CN110735126B - Method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate - Google Patents
Method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 163
- 239000011248 coating agent Substances 0.000 title claims abstract description 159
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 147
- 239000010432 diamond Substances 0.000 title claims abstract description 147
- 239000000758 substrate Substances 0.000 title claims abstract description 85
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 46
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 45
- 230000007704 transition Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 74
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims abstract description 15
- 238000004050 hot filament vapor deposition Methods 0.000 claims abstract description 12
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 11
- 229910000851 Alloy steel Inorganic materials 0.000 claims abstract description 6
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 19
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910000997 High-speed steel Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002113 nanodiamond Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 239000002344 surface layer Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
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- 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
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/277—Diamond only using other elements in the gas phase besides carbon and hydrogen; using other elements besides carbon, hydrogen and oxygen in case of use of combustion torches; using other elements besides carbon, hydrogen and inert gas in case of use of plasma jets
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- 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
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- 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
- C23C16/50—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 using electric discharges
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- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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- C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
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Abstract
The invention discloses a method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate. The method aims at taking low carbon steel, low alloy steel and the like as matrixes, firstly, tungsten fluoride and methane are taken as precursors, a Plasma Enhanced Chemical Vapor Deposition (PECVD) nanometer tungsten carbide coating is adopted, then a hot wire chemical vapor deposition method is adopted to deposit a nanocrystalline silicon-doped diamond coating on the tungsten carbide coating to form a double-layer transition layer, and then an intrinsic micrometer or nanometer diamond coating is deposited on the surface of the silicon-doped diamond coating. The method can prepare micron or nanometer diamond film coating with thickness adjustable between 2-30 μm. Compared with the prior art, the method solves the problem that the CVD diamond coating cannot be directly deposited due to the fact that the thermal expansion coefficient of the steel matrix is too large to be different from that of diamond, so that the steel matrix can be used for replacing conventional hard alloy to be used for depositing the diamond coating, and the economic performance is obvious.
Description
Technical Field
The invention relates to a preparation method in the technical field of films, in particular to a method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate.
Background
The diamond film has excellent physical and chemical properties, has the advantages of high hardness, small friction coefficient, high thermal conductivity and stable chemical property, is a good insulator, and is an excellent semiconductor material after being doped with B, N, Si and other elements. At present, the CVD diamond technology has been widely applied, such as coating dies, cutters and wear-resistant devices in the tool field, electrochemical corrosion-resistant anodes for water treatment, and the like.
Coating adhesion and surface finish are the main factors affecting the performance of CVD diamond coatings in wear resistant and antifriction device applications. The difference between the thermal expansion coefficient and the lattice constant of the diamond and the base material, and the deposited diamond coating has certain internal stress, so that the adhesive force of the coating is reduced and the coating is easy to fall off, and the application occasions of cutters, shaft devices and the like are particularly obvious. Because the substrate temperature is very high when the CVD method is used for depositing the diamond film, the temperature is about 850 ℃, the thermal expansion coefficient of diamond is small and is generally only 1/3-1/4 of the substrate material, and large internal stress can be generated in the coating after cooling and shrinking. In addition, because elements such as Fe and Co can catalyze the conversion of diamond to graphite at high temperature, a diamond coating cannot be directly deposited on steel and iron alloy which are widely applied in the field of tools, and common diamond deposition substrates comprise hard alloy, ceramic and the like. On the other hand, tungsten carbide coatings are often used to be thermally sprayed on the surface of steel substrates to improve the hardness and wear resistance of the substrate surface. The Chinese patent application 'a tungsten carbide gradient composite coating and a preparation method thereof' (109023354A) adopts a laser cladding method to prepare a tungsten carbide coating on the surface of steel. Chinese patent 'H13 steel surface supersonic flame spraying high hardness wear resistant WC-17Co cermet coating' (CN 109136812A) adopts supersonic flame spraying to prepare WC-17Co coating on the steel surface. The surface hardness and wear resistance of the steel can be improved. However, the hardness and wear resistance of the tungsten carbide coating are still far less than those of diamond, which affects the improvement of the service efficiency and service life of the tool.
In addition, the deposition of diamond coatings directly on the surface of steel substrates coated with tungsten carbide coatings is problematic. Firstly, the sprayed tungsten carbide often contains elements such as Co, and the like, which can cause diamond graphitization and coating peeling. Secondly, insufficient surface hardness of tungsten carbide also results in a reduction in the excellent surface hardness of the surface diamond coating itself.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate, so that the selection range of the substrate material is greatly expanded and the cost is reduced.
The technical purpose of the invention is realized by the following technical scheme:
a method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate comprises the following operation steps:
s1, after a substrate is pretreated, depositing a layer of nanocrystalline tungsten carbide coating by adopting a plasma enhanced chemical vapor deposition method;
s2, depositing a silicon-doped diamond coating on the surface of the nanocrystalline tungsten carbide coating by adopting a hot filament chemical vapor deposition method;
s3, continuously depositing an intrinsic diamond coating on the surface of the silicon-doped diamond coating by adopting a hot wire chemical vapor deposition method;
the substrate is any one of low-carbon steel or low-alloy steel.
The method provided by the invention can be used for preparing the micro-diamond or nano-diamond film coating, and the thickness of the coating can be adjusted between 2 and 30 mu m. Compared with the prior art, the method provided by the invention solves the problem that the CVD diamond coating cannot be directly deposited due to the fact that the thermal expansion coefficient of the steel matrix is too large to be different from that of diamond, so that the steel matrix can be used for replacing the conventional hard alloy to be used for depositing the diamond coating, and the economic performance is obvious. In addition, the tungsten carbide-silicon doped nano double-layer transition layer has a compact structure and can effectively reduce residual thermal stress, so that an intrinsic diamond coating with excellent adhesive force and wear resistance can be deposited on the surface. Has wide application prospect in the cutter and shaft device with abrasion-proof requirement.
Further, in S2, the nano-crystalline tungsten carbide coating is deposited by the plasma enhanced chemical vapor deposition method, and tungsten fluoride, methane and hydrogen are used as raw material gases, wherein the flow rate of the tungsten fluoride gas is 6sccm, the flow rate of the methane is 160sccm, and the flow rate of the hydrogen is 200 sccm. Although the technology of coating the transition layer on the steel substrate and then depositing the diamond coating can isolate the contact of Fe and the diamond coating, the hardness of the steel substrate is too low, and the exertion of excellent hardness of the diamond coating is influenced. In the invention, the nano tungsten carbide (WC) coating on the surface of the steel matrix can isolate Fe element and the diamond coating in the matrix, thereby avoiding diamond graphitization in the high-temperature preparation process. And the hardness of the substrate, the tungsten carbide, the silicon-doped diamond coating and the intrinsic diamond coating is gradually increased, so that the wear-resisting and antifriction performance of the intrinsic diamond on the outermost layer can be better exerted, and the harder tungsten carbide-silicon-doped diamond transition layer avoids the problem that the surface layer diamond is easy to layer and fall off due to insufficient hardness of the substrate. In addition, the silicon-doped diamond coating in the intermediate transition layer can reduce the residual compressive stress of the coating, so that the intrinsic diamond coating can be better deposited, and the stress deformation of the coating is reduced. The transition layers of the tungsten carbide-silicon doped diamond are connected by adopting nano-scale grains, the combination is compact, the adhesion is favorably improved, and meanwhile, the structure with multiple grain boundaries is favorable for preventing crack propagation and avoiding the falling of the coating.
Further, in S2, the deposition conditions for depositing the nanocrystalline tungsten carbide coating by chemical vapor deposition are as follows: the deposition pressure is 100-.
Furthermore, the grain diameter of the tungsten carbide of the nanocrystalline tungsten carbide coating is 20-50 nm.
Further, S2 and S3 were deposited continuously by HFCVD.
Further, when the silicon-doped diamond coating is deposited, acetone is adopted as a carbon source, tetraethoxysilane is doped in the carbon source to serve as a silicon source, and the concentration is 1000-9000 ppm.
Further, when the silicon-doped diamond coating is deposited, the hydrogen flow is 2000sccm, the volume ratio of the mixed solution to the hydrogen is 1-2%, the reaction pressure is 1200Pa, the hot wire temperature is 2200 ℃, the matrix temperature is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the deposited silicon-doped diamond grains is 200nm-1 μm.
Further, depositing the intrinsic diamond coating on the surface of the silicon-doped diamond coating, wherein the carbon source adopts acetone, the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 1200-4500Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, and the deposition time is 2-20 h.
In conclusion, the invention has the following beneficial effects:
1. the tungsten carbide transition layer-silicon doped diamond composite coating on the steel substrate prepared by the method can deposit the diamond coating on the steel substrate which cannot be adopted by the conventional CVD method;
2. the tungsten carbide transition layer-silicon doped diamond composite coating on the steel substrate prepared by the method has the advantages that the hardness of the substrate, the tungsten carbide coating, the silicon doped diamond coating and the intrinsic diamond coating is gradually increased, and the structure with gradually increased surface hardness can better exert the excellent hardness and wear resistance of the intrinsic diamond on the outermost layer. The deformation and the falling off of the coating caused by the excessively low hardness of the matrix are avoided;
3. the composite coating of the tungsten carbide transition layer-silicon doped diamond on the steel substrate prepared by the method is compact in combination with the nano-crystalline silicon doped diamond coating, so that the adhesive force of the whole diamond coating is improved;
4. the tungsten carbide transition layer-silicon doped diamond composite coating on the steel matrix prepared by the method adopts nano-scale grains, has more crystal boundaries, can reduce residual stress and is beneficial to preventing crack propagation. Therefore, the structure can effectively avoid the coating from cracking and falling off;
5. the tungsten carbide transition layer-silicon doped diamond composite coating on the steel substrate prepared by the method can be deposited simultaneously with the silicon doped diamond coating and the intrinsic diamond coating, the steps are simple and convenient, and the production cost is effectively reduced.
Drawings
FIG. 1 is a schematic illustration of a tungsten carbide transition layer-silicon doped diamond composite coating prepared on a steel substrate;
FIG. 2 is a surface topography of a tungsten carbide transition layer-silicon doped diamond composite coating prepared on a steel substrate;
FIG. 3 is a Raman spectroscopic examination of a tungsten carbide transition layer-silicon doped diamond composite coating prepared on a steel substrate;
in the figure, 1 is a substrate, 2 is a nano tungsten carbide coating, 3 is a silicon-doped diamond coating, and 4 is an intrinsic diamond coating.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
In which like parts are designated by like reference numerals. It should be noted that the terms "front," "back," "left," "right," "upper" and "lower" used in the following description refer to directions in the drawings, and the terms "bottom" and "top," "inner" and "outer" refer to directions toward and away from, respectively, the geometric center of a particular component.
Example 1: method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate
A steel substrate having dimensions of phi 20mm x 5mm was selected.
S1, soaking a substrate 1 in an acetone solution, ultrasonically cleaning for 15 minutes, taking out and drying, placing the substrate on a workbench of a PECVD device, starting to deposit a tungsten carbide coating 2, vacuumizing a reaction cavity, and introducing mixed gas of methane, tungsten fluoride and hydrogen. The tungsten fluoride gas flow rate was 6sccm, the methane flow rate was 160sccm, and the hydrogen flow rate was 200 sccm. The deposition conditions are that the air pressure is 100-150 Pa, the radio frequency power is 80kW, the matrix temperature is 800 ℃, and the reaction duration is 180 min.
S2, taking out the substrate 1 after deposition is finished, and placing the substrate in an HFCVD device for continuous deposition of the silicon-doped diamond coating 2 and the intrinsic diamond coating 4. The deposition conditions for the silicon doped diamond coating 3 were: the hydrogen flow rate was 2000sccm, and 2% ethyl orthosilicate/acetone mixed vapor was mixed into the gas flow, with the ethyl orthosilicate concentration being 5000 ppm. The reaction pressure is 1200Pa, the temperature of the hot wire is 2200 ℃, the temperature of the matrix is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the silicon-doped diamond crystal grain obtained by deposition is 200nm-1 μm.
S3, depositing an intrinsic diamond coating 4 on the surface of the silicon-doped diamond coating, wherein the deposition conditions are as follows: the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 1200Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, the deposition time is 20h, and the thickness of the prepared diamond coating is 15 μm.
After 20h of intrinsic diamond deposition, high purity diamond with a thickness of 15 μm was prepared on the surface of the steel substrate, and the purity of the diamond was measured by raman spectroscopy, as shown in fig. 2. The map is at 1332cm-1Has sharp diamond peaks, shows that high-purity diamond is obtained by deposition on the surface of steel, and has excellent hardness and wear resistance. And because the lattice constants of the tungsten carbide-silicon doped diamond transition layer are close and the grain sizes are close, the combination is compact and the adhesion is excellent. In the cooling process, the coating does not crack or fall off.
Example 2: method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate
A high-speed steel turning tool with a matrix 1 of 100mm x 20mm is selected.
S1, soaking a substrate 1 in an acetone solution for ultrasonic cleaning for 15 minutes, taking out and drying, placing the substrate on a workbench of a PECVD device, and beginning to deposit a tungsten carbide coating 2, firstly vacuumizing a reaction cavity, then introducing mixed gas of methane, tungsten fluoride and hydrogen, wherein the flow rate of the tungsten fluoride gas is 6sccm, the flow rate of methane is 160sccm, the flow rate of hydrogen is 200 sccm, the deposition conditions are that the air pressure is 100-flow-assistant 150 Pa, the radio frequency power is 80kW, the substrate temperature is 800 ℃, and the reaction duration is 180 min;
s2, taking out the substrate 1 after deposition is finished, and placing the substrate in an HFCVD device for continuous deposition of the silicon-doped diamond coating 3 and the intrinsic diamond coating 4, wherein the deposition conditions of the silicon-doped diamond coating are as follows: hydrogen flow rate is 2000sccm, and tetraethoxysilane/acetone mixed steam with the concentration of 2% is mixed in the gas flow, and the tetraethoxysilane concentration is 5000 ppm; the reaction pressure is 1200Pa, the temperature of the hot wire is 2200 ℃, the temperature of the matrix is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the silicon-doped diamond crystal grain obtained by deposition is 200nm-1 μm;
s3, depositing an intrinsic diamond coating 4 on the surface of the silicon-doped diamond coating 3, wherein the deposition conditions are as follows: the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 4000Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, the deposition time is 10h, and the thickness of the prepared diamond coating is 8-10 μm.
The high-speed steel turning tool prepared by the method has the micron diamond coating on the surface of the front tool surface, is used for turning silicon-aluminum alloy, obviously reduces the abrasion of the rear tool surface of the tool, and prolongs the service life by more than 10 times compared with that before the coating.
Example 3: method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate
High speed steel turning inserts were selected with a base 1 of 17mm x 5 mm.
S1, soaking a substrate 1 in an acetone solution for ultrasonic cleaning for 15 minutes, then taking out and drying, placing the substrate on a workbench of a PECVD device, starting to deposit a tungsten carbide coating 2, firstly vacuumizing a reaction cavity, and then introducing mixed gas of methane, tungsten fluoride and hydrogen; the flow rate of the tungsten fluoride gas is 6sccm, the flow rate of the methane is 160sccm, and the flow rate of the hydrogen is 200 sccm; the deposition conditions are that the air pressure is 100-150 Pa, the radio frequency power is 80kW, the matrix temperature is 800 ℃, and the reaction duration is 180 min;
s2, taking out the substrate 1 after deposition is finished, and placing the substrate in an HFCVD device for continuous deposition of the silicon-doped diamond coating 3 and the intrinsic diamond coating 4, wherein the deposition conditions of the silicon-doped diamond coating 3 are as follows: hydrogen flow rate is 2000sccm, and tetraethoxysilane/acetone mixed steam with the concentration of 2% is mixed in the gas flow, and the tetraethoxysilane concentration is 5000 ppm; the reaction pressure is 1200Pa, the temperature of the hot wire is 2200 ℃, the temperature of the matrix is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the silicon-doped diamond crystal grain obtained by deposition is 200nm-1 μm;
s3, depositing an intrinsic diamond coating 4 on the surface of the silicon-doped diamond coating 3, wherein the deposition conditions are as follows: the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 1200Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, the deposition time is 10h, and the thickness of the prepared diamond coating is 8-10 μm.
The surface of the high-speed steel turning tool blade prepared by the method is deposited with a layer of nano diamond coating, the turning tool is used for turning silicon-aluminum alloy, the service life is prolonged by more than 10 times compared with that before the coating, and the surface finish of a processed workpiece is also obviously improved.
Example 4: method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate
The substrate 1 is selected to be a low carbon steel sealing ring with the outer diameter phi 55mm, the inner diameter phi 42mm and the thickness of 8 mm.
S1, soaking a substrate 1 in an acetone solution for ultrasonic cleaning for 15 minutes, then taking out and drying, placing the substrate on a workbench of a PECVD device, starting to deposit a tungsten carbide coating 2, firstly vacuumizing a reaction cavity, and then introducing mixed gas of methane, tungsten fluoride and hydrogen; the flow rate of the tungsten fluoride gas is 6sccm, the flow rate of the methane is 160sccm, and the flow rate of the hydrogen is 200 sccm; the deposition conditions are that the air pressure is 100-150 Pa, the radio frequency power is 80kW, the matrix temperature is 800 ℃, and the reaction duration is 180 min;
s2, taking out the substrate 1 after deposition is finished, and placing the substrate in an HFCVD device for continuous deposition of the silicon-doped diamond coating 3 and the intrinsic diamond coating 4, wherein the deposition conditions of the silicon-doped diamond coating 3 are as follows: hydrogen flow rate is 2000sccm, and tetraethoxysilane/acetone mixed steam with the concentration of 2% is mixed in the gas flow, and the tetraethoxysilane concentration is 5000 ppm; the reaction pressure is 1200Pa, the temperature of the hot wire is 2200 ℃, the temperature of the matrix is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the silicon-doped diamond crystal grain obtained by deposition is 200nm-1 μm;
s3, depositing an intrinsic diamond coating 4 on the surface of the silicon-doped diamond coating 3, wherein the deposition conditions are as follows: the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 1200Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, the deposition time is 5h, and the thickness of the prepared diamond coating is 3-5 μm.
The intrinsic nano diamond coating crystal grains deposited on the surface of the sealing ring prepared by the method are about 50-60 nanometers, the polishing workload of the diamond coating is obviously reduced due to the good surface smoothness of the coating, the diamond coating on the end face of the sealing ring can reach the mirror surface degree after 2 hours of mechanical grinding and polishing, and Ra can reach 0.05 mu m.
Example 5: method for preparing tungsten carbide transition layer-silicon-doped diamond composite coating on steel substrate
The substrate 1 is a 3-inch non-polished stainless steel electrode sheet.
S1, firstly, soaking a substrate 1 in an acetone solution for ultrasonic cleaning for 15 minutes, then taking out and drying, placing the substrate on a workbench of a PECVD device, and beginning to deposit a tungsten carbide coating 2, firstly vacuumizing a reaction cavity, then introducing mixed gas of methane, tungsten fluoride and hydrogen, wherein the flow rate of the tungsten fluoride gas is 6sccm, the flow rate of methane is 160sccm, the flow rate of hydrogen is 200 sccm, the deposition conditions are that the air pressure is 100-flow-assistant 150 Pa, the radio frequency power is 80kW, the substrate temperature is 800 ℃, and the reaction duration is 180 min;
s2, taking out the substrate 1 after deposition is finished, and placing the substrate in an HFCVD device for continuous deposition of the silicon-doped diamond coating 3 and the intrinsic diamond coating 4, wherein the deposition conditions of the silicon-doped diamond coating 3 are as follows: hydrogen flow rate is 2000sccm, 2% tetraethyl orthosilicate/acetone mixed steam is mixed into the gas flow, the tetraethyl orthosilicate concentration is 5000ppm, the reaction gas pressure is 1200Pa, the hot wire temperature is 2200 ℃, the matrix temperature is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the silicon-doped diamond crystal grain obtained by deposition is 200nm-1 μm;
s3, depositing an intrinsic diamond coating 4 on the surface of the silicon-doped diamond coating 3, wherein the deposition conditions are as follows: the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, trimethyl borate with the concentration of 5000ppm is doped in acetone, the reaction pressure is 4500Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, and the bias current is 4A.
After 20 hours of deposition, a boron-doped diamond coating with the thickness of 20 microns is obtained on the surface of the substrate 1, the surface of the coating is a conductive micron diamond coating, the chemical property is stable, the acid and alkali resistance is good, the service life of the electrode can be greatly prolonged, and compared with metal electrodes such as titanium and the like, the boron-doped diamond coating has the advantages of low cost and easiness in processing.
From the above examples, it can be seen that in order to achieve the purpose of depositing a diamond coating on a low carbon steel or low alloy steel substrate, a tungsten carbide-silicon doped diamond transition coating needs to be deposited on the surface of the substrate. The transition layer has nano-crystalline grains and can be tightly combined with the substrate and the diamond coating on the surface layer at the same time. And the transition layer improves the surface hardness of the matrix, and is beneficial to the exertion of excellent wear resistance of the surface layer diamond. The silicon-doped diamond coating in the transition layer can reduce the residual stress of the coating and reduce the shedding phenomenon of the coating. And the crystal grains of the transition layer are fine, which is beneficial to inhibiting the generation and the propagation of cracks. In summary, the present invention provides a method for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate, which extends the substrate selection range of CVD diamond coating deposition to low carbon steel and low alloy steel.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. A method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate is characterized by comprising the following operation steps:
s1, after a substrate (1) is pretreated, depositing a nanocrystalline tungsten carbide coating (2) by adopting a plasma enhanced chemical vapor deposition method;
s2, depositing a silicon-doped diamond coating (3) on the surface of the nanocrystalline tungsten carbide coating (2) by adopting a hot wire chemical vapor deposition method;
s3, continuously depositing an intrinsic diamond coating (4) on the surface of the silicon-doped diamond coating (3) by adopting a hot wire chemical vapor deposition method;
the substrate (1) is any one of low-carbon steel or low-alloy steel, and the hardness of the substrate, the tungsten carbide, the silicon-doped diamond coating and the intrinsic diamond coating is gradually increased.
2. The method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 1, wherein in the step S2, the nanocrystalline tungsten carbide coating (2) is deposited by plasma enhanced chemical vapor deposition, and tungsten fluoride, methane and hydrogen are used as raw material gases, wherein the tungsten fluoride gas flow rate is 6sccm, the methane flow rate is 160sccm, and the hydrogen flow rate is 200 sccm.
3. The process for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 2, characterized in that in said S2, the deposition conditions for depositing the nanocrystalline tungsten carbide coating (2) by chemical vapour deposition are: the deposition pressure is 100-.
4. The method for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 1, characterized in that the nanocrystalline tungsten carbide coating (2) has a tungsten carbide grain diameter of 20-50 nm.
5. The method for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 1, characterised in that said S2 and S3 are continuously deposited using HFCVD method.
6. The method for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 1, characterized in that during the deposition of said silicon doped diamond coating (3) acetone is used as carbon source, which is doped with tetraethoxysilane as silicon source, at a concentration of 1000-9000 ppm.
7. The method for producing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate according to claim 1, characterized in that, in depositing the silicon doped diamond coating (3), the hydrogen flow is 2000sccm, the volume ratio of the mixed solution to hydrogen is 1-2%, the reaction pressure is 1200Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, the deposition time is 2h, and the diameter of the deposited silicon doped diamond grains is 200nm-1 μm.
8. The method for preparing the tungsten carbide transition layer-silicon doped diamond composite coating on the steel substrate according to the claim 1, wherein the intrinsic diamond coating is deposited on the surface of the silicon doped diamond coating, the carbon source adopts acetone, the hydrogen flow is 2000sccm, the volume ratio of acetone vapor to hydrogen is 1-2%, the reaction pressure is 1200-4500Pa, the hot wire temperature is 2200 ℃, the substrate temperature is about 800 ℃, the bias current is 4A, and the deposition time is 2-20 h.
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