CN113278939A - Fullerene-like nano-structure hydrogen-containing carbon film and preparation method thereof - Google Patents

Fullerene-like nano-structure hydrogen-containing carbon film and preparation method thereof Download PDF

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Publication number
CN113278939A
CN113278939A CN202110571745.3A CN202110571745A CN113278939A CN 113278939 A CN113278939 A CN 113278939A CN 202110571745 A CN202110571745 A CN 202110571745A CN 113278939 A CN113278939 A CN 113278939A
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hydrogen
fullerene
nano
carbon film
containing carbon
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郑小平
张星
刘广桥
陈奎
张天云
董向成
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Lanzhou City University
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Lanzhou City University
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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
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/0605—Carbon
    • 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
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon 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
    • C23C14/3457—Sputtering using other particles than noble gas ions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention belongs to the technical field of carbon-based coatings. The invention provides a preparation method of a fullerene-like nano-structure hydrogen-containing carbon film, which comprises the steps of placing a pretreated metal substrate under a vacuum condition, introducing argon, and carrying out activation treatment under an argon atmosphere; depositing a transition layer on the activated metal matrix in an argon atmosphere to obtain a metal matrix containing the transition layer; introducing mixed gas, and depositing fullerene-like nano particles on the transition layer to obtain a fullerene-like nano structure hydrogen-containing carbon film; the mixed gas comprises the following components in a flow ratio of 1: 0.5-0.8: 1-3 argon, hydrogen and carbon-hydrogen sources. The fullerene-like nano-structure hydrogen-containing carbon film has the advantages that the friction coefficient is remarkably reduced, the wear resistance and the wear-resistant service life are remarkably improved, and the fullerene-like nano-structure hydrogen-containing carbon film has excellent anti-friction and anti-wear effects; the hydrogen-containing carbon film has high hardness and high toughness, and forms strong binding force with a metal matrix.

Description

Fullerene-like nano-structure hydrogen-containing carbon film and preparation method thereof
Technical Field
The invention relates to the technical field of carbon-based coatings, in particular to a fullerene-like nano-structure hydrogen-containing carbon film and a preparation method thereof.
Background
Statistics show that there is a worldwide loss of energy from 1/3 to 1/2 in frictional losses, with about 70% of equipment damage worldwide due to various forms of wear. The solid lubrication technology is adopted to reduce the friction and the abrasion of key moving parts of equipment, and the key way is to prolong the service life, improve the reliable operation and realize the energy conservation and the consumption reduction.
The nano-structure carbon-based coating has the advantages of high hardness, ultralow friction coefficient and wear rate, high resistivity, excellent light transmittance, chemical inertness, adjustable structure and components and the like, and has good application prospect when being used as a new-generation solid super-lubricating material. However, the friction performance of carbon-based coatings is greatly affected by the structure and the test environment. The internal stress and the bonding strength of the carbon-based coating are two important parameters determining the service life and reliability of the carbon-based coating in practical application. However, carbon-based coatings generally have higher internal stress, which reduces the bonding strength with the substrate; the carbon-based coating has large low-temperature brittleness, and is easy to have brittle fracture at low vacuum temperature; carbon based coatings have a very short wear life under vacuum. Carbon-based coatings with nanoscale microstructures (such as carbon nano tubes, fullerene, graphene and other structures) are important ways for realizing integration of high hardness, high toughness, low friction and environmental suitability of carbon-based films. The strength of the direct bonding of carbon-based coatings with nanoscale microstructures to metal substrates remains low, limiting the coating thickness, resulting in their inability to be deposited directly on metal substrates.
Therefore, the research and development of the metal substrate carbon-based coating with low friction coefficient, wear resistance, high bonding strength and long service life has very important application prospect and value.
Disclosure of Invention
The invention aims to provide a fullerene-like nano-structure hydrogen-containing carbon film and a preparation method thereof aiming at the defects of the prior art. The friction coefficient of the fullerene-like nano-structure hydrogen-containing carbon film is less than or equal to 0.013; the hardness of the hydrogen-containing carbon film is more than or equal to 17GPa through the test of a nano indenter; the bonding force between the hydrogen-containing carbon film and the metal substrate is more than or equal to 220mN through the test of a nanometer scratch instrument.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a fullerene-like nano-structure hydrogen-containing carbon film, which comprises the following steps:
1) placing the pretreated metal matrix under a vacuum condition, introducing argon, and performing activation treatment under an argon atmosphere;
2) depositing a transition layer on the activated metal matrix in an argon atmosphere to obtain a metal matrix containing the transition layer;
3) introducing mixed gas, and depositing fullerene-like nano particles on the transition layer in the step 2) to obtain a fullerene-like nano structure hydrogen-containing carbon film;
step 3) the mixed gas contains argon, hydrogen and carbon-hydrogen gas sources; the flow ratio of the argon gas, the hydrogen gas and the carbon-hydrogen gas source is 1: 0.5-0.8: 1-3; the carbon-hydrogen source comprises one or more of methane, ethane, acetylene and ethylene.
Preferably, the pretreatment in the step 1) is that the metal matrix is ultrasonically cleaned in absolute ethyl alcohol and acetone sequentially, the time for ultrasonically cleaning in the absolute ethyl alcohol is 5-15 min, and the time for ultrasonically cleaning in the acetone is 15-30 min; and drying the metal matrix by using nitrogen after the ultrasonic cleaning is finished.
Preferably, the vacuum degree of the vacuum condition in the step 1) is 6X 10-4～12×10-4Pa; the metal matrix is steel, stainless steel, aluminum alloy or titanium.
Preferably, in the activation treatment in the step 1), the deposition pressure is 0.4-1 Pa, and the pulse voltage is 700-850V; the activation treatment is argon plasma cleaning; the activation treatment time is 30-50 min.
Preferably, the element of the transition layer in the step 2) is silicon, titanium or chromium.
Preferably, in the process of depositing the transition layer in the step 2), the substrate is applied with a direct current bias of-150V to-300V, and the deposition pressure is 0.5Pa to 0.8 Pa; the deposition adopts a magnetron sputtering physical vapor deposition method, and takes a transition layer material as a target material; the sputtering current of the target is 2.5-4.5A.
Preferably, in the process of depositing the fullerene-like nanoparticles in the step 3), the matrix is applied with a direct current bias of-150 to-300V, and the deposition pressure is 0.4 to 1.0 Pa; the deposition adopts a magnetron sputtering physical vapor deposition method, and takes a graphite target as a target material; the sputtering current of the target is 2.5-4.5A.
Preferably, the thickness of the transition layer in the step 2) is 200-500 nm; and 3) the thickness of the fullerene-like nano-structure hydrogen-containing carbon film is 1.5-3.5 microns.
Preferably, the pulse voltage of the magnetron sputtering physical vapor deposition in the step 2) and the step 3) is 500-700V, and the frequency is 20-80 kHz.
The invention also provides the fullerene-like nano-structure hydrogen-containing carbon film prepared by the preparation method.
The beneficial effects of the invention include the following:
1) the fullerene-like nano-structure hydrogen-containing carbon film has the advantages of obviously reduced friction coefficient, obviously improved wear resistance and wear resistance life, and excellent antifriction and wear resistance effects.
2) The fullerene-like nano-structure hydrogen-containing carbon film has high hardness and high toughness, and forms strong bonding force with a metal matrix.
3) The method has simple process and low cost, and can be widely used for growing the fullerene-like nano-structure hydrogen-containing carbon film with excellent comprehensive performance on a metal substrate.
Detailed Description
The invention provides a preparation method of a fullerene-like nano-structure hydrogen-containing carbon film, which comprises the following steps:
1) placing the pretreated metal matrix under a vacuum condition, introducing argon, and performing activation treatment under an argon atmosphere;
2) depositing a transition layer on the activated metal matrix in an argon atmosphere to obtain a metal matrix containing the transition layer;
3) introducing mixed gas, and depositing fullerene-like nano particles on the transition layer in the step 2) to obtain a fullerene-like nano structure hydrogen-containing carbon film;
step 3) the mixed gas contains argon, hydrogen and carbon-hydrogen gas sources; the flow ratio of the argon gas, the hydrogen gas and the carbon-hydrogen gas source is 1: 0.5-0.8: 1-3; the carbon-hydrogen source comprises one or more of methane, ethane, acetylene and ethylene.
The pre-treatment in the step 1) is preferably that the metal substrate is ultrasonically cleaned in absolute ethyl alcohol and acetone in sequence, and the ultrasonic cleaning time in the absolute ethyl alcohol is preferably 5-15 min, more preferably 7-12 min, and more preferably 9-10 min; the ultrasonic cleaning time in acetone is preferably 15-30 min, more preferably 18-25 min, and even more preferably 20-22 min; after the ultrasonic cleaning is finished, the metal matrix is preferably dried by using nitrogen.
The degree of vacuum of the vacuum condition in step 1) of the present invention is preferably 6X 10-4～12×10-4Pa, more preferably 8X 10-4～10×10-4Pa; the metal substrate is preferably steel, stainless steel, aluminum alloy or titanium.
In the activation treatment in the step 1), the deposition pressure is preferably 0.4-1 Pa, and more preferably 0.6-0.8 Pa; the pulse voltage is preferably 700-850V, more preferably 750-800V, and more preferably 770-790V; the activation treatment is preferably argon plasma cleaning; the time of the activation treatment is preferably 30 to 50min, more preferably 35 to 45min, and still more preferably 40 min.
The argon plasma cleaning of the present invention is used to remove oxide layers and other contaminants from the surface of metal substrates.
The element of the transition layer in step 2) of the present invention is preferably silicon, titanium or chromium.
During the deposition of the transition layer in the step 2), the substrate is preferably applied with a DC bias of-150V to-300V, more preferably-200V to-250V; the deposition pressure is preferably 0.5 to 0.8Pa, and more preferably 0.6 to 0.7 Pa; the deposition preferably adopts a magnetron sputtering physical vapor deposition method, and preferably takes a transition layer material as a target material; the sputtering current of the target is preferably 2.5-4.5A, more preferably 3-4A, and even more preferably 3.5A; the purity of the transition layer material target is preferably more than or equal to 99.9%.
In the process of depositing the fullerene-like nanoparticles in the step 3), the matrix is preferably applied with a direct current bias of-150 to-300V, and more preferably-200 to-250V; the deposition pressure is preferably 0.4 to 1.0Pa, more preferably 0.6 to 0.9V, and still more preferably 0.7 to 0.8V; the deposition preferably adopts a magnetron sputtering physical vapor deposition method, and preferably takes a graphite target as a target material; the sputtering current of the target is preferably 2.5-4.5A, more preferably 3-4A, and even more preferably 3.5A; the purity of the graphite target is preferably more than or equal to 99.9%.
The deposition air pressure and the substrate bias voltage in the step 2) and the step 3) of the invention can ensure that the deposited ions have enough energy, and the fullerene-like nano particles with uniform size are grown on the surface of the graphite target material.
The thickness of the transition layer in the step 2) is preferably 200-500 nm, more preferably 250-450 nm, and even more preferably 300-400 nm; the thickness of the fullerene-like nano-structure hydrogen-containing carbon film in the step 3) is preferably 1.5-3.5 μm, more preferably 2-3 μm, and even more preferably 2.5 μm.
The pulse voltage of the magnetron sputtering physical vapor deposition in the step 2) and the step 3) is preferably 500-700V, more preferably 550-650V, and even more preferably 600V; the frequency is preferably 20 to 80kHz, more preferably 30 to 60kHz, and even more preferably 40 to 50 kHz.
The flow ratio of the argon, hydrogen and hydrocarbon sources in step 3) of the invention is preferably 1: 0.6-0.7: 1.5-2.5, more preferably 1:0.6: 2; the carbon hydrogen gas source preferably comprises methane and/or acetylene; when the hydrocarbon gas source contains several components at the same time, the components are preferably mixed in equal flow ratios.
The ratio of the carbon-hydrogen gas source to the argon gas can ensure that enough carbon-hydrogen gas source is cracked into carbon-hydrogen active ions, and fullerene-like nano-particles with uniform sizes can be formed on the surface of the graphite target material.
The invention also provides the fullerene-like nano-structure hydrogen-containing carbon film prepared by the preparation method.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Ultrasonically cleaning a stainless steel substrate in absolute ethyl alcohol for 7min, then ultrasonically cleaning in acetone for 27min, and blow-drying the stainless steel substrate by nitrogen after the ultrasonic cleaning is finished. The stainless steel substrate was placed in a vacuum of 7X 10-4And introducing argon under the vacuum condition of Pa, and performing activation treatment under the argon atmosphere, wherein in the activation treatment, the deposition pressure is 0.5Pa, the pulse voltage is 750V, and the activation treatment is performed for 32min by adopting argon plasma.
Depositing silicon on the activated stainless steel substrate in an argon atmosphere, applying-180V direct current bias to the substrate in the silicon deposition process, wherein the deposition pressure is 0.6Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 520V, the frequency is 25kHz, the silicon material with the purity of 99.92 percent is used as a target material, and the sputtering current of the target material is 2.8A, so that the stainless steel substrate containing the silicon layer with the thickness of 220nm is obtained. And introducing mixed gas consisting of argon, hydrogen and methane, wherein the flow ratio of the argon to the hydrogen to the methane is 1:0.5:1, and depositing fullerene-like nano particles on the silicon transition layer. In the deposition process, a direct current bias of-180V is applied to the substrate, the deposition pressure is 0.5Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 560V, the frequency is 30kHz, a graphite target with the purity of 99.92 percent is used as a target material, the sputtering current of the graphite target material is 2.8A, and the fullerene-like nano-structure hydrogen-containing carbon film with the thickness of 1.7 mu m is obtained.
The fullerene-like nanostructure hydrogen-containing carbon film of example 1 had a friction coefficient of 0.013; the hardness of the hydrogen-containing carbon film is 17GPa through the test of a nano indenter; the bonding force between the hydrogen-containing carbon film and the metal substrate is 225mN by the test of a nanometer scratch instrument.
Example 2
Ultrasonically cleaning the aluminum alloy matrix in absolute ethyl alcohol for 15min, then ultrasonically cleaning in acetone for 16min, and blow-drying the aluminum alloy matrix by using nitrogen after the ultrasonic cleaning is finished. Placing the aluminum alloy substrate in a vacuum degree of 1.1 × 10-3Under the condition of vacuum of Pa, the air conditioner,and introducing argon, and performing activation treatment in an argon atmosphere, wherein in the activation treatment, the deposition pressure is 0.9Pa, the pulse voltage is 850V, and argon plasma is adopted for cleaning for 48 min.
Depositing titanium on the aluminum alloy substrate subjected to activation treatment in an argon atmosphere, applying a direct current bias of-280V to the substrate in the titanium deposition process, wherein the deposition air pressure is 0.8Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 680V, the frequency is 70kHz, the titanium material with the purity of 99.95 percent is used as a target material, and the sputtering current of the target material is 4.3A, so that the aluminum alloy substrate containing the titanium layer with the thickness of 480nm is obtained. Introducing mixed gas consisting of argon, hydrogen and carbon-hydrogen gas sources (the flow ratio of ethane to acetylene is 1:1), wherein the flow ratio of the argon, the hydrogen and the carbon-hydrogen gas sources is 1:0.7:2.8, and depositing fullerene-like nano particles on the titanium transition layer. In the deposition process, a matrix is applied with a direct current bias voltage of-280V, the deposition pressure is 0.9Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 660V, the frequency is 75kHz, a graphite target with the purity of 99.95 percent is used as a target material, the sputtering current of the graphite target material is 4.3A, and the fullerene-like nano-structure hydrogen-containing carbon film with the thickness of 3.2 mu m is obtained.
The fullerene-like nanostructure hydrogen-containing carbon film of example 2 had a coefficient of friction of 0.012; the hardness of the hydrogen-containing carbon film is 17.5GPa after the test of a nano indenter; the bonding force of the hydrogen-containing carbon film and the metal substrate is 230mN through the test of a nanometer scratch meter.
Example 3
Ultrasonically cleaning the steel matrix in absolute ethyl alcohol for 10min, then ultrasonically cleaning in acetone for 20min, and blow-drying the steel matrix by nitrogen after the ultrasonic cleaning is finished. The steel substrate was placed under a vacuum of 0.9X 10-4And introducing argon under the vacuum condition of Pa, and performing activation treatment under the argon atmosphere, wherein in the activation treatment, the deposition pressure is 0.7Pa, the pulse voltage is 800V, and argon plasma is adopted for cleaning for 40 min.
Depositing chromium on the activated steel substrate in an argon atmosphere, applying a direct current bias of-220V to the substrate in the chromium deposition process, wherein the deposition pressure is 0.7Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 600V, the frequency is 50kHz, a chromium material with the purity of 99.96 percent is used as a target material, and the sputtering current of the target material is 3.5A, so that the steel substrate containing the chromium layer with the thickness of 350nm is obtained. And introducing mixed gas consisting of argon, hydrogen and acetylene, wherein the flow ratio of the argon to the hydrogen to the acetylene is 1:0.6:2, and depositing fullerene-like nano particles on the chromium transition layer. In the deposition process, a direct current bias of-200V is applied to the substrate, the deposition pressure is 0.7Pa, the deposition adopts a magnetron sputtering physical vapor deposition method, the pulse voltage is 600V, the frequency is 65kHz, a graphite target with the purity of 99.96 percent is used as a target material, the sputtering current of the graphite target material is 3.5A, and the fullerene-like nano-structure hydrogen-containing carbon film with the thickness of 2.5 mu m is obtained.
The fullerene-like nanostructure hydrogen-containing carbon film of example 3 had a coefficient of friction of 0.011; the hardness of the hydrogen-containing carbon film is 18GPa after the test of a nano indenter; the bonding force between the hydrogen-containing carbon film and the metal substrate is 235mN through the test of a nanometer scratch meter.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a fullerene-like nano-structure hydrogen-containing carbon film is characterized by comprising the following steps:
1) placing the pretreated metal matrix under a vacuum condition, introducing argon, and performing activation treatment under an argon atmosphere;
2) depositing a transition layer on the activated metal matrix in an argon atmosphere to obtain a metal matrix containing the transition layer;
3) introducing mixed gas, and depositing fullerene-like nano particles on the transition layer in the step 2) to obtain a fullerene-like nano structure hydrogen-containing carbon film;
step 3) the mixed gas contains argon, hydrogen and carbon-hydrogen gas sources; the flow ratio of the argon gas, the hydrogen gas and the carbon-hydrogen gas source is 1: 0.5-0.8: 1-3; the carbon-hydrogen source comprises one or more of methane, ethane, acetylene and ethylene.
2. The preparation method according to claim 1, wherein the pretreatment of step 1) is ultrasonic cleaning of the metal substrate in absolute ethyl alcohol and acetone sequentially, wherein the ultrasonic cleaning time in absolute ethyl alcohol is 5-15 min, and the ultrasonic cleaning time in acetone is 15-30 min; and drying the metal matrix by using nitrogen after the ultrasonic cleaning is finished.
3. The method according to claim 1 or 2, wherein the degree of vacuum of the vacuum condition in step 1) is 6 x 10-4～12×10-4Pa; the metal matrix is steel, stainless steel, aluminum alloy or titanium.
4. The method according to claim 3, wherein in the activation treatment in step 1), the deposition pressure is 0.4 to 1Pa, and the pulse voltage is 700 to 850V; the activation treatment is argon plasma cleaning; the activation treatment time is 30-50 min.
5. The method according to claim 4, wherein the element of the transition layer in step 2) is silicon, titanium or chromium.
6. The preparation method according to claim 4 or 5, characterized in that, in the process of depositing the transition layer in the step 2), the substrate is applied with a DC bias of-150V to-300V, and the deposition pressure is 0.5Pa to 0.8 Pa; the deposition adopts a magnetron sputtering physical vapor deposition method, and takes a transition layer material as a target material; the sputtering current of the target is 2.5-4.5A.
7. The method according to claim 6, wherein during the step 3) of depositing the fullerene-like nanoparticles, the substrate is biased by a direct current of-150 to-300V, and the deposition pressure is 0.4 to 1.0 Pa; the deposition adopts a magnetron sputtering physical vapor deposition method, and takes a graphite target as a target material; the sputtering current of the target is 2.5-4.5A.
8. The preparation method according to claim 7, wherein the thickness of the transition layer in the step 2) is 200 to 500 nm; and 3) the thickness of the fullerene-like nano-structure hydrogen-containing carbon film is 1.5-3.5 microns.
9. The preparation method of claim 8, wherein the pulse voltage of the magnetron sputtering physical vapor deposition in the step 2) and the step 3) is 500-700V, and the frequency is 20-80 kHz.
10. The fullerene-like nanostructure hydrogen-containing carbon film obtained by the preparation method of claim 1 to 9.
CN202110571745.3A 2021-05-25 2021-05-25 Fullerene-like nano-structure hydrogen-containing carbon film and preparation method thereof Pending CN113278939A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114142763A (en) * 2021-12-03 2022-03-04 中国科学院兰州化学物理研究所 Nano friction generator
TWI802501B (en) * 2022-09-03 2023-05-11 明新學校財團法人明新科技大學 Anti-wear low resistance coating material composition and manufacturing method thereof

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