CN112759423A - Coating carbon-carbon composite material crucible and preparation method thereof - Google Patents

Coating carbon-carbon composite material crucible and preparation method thereof Download PDF

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CN112759423A
CN112759423A CN202011577293.1A CN202011577293A CN112759423A CN 112759423 A CN112759423 A CN 112759423A CN 202011577293 A CN202011577293 A CN 202011577293A CN 112759423 A CN112759423 A CN 112759423A
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crucible
carbon
carbon composite
composite material
coating
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CN112759423B (en
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肖天梁
沈益顺
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Hunan Shixin New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5035—Silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5049—Zinc or bismuth oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention discloses a coated carbon-carbon composite crucible and a preparation method thereof. The preparation method comprises the following steps: coating the coating liquid on the inner surface of the carbon-carbon composite crucible body, and performing high-temperature heat treatment to obtain a coated carbon-carbon composite crucible; the coating liquid consists of resin, fused quartz sand, silicon powder and an additive, wherein the resin comprises the following components in percentage by mass: fused silica sand: silicon powder: 100 parts of (20-50) parts of (10-30) parts of (2-8) additives; the additive is selected from Al2O3、ZnO、Li2O, BaO. The silicon carbide coating prepared by the invention can effectively improve the surface state of the crucible and avoid silicon vapor, silicon-containing gas and stone at high temperatureThe quartz crucible can corrode the carbon-carbon composite material crucible through reaction, so that the service life of the carbon-carbon composite material crucible is prolonged.

Description

Coating carbon-carbon composite material crucible and preparation method thereof
Technical Field
The invention belongs to the technical field of thermal field tools/components for monocrystalline silicon drawing furnaces, and particularly relates to a coated carbon-carbon composite crucible and a preparation method thereof.
Background
With the rapid development of monocrystalline silicon solar cells, the monocrystalline solar cells are reversed to super-polycrystalline solar cells, and occupy the leading position of the solar cell market (the market occupancy of the monocrystalline solar cells reaches more than 50%): the demand of the solar energy industry on monocrystalline silicon is pulled. The crucible is also developed rapidly as an important thermal field material for producing monocrystalline silicon (rod), namely a carbon-carbon composite material crucible.
At present, when a single crystal silicon furnace pulls a single crystal silicon rod, a quartz crucible containing polycrystalline silicon is placed in a carbon-carbon composite crucible. In the process of pulling the silicon single crystal rod, the temperature in the furnace is as high as about 1500 ℃, the quartz crucible becomes soft, and the force is supported by the carbon-carbon composite material crucible. Under the working condition, high-temperature silicon vapor, silicon-containing gas and silicon dioxide (main components of the quartz crucible) can react with the carbon-carbon composite material crucible, so that the carbon-carbon composite material crucible is corroded and even loses efficacy, and the service life of the carbon-carbon composite material crucible is seriously influenced.
How to effectively solve the problem that the carbon-carbon composite material is eroded under the working condition of pulling the monocrystalline silicon rod so as to prolong the service life of the carbon-carbon composite material crucible is a problem which needs to be solved urgently to further reduce the cost of the monocrystalline silicon solar cell.
The silicon dioxide/silicon coating is prepared on the carbon-carbon composite material crucible body, so that the erosion resistance of the carbon-carbon composite material crucible can be improved, and the service life of the carbon-carbon composite material crucible is effectively prolonged.
Patent CN 201220240145.5 discloses a preparation process of a carbon/carbon composite material crucible for a monocrystalline silicon furnace, which adopts a chemical reaction method, takes silicon dioxide and metallic silicon as raw materials, controls the mass ratio of the silicon dioxide and the metallic silicon, and generates a uniform silicon carbide coating on the surface of the carbon/carbon composite material crucible under a certain temperature condition and the protection of carrier gas, the preparation of the coating avoids the corrosion phenomenon of the crucible in monocrystalline silicon, improves the strength of the crucible and prolongs the service life of the crucible; patent CN 201310455254.8 discloses a composite coating carbon/carbon composite material crucible and a preparation method thereof, wherein a chemical vapor deposition process is adopted to generate a silicon carbide coating and a silicon nitride coating in situ reaction on the inner surface of the carbon/carbon composite material crucible, so that the corrosion of silicon-containing steam on the inner surface of the carbon/carbon crucible can be effectively inhibited. Patent CN 111848201A discloses a carbon/carbon crucible with a silicon carbide/silicon coating and a preparation method thereof, which adopts a plasma method to prepare the crucible with the silicon carbide/silicon coating on the inner surface of the crucible, thereby prolonging the service life of the crucible. The above patents have the disadvantages of high production cost and difficult control of the process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a coating carbon-carbon composite material crucible and a preparation method thereof. The invention prepares and brushes coating liquid containing silicon dioxide and silicon on the inner surface of the carbon-carbon composite material crucible, and then prepares the silicon carbide coating on the inner surface of the carbon-carbon composite material crucible through high-temperature heat treatment. The invention effectively improves the surface state of the crucible, and avoids the reaction erosion of silicon vapor, silicon-containing gas and a quartz crucible to the carbon-carbon composite material crucible at high temperature, thereby prolonging the service life of the carbon-carbon composite material crucible.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a coating carbon-carbon composite material crucible, which comprises the following steps: coating the coating liquid on the inner surface of the carbon-carbon composite crucible body, and performing high-temperature heat treatment to obtain the carbon-carbon composite crucible; the coating liquid consists of resin, fused quartz sand, silicon powder and an additive, wherein the mass ratio of the resin: fused silica sand: silicon powder: 100 parts of (20-50) parts of (10-30) parts of (2-8) additives; the additive is selected from Al2O3、ZnO、Li2O, BaO.
In the invention, coating liquid consisting of resin, fused quartz sand, silicon powder and additives is used as a silicon carbide precursor, and then the silicon carbide coating is obtained through high-temperature treatment. In the coating liquid, resin is used as a binder and a material carrier to ensure that the coating liquid containing silicon dioxide and silicon can penetrate into the pores on the surface of the crucible and stay on the surface of the crucible and in the pores on the surface; silicon and silicon dioxide are used as raw materials for preparing the silicon carbide coating, and the silicon dioxide is also used as an accelerator for preparing the silicon carbide, so that the excellent performance of the coating is ensured; the function of the additive is to effectively reduce the temperature of the subsequent heat treatment.
In the actual operation process, the fused quartz sand, the silicon powder and the additive are added into the resin and fully and uniformly mixed to obtain the coating liquid. The resin is a viscous liquid phase, so that the prepared coating liquid can be uniformly coated on the inner surface of the carbon-carbon composite material crucible body. The inventors have found that the addition of organic solvents, instead, results in a less effective coating.
In a preferred embodiment, the coating liquid comprises, by mass, resin: fused silica sand: silicon powder: the additives are 100 (30-40) and 15-25 (4-6).
With a coating solution in this preferred range, the performance of the final silicon carbide coating will be superior.
Preferably, the resin is furan resin, and the viscosity of the resin is not more than 350Pa.S, preferably not more than 200 Pa.S. The viscosity was measured at 60 ℃.
Too high a resin viscosity will affect the fluidity of the coating solution and, in turn, the uniformity of the final silicon carbide coating thickness.
In a preferred embodiment, the fused silica sand comprises: SiO 22The content of (B) is more than 99.9 wt%.
Preferably, the particle size of the fused quartz is 6.5-75 μm.
In the invention, the fused quartz sand can reduce the temperature of silicon carbide generated by silicon carbon reaction and improve the binding force between the silicon carbide coating and the crucible.
The inventors have found that it is critical to select fused silica, that the silicon carbide coatings produced using conventional quartz exhibit visually observable cracks in appearance, and that smooth, dense, crack-free coatings can only be achieved using fused silica, which has been surprisingly discovered by the inventors after extensive experimentation.
In a preferred scheme, the purity of the silicon powder is more than 99.5 wt%.
In a preferred scheme, the particle size of the silicon powder is 13-106 μm, and is preferably 50-90 μm. The inventor finds that the particle size of the silicon powder has certain influence on the coating performance and the preparation process, if the particle size is too large, the coating liquid cannot be well paved on the surface of a crucible and permeate into pores on the surface of the crucible, if the particle size is too small, the preparation of the coating liquid is difficult, and the activation energy of chemical reaction is sharply reduced, so that the performance of a silicon carbide coating prepared by subsequent heat treatment is abnormal.
In a preferred scheme, the particle size of the additive is 10-100 nm, and more preferably 40-80 nm. The addition of a proper amount of additives can reduce the heat treatment temperature so as to save the energy consumption for preparing the coating.
In the actual operation process, the brushing needs to be repeated for several times, on one hand, the uniformity can be further increased, and on the other hand, the thickness of the silicon carbide coating is enabled to be 100-1000 μm.
In the preferable scheme, the temperature of the high-temperature heat treatment is 1300-1650 ℃, the temperature is preferably 1400-1550 ℃, and the heat preservation time of the high-temperature heat treatment is 0.5-2 h.
In the invention, the high-temperature heat treatment process is very important, and the final coating is compact and has high purity and good bonding performance with the crucible body by performing the high-temperature heat treatment in the process within the range, so that the performance of the crucible is optimal.
At the heat treatment temperature, the silicon powder and the resin carbon carry out silicon-carbon reaction: c + Si ═ SiC, silicon carbide is produced, with the reaction: SiO 22The produced silicon continues to react with silicon and carbon to produce silicon carbide, which reacts with SiO2And (resin) carbon to perform silicon-carbon reaction to make SiO2The silicon in the silicon and the silicon powder generate the silicon carbide coating finally.
In the present invention, the inventors have unexpectedly found that the additive (Al)2O3、ZnO、Li2O and BaO) can effectively lower the heat treatment temperature and promote the formation of a dense silicon carbide coating.
Preferably, the temperature rise rate of the high-temperature heat treatment is less than 300 ℃/h, and more preferably less than 200 ℃/h.
In the invention, the temperature rise rate needs to be controlled within the slower speed range, the temperature rise rate is slowed down to be beneficial to the cross-linking polymerization of resin, and finally the silicon carbide coating with good performance is obtained, in the whole heat treatment temperature rise and heat preservation process, the absolute pressure in the furnace is controlled to be less than 800Pa by a vacuumizing mode, and reaction volatile matters are discharged.
In a preferable scheme, the thickness of the silicon carbide coating in the coating carbon-carbon composite material crucible is 100-1000 μm.
In a preferred scheme, the process for obtaining the carbon-carbon composite material crucible body comprises the following steps: the density is 0.25 to 0.65g/cm3The carbon fiber crucible preform is densified to a density of 1.3 to 1.7g/cm3(ii) a Machining, cleaning the surface, and drying for later use.
Further preferably, the densification is chemical vapor deposition densification and/or resin impregnation densification.
The invention also provides the coating carbon composite material crucible prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. the silicon carbide coating prepared by the invention has excellent performance: the bonding strength with the crucible body is high, and the coating thickness is uniform and compact.
2. The coating liquid of the invention has simple preparation, low heat treatment temperature and low comprehensive cost.
3. The silicon carbide coating prepared by the invention effectively avoids the corrosion of silicon vapor and silicon-containing gas at high temperature and the corrosion of a quartz crucible to a carbon-carbon composite material crucible, and greatly prolongs the service life of the carbon-carbon composite material crucible.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Preparing coating liquid
Adding 25g of each of 350g of fused quartz sand with the particle size of 10-70 mu m, 200g of silicon powder with the particle size of 50-90 mu m and additives of ZnO and BaO with the particle size of 40-80 nm into 1000g of furan resin liquid with the viscosity of 50Pa.S, and fully and uniformly mixing to obtain coating liquid; wherein, the purity of the fused quartz sand is more than 99.9 wt%, and the purity of the silicon powder is more than 99.5 wt%.
Coated crucible
The density is 0.50g/cm3The carbon fiber crucible preform is densified to a density of 1.40g/cm by CVD3(ii) a Machining, cleaning the surface, drying to obtain a carbon-carbon composite crucible body, brushing coating liquid on the inner surface of the carbon-carbon composite crucible body, heating to 1450 ℃ at a speed of 180 ℃/h in a vacuum environment (the absolute pressure in the furnace is less than 400Pa) for high-temperature heat treatment, and preserving heat for 1h to obtain the carbon-carbon composite crucible.
After the crucible is taken out of the furnace, the silicon carbide coating is uniformly and densely covered on the inner surface of the carbon-carbon composite material, the thickness of the coating is 800 microns, the crucible is used for drawing the monocrystalline silicon, the using frequency reaches 84 times, when the carbon-carbon composite material crucible without the coating is used for drawing the same monocrystalline silicon, the service life is only 30 times, and the service life of the crucible prepared in the example 1 is 2.8 times of that of the crucible without the coating.
Example 2
Preparing coating liquid
450g of fused quartz sand with the grain diameter of 10-70 mu m, 250g of silicon powder with the grain diameter of 50-90 mu m and additive Al with the grain diameter of 40-90 nm2O3Adding 30g of BaO and 1000g of furan resin liquid with the viscosity of 100Pa.S into the mixture, and fully and uniformly mixing the mixture to obtain coating liquid; wherein, the purity of the fused quartz sand is more than 99.9 wt%, and the purity of the silicon powder is more than 99.5 wt%.
Coated crucible
The density is 0.50g/cm3The carbon fiber crucible preform is densified to a density of 1.35g/cm by CVD3(ii) a Machining, cleaning the surface, drying to obtain a carbon-carbon composite crucible body, painting coating liquid on the inner surface of the carbon-carbon composite crucible body, heating to 1650 ℃ at the speed of 200 ℃/h in a vacuum environment (the absolute pressure in the furnace is less than 600Pa), carrying out high-temperature heat treatment, and preserving heat for 2h to obtain the carbon-carbon composite crucible.
After the crucible is taken out of the furnace, the silicon carbide coating is uniformly and compactly covered on the inner surface of the carbon-carbon composite material, the thickness of the coating is 750 mu m, the crucible is used for drawing monocrystalline silicon, and the service life of the crucible is 2.1 times of that of an uncoated crucible.
Example 3
Preparing coating liquid
300g of fused quartz sand with the particle size of 6.5-75 mu m, 150g of silicon powder with the particle size of 30-90 mu m and 40g of additive Al with the particle size of 10-80 nm2O3Adding the mixture into 1000g of furan resin liquid with the viscosity of 80Pa.S, and fully and uniformly mixing to obtain coating liquid; wherein, the purity of the fused quartz sand is more than 99.9 wt%, and the purity of the silicon powder is more than 99.5 wt%.
Coated crucible
The density is 0.50g/cm3The carbon fiber crucible preform is densified to a density of 1.65g/cm by CVD3(ii) a Machining, cleaning the surface, drying to obtain a carbon-carbon composite crucible body, painting coating liquid on the inner surface of the carbon-carbon composite crucible body, heating to 1300 ℃ at the speed of 100 ℃/h in a vacuum environment (the absolute pressure in the furnace is less than 600Pa) to perform high-temperature heat treatment, and preserving heat for 0.5h to obtain the carbon-carbon composite crucible.
After the crucible is taken out of the furnace, the silicon carbide coating is uniformly and densely covered on the inner surface of the carbon-carbon composite material, the thickness of the coating is 700 mu m, the crucible is used for drawing monocrystalline silicon, and the service life of the crucible is 2.0 times that of the uncoated crucible.
Example 4
Preparing coating liquid
Adding 400g of fused quartz sand with the particle size of 10-70 mu m, 200g of silicon powder with the particle size of 50-90 mu m, and 20g of additives ZnO and LiO with the particle size of 10-100 nm into 1000g of furan resin liquid with the viscosity of 350Pa.S, and fully and uniformly mixing to obtain coating liquid; wherein, the purity of the fused quartz sand is more than 99.9 wt%, and the purity of the silicon powder is more than 99.5 wt%.
Coated crucible
The density is 0.50g/cm3The carbon fiber crucible preform is densified to a density of 1.65g/cm by CVD3(ii) a Machining, surface cleaning, baking to obtain the crucible body, and coating the crucible body on the inner surface of the crucible bodyAnd (3) coating the coating liquid, heating to 1550 ℃ at the speed of 150 ℃/h in a vacuum environment (the absolute pressure in the furnace is less than 400Pa) for high-temperature heat treatment, and preserving heat for 1h to obtain the carbon-carbon composite material crucible.
After the crucible is taken out of the furnace, the silicon carbide coating is uniformly and densely covered on the inner surface of the carbon-carbon composite material, the thickness of the coating is 710 mu m, the crucible is used for drawing monocrystalline silicon, and the service life of the crucible is 2.2 times that of the uncoated crucible.
Example 5
Preparing coating liquid
380g of fused quartz sand with the particle size of 6.5-75 mu m, 240g of silicon powder with the particle size of 10-100 mu m and additives of ZnO and Li with the particle size of 10-90 nm2Adding 15g of O and BaO into 1000g of furan resin liquid with the viscosity of 90Pa.S, and fully and uniformly mixing to obtain coating liquid; wherein, the purity of the fused quartz sand is more than 99.9 wt%, and the purity of the silicon powder is more than 99.5 wt%.
Coated crucible
The density is 0.50g/cm3The carbon fiber crucible preform is densified to a density of 1.60g/cm by CVD3(ii) a Machining, cleaning the surface, drying to obtain a carbon-carbon composite crucible body, brushing coating liquid on the inner surface of the carbon-carbon composite crucible body, heating to 1400 ℃ at the speed of 300 ℃/h in a vacuum environment (the absolute pressure in the furnace is less than 400Pa), carrying out high-temperature heat treatment, and preserving heat for 1.5h to obtain the carbon-carbon composite crucible.
After the crucible is taken out of the furnace, the silicon carbide coating is uniformly and densely covered on the inner surface of the carbon-carbon composite material, the thickness of the coating is 620 mu m, the crucible is used for drawing monocrystalline silicon, and the service life of the crucible is 1.9 times that of an uncoated crucible.
Comparative example 1
The other conditions were the same as in example 1 except that ordinary quartz was added.
After the crucible is taken out of the furnace, the silicon carbide coating is uneven, the compactness is poor and cracks can be seen by naked eyes, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, and the service life of the crucible is about 0.9 time of that of the uncoated crucible.
Comparative example 2
The other conditions were the same as in example 1 except that the viscosity of the furan resin was 400 pa.s.
After the crucible is taken out of the furnace, the silicon carbide coating is uneven in thickness and general in compactness, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, and the service life of the crucible is 1.2 times that of an uncoated crucible.
Comparative example 3
The other conditions were the same as in example 1 except that no additive was added.
After the crucible is taken out of the furnace, the silicon carbide coating is uneven in thickness and poor in compactness, the silicon carbide coating is not covered on the part of the crucible, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, the phenomenon that the crucible body is damaged by the coating occurs, and the service life of the crucible is 0.8 times that of the uncoated crucible.
Comparative example 4
The other conditions were the same as in example 1 except that the particle size of the additive was 1 μm to 10 μm.
After the crucible is taken out of the furnace, the silicon carbide coating is relatively uniform in thickness and general in compactness, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, and the service life of the crucible is 1.2 times that of an uncoated crucible.
Comparative example 5
The other conditions were the same as in example 1 except that the high temperature heat treatment temperature was 1700 ℃.
After the crucible is taken out of the furnace, the uniformity of the silicon carbide coating is poor through detection, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, and the service life of the crucible is equivalent to that of an uncoated crucible.
Comparative example 6
The other conditions were the same as in example 1 except that the temperature rising rate was 350 ℃ C/h.
After the crucible is taken out of the furnace, the silicon carbide coating is discontinuous, the cracks are more visible to naked eyes, the compactness is poor, the crucible is used for drawing monocrystalline silicon, after the crucible is used for multiple times, the silicon carbide coating is easily separated from the crucible body, and the service life of the crucible is about 0.9 time of that of the uncoated crucible.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all modifications, alterations and equivalent structural changes made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of a coating carbon-carbon composite material crucible is characterized by comprising the following steps: coating liquid on the inner surface of a carbon-carbon composite crucible body, and performing high-temperature heat treatment to obtain a coated carbon-carbon composite crucible; the coating liquid consists of resin, fused quartz sand, silicon powder and an additive, wherein the mass ratio of the resin: fused silica sand: silicon powder: 100 parts of (20-50) parts of (10-30) parts of (2-8) additives; the additive is selected from Al2O3、ZnO、Li2O, BaO.
2. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the coating liquid comprises the following components in percentage by mass: fused silica sand: silicon powder: the additives are 100 (30-40) and 15-25 (4-6).
3. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the resin is furan resin, and the viscosity of the resin is not more than 350 Pa.S.
4. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: in the fused silica sand: SiO 22The content of (A) is more than 99.9 wt%; the particle size of the fused quartz is 6.5-75 μm.
5. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the purity of the silicon powder is more than 99.5 wt%, and the particle size of the silicon powder is 13-106 microns.
6. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the particle size of the additive is 10-100 nm.
7. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature heat treatment is 1300-1650 ℃, and the heat preservation time of the high-temperature heat treatment is 0.5-2 h;
the temperature rise speed of the high-temperature heat treatment is less than 300 ℃/h.
8. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the thickness of the silicon carbide coating in the coating carbon-carbon composite material crucible is 100-1000 mu m.
9. The method for preparing the crucible made of the coated carbon composite material according to claim 1, wherein the method comprises the following steps: the carbon-carbon composite material crucible body is obtained by the following steps: the density is 0.25 to 0.65g/cm3The carbon fiber crucible preform is densified to a density of 1.3 to 1.7g/cm3(ii) a Machining, then cleaning the surface, and drying for later use; the densification is chemical vapor deposition densification and/or resin impregnation densification.
10. The coated carbon composite crucible prepared by the preparation method according to any one of claims 1 to 9.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114368976A (en) * 2022-02-08 2022-04-19 中南大学 Quartz fiber reinforced carbon-silicon dioxide composite material crucible and preparation method thereof
CN114409423A (en) * 2022-01-25 2022-04-29 烟台凯泊复合材料科技有限公司 Preparation method of high-temperature-resistant light-weight alternate composite ceramic heat shield
CN114455963A (en) * 2021-12-30 2022-05-10 西安超码科技有限公司 Containing alpha-Al2O3Coated carbon/carbon-silicon carbide composite crucible
CN114455964A (en) * 2021-12-30 2022-05-10 西安超码科技有限公司 C/SiC composite material crucible containing alumina coating
CN114523734A (en) * 2022-01-25 2022-05-24 烟台凯泊复合材料科技有限公司 Preparation method of high-temperature-resistant light composite ceramic heat shield
CN115536418A (en) * 2022-10-12 2022-12-30 贵州省紫安新材料科技有限公司 Preparation method of C-SiC double-coating carbon/carbon composite material crucible

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928480A (en) * 2010-09-07 2010-12-29 武汉科技大学 Method for preparing magnesia carbon brick non-aluminum antioxidant coating
CN202643896U (en) * 2012-05-26 2013-01-02 保定顺天新材料股份有限公司 Crucible made of carbon/carbon composite material
CN104387093A (en) * 2014-10-13 2015-03-04 瑞泰科技股份有限公司 Flow controlling water gap for production of mineral wool from blast furnace slag and production process thereof
CN111825477A (en) * 2020-08-13 2020-10-27 中钢南京环境工程技术研究院有限公司 Preparation method of anti-oxidation silicon carbide kiln furniture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928480A (en) * 2010-09-07 2010-12-29 武汉科技大学 Method for preparing magnesia carbon brick non-aluminum antioxidant coating
CN202643896U (en) * 2012-05-26 2013-01-02 保定顺天新材料股份有限公司 Crucible made of carbon/carbon composite material
CN104387093A (en) * 2014-10-13 2015-03-04 瑞泰科技股份有限公司 Flow controlling water gap for production of mineral wool from blast furnace slag and production process thereof
CN111825477A (en) * 2020-08-13 2020-10-27 中钢南京环境工程技术研究院有限公司 Preparation method of anti-oxidation silicon carbide kiln furniture

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455963A (en) * 2021-12-30 2022-05-10 西安超码科技有限公司 Containing alpha-Al2O3Coated carbon/carbon-silicon carbide composite crucible
CN114455964A (en) * 2021-12-30 2022-05-10 西安超码科技有限公司 C/SiC composite material crucible containing alumina coating
CN114455964B (en) * 2021-12-30 2023-09-05 西安超码科技有限公司 C/SiC composite material crucible containing alumina coating
CN114409423A (en) * 2022-01-25 2022-04-29 烟台凯泊复合材料科技有限公司 Preparation method of high-temperature-resistant light-weight alternate composite ceramic heat shield
CN114523734A (en) * 2022-01-25 2022-05-24 烟台凯泊复合材料科技有限公司 Preparation method of high-temperature-resistant light composite ceramic heat shield
CN114368976A (en) * 2022-02-08 2022-04-19 中南大学 Quartz fiber reinforced carbon-silicon dioxide composite material crucible and preparation method thereof
CN115536418A (en) * 2022-10-12 2022-12-30 贵州省紫安新材料科技有限公司 Preparation method of C-SiC double-coating carbon/carbon composite material crucible

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