CN114853507B - Composite carbon material and preparation method and application thereof - Google Patents
Composite carbon material and preparation method and application thereof Download PDFInfo
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- CN114853507B CN114853507B CN202210786090.6A CN202210786090A CN114853507B CN 114853507 B CN114853507 B CN 114853507B CN 202210786090 A CN202210786090 A CN 202210786090A CN 114853507 B CN114853507 B CN 114853507B
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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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate
Abstract
The invention discloses a composite carbon material and a preparation method and application thereof, the composite carbon material can be used for manufacturing a tray of MOCVD equipment, and comprises a carbon substrate and a composite coating arranged on the surface of the carbon substrate, wherein the composite coating comprises a silicon carbide composite layer, a silicon carbide-tantalum carbide composite layer and a tantalum carbide layer which are sequentially overlapped from inside to outside, and the preparation method comprises the following steps: (1) Preparing a silicon carbide nanowire layer in situ on a carbon substrate, and depositing silicon carbide after the preparation is finished to form a silicon carbide composite layer; (2) Depositing a silicon carbide-tantalum carbide composite layer on the surface of the silicon carbide composite layer; (3) And depositing a tantalum carbide layer on the surface of the silicon carbide-tantalum carbide composite layer. The invention improves the use stability of the carbon substrate, widens the application range and the application scene, solves the problem of thermal mismatch, improves the bonding strength of the coating and prolongs the service life; and the production period and the production cost are effectively reduced, and large-scale industrial production can be effectively realized.
Description
Technical Field
The invention relates to the technical field of carbon materials and carbon material coatings, in particular to a composite carbon material and a preparation method and application thereof.
Background
The third generation semiconductor, namely a wide bandgap semiconductor, is represented by silicon carbide and gallium nitride, has high frequency, high efficiency, high power, high voltage resistance, high temperature resistance, strong radiation resistance and other superior performances, and is a key core material and an electronic component for supporting independent innovation development and transformation upgrading of industries such as new generation mobile communication, new energy automobiles, high-speed rail trains, energy internet and the like. And secondly, the inherent characteristics of the third-generation semiconductor power chip and the device determine the electric energy efficient conversion advantages of the third-generation semiconductor power chip and the device in the fields of realization of new energy power generation such as photovoltaic and wind power, direct-current extra-high voltage transmission, electric traffic such as new energy automobiles, industrial power supplies, civil household appliances and the like. In addition, in the land, sea, air and air electric transportation represented by new energy vehicles and the emerging industries represented by intelligent robots, unmanned planes and numerical control machines, a third-generation power semiconductor with high frequency, high efficiency and temperature resistance is urgently needed.
However, for the requirements of the third-generation power semiconductor device (two major material systems of silicon carbide and gallium nitride), the autonomous and controllable development of the third-generation semiconductor industry chain is accelerated, the mass production of high-performance 6-inch and 8-inch silicon carbide single crystal substrates, epitaxial materials and power devices thereof is realized, and the mass production of 6-inch and 8-inch silicon-based gallium nitride epitaxial materials and power devices thereof is one of the core works of the third-generation semiconductor industry at present. In addition, in order to make wide-band gap power devices widely available, the production costs thereof must be greatly reduced, especially in the formation of an epitaxyOn the one hand (epitaxy cost), this accounts for almost half of the production cost of an epitaxial wafer (monocrystalline substrate with epitaxial layer). The CVD-SiC or MOCVD-GaN epitaxial growth conditions are more corrosive than conventional CVD-Si process conditions. And the CVD-SiC epitaxial growth gas system is H 2 -SiCl 4 -C 3 H 8 Nitrogen, ammonia, etc. and the epitaxial growth temperature is up to 1500-1700 deg.c. When a common carbon material is exposed to a reducing gas atmosphere such as nitrogen or ammonia, the common carbon material is deteriorated or damaged due to a reaction with the reducing gas, and thus a single carbon material cannot meet the demand. However, the main problems faced by SiC-coated graphite trays are: the performance stability of SiC ceramic in a service environment at a higher temperature (the preparation temperature of a third-generation semiconductor material is more than 1500 ℃) is poor, and SiC begins to be slowly decomposed at the temperature of more than 1200 ℃, so that the coating is difficult to be reliably used for a long time in such a harsh environment, and therefore, the current single SiC coating graphite base cannot meet the preparation requirement of a new-generation semiconductor.
At present, the ultrahigh-temperature ceramic (ZrC, hfC, taC and NbC) has the advantages of excellent high-temperature stability, high strength, corrosion resistance and good chemical stability, and the melting points of the ultrahigh-temperature ceramic are higher than 3000 ℃, so that the ultrahigh-temperature ceramic coating graphite tray and the ultrahigh-temperature ceramic coating graphite heater have superiority and irreplaceability in the CV (constant temperature plasma) or MOCVD (metal organic chemical vapor deposition) process of wide band gap semiconductors. Although the ultrahigh-temperature ceramic has excellent chemical stability and mechanical strength under extreme environments such as high temperature, acid-base corrosion and the like, the coefficients of thermal expansion of the ultrahigh-temperature ceramic ZrC, hfC, taC, nbC and the like are respectively 6.7 multiplied by 10 -6 C -1 、6.73×10 -6 C -1 、8.3×10 -6 C -1 、6.65×10 -6 C -1 The coefficient of thermal expansion is far larger than that of graphite material (the coefficient of thermal expansion is 4.0 multiplied by 10) -6 C -1 ) Under the high-temperature and acid-base corrosion environment, the problems of coating cracking and coating peeling failure under high-speed rotation caused by the mismatching factors of the thermal expansion coefficients of the ultrahigh-temperature ceramic coating and the graphite material are difficult to avoid, and the problems finally influence the service performance stability and the service life of the coating. Thereby stabilizing the ultra-high temperature ceramics with excellent self performanceThe coating is excellently applied to core consumables of a third-generation semiconductor industry chain, supports the steady and rapid development of the third-generation semiconductor industry, and solves the problem of thermal mismatch between the coating and the matrix graphite, which becomes a critical problem to be solved urgently at present.
Disclosure of Invention
The invention provides a composite carbon material and a preparation method and application thereof, which are used for solving the technical problems that the prior carbon material has poor stability in a high-temperature environment, a silicon carbide coating is easy to decompose, and the thermal expansion coefficient of the prior ultra-high temperature ceramic material coating is not matched with that of the carbon material, so that the coating is easy to fall off.
In order to solve the technical problems, the invention adopts the following technical scheme:
the composite carbon material comprises a carbon substrate and a composite coating arranged on the surface of the carbon substrate, wherein the composite coating comprises a silicon carbide composite layer, a silicon carbide-tantalum carbide composite layer and a tantalum carbide layer which are sequentially overlapped from inside to outside.
The design idea of the technical scheme is that on one hand, the silicon carbide-tantalum carbide composite layer and the tantalum carbide layer are added outside the silicon carbide coating, so that the problem that a single silicon carbide layer is difficult to meet the use requirement under the ultrahigh-temperature service working condition is solved, the use stability of the carbon substrate is improved, and the application range and the application scene of the composite carbon material are widened; on the other hand, the silicon carbide composite layer, the silicon carbide-tantalum carbide composite layer and the tantalum carbide layer are in a sequential transition relationship to form the integral coating, so that the thermal expansion coefficients of the layers are kept relatively consistent.
As a further preferable mode of the above technical solution, the silicon carbide composite layer includes silicon carbide nanowires and a silicon carbide layer covering the surface of the carbon substrate, and the silicon carbide nanowires extend into the carbon substrate and the silicon carbide layer. According to the preferred scheme, the carbon nanowires are distributed in the silicon carbide layer and the carbon substrate, the carbon substrate and the coating are anchored and connected through the silicon carbide nanowires, the bonding strength between the silicon carbide composite layer and the carbon substrate is improved, the bonding strength between the coating and the carbon substrate is improved from another dimension, and the condition that the coating is peeled off and fails is avoided.
Preferably, the thickness of the silicon carbide layer is 20 to 30 μm, and the distribution thickness of the silicon carbide nanowires in the silicon carbide layer is 10 to 20 μm. Silicon carbide layers and nanowire layers within the above thickness ranges have the best carbon substrate, coating bond strength, and thermal stability.
As a further preferable mode of the above technical means, the concentration of silicon carbide in the silicon carbide-tantalum carbide composite layer decreases from the inside to the outside in this order. This preferred scheme uses the compound gradient coating structure of the carborundum ceramic that the starting point outwards grows and the tantalum carbide ceramic through accurate control for carborundum content decreases progressively in proper order, and tantalum carbide content increases progressively in proper order, thereby realizes having the transitional coupling effect between the graphite base body of high thermal expansion coefficient's tantalum carbide ceramic and low thermal expansion coefficient, makes the two produce good heat matching, has further avoided the coating to appear the circumstances of peeling off the inefficacy.
As a further preferable mode of the above technical solution, the silicon carbide-tantalum carbide composite layer includes four layers having different silicon carbide concentrations, and the molar ratios of silicon carbide to tantalum carbide in each layer from the inside to the outside are (7~8): (2~3), 5: (4~6), (3~4): (6~7) and (1~2): (8~9) and the thickness of each layer is 6 to 15 μm.
Preferably, the tantalum carbide layer is a nano tantalum carbide layer with a thickness of 6 to 15 μm.
Based on the same technical concept, the invention also provides a preparation method of the composite carbon material, which comprises the following steps:
(1) Preparing a silicon carbide nanowire layer in situ on the carbon substrate, and depositing silicon carbide after the preparation is finished to form a silicon carbide composite layer;
(2) Depositing a silicon carbide-tantalum carbide composite layer on the surface of the silicon carbide composite layer by adopting a mixed raw material of silicon carbide and tantalum carbide;
(3) And depositing on the surface of the silicon carbide-tantalum carbide composite layer to form a tantalum carbide layer, thus obtaining the composite carbon material.
As a further preferred embodiment of the above technical solution, in step (1), the in-situ preparation of the silicon carbide nanowire layer on the carbon substrate is realized by using a pressure infiltration method and a high-temperature treatment, and the specific operations include: uniformly mixing the silicon carbide nanowire layer with the liquid paraffin to obtain mixed slurry, putting the mixed slurry and the carbon substrate into a vacuum pressure kettle for pressure impregnation, and then carrying out high-temperature treatment on the carbon substrate subjected to the pressure impregnation to finish the in-situ preparation of the silicon carbide nanowire layer. In the prior art, when the silicon carbide nanowire is prepared, a metal catalyst layer or an oxide catalyst layer is formed in advance, and the silicon carbide nanowire is reacted and separated out by melting and covering gas-phase silicon and carbon through a catalyst. The method can not avoid residual catalyst impurity phase, which affects the purity of the coating. The preparation method of the in-situ silicon carbide nanowire adopted by the invention does not involve the participation of a metal catalyst, effectively avoids the impurity source and impurity removal process of a finished product, has lower preparation temperature of the silicon carbide nanowire, does not need specific equipment, can be carried out in one equipment with a coating in sequence, has lower preparation cost, and has better connecting effect on the coating and a carbon substrate because the silicon carbide nanowire is directly grown in the pores of the carbon substrate.
In the above aspect, it is further preferable that, when the carbon base material is pressure-impregnated in step (1), the impregnation pressure is 0.8 to 1.2mpa, and the impregnation time is 1 to 3h.
As a further optimization of the technical scheme, when the carbon substrate after pressure impregnation is subjected to high-temperature treatment, the treatment temperature is 1200-1400 ℃, the treatment time is 1-3h, and vacuum is kept in the treatment process.
Preferably, when the silicon carbide is deposited in the step (1), the deposition temperature is 1000 to 1200 ℃, the deposition time is 5 to 10 hours, and the vacuum is kept in the deposition process.
As a further preferred aspect of the above technical solution, in the step (2), an electrophoretic deposition process and a sintering process are used to prepare the silicon carbide-tantalum carbide composite layer, and the electrophoretic deposition process specifically includes: preparing mixed powder of silicon carbide and tantalum carbide, adding a solvent and an iodine simple substance into the mixed powder, and uniformly mixing to obtain a suspension; and placing the carbon substrate with the silicon carbide composite layer formed in the suspension, taking the carbon substrate with the silicon carbide composite layer formed as a cathode and a graphite electrode as an anode for electrophoretic deposition, and sintering the carbon substrate after the electrophoretic deposition is finished, so as to finish the preparation of the silicon carbide-tantalum carbide composite layer. The inventor researches and discovers that in the prior art, a chemical vapor deposition method of chemical reaction is generally adopted to prepare the silicon carbide-tantalum carbide coating, and in the method, the sequence of the silicon gas source and the tantalum gas source reacting on the surface layer of the substrate to form carbide is limited by the activation energy of the reaction, so that the sequence of the reaction and the generation of new phases is influenced, and the uniformity of phase distribution is influenced; the uniformity of phase distribution in the coating can be influenced by the nonuniformity of silicon and tantalum atmospheres in the hearth; the flow field and the temperature field in the hearth can influence the uniformity and the thickness controllability of the coating. According to the method, a silicon carbide-tantalum carbide composite layer is prepared by a physical electrophoretic deposition method, silicon carbide and tantalum carbide powder are physically adsorbed on the surface layer of a substrate, and the adsorption and coating rates are the same, so that all phases in the coating are uniform and controllable; the thickness of the coating can be accurately controlled by accurately controlling the deposition time; the preparation time of the coating is short, and the cost is low.
As a further preferable mode of the above technical solution, the mixed powder of silicon carbide and tantalum carbide includes four powders having different silicon carbide concentrations, and four groups of suspensions are formed, and the molar ratios of silicon carbide and tantalum carbide in the first to fourth groups of suspensions are (7~8): (2~3), 5: (4~6), (3~4): (6~7) and (1~2): (8~9), and performing electrophoretic deposition on the carbon substrate after the silicon carbide composite layer is formed in the first to fourth groups of suspensions in sequence. The content of the coating phase can be effectively controlled by quantitatively changing the content of the silicon carbide and the tantalum carbide in the slurry, so that the concentration gradient coating is formed.
Preferably, when the carbon substrate with the silicon carbide composite layer formed is placed in a suspension for electrophoretic deposition, the temperature of the suspension is 80-100 ℃, and the single deposition time is 1-3 min.
Preferably, when the solvent and the iodine simple substance are added into the mixed powder, the mixture is mixed by ultrasonic and electromagnetic stirring, wherein the ultrasonic power is 1000 to 1500W, the ultrasonic time is 20 to 30min, the electromagnetic stirring speed is 300 to 450r/min, and the electromagnetic stirring time is 50 to 100min.
Preferably, when the carbon substrate after the electrophoretic deposition is sintered, the sintering temperature is 1500 to 1600 ℃, the sintering time is 1 to 2h, and an inert atmosphere is kept in the sintering process.
Preferably, the tantalum carbide layer is prepared in the step (3) by a chemical vapor deposition process, wherein the deposition temperature is 1100-1700 ℃, and the deposition time is 5-7 h.
As a further preferred aspect of the above technical solution, when the tantalum carbide layer is prepared by chemical vapor deposition, the sintering and the sintering of the electrophoretic deposition layer may be performed in the same equipment and in sequence. The requirement on equipment is low, the period is effectively reduced, and the compactness of the tantalum carbide layer and the bonding strength of the tantalum carbide layer and the base material can be ensured under the condition of effectively ensuring the gradient characteristic.
Based on the same technical concept, the invention also provides an application of the composite carbon material or the composite carbon material prepared by the preparation method, and the composite carbon material is applied to manufacturing of a tray of MOCVD equipment.
Compared with the prior art, the invention has the advantages that:
(1) The composite carbon material improves the use stability of the carbon substrate, widens the application range and application scene of the composite carbon material, solves the problem of thermal mismatch between the coating and the carbon substrate and between the coating and the coating from multiple aspects, improves the bonding strength between the coating and the carbon substrate and between the coating, avoids the condition of peeling failure of the coating, promotes each coating to have an optimal mechanical property matching degree through the precise design and preparation of parameters such as the structure, the composition, the thickness and the like of each coating, fully plays the role of the coating to realize the optimal performance of the coating, and improves the service life of the composite carbon material to nearly ten times of the prior art through the mutual synergistic effect between the coatings;
(2) The preparation method of the composite carbon material solves the problem that the service life of the coating is not prolonged in the process of preparing the carbon substrate coating by the conventional method, avoids introducing impurities, simplifies the process flow, effectively reduces the production period and the production cost, improves the bonding strength among the carbon substrate, the coating and the coating from multiple aspects, and can effectively realize large-scale industrial production.
Drawings
Fig. 1 is a schematic structural view of a composite carbon material of example 1.
Illustration of the drawings:
1. a graphite substrate; 2. a silicon carbide nanowire; 3. a silicon carbide layer; 4. a first silicon carbide-tantalum carbide composite layer; 5. a second silicon carbide-tantalum carbide composite layer; 6. a third silicon carbide-tantalum carbide composite layer; 7. a fourth silicon carbide-tantalum carbide composite layer; 8. a tantalum carbide layer.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
as shown in FIG. 1, the composite carbon material of the present example includes a carbon substrate and a composite coating layer disposed on the surface of the carbon substrate, and the carbon substrate is selected to have a density of 1.8g/cm 3 The graphite coating comprises a graphite substrate 1 with the graphite purity of 5ppm, and a composite coating sequentially comprises a silicon carbide composite layer, a first silicon carbide-tantalum carbide composite layer 4, a second silicon carbide-tantalum carbide composite layer 5, a third silicon carbide-tantalum carbide composite layer 6, a fourth silicon carbide-tantalum carbide composite layer 7 and a tantalum carbide layer 8 from inside to outside; the silicon carbide composite layer comprises a silicon carbide layer 3 and silicon carbide nanowires 2 dispersed in the silicon carbide layer 3 and the graphite substrate 1, the silicon carbide nanowires 2 extend into the graphite substrate 1 and the silicon carbide layer 3, the thickness of the silicon carbide layer 3 is 20 micrometers, and the distribution thickness of the silicon carbide nanowires 2 in the silicon carbide layer 3 is 10 micrometers; the first silicon carbide-tantalum carbide composite layer 4 has a thickness of 6 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 8:2, the second silicon carbide-tantalum carbide composite layer 5 has a thickness of 6 μm, of which silicon carbide and tantalum carbideThe molar ratio is 6:4; the third silicon carbide-tantalum carbide composite layer 6 has a thickness of 6 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 4:6; the fourth silicon carbide-tantalum carbide composite layer 7 has a thickness of 6 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 2:8; the tantalum carbide layer 8 has a thickness of 6 μm.
The preparation method of the composite carbon material of the embodiment comprises the following steps:
(1) Selecting the material with the density of 1.8g/cm 3 The graphite material with the graphite purity of 5ppm is a carbon substrate;
(2) Processing the graphite substrate 1 into a round tray with the diameter of 380mm according to the model requirement of MOCVD equipment, then putting the round tray into deionized water for ultrasonic cleaning for 30 min/time, replacing the deionized water for cleaning again after cleaning, circularly performing ultrasonic cleaning for 4 times, and putting the round tray into a drying oven with the temperature of 200 ℃ for drying treatment, wherein the drying time is 10h;
(3) And (3) infiltrating the mixed liquid of the liquid paraffin and the nano silicon powder into the surface pores of the graphite substrate 1 by adopting a pressure infiltration method:
mixing the nano silicon powder and the liquid paraffin by adopting an electric stirrer, wherein the volume ratio of the nano silicon powder to the liquid paraffin is 1:2, stirring for 3 hours to obtain mixed slurry for later use; adopting a vacuum pressure kettle injection method (the selected vacuum pressure kettle injection device is a self-designed specific device, the size of a pressure kettle hearth is not too large, the diameter of the pressure kettle hearth is similar to that of a 380mm graphite tray for MOCVD, and the diameter of the pressure kettle hearth is 1cm larger than that of the graphite tray), and repeatedly injecting the mixed slurry in batches for pressure infiltration; when pressure infiltration is carried out in the kettle, the infiltration pressure is 1.2MPa, the infiltration time is 1h, the graphite base material 1 is taken out for standby after the infiltration is completed, and the mass is increased by 50g after the infiltration;
(4) Placing the graphite substrate 1 infiltrated with the nano silicon powder and the liquid paraffin into a chemical vapor deposition furnace, carrying out high-temperature heat treatment to form a silicon carbide nanowire layer, and then forming a silicon carbide layer 3 on the silicon carbide nanowire layer by adopting a chemical vapor deposition method; wherein the preparation temperature of the silicon carbide nanowire layer is 1200 ℃, the preparation time is 1h, and the reaction environment is in a vacuum state; the thickness of the formed silicon carbide nanowire layer was 10 μm (the thickness from the surface layer of the graphite substrate 1 to the silicon carbide nanowire layer); the chemical vapor deposition silicon carbide layer 3 belongs to the densification process of a silicon carbide nanowire layer, in the preparation process, a chemical vapor deposition method is adopted to deposit a silicon carbide phase in gaps of the silicon carbide nanowire layer and on a graphite surface layer, the deposition temperature is 1200 ℃, the deposition time is 5 hours, the deposition state is a vacuum state, and finally the thickness of the silicon carbide layer 3 is 20 microns;
(5) Forming the silicon carbide nanoparticle reinforced tantalum carbide gradient coating by adopting an electrophoretic deposition process:
preparing four types of powder according to a specific mass ratio: the molar ratio of the first powder silicon carbide nano powder (with the grain diameter of 50nm and the purity of 99.99%) to the tantalum carbide powder (with the grain diameter of 50nm and the purity of 99.99%) is 8:2; the mol ratio of the second powder silicon carbide to the tantalum carbide is 6:4; the molar ratio of the third powder silicon carbide to the tantalum carbide is 4:6, the mol ratio of the fourth powder silicon carbide to the tantalum carbide is 2:8; adding isopropanol (purity 99.99%) into the four types of powder, and performing ultrasonic oscillation (ultrasonic power is 1000W, 30min) and electromagnetic stirring (electromagnetic stirring speed is 350r/min,100 min) to obtain four types of suspension; placing the suspension in a hydrothermal kettle suitable for electrophoretic deposition of a graphite substrate 1, then adding iodine (the purity of the iodine is 99.9 percent, and the concentration is 5 g/L), obtaining four types of suspensions with sequentially reduced silicon carbide concentration by adopting ultrasound (the ultrasonic power is 1000W, 30min) and electromagnetic stirring (the electromagnetic stirring speed is 450r/min, and 100 min), then placing the graphite substrate 1 in the hydrothermal kettle in sequence from high to low according to the silicon carbide concentration, respectively taking a graphite base as a cathode and a graphite electrode as an anode to carry out electrophoretic deposition, wherein the electromagnetic stirring speed is controlled at 350r/min, the hydrothermal temperature is 100 ℃, and the deposition time is respectively 1min in each time in the electrophoretic deposition process; after deposition, placing the graphite substrate 1 in a chemical vapor deposition furnace for sintering, wherein the sintering temperature is 1600 ℃, the sintering atmosphere is argon protective gas, and the sintering time is 1h, so as to obtain the graphite substrate 1 covered with a silicon carbide composite layer and a silicon carbide-tantalum carbide composite layer;
(6) And (3) forming the high-purity nanoscale dense tantalum carbide layer 8 on the graphite substrate 1 obtained in the step (5) by adopting a chemical vapor deposition process, wherein gaseous tantalum chloride is used as a tantalum source material in the deposition process, the deposition temperature is 1700 ℃, the deposition time is 5 hours, and the deposition thickness of the tantalum carbide layer 8 is 6 microns, so that the composite carbon material of the embodiment is obtained, and the carbon material can be used as a 380mm graphite tray for MOCVD. The coating ash was 3ppm.
The composite carbon material of the embodiment was subjected to corrosion resistance testing, specifically, the composite carbon material was placed in a 100% hydrofluoric acid and nitric acid mixed melt for testing, and the results showed that after 300h of corrosion, the mass of the sample was reduced by 0.09g/m 2 。
The composite carbon material of the present example was subjected to mechanical property testing, and the joint strength of a 10 × 10 × 10mm coating sample was tested by a tensile method, and the test result showed that the joint strength of the coating and the substrate was 55MPa.
Example 2:
the composite carbon material of this example includes a carbon substrate and a composite coating layer disposed on the surface of the carbon substrate, wherein the carbon substrate has a density of 1.8g/cm 3 The graphite coating comprises a graphite substrate 1 with the graphite purity of 5ppm, and a composite coating sequentially comprises a silicon carbide composite layer, a first silicon carbide-tantalum carbide composite layer 4, a second silicon carbide-tantalum carbide composite layer 5, a third silicon carbide-tantalum carbide composite layer 6, a fourth silicon carbide-tantalum carbide composite layer 7 and a tantalum carbide layer 8 from inside to outside; the silicon carbide composite layer comprises a silicon carbide layer 3 and silicon carbide nanowires 2 dispersed in the silicon carbide layer 3 and the graphite substrate 1, the silicon carbide nanowires 2 extend into the graphite substrate 1 and the silicon carbide layer 3, the thickness of the silicon carbide layer 3 is 20 micrometers, and the distribution thickness of the silicon carbide nanowires 2 in the silicon carbide layer 3 is 15 micrometers; the first silicon carbide-tantalum carbide composite layer 4 has a thickness of 10 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 8: and 2, the thickness of the second silicon carbide-tantalum carbide composite layer 5 is 10 microns, wherein the molar ratio of silicon carbide to tantalum carbide is 6:4; the third silicon carbide-tantalum carbide composite layer 6 has a thickness of 10 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 4:6; the fourth silicon carbide-tantalum carbide composite layer 7 has a thickness of 10 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 2:8; the thickness of the tantalum carbide layer 8 was 10 μm.
The preparation method of the composite carbon material of the embodiment comprises the following steps:
(1) Selecting the material with the density of 1.8g/cm 3 The graphite material with the graphite purity of 5ppm is a carbon substrate;
(2) Processing the graphite substrate 1 into a round tray with the diameter of 380mm according to the model requirement of MOCVD equipment, then putting the round tray into deionized water for ultrasonic cleaning for 30 min/time, replacing the deionized water for cleaning again after cleaning, circularly performing ultrasonic cleaning for 4 times, and putting the round tray into a 200 ℃ drying oven for drying for 10 hours;
(3) And (3) infiltrating the mixed liquid of the liquid paraffin and the nano silicon powder into the surface pores of the graphite substrate 1 by adopting a pressure infiltration method:
mixing the nano silicon powder and the liquid paraffin by adopting an electric stirrer, wherein the volume ratio of the nano silicon powder to the liquid paraffin is 1:2, stirring for 3 hours to obtain mixed slurry for later use; adopting a vacuum pressure kettle injection method (the selected vacuum pressure kettle injection device is a self-designed specific device, the size of a pressure kettle hearth is not too large, the diameter of the pressure kettle hearth is similar to that of a 380mm graphite tray for MOCVD, and the diameter of the pressure kettle hearth is 1cm larger than that of the graphite tray), and repeatedly injecting the mixed slurry in batches for pressure infiltration; when pressure infiltration is carried out in the kettle, the infiltration pressure is 1.2MPa, the infiltration time is 1h, the graphite substrate 1 is taken out for standby after the complete infiltration, and the mass is increased by 50g after the infiltration;
(4) Putting the graphite substrate 1 infiltrated with the nano silicon powder and the liquid paraffin into a chemical vapor deposition furnace, carrying out high-temperature heat treatment to form a silicon carbide nanowire layer, and then forming a silicon carbide layer 3 on the silicon carbide nanowire layer by adopting a chemical vapor deposition method; wherein the preparation temperature of the silicon carbide nanowire layer is 1300 ℃, the preparation time is 2 hours, and the reaction environment is in a vacuum state; the thickness of the formed silicon carbide nanowire layer was 15 μm (the thickness from the surface layer of the graphite substrate 1 to the silicon carbide nanowire layer); the chemical vapor deposition silicon carbide layer 3 belongs to the densification process of a silicon carbide nanowire layer, in the preparation process, a chemical vapor deposition method is adopted to deposit a silicon carbide phase in gaps of the silicon carbide nanowire layer and on a graphite surface layer, the deposition temperature is 1200 ℃, the deposition time is 5 hours, the deposition state is a vacuum state, and finally the thickness of the silicon carbide layer 3 is 20 micrometers;
(5) Forming the silicon carbide nanoparticle reinforced tantalum carbide gradient coating by adopting an electrophoretic deposition process:
preparing four types of powder according to a specific mass ratio: the mol ratio of the first powder silicon carbide nano powder (with the grain diameter of 50nm and the purity of 99.99%) to the tantalum carbide powder (with the grain diameter of 50nm and the purity of 99.99%) is 8:2; the mol ratio of the second powder silicon carbide to the tantalum carbide is 6:4; the molar ratio of the third powder silicon carbide to the tantalum carbide is 4:6, the mol ratio of the fourth powder silicon carbide to the tantalum carbide is 2:8; adding isopropanol (purity 99.99%) into the four types of powder, and performing ultrasonic oscillation (ultrasonic power is 1000W, 30min) and electromagnetic stirring (electromagnetic stirring speed is 350r/min,100 min) to obtain four types of suspension; placing the suspension in a hydrothermal kettle suitable for electrophoretic deposition of a graphite substrate 1, then adding iodine (the purity of the iodine is 99.9 percent, and the concentration is 5 g/L), obtaining four types of suspensions with sequentially reduced silicon carbide concentration by adopting ultrasound (the ultrasonic power is 1000W, 30min) and electromagnetic stirring (the electromagnetic stirring speed is 450r/min, and 100 min), then placing the graphite substrate 1 in the hydrothermal kettle in sequence from high to low according to the silicon carbide concentration, respectively taking a graphite base as a cathode and a graphite electrode as an anode to carry out electrophoretic deposition, wherein the electromagnetic stirring speed is controlled at 350r/min, the hydrothermal temperature is 100 ℃, and the deposition time is 2min each time in the electrophoretic deposition process; after deposition, placing the graphite substrate 1 in a chemical vapor deposition furnace for sintering, wherein the sintering temperature is 1600 ℃, the sintering atmosphere is argon protective gas, and the sintering time is 1h, so as to obtain the graphite substrate 1 covered with a silicon carbide composite layer and a silicon carbide-tantalum carbide composite layer;
(6) And (3) forming the high-purity nanoscale dense tantalum carbide layer 8 on the graphite substrate 1 obtained in the step (5) by adopting a chemical vapor deposition process, wherein gaseous tantalum chloride is used as a tantalum source material in the deposition process, the deposition temperature is 1700 ℃, the deposition time is 5 hours, and the deposition thickness of the tantalum carbide layer 8 is 6 microns, so that the composite carbon material of the embodiment is obtained, and the carbon material can be used as a 380mm graphite tray for MOCVD. The coating ash was 3ppm.
The composite carbon material of the embodiment is subjected to corrosion resistance test, and the corrosion resistance test toolThe method comprises the step of placing the composite carbon material in a mixed solution of hydrofluoric acid and nitric acid with the concentration of 100% for detection, and the result shows that the mass of a sample is reduced by 0.06g/m after the sample is corroded for 300 hours 2 。
The composite carbon material of the embodiment is subjected to mechanical property test, the connection strength of a coating sample of 10 × 10 × 10mm is tested by a tensile method, and the test result shows that the connection strength of the coating and the substrate is 75MPa.
Example 3:
the composite carbon material of this example includes a carbon substrate and a composite coating layer disposed on the surface of the carbon substrate, wherein the carbon substrate has a density of 1.8g/cm 3 The graphite coating comprises a graphite substrate 1 with the graphite purity of 5ppm, and a composite coating sequentially comprises a silicon carbide composite layer, a first silicon carbide-tantalum carbide composite layer 4, a second silicon carbide-tantalum carbide composite layer 5, a third silicon carbide-tantalum carbide composite layer 6, a fourth silicon carbide-tantalum carbide composite layer 7 and a tantalum carbide layer 8 from inside to outside; the silicon carbide composite layer comprises a silicon carbide layer 3 and silicon carbide nanowires 2 dispersed in the silicon carbide layer 3 and the graphite substrate 1, the silicon carbide nanowires 2 extend into the graphite substrate 1 and the silicon carbide layer 3, the thickness of the silicon carbide layer 3 is 30 micrometers, and the distribution thickness of the silicon carbide nanowires 2 in the silicon carbide layer 3 is 20 micrometers; the first silicon carbide-tantalum carbide composite layer 4 has a thickness of 15 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 8: and 2, the thickness of the second silicon carbide-tantalum carbide composite layer 5 is 15 microns, wherein the molar ratio of silicon carbide to tantalum carbide is 6:4; the third silicon carbide-tantalum carbide composite layer 6 has a thickness of 15 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 4:6; the fourth silicon carbide-tantalum carbide composite layer 7 has a thickness of 15 μm, wherein the molar ratio of silicon carbide to tantalum carbide is 2:8; the tantalum carbide layer 8 has a thickness of 15 μm.
The preparation method of the composite carbon material of the embodiment comprises the following steps:
(1) Selecting the material with the density of 1.8g/cm 3 The graphite material with the graphite purity of 5ppm is a carbon substrate;
(2) Processing the graphite substrate 1 into a round tray with the diameter of 380mm according to the model requirement of MOCVD equipment, then putting the round tray into deionized water for ultrasonic cleaning for 30 min/time, replacing the deionized water for cleaning again after cleaning, circularly performing ultrasonic cleaning for 4 times, and putting the round tray into a 200 ℃ drying oven for drying for 10 hours;
(3) And (2) infiltrating the mixed liquid of the liquid paraffin and the nano silicon powder into the surface pores of the graphite substrate 1 by adopting a pressure infiltration method: mixing the nano silicon powder and the liquid paraffin by adopting an electric stirrer, wherein the volume ratio of the nano silicon powder to the liquid paraffin is 1:2, stirring for 3 hours to obtain mixed slurry for later use; adopting a vacuum pressure kettle injection method (the selected vacuum pressure kettle injection device is a self-designed specific device, the size of a pressure kettle hearth is not too large, the diameter of the pressure kettle hearth is similar to that of a 380mm graphite tray for MOCVD, and the diameter of the pressure kettle hearth is 1cm larger than that of the graphite tray), and repeatedly injecting the mixed slurry in batches for pressure infiltration; when pressure infiltration is carried out in the kettle, the infiltration pressure is 1.2MPa, the infiltration time is 1h, the graphite substrate 1 is taken out for standby after the complete infiltration, and the mass is increased by 50g after the infiltration;
(4) Placing the graphite substrate 1 infiltrated with the nano silicon powder and the liquid paraffin into a chemical vapor deposition furnace, carrying out high-temperature heat treatment to form a silicon carbide nanowire layer, and then forming a silicon carbide layer 3 on the silicon carbide nanowire layer by adopting a chemical vapor deposition method; wherein the preparation temperature of the silicon carbide nanowire layer is 1300 ℃, the preparation time is 1h, and the reaction environment is in a vacuum state; the thickness of the formed silicon carbide nanowire layer was 20 μm (the thickness from the surface layer of the graphite substrate 1 to the silicon carbide nanowire layer); the chemical vapor deposition silicon carbide layer 3 belongs to the densification process of a silicon carbide nanowire layer, in the preparation process, a chemical vapor deposition method is adopted to deposit a silicon carbide phase in gaps of the silicon carbide nanowire layer and on a graphite surface layer, the deposition temperature is 1200 ℃, the deposition time is 10 hours, the deposition state is a vacuum state, and finally the thickness of the silicon carbide layer 3 is 30 microns;
(5) Forming the silicon carbide nanoparticle reinforced tantalum carbide gradient coating by adopting an electrophoretic deposition process:
preparing four types of powder according to a specific mass ratio: the molar ratio of the first powder silicon carbide nano powder (with the grain diameter of 50nm and the purity of 99.99%) to the tantalum carbide powder (with the grain diameter of 50nm and the purity of 99.99%) is 8:2; the mol ratio of the second powder silicon carbide to the tantalum carbide is 6:4; the molar ratio of the third powder silicon carbide to the tantalum carbide is 4:6, the molar ratio of the fourth powder silicon carbide to the tantalum carbide is 2:8; adding isopropanol (purity 99.99%) into the four types of powder, and performing ultrasonic oscillation (ultrasonic power is 1000W, 30min) and electromagnetic stirring (electromagnetic stirring speed is 350r/min,100 min) to obtain four types of suspension; placing the suspension in a hydrothermal kettle suitable for electrophoretic deposition of a graphite substrate 1, then adding iodine (the purity of the iodine is 99.9 percent, and the concentration is 5 g/L), obtaining four types of suspensions with sequentially reduced silicon carbide concentration by adopting ultrasound (the ultrasonic power is 1000W, 30min) and electromagnetic stirring (the electromagnetic stirring speed is 450r/min, and 100 min), then placing the graphite substrate 1 in the hydrothermal kettle in sequence from high to low according to the silicon carbide concentration, respectively taking a graphite base as a cathode and a graphite electrode as an anode to carry out electrophoretic deposition, wherein the electromagnetic stirring speed is controlled at 350r/min, the hydrothermal temperature is 100 ℃, and the deposition time is respectively 1min in each time in the electrophoretic deposition process; after deposition, placing the graphite substrate 1 in a chemical vapor deposition furnace for sintering, wherein the sintering temperature is 1600 ℃, the sintering atmosphere is argon protective gas, and the sintering time is 2 hours, so as to obtain the graphite substrate 1 covered with a silicon carbide composite layer and a silicon carbide-tantalum carbide composite layer;
(6) And (3) forming the high-purity nanoscale dense tantalum carbide layer 8 on the graphite substrate 1 obtained in the step (5) by adopting a chemical vapor deposition process, wherein gaseous tantalum chloride is used as a tantalum source material in the deposition process, the deposition temperature is 1700 ℃, the deposition time is 5 hours, and the deposition thickness of the tantalum carbide layer 8 is 15 microns, so that the composite carbon material of the embodiment is obtained, and the carbon material can be used as a 380mm graphite tray for MOCVD.
The composite carbon material of the embodiment was subjected to corrosion resistance testing, specifically, the composite carbon material was placed in a 100% hydrofluoric acid and nitric acid mixed melt for testing, and the results showed that after 300h of corrosion, the mass of the sample was reduced by 0.02g/m 2 。
The composite carbon material of the embodiment is subjected to mechanical property test, the connection strength of a coating sample of 10 × 10 × 10mm is tested by a tensile method, and the test result shows that the connection strength of the coating and a substrate is 80MPa, and compared with the coating prepared in embodiment 1 and having a lower thickness, the mechanical property of the coating is improved. The coating ash was 3ppm.
Comparative example 1:
the composite carbon material of the present comparative example differs from example 3 in that the thickness of the silicon carbide layer in the silicon carbide composite layer was 40 μm (the deposition time was adjusted to 20 hours upon deposition of the silicon carbide layer corresponding to the production method).
The composite carbon material of the comparative example is subjected to mechanical property test, the connection strength of a coating sample of 10 multiplied by 10mm is tested by a stretching method, and the test result shows that the connection strength of the coating and the matrix is 30Mpa, and compared with the coating prepared by the examples 1-3, the mechanical property between the composite carbon material coating and the matrix of the comparative example is obviously reduced.
Comparative example 2:
the composite carbon material of this comparative example is different from example 3 in that the composite coating layer includes only the silicon carbide-tantalum carbide composite layer and the tantalum carbide layer, but does not include the silicon carbide composite layer, and the rest of the structure and parameters are consistent with example 3 (the preparation method corresponds to the deletion of the preparation flow of the silicon carbide composite coating layer, and the silicon carbide-tantalum carbide composite layer is directly prepared on the surface of the carbon substrate, and the rest of the method is consistent with example 3).
The composite carbon material of the comparative example is subjected to mechanical property test, the connection strength of a coating sample of 10 multiplied by 10mm is tested by a stretching method, and the test result shows that the connection strength of the coating and the substrate is 26Mpa, and compared with examples 1-3, the mechanical property between the coating and the substrate of the composite carbon material of the comparative example is obviously reduced under the condition that an interface layer of a silicon carbide composite layer is not arranged.
Comparative example 3:
compared with the embodiments, the composite carbon material of the comparative example is different in the preparation process of the silicon carbide-tantalum carbide composite layer, and the specific manufacturing method comprises the following steps:
(1) Selecting the material with the density of 1.8g/cm 3 The graphite material with the graphite purity of 5ppm is a carbon substrate;
(2) Processing a graphite substrate into a round tray with the diameter of 380mm according to the model requirement of MOCVD equipment, then putting the round tray into deionized water for ultrasonic cleaning for 30 min/time, replacing the deionized water for cleaning again after cleaning, circularly performing ultrasonic cleaning for 4 times, and putting the round tray into a drying oven with the temperature of 200 ℃ for drying treatment, wherein the drying time is 10h;
(3) And (3) infiltrating the mixed liquid of the liquid paraffin and the nano silicon powder into the pores on the surface layer of the graphite substrate by adopting a pressure infiltration method:
mixing the nano silicon powder and the liquid paraffin by adopting an electric stirrer, wherein the volume ratio of the nano silicon powder to the liquid paraffin is 1:2, stirring for 3 hours to obtain mixed slurry for later use; adopting a vacuum pressure kettle injection method (the selected vacuum pressure kettle injection device is a self-designed specific device, the size of a pressure kettle hearth is not too large, the diameter of the pressure kettle hearth is similar to that of a 380mm graphite tray for MOCVD, and the diameter of the pressure kettle hearth is 1cm larger than that of the graphite tray), and repeatedly injecting the mixed slurry in batches for pressure infiltration; when pressure infiltration is carried out in the kettle, the infiltration pressure is 1.2MPa, the infiltration time is 1h, the graphite base material is taken out for standby after the infiltration is completed, and the mass is increased by 50g after the infiltration;
(4) Placing the graphite substrate permeated with the nano silicon powder and the liquid paraffin into a chemical vapor deposition furnace, carrying out high-temperature heat treatment to form a silicon carbide nanowire layer, and then forming a silicon carbide layer on the silicon carbide nanowire layer by adopting a chemical vapor deposition method; wherein the preparation temperature of the silicon carbide nanowire layer is 1200 ℃, the preparation time is 1h, and the reaction environment is in a vacuum state; the thickness of the formed silicon carbide nanowire layer is 10 μm (the thickness from the surface layer of the graphite substrate to the silicon carbide nanowire layer); the chemical vapor deposition silicon carbide layer belongs to the densification process of a silicon carbide nanowire layer, and in the preparation process, a chemical vapor deposition method is adopted to deposit a silicon carbide phase in gaps of the silicon carbide nanowire layer and on a graphite surface layer, wherein the deposition temperature is 1200 ℃, the deposition time is 5 hours, the deposition state is a vacuum state, and the thickness of the final silicon carbide layer is 20 microns;
(5) Preparing a gradient silicon carbide-tantalum carbide composite layer directly on the surface layer of the graphite tray coated with the silicon carbide nanowire reinforced silicon carbide composite layer by adopting a chemical vapor deposition method;
the gradient silicon carbide-tantalum carbide composite layer is prepared by adopting a chemical vapor deposition method, the deposition temperature is 1700 ℃, and different gases are selected to be introduced into the flow to control the component content gradient change structure of the coating. Selecting a molar ratio of 8:2 (first type), 6:4 (second type), 4:6 (third type), 2:8 (fourth type), 0:10 (fifth type) silicon tetrachloride and tantalum pentachloride gases are used as a Si source and a Ta source, and 1:1 mol ratio of methane is used as a gas phase carbon source, hydrogen is used as reaction gas (the mol ratio of the methane to the sum of the moles of silicon tetrachloride and tantalum pentachloride is 1:1), argon is used as diluent gas (the mol ratio of the argon to the sum of the moles of silicon tetrachloride and tantalum pentachloride is 1:1), and the deposition time is respectively 2h. The results after deposition showed coating thicknesses after deposition of the first-fifth atmospheres of 30 μm,23 μm,12 μm,11 μm,10 μm,8 μm, respectively. The silicon carbide phase and the tantalum carbide phase in the coating are not uniformly distributed, and the component content of the coating is not 8:2,6:4,4:6,2:8 mol ratio.
The composite carbon material of the comparative example is subjected to corrosion resistance test, the specific method is to place the composite carbon material in a mixed solution of hydrofluoric acid and nitric acid with the concentration of 100% for detection, and the result shows that after the composite carbon material is corroded for 300 hours, the mass of a sample is reduced by 0.14g/m 2 。
The composite carbon material of the comparative example is subjected to mechanical property test, a coating sample of 10 multiplied by 10mm is subjected to tensile method to test the connection strength, the test result shows that the connection strength of the coating and the substrate is 47Mpa, and compared with examples 1-3, the thickness and phase distribution uniformity of the gradient silicon carbide-tantalum carbide composite layer prepared by the composite carbon material of the comparative example through chemical vapor deposition are reduced, the mechanical property of the coating tends to be reduced, and the mechanical strength is reduced. The coating with poor interface bonding strength has uneven corrosion resistance in the service process, so that the overall corrosion resistance of the coating is reduced, and the method can effectively solve the problems in the prior art and improve the final performance of the coating.
Comparative example 4:
compared with the embodiments, the composite carbon material of the comparative example is different in the preparation process of the silicon carbide nanowire, and the specific preparation method comprises the following steps:
(1) Selecting the material with the density of 1.8g/cm 3 The graphite material with the graphite purity of 5ppm is a carbon substrate;
(2) Processing a graphite substrate into a round tray with the diameter of 380mm according to the model requirement of MOCVD equipment, then putting the round tray into deionized water for ultrasonic cleaning for 30 min/time, replacing the deionized water for cleaning again after cleaning, circularly performing ultrasonic cleaning for 4 times, and putting the round tray into a 200 ℃ drying oven for drying for 10 hours;
(3) Depositing a metal Ni layer on the surface layer of the graphite by a direct-current magnetron sputtering method, wherein the thickness of the metal Ni layer is 2nm;
(4) Preparing the silicon carbide nanowire reinforced silicon carbide coating by adopting a chemical vapor deposition process: introducing silicon tetrachloride and methane (the molar ratio is 1:1) by taking hydrogen as a carrier gas, heating to 1200 ℃, and keeping the temperature for 2 hours, wherein the thickness of the deposited silicon carbide nanowire coating is 30 micrometers;
(5) The preparation of the silicon carbide coating is carried out by adopting a chemical vapor deposition method. In the preparation process, the deposition temperature is 1200 ℃, the deposition time is 5 hours, the deposition state is a vacuum state, and the thickness of the final silicon carbide layer is 35 μm;
(6) Forming the silicon carbide nanoparticle reinforced tantalum carbide gradient coating by adopting an electrophoretic deposition process:
preparing four types of powder according to a specific mass ratio: the molar ratio of the first powder silicon carbide nano powder (with the grain diameter of 50nm and the purity of 99.99%) to the tantalum carbide powder (with the grain diameter of 50nm and the purity of 99.99%) is 8:2; the mol ratio of the second powder silicon carbide to the tantalum carbide is 6:4; the molar ratio of the third powder silicon carbide to the tantalum carbide is 4:6, the molar ratio of the fourth powder silicon carbide to the tantalum carbide is 2:8; adding isopropanol (purity 99.99%) into the four types of powder, and performing ultrasonic oscillation (ultrasonic power is 1000W, 30min) and electromagnetic stirring (electromagnetic stirring speed is 350r/min,100 min) to obtain four types of suspension; placing the suspension in a hydrothermal kettle suitable for electrophoretic deposition of a graphite substrate, adding iodine (the purity of the iodine is 99.9 percent, and the concentration is 5 g/L), performing ultrasonic (the ultrasonic power is 1000W, 30min) and electromagnetic stirring (the electromagnetic stirring speed is 450r/min, and 100 min) to obtain four types of suspensions with sequentially reduced silicon carbide concentration, sequentially placing the graphite substrate in the hydrothermal kettle according to the sequence of the silicon carbide concentration from high to low, placing the prepared four types of suspensions in the hydrothermal kettle, respectively taking a graphite base as a cathode and a graphite electrode as an anode, and performing electrophoretic deposition, wherein the electromagnetic stirring speed is controlled at 350r/min, the hydrothermal temperature is 100 ℃, and the deposition time is respectively 1min in the electrophoretic deposition process; after deposition, placing the graphite substrate in a chemical vapor deposition furnace for sintering, wherein the sintering temperature is 1600 ℃, the sintering atmosphere is argon protective gas, and the sintering time is 1h, so as to obtain the graphite substrate covered with a silicon carbide composite layer and a silicon carbide-tantalum carbide composite layer;
(7) And (3) forming a high-purity nanoscale compact tantalum carbide layer on the graphite substrate obtained in the step (6) by adopting a chemical vapor deposition process, wherein gaseous tantalum chloride is used as a tantalum source substance in the deposition process, the deposition temperature is 1700 ℃, the deposition time is 5 hours, and the deposition thickness of the tantalum carbide layer is 6 microns, so that the composite carbon material of the embodiment is obtained, and the carbon material can be used as a 380mm graphite tray for MOCVD. The coating ash was 25ppm. Compared with the coating prepared by the method created by the invention, the purity of the coating is lower.
The composite carbon material of the comparative example is subjected to corrosion resistance test, the specific method is to place the composite carbon material in a mixed solution of hydrofluoric acid and nitric acid with the concentration of 100% for detection, and the result shows that after the composite carbon material is corroded for 300 hours, the mass of a sample is reduced by 0.12g/m 2 And preferentially etching holes in the region having the impurity phase. Therefore, during the preparation of the conventional nanowires, an impurity phase is often introduced, which increases the corrosion sites of the coating and reduces the corrosion resistance of the coating, thereby affecting the service life of the product.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (15)
1. The composite carbon material is characterized by comprising a carbon substrate and a composite coating arranged on the surface of the carbon substrate, wherein the composite coating comprises a silicon carbide composite layer, a silicon carbide-tantalum carbide composite layer and a tantalum carbide layer (8) which are sequentially overlapped from inside to outside; the silicon carbide composite layer comprises silicon carbide nanowires (2) and a silicon carbide layer (3) covering the surface of the carbon substrate, and the silicon carbide nanowires (2) extend into the carbon substrate and the silicon carbide layer (3); the thickness of the silicon carbide layer (3) is 20 to 30 micrometers, wherein the distribution thickness of the silicon carbide nanowires (2) in the silicon carbide layer (3) is 10 to 20 micrometers; the silicon carbide nanowire (2) is prepared on a carbon substrate in situ by adopting a pressure infiltration method and high-temperature treatment, and the specific operations comprise: uniformly mixing the nano silicon powder and the liquid paraffin to obtain mixed slurry, putting the mixed slurry and the carbon substrate into a vacuum pressure kettle for pressure impregnation, and then carrying out high-temperature treatment on the carbon substrate subjected to pressure impregnation.
2. The composite carbon material according to claim 1, wherein the concentration of silicon carbide in the silicon carbide-tantalum carbide composite layer decreases sequentially from the inside to the outside.
3. The composite carbon material of claim 2, wherein the silicon carbide-tantalum carbide composite layer comprises a four-layer structure with different silicon carbide concentrations, and the molar ratio of silicon carbide to tantalum carbide in each layer structure from inside to outside is (7~8): (2~3), 5: (4~6), (3~4): (6~7) and (1~2): (8~9) and the thickness of each layer is 6 to 15 μm.
4. A composite carbon material according to any one of claims 1 to 3, characterized in that the tantalum carbide layer (8) is a nano tantalum carbide layer having a thickness of 6 to 15 μm.
5. A method for producing the composite carbon material according to any one of claims 1 to 4, comprising the steps of:
(1) Preparing a silicon carbide nanowire layer in situ on the carbon substrate, and depositing silicon carbide after the preparation is finished to form a silicon carbide composite layer; in the step, the in-situ preparation of the silicon carbide nanowire layer on the carbon substrate is realized by adopting a pressure infiltration method and high-temperature treatment, and the specific operations comprise: uniformly mixing nano silicon powder and liquid paraffin to obtain mixed slurry, putting the mixed slurry and a carbon substrate into a vacuum pressure kettle for pressure impregnation, and then carrying out high-temperature treatment on the carbon substrate subjected to pressure impregnation to finish the in-situ preparation of the silicon carbide nanowire layer;
(2) Depositing a silicon carbide-tantalum carbide composite layer on the surface of the silicon carbide composite layer by adopting a mixed raw material of silicon carbide and tantalum carbide;
(3) And depositing a tantalum carbide layer (8) on the surface of the silicon carbide-tantalum carbide composite layer to obtain the composite carbon material.
6. The method for producing a composite carbon material according to claim 5, wherein the impregnation pressure is 0.8 to 1.2MPa and the impregnation time is 1 to 3h when the carbon substrate is pressure-impregnated in step (1).
7. The method for producing a composite carbon material as claimed in claim 5, wherein the carbon substrate after pressure impregnation is subjected to high-temperature treatment at a temperature of 1200 to 1400 ℃ for 1 to 3 hours, and a vacuum is maintained during the treatment.
8. The method for producing a composite carbon material according to claim 5, wherein the deposition temperature is 1000 to 1200 ℃ and the deposition time is 5 to 10 hours when the silicon carbide is deposited in step (1), and the vacuum is maintained during the deposition.
9. The method for preparing a composite carbon material according to claim 5, wherein the step (2) is implemented by an electrophoretic deposition process and a sintering process, and the electrophoretic deposition process and the sintering process specifically comprise the following steps: preparing mixed powder of silicon carbide and tantalum carbide, adding a solvent and an iodine simple substance into the mixed powder, and uniformly mixing to obtain a suspension; and placing the carbon substrate after the silicon carbide composite layer is formed into the suspension, performing electrophoretic deposition by taking the carbon substrate after the silicon carbide composite layer is formed as a cathode and a graphite electrode as an anode, and sintering the carbon substrate after the electrophoretic deposition is completed to complete the preparation of the silicon carbide-tantalum carbide composite layer.
10. The method of claim 9, wherein the mixed powder of silicon carbide and tantalum carbide comprises four powders having different silicon carbide concentrations, and four suspensions are formed, and the molar ratios of silicon carbide and tantalum carbide in the first to fourth suspensions are (7~8): (2~3), 5: (4~6), (3~4): (6~7) and (1~2): (8~9), and performing electrophoretic deposition on the carbon substrate with the silicon carbide composite layer formed in sequence in the first to fourth groups of suspensions.
11. The method for producing a composite carbon material according to claim 9, wherein the carbon substrate after the silicon carbide composite layer is formed is placed in a suspension, and the electrophoretic deposition is carried out at a temperature of 80 to 100 ℃ for 1 to 3min per deposition.
12. The method for preparing a composite carbon material according to claim 9, wherein when the solvent and the iodine simple substance are added to the mixed powder, the mixture is mixed by ultrasonic and electromagnetic stirring, wherein the ultrasonic power is 1000 to 1500W, the ultrasonic time is 20 to 30min, the electromagnetic stirring speed is 300 to 450r/min, and the electromagnetic stirring time is 50 to 100min.
13. The method for producing a composite carbon material according to claim 9, wherein the carbon substrate after completion of the electrophoretic deposition is sintered at a sintering temperature of 1500 to 1600 ℃ for 1 to 2h while maintaining an inert atmosphere during the sintering.
14. The method for preparing a composite carbon material according to claim 5, wherein the tantalum carbide layer (8) is prepared in step (3) by a chemical vapor deposition process, wherein the deposition temperature is 1100-1700 ℃, and the deposition time is 5-7 h.
15. Use of the composite carbon material according to any one of claims 1 to 4 or the composite carbon material produced by the production method according to any one of claims 5 to 14 for producing a tray for an MOCVD apparatus.
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| CN101152776B (en) * | 2006-09-28 | 2010-05-26 | 中南大学 | Double -gradient composite coating |
| CN101386551B (en) * | 2008-10-29 | 2011-12-28 | 陕西科技大学 | Method for preparing carbon/carbon compound material nano silicon carbide-silicon molybdenum composite coating |
| CN101407433B (en) * | 2008-11-06 | 2011-08-10 | 陕西科技大学 | Preparation of carbon/carbon composite material molybdenum disilicide outer coating |
| CN103601532B (en) * | 2013-11-05 | 2014-12-24 | 陕西科技大学 | Preparation method of carbon/carbon composite material MoB2 anti-oxidation outer coating |
| CN103922745A (en) * | 2014-04-03 | 2014-07-16 | 西北工业大学 | SiC nanowire toughened high temperature ablation resistant ZrB2-SiC composite coating and preparation method thereof |
| CN103951470B (en) * | 2014-04-04 | 2015-05-13 | 西北工业大学 | Hafnium carbide nanowire-toughened ceramic coating layer of surface of carbon/carbon composites and preparation method thereof |
| CN104193420B (en) * | 2014-07-14 | 2016-08-24 | 广东省工业技术研究院(广州有色金属研究院) | A kind of carbon/carbon compound material laminated coating and preparation method thereof |
| CN105712746B (en) * | 2016-01-18 | 2018-04-06 | 西北工业大学 | A kind of method that C/C composite material surfaces prepare the superior Si Mo Cr coatings of thermal shock resistance |
| CN106673708B (en) * | 2016-12-02 | 2019-07-05 | 西北工业大学 | A kind of method that surface of carbon/carbon composite prepares silicon carbide nanometer line porous layer |
| CN106673710A (en) * | 2016-12-02 | 2017-05-17 | 西北工业大学 | HfC nanowire-toughened anti-ablation ceramic coating on surface of carbon/carbon composite material and preparation method |
| CN108395279B (en) * | 2018-02-08 | 2021-09-17 | 西北工业大学 | Method for preparing HfC-SiC complex phase gradient coating by chemical vapor codeposition method |
| CN108530109B (en) * | 2018-03-23 | 2021-03-23 | 西北工业大学 | Anti-oxidation coating with 1500-1700 ℃ on surface of carbon/carbon composite material and preparation method thereof |
| CN109485423B (en) * | 2018-11-29 | 2021-07-16 | 西北工业大学 | Preparation method of SiC nanowire toughened HfC-SiC complex phase coating by chemical vapor codeposition |
| CN111485220A (en) * | 2020-05-28 | 2020-08-04 | 西北工业大学 | SiC nanowire toughened chemical vapor deposition ZrC coating and preparation method thereof |
| CN112457061A (en) * | 2020-12-22 | 2021-03-09 | 中国科学院上海硅酸盐研究所 | Environment barrier coating with gradient change of components and preparation method thereof |
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