CN115583835B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 239000007770 graphite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 42
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 21
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
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- 238000000748 compression moulding Methods 0.000 claims description 7
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- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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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
- C04B35/532—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 containing a carbonisable binder
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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 the raw 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 the 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 the defects of large porosity, wide distribution and nonuniform 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, poor manufacturability and low yield are caused, products with larger specifications are extremely difficult to prepare, and the maximum specification diameter is more 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 carbon graphite material with low porosity and high mechanical strength and a preparation method thereof, which can prepare a carbon graphite material with 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 a catalyst 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 a 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 to 5 times at 160 to 180 ℃, cooling to room temperature, crushing, and sieving with a sieve at 160 to 325 meshes 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, and then heating to 350-550 ℃ by a program, and keeping the temperature for 8-12 h, wherein the pressure is controlled to be 1-5 MPa; cooling to room temperature, and grinding to obtain green coke coated graphite powder with the granularity D50 of 4-6 mu m;
s4: uniformly mixing the green coke coated graphite powder with green coke according to the mass ratio of 1 to 20; 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 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 B at 160 to 180 ℃ into the kneading pot, kneading for 0.5 to 2 hours, uncapping, kneading for 10 to 30 minutes, hot-rolling for 3 to 5 times, cooling to room temperature, crushing, and sieving through 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.
Further, the graphite powder is artificial graphite or natural graphite powder, and is obtained by firstly grinding the artificial graphite or the natural graphite 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 the temperature of 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, 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.
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 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 。
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 green coke on the surface and in pores of low-activity graphite powder, which not only can effectively reduce the difference of the thermal expansion coefficients of the graphite powder and the green coke, but also can increase the heteroatom content and active functional groups of carbon atoms at the edge of the graphite powder, improve the interface bonding force between the graphite powder and the green coke, increase the permeability of a pitch binder and promote the formation of a sintering neck, thereby increasing the self-sintering property, the self-adhesion property, the mechanical strength and the yield, and being simultaneously beneficial to preparing carbon graphite materials with larger size specifications.
4. The invention adopts graphite powder 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 of polished surfaces and sections of the carbon graphite material prepared in example 2.
Fig. 3-topography and backscatter 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 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 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 active functional groups, and the lipophilic hydrocarbon group end of the graphite powder can face outwards by adopting surfactants such as oleic acid, stearic acid, anthracene oil and the like, and an active layer is coated on the surface of the graphite powder and is convenient to be combined with oil binders such as asphalt, coal tar and the like subsequently, so that the infiltration capacity and the adsorption capacity of the binders to aggregates are 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 ℃, removing 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 to 5 times, cooling to room temperature, crushing, and sieving through a 160 to 325-mesh sieve to obtain the binder-coated graphite powder.
The catalytic 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; the mass ratio of the second binder to the composite graphite powder is 25 to 35, and is 65 to 75.
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 and the catalytic promoter with water removed) 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 heating process, and the situation that the binder A is in a slurry state after being mixed with the materials in the kneading pot due to too good fluidity is avoided.
The catalytic promoters such as aluminum trichloride, ferric trichloride, ammonium chloride and the like can enable hydrogen on polycyclic aromatic compound aromatic hydrocarbons in the intermediate phase asphalt, the impregnating asphalt and the medium temperature asphalt to be replaced by alkyl or acyl to generate a 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 the 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; then heating to 350-550 ℃ at a speed of 30-50 ℃/h, keeping the temperature for 8-12 h, and controlling the pressure to be 5 MPa; and finally, controlling the temperature by a program and cooling to room temperature by a program at a speed of 50 ℃/h, and then grinding by a Raymond mill and air flow to prepare the green coke coated graphite powder with the granularity D50 of 4-6 mu m.
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 the green coke according to the mass ratio of 1-20 to 80-100 to obtain mixed powder for later use; 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 a catalytic promoter B into a mixing machine according to the mass ratio of 100: 0.1-1, mixing for 1-5 h, then putting into a kneading pot, carrying out dry mixing for 1-2 h at 110-150 ℃, discharging water, continuously heating to 130-160 ℃, then adding a binder B at 160-180 ℃ into the kneading pot, carrying out kneading for 0.5-2 h, then carrying out cover opening kneading for 10-30 min, carrying out hot-rolling for 3-5 times, cooling to room temperature, crushing, and then sieving through a 160-325-mesh sieve to obtain a 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; the mass ratio of the second binder to the composite aggregate is as follows: 10 to 20, 80 to 95.
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 invention is described in further detail below with reference to the drawings and the detailed description.
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 for 2 hours, and removing absolute ethyl alcohol at 80 ℃ to obtain graphite powder rich in active polarizing groups, wherein the mass ratio of oleic acid to 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 for 3 h, then putting the mixture into a kneading pot, carrying out dry mixing for 1h at 130 ℃, removing moisture, continuously heating to 150 ℃, and after the temperature is reached; mixing ethylene tar, coal tar (the mass ratio of the ethylene tar to the coal tar is 1: 7, carrying out melt compounding, adding the mixture into a kneading pot at 160 ℃, kneading for 1h, uncovering and kneading for 20 min, carrying out hot rolling on the mixture for 3 times at 160 ℃, 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 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 raising the temperature to 420 ℃ by a program of 40 ℃/h, preserving the temperature for 10 h, and controlling the pressure at 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 2 hours, 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 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 mixer according to the mass ratio of 100.5, uniformly mixing for 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, carrying out melt compounding, adding the mixture into a kneading pot at 170 ℃, carrying out kneading for 1h, uncapping and kneading for 20 min, carrying out hot rolling on the slices for 3 times at 170 ℃, cooling to room temperature, crushing, sieving by using a 300-mesh sieve, and preparing to obtain 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 for 10 h, carrying out vacuum-pumping packaging on the blank by using an aluminum-plastic film, and preheating in a 90 ℃ oven for 6 h; meanwhile, heating the pressurizing medium (the medium is hydraulic oil) of the isostatic pressing machine 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 green carbon-graphite material prepared in the step 7) into a down-draft kiln, burying with a burying material, heating to 1100 ℃ at a rate of 6 ℃/h, keeping the temperature for 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: adding 100 parts of 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 for 2 hours, 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 prepared in the step 2), 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 0.5, mixing for 2h, putting the mixture into a kneading pot, dry-mixing for 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: 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 for 1h, uncovering and kneading for 10 min, hot-rolling 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 asphalt 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 ℃ at the speed of 50 ℃/h, and keeping the temperature for 8 h, wherein the pressure is controlled 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 be continuously subjected to ultrasonic and mechanical stirring for 2 hours, and the absolute ethyl alcohol is removed at 80 ℃ to prepare 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 for 2h, putting the mixture into a kneading pot, dry-mixing for 1h at 130 ℃, removing water, and continuously heating to 150 ℃ until the temperature reaches; coal tar, heavy oil (the mass ratio of the coal tar to the heavy oil is 1: 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 for 1h, uncovering and kneading for 10 min, hot-rolling for 3 times at 170 ℃, cooling to room temperature, crushing, and sieving with a 300-mesh sieve to prepare pressed powder; the mass ratio of the modified mesophase pitch to the composite aggregate is 15:85.
7) Carrying out compression molding on the pressed powder prepared in the step 6) at 3 MPa, standing for 12 h, carrying out vacuum-pumping packaging on the blank by using an aluminum-plastic film, and preheating in a 90 ℃ oven for 6 h; 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) Putting 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 a speed of 8 ℃/h, preserving the heat for 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: adding 100 parts of 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 for 4 hours, 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 for 3 h, putting the mixture into a kneading pot, dry-mixing for 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: 7 adding the prepared melting composite binder with low softening point and good fluidity into a kneading pot at 170 ℃, kneading for 1.5 h, uncovering and kneading for 30 min, hot rolling the sheet at 170 ℃ for 5 times, cooling to room temperature, crushing, and sieving with 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 for 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 the 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 hours, removing the absolute ethyl alcohol at 80 ℃ to prepare the composite aggregate 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 100:1, adding the mixture into a mixing machine, mixing for 2 hours, then putting the mixture into a kneading pot, carrying out dry mixing for 2 hours at 110 ℃, removing moisture, continuously heating to 155 ℃, and after the temperature is reached; mixing anthracene oil, heavy oil (the mass ratio of anthracene oil to heavy oil is 2: 7 adding the prepared melting composite binder with low softening point and good fluidity into a kneading pot at 170 ℃, kneading for 1.5 h, uncovering and kneading for 30 min, hot rolling the sheet at 165 ℃ for 5 times, cooling to room temperature, crushing, and sieving with a 300-mesh sieve to prepare pressed powder; the mass ratio of the modified mesophase pitch to the composite aggregate is 20:80.
7) Carrying out compression molding on the pressed powder prepared in the step 6) at 2 MPa, standing for 10 h, carrying out vacuum-pumping packaging on the blank by using an aluminum-plastic film, and preheating in an oven at 100 ℃ for 6 h; 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 isostatic pressing at 150 MPa to prepare the carbon graphite material green blank.
8) Placing the green carbon-graphite material prepared in the step 7) into a down-draft kiln, burying with a burying material, heating to 1050 ℃ at a rate of 8 ℃/h, keeping the temperature for 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 a carbon graphite material green body.
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 compaction 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 kept, which shows that the carbon graphite material prepared by the method can meet the requirements without impregnation reinforcement, and can be used only after being impregnated with substances such as resin, babbit alloy, antimony, copper and the like according to purposes.
(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 dispersed 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 is 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 diameter of the prepared carbon graphite block is larger than 380 mm, the size of the prepared carbon graphite block is far larger than 200 mm, and the carbon graphite block with the size can be suitable for the fields of carbon graphite sealing for multi-specification aircraft engines, graphite for mobile phone hot bending glass molds, semiconductor graphite and the like.
Finally, it should be noted that the above examples of the present invention are only 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 (8)
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 catalyst 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 a 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 to 5 times at 160 to 180 ℃, cooling to room temperature, crushing, and sieving with a sieve at 160 to 325 meshes 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, and then heating to 350-550 ℃ by a program, and keeping the temperature for 8-12 h, wherein the pressure is controlled to be 1-5 MPa; cooling to room temperature, and grinding to obtain green coke coated graphite powder with the granularity D50 of 4-6 mu m;
s4: uniformly mixing the green coke coated graphite powder with green coke according to the mass ratio of 1 to 20; 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 a catalytic promoter B 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 B at 160-180 ℃ into the kneading pot, kneading for 0.5-2 h, opening a cover, kneading for 10-30 min, hot-rolling for 3-5 times, cooling to room temperature, crushing, and sieving through a 160-325-mesh sieve to obtain a pressed powder;
s6: carrying out compression molding and vacuumizing on the pressed powder, then carrying out warm isostatic pressing at 150-200 MPa to obtain a green body, and roasting to obtain the carbon graphite material;
the surfactant A and the surfactant B are one or more of oleic acid, stearic acid and anthracene oil; the catalyst accelerator A and the catalyst accelerator B are one or more of aluminum trichloride, ferric trichloride and ammonium chloride;
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, impregnation pitch and medium temperature pitch.
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 preparation method of the carbon graphite material with low porosity and high mechanical strength according to claim 1, wherein 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.
4. 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 when the temperature is programmed; 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.
5. The method for preparing the carbon graphite material with low porosity and high mechanical strength 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 mesocarbon microbeads; the average particle diameter D50 of the green coke is less than 2 μm.
6. 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 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 。
7. 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.
8. A low-porosity high-mechanical-strength carbon graphite material, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
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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 |