CN115677380A - Preparation method of composite ceramic coating of thermal field heat-insulating part - Google Patents
Preparation method of composite ceramic coating of thermal field heat-insulating part Download PDFInfo
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Abstract
The invention provides a preparation method of a composite ceramic coating of a thermal field heat-insulating piece, which comprises the steps of coating a priming coating slurry on the surface of the thermal field heat-insulating piece, then carrying out CVD deposition, mixing zirconium modified polymethyl silane, siC and a solvent to prepare an outer coating slurry, coating the outer coating slurry on the surface of the thermal field heat-insulating piece, and finally sintering. The ceramic composite coating prepared by the method has excellent silicon erosion resistance and oxidation resistance, is low in production cost and is easy to produce on a large scale.
Description
Technical Field
The invention belongs to the technical field of composite ceramic coatings, and particularly relates to a preparation method of a composite ceramic coating of a thermal field heat-insulating part.
Background
The photovoltaic industry has a good development prospect due to mature technical conditions. At present, the monocrystalline silicon solar cell belongs to the technology with the mature technology and relatively high photoelectric conversion efficiency, and therefore, the market demand for monocrystalline silicon is huge.
The monocrystalline silicon growth furnace consists of a heating system, a heat preservation system, a vacuum system and the like. The value of crucible, heater and heat-insulating material consumed by a medium-sized single crystal growth furnace every year exceeds 20 ten thousand yuan, and the loss of spare parts of a thermal field system of a large-sized single crystal growth furnace can even reach 30-40 ten thousand yuan every year. Therefore, how to prolong the service life of the material and reduce the production cost becomes a problem to be solved urgently for each photovoltaic enterprise.
With the rise of new materials, carbon fibers are widely applied to single crystal growing furnaces because of low density, high temperature resistance, excellent mechanical properties, excellent heat insulation performance and the like. However, during the pulling process of the monocrystalline silicon, certain silicon vapor and some SiO gas with oxidizability are formed in the furnace, and erode the thermal field heat preservation piece prepared from the carbon/carbon composite material, so that the heat preservation performance and the service life of the whole thermal field are affected. Therefore, it is very important to improve the requirements of the thermal field insulation piece on resisting silicification corrosion and oxidation. In the related art, the main ways are to add carbon bushings in the thermal field insulation and replace worn parts, however, these ways are not ideal and have high production cost.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a preparation method of the composite ceramic coating of the thermal field heat-insulating part, and the ceramic composite coating prepared by the method has excellent silicon corrosion resistance and oxidation resistance, is low in production cost and is easy for large-scale production.
The invention provides a preparation method of a composite ceramic coating of a thermal field heat-insulating part, which comprises the following steps:
s1: mixing flake graphite powder and epoxy resin to prepare a primer coating slurry, and coating the primer coating slurry on the surface of a thermal field heat-insulating part;
s2: conveying the thermal field heat-insulating piece treated in the step S1 into a deposition furnace for CVD deposition;
s3: mixing zirconium modified polymethyl silane, siC and a solvent to prepare outer layer coating slurry, and coating the outer layer coating slurry on the surface of the thermal field heat preservation piece treated in the step S2;
s4: and (4) sintering the thermal field heat-insulating piece treated in the step (S3).
In the invention, the thermal field heat preservation part mainly refers to a carbon felt, namely a felt made of carbon fibers. Thermal field insulation is typically purchased directly from the market.
The invention relates to a technical scheme in a preparation method of a composite ceramic coating of a thermal field heat-insulating part, which at least comprises the following steps
Has the advantages that:
the density of the thermal field insulation member, namely the carbon felt is very low, and is usually 0.2g/cm 3 In the preparation method, the priming coating slurry is coated on the surface of the thermal field heat-insulating piece, so that a compact layer with higher hardness is formed on the surface of the thermal field heat-insulating piece, and the external coating can be prevented from greatly permeating into the carbon felt. And then the thermal field heat-insulating piece is sent into a deposition furnace for CVD deposition and consolidation, so that the density of the surface of the thermal field heat-insulating piece is further increased, and the bonding strength of the thermal field heat-insulating piece and the outer coating can be increased. Under the combined action of the priming coating, the CVD deposition and the outer coating, the composite ceramic coating of the thermal field thermal insulation part, prepared by the invention, meets the mechanical property and thermal insulation property requirements of a thermal field, and the prepared ceramic composite coating has controllable components and thickness, has good bonding strength with a matrix, meets the high temperature resistance, and has excellent silicon erosion resistance and oxidation resistance. Meanwhile, the preparation process is simple, the production cost is low, and large-scale industrial production is easy to realize.
According to the preparation method, a uniform SiC-ZrC ceramic composite coating is prepared on the surface of the thermal field heat-insulating part through a coating process. From the process, the operation is simple and convenient, and the equipment requirement is low. Firstly, performing surface cherry blossom and hole sealing treatment on a thermal field heat preservation piece by a first step of priming carbon coating and a second step of CVD deposition. Secondly, the primer coating and the CVD carbon deposition are well combined with the felt body, the thermal expansion coefficients are basically consistent, and proper interface conditions are provided for subsequent ceramic coatings.
Meanwhile, the product obtained after sintering the zirconium modified polymethyl silane is a SiC-ZrC composite phase, and the composite phase has good high temperature resistance, silicon corrosion resistance and oxidation resistance. Provides basic guarantee on materials for the outer coating to have excellent high temperature resistance, silicon resistance and oxygen corrosion resistance. However, the problems of small molecule volatilization and sintered ceramic shrinkage inevitably occur in the sintering process of the zirconium modified polymethylsilane, so that the SiC-ZrC coating prepared by a precursor conversion method has insufficient density and holes and cracks, and therefore, siC powder needs to be added into the zirconium modified polymethylsilane with a certain concentration, and linear 0 shrinkage of the sintered SiC-ZrC ceramic can be realized by adjusting the powder ratio, so that a completely compact SiC-ZrC coating is obtained on the surface of a thermal field. In addition, the preparation method of the invention can well control the thickness of the coating by adjusting the concentration of the coating slurry and the brushing times.
In conclusion, the ceramic composite coating prepared by the preparation method disclosed by the invention has the advantage of easily adjustable thickness, and also has excellent high temperature resistance, silicon corrosion resistance and oxidation resistance.
According to some embodiments of the invention, in step S1, the flake graphite powder is 400-600 mesh flake graphite powder.
According to some embodiments of the invention, in step S1, the crystalline flake graphite powder has a purity of 99.9%.
According to some embodiments of the invention, in step S1, the mass ratio of the scaly graphite powder to the epoxy resin is 2 to 3.
According to some embodiments of the invention, in step S1, the epoxy resin is a waterborne epoxy resin.
According to some embodiments of the present invention, in step S1, the thermal field insulation member is coated with a primer, and a soft brush is used to dip primer slurry on the surface of the thermal field to brush the primer slurry on the surface of the thermal field, so that a layer of primer is uniformly coated on the surface of the carbon felt, and the carbon felt is completely dried after the primer slurry is coated.
And (5) priming the coating, and controlling the thickness of the coating within 1mm.
The coating can be dried in the air for about 2 to 4 hours after being sufficiently dried, and the coating is not sticky to touch.
According to some embodiments of the invention, the CVD deposition time in step S2 is 8h to 12h.
According to some embodiments of the invention, the CVD deposition time in step S2 is 10h to 12h.
After CVD deposition, a layer of compact prime carbon coating can be formed on the surface of the thermal field heat-insulating part, and most of pores on the surface of the carbon felt are filled, so that a good coating interface is provided for a subsequent SiC-ZrC outer layer coating.
And (4) setting the CVD deposition process parameters according to the size and the charging quantity of the deposition furnace.
According to some embodiments of the invention, in step S3, the outer layer coating slurry is coated on the surface of the thermal field insulation piece treated in step S2, and the thickness of the outer layer coating slurry is less than or equal to 1mm.
According to some embodiments of the invention, in step S3, the mass ratio of the zirconium-modified polymethylsilane, siC and solvent is 1.0 to 1.5.
According to some embodiments of the invention, in step S3, the mass ratio of the zirconium-modified polymethylsilane, siC and solvent is 1.2 to 1.5.
The purity of SiC was 99.9%, and the particle size was about 5 μm.
According to some embodiments of the invention, the method for preparing the zirconium-modified polymethylsilane comprises: and (2) dripping a tetrahydrofuran solution of zirconium tetrachloride into a solution of polymethylsilane in a protective atmosphere, heating for reaction, filtering, carrying out reduced pressure distillation on the filtrate, separating out the solvent, and obtaining the remaining viscous liquid, namely the zirconium-modified polymethylsilane.
According to some embodiments of the invention, the method for preparing the zirconium-modified polymethylsilane comprises: slowly and dropwise adding a tetrahydrofuran solution of 10% by mass of zirconium tetrachloride into a solution of polymethylsilane under a protective atmosphere at a temperature of below 5 ℃, wherein the mass ratio of the added zirconium tetrachloride to the polymethylsilane is 1.5: controlling the reaction temperature within 0-5 ℃, stirring and reacting for a certain time, sequentially heating to normal temperature, 80 ℃ and 120 ℃, reacting, filtering, carrying out reduced pressure distillation on the filtrate, separating out the solvent, and taking the remaining viscous liquid as the zirconium modified polymethylsilane.
The molecular weight of the prepared zirconium modified polymethyl silicane is 1000-1500.
According to some embodiments of the present invention, in step S3, the zirconium-modified polymethylsilane, the SiC and the solvent are subjected to vacuum ball milling to obtain an outer layer coating slurry, the prepared outer layer coating slurry is used to perform a second coating treatment on the surface of the thermal field insulation member, and the coated thermal field insulation member is placed in a sintering furnace to be sintered.
After sintering, a layer of uniform and compact SiC-ZrC ceramic composite coating can be obtained on the surface of the thermal field heat-insulating part.
According to some embodiments of the present invention, in step S3, the solvent of the zirconium outer layer coating slurry may be selected from toluene or xylene.
The purity of toluene or xylene was 99.9%.
According to some embodiments of the invention, in step S4, the sintering is temperature programmed sintering from room temperature to 1000 ℃.
According to some embodiments of the invention, the temperature-programmed sintering is carried out by sequentially raising the temperature from room temperature to 120 ℃, 200 ℃, 350 ℃, 1000 ℃ and keeping the temperature.
According to some embodiments of the invention, the temperature programmed sintering is programmed to: room temperature is 120 ℃ to 100min; keeping the temperature at 120 ℃ for 60min; 120-200 ℃ to-100 min; keeping the temperature at 200 ℃ for 120min; 200-350 ℃ for-100 min; keeping the temperature at 350 ℃ for 60min;350 to (900 to-1000) to-220 min; preserving the heat for 120min at the temperature of 900-1000 ℃; the whole sintering process is a nitrogen normal-pressure environment, and the temperature is naturally reduced after sintering.
According to some embodiments of the invention, the nitrogen purity is 99.99%.
According to some embodiments of the invention, in step S1, the thermal field insulation is a pre-treated thermal field insulation.
According to some embodiments of the invention, the pre-treatment comprises a curing treatment, a charring treatment, a high temperature treatment and machining.
According to some embodiments of the invention, the thermal field heat preservation member with the size and the shape meeting the requirements can be prepared by adopting a carbon felt laminating method according to the shape and the size requirements of the required thermal field, the specific mode can be that the carbon felt and the carbon felt are laminated, resin is coated and adhered between layers, and finally the density of the prepared thermal field heat preservation member is 0.2g/cm 3 Left and right sides whole thermal field heat preservation spare part structure.
The density of the carbon felt is 0.2g/cm 3 About, the thickness is generally 5mm/10mm specification, brush on phenolic resin between the carbon felt layer and the layer and bond, leave the machine during preparationAdding the rest, generally increasing the length and width by 30mm and the height by 10mm, and preparing the product with the density of 0.2g/cm 3 Left and right overall thermal field component structures. After the preparation is finished, in order to prevent deformation, the graphite plates can be pressed and placed into an oven together for curing treatment.
According to some embodiments of the present invention, the curing process may be performed by placing the integrated thermal field component into a curing oven.
The curing program was set to: the temperature is between room temperature and 120 ℃, and the heating time is 120min; keeping the temperature at 120 ℃ for 120min; the temperature is increased for 160min at the temperature of 120 ℃ to (240 ℃ to 260 ℃); keeping the temperature for 300min at the temperature of 240-260 ℃.
According to some embodiments of the present invention, the carbonization treatment process may be performed by placing the integral thermal field component in a carbonization furnace.
The carbonization program is set as follows: the temperature is raised for 60min at room temperature to 240-260 ℃; (240 ℃ -260 ℃) to (700 ℃ -750 ℃), and the temperature rise time is 260min; keeping the temperature at 700-750 ℃ for 180min. The carbonization process is a nitrogen-protected micro-positive pressure environment, and substances such as waste liquid tar and the like need to be discharged at any time in the carbonization process.
According to some embodiments of the invention, the high temperature treatment process may be performed by placing the integrated thermal field component into a high temperature furnace.
The high temperature program was set to: the room temperature is 800 ℃, and the temperature rise time is 160min; the temperature is raised for 120min at 800-1200 ℃; the temperature is increased for 240min at 1200 ℃ to 1700 ℃ to 1800 ℃; (1700 ℃ -1800 ℃) and keeping the temperature for 180min. And vacuumizing the whole environment.
And after the high-temperature treatment is finished, performing machining according to the drawing of the thermal field component to obtain the thermal field heat-insulating component.
The machining drawing paper considers the matching size of the thermal field component, simultaneously considers the thickness factor of the coating surface coating, and carries out machining amount confirmation according to the thickness of the coating of 1 mm-1.5 mm.
According to the preparation method, the SiC-ZrC ceramic composite coating with silicon and oxygen corrosion resistance is prepared on the surface of the thermal field heat-insulating piece, so that the service life of the thermal field is prolonged. Meanwhile, the carbon-carbon lining added for preventing the erosion of the thermal field heat preservation piece and maintaining the crystal pulling environment of the whole single crystal growing furnace can be removed from the structure, thereby further saving the production cost.
Drawings
FIG. 1 is a schematic diagram of the structure of a thermal field insulator prepared in the example.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the present invention, the present invention provides a method for preparing a composite ceramic coating for a thermal field insulation member, comprising the steps of:
s1: mixing the flake graphite powder and epoxy resin to prepare a priming coating slurry, and coating the priming coating slurry on the surface of a thermal field heat-insulating part;
s2: conveying the thermal field heat preservation piece processed in the step S1 into a deposition furnace for CVD deposition;
s3: mixing zirconium modified polymethyl silane, siC and a solvent to prepare outer coating slurry, and coating the outer coating slurry on the surface of the thermal field heat preservation piece treated in the step S2;
s4: and (4) sintering the thermal field heat preservation piece processed in the step S3.
In the invention, the thermal field insulation member mainly refers to a carbon felt, i.e. a felt made of carbon fibers. Thermal field insulation is typically purchased directly from the market.
It will be appreciated that the density of the thermal field insulation, i.e. carbon felt, is very low, typically at 0.2g/cm 3 In the preparation method, the priming coating slurry is coated on the surface of the thermal field heat-insulating piece, so that a compact layer with higher hardness is formed on the surface of the thermal field heat-insulating piece, and the external coating can be prevented from greatly permeating into the carbon felt. And then the thermal field heat-insulating piece is sent into a deposition furnace for CVD deposition for consolidation, so that the density of the surface of the thermal field heat-insulating piece is further increased, and the bonding strength of the thermal field heat-insulating piece and the outer layer coating can be increased. Under the combined action of the priming coating, the CVD deposition and the outer coating, the thermal field heat-insulating part composite ceramic coating prepared by the invention meets the mechanical requirements of a thermal fieldThe prepared ceramic composite coating has controllable components and thickness, has good bonding strength with a matrix, meets the high temperature resistance, and has excellent silicon erosion resistance and oxidation resistance. Meanwhile, the preparation process is simple, the production cost is low, and large-scale industrial production is easy to realize.
Furthermore, the preparation method of the invention prepares a uniform SiC-ZrC ceramic composite coating on the surface of the thermal field heat preservation piece by a painting process. From the process, the operation is simple and convenient, and the equipment requirement is low. Firstly, a bottom carbon coating is applied to carry out surface hole sealing coating treatment on the thermal field heat-insulating piece in the first step. And secondly, the carbon coating is well combined with the felt body, the thermal expansion coefficients are consistent, and proper interface conditions are provided for subsequent ceramic coatings.
Meanwhile, the product obtained after sintering the zirconium modified polymethyl silane is a SiC-ZrC composite phase, and the composite phase has good high temperature resistance, silicon corrosion resistance and oxidation resistance. Provides basic guarantee on materials for the outer coating to have excellent high temperature resistance, silicon resistance and oxidation corrosion resistance. However, in the sintering process of the zirconium modified polymethylsilane, the problems of small molecule volatilization and sintered ceramic shrinkage inevitably occur, so that the density of the SiC-ZrC coating prepared by a precursor conversion method is insufficient, and holes and cracks exist, therefore, siC powder needs to be added into the zirconium modified polymethylsilane with a certain concentration, and the linear '0' shrinkage of the sintered SiC-ZrC ceramic can be realized by adjusting the powder proportion, so that a completely compact SiC-ZrC coating can be obtained on the surface of a thermal field. In addition, the preparation method of the invention can well control the thickness of the coating by adjusting the concentration of the coating slurry and the brushing times.
In conclusion, the ceramic composite coating prepared by the preparation method disclosed by the invention has the advantage of easily adjustable thickness, and also has excellent high temperature resistance, silicon corrosion resistance and oxidation resistance.
Specifically, in some embodiments of the present invention, in step S1, the flake graphite powder is 400-600 mesh flake graphite powder.
In some embodiments of the invention, in step S1, the flake graphite powder is 99.9% pure.
In some embodiments of the present invention, in step S1, the mass ratio of the crystalline graphite powder to the epoxy resin is 2 to 3.
In some embodiments of the present invention, in step S1, the epoxy resin is a waterborne epoxy resin.
Since the epoxy resin functions as a primer paste prepared with the flake graphite powder, there is no particular requirement for the selection of the aqueous epoxy resin, and any commercially available aqueous epoxy resin can be used in the present invention.
In some embodiments of the present invention, in step S1, a thermal field thermal insulation piece is subjected to priming coating, a soft brush is used to dip the priming coating slurry and brush the priming coating slurry on the surface of the thermal field, so that a layer of priming coating is uniformly coated on the surface of the carbon felt, and the carbon felt is completely dried after the priming coating.
And (5) priming the coating, wherein the thickness of the coating is controlled within 1mm.
The coating can be fully dried in the air for about 2 to 4 hours, and the coating is not sticky to the touch.
In some embodiments of the present invention, the time of the CVD deposition in step S2 is 8h to 12h.
In some embodiments of the present invention, the time of the CVD deposition in step S2 is 10h to 12h.
After CVD deposition, a layer of compact prime carbon coating can be formed on the surface of the thermal field heat-insulating part, and most of pores on the surface of the carbon felt are filled, so that a good coating interface is provided for a subsequent SiC-ZrC outer layer coating.
And (4) setting the CVD deposition process parameters according to the size and the charging quantity of the deposition furnace.
In some embodiments of the invention, in step S3, the outer layer coating slurry is coated on the surface of the thermal field insulation member treated in step S2, and the thickness of the outer layer coating slurry is less than or equal to 1mm.
In some embodiments of the present invention, in step S3, the mass ratio of the zirconium-modified polymethylsilane, siC and solvent is 1.0 to 1.5.
In some embodiments of the present invention, in step S3, the mass ratio of the zirconium-modified polymethylsilane, siC and solvent is 1.2 to 1.5.
The purity of SiC was 99.9%, and the particle size was about 5 μm.
In some embodiments of the present invention, the zirconium-modified polymethylsilane is prepared by: slowly and dropwise adding a tetrahydrofuran solution of 10% by mass of zirconium tetrachloride into a solution of polymethylsilane under a protective atmosphere at a temperature of below 5 ℃, wherein the mass ratio of the added zirconium tetrachloride to the polymethylsilane is 1.5: controlling the reaction temperature within 0-5 ℃, stirring and reacting for a certain time, sequentially heating to normal temperature, 80 ℃ and 120 ℃, reacting, filtering, carrying out reduced pressure distillation on the filtrate, separating out the solvent, and obtaining the residual viscous liquid which is the zirconium modified polymethylsilane.
The molecular weight of the prepared zirconium modified polymethyl silane is 1000-1500.
In some embodiments of the invention, in step S3, the zirconium-modified polymethylsilane, the SiC and the solvent are subjected to vacuum ball milling to obtain outer layer coating slurry, the prepared outer layer coating slurry is used to perform a second coating treatment on the surface of the thermal field thermal insulation member, and the coated thermal field thermal insulation member is placed in a sintering furnace to be sintered.
After sintering, a layer of uniform and compact SiC-ZrC ceramic composite coating can be obtained on the surface of the thermal field heat-insulating part.
In some embodiments of the present invention, in step S3, the solvent of the zirconium overcoat slurry may be toluene or xylene.
The purity of toluene or xylene was 99.9%.
In some embodiments of the invention, in step S4, the sintering is temperature programmed sintering from room temperature to 1000 ℃.
In some embodiments of the invention, the temperature programmed sintering is carried out by sequentially raising the temperature from room temperature to 120 ℃, 200 ℃, 350 ℃, 1000 ℃ and keeping the temperature.
In some embodiments of the invention, the temperature programmed sintering is programmed to: room temperature is 120 ℃ to 100min; keeping the temperature at 120 ℃ for 60min; 120-200 ℃ for-100 min; keeping the temperature at 200 ℃ for 120min; 200-350 deg.C-100 min; keeping the temperature at 350 ℃ for 60min;350 ℃ to (900 ℃ to-1000 ℃) to-220 min; preserving the heat for 120min at the temperature of 900-1000 ℃; the whole sintering process is in a nitrogen normal-pressure environment, and the temperature is naturally reduced after sintering. Wherein, the purity of the nitrogen is 99.99%.
In some embodiments of the present invention, in step S1, the thermal field insulator is a pretreated thermal field insulator.
In some embodiments of the invention, the pre-treatment comprises a curing treatment, a charring treatment, a high temperature treatment, and machining.
Specifically, the thermal field heat preservation piece with the size and the shape meeting the requirements can be prepared by adopting a carbon felt lamination method according to the shape and the size requirements of the required thermal field, the specific mode can be that the carbon felt and the carbon felt are laminated, resin is coated between layers for bonding, and finally the density is 0.2g/cm 3 Left and right sides whole thermal field heat preservation spare part structure.
The density of the carbon felt is 0.2g/cm 3 About, the thickness is generally 5mm/10mm specification, brush on phenolic resin between the carbon felt layer and the layer and bond, leave the machine and add the allowance when preparing, generally increase 30mm in the length and width direction, increase 10mm in the height direction, prepare the density and is 0.2g/cm 3 Left and right overall thermal field component structures. After the preparation is finished, in order to prevent deformation, the graphite plates can be pressed and placed into an oven together for curing treatment.
In some embodiments of the invention, the curing process may be performed by placing the integral thermal field component into a curing oven.
The curing program was set to: the temperature is between room temperature and 120 ℃, and the heating time is 120min; keeping the temperature at 120 ℃ for 120min; the temperature is increased to (240-260 ℃) at 120 ℃, and the temperature rise time is 160min; keeping the temperature for 300min at the temperature of 240-260 ℃.
In some embodiments of the invention, the carbonization process may be performed by placing the integrated thermal field component into a carbonization furnace.
The carbonization program is set as follows: the temperature is increased for 60min at room temperature to (240-260 ℃); (240 ℃ -260 ℃) to (700 ℃ -750 ℃), and the heating time is 260min; keeping the temperature for 180min at 700-750 ℃. The carbonization process is a nitrogen-protected micro-positive pressure environment, and substances such as waste liquid, tar and the like need to be discharged at any time in the carbonization process.
In some embodiments of the invention, the high temperature treatment process may be performed by placing the integrated thermal field component in a high temperature furnace.
The high temperature program was set to: the temperature is between room temperature and 800 ℃, and the heating time is 160min; the temperature is raised for 120min at 800-1200 ℃; the temperature is increased for 240min at 1200 ℃ to 1700 ℃ to 1800 ℃; (1700 ℃ to 1800 ℃) and keeping the temperature for 180min. And vacuumizing the whole environment.
And after the high-temperature treatment is finished, performing machining according to the drawing of the thermal field component to obtain the thermal field heat-insulating component.
The machining drawing paper considers the matching size of the thermal field component, simultaneously considers the thickness factor of the coating surface coating, and carries out machining amount confirmation according to the thickness of the coating of 1 mm-1.5 mm.
The preparation method can be understood that the SiC-ZrC ceramic composite coating with silicon and oxygen corrosion resistance is prepared on the surface of the thermal field heat-insulating part, so that the service life of the thermal field is prolonged. Meanwhile, the carbon-carbon lining added for preventing the erosion of the thermal field heat preservation piece and maintaining the crystal pulling environment of the whole single crystal growing furnace can be removed from the structure, thereby further saving the production cost.
The technical scheme of the invention is better understood by combining the specific embodiments.
In the examples and comparative examples, the zirconium-modified polymethylsilanes used were prepared by the following methods: slowly dripping 10% of tetrahydrofuran solution of zirconium tetrachloride into the solution of the polymethylsilane at the temperature of below 5 ℃ in a protective atmosphere, wherein the mass ratio of the added zirconium tetrachloride to the polymethylsilane is 1.5: controlling the reaction temperature within 0-5 ℃, stirring and reacting for a certain time, sequentially heating to normal temperature, 80 ℃ and 120 ℃, reacting, filtering, carrying out reduced pressure distillation on the filtrate, separating out the solvent, and taking the remaining viscous liquid as the zirconium modified polymethylsilane.
Examples
In this embodiment, a thermal field insulating member is prepared, and the structure is shown in fig. 1, and the detailed steps are as follows:
(1) Preparing a thermal field heat-insulating piece: according to the shape and size requirements of the required thermal field, the whole size is prepared by adopting a carbon felt lamination method, wherein the carbon felt and the carbon felt are laminated and layeredCoating phenolic resin between layers for bonding to obtain the product with density of 0.2g/cm 3 The left and right parts are of an integral thermal field component structure with the length, width, allowance and height of 30mm and 10 mm;
(2) And (2) curing the thermal field heat-insulating piece, namely putting the integral thermal field part obtained in the step (1) into a curing furnace for curing treatment, and setting a curing program as follows: room temperature is 120 ℃ to 120min; keeping the temperature at 120 ℃ for 120min;120 to-260 to-160 min; keeping the temperature at 260 ℃ for 300min;
(3) And (3) carbonizing treatment, namely putting the integral thermal field component obtained in the step (2) into a carbonizing furnace for carbonizing treatment, and setting a carbonizing program as follows: room temperature is 260 ℃ to 60min; 260-750 ℃ for-260 min; keeping the temperature at 750 ℃ for 180min; the carbonization process is a nitrogen-protected micro-positive pressure environment, and substances such as waste liquid tar and the like are discharged at any time in the carbonization process;
(4) High-temperature treatment: putting the integral thermal field component obtained in the step (3) into a high-temperature furnace for high-temperature treatment, and setting a high-temperature program as follows: room temperature is 800-160min; 800-1200-120 min; 1200-1750-240 min;1750 ℃ and keeping the temperature for 180min; vacuumizing environment in the whole process;
(5) Mechanically adding: after the high temperature is finished, paper processing is carried out according to the thermal field component drawing to obtain a thermal field heat preservation component, and the size of the part with a coating matched with the thermal field heat preservation component is additionally processed by 1.5mm;
(6) Preparing a priming coating slurry: the flake graphite powder is 400 meshes, and the mass of the flake graphite powder is as follows: waterborne epoxy =2:1 preparing a priming coating slurry, and fully and uniformly stirring;
(7) Priming coating: priming the thermal field heat-insulating piece, dipping the priming coating slurry on the surface of the thermal field by using a soft brush, and brushing a coating, wherein the thickness of the coating is controlled to be 0.5-1mm;
(8) Drying: drying for 3 hours in the air after finishing brushing;
(9) CVD deposition: and (3) putting the coated thermal field heat preservation part into a deposition furnace for 10 hours for deposition treatment, setting deposition parameters by taking a W2600 horizontal deposition furnace as a column as follows: n is a radical of 2 15L/Min, 20L/Min propane, 1050 ℃ and 10h sedimentation time;
(10) A layer of compact bottoming carbon coating can be formed on the surface of the thermal field heat-insulating part after CVD deposition, most of pores on the surface of the carbon felt are filled, and a good coating interface is provided for a subsequent SiC-ZrC outer layer coating;
(11) Preparing SiC-ZrC coating slurry: according to the mass ratio, zirconium modified polymethylsilane: siC: solvent =1:1.2:1, carrying out vacuum ball milling for 5 hours, wherein a solvent is dimethylbenzene;
(12) Then, performing secondary coating treatment on the surface of the thermal field heat-insulating piece by using the prepared SiC-ZrC coating slurry, wherein the thickness of the coating is controlled to be 0.5-1mm;
(13) And (3) putting the coated thermal field heat-insulating part into a sintering furnace for sintering, wherein the sintering procedure is set as follows: room temperature is 120 ℃ to 100min; keeping the temperature at 120 ℃ for 60min; 120-200 ℃ to-100 min; keeping the temperature at 200 ℃ for 120min; 200-350 deg.C-100 min; keeping the temperature at 350 ℃ for 60min; 350-1000 ℃ to 220min; keeping the temperature at 1000 ℃ for 120min; the whole sintering process is a nitrogen normal-pressure environment, and the temperature is naturally reduced after sintering.
(14) After sintering, a layer of uniform and compact SiC-ZrC ceramic composite coating can be obtained on the surface of the thermal field heat-insulating part.
Comparative example
The thermal field heat preservation piece is prepared according to the comparative example, the structure of the thermal field heat preservation piece is the same as that of the thermal field heat preservation piece prepared according to the embodiment, and the detailed steps are as follows:
(1) Preparing a thermal field heat-insulating piece: preparing the whole size by adopting a carbon felt lamination method according to the shape and size requirements of the required thermal field, wherein the carbon felt and the carbon felt are laminated, and the layers are coated with phenolic resin for bonding to prepare the carbon felt with the density of 0.2g/cm 3 The left and right parts are of an integral thermal field component structure with the length, width, allowance and height of 30mm and 10 mm;
(2) And (2) curing the thermal field heat-insulating piece, namely putting the integral thermal field part obtained in the step (1) into a curing furnace for curing treatment, and setting a curing program as follows: room temperature is 120 ℃ to 120min; keeping the temperature at 120 ℃ for 120min;120 to-260 to-160 min; keeping the temperature at 260 ℃ for 300min;
(3) And (3) carbonizing treatment, namely putting the integral thermal field component obtained in the step (2) into a carbonization furnace for carbonizing treatment, and setting a carbonizing program as follows: room temperature is 260 ℃ to 60min; 260-750 ℃ for-260 min; keeping the temperature at 750 ℃ for 180min; the carbonization process is a nitrogen-protected micro-positive pressure environment, and substances such as waste liquid tar and the like are discharged at any time in the carbonization process;
(4) High-temperature treatment: putting the integral thermal field component obtained in the step (3) into a high-temperature furnace for high-temperature treatment, and setting a high-temperature program as follows: room temperature is 800-160min; 800-1200-120 min; 1200-1750-240 min;1750 ℃ and keeping the temperature for 180min; vacuumizing environment in the whole process;
(5) Mechanically adding: after the high temperature is finished, the thermal field heat preservation part is obtained according to the thermal field part drawing and paper processing, and the size of the part with the coating matched with the thermal field heat preservation part is more processed by 1.5mm;
(6) Preparing a priming coating slurry: the flake graphite powder is 400 meshes, and the mass of the flake graphite powder is as follows: waterborne epoxy =2:1 preparing a priming coating slurry, and fully and uniformly stirring;
(7) Priming coating: priming the thermal field heat-insulating piece, dipping the priming coating slurry on the surface of the thermal field by using a soft brush, and brushing a coating, wherein the thickness of the coating is controlled to be 0.5-1mm;
(8) Drying: drying for 3 hours in air after finishing brushing;
(9) CVD deposition: and (3) putting the coated thermal field heat preservation part into a deposition furnace for 10 hours for deposition treatment, setting deposition parameters by taking a W2600 horizontal deposition furnace as a column as follows: n is a radical of hydrogen 2 15L/Min, 20L/Min propane, 1050 ℃ and 10h sedimentation time;
(10) A layer of compact bottoming carbon coating can be formed on the surface of the thermal field heat-insulating part after CVD deposition, most of pores on the surface of the carbon felt are filled, and a good coating interface is provided for a subsequent SiC-ZrC outer layer coating;
(11) Preparing the SiC-ZrC coating: preparing zirconium modified polymethylsilane into a xylene solution with the weight percent of 50;
(12) Then, performing secondary coating treatment on the surface of the thermal field heat-insulating piece by using the prepared SiC-ZrC coating;
(13) And (3) putting the coated thermal field heat preservation part into a sintering furnace for sintering, wherein the sintering procedure is set as follows: room temperature is 120 ℃ to 100min; keeping the temperature at 120 ℃ for 60min; 120-200 ℃ for-100 min; keeping the temperature at 200 ℃ for 120min; 200-350 ℃ for-100 min; keeping the temperature at 350 ℃ for 60min; 350-1000 ℃ to 220min; keeping the temperature at 1000 ℃ for 120min; the whole sintering process is in a nitrogen normal-pressure environment, and the temperature is naturally reduced after sintering.
(14) And obtaining an incompletely compact SiC-ZrC coating on the surface of the thermal field heat-insulating part after sintering, wherein cracks are generated on the surface of the coating, and part of the coating falls off.
In the embodiment, the SiC-ZrC coating slurry contains zirconium modified polymethylsilane and SiC, while in the comparative example, the SiC-ZrC coating is only a xylene solution of the zirconium modified polymethylsilane, but as the problems of small molecule volatilization and sintered ceramic shrinkage inevitably occur in the sintering process of the zirconium modified polymethylsilane, the SiC-ZrC coating prepared by a precursor conversion method has insufficient density and holes and cracks, therefore, siC powder needs to be added into the zirconium modified polymethylsilane with a certain concentration, and linear 0-shaped shrinkage of the sintered SiC-ZrC ceramic can be realized by adjusting the powder proportion, so that the completely compact SiC-ZrC coating is obtained on the surface of a thermal field. And SiC powder is not added in the comparative example, an incompletely compact SiC-ZrC coating is obtained on the surface of the thermal field heat-insulating part after sintering is finished, cracks are generated on the surface of the coating, and part of the coating falls off.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A preparation method of a composite ceramic coating of a thermal field heat-insulating part is characterized by comprising the following steps:
s1: mixing flake graphite powder and epoxy resin to prepare a primer coating slurry, and coating the primer coating slurry on the surface of a thermal field heat-insulating part;
s2: conveying the thermal field heat preservation piece processed in the step S1 into a deposition furnace for CVD deposition;
s3: mixing zirconium modified polymethyl silane, siC and a solvent to prepare outer layer coating slurry, and coating the outer layer coating slurry on the surface of the thermal field heat preservation piece treated in the step S2;
s4: and (4) sintering the thermal field heat preservation piece processed in the step S3.
2. The preparation method according to claim 1, wherein in step S1, the mass ratio of the crystalline flake graphite powder to the epoxy resin is 2 to 3.
3. The method according to claim 1, wherein the CVD deposition time in step S2 is 8-12 h.
4. The preparation method of claim 1, wherein in the step S3, the outer layer coating slurry is coated on the surface of the thermal field insulation piece treated in the step S2, and after coating, the thickness of the outer layer coating slurry is less than or equal to 1mm.
5. The production method according to claim 1, wherein in step S3, the mass ratio of the zirconium-modified polymethylsilane to the SiC to the solvent is 1.0 to 1.5.
6. The preparation method according to claim 5, wherein the preparation method of the zirconium-modified polymethylsilane comprises the following steps: and (2) dripping a tetrahydrofuran solution of zirconium tetrachloride into a solution of polymethylsilane in a protective atmosphere, heating for reaction, filtering, carrying out reduced pressure distillation on the filtrate, separating out the solvent, and obtaining the remaining viscous liquid, namely the zirconium-modified polymethylsilane.
7. The production method according to any one of claims 1 to 6, wherein in step S4, the sintering is temperature-programmed sintering from room temperature to 1000 ℃.
8. The method according to claim 7, wherein the temperature-programmed sintering is carried out by sequentially raising the temperature from room temperature to 120 ℃, 200 ℃, 350 ℃ and 1000 ℃ and maintaining the temperature.
9. The production method according to any one of claims 1 to 6, wherein in step S1, the thermal field insulator is a pretreated thermal field insulator.
10. The method of claim 9, wherein the pre-treatment comprises a curing treatment, a carbonization treatment, a high temperature treatment, and machining.
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