CN111074226A - Carbon-based composite film and preparation method thereof - Google Patents

Carbon-based composite film and preparation method thereof Download PDF

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CN111074226A
CN111074226A CN202010084685.8A CN202010084685A CN111074226A CN 111074226 A CN111074226 A CN 111074226A CN 202010084685 A CN202010084685 A CN 202010084685A CN 111074226 A CN111074226 A CN 111074226A
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carbon
nano
composite film
metal
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CN111074226B (en
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何东青
李文生
尚伦霖
张广安
翟海民
张辛健
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Lanzhou Institute of Chemical Physics LICP of CAS
Lanzhou University of Technology
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Lanzhou Institute of Chemical Physics LICP of CAS
Lanzhou University of Technology
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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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • 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
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • 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
    • C23C14/50—Substrate holders
    • C23C14/505—Substrate holders for rotation of the substrates
    • 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
    • C23C14/54—Controlling or regulating the coating process

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Abstract

The invention provides a carbon-based composite film and a preparation method thereof, belonging to the field of surface engineering. The invention takes the carbon target and the metal carbide target as the sputtering target materials, and only by the periodic control of the 'fast-slow' rotation of the sample rotating stand based on the space distribution characteristics of the closed field unbalanced magnetron sputtering plasma and the influence rule of the rotating speed of the sample rotating stand on the film structure, a carbon-based composite film with a double structure of a nano-layer structure and a nano-composite structure is spontaneously formed in the deposition process, a carbon target and a metal carbide target are oppositely arranged in a vacuum cavity, when the rotating speed of the rotating frame is high, the composite film with the nano composite structure is deposited, when the rotating speed of the rotating frame is low, the composite film with the nano multilayer structure is deposited, the size of the nanocrystalline in the nano composite structure and the modulation period in the nano multilayer structure can be realized through the adjustment of the rotating speed of the rotating frame, the thickness of the nano composite structure layer and the nano multilayer structure layer can be realized by controlling the time of the periodic adjustment of the rotating speed of the sample rotating frame.

Description

Carbon-based composite film and preparation method thereof
Technical Field
The invention relates to the technical field of surface engineering, in particular to a carbon-based composite film and a preparation method thereof.
Background
The diamond-like carbon-based film is the only solid lubricating film material with high hardness and self-lubricating property at present. The toughness and lubrication integrated carbon-based film is an important guarantee for reliable and long-life operation of key parts of mechanical equipment under severe working conditions of heavy load, high speed, impact and the like. However, the hardness and toughness of the carbon-based film are mutually balanced, and how to realize the integration of high hardness, high toughness, low friction and low abrasion of the diamond-like carbon-based film is a key technical problem acknowledged in the field.
In the process of improving the comprehensive performance of the diamond-like carbon-based film, the film structure regulation and multi-scale design are considered to be one of effective ways for solving the problems of high stress, high brittleness and friction behavior environmental sensitivity. In recent years, research shows that the carbon-based composite film can obtain more excellent mechanical and tribological properties by constructing a multilayer film. Coherent, semi-coherent and non-coherent strains at heterointerfaces in the multilayer structure can significantly reduce the internal stress of the thin film. Meanwhile, a large number of heterogeneous interlayer interfaces can effectively inhibit crack propagation, so that the toughness of the film is improved. Compared with single-layer films, the multi-layer film has the advantages that the hardness, the fracture toughness, the wear resistance and the like are obviously improved. Especially, the performance of the film in the nano-scale multilayer film body can change along with the change of the modulation period, and abnormal effects such as super-hardness and the like appear in a certain specific range. The organic combination of the performance advantages of the transition metal carbide and the amorphous carbon matrix with high hardness, high thermal stability and high wear resistance can be realized by constructing a nano multilayer structure and compounding the transition metal carbide and the amorphous carbon matrix. However, although the toughness of the composite film can be significantly improved by the nano multilayer structure design, the friction coefficient of the film and the probability of abrasive wear are increased by the metal carbide hard particles at the sliding interface in the friction process, so that the tribological performance of the composite film is prone to be deteriorated compared with that of an amorphous carbon-based film.
Disclosure of Invention
In view of the above, the present invention is directed to a carbon-based composite film and a method for preparing the same. According to the invention, the strength, toughness and tribological performance of the film are simultaneously improved by preparing the nano multilayer-nano composite double-structure composite film, and the strength, toughness and lubrication of the carbon-based film are integrated.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon-based composite film, which comprises the following steps:
activating the metal substrate to obtain an activated metal substrate;
performing closed field unbalanced magnetron sputtering on the activated metal substrate by taking a metal target, a carbon target and a metal carbide target as sputtering target materials to form a gradient transition layer;
performing magnetron deposition on the surface of the gradient transition layer by taking a carbon target and a metal carbide target as sputtering target materials to form a nano multilayer-nano composite double structure to obtain the carbon-based composite film;
when the rotating speed of the sample rotating frame for magnetron deposition is 0.5-5 rpm, a nano multilayer structure is formed, and when the rotating speed of the sample rotating frame for magnetron deposition is 5-8 rpm, a nano composite structure is formed;
the metal carbide targets are all Cr3C2A WC target or a TiC target.
Preferably, the activation process is carried out when the vacuum degree of the closed field unbalanced magnetron sputtering deposition cavity reaches 2 x 10-4～5×10-4When Pa is needed, argon is introduced, the air pressure is controlled to be 0.5-2.0 Pa, and the activated metal substrate is subjected to direct current bias voltage of-300 to-500VSurface with Ar+And (4) bombarding and cleaning for 15-20 min.
Preferably, the argon pressure of the closed-field unbalanced magnetron sputtering is 0.3-1.5 Pa, the bias voltage is-50-70V, the metal target is deposited for 5-15 min under 500-900W, then the target power of the carbon target is linearly reduced to 0W within 15-45 min, the target power of the carbon target is linearly increased to 1.8-2.3 kW from 0W, the target power of the metal carbide target is linearly increased to 300-800W from 0W, and the rotating speed of the sample rotating frame is 3-5 rpm.
Preferably, the metal target is a Cr target or a Ti target.
Preferably, the pressure of argon gas for magnetron deposition is 0.3-1.5 Pa, the bias voltage is-50 to-70V, the target power of the carbon target is 1.8-2.3 kW, and the target power of the metal carbide target is 300-800W.
Preferably, the number of times of alternation of the rotating speed of the sample rotating frame in the magnetron deposition process being 0.5-5 rpm and 5-8 rpm is 10-100 times, and the magnetron deposition time is 10-350 min.
Preferably, the metal substrate is sequentially subjected to step-by-step grinding and polishing until the surface roughness Ra is less than or equal to 0.2 mu m, acetone ultrasonic cleaning, absolute ethyl alcohol ultrasonic cleaning and nitrogen blow-drying, and then is activated.
Preferably, the time of acetone ultrasonic cleaning and absolute ethyl alcohol ultrasonic cleaning is independently 15-20 min, the temperature is independently 20-30 ℃, and the power is independently 500-800W.
The invention also provides the carbon-based composite film prepared by the preparation method of the technical scheme, which comprises a nano multilayer structure and a nano composite structure which are sequentially alternated.
Preferably, the alternation period of the nano multilayer structure and the nano composite structure is 10-100 times.
The invention provides a preparation method of a carbon-based composite film, which comprises the following steps: activating the metal substrate to obtain an activated metal substrate; performing closed field unbalanced magnetron sputtering on the activated metal substrate by taking a metal target, a carbon target and a metal carbide target as sputtering target materials to form a gradient transition layer; performing magnetron deposition on the surface of the gradient transition layer by taking a carbon target and a metal carbide target as sputtering target materials to form the nanometer multi-layerA layer-nano composite double structure to obtain the carbon-based composite film; when the rotating speed of the sample rotating frame for magnetron deposition is 0.5-5 rpm, a nano multilayer structure is formed, and when the rotating speed of the sample rotating frame for magnetron deposition is 5-8 rpm, a nano composite structure is formed; the metal carbide targets are all Cr3C2A WC target or a TiC target. The invention utilizes physical vapor deposition technology, takes a carbon target and a metal carbide target as sputtering target materials, and spontaneously forms a carbon-based composite film with a double structure of a nano-layer structure and a nano-composite structure in the deposition process only through the periodic control of the rotation speed of a sample rotating frame on the basis of the space distribution characteristics of closed-field unbalanced magnetron sputtering plasma and the influence rule of the rotation speed of the sample rotating frame on the film structure, the carbon target and the metal carbide target are oppositely arranged in a vacuum cavity, when the rotation speed of the rotating frame is high, the composite film with the nano-composite structure is deposited, when the rotation speed of the rotating frame is low, the composite film with the nano-multilayer structure is deposited, the size of a nano crystal in the nano-composite structure and the modulation period in the nano-multilayer structure can be realized through the adjustment of the rotation speed of the rotating frame, the thicknesses of the nano-composite structure layer and the nano-multilayer structure layer can be realized through the control of the periodic adjustment time of, namely, the modulation period of the nano multilayer-nano composite multilayer structure, and in macroscopic view, the nano multilayer structure and the nano composite structure are in a multilayer mode of alternating layer by layer in the film layer. The carbon-based composite film prepared by the invention has a nano multilayer-nano composite double structure, not only realizes the remarkable improvement of the toughness of the film, but also greatly improves the tribological performance of the film, thereby really realizing the integration of the toughness and the lubrication of the diamond-like carbon-based film.
Drawings
FIG. 1 is a TEM image of a cross-section of a carbon-based composite film obtained in example one, wherein 1 is a nano-composite structure layer and 2 is a nano-multilayer structure layer;
FIG. 2 is a graph of the Vickers indentation morphology of the carbon-based composite film at 500gf prepared in the first example;
FIG. 3 shows the carbon-based composite film obtained in the first embodiment under the conditions of Hertz contact stress of 1.5GPa, reciprocation frequency of 5Hz, and dry friction
Figure BDA0002381633530000032
The friction coefficient curve of mm GCr15 pellets in the case of rubbing;
FIG. 4 shows the results of the dry friction of films of different structures under the conditions of Hertz contact stress of 1.5GPa, reciprocating frequency of 5Hz
Figure BDA0002381633530000031
The friction coefficient curve of mm GCr15 pellets in relative friction;
FIG. 5 shows the results of the dry friction of films of different structures under the conditions of Hertz contact stress of 1.5GPa, reciprocating frequency of 5Hz
Figure BDA0002381633530000041
Graph of wear rate for mm GCr15 beads versus moles.
Detailed Description
The invention provides a preparation method of a carbon-based composite film, which comprises the following steps:
activating the metal substrate to obtain an activated metal substrate;
performing closed field unbalanced magnetron sputtering on the activated metal substrate by taking a metal target, a carbon target and a metal carbide target as sputtering target materials to form a gradient transition layer;
performing magnetron deposition on the surface of the gradient transition layer by taking a carbon target and a metal carbide target as sputtering target materials to form a nano multilayer-nano composite double structure to obtain the carbon-based composite film;
when the rotating speed of the sample rotating frame for magnetron deposition is 0.5-5 rpm, a nano multilayer structure is formed, and when the rotating speed of the sample rotating frame for magnetron deposition is 5-8 rpm, a nano composite structure is formed;
the metal carbide targets are all Cr3C2A WC target or a TiC target.
The method activates the metal substrate to obtain the activated metal substrate. In the invention, the activation process is preferably carried out when the vacuum degree of the closed field unbalanced magnetron sputtering deposition cavity reaches 2X 10-4～5×10-4When the pressure is Pa, the pressure is higher,introducing argon gas, controlling the air pressure to be 0.5-2.0 Pa, and applying Ar to the surface of the activated metal substrate under the condition of DC bias voltage of-300-500V+And (4) bombarding and cleaning for 15-20 min.
In the invention, the metal substrate is preferably sequentially subjected to step-by-step grinding and polishing until the surface roughness Ra is less than or equal to 0.2 mu m, acetone ultrasonic cleaning, absolute ethyl alcohol ultrasonic cleaning and nitrogen blow-drying, and then activated. The specific mode of the step-by-step grinding and polishing is not particularly limited, and the technical scheme known to those skilled in the art can be adopted.
In the invention, the time of acetone ultrasonic cleaning and absolute ethyl alcohol ultrasonic cleaning is preferably 15-20 min independently, the temperature is preferably 20-30 ℃ independently, and the power is preferably 500-800W independently, and more preferably 600W independently.
In the present invention, the metal substrate is preferably a 316L stainless steel substrate.
After the activated metal substrate is obtained, the method takes a metal target, a carbon target and a metal carbide target as sputtering targets, and carries out closed field unbalanced magnetron sputtering on the activated metal substrate to form a gradient transition layer.
In the invention, the argon gas pressure of the closed field unbalanced magnetron sputtering is preferably 0.3-1.5 Pa, more preferably 0.8Pa, the bias voltage is preferably-50-70V, the metal target is preferably deposited at 500-900W for 5-15 min, more preferably deposited at 800W for 15min, then linearly reduced to 0W within 15-45 min, more preferably linearly reduced to 0W within 30min, the target power of the carbon target is preferably linearly increased from 0W to 1.8-2.3 kW, more preferably increased to 2.1kW, the target power of the metal carbide target is preferably linearly increased from 0W to 300-800W, and the rotating speed of the sample rotating frame is preferably 3-5 rpm.
In the present invention, the metal target is preferably a Cr target or a Ti target.
In the present invention, the metal carbide target is Cr3C2A WC target or a TiC target.
In the invention, the metal target, the carbon target and the metal carbide target are preferably placed on top, the metal substrate fixed on the sample rotating frame is kept parallel to the surface of the sputtering target, the distance is kept between 5 and 10cm, and the C target and the metal carbide target are oppositely placed.
After the gradient transition layer is formed, performing magnetron deposition on the surface of the gradient transition layer by taking a carbon target and a metal carbide target as sputtering target materials to form a nano multilayer-nano composite double structure to obtain the carbon-based composite film;
when the rotating speed of the sample rotating frame for magnetron deposition is 0.5-5 rpm, a nano multilayer structure is formed, and when the rotating speed of the sample rotating frame for magnetron deposition is 5-8 rpm, a nano composite structure is formed;
the metal carbide target is Cr3C2A WC target or a TiC target.
In the invention, the argon gas pressure of the magnetron deposition is preferably 0.3-1.5 Pa, more preferably 0.8Pa, the bias voltage is-50 to-70V, the target power of the carbon target is preferably 1.8-2.3 kW, more preferably 2.1kW, and the target power of the metal carbide target is preferably 300-800W.
In the invention, the sample rotating stand with the rotating speed of 0.5-5 rpm is preferably 0.6-2.2 rpm, more preferably 1.1rpm, and the sample rotating stand with the rotating speed of 5-8 rpm is preferably 6 rpm.
In the invention, the number of times of alternation of the rotating speed of the sample rotating frame in the magnetron deposition process of 0.5-5 rpm and 5-8 rpm is preferably 10-100 times, more preferably 25-50 times, and the magnetron deposition time is preferably 10-350 min, more preferably 330 min.
The invention also provides the carbon-based composite film prepared by the preparation method of the technical scheme, which comprises a nano multilayer structure and a nano composite structure which are sequentially alternated.
In the invention, the alternation period of the nano multilayer structure and the nano composite structure is preferably 10 to 100 times, and more preferably 25 to 50 times.
In the present invention, the thickness of the nano-multilayer structure and the nano-composite structure is independently preferably 11, 22 or 44 nm.
In the present invention, the modulation period of the nano-multilayer structure is preferably 2.9, 5.8 or 10 nm.
To further illustrate the present invention, the carbon-based composite film and the method for preparing the same according to the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example one
The preparation method comprises the following steps:
(1) presetting of sputtering plane target: the metal substrate fixed on the sample rotating stand was ensured to be kept parallel to the sputtering target surface and at a distance of 10cm from the sputtering target surface, and the C target and the WC target were placed opposite to each other.
(2) Polishing and cleaning a substrate: gradually grinding and polishing the surface of a 316L stainless steel substrate until the surface roughness Ra is less than or equal to 0.2 mu m, then respectively ultrasonically cleaning for 20min by adopting acetone and absolute ethyl alcohol under the ultrasonic power of 600W and the temperature of 25 ℃, and fixing on a sample rotating stand after drying by nitrogen.
(3) Activating the surface of the substrate: when the vacuum degree of the closed field unbalanced magnetron sputtering deposition cavity reaches 5 multiplied by 10-4Introducing high-purity argon gas when Pa, controlling the gas pressure at 2.0Pa, and applying Ar to the surface of the metal substrate under the condition of DC bias voltage of-500V+And (4) bombardment cleaning for 15min to remove impurities and oxides on the surface of the substrate and realize surface activation.
(3) Depositing a gradient transition layer: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, depositing the metal Cr target power at 800W for 15min, then linearly reducing the Cr target power to 0W within 30min, linearly increasing the C target power from 0W to 2.1kW, linearly increasing the WC target power from 0W to 300W, and rotating the sample rotating frame at 5 rpm.
(4) Depositing a nano multilayer-nano composite double-structure carbon-based composite film: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, the carbon target power at 2.1kW and the WC target power at 300W, periodically adjusting the rotating speed of the sample rotating stand to alternate between 1.1rpm and 8rpm for 50 times, and depositing a coating film for 330 min.
The prepared composite film has two structures of obvious nano composite structure and nano multilayer structure, the nano composite structure layer and the nano multilayer structure layer are continuously and alternately arranged for 50 layers, the thickness of each structure layer is 22nm, the modulation period of the nano multilayer structure is 5.8nm, namely the thickness of the nano composite structure layer and the thickness of the nano multilayer structure layer are both 22nm, the added thickness of two single layers in the nano multilayer structure is 5.8nm, and the double-structure composite film has the advantages of obvious nano composite structure and nano multilayer structureThe hardness of the combined film is 18.7GPa, the elastic modulus is 269GPa, the film-substrate bonding strength is 46.4N, the internal stress is-0.82 GPa, and the effective fracture toughness is 1.72 KPa.m0.5Under the conditions of Hertz contact stress of about 1.5GPa, reciprocating frequency of 5Hz and dry friction
Figure BDA0002381633530000061
The average friction coefficient of GCr15 balls in the stable stage is 0.056, and the wear rate is 1.6 multiplied by 10-7mm3/N·m。
Fig. 1 is a TEM photograph of a cross-section of a carbon-based composite film obtained in example one, wherein 1 is a nano composite structure layer, and 2 is a nano multi-layer structure layer.
Fig. 2 shows the features of the carbon-based composite film obtained in example one under the condition of 500gf, and it can be seen that only short cracks are generated around the indentation, indicating that the composite film has high fracture toughness.
FIG. 3 shows the carbon-based composite film obtained in the first embodiment under the conditions of Hertz contact stress of 1.5GPa, reciprocation frequency of 5Hz, and dry friction
Figure BDA0002381633530000071
The friction coefficient curve of mm GCr15 spheres in the friction direction shows that the composite film has better friction performance.
FIG. 4 shows the results of the dry friction of films of different structures under the conditions of Hertz contact stress of 1.5GPa, reciprocating frequency of 5Hz
Figure BDA0002381633530000072
The friction coefficient curve of mm GCr15 spheres in the case of friction, FIG. 5 is the curve obtained by comparing films of different structures under the conditions of Hertz contact stress of 1.5GPa, reciprocating frequency of 5Hz and dry friction
Figure BDA0002381633530000073
The graph of the wear rate of mm GCr15 beads in the case of friction is shown in FIGS. 4-5, which shows that the carbon-based composite film prepared in the present example maintains the friction resistance of the nanocomposite structure.
Example two
The preparation method comprises the following steps:
(1) presetting of sputtering plane target: the metal substrate fixed on the sample rotating stand was ensured to be kept parallel to the sputtering target surface and at a distance of 10cm from the sputtering target surface, and the C target and the WC target were placed opposite to each other.
(2) Polishing and cleaning a substrate: gradually grinding and polishing the surface of a 316L stainless steel substrate until the surface roughness Ra is less than or equal to 0.2 mu m, then respectively ultrasonically cleaning for 20min by adopting acetone and absolute ethyl alcohol under the ultrasonic power of 600W and the temperature of 25 ℃, and fixing on a sample rotating stand after drying by nitrogen.
(3) Activating the surface of the substrate: when the vacuum degree of the closed field unbalanced magnetron sputtering deposition cavity reaches 5 multiplied by 10-4Introducing high-purity argon gas when Pa, controlling the gas pressure at 2.0Pa, and applying Ar to the surface of the metal substrate under the condition of DC bias voltage of-500V+And (4) bombardment cleaning for 15min to remove impurities and oxides on the surface of the substrate and realize surface activation.
(3) Depositing a gradient transition layer: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, depositing the metal Cr target power at 800W for 15min, then linearly reducing the Cr target power to 0W within 30min, linearly increasing the C target power from 0W to 2.1kW, linearly increasing the WC target power from 0W to 300W, and rotating the sample rotating frame at 5 rpm.
(4) Depositing a nano multilayer-nano composite double-structure carbon-based composite film: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, the carbon target power at 2.1kW and the WC target power at 300W, periodically adjusting the rotating speed of the sample rotating stand to alternate between 2.2rpm and 6rpm for 100 times, and depositing a coating film for 330 min.
The prepared carbon-based composite film has two obvious structures of nano composite and nano multilayer, the nano composite structure layer and the nano multilayer structure layer are continuously alternated for 100 layers, the thickness of each structure layer is about 11nm, and the modulation period of the nano multilayer structure is 2.9 nm. The hardness of the dual-structure composite film is 19.2GPa, the elastic modulus is 280GPa, the film-substrate bonding strength is 47.8N, the internal stress is-0.64 GPa, and the effective fracture toughness is 1.96 KPa.m0.5Under the conditions of Hertz contact stress of about 1.5GPa, reciprocating frequency of 5Hz and dry friction
Figure BDA0002381633530000081
The average friction coefficient of the mm GCr15 balls in the stable stage is 0.052 in the friction pair, and the wear rate is 1.1 multiplied by 10-7mm3/N·m。
EXAMPLE III
The preparation method comprises the following steps:
(1) presetting of sputtering plane target: the metal substrate fixed on the sample rotating stand was ensured to be kept parallel to the sputtering target surface and at a distance of 10cm from the sputtering target surface, and the C target and the WC target were placed opposite to each other.
(2) Polishing and cleaning a substrate: gradually grinding and polishing the surface of a 316L stainless steel substrate until the surface roughness Ra is less than or equal to 0.2 mu m, then respectively ultrasonically cleaning for 20min by adopting acetone and absolute ethyl alcohol under the ultrasonic power of 600W and the temperature of 25 ℃, and fixing on a sample rotating stand after drying by nitrogen.
(3) Activating the surface of the substrate: when the vacuum degree of the closed field unbalanced magnetron sputtering deposition cavity reaches 5 multiplied by 10-4Introducing high-purity argon gas when Pa, controlling the gas pressure at 2.0Pa, and applying Ar to the surface of the metal substrate under the condition of DC bias voltage of-500V+And (4) bombardment cleaning for 15min to remove impurities and oxides on the surface of the substrate and realize surface activation.
(3) Depositing a gradient transition layer: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, depositing the metal Cr target power at 800W for 15min, then linearly reducing the Cr target power to 0W within 30min, linearly increasing the C target power from 0W to 2.1kW, linearly increasing the WC target power from 0W to 300W, and rotating the sample rotating frame at 5 rpm.
(4) Depositing a nano multilayer-nano composite double-structure carbon-based composite film: controlling the argon gas pressure at 0.8Pa, the bias voltage at-70V, the carbon target power at 2.1kW and the WC target power at 300W, periodically adjusting the rotating speed of the sample rotating stand to alternate between 0.6rpm and 5rpm for 25 times, and depositing a coating film for 330 min.
The prepared carbon-based composite film has two obvious structures of nano composite and nano multilayer, the nano composite structure layer and the nano multilayer structure layer are continuously alternated for 25 layers, the thickness of each structure layer is about 44nm, and the modulation period of the nano multilayer structure is about 10 nm. The hardness of the double-structure composite film is 17.8GPa, the elastic modulus is 260GPa, the film-substrate bonding strength is 44.3N, and the internal stress is-1.12GPa and an effective fracture toughness of 1.55 KPa.m0.5Under the conditions of Hertz contact stress of about 1.5GPa, reciprocating frequency of 5Hz and dry friction
Figure BDA0002381633530000091
The average friction coefficient of the mm GCr15 small ball pair in the stable stage is 0.065, and the wear rate is 2.4 multiplied by 10-7mm3/N·m。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. A preparation method of a carbon-based composite film is characterized by comprising the following steps:
activating the metal substrate to obtain an activated metal substrate;
performing closed field unbalanced magnetron sputtering on the activated metal substrate by taking a metal target, a carbon target and a metal carbide target as sputtering target materials to form a gradient transition layer;
performing magnetron deposition on the surface of the gradient transition layer by taking a carbon target and a metal carbide target as sputtering target materials to form a nano multilayer-nano composite double structure to obtain the carbon-based composite film;
when the rotating speed of the sample rotating frame for magnetron deposition is 0.5-5 rpm, a nano multilayer structure is formed, and when the rotating speed of the sample rotating frame for magnetron deposition is 5-8 rpm, a nano composite structure is formed;
the metal carbide targets are all Cr3C2A WC target or a TiC target.
2. The method for preparing a ceramic material according to claim 1, wherein the activating process is performed when the vacuum degree of the closed field unbalanced magnetron sputtering deposition chamber reaches 2 x 10-4～5×10-4When Pa is needed, argon is introduced, the pressure is controlled to be 0.5-2.0 Pa, and the pressure is controlled to be in direct currentApplying Ar to the surface of the activated metal substrate under the bias voltage of-300 to-500V+And (4) bombarding and cleaning for 15-20 min.
3. The preparation method of claim 1, wherein the argon gas pressure of the closed field unbalanced magnetron sputtering is 0.3 to 1.5Pa, the bias voltage is-50 to-70V, the metal target is deposited at 500 to 900W for 5 to 15min, then the linear reduction is 0W within 15 to 45min, the target power of the carbon target is linearly increased from 0W to 1.8 to 2.3kW, the target power of the metal carbide target is linearly increased from 0W to 300 to 800W, and the rotating speed of the sample rotating frame is 3 to 5 rpm.
4. The production method according to claim 1 or 3, wherein the metal target is a Cr target or a Ti target.
5. The method according to claim 1, wherein the magnetron deposition is performed under an argon pressure of 0.3 to 1.5Pa, a bias voltage of-50 to-70V, a target power of the carbon target of 1.8 to 2.3kW, and a target power of the metal carbide target of 300 to 800W.
6. The preparation method according to claim 1 or 5, wherein the number of times of alternation of the rotation speed of the sample rotating stand during the magnetron deposition of 0.5-5 rpm and 5-8 rpm is 10-100, and the time of the magnetron deposition is 10-350 min.
7. The preparation method according to claim 1, wherein the metal substrate is sequentially subjected to stepwise grinding, polishing until the surface roughness Ra is less than or equal to 0.2 μm, acetone ultrasonic cleaning, absolute ethanol ultrasonic cleaning and nitrogen blow-drying, and then activated.
8. The preparation method according to claim 7, wherein the acetone ultrasonic cleaning and the absolute ethyl alcohol ultrasonic cleaning are independently carried out for 15-20 min at 20-30 ℃ and at 500-800W.
9. The carbon-based composite film prepared by the preparation method of any one of claims 1 to 8, which comprises a nano multilayer structure and a nano composite structure which are sequentially alternated.
10. The carbon-based composite film according to claim 9, wherein the nano multilayer structure and the nano composite structure have an alternating period of 10 to 100 times.
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