundum ball milling tanks, and 40ml of water is injected. Setting the rotating speed of the ball mill to be 200r/min, ball milling for 1h, and then placing the ball mill in a baking oven at 75 ℃ to dry the water to obtain the refined phenolic resin coated carbon-carbon waste.
Step 5: filling the refined phenolic resin coated carbon waste into a stainless steel die with the size of 40X 60mm 2 The loading height was 40mm. Then the mixture is placed in a flat vulcanizing machine for cold compression molding, the molding pressure is 2-10MPa, and the pressure maintaining time is 3min. And after pressure relief, obtaining the high-density high-strength carbon material green body.
Step 6: step 6 was performed as in example 3.
The high-density and high-strength carbon material prepared in this example had a density of 1.12g/cm 3 The open porosity was 43.3%, the compressive strength was 28.65MPa, the electrical resistivity was 17.74mΩ & cm, and the electrical conductivity was 5636.98S/m.
Claims (9)
1. A method for preparing a high-density high-strength carbon material based on recovery of waste carbon-carbon composite materials comprises the following steps:
step one, mechanically crushing the waste carbon-carbon composite material to obtain waste carbon-carbon coarse material particles;
step two, using alcohol as a ball milling medium, performing high-energy ball milling on the waste carbon-carbon coarse material particles in the step one, and mechanically shaping to obtain waste carbon-carbon fine material particles dissociated from carbon fiber and pyrolytic carbon interfaces;
step three, adding the waste carbon fine material particles in the step two into phenolic resin alcohol solution, fully stirring, and then drying to obtain waste carbon coarse material particles coated by phenolic resin;
step four, ball milling, crushing and refining the phenolic resin coated waste carbon-carbon coarse material particles in the step three by taking water as a ball milling medium to obtain phenolic resin coated waste carbon-carbon fine material particles;
adding the intermediate phase carbon microspheres into waste carbon fine particles coated with phenolic resin according to a preset proportion, fully ball-milling, and drying moisture to obtain a refined mixture of the waste carbon particles coated with the phenolic resin and the intermediate phase carbon microspheres;
step six, carrying out cold molding on the mixed material obtained in the step five to obtain a green body;
and step seven, carbonizing the green body obtained in the step six under the protection of inert atmosphere to obtain the high-density high-strength carbon material taking the carbon-carbon waste as the aggregate.
2. The method according to claim 1, wherein in the second step, the ball milling speed is 800-1000r/min and the ball milling time is 1-2h.
3. The method according to claim 1, wherein in the third step, the mass ratio of the waste carbon fine particles to the phenolic resin is (11-14): 7, and the mass concentration of the phenolic resin in the phenolic resin alcoholic solution is 0.16g/ml.
4. The method according to claim 1, wherein in the third step, the stirring speed is 600-800r/min and the stirring time is 1-2h.
5. The method according to claim 1, wherein in the fourth step, the ball milling speed is 200-400r/min and the ball milling time is 1-2h.
6. The method according to claim 1, wherein in the fifth step, the mass of the mesophase carbon microspheres is 25% -50% of the total mass of the mesophase carbon microspheres and the phenolic resin coated waste carbon fine particles.
7. The method according to claim 1, wherein in the fifth step, the ball milling speed is 100-200r/min and the ball milling time is 1-2h.
8. The method according to claim 1, wherein in the sixth step, the molding pressure of the cold molding is 2 to 10MPa and the dwell time is 3min.
9. The method according to claim 1, wherein in the seventh step, the process parameters of the carbonization treatment are specifically: RT-300 ℃ for 3 hours; 300-800 ℃ for 12 hours; 800-1000 ℃ for 2 hours; 1000-1000 ℃ for 1h;1000-600 ℃ for 6.5h; 600-RT, naturally cooling.
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