CN115584486A - Tantalum carbide coating product and preparation method thereof - Google Patents
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- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910003468 tantalcarbide Inorganic materials 0.000 title claims abstract description 94
- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000000151 deposition Methods 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 150
- 239000007789 gas Substances 0.000 claims description 118
- 229910052786 argon Inorganic materials 0.000 claims description 75
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 43
- 150000001336 alkenes Chemical class 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000005229 chemical vapour deposition Methods 0.000 claims description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 238000002309 gasification Methods 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- -1 tantalum halide Chemical class 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000007740 vapor deposition Methods 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 38
- 238000002156 mixing Methods 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000007770 graphite material Substances 0.000 description 20
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 229910002804 graphite Inorganic materials 0.000 description 16
- 239000010439 graphite Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000012495 reaction gas Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
-
- 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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
-
- 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
- C23C16/52—Controlling or regulating the coating process
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a tantalum carbide coating product and a preparation method thereof. The invention can effectively lead the base material to obtain excellent high temperature resistance, corrosion resistance and friction resistance, simultaneously has low reaction temperature and high deposition speed, is more suitable for industrial production, can effectively control the impurity components in the base material to overflow, improves the surface smoothness, improves the aesthetic degree of the product, and realizes large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of ceramic coating materials, and particularly relates to a tantalum carbide coating product and a preparation method thereof.
Background
Tantalum carbide is a ceramic material, has superconductivity, is golden yellow in appearance, has the advantages of high hardness (2100HV0.05), high melting point (3880 ℃), corrosion resistance and difficult adhesion, is a newly emerging ceramic material in recent years, is widely applied to the smelting process of special alloys, has wide application prospects in the fields of semiconductors, chemical engineering, metallurgy, die processing, aerospace, nuclear industry and the like, and is an excellent shielding and wear-resistant material. However, the poor ductility, brittleness, high processing cost and the like restrict the wide use of the alloy.
The tantalum carbide material is difficult to be processed and formed by a machining process due to high melting point, high hardness and poor ductility, and the common hot-pressing sintering method is difficult to be compact and free of pores. Therefore, the preparation of tantalum carbide coating products by Chemical Vapor Deposition (CVD) has great significance and wide application prospect.
CVD refers to a gas phase reaction at a high temperature, for example, a method of depositing an inorganic material such as a metal, an oxide, or a carbide by thermally decomposing a metal halide, an organic metal compound, or the like, reducing, or chemically reacting a mixed gas thereof at a high temperature. The technology is not only applied to the coating of heat-resistant substances, but also applied to the preparation of fiber reinforced composite materials, the refining of high-purity metals and the like, and is an advanced technical field with wider application range. Chemical vapor deposition is a process that uses gaseous materials to chemically react on a solid and produce a solid deposit, and generally comprises three steps: (1) forming a volatile substance; (2) transferring said material to a deposition area; (3) a chemical reaction occurs on the solid and a solid mass is produced. The most basic chemical vapor deposition processes include energy transfer, mass transfer, and the like.
Because the difference between the thermal expansion coefficients of the tantalum carbide coating and the base material, especially the carbon material, is large, cracks are easy to appear in the preparation process, and the difficulty in preparing the high-quality tantalum carbide coating is high. Therefore, it is common practice to use a carbon substrate (such as graphite) as a carbon source, and to deposit tantalum and then react with carbon on the surface of the carbon substrate (such as graphite) to form a tantalum carbide coating on the surface of the carbon substrate. The method takes carbon on the surface of the carbon matrix as a carbon source, namely the matrix is also part of reactants, so that the deposition thickness cannot meet the use requirement, and the deposition cannot be carried out on the surface of a non-carbon-based material.
Disclosure of Invention
Aiming at the defects of the existing tantalum carbide coating product, the invention provides a preparation method of the tantalum carbide coating product with corrosion resistance, wear resistance, high bonding strength and good appearance quality by preparing the tantalum carbide coating on the surface of a substrate by using a chemical vapor deposition method.
In order to achieve the above object, the present invention provides a method for preparing a tantalum carbide coated article, comprising the steps of:
(1) a heating step, namely putting a base material into a reaction chamber, vacuumizing the reaction chamber, and heating under the protection of inert gas, wherein the heating temperature is 550 to 750 ℃;
(2) a deposition step, after the heating step, introducing tantalum pentachloride or tantalum pentafluoride gas, hydrogen and mixed olefin into a reaction chamber, heating for a certain time under the pressure of 5000Pa to 10000Pa, and depositing a tantalum carbide coating on the surface of the substrate;
(3) a cooling step of cooling the tantalum carbide coated product to normal temperature after the above step;
(4) and a cleaning step of taking out the product and cleaning the product with acetone after cooling to normal temperature.
Further, the gasification temperature of the tantalum pentachloride or the tantalum pentafluoride is 300-500 ℃.
Further, the mixed olefin is a mixture of ethylene and propylene. Preferably, the volume ratio of the ethylene to the propylene is 1 to 1.
Further, the volume ratio of the tantalum pentachloride or the tantalum pentafluoride gas to the mixed olefin is 1 to 1, and the volume ratio of the tantalum pentachloride or the tantalum pentafluoride gas to the hydrogen is 1 to 1.
Preferably, the flow rate of the tantalum pentachloride or tantalum pentafluoride gas is 2 to 6SLM, the gas flow rate of the mixed olefin is 2 to 60SLM, and the hydrogen flow rate is 2 to 30SLM.
Preferably, the tantalum pentachloride or tantalum pentafluoride gas is introduced into the reaction chamber through 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 to 4.
Preferably, the reaction chamber is an alumina reaction chamber.
Preferably, the heating step further comprises a pretreatment of the substrate: cleaning the surface of the base material to be deposited by distilled water, decontaminating, and drying at 150-200 ℃ for 8-15 hours until completely drying.
Preferably, the base material may be a metal, a carbon material, or a high-temperature-resistant material such as ceramic or quartz.
Has the advantages that: the method takes tantalum halide, hydrogen and mixed olefin as raw materials, and produces the high-purity tantalum carbide coating material by a chemical vapor deposition method, thereby effectively overcoming the defects of the existing tantalum carbide coating product, greatly improving the production efficiency and reducing the production cost.
(1) The invention has low reaction temperature and high deposition speed, and is more suitable for large-scale industrial production.
(2) The invention adopts the mixed olefin gas, and has the greatest advantages of lower reaction temperature, higher reaction rate and higher safety factor in the production process. On the other hand, the use of mixed olefins can reduce the amount of carbon residue in the reaction.
(3) The tantalum carbide coating prepared by the method has high purity and no impurities.
(4) The tantalum carbide coating prepared by the method effectively isolates the substrate from the external environment, and can effectively protect the substrate.
(5) The chemical vapor deposition method is used for preparing the corrosion-resistant and wear-resistant tantalum carbide isolation coating on the surface of the base material, the thickness of the coating can be adjusted according to the actual product requirement and can reach the millimeter-scale range, and the fact shows that the coating product prepared by the method is strong in binding force.
(6) The tantalum halide is heated and gasified and then reacts with lower hydrocarbons to directly generate the tantalum carbide coating, the base material does not participate in chemical reaction, so the requirement on the material of the base material is looser, and the coating can be resistant to high temperature, except carbon materials (graphite, carbon/carbon and the like), the coating can also be deposited on the surface of materials such as corundum, high-temperature alloy, quartz and the like; the shape of the base material is not required, the base material can be deposited on various irregular surfaces, and the base material has good uniformity and compact structure. The graphite substrate is required to participate in the carbonization reaction in the prior art, the method cannot deposit on the surface of the non-carbon-based material, and the deposition thickness is not comparable to that of the invention.
Drawings
FIG. 1 is a cross-sectional view of a tantalum carbide coating prepared in example 1;
FIG. 2 is a cross-sectional view of a tantalum carbide coating of example 2 (without polishing);
FIG. 3 is a cross-sectional view of a tantalum carbide coating of example 1;
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 Raman spectrum of the tantalum carbide coating of the examples;
FIG. 7 is an XRD spectrum of the tantalum carbide coating in the example;
FIG. 8 is a metallographic photograph of a tantalum carbide coating in an example;
FIG. 9 is a schematic structural diagram of a chemical vapor deposition apparatus system used in the present invention.
Detailed Description
Some embodiments are specifically illustrated to facilitate a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a tantalum carbide coating product and a preparation method thereof. Chemical vapor deposition is a complex process involving the thermodynamics of chemical reactions and the kinetics of reactions as well as various processes of heat transfer, mass transfer, etc. On the one hand, the chemical reaction is controlled to take place in the reaction chamber, and on the other hand, the product is made to nucleate and grow on the surface of the substrate. That is, there is a possibility of chemical reaction between chemical substances but it cannot be guaranteed that the reaction process will occur efficiently, and it is necessary to continuously optimize process parameters through a plurality of testsAnd (4) counting. The tantalum halide provides a convenient source of tantalum compounds for depositing tantalum carbide, particularly tantalum pentahalide (TaX) 5 ) Wherein X represents halogen fluorine (F), chlorine (Cl). The chemical reaction equation is as follows:
2TaCl 5 +C 2 H 4 +3H 2 ——2TaC+10HCl
6TaCl 5 +2C 3 H 6 +9H 2 ——6TaC+30HCl
the carbon source gas used for depositing the tantalum carbide by the traditional CVD process is methane or propane, the alkane stability is good, the chemical reaction activity is lower than that of alkene and alkyne, the reaction temperature of the alkane is higher, side reaction can occur, the requirement on equipment is high, and the reaction rate is slower; the alkyne has the highest reaction activity, the reaction temperature is very low, the coating deposition rate is very fast, and the production efficiency is very high; the reaction temperature is low, and the requirements on equipment are also low. But alkyne is easy to be explosively cracked, which affects production safety, and alkyne can be subjected to polymerization reaction, which has higher quality requirements on control equipment and personnel.
The two points are combined, the production cost of the olefin is low, the production efficiency is high, and the safety is greatly improved.
A method of making a tantalum carbide coated article, comprising the steps of:
(1) Flushing and evacuating the vapor deposition equipment and all pipelines by using inert gas, wherein the inert gas is argon;
(2) Cleaning and decontaminating a blank to be deposited, drying and then putting the blank into a reaction chamber;
(3) Evacuating gas and impurities which are not required by the reaction and enter the vapor deposition equipment in the blank placing process;
(4) After the vapor deposition equipment is checked to be well sealed, controlling the vacuum degree in the vapor deposition equipment to be 5000-10000Pa through a vacuum pump, and simultaneously heating the temperature in the reaction chamber to be 550-750 ℃;
(5) Putting tantalum pentachloride or tantalum pentafluoride into a gasification chamber, heating to 300-500 ℃ to gasify the tantalum pentachloride or tantalum pentafluoride, introducing gasified tantalum pentachloride or tantalum pentafluoride gas into a gas mixing tank, wherein the gas flow is 2-6SLM, meanwhile, introducing hydrogen and mixed olefin into the gas mixing tank, the hydrogen flow is 2-30SLM, the gas flow of the mixed olefin is 2-60SLM, fully mixing the three gases in the gas mixing tank, introducing the three gases into a reaction chamber to perform chemical vapor deposition reaction on a blank, and reacting for 1-20 hours to form a tantalum carbide coating with the thickness of 30-600 mu m on the surface of a substrate;
(6) Cutting 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, continuously introducing 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 carbide coating material.
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 is connected to a vacuum pipe 14. The reaction chamber 11 is further provided with a heating device (not shown) for heating the reaction chamber, and the outer end of the vacuum pipe 14 is connected to a vacuum pump 17. The gas inlet pipe 13 is connected to a gas mixing tank 16, and the gas mixing tank 16 is connected to at least one vent pipe 161, two of which are provided in the embodiment, so as to respectively introduce the reducing gas and the inert argon gas from the vent pipe 161. The gas mixing tank 16 is connected with a gasification chamber 15, the gasification chamber 15 can heat and gasify initial metal halide, and gasified metal halide gas enters the gas mixing tank 16 to be fully mixed with other gas. The flow rate of the reaction gas is regulated by a gas control device 18.
A solid reactant, such as tantalum chloride or other tantalum halide, is vaporized in a gasification chamber into a gaseous state with thermal energy. The gaseous reactants react within the reaction chamber to convert the tantalum halide to a tantalum deposition layer.
The reaction chamber for vapor deposition adopts an alumina reaction chamber. Compared with a common reaction chamber such as a stainless steel reaction chamber, the long-term stable operation of the stainless steel reaction chamber cannot be ensured due to the corrosion of reactants and product gas, and the alumina reaction chamber can be selected to ensure the long-term stable operation, which is the best choice.
The purpose of steps (1) - (3) is to increase the bonding force between the coating or composite material and the blank, and the pretreatment is carried out before the chemical vapor deposition.
In step (4), the temperature of the reaction chamber needs to be high to ensure that the tantalum-chlorine bond or tantalum-fluorine bond in the tantalum pentachloride or tantalum pentafluoride is completely dissociated, but the temperature of the reaction chamber is not too high, otherwise, the chemical deposition reaction is performed prematurely in other places before the blank is contacted. Temperature affects the degree of activation of the reactants. On the other hand, if the temperature of the reaction chamber is too high, side reactions increase, which affects the purity of the coating. Too low a temperature results in slow deposition rate, or even no deposition.
In the step (5), the tantalum halide is gasified by a carrier gas and then introduced into the reaction chamber, wherein the carrier gas may be an inert gas which does not chemically react with the reactant, such as argon or neon or a mixed gas of argon and neon. In addition, tantalum carbide material can be deposited without a carrier gas. Controlling the delivery of the tantalum halide vapor directly into the reaction chamber can be accomplished by heating the solid tantalum halide within a temperature range of about 300-500 c, depending on the particular reactants. The temperature is selected to be sufficient to vaporize the reactants to provide a vapor pressure to transport the tantalum halide vapor into the reaction chamber. Therefore, a carrier gas is not necessary.
Compared with alkane and alkyne, the mixed olefin gas has the greatest advantages of lower reaction temperature, higher reaction rate and higher safety factor in the production process. On the other hand, the use of mixed olefins can reduce the amount of carbon residue in the reaction. The reaction temperature, vacuum degree, reaction gas flow and proportion in the preparation process have main influence on the proceeding speed of the deposition reaction and the structure and performance of the deposition layer. The ratio of the mixed olefin gas to the metal halide gas and the carrier gas affects the concentration of the reactants, and too low or too high a concentration of the reactants affects the deposition efficiency. The reaction gas has enough residence time on the surface of the blank 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. When the gas flow is increased, the source substances participating in the reaction in unit time are increased, which is beneficial to the reaction 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 can directly pass through the surface of the blank without participating in the reaction, which causes waste. The technological parameters such as the temperature of the reaction chamber, the vacuum degree of the equipment, the flow and proportion of the reaction gas, the gasification temperature of the metal halide, the deposition time and the heat treatment process in the chemical vapor deposition preparation process all influence the material performance of the prepared product, and the parameters are in a relationship of mutual restriction and mutual compensation, and need to be analyzed and adjusted in a unified way when the process is adjusted.
Preferably, after the metal halide gas and the mixed olefin are fully mixed in the gas mixing tank, the mixture is introduced into the reaction chamber to perform chemical vapor deposition reaction, and the mixed gas inlet can ensure that the deposition is more uniform without excessive deposition or non-deposition.
In order to further explain the technical scheme of the invention, the invention is explained in detail by the specific examples below. In the industrial production, in consideration of economic cost, the embodiment uses argon as inert gas for protection, and can also be popularized to other inert gases which do not participate in chemical reaction. The following examples will assist the researcher 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 it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
If the following test equipment is not specially described, general equipment is used, and the judgment of a final result is not influenced; the electron microscope is Sammer-Fei Apero2, the element analyzer is Sammer-Fei Flash 2000, and the ICP is Shimadzu ICPE-9000.
Example 1
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high-purity graphite blank (30mm 40mm 50mm), high-purity mixed olefin (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 the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating a high-purity graphite blank by distilled water, drying for 8 hours at 170 ℃, and then putting 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 a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 5000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 550 ℃;
(5) Putting tantalum pentachloride into a gasification chamber, heating to 300 ℃, gasifying the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing hydrogen, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:2:2:3, the flow rates are respectively 2SLM, 4SLM and 6SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 3 hours; preparing a tantalum carbide coating graphite material;
(6) Cutting 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, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum carbide coating of the prepared graphite material with the tantalum carbide coating is detected by using an electron microscope, and the detection result shows that the thickness of the coating is 60 mu m. According to the ISO 4624-2016 coating adhesion test standard, the prepared tantalum carbide coating graphite material is tested for the adhesion of the tantalum carbide coating, the peel strength is 25MPa, the graphite substrate is broken by pulling, and the coating is not separated. FIGS. 1 and 3 are sectional views of tantalum carbide coatings according to example 1, FIG. 4 is a surface topography of tantalum carbide coatings according to example 1, and FIG. 8 is a gold phase diagram, both of which show no cracking. The raman spectrum of fig. 6 illustrates that the coating material is tantalum carbide. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere and is difficult to remove in the XPS test. Figure 7 is an XRD pattern of the tantalum carbide coating prepared.
Example 2
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high-purity graphite blank (100mm x 50mm x 20mm), high-purity mixed olefin (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 the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon gas, opening a gas valve for emptying, continuing introducing the argon gas for 10 minutes, closing an exhaust valve, and emptying various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating a high-purity graphite blank by distilled water, drying at 150 ℃ for 8 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank faces the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon gas, opening a gas valve to evacuate, continuing introducing argon gas for 15 minutes, closing a gas exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank body of the vapor deposition equipment;
(4) Vacuumizing to 1000Pa vacuum state, keeping the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 10000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 750 ℃;
(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, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:4:6:6, the flow rates are respectively 2SLM, 8SLM, 12SLM and 12SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank for 10 hours; preparing a tantalum carbide coating graphite material;
(6) Cutting 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, continuously introducing 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 carbide coating graphite carbon material.
The thickness of the tantalum carbide coating layer of the prepared graphite material with the tantalum carbide coating layer is detected by using an electron microscope, and the detection result shows that the thickness of the coating layer is 65 mu m. FIGS. 2 and 5 are a cross-sectional view and a surface topography of the tantalum carbide coating of example 2, respectively, showing no cracking. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere and is difficult to remove in the XPS test.
Example 3
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high-purity graphite blank (30mm), high-purity mixed olefin (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 the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating high-purity blanks by distilled water, drying for 8 hours at 150 ℃, and then putting the blanks into a reaction chamber to ensure that the surfaces of the blanks to be deposited are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 5000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 550 ℃;
(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, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:3:4:5, the flow rates are respectively 1SLM, 3SLM, 4SLM and 5SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank for 10 hours; preparing a tantalum carbide coating graphite material;
(6) Cutting 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, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum carbide coating layer of the prepared graphite material with the tantalum carbide coating layer is detected by using an electron microscope, and the detection result shows that the thickness of the coating layer is 80 mu m. According to the ISO 4624-2016 coating adhesion test standard, the prepared tantalum carbide coating graphite material is tested for the adhesion of the tantalum carbide coating, the peel strength is 24MPa, the graphite substrate is broken by pulling, and the coating is not separated. The surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide adsorbed from the sample in the atmosphere and is difficult to remove in the XPS test.
Example 4
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high purity carbon/carbon green body (30mm), high purity mixed olefins (99.999%), high purity hydrogen (99.999%), high purity argon (99.999%); high purity tantalum pentachloride (99.99%); the implementation steps are as follows:
(1) Vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon gas, opening a gas valve for emptying, continuing introducing the argon gas for 10 minutes, closing an exhaust valve, and emptying various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating high-purity carbon/carbon blanks by distilled water, drying for 8 hours at 150 ℃, and then putting the blanks into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon gas, opening a gas valve to evacuate, continuing introducing argon gas for 15 minutes, closing a gas exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank body of the vapor deposition equipment;
(4) Vacuumizing to 1000Pa vacuum state, keeping the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 10000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 750 ℃;
(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, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:3:4:4, the flow rates are respectively 1SLM, 3SLM, 4SLM and 4SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank for 10 hours; preparing a tantalum carbide coating carbon/carbon material;
(6) Cutting 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, continuously introducing 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 carbide coating carbon/carbon material.
The thickness of the tantalum carbide coating layer of the prepared tantalum carbide coating layer carbon/carbon material is detected by using an electron microscope, and the detection result shows that the thickness of the coating layer is 77 mu m. According to the ISO 4624-2016 coating adhesion test standard, the adhesion of the tantalum carbide coating of the prepared graphite material with the tantalum carbide coating is detected, the peel strength is 125MPa through the test, the upper surface of the carbon/carbon substrate is peeled, and the coating is not separated. The surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere and is difficult to remove in the XPS test.
Example 5
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high-purity graphite blank (30mm), high-purity mixed olefin (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 the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating high-purity blanks by distilled water, drying for 8 hours at 150 ℃, and then putting the blanks into a reaction chamber to ensure that the surfaces of the blanks to be deposited are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) Vacuumizing to 1000Pa vacuum state, maintaining the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 5000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 750 ℃;
(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, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:1:1:1, the flow rates are respectively 1SLM, 1SLM and 1SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 8 hours; preparing a tantalum carbide coating graphite material;
(6) Cutting 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, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared tantalum carbide coating graphite material.
The thickness of the tantalum carbide coating of the prepared graphite material with the tantalum carbide coating is detected by using an electron microscope, and the detection result shows that the thickness of the coating is 23 mu m. According to the ISO 4624-2016 coating adhesion test standard, the prepared tantalum carbide coating graphite material is tested for the adhesion of the tantalum carbide coating, the peel strength is 25MPa, the graphite substrate is broken by pulling, and the coating is not separated. The surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide from the adsorption of the sample in the atmosphere and is difficult to remove in the XPS test.
Example 6
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: high-purity graphite blank (30mm), high-purity mixed olefin (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 the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon gas, opening a gas valve for emptying, continuing introducing the argon gas for 10 minutes, closing an exhaust valve, and emptying various residual gases and impurities in the vapor deposition equipment through the steps;
(2) Cleaning and decontaminating high-purity blanks by distilled water, drying for 8 hours at 150 ℃, and then putting into a reaction chamber to ensure that the surface to be deposited of the blanks is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) Vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating various gases and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) Vacuumizing to 1000Pa vacuum state, maintaining the 1000Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 5000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 750 ℃;
(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, argon and mixed olefin gas into the gas mixing tank, wherein the ratio of the four gases of the tantalum pentachloride, the mixed olefin, the hydrogen and the argon is 1:3:4:5, the flow rates are respectively 1SLM, 3SLM, 4SLM and 5SLM, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank for 8 hours; preparing a tantalum carbide coating graphite material;
(6) Cutting 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, continuously introducing 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 carbide coating graphite material.
The thickness of the tantalum carbide coating layer of the prepared graphite material with the tantalum carbide coating layer is detected by using an electron microscope, and the detection result shows that the thickness of the coating layer is 91 mu m. According to the ISO 4624-2016 coating adhesion test standard, the prepared tantalum carbide coating graphite material is tested for the adhesion of the tantalum carbide coating, the peel strength is 23MPa, the graphite substrate is broken by pulling, and the coating is not separated. The surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. The tantalum carbide coating was analyzed by X-ray photoelectron spectroscopy (XPS) and no other elements were determined except for Ta, C, O elements. The oxygen element is oxygen and carbon dioxide adsorbed from the sample in the atmosphere and is difficult to remove in the XPS test.
The above embodiments and drawings are not intended to limit the form and style of the product of the present invention, and any suitable changes or modifications, such as changes in reaction temperature, gasification temperature, gas flow rate, etc., made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. A method for preparing a tantalum carbide coated article by chemical vapor deposition using an inorganic tantalum halide and an olefin, comprising the steps of:
(1) a heating step, namely placing the base material in a reaction chamber, vacuumizing the reaction chamber, and heating under the protection of inert gas, wherein the heating temperature is 550-750 ℃;
(2) a deposition step, after the heating step, introducing tantalum pentachloride or tantalum pentafluoride gas, hydrogen and mixed olefin into a reaction chamber, heating at 550-750 ℃ under the pressure of 5000-10000Pa, and depositing a tantalum carbide coating on the surface of the substrate;
(3) and a cooling step, after the deposition step, cooling the tantalum carbide coating product to normal temperature.
2. The method of claim 1, wherein the tantalum carbide coated article is prepared by: the mixed olefin is a mixture of ethylene and propylene.
3. The method of claim 2, wherein the tantalum carbide coated article is prepared by: the volume ratio of the ethylene to the propylene is 1 to 2.
4. The method of claim 1, wherein the tantalum carbide coated article is prepared by: the gasification temperature of the tantalum pentachloride or the tantalum pentafluoride is 300 to 550 ℃.
5. The method of claim 1, wherein the tantalum carbide coated article is prepared by: the volume ratio of the tantalum pentachloride or the tantalum pentafluoride gas to the mixed olefin is 1 to 1, and the volume ratio of the tantalum pentachloride or the tantalum pentafluoride gas to the hydrogen is 1 to 1.
6. The method of claim 5, wherein the tantalum carbide coated article is prepared by: the flow rate of the tantalum pentachloride or tantalum pentafluoride gas is 2 to 6SLM, the gas flow rate of the mixed olefin is 2 to 60SLM, and the hydrogen flow rate is 2 to 30SLM.
7. The method of claim 1, wherein the tantalum carbide coated article is prepared by: and introducing the tantalum pentachloride or tantalum pentafluoride gas into a reaction chamber by a carrier gas, wherein the carrier gas is argon.
8. The method of claim 7, wherein the tantalum carbide coated article is prepared by: the volume ratio of the tantalum pentachloride or tantalum pentafluoride gas to the carrier gas is 1 to 4.
9. The method of claim 1, wherein the tantalum carbide coated article is prepared by: the reaction chamber is an alumina reaction chamber.
10. The method of claim 1, wherein the tantalum carbide coated article is prepared by: the substrate comprises at least one of a metal, a carbon material, a ceramic, or quartz.
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| CN115948721A (en) * | 2023-03-15 | 2023-04-11 | 杭州幄肯新材料科技有限公司 | Method for preparing tantalum carbide coating by CVD (chemical vapor deposition) method |
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