CN111153706A - Graphite-based silicon carbide ceramic composite heat-insulating material and preparation method thereof - Google Patents
Graphite-based silicon carbide ceramic composite heat-insulating material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graphite-based silicon carbide ceramic composite heat-insulating material and a preparation method thereof. The graphite-based silicon carbide ceramic composite heat-insulating material mainly comprises natural crystalline flake graphite, silicon carbide, glassy carbon and pores. Weighing natural crystalline flake graphite powder, phenolic resin powder, silicon powder and expandable graphite powder, and uniformly mixing in a mechanical stirring manner to obtain graphite-based 3D printing mixed powder; rapidly preparing a graphite prototype by using a selective laser sintering molding process, and carrying out secondary curing treatment; vacuum pressure dipping liquid phenolic resin, drying and curing; carbonizing treatment; dipping the silica sol solution under vacuum pressure and drying; and sintering at high temperature to obtain the graphite-based silicon carbide ceramic composite heat-insulating material. The prepared graphite-based silicon carbide ceramic composite heat-insulating material has the heat conductivity coefficient of less than or equal to 2.0W/m.k, the higher compressive strength of more than or equal to 10MPa, the capability of bearing the impact of high-temperature molten metal of more than or equal to 1600 ℃ and the capability of being repeatedly used for not less than 50 times.
Description
Technical Field
The invention relates to a graphite-based silicon carbide ceramic composite heat-insulating material and a preparation method thereof, belonging to the technical field of composite material forming and manufacturing.
Technical Field
In the process of continuously producing complex steel castings on a large scale by using graphite molds, the graphite mold sand lining casting process is generally adopted in consideration of the non-uniformity of the wall thickness of each part of the castings and the high-heat-conductivity characteristic (the heat conductivity coefficient is 60-150W/m.k) of the high-density high-strength artificial graphite mold. The basic technological process of casting the graphite type sand-hanging liner comprises the following steps: firstly, mechanically cutting a high-density high-strength artificial graphite blank into a casting mold cavity, then building a sodium silicate sand lining on the casting mold cavity to obtain a graphite sodium silicate sand composite type mold, finally pouring high-temperature molten metal into the composite type mold cavity, and cooling and solidifying to obtain a casting. Although the process increases the process operation difficulty and the production cost, the sodium silicate sand mold has low heat conductivity coefficient (less than 2.0W/m.k) and good heat preservation effect, and can be matched with a high heat conductivity graphite mold to regulate a casting temperature field, adjust the cooling speed of each part of a casting, realize sequential solidification, ensure the smoothness of a high-temperature molten metal feeding channel, prevent the defects of insufficient casting, cold shut, shrinkage porosity, shrinkage cavity and the like and ensure the quality of the casting.
The graphite sand lining hanging process has the following defects: (1) the process has higher requirements on the quality of the sodium silicate sand and faces the problem of resource market shortage; (2) the development difficulty of the sodium silicate sand recycling technology is high, and the recycling rate is low; (3) the sodium silicate sand is solid waste, and the waste sand treatment is environment-friendly and has high cost; (4) the high temperature resistance of the sodium silicate sand is poor, and the sand-sticking defect on the surface of a casting is easily caused; (5) the forming process of the sodium silicate sand lining is complex, and the control requirements of the process procedures such as sand mixing, shooting, hardening, spraying, mould age and the like are higher; (6) the sodium silicate sand lining has low compressive strength (only 2-3 MPa), is only disposable and has relatively high production cost.
In a word, the composite heat insulation material with low heat conduction, high strength, high temperature resistance and repeated use needs to be developed to replace a sodium silicate sand lining, reduce the production cost and relieve the environmental protection pressure.
Disclosure of Invention
The invention provides a preparation method of a graphite-based silicon carbide ceramic composite heat-insulating material. The graphite-based silicon carbide ceramic composite heat-insulating material is composed of natural crystalline flake graphite powder, silicon carbide whiskers, glassy carbon and pores, wherein the mass fraction of the natural crystalline flake graphite is not less than 50wt%, the mass fraction of the silicon carbide is controlled to be 5-25%, the balance is the glassy carbon, the porosity of the composite heat-insulating material is not less than 50%, and the closed porosity is not less than 25%.
The preparation method mainly comprises the following process links: (1) weighing natural crystalline flake graphite powder, phenolic resin powder, silicon powder and expandable graphite powder according to a certain mass ratio, and uniformly mixing in a mechanical stirring manner to obtain graphite-based 3D printing mixed powder; (2) rapidly preparing a graphite prototype by using a selective laser sintering molding process, and carrying out secondary curing treatment on the graphite prototype; (3) vacuum pressure dipping liquid phenolic resin, drying and curing; (4) carbonizing treatment; (5) dipping the silica sol solution under vacuum pressure and drying; (6) and sintering at high temperature to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
The present invention thus achieves the above objects:
the graphite-based silicon carbide ceramic composite heat-insulating material has the advantages of low heat conductivity coefficient, high compressive strength, capability of bearing high-temperature molten metal impact and repeated use, and the performance is mainly influenced by the composition of various phases in the graphite-based silicon carbide ceramic composite heat-insulating material and the mutual combination state of the phases. The quantity, the form and the mutual combination state of all components in the graphite-based silicon carbide ceramic composite heat-insulating material can be adjusted by changing the composition of graphite-based 3D printing mixed powder and the post-treatment processes such as vacuum pressure impregnation, carbonization, high-temperature sintering and the like, so that the performance of the composite material can be regulated and controlled.
For example, the performance of the graphite ceramic composite heat-insulating material can be regulated and controlled by changing the size of the coarse and fine particles of the natural crystalline flake graphite powder and adjusting the powder accumulation state, the number, the size and the shape of pores in the graphite ceramic composite heat-insulating material. For example, the impregnation amount of the phenolic resin and the silica sol is controlled by changing the parameters of the vacuum pressure impregnation process (such as vacuum degree, impregnation time, applied pressure and impregnation times), thereby adjusting the performance of the composite heat-insulating material. For example, after carbonization, a plurality of tiny holes are generated due to pyrolysis of phenolic resin, and carbonization process parameters such as temperature rise rate influence the number, size and shape of the holes, thereby influencing the comprehensive performance of the graphite ceramic composite heat-insulating material. Under the protection of high-temperature and high-purity nitrogen or argon, silicon powder and glassy carbon (a product obtained after phenolic resin is carbonized) undergo a carbothermic reduction reaction to generate a silicon carbide reinforced phase, so that the density of the graphite ceramic composite heat-insulating material is improved, the heat-conducting property and the compressive strength of the graphite ceramic composite heat-insulating material are increased, and the performance of the composite material can be regulated and controlled by changing the adding amount of the silicon powder. For example, during carbonization, because the expandable graphite expands due to heating to form a plurality of closed air holes in the graphite ceramic composite heat-insulating material, the heat conducting property and the compressive strength of the composite heat-insulating material are influenced, and the synergy of low heat conduction and high compressive strength can be realized by changing the adding amount and the expansion rate of the expandable graphite powder.
The components of the graphite-based silicon carbide ceramic composite heat-insulating material are natural crystalline flake graphite, glassy carbon and silicon carbide, which have good high-temperature resistance, so that the composite heat-insulating material has high-temperature resistance. The selective laser sintering forming process can combine the flaky natural crystalline flake graphite powder, so that the flaky natural crystalline flake graphite powder has obvious directivity of heat conductivity and mechanical property, the heat conductivity coefficient is lower in the direction perpendicular to the arrangement of the natural crystalline flake graphite, and the compressive strength is higher. The natural crystalline flake graphite powder has good thermal shock resistance, and ensures that the composite heat-insulating material can be repeatedly used for many times.
The preparation method of the graphite ceramic composite heat insulation material mainly comprises the following process steps:
(1) preparation of graphite-based 3D printing mixed powder
Weighing natural crystalline flake graphite powder, phenolic resin powder, metal silicon powder and expandable graphite powder according to a certain mass ratio, and then placing the natural crystalline flake graphite powder, the phenolic resin powder, the metal silicon powder and the expandable graphite powder in batches into a roller ball mill for mechanical stirring and uniform mixing to obtain graphite 3D printing mixed powder.
(2) Selective laser sintering molding graphite prototype
Printing and forming the graphite 3D printing mixed powder prepared in the step (1) by adopting a selective laser sintering forming process, taking out a biscuit, and placing the biscuit into a drying oven for secondary curing to obtain a graphite prototype piece;
(3) vacuum pressure impregnation of phenolic resin liquid
Putting the graphite prototype in the step (2) into a vacuum pressure impregnator, vacuumizing, adding a phenolic resin solution, impregnating for a period of time under the action of pressure, taking out, cleaning the residual phenolic resin solution on the surface, drying and curing again;
(4) carbonization treatment
Placing the graphite prototype part subjected to vacuum pressure impregnation treatment into a carbonization furnace, vacuumizing, introducing high-purity argon or nitrogen, and performing carbonization treatment to obtain a graphite preform;
(5) vacuum pressure impregnation of silica sols
Putting the graphite preform into a vacuum pressure impregnator, impregnating a silica sol solution under the condition of vacuum pressure, taking out and drying;
(6) high temperature sintering
And placing the graphite preform subjected to vacuum pressure impregnation treatment into a high-temperature sintering furnace, vacuumizing, introducing high-purity argon or nitrogen, and sintering at high temperature to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
Preferably, the preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material is characterized in that the mass fraction of the natural crystalline flake graphite powder in the step (1) is 54-79.9%, the mass fraction of the phenolic resin powder is 15-30%, the mass fraction of the metal silicon powder is 5-15%, and the mass fraction of the expandable graphite is 0.1-1.0%.
Preferably, the natural crystalline flake graphite powder is 100-900 meshes, and the carbon content is more than 99%; the phenolic resin powder is 200-500 meshes; the metal silicon powder is 100-300 meshes, and the chemical purity is 99%; the expandable graphite is 50-200 meshes, the expansion ratio is 100-600, and the carbon content is more than 99%.
Preferably, the selective laser sintering molding process parameters are as follows: the layered thickness is 0.1-0.2 mm, the filling speed is 1500-3000 mm/s, the filling power is 10-30W, the filling distance is 0.1-0.2 mm, the profile speed is 500-1000 mm/s, and the preheating temperature is 30-40 ℃.
Preferably, the step of vacuum pressure impregnating the liquid phenolic resin solution is: putting the graphite prototype into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding 25-40 wt% of phenolic resin liquid, impregnating for 30-120s under the action of additional 0.1-0.8 MPa pressure, taking out, putting into a drying oven at 50-70 ℃ for drying, and curing again to obtain the graphite prototype impregnated with phenolic resin.
Preferably, the secondary curing and re-curing treatment process comprises the following steps: firstly, preserving heat for 15-30 min at 90-110 ℃; then preserving the heat for 15-30 min at 120-130 ℃; and finally, preserving the heat for 30-60 min at 160-180 ℃.
Preferably, the carbonization process is: firstly, vacuumizing to below 0.2MPa, and heating to 300 ℃ at a speed of 30-120 ℃/h; and introducing argon or nitrogen with the purity of 99%, heating to 800 ℃ at the speed of 60-120 ℃/h, preserving heat for 0.5-1 h, cooling to room temperature along with the furnace, and taking out to obtain the graphite preform.
Preferably, the vacuum pressure impregnation silica sol process is as follows: firstly putting the graphite preform into a vacuum pressure impregnator, then vacuumizing to below 0.1MPa, then adding a silica sol solution with the concentration of 25-30 wt%, impregnating for 30-120s under the action of the pressure of 0.1-0.8 MPa, then taking out, and drying in an oven at 120-180 ℃ to obtain the graphite preform impregnated with the silica sol.
Preferably, the parameters of the high-temperature sintering process are as follows: vacuumizing to below 0.2MPa, heating to 240 ℃ at a speed of 120-240 ℃/h, and keeping the temperature for 15-30 min; introducing argon or nitrogen with the purity of 99%, and heating to 800 ℃ at the speed of 180-360 ℃/h; finally, heating to 1450-1650 ℃ at a speed of 240-480 ℃/h, and preserving heat for 3-4 h; cooling to room temperature along with the furnace, and taking out to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
The graphite-based silicon carbide ceramic composite heat-insulating material and the preparation method thereof provided by the invention have the following characteristics:
the preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material has the advantages of short process flow, simple and convenient process operation, convenient implementation, low production cost and the like; the prepared graphite-based silicon carbide composite heat-insulating material has the advantages of low heat conductivity coefficient (less than 2.0W/m.k), high compressive strength (more than or equal to 10 MPa), capability of bearing high-temperature molten metal impact (more than or equal to 1600 ℃), repeated use (less than or equal to 50 times), safety, environmental protection, capability of replacing a sodium silicate sand lining in a graphite type sand lining casting process, and wide application in the industrial fields of thermal equipment, pipelines, buildings, aerospace and the like.
Drawings
Fig. 1 is a diagram of the graphite-based silicon carbide ceramic composite heat insulating material according to embodiment 1, where a is a morphology diagram and B is an SEM image of a.
Fig. 2 is a left view of the silicon carbide whiskers in the graphite-based silicon carbide ceramic composite heat insulating material according to example 1, and a right view of the left view is a partially enlarged view.
Fig. 3 a is a diagram of silicon carbide whiskers in the graphite-based silicon carbide ceramic composite heat insulating material according to embodiment 2, and B is a partially enlarged diagram of a.
Fig. 4 a is a diagram of silicon carbide whiskers in the graphite-based silicon carbide ceramic composite heat insulating material according to embodiment 3, and B is a partially enlarged diagram of a.
Detailed Description
Example 1
The embodiment provides a graphite-based silicon carbide ceramic composite heat-insulating material and a preparation method thereof.
(1) Preparation of graphite-based 3D printing mixed powder
Mixing natural crystalline flake graphite powder (carbon content is more than 99%, 500 meshes), phenolic resin (200 meshes), silicon powder (chemical purity is 99%, 200 meshes) and expandable graphite (carbon content is more than 99%, 100 meshes, expansion ratio is 200) uniformly according to a mass ratio of 55:25:19: 1.
(2) Selective laser sintering molding of graphite prototype
The biscuit is rapidly prepared by adopting a selective laser sintering molding technology according to the process parameters of the layering thickness of 0.1mm, the filling speed of 2000mm/s, the filling power of 17W, the filling interval of 0.1mm, the profile speed of 1000mm/s and the preheating temperature of 40 ℃. And (3) performing secondary curing treatment on the biscuit at 90 ℃ for 15min, 120 ℃ for 15min and 170 ℃ for 30min to obtain the graphite prototype.
(3) Vacuum pressure impregnation of phenolic resin liquid
Putting the graphite prototype into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding 30wt% phenolic resin liquid, impregnating for 60s under the action of additional 0.5MPa pressure, taking out, drying in a drying oven at 70 ℃, and curing again to obtain the graphite prototype impregnated with phenolic resin.
(4) Carbonization treatment
Putting the graphite prototype impregnated with the liquid phenolic resin into a carbonization furnace, vacuumizing to below 0.2MPa, and heating to 300 ℃ at a heating speed of 60 ℃/h; and introducing argon with the purity of 99 percent, heating to 800 ℃ at the heating speed of 120 ℃/h, preserving heat for 1h, cooling to room temperature along with the furnace, and taking out to obtain the graphite preform.
(5) Vacuum pressure impregnation of silica sols
Firstly putting the graphite preform into a vacuum pressure impregnator, then vacuumizing to below 0.1MPa, then adding a silica sol solution with the concentration of 30wt%, impregnating for 120s under the action of the pressure of 0.5MPa, then taking out, and drying in a 180 ℃ oven to obtain the graphite preform impregnated with the silica sol
(6) High temperature sintering
Carrying out high-temperature treatment on the graphite preform, vacuumizing to below 0.2MPa, heating to 120 ℃ at a heating speed of 180 ℃/h, and keeping the temperature for 30 min; introducing nitrogen with the purity of 99 percent, and heating to 800 ℃ at the heating speed of 300 ℃/h; and finally, heating to 1500 ℃ at a heating speed of 240 ℃/h, preserving the heat for 4h, cooling to room temperature along with the furnace, and taking out to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
The graphite-based silicon carbide ceramic composite heat-insulating material consists of natural crystalline flake graphite powder, silicon carbide whiskers, glassy carbon and pores, wherein the mass fraction of the natural crystalline flake graphite is 53.5wt%, the mass fraction of the silicon carbide is 20.3%, and the balance is the glassy carbon; the porosity of the composite heat-insulating material is 51.5%, wherein the closed porosity is 25.5%. The density of the graphite-based silicon carbide ceramic composite heat-insulating material is measured by experiments to be 1.92W/m.K, the compressive strength is 15.6MPa, the graphite-based silicon carbide ceramic composite heat-insulating material can bear the high temperature of 1650 ℃, the number of times of repeated use reaches 52 times, the graphite-based silicon carbide ceramic composite heat-insulating material is a composite heat-insulating material with low heat conductivity, high strength, high temperature resistance and repeated use, can replace a water glass sand liner, reduces the production cost and relieves the environmental protection pressure.
Example 2
The embodiment provides a graphite-based silicon carbide ceramic composite heat-insulating material and a preparation method thereof
(1) Preparation of graphite-based 3D printing mixed powder
Uniformly mixing natural crystalline flake graphite powder (with carbon content of more than 99 percent and 325 meshes), phenolic resin (with 500 meshes), metal silicon powder (with chemical purity of 99 percent and 200 meshes) and expandable graphite (with carbon content of more than 99 percent and 80 meshes and expansion ratio of 200) according to a mass ratio of 60:24:15: 1.
(2) Selective laser sintering molding of graphite prototype
The biscuit is rapidly prepared by adopting a selective laser sintering molding technology according to the process parameters of the layering thickness of 0.15mm, the filling speed of 1500mm/s, the filling power of 18W, the filling interval of 0.1mm, the profile speed of 1000mm/s and the preheating temperature of 40 ℃. And (3) carrying out secondary curing treatment on the biscuit according to the heat preservation of 90 ℃ for 15min, the heat preservation of 130 ℃ for 15min and the heat preservation of 160 ℃ for 30min to obtain the graphite prototype piece.
(3) Vacuum pressure impregnation of phenolic resin liquid
Putting the graphite prototype into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding 25wt% of phenolic resin liquid, impregnating for 30s under the action of additional 0.3MPa pressure, taking out, drying in a drying oven at 60 ℃, and curing again to obtain the graphite prototype impregnated with the phenolic resin.
(4) Carbonization treatment
Putting the graphite prototype impregnated with the liquid phenolic resin into a carbonization furnace, vacuumizing to below 0.2MPa, and heating to 300 ℃ at a heating speed of 120 ℃/h; and introducing argon with the purity of 99 percent, heating to 800 ℃ at the heating speed of 120 ℃/h, preserving heat for 1h, cooling to room temperature along with the furnace, and taking out to obtain the graphite preform.
(5) Vacuum pressure impregnation of silica sols
Putting the graphite preform into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding a silica sol solution with the concentration of 25wt%, impregnating for 60s under the action of the pressure of 0.5MPa, taking out, and drying in a drying oven at 150 ℃ to obtain the graphite preform impregnated with the silica sol.
(6) High temperature sintering
Carrying out high-temperature treatment on the graphite preform, vacuumizing to below 0.2MPa, heating to 120 ℃ at a heating speed of 120 ℃/h, and keeping the temperature for 30 min; introducing nitrogen with the purity of 99 percent, and heating to 800 ℃ at the heating speed of 240 ℃/h; and finally, heating to 1500 ℃ at a heating speed of 240 ℃/h, preserving the heat for 4h, cooling to room temperature along with the furnace, and taking out to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
The graphite-based silicon carbide ceramic composite heat-insulating material consists of natural crystalline flake graphite powder, silicon carbide whiskers, glassy carbon and pores, wherein the mass fraction of the natural crystalline flake graphite is 58.1wt%, the mass fraction of the silicon carbide is 17.2%, and the balance is the glassy carbon; the porosity of the composite heat-insulating material is 55.0%, wherein the closed porosity is 26.1%. The experiment shows that the heat conductivity coefficient of the graphite-based silicon carbide ceramic composite heat-insulating material is 1.35W/m.K, the compressive strength is 12.38MPa, the graphite-based silicon carbide ceramic composite heat-insulating material can bear 1600 ℃ of high temperature, the repeated use frequency reaches 50 times, the graphite-based silicon carbide ceramic composite heat-insulating material is a composite heat-insulating material with low heat conductivity, high strength, high temperature resistance and repeated use, can replace a sodium silicate sand liner, reduces the production cost and relieves the environmental protection pressure.
Example 3
The embodiment provides a graphite-based silicon carbide ceramic composite heat-insulating material and a preparation method thereof.
(1) Preparation of graphite-based 3D printing mixed powder
Uniformly mixing natural crystalline flake graphite powder (with carbon content of more than 99 percent and 200 meshes), phenolic resin powder (with 325 meshes), metal silicon powder (with chemical purity of 99 percent and 200 meshes) and expandable graphite (with carbon content of more than 99 percent and 200 meshes and expansion ratio of 200) according to a mass ratio of 56:28.5:15: 0.5.
(2) Selective laser sintering molding of graphite prototype
The biscuit is rapidly prepared by adopting a selective laser sintering molding technology according to the process parameters of the layering thickness of 0.1mm, the filling speed of 1500mm/s, the filling power of 15W, the filling interval of 0.1mm, the profile speed of 1000mm/s and the preheating temperature of 40 ℃. And (3) performing secondary curing treatment on the biscuit according to the heat preservation of 90 ℃ for 15min, the heat preservation of 130 ℃ for 15min and the heat preservation of 180 ℃ for 30min to obtain the graphite prototype piece.
(3) Vacuum pressure impregnation of phenolic resin liquid
Putting the graphite prototype into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding 28wt% phenolic resin liquid, impregnating for 90s under the action of additional 0.4MPa pressure, taking out, drying in a drying oven at 60 ℃, and curing again to obtain the graphite prototype impregnated with phenolic resin.
(4) Carbonization treatment
Putting the graphite prototype impregnated with the liquid phenolic resin into a carbonization furnace, vacuumizing to below 0.2MPa, and heating to 300 ℃ at a heating speed of 120 ℃/h; and introducing nitrogen with the purity of 99 percent, heating to 800 ℃ at the heating speed of 240 ℃/h, preserving heat for 1h, cooling to room temperature along with the furnace, and taking out to obtain the graphite preform.
(5) Vacuum pressure impregnation of silica sols
Putting the graphite preform into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding a silica sol solution with the concentration of 30wt%, impregnating for 60s under the action of the pressure of 0.6MPa, taking out, and drying in a 180 ℃ oven to obtain the graphite preform impregnated with the silica sol.
(6) High temperature sintering
Carrying out high-temperature treatment on the graphite preform, firstly vacuumizing to below 0.2MPa, heating to 120 ℃ at a heating speed of 240 ℃/h, and preserving heat for 30 min; introducing nitrogen with the purity of 99 percent, and heating to 800 ℃ at the heating speed of 360 ℃/h; and finally, heating to 1550 ℃ at a heating speed of 400 ℃/h, preserving heat for 4h, cooling to room temperature along with the furnace, and taking out to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
The graphite-based silicon carbide ceramic composite heat-insulating material consists of natural crystalline flake graphite powder, silicon carbide whiskers, glassy carbon and pores, wherein the mass fraction of the natural crystalline flake graphite is 54.2wt%, the mass fraction of the silicon carbide is 17.5%, and the balance is the glassy carbon; the porosity of the composite heat-insulating material is 53.2%, wherein the closed porosity is 27.0%. The experiment shows that the heat conductivity coefficient of the graphite-based silicon carbide ceramic composite heat-insulating material is 1.66W/m.K, the compressive strength is 15.39MPa, the graphite-based silicon carbide ceramic composite heat-insulating material can bear the high temperature of 1650 ℃, the repeated use frequency reaches 55 times, the graphite-based silicon carbide ceramic composite heat-insulating material is a composite heat-insulating material with low heat conductivity, high strength, high temperature resistance and repeated use, can replace a water glass sand liner, reduces the production cost and relieves the environmental protection pressure.
Claims (10)
1. The graphite-based silicon carbide ceramic composite heat-insulating material is characterized by comprising natural crystalline flake graphite powder, silicon carbide whiskers and glassy carbon, wherein the mass fraction of the natural crystalline flake graphite powder is not less than 50wt%, the mass fraction of the silicon carbide whiskers is controlled to be 5-25%, and the balance is the glassy carbon.
2. The graphite-based silicon carbide ceramic composite insulating material according to claim 1, wherein the graphite-based silicon carbide ceramic composite insulating material contains voids, wherein the porosity is not less than 50%, and wherein the closed porosity is not less than 25%.
3. The preparation method of the graphite-based silicon carbide ceramic composite heat insulating material according to claim 1 or 2, characterized by comprising the following processes:
(1) preparation of graphite-based 3D printing mixed powder
Weighing natural crystalline flake graphite powder, phenolic resin powder, metal silicon powder and expandable graphite powder, and then placing the natural crystalline flake graphite powder, the phenolic resin powder, the metal silicon powder and the expandable graphite powder into a roller ball mill in batches to be mechanically stirred and uniformly mixed to obtain graphite 3D printing mixed powder;
(2) selective laser sintering molding graphite prototype
Printing and forming the graphite 3D printing mixed powder prepared in the step (1) by adopting a selective laser sintering forming process, taking out a biscuit, and placing the biscuit into a drying oven for secondary curing to obtain a graphite prototype piece;
(3) vacuum pressure impregnation of phenolic resin liquid
Putting the graphite prototype in the step (2) into a vacuum pressure impregnator, vacuumizing, adding a phenolic resin solution, impregnating for a period of time under the action of pressure, taking out, drying and curing again;
(4) carbonization treatment
Placing the graphite prototype part subjected to vacuum pressure impregnation treatment into a carbonization furnace, vacuumizing, introducing high-purity argon or nitrogen, and performing carbonization treatment to obtain a graphite preform;
(5) vacuum pressure impregnation of silica sols
Putting the graphite preform into a vacuum pressure impregnator, impregnating a silica sol solution under the condition of vacuum pressure, taking out and drying;
(6) high temperature sintering
And placing the graphite preform subjected to vacuum pressure impregnation treatment into a high-temperature sintering furnace, vacuumizing, introducing high-purity argon or nitrogen, and sintering at high temperature to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
4. The preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material according to claim 3, wherein the mass fraction of the natural crystalline flake graphite powder in the step (1) is 54-79.9%, the mass fraction of the phenolic resin powder is 15-30%, the mass fraction of the metal silicon powder is 5-15%, and the mass fraction of the expandable graphite is 0.1-1.0%;
the natural crystalline flake graphite powder is 100-900 meshes, and the carbon content is more than 99%; the phenolic resin powder is 200-500 meshes; the metal silicon powder is 100-300 meshes, and the chemical purity is 99%; the expandable graphite is 50-200 meshes, the expansion ratio is 100-600, and the carbon content is more than 99%.
5. The preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material according to claim 4, wherein the selective laser sintering molding process parameters in the step (2) are as follows: the layered thickness is 0.1-0.2 mm, the filling speed is 1500-3000 mm/s, the filling power is 10-30W, the filling distance is 0.1-0.2 mm, the profile speed is 500-1000 mm/s, and the preheating temperature is 30-40 ℃.
6. The method for preparing a graphite-based silicon carbide ceramic composite heat insulating material according to claim 5, wherein the step of vacuum pressure impregnation of the liquid phenolic resin solution in the step (3) is: putting the graphite prototype into a vacuum pressure impregnator, vacuumizing to below 0.1MPa, adding 25-40 wt% of phenolic resin liquid, impregnating for 30-120s under the action of additional 0.1-0.8 MPa pressure, taking out, putting into a drying oven at 50-70 ℃, drying, and curing again to obtain the graphite prototype impregnated with phenolic resin.
7. The method for preparing the graphite-based silicon carbide ceramic composite heat insulating material according to claim 6, wherein the secondary curing and the secondary curing in the steps (2) and (3) are both carried out by: firstly, preserving heat for 15-30 min at 90-110 ℃; then preserving the heat for 15-30 min at 120-130 ℃; and finally, preserving the heat for 30-60 min at 160-180 ℃.
8. The preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material according to claim 7, wherein the carbonization process in the step (4) is as follows: firstly, vacuumizing to below 0.2MPa, and heating to 300 ℃ at a speed of 30-120 ℃/h; and introducing argon or nitrogen with the purity of 99%, heating to 800 ℃ at the speed of 60-120 ℃/h, preserving heat for 0.5-1 h, cooling to room temperature along with the furnace, and taking out to obtain the graphite preform.
9. The method for preparing the graphite-based silicon carbide ceramic composite heat insulating material according to claim 8, wherein the vacuum pressure impregnation silica sol process in the step (5) is as follows: firstly putting the graphite preform into a vacuum pressure impregnator, then vacuumizing to below 0.1MPa, then adding a silica sol solution with the concentration of 25-30 wt%, impregnating for 30-120s under the action of the pressure of 0.1-0.8 MPa, then taking out, and drying in an oven at 120-180 ℃ to obtain the graphite preform impregnated with the silica sol.
10. The preparation method of the graphite-based silicon carbide ceramic composite heat-insulating material according to claim 9, wherein the high-temperature sintering process parameters in the step (6) are as follows: vacuumizing to below 0.2MPa, heating to 240 ℃ at a speed of 120-240 ℃/h, and keeping the temperature for 15-30 min; introducing argon or nitrogen with the purity of 99%, and heating to 800 ℃ at the speed of 180-360 ℃/h; finally, heating to 1450-1650 ℃ at a speed of 240-480 ℃/h, and preserving heat for 3-4 h; cooling to room temperature along with the furnace, and taking out to obtain the graphite-based silicon carbide ceramic composite heat-insulating material.
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| CN112620582A (en) * | 2020-12-22 | 2021-04-09 | 辽宁科技大学 | SiC combined Al for 3D printing2O3Method for preparing sand mould |
| CN114478012A (en) * | 2021-12-29 | 2022-05-13 | 宁波伏尔肯科技股份有限公司 | Carbon part manufacturing method and carbon part manufactured by same |
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