CN114959699A - Low-friction metal/ultra-nano diamond composite coating and preparation method thereof - Google Patents

Low-friction metal/ultra-nano diamond composite coating and preparation method thereof Download PDF

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CN114959699A
CN114959699A CN202210918642.4A CN202210918642A CN114959699A CN 114959699 A CN114959699 A CN 114959699A CN 202210918642 A CN202210918642 A CN 202210918642A CN 114959699 A CN114959699 A CN 114959699A
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coating
metal
ultra
friction
uncd
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CN114959699B (en
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宋惠
江南
褚伍波
邓丽芬
李�赫
西村一仁
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C23C28/00—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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • 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
    • C23C28/00—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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Abstract

The invention discloses a low-friction metal/ultra-nano diamond composite coating and a preparation method thereof, belonging to the technical field of composite coatings, wherein the preparation method specifically comprises the following steps: (1) depositing ultra-nano diamond on the surface of the substrate through hot wire chemical vapor deposition to obtain a UNCD coating; (2) depositing a metal coating on the surface of the UNCD coating by utilizing a magnetron sputtering technology to obtain the UNCD-metal coating; (3) and carrying out heat treatment on the UNCD-metal coating to obtain the low-friction metal/ultra-nano diamond composite coating. The method utilizes high-temperature heat treatment and frictional heat catalysis to induce the ordered carbon nanostructure to generate on the UNCD coating, thereby improving the tribological performance of the coating; the metal/ultra-nano diamond composite coating prepared by the method disclosed by the invention is high-temperature resistant, high in hardness and excellent in friction performance.

Description

Low-friction metal/ultra-nano diamond composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of composite coatings, in particular to a low-friction metal/ultra-nano diamond composite coating and a preparation method thereof.
Background
The diamond has excellent force, heat, light, dielectric and other performances and wide application fields. Diamond, which has the largest hardness value among the currently known minerals, has the properties of wear reduction and wear resistance, and has become an ideal choice for surface protection materials of friction parts, wherein ultra-nano diamond (UNCD) films have attracted much attention of industrial researchers due to their extremely small grain size, special composition and low surface roughness. However, how to further reduce the friction coefficient of the UNCD film and improve the service behavior of the UNCD film in a harsh environment is an urgent technical problem to be solved for expanding the engineering application range of the UNCD film.
In recent years, the deep research and controllable preparation of carbon nanomaterials (carbon nanotubes, graphene and fullerene) provide a new idea for designing antifriction materials, and the two-dimensional material serving as a high-quality lubricating phase not only has a low friction coefficient, but also can be compounded with other lubricating phases to play a good role in synergistic lubrication.
Chinese patent publication No. CN108753106A discloses a nano hybrid material modified epoxy resin self-lubricating composite coating, which is prepared by first preparing a carbon nanotube/graphene oxide/molybdenum disulfide nano hybrid material, adding the material into epoxy resin, a curing agent and an organic solvent to obtain a mixed solution, spraying the mixed solution onto a base material, and curing and molding to obtain the high friction-reducing and wear-resisting epoxy resin self-lubricating composite coating. The tribological performance of the coating is fully improved by adding the carbon nano tube/graphene oxide/molybdenum disulfide nano hybrid material.
Chinese patent publication No. CN114015491A discloses a lubricating oil additive containing a modified nanocarbon material, wherein the modified nanocarbon material is a modified carbon nanotube, and the modified carbon nanotube has a large specific surface area, good dispersibility, and a tube wall cavity structure; the addition of the additive in the lubricating oil can improve the lubricating property and the wear resistance of the lubricating oil and reduce the friction coefficient of a mechanical friction surface.
Because the growth conditions of diamond and other carbon nanostructures (such as graphene, C60 and the like) are greatly different, the difficulty in designing and preparing a composite coating with good binding force between a UNCD film and the carbon nanostructures is high, and Chinese patent publication No. CN112126906A discloses a preparation method of a graphene/diamond-like lubricating film. The hydrogen-doped diamond-like carbon film is doped with boron carbide and amorphous carbon, so that the hardness and the low friction performance can be provided, and the composite film has a lower friction coefficient and a longer wear-resistant life. But the bonding force between graphene and diamond-like thin film needs to be further improved.
Disclosure of Invention
The invention provides a preparation method of a low-friction metal/ultra-nano diamond composite coating, the preparation process is simple and controllable, and the prepared metal/ultra-nano diamond composite coating comprises a metal layer, a UNCD coating and an ordered carbon nanostructure generated in situ by ultra-nano diamond, and has high temperature resistance, high hardness and excellent friction performance.
The technical scheme is as follows:
a preparation method of a low-friction metal/ultra-nano diamond composite coating comprises the following steps:
(1) depositing ultra-nano diamond on the surface of the substrate through hot wire chemical vapor deposition to obtain a UNCD coating;
(2) depositing a metal coating on the surface of the UNCD coating by utilizing a magnetron sputtering technology to obtain the UNCD-metal coating; the metal coating is a continuous coating or a non-continuous coating;
(3) and carrying out heat treatment on the UNCD-metal coating to obtain the low-friction metal/ultra-nano diamond composite coating.
Preferably, the metal coating is a copper coating, a gold coating or a nickel coating. In the friction process of the product coating prepared by the invention, the UNCD coating can form different ordered carbon nanostructures in situ under the catalysis of different metals, for example, the UNCD coating is easy to catalyze to form a graphene structure under the action of copper, and is easy to form a graphene or fullerene structure under the action of nickel. Copper, gold or nickel has good catalytic action on the generation of the ordered carbon nanostructure.
Sp in UNCD coating 3 Predominantly in phase, but with a certain sp 2 During the high-temperature heat treatment process, the UNCD coating can generate ordered carbon nanostructures such as graphene, carbon nano tubes, fullerene and the like in situ. The hardness of the UNCD coating is high, the most main failure mode in the friction process is abrasive particle abrasion, the ordered carbon nano structure has a curling effect on the abrasive particles, and the tribological performance of the UNCD coating can be further improved. In the subsequent friction process, under the catalytic action of metal, the friction heat can also induce the generation of the ordered carbon nano structure in situ, so that the friction performance is further improved.
Preferably, the thickness of the UNCD coating is 4-8 μm; the thickness of the metal coating is 50-800 nm. The thickness of the metal coating in the above range is advantageous for its catalytic action during annealing and rubbing.
Preferably, the substrate is pretreated before depositing the UNCD coating, and the pretreatment process comprises: sequentially cleaning a substrate by using ethanol and acetone to remove oil stains and impurities on the surface of the substrate; in order to facilitate nucleation in the growth process of the coating, the cleaned substrate is placed in ethanol suspension of ultrafine nano diamond powder for ultrasonic oscillation to complete surface crystal implantation treatment, and then ultrasonic cleaning is carried out in absolute ethyl alcohol, and then the substrate is taken out and dried by nitrogen.
The grain diameter of the superfine nano-diamond powder is 8-10 nm, and the concentration of the ethanol suspension of the superfine nano-diamond powder is 0.1-2 mol/L.
Preferably, in step (1), the hot filament chemical vapor deposition is divided into a first stage and a second stage, and the parameters of the first stage are as follows: the flow rate of methane is 8-10 sccm, the flow rate of hydrogen is 200-400 sccm, the deposition pressure is 1-4 KPa, and the deposition time is 20-30 min; the parameters of the second stage are: the flow rate of methane is 2-10 sccm, the flow rate of hydrogen is 100-400 sccm, the deposition pressure is 1-4 KPa, and the deposition time is 5-20 h; wherein the parameters of the first stage facilitate diamond nucleation and the parameters of the second stage facilitate diamond growth.
The grain size of the UNCD coating prepared under the above parameters is about 10 nm.
Preferably, in the step (2), the conditions of the magnetron sputtering process are as follows: the deposition pressure is 0.5-1.5 Pa, the argon flow is 30-45 scccm, the sputtering power of the metal target is 10-200W, the deposition temperature is 100-300 ℃, and the deposition time is 5-10 min.
Preferably, the inert gas is used as the shielding gas in the heat treatment process, and the heat treatment conditions are as follows: the temperature is 700 ℃ and 1000 ℃, and the time is 1-3 h. Too low a temperature is not conducive to the generation of ordered carbon nanostructures, and too high a temperature may affect the function and properties of the UNCD coating itself.
Further preferably, the inert gas is argon.
The heat treatment process is crucial to the preparation of the low-friction metal/ultra-nano diamond composite coating, the UNCD coating is high-temperature resistant, and part sp of the UNCD coating is in the heat treatment process under corresponding conditions 3 The phase conversion can be carried out, ordered carbon nanostructures such as graphene, carbon nano tubes, fullerene and the like are generated in situ on the UNCD coating, and the ordered carbon nanostructures formed after heat treatment improve the friction performance of the composite coating.
The invention also provides the low-friction metal/ultra-nano diamond composite coating prepared by the preparation method of the low-friction metal/ultra-nano diamond composite coating, the low-friction metal/ultra-nano diamond composite coating comprises a metal layer, a UNCD coating and an ordered carbon nano structure generated in situ by ultra-nano diamond, and the ordered carbon nano structure comprises a graphene structure, a carbon nano tube structure or a fullerene structure.
The low-friction metal/ultra-nano diamond composite coating prepared by the method can be further catalyzed by metal in situ to form an ordered carbon nano structure in the friction process; the metal/ultra-nano diamond composite coating can generate ordered carbon nano-structures no matter whether the metal coating is continuous or not.
The ordered carbon nanostructure in the low-friction metal/ultra-nano diamond composite coating can be generated in the high-temperature heat treatment process and also can be generated in the friction process; and the ordered carbon nanostructure has good binding force with the UNCD coating.
The invention also provides application of the low-friction metal/ultra-nano diamond composite coating in the field of surface treatment of friction parts. The metal/ultra-nano diamond composite coating disclosed by the invention is high-temperature resistant, high in hardness and excellent in friction performance, and is very suitable for surface treatment of friction parts.
The low-friction metal/ultra-nano diamond composite coating can generate ordered carbon nano structures in the friction process.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of preparing the UNCD layer by a hot wire vapor chemical deposition method, preparing the metal layer by utilizing a magnetron sputtering technology, and then carrying out high-temperature annealing treatment on the metal/UNCD composite coating, wherein the UNCD coating can generate an ordered carbon nano structure in situ in the high-temperature heat treatment process; the ordered carbon nanostructure can be compounded with the UNCD to play a role in synergy and friction reduction, and in the subsequent friction process, under the catalytic action of metal, the friction heat can also induce the generation of the ordered carbon nanostructure in situ, so that the friction performance is further improved.
(2) The invention adopts a mode of combining CVD and PVD, and the preparation method is simple and controllable; the generation of the ordered carbon nanostructure on the surface of the UNCD coating is induced by high-temperature heat treatment and friction heat catalysis, so that on one hand, a complex and complicated mode of preparing a composite structure by a transfer method can be avoided, and on the other hand, the ordered carbon nanostructure generated by in-situ induction has strong binding force with the UNCD coating.
(3) The low-friction metal/ultra-nano diamond composite coating prepared by the method comprises a metal layer, an UNCD layer and an ordered carbon nano structure generated in situ by ultra-nano diamond in a heat treatment process, and is different from a diamond-like carbon-based composite coating or a micron and nano diamond film material.
Drawings
Fig. 1 is a friction coefficient plot (5N, atmospheric environment) of the low friction metal/ultra-nano diamond composite coating made in example 1.
FIG. 2 is a cross-sectional topography of the low friction metal/ultra-nano diamond composite coating made in example 1.
FIG. 3 is a surface topography of the low friction metal/ultra-nano diamond composite coating made in example 1.
Detailed Description
The invention is further elucidated with reference to the following figures and examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) The ceramic is used as a substrate, and the substrate is ultrasonically cleaned in ethanol and acetone solution in turn and then is dried by nitrogen for standby. Then carrying out crystal implantation treatment on the substrate, putting the cleaned substrate in 0.5 mol/L superfine nano-diamond/ethanol solution for ultrasonic treatment for 30 min, then cleaning in the ethanol solution for 15min, taking out the substrate, drying by blowing with nitrogen, and placing the substrate in a hot wire CVD vacuum chamber.
(2) And performing UNCD coating deposition by hot filament chemical vapor deposition, wherein the deposition process comprises two stages of nucleation and film growth. The parameters of the nucleation stage are: the flow rate of methane is 8 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 1.5 KPa, and the deposition time is 20-30 min; the growth stage parameters of the UNCD film are as follows: the flow rate of methane is 6 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 2 KPa, and the deposition time is 6 h.
(3) Depositing a discontinuous metal layer on the UNCD coating in the step (2) by using a magnetron sputtering method, taking 99.99% high-purity Cu as a sputtering target material, wherein the deposition pressure is 0.5 Pa, the argon flow is 35 scccm, the metal target sputtering power is 150W, the deposition temperature is 100 ℃, and the deposition time is 10 min.
(4) And (4) placing the substrate with the Cu/UNCD composite coating prepared in the step (3) in a vacuum furnace, vacuumizing, introducing argon as protective gas, preserving the temperature for 1 hour at 1000 ℃, and then slowly cooling to room temperature to take out a sample.
The friction coefficient diagram (5N, atmospheric environment) of the low-friction metal/ultra-nano diamond composite coating prepared in this example is shown in fig. 1, and the average friction coefficient of the composite coating is 0.025, and the friction performance is excellent.
The cross-sectional topography of the low-friction metal/ultra-nano diamond composite coating prepared by the embodiment is shown in fig. 2, the surface topography is shown in fig. 3, and as can be seen from fig. 2 and 3, the low-friction metal/ultra-nano diamond composite coating comprises a metal layer, a UNCD coating and an ordered carbon nanostructure generated in situ by ultra-nano diamond, wherein the metal layer is a discontinuous coating, and the graphene nanostructure is successfully generated on the UNCD coating after high-temperature heat treatment.
Example 2
(1) The high-temperature alloy steel is used as a substrate, and the substrate is ultrasonically cleaned in ethanol and acetone solution in turn and then is dried by nitrogen for standby. And then carrying out crystal implantation treatment on the substrate, putting the cleaned substrate in 0.5 mol/L superfine nano-diamond/ethanol solution for ultrasonic treatment for 60 min, then cleaning in the ethanol solution for 15min, taking out the substrate, drying by blowing with nitrogen, and placing the substrate in a hot wire CVD vacuum chamber.
(2) And the UNCD coating deposition is carried out by utilizing hot filament chemical vapor deposition, and the deposition process is divided into two stages of nucleation and film growth. The parameters of the nucleation stage are: the flow rate of methane is 8 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 1.5 KPa, and the deposition time is 20-30 min; the growth stage parameters of the UNCD film are as follows: the flow rate of methane is 10 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 2 KPa, and the deposition time is 8 h.
(3) And (3) depositing a continuous metal layer on the UNCD coating in the step (2) by using a magnetron sputtering method, taking 99.99% high-purity Au as a sputtering target material, wherein the deposition pressure is 1.0 Pa, the argon flow is 30 scccm, the metal target sputtering power is 100W, the deposition temperature is 200 ℃, and the deposition time is 5 min.
(4) And (4) placing the substrate with the Au/UNCD composite coating prepared in the step (3) in a vacuum furnace, vacuumizing, introducing argon as protective gas, preserving the temperature for 1 hour at 800 ℃, and then slowly cooling to room temperature to take out a sample.
Example 3
(1) The ceramic is used as a substrate, and the substrate is ultrasonically cleaned in ethanol and acetone solution in turn and then is dried by nitrogen for standby. Then carrying out crystal implantation treatment on the substrate, putting the cleaned substrate in 0.5 mol/L superfine nano-diamond/ethanol solution for ultrasonic treatment for 30 min, then cleaning in the ethanol solution for 15min, taking out the substrate, drying by blowing with nitrogen, and placing the substrate in a hot wire CVD vacuum chamber.
(2) And the UNCD coating deposition is carried out by utilizing hot filament chemical vapor deposition, and the deposition process is divided into two stages of nucleation and film growth. The parameters of the nucleation stage are: the flow rate of methane is 10 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 1.5 KPa, and the deposition time is 20-30 min; the growth stage parameters of the UNCD film are as follows: the flow rate of methane is 8 sccm, the flow rate of hydrogen is 200 sccm, the deposition pressure is 2 KPa, and the deposition time is 8 h.
(3) And (3) depositing a continuous metal layer on the UNCD coating in the step (2) by using a magnetron sputtering method, taking 99.99% of high-purity Ni as a sputtering target material, wherein the deposition pressure is 1.5 Pa, the argon flow is 35 scccm, the metal target sputtering power is 150W, the deposition temperature is 200 ℃, and the deposition time is 8 min.
(4) And (4) placing the substrate with the Ni/UNCD composite coating prepared in the step (3) in a vacuum furnace, vacuumizing, introducing argon as protective gas, preserving the temperature for 1 hour at 800 ℃, and then slowly cooling to room temperature to take out a sample.
Comparative example 1
Comparative example 1 is the same as the method of example 1, except that only step (1) and step (2) are carried out to obtain a substrate with a UNCD coating, without the deposition of a metal coating and the subsequent high temperature heat treatment step.
Comparative example 2
Comparative example 2 is the same as example 1 except that only steps (1) to (3) are performed to obtain a substrate with a Cu/UNCD composite coating without a subsequent high temperature heat treatment step.
Sample analysis
In examples 1-3, the UNCD coating had a thickness of about 6 to 7 μm; when the prepared coating is a continuous metal coating, the thickness of the metal coating is about 60-80 nm, and when the prepared coating is a non-continuous metal coating, the thickness of the metal coating is about 600-700 nm.
The coatings prepared in example 1 and comparative examples 1-2 were examined for their frictional properties in an atmospheric environment using a CSM multi-environment friction tester with loading forces of 5N and 10N in a reciprocating sliding mode, and the results are shown in Table 1.
TABLE 1 tribological Performance testing of the coatings of the products of comparative examples 1-2 and example 1
Figure 747749DEST_PATH_IMAGE001
As can be seen from the data in the table above, the high temperature annealing treatment can significantly improve the tribological properties of the UNCD-metal coating.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a low-friction metal/ultra-nano diamond composite coating is characterized by comprising the following steps:
(1) depositing ultra-nano diamond on the surface of the substrate through hot wire chemical vapor deposition to obtain a UNCD coating;
(2) depositing a metal coating on the surface of the UNCD coating by utilizing a magnetron sputtering technology to obtain the UNCD-metal coating; the metal coating is a continuous coating or a discontinuous coating;
(3) carrying out heat treatment on the UNCD-metal coating to obtain the low-friction metal/ultra-nano diamond composite coating;
the metal coating is a copper coating, a gold coating or a nickel coating;
inert gas is used as protective gas in the heat treatment process, and the heat treatment conditions are as follows: the temperature is 700 ℃ and 1000 ℃, and the time is 1-3 h;
the low-friction metal/super nano-diamond composite coating comprises a metal layer, a UNCD coating and an ordered carbon nano-structure generated by super nano-diamond in situ, wherein the ordered carbon nano-structure comprises a graphene structure, a carbon nano-tube structure or a fullerene structure.
2. The method of preparing a low friction metal/ultra-nano diamond composite coating according to claim 1, wherein the UNCD coating has a thickness of 4-8 μm; the thickness of the metal coating is 50-800 nm.
3. The method of claim 1, wherein the substrate is pre-treated prior to depositing the UNCD coating, the pre-treatment comprising: cleaning the substrate by ethanol and acetone in sequence, and placing the cleaned substrate in ethanol suspension of ultrafine nano diamond powder for ultrasonic oscillation to complete surface crystal implantation treatment; and then washing in absolute ethyl alcohol.
4. The method for preparing a low-friction metal/ultra-nano diamond composite coating according to claim 1, wherein in the step (1), the hot wire chemical vapor deposition is divided into a first stage and a second stage, and the parameters of the first stage are as follows: the flow rate of methane is 8-10 sccm, the flow rate of hydrogen is 200-400 sccm, the deposition pressure is 1-4 KPa, and the deposition time is 20-30 min; the parameters of the second stage are: the flow rate of methane is 2-10 sccm, the flow rate of hydrogen is 100-400 sccm, the deposition pressure is 1-4 KPa, and the deposition time is 5-20 h.
5. The method for preparing a low-friction metal/ultra-nano diamond composite coating according to claim 1, wherein in the step (2), the conditions of the magnetron sputtering process are as follows: the deposition pressure is 0.5-1.5 Pa, the argon flow is 30-45 scccm, the sputtering power of the metal target is 10-200W, the deposition temperature is 100-300 ℃, and the deposition time is 5-10 min.
6. The method of claim 1, wherein the inert gas is argon.
7. The low-friction metal/ultra-nano diamond composite coating prepared by the method for preparing the low-friction metal/ultra-nano diamond composite coating according to any one of claims 1 to 6.
8. Use of the low-friction metal/ultra-nano diamond composite coating according to claim 7 in the field of surface treatment of friction parts.
9. The use of the low friction metal/ultra-nano diamond composite coating in the field of surface treatment of friction parts according to claim 7, wherein the low friction metal/ultra-nano diamond composite coating is capable of generating ordered carbon nanostructures during the friction process.
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