CN115637419B - A method for preparing a tantalum-tantalum carbide composite coating and its products - Google Patents
A method for preparing a tantalum-tantalum carbide composite coating and its products Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 38
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 137
- 239000007789 gas Substances 0.000 claims description 99
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- 238000000151 deposition Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
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- 239000005977 Ethylene Substances 0.000 claims description 14
- 238000002309 gasification Methods 0.000 claims description 14
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 239000012495 reaction gas Substances 0.000 claims description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
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- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a tantalum-tantalum carbide composite coating product and a preparation method thereof, and gasifying the inorganic tantalum halide by using a chemical vapor deposition method, and forming a tantalum-tantalum carbide composite coating on the surface of the substrate together with hydrogen and olefin. The invention can effectively obtain excellent corrosion resistance and friction resistance of the base material, can effectively control the overflow of impurity components in the base material, improves the surface finish, improves the product attractiveness, and realizes industrial mass production.
Description
Technical Field
The invention belongs to the technical field of metal ceramic composite materials, and particularly relates to a preparation method of a tantalum-tantalum carbide composite coating and a product thereof.
Background
The tantalum carbide ceramic is a ceramic material, has superconductivity, golden appearance, high hardness (2100HV0.05), high melting point (3880 ℃) and corrosion resistance, is not easy to adhere, is a ceramic material emerging in recent years, is powdered tantalum carbide which is widely applied to the smelting process of special alloy, has wide application prospect in the fields of semiconductors, chemical industry, metallurgy, mould processing, aerospace and the like, and is an excellent shielding and wear-resistant material. But the wide use thereof is restricted by the poor ductility, the fragility, the high processing cost and the like.
Chemical vapor deposition (CVD for short, english Chemical Vapor Deposition) is a complex process, and includes thermodynamic and kinetic effects of chemical reaction, and various effects of heat transfer and mass transfer. On the one hand, the chemical reaction is controlled to occur in the reaction chamber, and on the other hand, the product is allowed to form crystal nuclei on the surface of the green body and grow. That is, chemical reactions are possible among chemical substances, but the reaction process cannot be guaranteed to be performed with high efficiency, and the technological parameters are continuously optimized through multiple tests.
Tantalum carbide materials are difficult to process and form by adopting a machining process due to high melting point, high hardness and poor ductility, and are difficult to be compact and void-free by adopting a hot press sintering method. Tantalum carbide materials may exhibit poor adhesion to the surface of individual substrates due to higher hardness and poor ductility; therefore, the tantalum-tantalum carbide coating product prepared by the Chemical Vapor Deposition (CVD) method has great significance and wide application prospect.
The composite coating is mainly used for improving the binding force and the compactness of a product, particularly, between two layers of materials with larger thermal expansion coefficients, the metal layer can be used as a buffer layer, the toughness and the compactness of the metal are better than those of a ceramic material, and the porosity of the coating can be effectively reduced.
Disclosure of Invention
Aiming at the defects of the existing tantalum carbide coating product, the invention adopts a chemical vapor deposition method to prepare the tantalum-tantalum carbide composite coating on the surface of the substrate, and provides the preparation method of the tantalum-tantalum carbide coating product which has the advantages of corrosion resistance, abrasion resistance, good appearance quality and difficult adhesion.
In order to achieve the above object, the solution of the present invention is: an article of tantalum-tantalum carbide composite coating comprises a substrate and a tantalum-tantalum carbide coating formed on the surface of the substrate, wherein the substrate comprises a metal material and is also suitable for high-temperature resistant materials such as carbon materials, ceramic materials, quartz materials and the like.
The invention also provides a preparation method of the tantalum-tantalum carbide composite coating, which specifically comprises the following steps:
① And a heating step: placing a substrate in a reaction chamber, vacuumizing the reaction chamber, and heating the reaction chamber at 800-1100 ℃;
② A tantalum coating deposition step: after the heating step, firstly introducing tantalum pentachloride or tantalum pentafluoride gas and hydrogen into a reaction chamber, and depositing a tantalum coating on the surface of a substrate at a reaction temperature of 800-1100 ℃ under the pressure of 3000Pa to 6000 Pa;
③ And (3) cooling: stopping introducing reaction gas, cooling, and starting to keep the temperature when the temperature is reduced to 550-750 ℃;
④ A tantalum carbide coating deposition step: introducing tantalum pentachloride or tantalum pentafluoride gas, mixed olefin and hydrogen mixed gas into a reaction chamber, and depositing a tantalum carbide coating on the surface of a substrate at the reaction temperature of 550-750 ℃ under the pressure of 5000-10000 Pa; preparing a tantalum-tantalum carbide composite coating material;
⑤ And (3) a cooling step: after the steps, cooling the tantalum-tantalum carbide coated article to normal temperature;
⑥ And (3) cleaning: after cooling to room temperature, the product was removed and cleaned with deionized water and ethanol, respectively.
Further, the gasification temperature of the tantalum pentachloride or tantalum pentafluoride is 300-500 ℃.
Preferably, the reaction chamber is a stainless steel reaction chamber.
Preferably, the mixed olefin is a mixture of ethylene and propylene; the volume ratio of ethylene to propylene is 1:1-2.
Further, the volume ratio of tantalum pentachloride or tantalum pentafluoride gas to hydrogen in step ② or step ④ is 1:1-2.5.
Further, in step ④, the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the mixed olefin is 1:1-2.
Preferably, in step ②, the tantalum pentachloride or tantalum pentafluoride gas may be introduced into the reaction chamber by a carrier gas, wherein the carrier gas is argon; the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the carrier gas is 1:1-3.
Preferably, the flow rate of the tantalum pentachloride or tantalum pentafluoride gas is 2-6 SLM, the flow rate of the mixed olefin gas is 2-12 SLM, the flow rate of the argon gas is 1-6 SLM, and the flow rate of the hydrogen gas is 2-15 SLM.
After the scheme is adopted, the beneficial effects are that: the invention uses tantalum halide, hydrogen and olefin as raw materials, and produces the high-purity tantalum-tantalum carbide composite coating material by a chemical vapor deposition method, thereby effectively solving the defects of the existing tantalum carbide coating product, reducing the production cost and being suitable for industrial scale production.
(1) The tantalum-tantalum carbide composite coating prepared by the method has higher purity and no impurity.
(2) The tantalum coating in the tantalum-tantalum carbide composite coating prepared by the invention has high bonding strength with a base material and no pores.
(3) The tantalum carbide coating in the tantalum-tantalum carbide composite coating prepared by the method is high-temperature resistant, stable in chemical property and difficult to chemically react with other substances.
(4) The tantalum-tantalum carbide composite coating prepared by the invention combines the advantages of the tantalum coating and the tantalum carbide coating, effectively isolates the substrate from the external environment, and can effectively protect the substrate.
(5) The corrosion-resistant and wear-resistant tantalum-tantalum carbide isolation coating is prepared on the surface of the substrate by a chemical vapor deposition method, the thickness of the coating can be adjusted according to the actual product requirement and can reach the millimeter range, and the coating product prepared by the invention has strong binding force.
(6) The preparation method has loose material requirements on the base material, and the base material does not participate in chemical reaction, so that besides carbon materials (graphite, carbon/carbon and the like), the surface of materials which can resist high temperature, such as corundum, superalloy, quartz and the like, can be coated by deposition; the shape of the base material is not required, the base material can be deposited on various special-shaped surfaces, the uniformity is good, and the structure is compact.
(7) The invention adopts the mixed olefin of ethylene and propylene as one of reactants, the ethylene and the propylene are not easy to decompose at the current reaction temperature, and the microstructure and the performance of the product are better. The greatest advantage of mixed alkene gases over alkanes or alkynes is high efficiency and safety.
Drawings
FIG. 1 is a cross-sectional view of the composite coating of example 1 (without polishing);
FIG. 2 is a cross-sectional view of the composite coating of example 2;
FIG. 3 is another cross-sectional view of the composite coating of example 2;
FIG. 4 is a surface topography of the tantalum carbide coating of example 1;
FIG. 5 is a surface topography of the tantalum carbide coating of example 2;
FIG. 6 is a metallographic photograph of a tantalum carbide coating of example 1;
FIG. 7 is a schematic diagram of a system of a chemical vapor deposition apparatus used in the present invention.
Detailed Description
Tantalum carbide materials are difficult to process and form by adopting a machining process due to high melting point, high hardness and poor ductility, and are difficult to be compact and void-free by adopting a hot press sintering method. Tantalum carbide materials may exhibit poor adhesion to the surface of individual substrates due to higher hardness and poor ductility; therefore, the tantalum-tantalum carbide coating product prepared by the Chemical Vapor Deposition (CVD) method has great significance and wide application prospect.
Tantalum halides provide a convenient source of inorganic materials for depositing tantalum, tantalum carbide, and in particular tantalum pentahalides (TaX 5), where X represents the halogen fluorine (F), chlorine (Cl). Table 1 shows the physical and chemical properties of tantalum halides tantalum pentafluoride (TaF 5), tantalum pentachloride (TaCl 5). Tantalum pentafluoride and tantalum pentachloride are all solid at room temperature (18 ℃ -22 ℃).
TABLE 1 physical and chemical Properties of tantalum pentahalide (TaX 5) used for deposition
| Melting point (. Degree. C.) | Boiling point (. Degree. C.) | Variation of heat of generation (ΔHf) | |
| TaF5 | 97 | 230 | 455 Kcal/mol |
| TaCl5 | 216 | 242 | -205 Kcal/mol |
The carbon source gas used for depositing tantalum carbide by the traditional CVD process is methane or propane, the alkane has good stability, the chemical reaction activity is lower than that of alkene and alkyne, the alkane is used for reacting at a higher temperature, side reactions can occur, high requirements are provided for equipment, and the reaction rate is also slower; the alkyne has the highest reactivity, the reaction temperature is very low, the coating deposition rate is very fast, and the production efficiency is very high; the reaction temperature is lower, and the requirement on equipment is also low. However, alkyne is easy to crack explosively, so that the production safety is affected, and in addition, alkyne can undergo polymerization reaction, so that high quality requirements are provided for control equipment and personnel.
The invention adopts the mixed olefin of ethylene and propylene as one of reactants, the ethylene and the propylene are not easy to decompose at the current temperature, and the microstructure and the performance of the product are better.
A method of making a tantalum-tantalum carbide composite coated article comprising the steps of:
(1) Flushing and evacuating the vapor deposition equipment and all the pipelines by using inert gas, wherein the inert gas is argon;
(2) Cleaning and decontaminating a blank to be deposited, drying and then placing the blank into a reaction chamber;
(3) Evacuating non-reactive required gases and impurities which enter the vapor deposition equipment during the blank placement process;
(4) After checking that the vapor deposition equipment is sealed well, controlling the vacuum degree in the vapor deposition equipment to 3000-6000Pa by a vacuum pump, and simultaneously heating the temperature in the reaction chamber to 800-1100 ℃;
(5) Heating tantalum pentachloride or tantalum pentafluoride to 300-550 ℃ in a gasification chamber to gasify the tantalum pentachloride or tantalum pentafluoride, introducing gasified tantalum pentachloride or tantalum pentafluoride gas into a gas mixing tank with a gas flow of 2-6SLM, simultaneously introducing hydrogen into the gas mixing tank with a hydrogen flow of 2-15SLM, fully mixing the two gases in the gas mixing tank, introducing the two gases into a reaction chamber to perform chemical vapor deposition reaction on a blank, heating for a certain time, and depositing a tantalum coating on the surface of a substrate;
Stopping introducing reaction gas, cooling, and starting to keep the temperature when the temperature is reduced to 550-750 ℃; introducing tantalum pentachloride or tantalum pentafluoride gas, mixed olefin and hydrogen mixed gas into a reaction chamber, enabling the flow rate of the gasified tantalum pentachloride or tantalum pentafluoride gas to be 2-6SLM, the flow rate of the hydrogen to be 2-15SLM and the flow rate of the mixed olefin to be 2-12SLM, and keeping the reaction temperature for a certain time under the pressure of 5000Pa to 10000Pa, so as to deposit a tantalum carbide coating on the surface of a substrate; preparing a tantalum-tantalum carbide composite coating material;
(6) Switching off the heating power supply, stopping heating, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the air exhaust valve, opening the reaction chamber, and taking out the prepared tantalum-tantalum carbide composite coating material. The thickness of the tantalum coating or the tantalum carbide coating can be adjusted according to the actual product requirement.
The chemical vapor deposition equipment comprises a gasification chamber and a reaction chamber. As shown in fig. 1, the chemical vapor deposition apparatus 1 has a reaction chamber 11, a deposition workpiece 12 (e.g., a blank) is placed in the reaction chamber 11, and the reaction chamber 11 is provided with two vents, one of which is connected to an air inlet pipe 13 and the other of which is connected to a vacuum pipe 14. The reaction chamber 11 is further provided with heating means (not shown in the figures) for heating the reaction chamber, the outer end of the vacuum pipe 14 being connected to a vacuum pump 17. The gas inlet pipe 13 is connected to a gas mixing tank 16, and at least one gas outlet pipe 161 is connected to the gas mixing tank 16, and two gas outlet pipes are provided in this embodiment to respectively introduce a reducing gas and an inert argon gas from the gas outlet pipe 161. The gas mixing tank 16 is connected with a gasification chamber 15, the gasification chamber 15 can heat and gasify the initial tantalum halide, and the gasified tantalum halide gas enters the gas mixing tank 16 to be fully mixed with other gases. The flow rate of the reaction gas is regulated by the gas control device 18.
Solid reactants such as tantalum chloride or other tantalum halides are vaporized in a vaporization chamber with thermal energy to bring them into a gaseous state. The gaseous reactants react within the reaction chamber to convert vapors, such as tantalum halides, to tantalum deposits.
The reaction chamber for vapor deposition adopts a stainless steel reaction chamber, and the scheme of the invention adopts the stainless steel reaction chamber, so that the cost is low, the long-term stable operation can be ensured, and the method is the best choice.
The purpose of steps (1) - (3) is to increase the bonding force between the coating or composite and the green body, and to pre-treat the coating or composite before chemical vapor deposition.
In step (4), the reaction chamber temperature needs to be high to ensure complete dissociation of the tantalum-chlorine bond or tantalum-fluorine bond in tantalum pentachloride or tantalum pentafluoride, but the reaction chamber temperature should not be too high, otherwise the chemical deposition reaction is performed too early elsewhere before the blank is contacted. The temperature influences the degree of ionization of the reactants.
Controlling the delivery of tantalum halide vapor directly into the reaction chamber in step (5) may be accomplished by heating the solid tantalum halide to a temperature in the range of about 300-600 c, with the temperature being selected depending on the particular reactants. The temperature selected should be sufficient to vaporize the reactants to provide a vapor pressure that delivers the tantalum halide vapor into the reaction chamber.
The tantalum carbide is prepared by adopting the mixed olefin gas and tantalum pentachloride or tantalum pentafluoride gas, and compared with alkane or alkyne, the mixed olefin gas has the greatest advantage of high efficiency and safety. The reaction temperature, vacuum degree, flow rate and proportion of the reaction gas in the preparation process have major influence on the progress speed of the deposition reaction and the organization and performance of the deposition layer. The ratio of the mixed olefin gas to the tantalum halide gas to the hydrogen gas affects the concentration of the reactants, which may be too low or too high to affect deposition efficiency. The reaction gas has enough residence time on the surface of the blank body to participate in the reaction, and the deposition rate is controlled by the adsorption and desorption processes of the reaction gas and the surface of the blank body. When the gas flow rate is increased, the source substances participating in the reaction in unit time are increased, so that the reaction is facilitated to be carried out towards the direction of the product, and the deposition rate is increased. However, when the gas flow exceeds a certain range, part of the gas directly passes through the surface of the blank body without participating in the reaction, so that waste is caused. The technological parameters such as reaction chamber temperature, equipment vacuum degree, reaction gas flow and proportion, tantalum halide gasification temperature, deposition time and heat treatment process in the chemical vapor deposition preparation process have influence on the material properties of the prepared product, and the technological parameters are mutually restricted and mutually compensated, so that unified analysis and adjustment are needed when process adjustment is carried out.
Preferably, tantalum halide gas, mixed olefin and/or hydrogen are fully mixed in a gas mixing tank and then introduced into a reaction chamber for chemical vapor deposition reaction, and the mixed gas inlet can enable deposition to be more uniform, so that excessive deposition and undeposited phenomena are avoided.
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples. In industrial production, considering economic cost, argon is used as inert gas for protection in the embodiment, and the method can be popularized to other inert gases which do not participate in chemical reaction. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
If the test equipment is not specially described, the general equipment is used, so that the judgment of the final result is not affected; the electron microscope is the Siemens device Apero, the element analyzer is the Siemens device Flash 2000, the ICP is the Shimadzu ICPE-9000.
Example 1
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity graphite green body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating the high-purity graphite blank with distilled water, drying at 170 ℃ for 8 hours, and placing the high-purity graphite blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes and 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 3000Pa through a vacuum pump and heating the temperature in the reaction chamber to 800 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:1:1, the flow rates are 2SLM, 2SLM and 2SLM respectively, after being fully mixed in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on a green body, and the reaction is carried out for 5 hours; then cooling to 550 ℃, opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 2SLM, the vacuum is 5000Pa, and reacting for 5 hours to prepare the tantalum-tantalum carbide coating graphite material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the air exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum carbide coating graphite material is detected by using an electron microscope, and the detection result shows that the coating thickness is 38 mu m. According to the ISO 4624-2016 coating adhesion test standard, the adhesion of the tantalum carbide coating of the prepared tantalum carbide coating graphite material is detected, the peeling strength is 25MPa through the test, the graphite substrate is broken, and the coating is not separated. Fig. 1 is a cross-sectional view of the composite coating of example 1, fig. 4 is a surface topography of the tantalum carbide coating of example 1, and fig. 6 is a gold phase diagram, both of which are dense and void-free. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test.
Example 2
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity graphite green body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating the high-purity graphite blank with distilled water, drying at 170 ℃ for 8 hours, and placing the high-purity graphite blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes at 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 6000Pa through a vacuum pump and heating the temperature in the reaction chamber to 1100 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:2:1, the flow rates are respectively 2SLM, 4SLM and 2SLM, after being fully mixed in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on a green body, and the reaction is carried out for 5 hours; then cooling to 550 ℃, opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 2SLM, and the mixed olefin is vacuum 10000Pa, and reacting for 5 hours to prepare the tantalum-tantalum carbide coating graphite material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the air exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum carbide coating graphite material was detected by using an electron microscope, and the detection result shows that the coating thickness is 63 mu m. Fig. 2-3 are cross-sectional views of the composite coating of example 2, and fig. 5 is a surface topography of the tantalum carbide coating of example 1, both being dense and void-free. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test.
Example 3
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity graphite green body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating the high-purity graphite blank with distilled water, drying at 170 ℃ for 8 hours, and placing the high-purity graphite blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes at 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 6000Pa through a vacuum pump and heating the temperature in the reaction chamber to 1100 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:2.5:1, after the flow rates are 6SLM, 15SLM and 6SLM respectively and fully mixed in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on a green body, and reacting for 5 hours; then cooling to 550 ℃, opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 12SLM, and the mixed olefin is vacuum 10000Pa, and reacting for 5 hours to prepare the tantalum-tantalum carbide coating graphite material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the air exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum carbide coating graphite material is detected by using an electron microscope, and the detection result shows that the coating thickness is 118 mu m. According to the ISO 4624-2016 coating adhesion test standard, the adhesion of the tantalum carbide coating of the prepared tantalum-tantalum carbide composite coating graphite material is detected, the peeling strength is 24MPa through the test, the graphite substrate is broken, and the coating is not separated. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test. And the scanning electron microscope is adopted to observe that the surface morphology of the coating is compact and has no pores and no cracking phenomenon.
Example 4
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity carbon/carbon green body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating the high-purity carbon/carbon green body by distilled water, drying at 170 ℃ for 8 hours, and then placing the high-purity carbon/carbon green body into a reaction chamber, wherein the surface to be deposited of the green body is ensured to be opposite to the direction of a reaction gas outlet, and the green bodies are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes and 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 3000Pa through a vacuum pump and heating the temperature in the reaction chamber to 800 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:1:1, the flow rates are 2SLM, 2SLM and 2SLM respectively, after being fully mixed in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on a green body, and the reaction is carried out for 5 hours; then cooling to 750 ℃, opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 2SLM, the vacuum is 5000Pa, and reacting for 5 hours to prepare the tantalum-tantalum carbide composite coating carbon/carbon material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared tantalum-tantalum carbide composite coating carbon/carbon material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum carbide coating carbon/carbon material was detected by using an electron microscope, and the detection result shows that the coating thickness is 37 μm. The adhesion of the tantalum carbide coating of the prepared tantalum carbide coating carbon/carbon material is detected according to the ISO 4624-2016 coating adhesion test standard, the peeling strength is 125MPa, the upper surface of the carbon/carbon substrate is peeled, and the coating is not separated. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test. And the scanning electron microscope is adopted to observe that the surface morphology of the coating is compact and has no pores and no cracking phenomenon.
Example 5
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity silicon carbide body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating a high-purity silicon carbide blank with distilled water, drying at 170 ℃ for 8 hours, and then placing the silicon carbide blank into a reaction chamber, wherein the to-be-deposited surface of the blank is ensured to be opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes and 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 3000Pa through a vacuum pump and heating the temperature in the reaction chamber to 800 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:1:1, the flow rates are 2SLM, 2SLM and 2SLM respectively, after being fully mixed in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on a green body, and the reaction is carried out for 5 hours; then opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 2SLM, the vacuum is 10000Pa, and the mixed olefin reacts for 5 hours to prepare the tantalum-tantalum carbide composite coating silicon carbide material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared tantalum-tantalum carbide composite coating silicon carbide material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum-tantalum carbide composite coating silicon carbide material was detected by using an electron microscope, and the detection result shows that the coating thickness is 35 mu m. The adhesion of the tantalum-tantalum carbide coating of the prepared tantalum-tantalum carbide composite coating silicon carbide material is detected according to the ISO 4624-2016 coating adhesion test standard, the peeling strength is 117MPa, the silicon carbide substrate is broken, and the coating is not separated. And the scanning electron microscope is adopted to observe that the surface morphology of the coating is compact and has no pores and no cracking phenomenon. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test.
Example 6
The chemical vapor deposition equipment is a stainless steel reaction chamber.
The materials and reagents used are as follows: high purity graphite green body (30 mm x 40mm x 50 mm), high purity ethylene (99.999%), high purity propylene (99.999%), high purity hydrogen (99.999%) and high purity argon (99.999%); high purity tantalum pentafluoride (99.99%); the implementation steps are as follows:
(1) Vacuumizing chemical vapor deposition equipment to a vacuum state of 500Pa, maintaining the vacuum state of 500Pa for 15 minutes, checking that the vapor deposition equipment is sealed well, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 10 minutes, closing an exhaust valve, and emptying various gases and impurities remained in the vapor deposition equipment through the steps;
(2) Washing and decontaminating the high-purity graphite blank with distilled water, drying at 170 ℃ for 8 hours, and placing the high-purity graphite blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to 1000Pa vacuum state, maintaining the vacuum state for 15 minutes and 1000Pa vacuum state, checking that the vapor deposition equipment is sealed well, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for emptying, continuously introducing the argon for 15 minutes, closing an exhaust valve, and emptying various gases and impurities entering in the blank placing process of the vapor deposition equipment through the steps;
(4) Vacuumizing to 1000Pa, maintaining the vacuum state for 10 minutes and 1000Pa, and controlling the vacuum degree in the vapor deposition equipment to 3000Pa through a vacuum pump and heating the temperature in the reaction chamber to 1100 ℃ after the vapor deposition equipment is checked to be sealed well;
(5) Putting tantalum pentafluoride into a gasification chamber, heating to 500 ℃ to gasify the tantalum pentafluoride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen and argon into the gas mixing tank, wherein the ratio of the three gases of tantalum pentachloride, hydrogen and argon is 1:1:1, the flow rates are 2SLM, 2SLM and 2SLM respectively, after being fully mixed in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on a green body, and the reaction is carried out for 5 hours; then cooling to 750 ℃, opening a mixed olefin valve, wherein the flow rate of the mixed olefin is 2SLM, and the mixed olefin is vacuum 10000Pa, and reacting for 5 hours to prepare the tantalum-tantalum carbide coating graphite material;
(6) Switching off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuing to introduce argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the air exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum-tantalum carbide composite coating of the prepared tantalum carbide coating graphite material is detected by using an electron microscope, and the detection result shows that the coating thickness is 38 mu m. According to the ISO 4624-2016 coating adhesion test standard, the adhesion of the tantalum carbide coating of the prepared tantalum carbide coating graphite material is detected, the peeling strength is 27MPa through the test, the graphite substrate is broken, and the coating is not separated. And the scanning electron microscope is adopted to observe that the surface morphology of the coating is compact and has no pores and no cracking phenomenon. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements except Ta, C, O were determined. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere, which is difficult to remove in XPS test.
The above examples and drawings are not intended to limit the form or style of the present invention, and any suitable changes or modifications to the examples, such as changes in reaction temperature, gasification temperature, gas flow rate, etc. should be considered as not departing from the scope of the present invention.
Claims (7)
1. A method for preparing a tantalum-tantalum carbide composite coating, which forms the tantalum-tantalum carbide composite coating on a substrate by a chemical vapor deposition method, comprising the following steps:
① And a heating step: placing a substrate in a reaction chamber of CVD, vacuumizing the reaction chamber, and heating at 800-1100 ℃;
② A tantalum coating deposition step: after the heating step, gasifying tantalum pentachloride or tantalum pentafluoride, introducing the gasified tantalum pentachloride or tantalum pentafluoride and hydrogen into a reaction chamber, keeping the reaction temperature at 800-1100 ℃ under the air pressure of 3000 Pa-6000 Pa, and depositing a tantalum coating on the surface of a substrate;
③ And (3) cooling: stopping introducing reaction gas, cooling, and keeping the temperature at 550-750 ℃;
④ A tantalum carbide coating deposition step: introducing tantalum pentachloride or tantalum pentafluoride gas, mixed olefin and hydrogen mixed gas into a reaction chamber, and depositing a tantalum carbide coating on the surface of the tantalum coating at the pressure of 5000Pa to 10000Pa and the reaction temperature of 550-750 ℃ to prepare a tantalum-tantalum carbide composite coating material; the mixed olefin is a mixture of ethylene and propylene; the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the hydrogen is 1:1-2.5; the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the mixed olefin is 1:1-2; the volume ratio of ethylene to propylene in the mixed olefin is 1:1-2;
⑤ And (3) a cooling step: after the above steps, the tantalum-tantalum carbide coated article is cooled to ambient temperature.
2. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: the gasification temperature of the tantalum pentachloride or tantalum pentafluoride is 300-600 ℃.
3. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: in the step ②, the volume ratio of the tantalum pentachloride or the tantalum pentafluoride gas to the hydrogen is 1:1-2.5.
4. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: the flow rate of the tantalum pentachloride or tantalum pentafluoride gas is 2-6 SLM, the flow rate of the mixed olefin gas is 2-12 SLM, and the flow rate of the hydrogen gas is 2-15 SLM.
5. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: introducing the tantalum pentachloride or tantalum pentafluoride gas into a reaction chamber through a carrier gas in the step ②, wherein the carrier gas is argon; the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the carrier gas is 1:1-3.
6. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: the reaction chamber is a stainless steel reaction chamber.
7. The method for preparing the tantalum-tantalum carbide composite coating according to claim 1, wherein the method comprises the following steps: the substrate is a metallic material or a carbon material or a ceramic material or quartz.
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