CN115583835A - Low-porosity high-mechanical-strength carbon graphite material and preparation method thereof - Google Patents
Low-porosity high-mechanical-strength carbon graphite material and preparation method thereof Download PDFInfo
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
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Abstract
The invention discloses a low-porosity high-mechanical strength carbon graphite material and a preparation method thereof, which comprises the steps of mixing a surfactant A and absolute ethyl alcohol uniformly, adding superfine graphite powder, and removing the absolute ethyl alcohol to obtain composite graphite powder; mixing with a catalytic promoter A, putting into a kneading pot, removing water, adding a binder A into the kneading pot, kneading, hot-rolling, crushing, and sieving to obtain binder-coated graphite powder; then putting the mixture into a high-pressure reaction kettle, and carbonizing the mixture at a low temperature to obtain raw coke coated graphite powder; mixing with green coke to obtain mixed powder; uniformly mixing the surfactant B and absolute ethyl alcohol, adding the mixed powder, uniformly mixing, and removing the absolute ethyl alcohol to obtain composite aggregate powder; then mixing the mixture with a catalytic promoter B uniformly, putting the mixture into a kneading pot, removing water, adding a binder B into the kneading pot, kneading, and performing hot rolling, crushing and sieving to obtain pressed powder; and (3) pre-molding and pressing the pressed powder, performing warm isostatic pressing, and roasting and carbonizing in situ to obtain the low-porosity high-mechanical-strength carbon graphite material.
Description
Technical Field
The invention belongs to the technical field of carbon graphite materials, and particularly relates to a low-porosity high-mechanical-strength carbon graphite material and a preparation method thereof.
Background
The carbon graphite material is widely applied to the fields of aviation, aerospace, high-speed rail, chemical engineering, nuclear power, ships, photovoltaics, electric spark machining and the like. But the mechanical strength, homogeneity, stability and service life of the existing carbon graphite sealing material are relatively poor.
At present, the carbon graphite materials mainly comprise the following three types:
1) The traditional carbon graphite material has two preparation methods: a. solid phase mixing, using asphalt binder, calcined coke and artificial graphite as aggregate, and carrying out kneading, sheet rolling, crushing, pressing, roasting, dipping, roasting and graphitizing treatment to obtain the traditional carbon graphite material with the largest use amount at present. However, the fine aggregate particles used in the solid-phase mixing method often have relatively poor homogeneity, stability and service life of the carbon graphite sealing product due to the characteristics of overlarge surface energy, easy agglomeration and the like. b. Mixing liquid phases, dissolving soluble components in the asphalt by adopting organic solvents such as tetrahydrofuran, toluene and the like, and preparing a carbon graphite material by a wet process; compared with a solid-phase mixing process, the liquid-phase mixing process can improve the homogeneity of the carbon graphite sealing material, but the used organic solvent has high toxicity, serious environmental pollution and great industrialization difficulty. In addition, asphalt is used as a binder and an impregnant in the preparation process of the traditional carbon graphite material, so that the carbon graphite sealing material has large porosity, wide distribution and uneven density distribution.
2) The preparation method of the high-temperature pyrolytic carbon sealing material is characterized in that acetylene, methane and other gases are used as carbon sources, and the isotropic pyrolytic carbon sealing material is prepared by adopting Chemical Vapor Deposition (CVD), chemical Vapor Infiltration (CVI) and other processes. However, the production efficiency of the pyrolytic carbon sealing material is extremely low, the cost is high, products with larger specifications cannot be prepared, the graphitization degree is low, the friction coefficient is large, and the pyrolytic carbon sealing material is easy to be brittle and has poor processability.
3) Compared with the carbon graphite sealing materials 1) and 2), the novel carbon graphite sealing material mainly takes coal tar, anthracene oil and the like as volatile matter regulators, green coke as aggregate and oleic acid as a surfactant; the formation of a sintering neck is promoted by regulating and controlling the volatile matter of the aggregate and adopting an in-situ carbonization strategy, and the self-shrinkage performance of the novel self-sintering carbon graphite sealing material is utilized to prepare the novel self-sintering carbon graphite sealing material. However, the novel carbon graphite sealing material is usually in a typical amorphous structure due to coke formation, poor interlayer lubricity and high content of harmful light components, so that the self-sintering performance deviation, the manufacturability and the yield are poor, products with larger specifications are extremely difficult to prepare, and the maximum specification diameter is less than 200 mm at present.
Therefore, how to prepare a large-size carbon graphite material with a compact structure, low porosity, high strength and good homogeneity is one of the core problems that needs to be solved by the technical personnel in the field.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a low-porosity high-mechanical-strength carbon graphite material and a preparation method thereof, wherein the preparation method can prepare a carbon graphite material with a large size specification, and the prepared carbon graphite material has the advantages of compact structure, low porosity, high mechanical strength and good homogeneity.
The technical scheme of the invention is realized as follows:
a preparation method of a low-porosity high-mechanical-strength carbon graphite material specifically comprises the following steps:
s1: stirring and dispersing the surfactant A and the absolute ethyl alcohol uniformly according to the mass ratio of 1-3; the mass ratio of the surfactant A to the graphite powder is 0.1 to 1;
s2: mixing the composite graphite powder and the catalytic promoter A according to a mass ratio of 100 to 0.1 to 1, uniformly mixing, putting into a kneading pot, heating to remove water, heating to 130 to 160 ℃, adding the binder A at 160 to 180 ℃ into the kneading pot, kneading for 0.5 to 2 hours, uncovering and kneading for 10 to 30 minutes, hot-rolling for 3~5 times at 160 to 180 ℃, cooling to room temperature, crushing, and sieving with a 160 to 325-mesh sieve to obtain the binder-coated graphite powder;
s3: putting the binder-coated graphite powder into a high-pressure reaction kettle, vacuumizing, replacing air in the high-pressure reaction kettle with nitrogen or argon, programming to raise the temperature to 350 to 550 ℃, and keeping the temperature for 8 to 12 hours, wherein the pressure is controlled to be 1 to 5 MPa; cooling to room temperature, and grinding to obtain raw coke coated graphite powder with particle size D50 of 4~6 μm;
s4: uniformly mixing the green coke coated graphite powder with the green coke according to the mass ratio of 1-20 to 80-100 to obtain mixed powder for later use; stirring and dispersing the surfactant B and absolute ethyl alcohol uniformly according to the mass ratio of 1 to 3; the mass ratio of the surfactant B to the mixed powder is 0.1 to 1;
s5: mixing the composite bone powder and the catalytic promoter B according to the mass ratio of 100 to 0.1 to 1, uniformly mixing, putting into a kneading pot, heating to remove water, heating to 130 to 160 ℃, adding the binder B at 160 to 180 ℃ into the kneading pot, kneading for 0.5 to 2 hours, opening a cover, kneading for 10 to 30 minutes, hot-rolling for 3~5 times, cooling to room temperature, crushing, and sieving through 160 to 325 meshes to obtain a pressed powder;
s6: and (3) compression molding and vacuumizing the pressed powder, then carrying out warm isostatic pressing at 150-200 MPa to obtain a green body, and then roasting to obtain the carbon graphite material.
Further, the graphite powder is artificial graphite or natural graphite powder, and is obtained by firstly grinding by using a Raymond mill and a high-energy airflow mill and then removing air and water on the surface and in holes in a vacuum drying system at 110-150 ℃.
Further, the surfactant A and the surfactant B are one or more of oleic acid, stearic acid and anthracene oil.
Further, the catalyst accelerator A and the catalyst accelerator B are one or more of aluminum trichloride, ferric trichloride and ammonium chloride.
Further, the binder A and the binder B are both composed of a first binder and a second binder, and the first binder is one or more of ethylene tar, coal tar, anthracene oil and heavy oil; the second binder is one or more of mesophase pitch, impregnating pitch and medium-temperature pitch; the mass ratio of the first binder to the second binder is 10 to 30; the mass ratio of the second binder to the composite graphite powder in the binder A is 25 to 35; the mass ratio of the second binder to the composite bone meal in the binder B is 5-20 to 80-95.
Further, in the step S3, when the temperature is programmed to rise, the temperature rise rate is 30 to 50 ℃/h; when the temperature is reduced by the program, the temperature reduction rate is 50 ℃/h; when grinding, the grinding is carried out by a Raymond mill and air jet milling.
Further, in the step S4, the raw coke is one or more of raw petroleum coke, raw asphalt coke or raw intermediate phase carbon microspheres; the average particle diameter D50 of the green coke is less than 2 μm.
Further, the preparation process of the green body in the step S6 is as follows: carrying out compression molding on the pressed powder under the pressure of 1 to 3 MPa, standing for 10 to 20 hours, carrying out vacuum-pumping packaging on the blank by using an aluminum plastic film, and then preheating in an oven at the temperature of 80 to 120 ℃ for 2 to 10 hours; simultaneously, heating a pressurizing medium of the isostatic pressing machine; after the temperature of a medium in an isostatic pressing machine is 80 to 120 ℃ and is constant, putting a blank preheated in an oven into an isostatic pressing cylinder body, and carrying out warm isostatic pressing at 150 to 200 MPa to obtain a green blank, wherein the density of the green blank is 1.25 to 1.40 g/cm 3 。
Further, in the step S6, during roasting, the green body is placed into a down-draft kiln or an atmosphere resistor, buried by using a buried roasting material, heated to 1000 to 1200 ℃ at a speed of 5 to 10 ℃/h, then insulated for 2 to 6 h, and cooled to room temperature, so as to obtain the carbon graphite material.
The invention also provides a low-porosity high-mechanical-strength carbon graphite material which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts raw coke (raw petroleum coke, raw pitch coke or raw intermediate phase carbon microspheres) with the average grain diameter D50 of less than 2 mu m as a main aggregate, graphite powder with the average grain diameter D50 of less than 3 mu m as a secondary aggregate, promotes secondary migration, spreading and penetration of a binder among the aggregates by regulating and controlling the activity of volatile matters and surface interface functional groups contained in the aggregates and by means of a warm isostatic pressing technology, and then prepares the carbon graphite sealing material with large size specification, low structure compactness and porosity, high mechanical strength and good homogeneity by an in-situ carbonization technology.
2. The main aggregate and the secondary aggregate adopted by the invention have small particle size and few defects, and can effectively reduce the number of pores of the connecting holes between the aggregates, thereby being beneficial to reducing the porosity, improving the compactness and further improving the mechanical strength of the carbon graphite material.
3. The invention adopts coal tar, ethylene tar, anthracene oil, mesophase pitch, impregnated pitch, medium temperature pitch and the like to construct an active coking layer similar to the raw coke on the surface and in the pores of low-activity graphite powder, thereby not only effectively reducing the difference of the thermal expansion coefficients of the graphite powder and the raw coke, but also increasing the heteroatom content and active functional groups of carbon atoms at the edge of the graphite powder, improving the interface bonding force between the graphite powder and the raw coke, increasing the permeability of a pitch binder and promoting the formation of a sintering neck, thereby increasing the self-sintering property, the self-adhesion property, the mechanical strength and the yield, and being beneficial to preparing the carbon graphite material with larger size specification.
4. The graphite powder is adopted as the secondary aggregate, the binding force of the graphite powder is small, and sp is formed between carbon atoms on the same layer 2 The hybrid forms covalent bonds, the distance between layers is large, each layer can slide, and the self-lubricating performance is good.In addition, electrons in the graphite powder molecules move randomly all the time, and the moving orientations of the electrons are approximately consistent when an external temperature gradient exists, so that the graphite powder has good electrical conductivity and thermal conductivity. Superfine artificial graphite or natural graphite is adopted as a secondary aggregate to be dispersed in a matrix; is beneficial to improving the manufacturability, reducing the porosity and increasing the soaking property of heat treatment products, thereby improving the yield of the carbon graphite sealing material and further ensuring the preparation of the carbon graphite material with larger large-size specification.
Drawings
FIG. 1 is a topographical view and a back-scattered view of a polished surface and a cross-section of a carbon graphite material prepared in example 1.
FIG. 2-topography and backscatter plots of polished surfaces and sections of the carbon graphite material prepared in example 2.
Fig. 3-topography and backscatter plots of polished faces and sections of the carbon graphite material prepared in example 3.
FIG. 4-topography and backscatter plots of polished faces and sections of the carbon graphite material prepared in comparative example 1.
Fig. 5-macroscopic electron picture of the carbon graphite material prepared in example 1.
Detailed Description
A preparation method of a low-porosity high-mechanical-strength carbon graphite material specifically comprises the following steps:
s1: preparing graphite powder with the average particle size D50 of less than 3 mu m by using a Raymond mill and a high-energy airflow mill, wherein the graphite powder is artificial graphite or natural graphite powder, and removing partial air and water on the surface and in holes of the graphite powder at the temperature of 110-150 ℃ by using a vacuum drying system.
The artificial graphite is high-power graphite electrode waste powder, isostatic pressing graphite waste powder and graphite negative electrode undersize powder for the lithium ion battery; the natural graphite is flake graphite.
S2: adding a surfactant A and absolute ethyl alcohol into a container according to the mass ratio of 1-3 to 100, uniformly dispersing by ultrasonic and mechanical stirring, adding the graphite powder in the S1, continuously performing ultrasonic and mechanical stirring for 1-5 hours, and removing the absolute ethyl alcohol at 80 ℃ to obtain composite graphite powder; the mass ratio of the surfactant A to the graphite powder is 0.1 to 1; the surfactant A is one or more of oleic acid, stearic acid and anthracene oil.
The carbon atoms at the edge of the graphite powder have low heteroatom content and low active functional groups, and the adoption of surfactants such as oleic acid, stearic acid, anthracene oil and the like can enable oleophylic hydrocarbon groups of the graphite powder to face outwards, coat the surface of the graphite powder and form an active layer, so that the graphite powder can be conveniently combined with oil binders such as asphalt, coal tar and the like, and the infiltration capacity and the adsorption capacity of the binders to aggregates can be enhanced.
Meanwhile, surfactants such as oleic acid, stearic acid and anthracene oil have good intersolubility with adhesives such as asphalt and coal tar, and are easy to permeate and immerse into micropores of carbon particles after heating, so that the defect of the carbon aggregate is overcome, and the compactness of the carbon graphite material is improved.
S3: adding the composite graphite powder and the catalytic promoter A into a mixing machine according to the mass ratio of 100 to 0.1 to 1, mixing for 1 to 5 hours, putting into a kneading pot, dry-mixing for 1 to 2 hours at 110 to 150 ℃, discharging water, continuously heating to 130 to 160 ℃, adding the binder A at 160 to 180 ℃ into the kneading pot, kneading for 0.5 to 2 hours, uncovering and kneading for 10 to 30 minutes, hot-rolling for 3~5 times, cooling to room temperature, crushing, and sieving through a sieve of 160 to 325 meshes to obtain the binder-coated graphite powder.
The catalyst promoter A is one or more of aluminum trichloride, ferric trichloride and ammonium chloride.
The binder A is composed of a first binder and a second binder, wherein the first binder is one or more of ethylene tar, coal tar, anthracene oil and heavy oil; the second binder is one or more of mesophase pitch, impregnating pitch and medium-temperature pitch; the mass ratio of the first binder to the second binder is 10 to 30, and is 70 to 90; the mass ratio of the second binder to the composite graphite powder is 25-35.
The adhesive A is prepared from a first adhesive and a second adhesive, and the first adhesive can effectively reduce the softening point of the second adhesive, so that the softening point of the adhesive A is low, and the adhesive A is in a molten state at a temperature of 160 to 180 ℃, and has good fluidity and wettability.
The binder A and the materials in the kneading pot (the composite graphite powder excluding moisture and the catalytic promoter) have a certain temperature difference, so that the binder A can be uniformly coated on the surface of the graphite powder in the temperature programmed control and heating process, and the binder A is prevented from being in a slurry state after being mixed with the materials in the kneading pot due to too good fluidity.
The catalytic promoters such as aluminum trichloride, ferric trichloride, ammonium chloride and the like can replace hydrogen on polycyclic aromatic compound aromatic hydrocarbon in the mesophase pitch, the impregnating pitch and the medium-temperature pitch by alkyl or acyl to generate condensation reaction of heterogeneous molecules, so that the second binder is subjected to catalytic polycondensation modification at a lower temperature, and then is subjected to thermal polycondensation reaction, thereby being beneficial to improving the mechanical strength and coking value of the carbon graphite material.
S4: putting the binder coated graphite powder into a high-pressure reaction kettle, vacuumizing by using a vacuum pump, and replacing air in the high-pressure reaction kettle with nitrogen/argon; heating to 350 to 550 ℃ at a temperature of 30 to 50 ℃/h, keeping the temperature for 8 to 12 h, and controlling the pressure to be 5 MPa; finally, the temperature is controlled by a program and is reduced to the room temperature by a program at 50 ℃/h, and the raw coke coated graphite powder with the granularity D50 of 4~6 mu m is prepared by Raymond mill and airflow milling.
The pressure is controlled to be 1-5 MPa, and under a pressurized environment, the migration of asphalt and the generation of an intermediate phase are facilitated, so that the homogeneity and the self-sintering performance are facilitated to be increased, the porosity of graphite powder is reduced, and the coking value and the true density are increased.
The carbonization is carried out under the low temperature condition, which is beneficial to the coking layer on the surface of the graphite powder to have more heteroatoms and free radicals, and the activity of the graphite powder and the wettability to asphalt are increased, thereby improving the self-sintering capability and the self-bonding capability of the graphite powder.
S5: uniformly mixing the green coke coated graphite powder with green coke according to the mass ratio of 1 to 20; adding a surfactant B and absolute ethyl alcohol into a container according to the mass ratio of 1-3 to 100, uniformly dispersing by ultrasonic and mechanical stirring, adding the mixed powder, continuously performing ultrasonic and mechanical stirring for 1-5 hours, and removing the absolute ethyl alcohol at 80 ℃ to obtain composite aggregate powder; the mass ratio of the surfactant B to the mixed powder is 0.1 to 1; the surfactant B is one or more of oleic acid, stearic acid and anthracene oil; the raw coke is one or more of raw petroleum coke, raw asphalt coke or raw intermediate phase carbon microspheres, and the average grain diameter D50 of the raw coke is less than 2 mu m.
S6: adding the composite bone powder and the catalytic promoter B into a mixing machine according to the mass ratio of 100.1-1, mixing for 1-5 h, putting into a kneading pot, dry-mixing for 1-2 h at 110-150 ℃, discharging water, continuously heating to 130-160 ℃, adding the binder B at 160-180 ℃ into the kneading pot, kneading for 0.5-2 h, uncapping, kneading for 10-30 min, kneading, hot-rolling for 3~5 times, cooling to room temperature, crushing, and sieving with a 160-325-mesh sieve to obtain the pressed powder.
The catalytic promoter B is one or more of aluminum trichloride, ferric trichloride and ammonium chloride.
The binder B is composed of a first binder and a second binder, and the first binder is one or more of ethylene tar, coal tar, anthracene oil and heavy oil; the second binder is one or more of mesophase pitch, impregnating pitch and medium-temperature pitch; the mass ratio of the first binder to the second binder is 10 to 30, and is 70 to 90; the mass ratio of the second binder to the composite aggregate is as follows: 10 to 20.
S7: molding the powder under 1-3 MPa, standing for 10-20 h, carrying out vacuum packaging on the blank by using an aluminum plastic film, and then preheating in an oven at 80-120 ℃ for 2-10 h; simultaneously, heating a pressurizing medium of the isostatic pressing machine; after the temperature of the medium in the isostatic pressing machine is 80-120 ℃ and is constant, putting the blank preheated in the oven into an isostatic pressing cylinder body, and carrying out warm isostatic pressing at 150-200 MPa to obtain a green blank, wherein the density of the green blank is 1.25-1.40 g/cm 3 。
Compared with the existing cold static pressure forming technology, the warm isostatic pressure forming technology can effectively increase the plasticity and the activation energy of the blank, promote the secondary migration of the binder and the uniform spreading among the aggregates, and thus can effectively increase the interface binding force, the compactness and the pressing density among different aggregates.
S8: and (3) placing the green body into a down-draft kiln or an atmosphere resistor, burying with a buried burning material, heating to 1000 to 1200 ℃ at a speed of 5 to 10 ℃/h, keeping the temperature for 2 to 6 h, and cooling to room temperature to obtain the carbon graphite material with small porosity, high strength and high density.
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1:
1) Preparing artificial graphite or natural graphite powder with the particle size D50 of 2 mu m by using a Raymond mill and a high-energy airflow mill, and removing partial air and water on the surface and in holes of the graphite powder at 120 ℃ by using a vacuum drying system.
2) Oleic acid and absolute ethyl alcohol are mixed according to the mass ratio of 1:100, adding the graphite powder prepared in the step 1) into a container, uniformly dispersing the graphite powder through ultrasonic and mechanical stirring, continuously performing ultrasonic and mechanical stirring on the graphite powder for 2h, and removing absolute ethyl alcohol at 80 ℃ to obtain the graphite powder rich in active polarizing groups, wherein the mass ratio of oleic acid to the graphite powder is 0.3.
3) Mixing graphite powder rich in active polarization groups prepared in the step 2) and aluminum trichloride according to the mass ratio of 100: adding the mixture into a mixing machine according to the proportion of 0.3, mixing 3 h, putting the mixture into a kneading pot, dry-mixing 1h at 130 ℃, removing water, continuously heating to 150 ℃ until the temperature reaches; mixing ethylene tar, coal tar (the mass ratio of the ethylene tar to the coal tar is 1:2) and medium-temperature asphalt according to the mass ratio of 3:7, performing melt compounding, adding the mixture into a kneading pot at 160 ℃, kneading the mixture for 1h, uncovering the pot, kneading the mixture for 20 min, hot rolling the mixture for 3 times at 160 ℃, cooling the mixture to room temperature, crushing the mixture, and sieving the crushed mixture through a 300-mesh sieve to obtain binder-coated graphite powder; the mass ratio of the medium-temperature pitch to the graphite powder rich in active groups is 25:75.
4) Putting the binder-coated graphite powder prepared in the step 3) into a high-pressure reaction kettle, vacuumizing by using a vacuum pump, and replacing air in the high-pressure reaction kettle with nitrogen/argon; then heating to 420 ℃ by a program of 40 ℃/h, preserving the heat by 10 h, and controlling the pressure to be 3 MPa; finally, the temperature is controlled by a program and is reduced to the room temperature by a program of 50 ℃/h, and the raw coke coated graphite powder with the granularity D50 of 5 mu m is prepared by Raymond mill and airflow milling.
5) Mixing the raw coke coated graphite powder prepared in the step 4) with raw petroleum coke according to the mass ratio of 12:88 to obtain mixed powder, adding the mixed powder into the mixed solution of oleic acid and absolute ethyl alcohol prepared by the method in the step 2), continuously performing ultrasonic and mechanical stirring for 2h, and removing the absolute ethyl alcohol at 80 ℃ to prepare the composite bone material powder rich in the active polarizing groups, wherein the mass ratio of the oleic acid to the mixed powder in the step is 0.5.
6) Adding the composite aggregate powder rich in the active polarizing group prepared in the step 5) and aluminum trichloride into a mixing machine according to the mass ratio of 100.5, uniformly mixing 3 h to obtain composite aggregate, then putting the composite aggregate into a kneading pot, performing dry mixing for 1h at 130 ℃, removing moisture, continuously heating to 150 ℃, and then adding ethylene tar and coal tar (the mass ratio of the ethylene tar to the coal tar is 1: 2) And the medium temperature asphalt comprises the following components in percentage by mass 3:7, performing melt compounding, adding the mixture into a kneading pot at 170 ℃, kneading the mixture for 1h, uncovering the pot, kneading the mixture for 20 min, hot rolling the mixture for 3 times at 170 ℃, cooling the mixture to room temperature, crushing the mixture, and sieving the crushed mixture through a 300-mesh sieve to prepare pressed powder, wherein the mass ratio of the modified medium-temperature asphalt to the composite aggregate is 10:90.
7) Carrying out compression molding on the pressed powder prepared in the step 6) at 1 MPa, standing 10 h, carrying out vacuum-pumping packaging on the blank by using an aluminum plastic film, and preheating 6 h in a 90 ℃ oven; meanwhile, heating the isostatic pressing machine pressurizing medium (the medium is hydraulic oil) at 90 ℃; and after the temperature of the hydraulic oil in the isostatic pressing machine is constant, putting the blank preheated in the oven into an isostatic pressing cylinder, and carrying out temperature isostatic pressing at 150 MPa to prepare the carbon graphite material green blank.
8) Placing the carbon graphite material green blank prepared in the step 7) into a down-draft kiln, burying with a buried burning material, heating to 1100 ℃ at 6 ℃/h, preserving the heat at 4 h, and cooling to room temperature to obtain the carbon graphite material with small porosity, high strength and high density.
Example 2:
1) Preparing artificial graphite or natural graphite powder with the particle size D50 of 2 mu m by using a Raymond mill and a high-energy airflow mill, and removing partial air and water on the surface and in holes of the graphite powder at 120 ℃ by using a vacuum drying system.
2) Oleic acid and anthracene oil (the mass ratio of oleic acid to anthracene oil is 1: 1) And absolute ethyl alcohol according to a mass ratio of 2:100, adding the graphite powder into a container, uniformly dispersing the graphite powder by ultrasonic and mechanical stirring, adding the graphite powder prepared in the step 1), continuously performing ultrasonic and mechanical stirring on the graphite powder for 2h, and removing absolute ethyl alcohol at 80 ℃ to obtain graphite powder rich in active polarizing groups; the mass ratio of the surfactant A (oleic acid and anthracene oil) to the graphite powder is as follows: 0.5:100.
3) Preparing graphite powder rich in active polarization groups, aluminum trichloride and ferric trichloride (the mass ratio of aluminum trichloride to ferric trichloride is 1: 2) According to the mass ratio of 100: adding the mixture into a mixing machine according to the proportion of 0.5, mixing the mixture for 2h, putting the mixture into a kneading pot, dry-mixing 1h at 130 ℃, removing water, continuously heating to 160 ℃, and waiting for the temperature to reach; mixing coal tar, heavy oil (the mass ratio of the coal tar to the heavy oil is 1:2) and mesophase pitch according to the mass ratio of 3:7, adding the molten composite binder which is prepared at 160 ℃ and has a low softening point and good fluidity into a kneading pot at 160 ℃, kneading 1h, uncovering and kneading for 10 min, hot rolling the sheet for 3 times at 165 ℃, cooling to room temperature, crushing, and sieving with a 300-mesh sieve to obtain binder-coated graphite powder; the mass ratio of the medium-temperature phase pitch to the graphite powder rich in active groups is 33:67.
4) Putting the binder-coated graphite powder prepared in the step 3) into a high-pressure reaction kettle, vacuumizing by using a vacuum pump, and replacing air in the high-pressure reaction kettle with nitrogen/argon; then heating to 380 ℃ by a program of 50 ℃/h, preserving the heat by 8 h, and controlling the pressure at 3.5 MPa; finally, the temperature is controlled by a program and is reduced to the room temperature by a program of 50 ℃/h, and the raw coke coated graphite powder with the granularity D50 of 5 mu m is prepared by Raymond mill and airflow milling.
5) Mixing the raw coke coated graphite powder prepared in the step 4) with raw asphalt coke according to the mass ratio of 10:90 percent of the total weight of the components are added into a mixer to be mixed uniformly to obtain mixed powder, then the mixed powder is added into the mixed solution of oleic acid, anthracene oil and absolute ethyl alcohol prepared by the method in the step 2) to continue ultrasonic and mechanical stirring for 2h, and the absolute ethyl alcohol is removed at 80 ℃ to prepare the composite aggregate powder rich in active polarizing groups; in the step, the mass ratio of the surfactant B (oleic acid and anthracene oil) to the mixed powder is 1:100..
6) Mixing the composite aggregate powder rich in active polarizing groups prepared in the step 5) with aluminum trichloride and ferric trichloride (the mass ratio of the aluminum trichloride to the ferric trichloride is 1: 2) According to the mass ratio of 100: adding the mixture into a mixing machine according to the proportion of 0.3, mixing the mixture for 2h, putting the mixture into a kneading pot, dry-mixing the mixture for 1 hour at 130 ℃, removing water, and continuously heating to 150 ℃ until the temperature reaches; mixing coal tar, heavy oil (the mass ratio of the coal tar to the heavy oil is 1:2) and mesophase pitch according to the mass ratio of 3:7, adding the molten composite binder which is prepared at 160 ℃ and has a low softening point and good fluidity into a kneading pot at 170 ℃, kneading 1h, uncovering and kneading for 10 min, hot rolling the sheet at 170 ℃ for 3 times, cooling to room temperature, crushing, and sieving with a 300-mesh sieve to prepare the pressed powder; the mass ratio of the modified mesophase pitch to the composite aggregate is 15:85.
7) Molding the pressed powder prepared in the step 6) at 3 MPa, standing for 12 h, vacuumizing and packaging the blank by using an aluminum plastic film, and preheating 6 h in a 90 ℃ oven; meanwhile, heating the isostatic pressing machine pressurizing medium (the medium is hydraulic oil) at 90 ℃; and after the temperature of the hydraulic oil in the isostatic pressing machine is constant, putting the blank preheated in the oven into an isostatic pressing cylinder, and carrying out temperature isostatic pressing at 150 MPa to prepare the carbon graphite material green blank.
8) Placing the carbon graphite material green blank prepared in the step 7) into a down-draft kiln, burying with a buried burning material, heating to 1050 ℃ at 8 ℃/h, preserving the heat by 4 h, and cooling to room temperature to obtain the carbon graphite material with small porosity, high strength and high density.
Example 3:
1) Artificial graphite or natural graphite powder with the particle size D50 of 2 mu m is prepared by a Raymond mill and a high-energy airflow mill, and partial air and water on the surface and in holes of the graphite powder are removed by a vacuum drying system at 120 ℃.
2) Oleic acid and stearic acid (oleic acid and stearic acid in a mass ratio of 6: 4) And absolute ethyl alcohol according to a mass ratio of 3:100, adding the graphite powder into a container, uniformly dispersing the graphite powder by ultrasonic and mechanical stirring, adding the graphite powder prepared in the step 1), continuously performing ultrasonic and mechanical stirring on the graphite powder for 4 h, and removing absolute ethyl alcohol at 80 ℃ to obtain graphite powder rich in active polarizing groups; the mass ratio of the surfactant A (oleic acid and stearic acid) to the graphite powder is 1:100.
3) Mixing graphite powder rich in active polarization groups prepared in the step 2) and ferric trichloride according to the mass ratio of 100: adding the mixture into a mixing machine according to the proportion of 0.8, mixing 3 h, putting the mixture into a kneading pot, dry-mixing 2h at 110 ℃, removing water, continuously heating to 160 ℃, and waiting for the temperature to reach; mixing anthracene oil, heavy oil (the mass ratio of the anthracene oil to the heavy oil is 2:1) and mesophase asphalt according to the mass ratio of 3:7 adding the prepared molten composite binder with low softening point and good fluidity, adding the mixture into a kneading pot at 170 ℃, kneading the mixture for 1.5 h, uncovering the pot, kneading the mixture for 30 min, hot rolling the mixture for 5 times at 170 ℃, cooling the mixture to room temperature, crushing the mixture, and sieving the crushed mixture through a 300-mesh sieve to obtain binder-coated graphite powder; the mass ratio of the mesophase pitch to the graphite powder rich in active groups is 35:65.
4) Putting the binder-coated graphite powder prepared in the step 3) into a high-pressure reaction kettle, vacuumizing by using a vacuum pump, and replacing air in the high-pressure reaction kettle with nitrogen/argon; then raising the temperature to 500 ℃ by a program of 30 ℃/h, preserving the temperature by 10 h, and controlling the pressure at 4 MPa; finally, the temperature is controlled by a program and is reduced to the room temperature by a program of 50 ℃/h, and the raw coke coated graphite powder with the granularity D50 of 6 mu m is prepared by Raymond mill and airflow milling.
5) Mixing the raw coke coated graphite powder prepared in the step 4) with raw petroleum coke according to the mass ratio of 8: 92) to obtain mixed powder, adding the mixed powder into the mixed solution of oleic acid, stearic acid and absolute ethyl alcohol prepared by the method in the step 2), continuously performing ultrasonic and mechanical stirring for 4 h, removing the absolute ethyl alcohol at 80 ℃ to prepare the composite bone material powder rich in active polarizing groups, wherein the mass ratio of the surfactant B (oleic acid and stearic acid) to the graphite powder is 0.2:100.
6) Mixing the composite aggregate powder rich in active polarizing groups prepared in the step 5) with ferric trichloride according to the mass ratio of 100: adding the mixture into a mixing machine according to the proportion of 1, mixing 2h, then putting the mixture into a kneading pot, dry-mixing for 2 hours at 110 ℃, removing water, continuously heating to 155 ℃, and waiting for the temperature to reach; mixing anthracene oil, heavy oil (the mass ratio of anthracene oil to heavy oil is 2:1) and mesophase asphalt according to the mass ratio of 3:7 adding the prepared melting composite binder with low softening point and good fluidity into a kneading pot at 170 ℃, kneading the mixture for 1.5 h, uncovering the pot, kneading the mixture for 30 min, hot rolling the mixture for 5 times at 165 ℃, cooling the mixture to room temperature, crushing the mixture, and sieving the crushed mixture through a 300-mesh sieve to prepare pressed powder; the mass ratio of the modified mesophase pitch to the composite aggregate is 20:80.
7) Molding the pressed powder prepared in the step 6) under 2 MPa, standing for 10 h, vacuumizing and packaging the blank by using an aluminum plastic film, and preheating 6 h in a 100 ℃ oven; meanwhile, heating the isostatic pressing machine pressurizing medium (the medium is hydraulic oil) at 100 ℃; and after the temperature of the hydraulic oil in the isostatic pressing machine is constant, putting the blank preheated in the oven into an isostatic pressing cylinder, and carrying out temperature isostatic pressing at 150 MPa to prepare the carbon graphite material green blank.
8) Placing the carbon graphite material green blank prepared in the step 7) into a down-draft kiln, burying with a buried burning material, heating to 1050 ℃ at 8 ℃/h, preserving the heat by 4 h, and cooling to room temperature to obtain the carbon graphite material with small porosity, high strength and high density.
Comparative example 1:
this example is the same as example 1 except that step 7) is: and (3) carrying out compression molding on the pressed powder prepared in the step 6) at 1 MPa, standing for 10 h, carrying out vacuum-pumping packaging on the blank by using a polyethylene film, and carrying out isostatic pressing at 150 MPa to prepare the carbon graphite material green blank.
1. The graphite carbon materials obtained in examples 1 to 3 and comparative example 1 were subjected to the tests of volume density, open porosity, resistivity, flexural strength, compressive strength, shore hardness and the like with reference to the JB/T8133 standard, and the test results are shown in table 1.
Table 1 test results of examples 1 to 3 and comparative example 1
As can be seen from table 1: (1) Compared with the cold isostatic pressing of the comparative example 1, the warm isostatic pressing of the example 1 can increase the plasticity and the activation energy of the blank, promote the secondary migration of the composite binder and the uniform spreading among the aggregates, and is beneficial to increasing the interface bonding force and the compactness among different aggregates, so that the breaking strength, the compressive strength, the density and the porosity of the carbon graphite material prepared by the example 1 are effectively improved.
(2) The carbon graphite material prepared by adopting a warm isostatic pressing technology has excellent performance, the breaking strength is more than or equal to 80 MPa, the compressive strength is more than 270 MPa, the open porosity is less than 5 percent, and the density after primary roasting can reach 1.74 to 1.75 g/cm 3 The density after graphitization can reach 1.86 to 1.89 g/cm 3 And a good primary structure is maintained, which shows that the carbon graphite material prepared by the method can meet the requirements without impregnation reinforcement, and can be used only after impregnating resin, babbitt metal, antimony, copper and other substances according to the application.
(3) The preparation method of the invention has high yield, more than 99% and close to 100%.
2. The morphology and back scattering of the polished surface and the cross section of the carbon graphite material prepared in examples 1 to 3 and comparative example 1 are shown in fig. 1, fig. 2, fig. 3 and fig. 4, respectively.
FIGS. 1, 2, 3 and 4 (a), (b), (c) and (d) are respectively a polished surface topography, a polished surface back-scattering pattern, a cross-sectional topography and a cross-sectional back-scattering pattern of the carbon graphite material according to the corresponding examples.
As can be seen from fig. 1 to 3, the carbon graphite materials of examples 1 to 3 have compact microstructures, no obvious tip cracks and no obvious propagation cracks, many independent pores in unit area, and no through holes and through cracks; meanwhile, the graphite particles are inserted and dispersed in the aggregate in a strip shape, the density of the region with the graphite particles is high, the edge of the graphite particles is tightly combined with the edge of the aggregate, and the pores are small, so that a coking layer with coke-forming performance is constructed on the surface of the graphite powder, and the interface binding force of the graphite powder and the coke is effectively increased.
As can be seen from fig. 1 and 4, the polished surface of comparative example 1 clearly shows that the graphite particles are scattered in the aggregate particles, the bonding force between the particles and the inter-particle interface in the region where the graphite particles are distributed is weak, the compactness is relatively poor, and the outer contour of the aggregate shows the pores after the volatile component is volatilized, and the pores are accompanied with part of the through holes. The densification of fig. 1 (example 1) is better and the communication pores are reduced relative to fig. 4 (comparative example 1).
3. A macroscopic electron photograph of the carbon graphite material prepared in example 1 is shown in fig. 5. As can be seen from FIG. 5, the carbon graphite material prepared by the method has complete appearance and no cracks; the prepared block has the diameter larger than 380 mm and the size far exceeding 200 mm, and the carbon graphite block with the size can be applied to the fields of carbon graphite sealing for multi-specification aeroengines, graphite for mobile phone hot-bending glass molds, semiconductor graphite and the like.
Finally, it should be noted that the above-mentioned examples of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a low-porosity high-mechanical-strength carbon graphite material is characterized by comprising the following steps:
s1: stirring and dispersing the surfactant A and the absolute ethyl alcohol uniformly according to the mass ratio of 1-3; the mass ratio of the surfactant A to the graphite powder is 0.1 to 1;
s2: mixing the composite graphite powder and a catalytic promoter A according to a mass ratio of 100: 0.1-1, uniformly mixing, putting into a kneading pot, heating to remove water, heating to 130-160 ℃, adding a binder A at 160-180 ℃ into the kneading pot, kneading for 0.5-2 h, uncovering, kneading for 10-30 min, hot-rolling for 3~5 times at 160-180 ℃, cooling to room temperature, crushing, and sieving with a 160-325-mesh sieve to obtain a binder-coated graphite powder;
s3: putting the binder-coated graphite powder into a high-pressure reaction kettle, vacuumizing, replacing air in the high-pressure reaction kettle with nitrogen or argon, programming to raise the temperature to 350 to 550 ℃, and keeping the temperature for 8 to 12 hours, wherein the pressure is controlled to be 1 to 5 MPa; cooling to room temperature, and grinding to obtain raw coke coated graphite powder with the particle size D50 of 4~6 mu m;
s4: uniformly mixing the green coke coated graphite powder with the green coke according to the mass ratio of 1-20 to 80-100 to obtain mixed powder for later use; stirring and dispersing the surfactant B and the absolute ethyl alcohol uniformly according to the mass ratio of 1-3; the mass ratio of the surfactant B to the mixed powder is 0.1 to 1;
s5: mixing the composite bone meal and the catalytic promoter B according to the mass ratio of 100 to 0.1 to 1, uniformly mixing, putting into a kneading pot, heating to remove water, heating to 130 to 160 ℃, adding the binder B at 160 to 180 ℃ into the kneading pot, kneading for 0.5 to 2 hours, uncovering and kneading for 10 to 30 minutes, hot-rolling for 3~5 times, cooling to room temperature, crushing, and sieving with a sieve of 160 to 325 meshes to obtain pressed powder;
s6: and (3) compression molding and vacuumizing the pressed powder, then carrying out warm isostatic pressing at 150-200 MPa to obtain a green body, and then roasting to obtain the carbon graphite material.
2. The method for preparing the carbon graphite material with low porosity and high mechanical strength according to claim 1, wherein the graphite powder is artificial graphite or natural graphite powder, and is obtained by firstly grinding the graphite powder by a Raymond mill and a high-energy airflow mill and then removing air and water on the surface and in holes in a vacuum drying system at 110-150 ℃.
3. The method for preparing the low-porosity high-mechanical-strength carbon graphite material according to claim 1, wherein the surfactant A and the surfactant B are both one or more of oleic acid, stearic acid and anthracene oil.
4. The method for preparing the low-porosity high-mechanical-strength carbon graphite material according to claim 1, wherein the catalyst promoter A and the catalyst promoter B are one or more of aluminum trichloride, ferric trichloride and ammonium chloride.
5. The method for preparing the low-porosity high-mechanical-strength carbon graphite material according to claim 1, wherein the binder A and the binder B are both composed of a first binder and a second binder, and the first binder is one or more of ethylene tar, coal tar, anthracene oil and heavy oil; the second binder is one or more of mesophase pitch, impregnating pitch and medium-temperature pitch; the mass ratio of the first binder to the second binder is 10 to 30, and is 70 to 90; the mass ratio of the second binder to the composite graphite powder in the binder A is 25 to 35; the mass ratio of the second binder to the composite bone meal in the binder B is 5-20 to 80-95.
6. The preparation method of the carbon graphite material with low porosity and high mechanical strength as claimed in claim 1, wherein in the step S3, the temperature rise rate is 30 to 50 ℃/h during temperature programming; when the temperature is reduced by the program, the temperature reduction rate is 50 ℃/h; when grinding, the grinding is carried out by a Raymond mill and air jet milling.
7. The method for preparing the low-porosity high-mechanical strength carbon graphite material according to claim 1, wherein in the step S4, the raw coke is one or more of raw petroleum coke, raw asphalt coke or raw intermediate phase carbon microspheres; the average particle diameter D50 of the green coke is less than 2 μm.
8. The method for preparing the carbon graphite material with low porosity and high mechanical strength as claimed in claim 1, wherein the green body in the step S6 is prepared by the following steps: molding the pressed powder at 1 to 3 MPaAfter forming, standing for 10 to 20 hours, carrying out vacuum packaging on the blank by using an aluminum plastic film, and then preheating in an oven at 80 to 120 ℃ for 2 to 10 hours; simultaneously, heating a pressurizing medium of the isostatic pressing machine; after the temperature of the medium in the isostatic pressing machine is 80-120 ℃ and is constant, putting the blank preheated in the oven into an isostatic pressing cylinder body, and carrying out warm isostatic pressing at 150-200 MPa to obtain a green blank, wherein the density of the green blank is 1.25-1.40 g/cm 3 。
9. The method for preparing the carbon graphite material with low porosity and high mechanical strength as claimed in claim 1, wherein in the step S6, during baking, the green body is placed into a down-draft kiln or an atmosphere resistor, is buried by using a buried material, is heated to 1000 to 1200 ℃ at a speed of 5 to 10 ℃/h, is then kept warm for 2 to 6 h, and is cooled to room temperature, so as to obtain the carbon graphite material.
10. A low-porosity high-mechanical-strength carbon graphite material, which is characterized by being prepared by the preparation method of 1~9.
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Address after: 643000 Rongchuan 15, Yantan District, Zigong City, Sichuan Province Patentee after: Zigong Dongxin Carbon Co.,Ltd. Patentee after: Sichuan University of Light Chemical Technology Address before: 643000 Rongchuan 15, Yantan District, Zigong City, Sichuan Province Patentee before: ZIGONG DONGXIN CARBON CO.,LTD. Patentee before: Sichuan University of Light Chemical Technology |