CN111038022B - Anti-corrosion composite heat-preservation cover felt for industrial vacuum furnace and preparation method thereof - Google Patents

Anti-corrosion composite heat-preservation cover felt for industrial vacuum furnace and preparation method thereof Download PDF

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CN111038022B
CN111038022B CN201911262256.9A CN201911262256A CN111038022B CN 111038022 B CN111038022 B CN 111038022B CN 201911262256 A CN201911262256 A CN 201911262256A CN 111038022 B CN111038022 B CN 111038022B
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silicon carbide
felt
graphite
density
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CN111038022A (en
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卞光煜
李娜
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Gansu Haoshi Carbon Fiber Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/752—Corrosion inhibitor

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Abstract

The invention discloses an anti-corrosion composite heat-insulation blanket for an industrial vacuum furnace and a preparation method thereof. The surface graphite foil or the antipyretic carbon coating and the silicon steam are used for producing the silicon carbide surface in situ, and the silicon carbide layer and the carbon/silicon carbide layer are combined to provide high-efficiency corrosion resistance. Compared with the traditional heat-insulating cover material, the added carbon/silicon carbide layer not only improves the physical strength, but also optimizes the matching of the thermal expansion coefficient and the hardness of the surface silicon carbide and the matrix, and obviously prolongs the service life of the cover felt under the conditions of oxidation and silicon vapor corrosion. The blanket damage is primarily at the surface and part of the carbon/silicon carbide layer and can be repaired by grinding and recoating. The invention has low cost and long service life and is suitable for industrial production.

Description

Anti-corrosion composite heat-preservation cover felt for industrial vacuum furnace and preparation method thereof
Technical Field
The invention relates to the technical field of carbon fiber composite materials, in particular to an anti-corrosion composite heat-preservation cover felt for an industrial vacuum furnace and a preparation method thereof, which are applied to heat insulation of the vacuum furnace under the conditions of silicon steam corrosion atmosphere, a small amount of oxygen and high temperature.
Background
In the production of photovoltaic single crystal silicon, high-temperature ceramic reaction sintering or ceramic matrix composite preparation, the thermal insulation material is usually subjected to high temperature of 1400-1800 ℃, accompanied by scouring of air flow, corrosion of high-temperature steam (usually silicon steam) and trace oxidation. The requirements for the insulation material under this extreme condition are: the heat conductivity is low, the heat transfer to the furnace cover is reduced, and the heat preservation effect is achieved; the relatively smooth surface reflects heat into the furnace in a high-temperature environment, and plays roles of energy conservation and auxiliary temperature rise; can resist the corrosion of high-temperature silicon vapor and the scouring of air flow; the material is stable and does not decompose in high temperature environment.
The traditional heat insulation material mainly comprises carbon felt or graphite felt. In order to improve the heat insulation performance, the heat insulation material is a non-woven fabric felt made by scattering low-density monofilament chopped fibers. Since the fibers are mostly monofilaments or filament bundles in the graphite or carbon felt and have a large specific surface, high-temperature silicon vapor easily penetrates the surface of the felt to erode the fibers themselves. Although the graphite hard felt has a part of the resin carbon protection fiber filaments, the porous structure of the graphite hard felt is not enough to resist the invasion of silicon vapor. Silicon vapor attacks the surface of the carbon fiber to generate silicon carbide, and the silicon carbide on the surface of the outer ring is subjected to tensile stress due to volume shrinkage to generate cracks so that the fiber shows brittleness, which is particularly shown by slag falling. Another possible failure mode is the inevitable presence of traces of oxygen in the vacuum furnace, which results in oxidation of the fibrous material. In order to prevent slag and oxidation, graphite foil, large-tow carbon cloth or carbon-based coating is attached to the surface of a heat-insulating material in a common method at present. During use, the high temperature silicon vapor causes the surface to be ceramized to form a dense silicon carbide-based layer to retard erosion by the silicon vapor. Another solution is to directly prepare a silicon carbide coating on the surface of a heat insulation material to play a role in protection, for example, chinese patent No. CN103993474A discloses a method for preparing a silicon carbide coating on the surface of a hard carbon fiber felt, in which a reaction-sintered silicon carbide layer is generated by the reaction of graphite emulsion coated on the surface of a graphite felt and then silicon vapor. However, the coating is easy to crack and fall off during the use process, so that the service life of the heat insulation material is mostly between half a year and a year. Patent No. CN105951301A discloses a method for preparing an antioxidant carbon fiber heat insulation felt, in which a silicon carbide layer is deposited on the surface of carbon fiber to protect the fiber by branching polysilane on the carbon fiber felt and high temperature treatment. This method has the following drawbacks: the heat insulation material generally needs a smooth surface to reflect heat into the furnace, so as to achieve the effects of heat insulation and energy saving; the polysilane precursor generally has low porcelain forming rate and can form a compact protective layer after being soaked for many times; the method described in the patent can only form loose silicon carbide by dipping once, but does not achieve the ideal protection effect; polysilanes are currently expensive and not suitable for large-scale production.
Disclosure of Invention
The invention aims to provide an anti-corrosion composite heat-insulation cover felt for an industrial vacuum furnace and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the utility model provides an industrial vacuum furnace is with compound heat preservation of anticorrosion lid felt, the structure of this lid felt's cross section is: the middle main body is a graphite hard felt, carbon/silicon carbide chips subjected to silicon removal and secondary siliconizing treatment are bonded to two sides of the graphite hard felt through a carbon-based/ceramic mixed binder, and a graphite foil is bonded to the outer surfaces of the carbon/silicon carbide chips through the carbon-based binder or an antipyretic carbon coating is deposited on the outer surfaces of the carbon/silicon carbide chips; the composite heat-preservation blanket felt with the graphite foil adhered on the outer surface is used for heating an industrial vacuum furnace with the temperature lower than 1700 ℃; the composite heat-insulating cover felt with the antipyretic carbon coating deposited on the outer surface is used for an industrial vacuum furnace with the heating temperature of 1700-1800 ℃.
The graphite foil or pyrolytic carbon coating on the outermost layer of the composite heat-preservation cover felt can further react with a small amount of free silicon volatilized by silicon steam or carbon/silicon carbide chips in the vacuum furnace to generate a silicon carbide protective layer in the use process of the industrial vacuum furnace.
Preferably, the graphite hard felt is prepared by performing gum dipping, hot pressing, curing and carbonizing treatment on a PAN-based fiber graphite soft felt, wherein the thickness of the graphite hard felt is 10-150mm, and the density of the graphite hard felt is 0.19-0.24g/cm3。
The preparation method of the anti-corrosion composite heat-preservation cover felt for the industrial vacuum furnace comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, and selecting a carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment to be processed into a shape required by design, wherein the thickness of the carbon/silicon carbide wafer is 1-5 mm; respectively bonding a carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder, coating the carbon-based binder on the side edge of the graphite felt, standing for 5-10 hours, and airing to obtain a covering felt primary material;
step two, sticking a graphite foil on the surface of the primary cover felt material: and (2) adhering a graphite foil to the outer surface of the primary material of the blanket prepared in the step one by using a carbon-based adhesive, wherein the thickness of the graphite foil is 0.1-0.5mm, fixing the periphery of the blanket by using a clamp, then placing the blanket into an oven, heating the oven to 150-plus-one temperature, keeping the temperature for 10 hours, curing, heating to 1650 ℃, carrying out high-temperature carbonization and sintering for 3-8 hours under the protection of argon, heating the blanket to 1900-plus-one temperature 2000 ℃, and carrying out graphitization treatment for 4 hours under the atmosphere of argon to obtain the heat-preservation blanket with the graphite foil adhered to the surface.
The preparation method of the anti-corrosion composite heat-preservation cover felt for the industrial vacuum furnace is as described in the specification, and comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, selecting a carbon/silicon carbide chip subjected to high-temperature silicon removal and secondary siliconizing treatment, processing to the shape required by the design, bonding the carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder respectively, coating the carbon-based binder on the side edge of the graphite felt, standing for 5-10 hours, and airing to obtain a primary cover felt material;
wherein the graphite hard felt has a thickness of 10-150mm and a density of 0.19-0.24g/cm3The thickness of the carbon/silicon carbide wafer is 1-5 mm;
step two, performing vapor deposition of pyrolytic carbon on the surface of the blanket initial material: fixing the primary material of the blanket prepared in the step one by a clamp, then placing the fixed material into an oven, heating the oven to 150-plus-one temperature for 10 hours for curing, then heating to 1650 ℃, carrying out high-temperature carbonization and sintering under the protection of argon for 3-8 hours, heating the blanket to 900 ℃, carrying out heat preservation for 100-plus-one time for 600 hours, and carrying out chemical vapor deposition under the atmosphere of propylene and argon, wherein the gas content of the propylene is 3-5m3The amount of argon is 8-12m3And/h, depositing the antipyretic carbon coating with the thickness of 100-500 mu m, then heating the blanket to 2000 ℃, and carrying out graphitization treatment for 4 hours in the argon atmosphere to obtain the heat-preservation blanket with the antipyretic carbon coating deposited on the surface.
Preferably, the surface of the heat-insulating cover felt with the antipyretic carbon coating deposited on the surface is polished by 1000-mesh sand paper.
Preferably, the preparation method of the carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment comprises the following steps:
(1) the 2.5D carbon fiber preform with a needling structure is used as a substrate, and is formed by sequentially stacking 0-degree carbon fiber single cloth, a carbon fiber net tire and 90-degree carbon fiber single cloth, wherein the thickness of the carbon fiber preform is 2-5mm, and the density of the carbon fiber preform is 0.2-0.5g/cm3(ii) a The carbon fiber single-layer cloth is 12k carbon fiber cloth, the grade of the fiber is T300, the density of the net tire is 200-one-layer 220g/cm3；
(2) Performing vapor deposition on the carbon fiber preform at 900 ℃ for 100-600 hours by using propylene and argon through a vapor deposition method to obtain the carbon fiber preform with the density of 0.9-1.2g/cm3The low-density carbon-carbon composite material has the propylene content of 3-5m3H, the argon gas amount is 8-12m3/h；
(3) Preparing the low-density carbon-carbon composite material prepared in the step (2) by a gas-phase melting siliconizing method at 1650 ℃ under vacuum condition to obtain the carbon-carbon composite material with the density of 1.8-2.0g/cm3The carbon/silicon carbide composite of (a);
(4) embedding the carbon/silicon carbide composite material prepared in the step (3) into graphite powder, heating to 1800-1900 ℃, and preserving heat for 1-4 hours for silicon removal treatment to obtain the carbon/silicon carbide composite material with the density of 1.3-1.7g/cm3The carbon/silicon carbide composite of (a);
(5) performing vapor deposition on the carbon/silicon carbide composite material prepared in the step (4) at 900 ℃ for 200-600 hours by using propylene and argon through a propane vapor deposition method, wherein the amount of the propylene is 3-5m3H, the argon gas amount is 8-12m3H, depositing pyrolytic carbon into the silicon voids to obtain a density of 1.5-1.9g/cm3The carbon/silicon carbide/carbon composite of (a); wherein the amount of propylene is 3-5m3H, the argon gas amount is 8-12m3H; finally, carrying out secondary gas-phase melting siliconizing treatment on the carbon/silicon carbide/carbon composite material at 1700 ℃;
(6) and (3) grinding the carbon/silicon carbide composite material prepared in the step (5) into a 1-5mm slice by using a surface grinder, and washing and drying by using purified water to obtain the carbon/silicon carbide slice.
The gas-phase melting siliconizing method in the step (3) comprises the specific steps of charging and vacuum heat treatment; the specific operation steps are as follows:
a. preparing a plurality of graphite crucibles with proper sizes, wherein the graphite density is preferably 1.8g/cm3In the above, the effective diameter of the crucible is required to be larger than the required size of the cover felt by 100-;
b. coating a mixture of silicon nitride or boron nitride powder and a small amount of purified water around the graphite crucible for demoulding, wherein the addition of water is based on the condition that the mixture is pasty;
c. uniformly placing 8-12 graphite cushion blocks with the length, width, 50x50mm and height of 100mm at the bottom of the crucible, wherein the cushion blocks are required to be uniformly distributed at the bottom of the crucible to support the carbon-carbon composite plate in the step 2, but the specific positions are not required to be determined;
d. pouring silicon powder with the weight 4-6 times of the total weight of the filled carbon-carbon composite material and the purity of more than 99 percent into a crucible;
e. placing 3-5 carbon-carbon composite material plates on graphite cushion blocks, and separating the carbon-carbon composite material plates by using 8-12 graphite cushion blocks with the length, width, 50x50mm and height of 30mm, wherein the graphite cushion blocks are required to be uniformly distributed to support the carbon-carbon composite material plates, and the specific positions are not required to be determined;
f. and sequentially stacking the crucibles, putting the crucibles into a vacuum furnace, adding a graphite cover with the thickness of 30mm to the crucible at the top, and finally heating the vacuum furnace to 1650 ℃ in a vacuum atmosphere and sintering for 4 hours.
Preferably, the preparation method of the carbon-based binder comprises the following steps:
mixing 30 parts of phenolic resin or furan resin, 35 parts of graphite powder, 22 parts of petroleum coke, 10-30 parts of methanol and 3 parts of curing agent in parts by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based binder; wherein: the curing agent is one of hexamethylene tetramine or sodium benzenesulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.
Preferably, the preparation method of the carbon-based/ceramic binder comprises the following steps:
mixing 20 parts of phenolic resin or furan resin, 15 parts of graphite powder, 22 parts of petroleum coke, 20 parts of silicon powder with the granularity of 1000 meshes, 10 parts of silicon carbide powder with the granularity of 800 meshes, 10-30 parts of methanol and 3 parts of curing agent by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based/ceramic binder; wherein: the curing agent is preferably hexamethylenetetramine or one of sodium benzene sulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.
The traditional coating or graphite foil method can meet the basic requirements of heat reflection and corrosion and erosion resistance in a high-temperature furnace. In order to slow down the damage of the surface ceramic layer and reduce the thermal stress gradient change in the heating and cooling processes, the gradient structure can effectively reduce the thermal stress. The MTS-based gas phase infiltration method can cover the interior and the surface of the graphite felt with a compact nano silicon carbide coating, and can realize a gradient structure. The carbon/silicon carbide material has the following characteristics: the coefficient of thermal expansion and the modulus are between those of the silicon carbide and the graphite felt; good oxidation resistance; good thermal shock resistance; good toughness. However, the common carbon/silicon carbide material generally contains 2% -10% of free silicon with low melting point (1450 ℃), and the volatilization of the silicon can cause pores, thereby affecting the anti-corrosion performance. The method of the invention is to react free silicon in the carbon/silicon carbide material with carbon powder at high temperature, then to fill dense graphite carbon on the surface and near the surface, and to add a carbon/silicon carbide transition layer processed by silicon treatment between the surface and the graphite felt to improve the service life of the heat preservation covering felt under the environment of high temperature silicon steam and micro-oxidation.
According to the invention, graphite foil is pasted on the surface of the graphite hard felt or pyrolytic carbon is deposited on the surface of the graphite hard felt in a vapor phase mode, and the graphite foil or pyrolytic carbon coating on the outermost layer of the composite heat-preservation cover felt can further react with a small amount of free silicon volatilized by silicon steam or carbon/silicon carbide chips in a vacuum furnace in the use process of the industrial vacuum furnace to generate a silicon carbide protective layer. Because the thermal stress of the silicon carbide is not matched with that of the graphite hard felt, the silicon carbide on the surface is easy to damage and fall off; in order to slow down the damage of the surface ceramic layer and reduce the thermal stress gradient change in the heating and cooling processes, the gradient structure can effectively reduce the thermal stress, a carbon/silicon carbide layer is added between the surface ceramic layer and the graphite felt layer, and the carbon/silicon carbide material has the following characteristics: the coefficient of thermal expansion and the modulus are between those of the silicon carbide and the graphite felt; good oxidation resistance; good thermal shock resistance; good toughness. Therefore, the invention designs a gradient structure of the surface carbon coating or the graphite foil-carbon/silicon carbide sheet-graphite hard felt, and the structure has the following advantages:
(1) the gradient structure is prepared, so that the difference of the thermal expansion coefficients between the surface ceramic layer and the carbon/silicon carbide layer is reduced, the thermal stress is reduced, and the service life is prolonged;
(2) the difference of the modulus between the surface ceramic layer and the carbon/silicon carbide layer is reduced, and the overall rigidity of the cover felt is improved;
(3) the cover felt damage is mainly on the surface and part of the carbon/silicon carbide layer, and can be repaired and renewed by polishing and recoating; under the standard working condition (silicon vapor corrosion at 1650 ℃), the service life of the product produced by the invention is more than 2 years, and the service life of the product can be prolonged by about 1 year by adding surface renovation, and the total service life is 3-5 times of that of the existing material;
(4) the oxidation resistance of the product is further improved;
(5) because the common carbon/silicon carbide material generally contains 2 to 10 percent of free silicon with low melting point (1450 ℃), the volatilization of the silicon can cause pores, thereby affecting the anti-corrosion performance of the product; according to the invention, the silicon carbide content is further improved through high-temperature silicon removal and secondary siliconizing treatment, the content of free silicon is reduced, and the high-temperature corrosion resistance is improved;
(6) the method has the advantages of simple process, modular production of the graphite felt, the binder and the carbon/silicon carbide protective layer, low cost and suitability for large-scale industrial production.
Drawings
FIG. 1 is a schematic structural diagram of an anti-corrosion composite heat-insulating cover felt for an industrial vacuum furnace.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
As shown in figure 1, the anti-corrosion composite heat preservation cover felt for the industrial vacuum furnace has the following cross section structure: the middle main body is a graphite hard felt with the thickness of 26mm, the two sides of the graphite hard felt are bonded with a carbon/silicon carbide wafer with the thickness of 1.5mm which is subjected to high-temperature silicon removal and secondary silicon infiltration treatment through a carbon-based/ceramic mixed binder, and the outer surface of the carbon/silicon carbide wafer is bonded with a graphite foil with the thickness of 0.5mm through a carbon-based binder; the composite heat-insulating cover felt is used for an industrial vacuum furnace with the heating temperature lower than 1700 ℃. The veil diameter was 1000 mm.
The graphite hard felt is prepared by carrying out gum dipping, hot pressing, curing and carbonizing on PAN-based fiber graphite soft felt, and the density of the graphite hard felt is 0.19g/cm3。
The preparation method of the anti-corrosion composite heat-insulation cover felt for the industrial vacuum furnace comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, and selecting a carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment to be processed into a shape required by design, wherein the thickness of the carbon/silicon carbide wafer is 1.5 mm; respectively bonding a carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder, coating the carbon-based binder on the side edge of the graphite felt, standing for 10 hours, and airing to obtain a cover felt primary material;
step two, sticking a graphite foil on the surface of the primary cover felt material: and (3) adhering a graphite foil to the outer surface of the primary cover felt material prepared in the step one by using a carbon-based adhesive, fixing the periphery of the cover felt by using a clamp, then placing the cover felt into an oven, heating the oven to 200 ℃, preserving heat for 10 hours, curing, then heating to 1650 ℃, carrying out high-temperature carbonization and sintering for 4 hours under the protection of argon, heating the cover felt to 2000 ℃, and carrying out graphitization treatment for 4 hours under the atmosphere of argon to obtain the heat preservation cover felt with the graphite foil adhered to the surface.
Example 2
As shown in figure 1, the anti-corrosion composite heat preservation cover felt for the industrial vacuum furnace has the following cross section structure: the middle main body is a graphite hard felt with the thickness of 26mm, a carbon/silicon carbide wafer with the thickness of 1.5mm subjected to silicon removal and secondary siliconizing treatment is bonded on two sides of the graphite hard felt through a carbon-based/ceramic mixed binder, and an antipyretic carbon coating with the thickness of 0.4mm is deposited on the outer surface of the carbon/silicon carbide wafer; the composite heat-insulating cover felt is used for an industrial vacuum furnace with the heating temperature of 1700-1800 ℃. The veil diameter was 1000 mm.
The graphite hard felt is prepared by carrying out gum dipping, hot pressing, curing and carbonizing on PAN-based fiber graphite soft felt, and the density of the graphite hard felt is 0.19g/cm3。
The preparation method of the anti-corrosion composite heat-insulation cover felt for the industrial vacuum furnace comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, selecting a carbon/silicon carbide chip subjected to high-temperature silicon removal and secondary siliconizing treatment, processing to the shape required by the design, bonding the carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder respectively, coating the carbon-based binder on the side edge of the graphite felt, standing for 5-10 hours, and airing to obtain a primary cover felt material;
step two, performing vapor deposition of pyrolytic carbon on the surface of the blanket initial material: fixing the primary material of the blanket prepared in the first step by a clamp, then placing the fixed material into a baking oven, heating the baking oven to 150-.
The preparation method of the carbon/silicon carbide wafer subjected to the high-temperature silicon removal and secondary siliconizing treatment in the embodiment 1 and the embodiment 2 comprises the following steps:
(1) the 2.5D carbon fiber preform with the needling structure is used as a substrate, and is formed by sequentially stacking 0-degree carbon fiber single cloth, a carbon fiber net tire and 90-degree carbon fiber single cloth, wherein the thickness of the carbon fiber preform is 3mm, and the density of the carbon fiber preform is 0.5g/cm3(ii) a The carbon fiber single-layer cloth is 12k carbon fiber cloth, the grade of the fiber is T300, the density of the net tire is 200-one-layer 220g/cm3；
(2) Vapor-depositing a carbon fiber preform by using propylene and argon at 900 deg.C for 400 hours by a propane vapor deposition method, wherein the amount of propylene is preferably 3-5m3The argon gas amount is preferably 8-12m3Per hour, a density of 1.1g/cm is obtained3The low-density carbon-carbon composite of (1);
(3) preparing the low-density carbon-carbon composite material prepared in the step (2) by a gas-phase melting siliconizing method at 1650 ℃ to obtain the carbon-carbon composite material with the density of 1.8-2.0g/cm3The carbon/silicon carbide composite of (a);
(4) putting the carbon/silicon carbide composite material prepared in the step (3) into a crucible and embedding the crucible into graphite powder, heating to 1800 ℃, preserving heat for 4 hours, and performing high-temperature silicon removal treatment to obtain the carbon/silicon carbide composite material with the density of 1.7g/cm3The carbon/silicon carbide composite of (a);
(5) performing vapor deposition on the carbon/silicon carbide composite material prepared in the step (4) at 900 ℃ for 300 hours by using propylene and argon through a propane vapor deposition method, and depositing pyrolytic carbon into the gaps of silicon, wherein the amount of the propylene is preferably 3-5m3The argon gas amount is preferably 8-12m3H, a density of 1.7g/cm3The carbon/silicon carbide/carbon composite of (a); then carrying out secondary gas-phase melting siliconizing treatment on the carbon/silicon carbide/carbon composite material at 1700 ℃, wherein the charging operation is the same as the step (3), but the subsequent sintering temperature is slightly increased; (ii) a
(6) And (4) grinding the carbon/silicon carbide composite material prepared in the step (5) into a sheet with the thickness of 1.5mm by using a surface grinding machine, and washing and drying the sheet by using purified water to obtain the carbon/silicon carbide chip.
The gas-phase melting siliconizing method in the step (3) comprises the specific steps of charging and vacuum heat treatment; the specific operation steps are as follows:
a. preparing a plurality of graphite crucibles with proper sizes, wherein the graphite density is preferably 1.8g/cm3In the above, the effective diameter of the crucible is required to be larger than the required size of the cover felt by 100-;
b. coating a mixture of silicon nitride or boron nitride powder and a small amount of purified water around the graphite crucible for demoulding, wherein the addition of water is based on the condition that the mixture is pasty;
c. uniformly placing 8-12 graphite cushion blocks with the length, width, 50x50mm and height of 100mm at the bottom of the crucible, wherein the cushion blocks are required to be uniformly distributed at the bottom of the crucible to support the carbon-carbon composite plate in the step 2, but the specific positions are not required to be determined;
d. pouring silicon powder with the weight 4-6 times of the total weight of the filled carbon-carbon composite material and the purity of more than 99 percent into a crucible;
e. placing 3-5 carbon-carbon composite material plates on graphite cushion blocks, and separating the carbon-carbon composite material plates by using 8-12 graphite cushion blocks with the length, width, 50x50mm and height of 30mm, wherein the graphite cushion blocks are required to be uniformly distributed to support the carbon-carbon composite material plates, and the specific positions are not required to be determined;
f. and sequentially stacking the crucibles, putting the crucibles into a vacuum furnace, adding a graphite cover with the thickness of 30mm to the crucible at the top, and finally heating the vacuum furnace to 1650 ℃ in a vacuum atmosphere and sintering for 4 hours.
Preferably, the preparation method of the carbon-based binder comprises the following steps:
mixing 30 parts of phenolic resin or furan resin, 35 parts of graphite powder, 22 parts of petroleum coke, 10-30 parts of methanol and 3 parts of curing agent in parts by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based binder; wherein: the curing agent is one of hexamethylene tetramine or sodium benzenesulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.
Preferably, the preparation method of the carbon-based/ceramic binder comprises the following steps:
mixing 20 parts of phenolic resin or furan resin, 15 parts of graphite powder, 22 parts of petroleum coke, 20 parts of silicon powder with the granularity of 1000 meshes, 10 parts of silicon carbide powder with the granularity of 800 meshes, 10-30 parts of methanol and 3 parts of curing agent by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based/ceramic binder; wherein: the curing agent is preferably hexamethylenetetramine or one of sodium benzene sulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.

Claims (6)

1. A preparation method of an anti-corrosion composite heat-preservation cover felt for an industrial vacuum furnace is characterized by comprising the following steps: the structure of the cross section of the cover felt is as follows: the middle main body is a graphite hard felt, carbon/silicon carbide chips subjected to high-temperature silicon removal and secondary siliconizing treatment are bonded to the two sides of the graphite hard felt through a carbon-based/ceramic mixed binder, and a graphite foil is bonded to the outer surfaces of the carbon/silicon carbide chips through the carbon-based binder or an antipyretic carbon coating is deposited on the outer surfaces of the carbon/silicon carbide chips; the composite heat-preservation blanket felt with the graphite foil adhered on the outer surface is used for heating an industrial vacuum furnace with the temperature lower than 1700 ℃; the composite heat-insulating cover felt with the antipyretic carbon coating deposited on the outer surface is used for an industrial vacuum furnace with the heating temperature of 1700-1800 ℃, and the preparation method comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, and selecting a carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment to be processed into a shape required by design, wherein the thickness of the carbon/silicon carbide wafer is 1-5 mm; respectively bonding a carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder, coating the carbon-based binder on the side edge of the graphite felt, standing for 5-10 hours, and airing to obtain a covering felt primary material;
step two, sticking a graphite foil on the surface of the primary cover felt material: bonding a graphite foil on the outer surface of the primary material of the blanket prepared in the step one by using a carbon-based binder, wherein the thickness of the graphite foil is 0.1-0.5mm, fixing the periphery of the blanket by using a clamp, then placing the blanket into an oven, heating the oven to 150-;
the preparation method of the carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment comprises the following steps:
(1) the 2.5D carbon fiber preform with a needling structure is used as a substrate, and is formed by sequentially stacking 0-degree carbon fiber single cloth, a carbon fiber net tire and 90-degree carbon fiber single cloth, wherein the thickness of the carbon fiber preform is 2-5mm, and the density of the carbon fiber preform is 0.2-0.5g/cm3(ii) a The carbon fiber single-layer cloth is 12k carbon fiber cloth, the grade of the fiber is T300, the density of the net tire is 200-one-layer 220g/cm3；
(2) Performing vapor deposition on the carbon fiber preform at 900 ℃ for 100-600 hours by using propylene and argon through a vapor deposition method, wherein the amount of the propylene is 3-5m3H, the argon gas amount is 8-12m3Per hour, a density of 0.9 to 1.2g/cm3The low-density carbon-carbon composite of (1);
(3) preparing the low-density carbon-carbon composite material prepared in the step (2) by a gas-phase melting siliconizing method at 1650 ℃ under vacuum condition to obtain the carbon-carbon composite material with the density of 1.8-2.0g/cm3The carbon/silicon carbide composite of (a);
(4) embedding the carbon/silicon carbide composite material prepared in the step (3) into graphite powder, heating to 1800-1900 ℃, and preserving heat for 1-4 hours for silicon removal treatment to obtain the carbon/silicon carbide composite material with the density of 1.3-1.7g/cm3The carbon/silicon carbide composite of (a);
(5) performing vapor deposition on the carbon/silicon carbide composite material prepared in the step (4) at 900 ℃ for 200-600 hours by using propylene and argon through a vapor deposition method, wherein the amount of the propylene is 3-5m3H, the argon gas amount is 8-12m3H, depositing pyrolytic carbon into the silicon voids to obtain a density of 1.5-1.9g/cm3The carbon/silicon carbide/carbon composite of (a); wherein the amount of propylene is 3-5m3H, the argon gas amount is 8-12m3H; finally, carrying out secondary gas-phase melting siliconizing treatment on the carbon/silicon carbide/carbon composite material at 1700 ℃;
(6) and (3) grinding the carbon/silicon carbide composite material prepared in the step (5) into a 1-5mm slice by using a surface grinder, and washing and drying by using purified water to obtain the carbon/silicon carbide slice.
2. A preparation method of an anti-corrosion composite heat-preservation cover felt for an industrial vacuum furnace is characterized by comprising the following steps: the structure of the cross section of the cover felt is as follows: the middle main body is a graphite hard felt, carbon/silicon carbide chips subjected to high-temperature silicon removal and secondary siliconizing treatment are bonded to the two sides of the graphite hard felt through a carbon-based/ceramic mixed binder, and a graphite foil is bonded to the outer surfaces of the carbon/silicon carbide chips through the carbon-based binder or an antipyretic carbon coating is deposited on the outer surfaces of the carbon/silicon carbide chips; the composite heat-preservation blanket felt with the graphite foil adhered on the outer surface is used for heating an industrial vacuum furnace with the temperature lower than 1700 ℃; the composite heat-insulating cover felt with the antipyretic carbon coating deposited on the outer surface is used for an industrial vacuum furnace with the heating temperature of 1700-1800 ℃, and the preparation method comprises the following steps:
step one, preparing a composite heat-preservation cover felt initial material: selecting a graphite hard felt with a proper specification according to the density and thickness requirements of a product, selecting a carbon/silicon carbide chip subjected to high-temperature silicon removal and secondary siliconizing treatment, processing to the shape required by the design, bonding the carbon/silicon carbide chip on the upper surface and the lower surface of the graphite hard felt by using a carbon-based/ceramic mixed binder respectively, coating the carbon-based binder on the side edge of the graphite felt, standing for 5-10 hours, and airing to obtain a primary cover felt material;
wherein the graphite hard felt has a thickness of 10-150mm and a density of 0.19-0.24g/cm3The thickness of the carbon/silicon carbide wafer is 1-5 mm;
step two, performing vapor deposition of pyrolytic carbon on the surface of the blanket initial material: fixing the primary material of the blanket prepared in the step one by a clamp, then placing the fixed material into an oven, heating the oven to 150-plus-one temperature for 10 hours for curing, then heating to 1650 ℃, carrying out high-temperature carbonization and sintering under the protection of argon for 3-8 hours, heating the blanket to 900 ℃, carrying out heat preservation for 100-plus-one time for 600 hours, and carrying out chemical vapor deposition under the atmosphere of propylene and argon, wherein the gas content of the propylene is 3-5m3The amount of argon is 8-12m3Depositing an antipyretic carbon coating with the thickness of 100-500 mu m, heating the blanket to 2000 ℃, and graphitizing for 4 hours in an argon atmosphere to obtain a heat-preservation blanket with the antipyretic carbon coating deposited on the surface;
the preparation method of the carbon/silicon carbide wafer subjected to high-temperature silicon removal and secondary siliconizing treatment comprises the following steps:
(1) the 2.5D carbon fiber preform with a needling structure is used as a substrate, and is formed by sequentially stacking 0-degree carbon fiber single cloth, a carbon fiber net tire and 90-degree carbon fiber single cloth, wherein the thickness of the carbon fiber preform is 2-5mm, and the density of the carbon fiber preform is 0.2-0.5g/cm3(ii) a The carbon fiber single-layer cloth is 12k carbon fiber cloth, the grade of the fiber is T300, the density of the net tire is 200-one-layer 220g/cm3；
(2) Performing vapor deposition on the carbon fiber preform at 900 ℃ by using propylene and argon through a vapor deposition methodPhase deposition for 100-600 hours, wherein the amount of propylene is 3-5m3H, the argon gas amount is 8-12m3Per hour, a density of 0.9 to 1.2g/cm3The low-density carbon-carbon composite of (1);
(3) preparing the low-density carbon-carbon composite material prepared in the step (2) by a gas-phase melting siliconizing method at 1650 ℃ under vacuum condition to obtain the carbon-carbon composite material with the density of 1.8-2.0g/cm3The carbon/silicon carbide composite of (a);
(4) embedding the carbon/silicon carbide composite material prepared in the step (3) into graphite powder, heating to 1800-1900 ℃, and preserving heat for 1-4 hours for silicon removal treatment to obtain the carbon/silicon carbide composite material with the density of 1.3-1.7g/cm3The carbon/silicon carbide composite of (a);
(5) performing vapor deposition on the carbon/silicon carbide composite material prepared in the step (4) at 900 ℃ for 200-600 hours by using propylene and argon through a vapor deposition method, wherein the amount of the propylene is 3-5m3H, the argon gas amount is 8-12m3H, depositing pyrolytic carbon into the silicon voids to obtain a density of 1.5-1.9g/cm3The carbon/silicon carbide/carbon composite of (a); wherein the amount of propylene is 3-5m3H, the argon gas amount is 8-12m3H; finally, carrying out secondary gas-phase melting siliconizing treatment on the carbon/silicon carbide/carbon composite material at 1700 ℃;
(6) and (3) grinding the carbon/silicon carbide composite material prepared in the step (5) into a 1-5mm slice by using a surface grinder, and washing and drying by using purified water to obtain the carbon/silicon carbide slice.
3. The method for preparing the anti-corrosion composite heat preservation cover felt for the industrial vacuum furnace according to claim 1 or 2, which is characterized by comprising the following steps: the preparation method of the carbon-based binder comprises the following steps:
mixing 30 parts of phenolic resin or furan resin, 35 parts of graphite powder, 22 parts of petroleum coke, 10-30 parts of methanol and 3 parts of curing agent in parts by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based binder; wherein: the curing agent is one of hexamethylene tetramine or sodium benzenesulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.
4. The method for preparing the anti-corrosion composite heat-preservation cover felt for the industrial vacuum furnace according to claim 3, which is characterized by comprising the following steps of: the preparation method of the carbon-based/ceramic mixed binder comprises the following steps:
mixing 20 parts of phenolic resin or furan resin, 15 parts of graphite powder, 22 parts of petroleum coke, 20 parts of silicon powder with the granularity of 1000 meshes, 10 parts of silicon carbide powder with the granularity of 800 meshes, 10-30 parts of methanol and 3 parts of curing agent by weight, stirring for 30 minutes, and dispersing the mixture for 5 minutes by using ultrasound to prepare the carbon-based/ceramic mixed binder; wherein: the curing agent is preferably one of hexamethylenetetramine, sodium benzenesulfonate or phosphoric acid; the mass percentage concentration of the methanol is more than 99 percent.
5. The method for preparing the anti-corrosion composite heat-preservation cover felt for the industrial vacuum furnace according to claim 4, which is characterized by comprising the following steps of: the graphite hard felt is prepared by performing gum dipping, hot pressing, curing and carbonizing treatment on a PAN-based fiber graphite soft felt, wherein the thickness of the graphite hard felt is 10-150mm, and the density of the graphite hard felt is 0.19-0.24g/cm3。
6. The method for preparing the anti-corrosion composite heat-preservation cover felt for the industrial vacuum furnace according to claim 5, which is characterized by comprising the following steps of: and polishing the surface of the heat-insulating cover felt with the antipyretic carbon coating deposited on the surface by using 1000-mesh sand paper.
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