CN113201712B - Conductive wear-resistant self-lubricating carbon-based film and preparation method thereof - Google Patents

Conductive wear-resistant self-lubricating carbon-based film and preparation method thereof Download PDF

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CN113201712B
CN113201712B CN202110393569.9A CN202110393569A CN113201712B CN 113201712 B CN113201712 B CN 113201712B CN 202110393569 A CN202110393569 A CN 202110393569A CN 113201712 B CN113201712 B CN 113201712B
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based film
carbon
substrate
layer
resistant self
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CN113201712A (en
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许伟
王磊
苏一凡
唐春梅
汪唯
王红莉
林松盛
代明江
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Institute of New Materials of Guangdong Academy of Sciences
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Abstract

The invention discloses a conductive wear-resistant self-lubricating carbon-based film and a preparation method thereof, and belongs to the technical field of hard films. According to the preparation method disclosed by the invention, the nano two-dimensional layered structure is innovatively introduced into the amorphous carbon-based film, and excellent conductivity is obtained on the basis of excellent wear-resistant self-lubricating property of the carbon-based film. According to the method, a high-power pulse magnetron sputtering technology is adopted, carbon atoms in the amorphous carbon-based film are arranged in a two-dimensional layered manner through process regulation and control, and simultaneously, a non-metal element N and a metal element Ni are doped in the carbon-based film, so that the film forms a nanocrystalline-amorphous composite structure, the synergistic effect among composite elements is fully exerted, the internal stress of the film is relieved, and the conductivity, antifriction and wear resistance of the film are improved. In addition, the method does not need to prepare products and post-treatment procedures, the preparation flow is simple and controllable, and industrialized mass production can be realized. The invention also discloses the conductive wear-resistant self-lubricating carbon-based film prepared by the method.

Description

Conductive wear-resistant self-lubricating carbon-based film and preparation method thereof
Technical Field
The invention relates to the technical field of hard films, in particular to a conductive wear-resistant self-lubricating carbon-based film and a preparation method thereof.
Background
Amorphous carbon-based films (a-C) are a type of material composed of graphite structures sp 2 Hybrid bond carbon atom and diamond structure sp 3 The metastable amorphous substance formed by mixing the carbon atoms of the hybrid bond has high hardness, low friction coefficient, strong bearing capacity, good self-adaptive antifriction and wear-resistant properties in the environment of atmosphere, water and the like, is considered to be an ideal wear-resistant self-lubricating film material, and has wide application prospect in the fields of aerospace, electronic machinery, modern rail transit systems and the like. With the development of technology, more and more key mechanical components such as collector rings and electromagnetism of power electronic systemsRails, MEMS and the like of the track cannon need to operate under the sliding electric contact friction condition, and due to the introduction of electric factors, the electric contact current-carrying friction wear needs to consider the influence of an electric field, current and even an electric arc on a sliding friction pair on the basis of traditional mechanical friction wear. As a surface protective coating for current-carrying frictional wear applications, carbon-based films are required to have not only good mechanical properties, lower contact resistance, but also excellent friction-reducing and wear-resisting properties and thermal stability. Therefore, how to realize the controllable preparation of the high-conductivity, high-wear-resistance and self-lubricating carbon-based film has positive significance for developing the surface protection of the key friction pair parts with high reliability.
The doping of the hetero elements forms a nano composite structure by introducing hetero atoms into the carbon-based film, so that the residual stress of the film can be effectively reduced, the binding force between the film and a matrix is improved, the toughness of the film is enhanced, and the mechanical and electrical properties of the film can be regulated in a larger range. In 2018, schultes et al reported a technique for preparing Ni element doped amorphous carbon-based film by PVD/CVD composite technology, fcc-Ni and Ni in the carbon-based network of the prepared product 3 The C nanocrystalline is tightly wrapped by a carbon atom network to form a core-shell structure, and electrons can be transmitted and migrated among different nanocrystalline particles through a tunnel effect, so that the prepared film shows certain electrical properties. However, the amorphous carbon-based network of the product wrapping the nano crystal grains is in a disordered arrangement state, and a large number of hydrogen atoms can obstruct the transmission movement of electrons, so that the conductivity of the film has a larger limitation.
The nitrogen doping not only can improve the carrier concentration of the film and change the sp in the film 3 And sp (sp) 2 The relative proportion of hybridized carbon atoms, high-concentration nitrogen doping can also induce the carbon atoms to be distributed in a hexagonal ring form to form sp 2 And the hybridization bonds form a unique nano two-dimensional layered structure. In addition, the nitrogen source is rich and nontoxic, so that the doping of nitrogen element becomes one of the most common measures for improving the conductivity of the amorphous carbon film. The unique nano two-dimensional layered structure of carbon atoms in the graphene enables the graphene to have extremely high mechanical properties, electric conductivity and heat conductivity.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a preparation method of a conductive wear-resistant self-lubricating carbon-based film, which adopts a high-power pulse magnetron sputtering technology, utilizes a Ni and N binary element doping modification and regulation and control technology, introduces a nano two-dimensional layered carbon network structure into an amorphous carbon-based film at high temperature, fully plays the synergistic effect of composite elements, not only ensures that the excellent conductive performance is obtained, but also fully relieves the internal stress of a product, and effectively improves the antifriction wear resistance of the obtained film.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the conductive wear-resistant self-lubricating carbon-based film comprises the following steps:
(1) Pretreatment of a matrix: placing the cleaned substrate in a vacuum environment, then introducing argon, applying negative bias voltage on the substrate, and generating plasma by glow discharge to carry out ion etching on the surface of the substrate;
(2) Depositing a gradient transition layer: introducing nitrogen and adjusting the power of a Cr target to 500-600W, depositing a metal CrN layer on the surface of the substrate after ion etching, then starting a high-power pulse power supply of a high-purity graphite target, gradient-lifting the power to 30kW, simultaneously reducing the power of the Cr target, and continuously depositing a metal carbide CrC on the deposited metal CrN layer x N y A layer;
(3) Depositing a functional carbon-based film: heating the substrate deposited with the gradient transition layer in the step (2), controlling negative bias, starting a high-power pulse power supply of a high-purity graphite target embedded with metal Ni, introducing nitrogen and performing CrC in the step (2) x N y And depositing a functional carbon-based film layer above the layer to obtain the conductive wear-resistant self-lubricating carbon-based film.
According to the preparation method of the conductive wear-resistant self-lubricating carbon-based film, a nano two-dimensional layered structure is innovatively introduced into the amorphous carbon-based film, and excellent conductive performance is obtained on the basis of excellent wear-resistant self-lubricating property of the carbon-based film. According to the method, a high-power pulse magnetron sputtering technology is adopted, carbon atoms in the amorphous carbon-based film are arranged in a two-dimensional layered manner through process regulation and control, and simultaneously, a non-metal element N and a metal element Ni are doped in the carbon-based film, so that the film forms a nanocrystalline-amorphous composite structure, the synergistic effect among composite elements is fully exerted, the internal stress of the film is relieved, and the conductivity, antifriction and wear resistance of the film are improved.
Preferably, the substrate comprises at least one of copper alloy, aluminum alloy, titanium alloy, die steel, stainless steel.
Preferably, the air pressure of the vacuum environment in the step (1) is less than or equal to 5 multiplied by 10 -3 Pa。
Preferably, in the pretreatment process of the substrate in the step (1), the air pressure after introducing argon is 1-1.5 Pa, negative bias voltage is applied to the substrate to be more than or equal to 800V, and the ion etching time for the surface of the substrate is 20-30 min.
Under the conditions, the high purity of the plasma and the ion cleaning cleanliness of the surface of the substrate can be ensured, the pollutant on the surface of the substrate can be cleaned, the fresh atomic surface is exposed, and the subsequent deposition is facilitated.
Preferably, the negative bias voltage of the substrate is 100-200V and the nitrogen gas flow rate is 30-50 sccm when the metal CrN layer is deposited on the surface of the substrate in the step (2).
A metal CrN layer and a metal carbide CrC introduced by the step (2) under the conditions x N y The layer can be used as a transition layer to increase the bonding strength between the functional carbon-based film and the matrix which are deposited later.
More preferably, the deposition thickness of the metal CrN layer is 50-100 nm, and the metal carbide CrC x N y The deposition thickness of the layer is 100-200 nm, and the metal CrN layer and the metal carbide CrC x N y The total thickness of the layer is 150-300 nm.
Preferably, in the step (3), the negative bias voltage of the substrate is 80-150V, the heating temperature is 300-350 ℃, the nitrogen gas inlet flow is 30-50 sccm, and the deposition air pressure is 0.35-0.5 Pa.
Under the environmental conditions, the functional carbon-based film can be effectively deposited on the surface of the substrate, and the deposited film has high purity, uniform texture and high deposition efficiency.
Preferably, the power of the high-purity graphite target high-power pulse power supply embedded with metal Ni in the step (3) when the functional carbon-based film layer is deposited is 25-30 kW, the pulse width is 100-200 mu s, and the frequency is 100-200 HZ.
According to the high-purity graphite target high-power pulse power supply inlaid with metal Ni, a nano Ni-doped carbon-based film can be introduced, the use condition can ensure that the generated film is stable in power, the deposited film is high in quality, and the obtained product has excellent uniformity.
Preferably, the deposition thickness of the functional carbon-based film layer in the step (3) is 500-5000 nm.
Preferably, the deposition process is implemented by using a closed-field unbalanced magnetron sputtering ion plating device.
The invention also aims at providing the conductive wear-resistant self-lubricating carbon-based film prepared by the preparation method of the conductive wear-resistant self-lubricating carbon-based film.
The internal structure of the conductive wear-resistant self-lubricating carbon-based film prepared by the invention has no hydrogen atoms, the internal structure of the carbon-based film is a nanocrystalline-amorphous composite structure, part of carbon atoms are arranged like graphene sheets in a lamellar manner, N atoms replace part of C atoms and C atoms to form chemical bonds, and the special structure enables the carbon-based film to have the functional characteristics of conductivity, wear resistance and self lubrication, and can be used for surface protection coatings of key parts serving under the electrical contact friction condition to be applied to the fields of MEMS, electronic control and the like.
The invention has the beneficial effects that the invention provides the preparation method of the conductive wear-resistant self-lubricating carbon-based film, the method innovatively introduces the nano two-dimensional layered structure into the amorphous carbon-based film, and excellent conductive performance is obtained on the basis of excellent wear-resistant self-lubricating property of the carbon-based film. According to the method, a high-power pulse magnetron sputtering technology is adopted, carbon atoms in the amorphous carbon-based film are arranged in a two-dimensional layered manner through process regulation and control, and simultaneously, a non-metal element N and a metal element Ni are doped in the carbon-based film, so that the film forms a nanocrystalline-amorphous composite structure, the synergistic effect among composite elements is fully exerted, the internal stress of the film is relieved, and the conductivity, antifriction and wear resistance of the film are improved. In addition, the method does not need to prepare products and post-treatment procedures, the preparation flow is simple and controllable, and industrialized mass production can be realized. The invention also provides the conductive wear-resistant self-lubricating carbon-based film prepared by the method.
Drawings
FIG. 1 is a schematic structural diagram of a conductive wear-resistant self-lubricating carbon-based film according to the invention, wherein 1 is a substrate, 2 is a gradient transition layer, and 3 is a functional carbon-based film layer;
FIG. 2 is a cross-sectional structural diagram of a scanning electron microscope of the conductive wear-resistant self-lubricating carbon-based film;
FIG. 3 is a graph of the coefficient of friction of the conductive abrasion resistant self-lubricating carbon-based film of the present invention.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments designed for the implementation of the invention are common reagents and instruments unless otherwise specified.
Example 1
An embodiment of the preparation method of the conductive wear-resistant self-lubricating carbon-based film comprises the following steps:
(1) Pretreatment of a matrix: placing the cleaned substrate on a vacuum chamber work frame in vacuum environment, and vacuumizing to air pressure of 5×10 -3 Pa, then introducing argon to the air pressure of 1Pa through an automatic flow control system, applying 800V negative bias to the substrate, and generating plasma through glow discharge to carry out ion etching on the surface of the substrate for 20min;
(2) Depositing a gradient transition layer: reducing the negative bias of the substrate to 100V, introducing 30sccm nitrogen, adjusting the power of the Cr target to 500W, depositing a metal CrN layer with the thickness of 50nm on the surface of the substrate after ion etching, and then starting the high-purity graphite targetHigh-power pulse power supply and gradient power increase to 30kW, and simultaneously reduce Cr target power, and continuously deposit metal carbide CrC with thickness of 100nm on deposited metal CrN layer x N y A layer;
(3) Depositing a functional carbon-based film: heating the substrate subjected to gradient transition layer deposition in the step (2) to 300 ℃, controlling negative bias voltage to 80V, starting a high-purity graphite target high-power pulse power supply embedded with metal Ni, introducing 30sccm nitrogen, keeping the air pressure at 0.35Pa, and depositing a functional carbon-based film layer above the CrCxNy layer in the step (2) for 30min to 500nm in thickness to obtain the conductive wear-resistant self-lubricating carbon-based film; the power of the power supply is 25kW, the pulse width is 100 mu s, and the frequency is 100HZ.
The theoretical schematic structural diagram of the deposited conductive wear-resistant self-lubricating carbon-based film in the embodiment is shown in fig. 1, and the product in the embodiment is found to be consistent with theoretical expectation after being observed by a scanning electron microscope, and the deposited layer has a nano two-dimensional layered structure as shown in fig. 2.
The friction coefficient of the obtained product is tested in the atmospheric environment, an MS-T3001 type ball-disc friction and abrasion tester is adopted, the opposite grinding object of the product is silicon nitride balls, the result is shown in figure 3, and the friction coefficient of the prepared conductive wear-resistant self-lubricating carbon-based film is always about 0.1-0.15, so that the product has excellent antifriction self-lubricating performance.
Example 2
An embodiment of the preparation method of the conductive wear-resistant self-lubricating carbon-based film comprises the following steps:
(1) Pretreatment of a matrix: placing the cleaned substrate on a vacuum chamber working frame in vacuum environment, and vacuumizing to air pressure of 4×10 -3 Pa, then introducing argon to the air pressure of 1.2Pa through an automatic flow control system, applying 850V negative bias voltage on the substrate, generating plasma through glow discharge, and carrying out ion etching on the surface of the substrate for 25min;
(2) Depositing a gradient transition layer: reducing the negative bias of the substrate to 150V, introducing 40sccm nitrogen and adjusting the power of the Cr target to 550W, depositing a metal CrN layer with the thickness of 75nm on the surface of the substrate after ion etching, and thenThen a high-power pulse power supply of a high-purity graphite target is started, the power is increased to 30kW in a gradient way, meanwhile, the power of a Cr target is reduced, and a metal carbide CrC with the thickness of 150nm is continuously deposited on a deposited metal CrN layer x N y A layer;
(3) Depositing a functional carbon-based film: heating the substrate subjected to gradient transition layer deposition in the step (2) to 330 ℃, controlling negative bias voltage to 100V, starting a high-purity graphite target high-power pulse power supply embedded with metal Ni, introducing 40sccm nitrogen, keeping the air pressure at 0.4Pa, and depositing a functional carbon-based film layer above the CrCxNy layer in the step (2) for 180min to 3000nm in thickness to obtain the conductive wear-resistant self-lubricating carbon-based film; the power of the power supply is 28kW, the pulse width is 150 mu s, and the frequency is 150HZ.
Example 3
An embodiment of the preparation method of the conductive wear-resistant self-lubricating carbon-based film comprises the following steps:
(1) Pretreatment of a matrix: placing the cleaned substrate on a vacuum chamber work frame in vacuum environment, and vacuumizing to air pressure of 4.5X10 -3 Pa, then introducing argon to the air pressure of 1.5Pa through an automatic flow control system, applying 900V negative bias on the substrate, and generating plasma through glow discharge to carry out ion etching on the surface of the substrate for 30min;
(2) Depositing a gradient transition layer: reducing the negative bias of the matrix to 200V, introducing 50sccm nitrogen and adjusting the power of a Cr target to 600W, depositing a metal CrN layer with the thickness of 100nm on the surface of the matrix after ion etching, then starting a high-power pulse power supply of a high-purity graphite target and gradient-lifting the power to 30kW, simultaneously reducing the power of the Cr target, and continuously depositing metal carbide CrC with the thickness of 200nm on the deposited metal CrN layer x N y A layer;
(3) Depositing a functional carbon-based film: heating the substrate subjected to gradient transition layer deposition in the step (2) to 350 ℃, controlling negative bias voltage to 150V, starting a high-purity graphite target high-power pulse power supply embedded with metal Ni, introducing 50sccm nitrogen, keeping the air pressure at 0.5Pa, and depositing a functional carbon-based film layer above the CrCxNy layer in the step (2) for 300min to 5000nm in thickness to obtain the conductive wear-resistant self-lubricating carbon-based film; the power of the power supply is 30kW, the pulse width is 200 mu s, and the frequency is 200HZ.
Effect example 1
To verify the performance of the conductive and wear-resistant self-lubricating carbon-based film of the present invention, the products obtained in examples 1 to 3 were tested for mechanical properties, conductivity and wear resistance, wherein the bonding force rating was determined using DIN-VDI3198 standard, the hardness rating was tested using a nanoindentation (Anton Parr, switzerland) sample tester, the resistivity was tested using a Hall effect tester, and the average coefficient of friction was tested as in example 1. The test results are shown in Table 1.
TABLE 1
Project Binding force rating Hardness (GPa) Resistivity (Ω. Cm) Average coefficient of friction
Example 1 HF1 13.5 3.6×10 -5 0.15
Example 2 HF1 12.5 4.5×10 -5 0.15
Example 3 HF1 14.1 6.5×10 -5 0.12
As can be seen from Table 1, the conductive wear-resistant self-lubricating carbon-based film prepared by the embodiment of the invention has excellent mechanical properties and conductivity, and the two-dimensional layered structure in the material fully relieves the stress in the film, and simultaneously effectively improves the antifriction and wear resistance of the product.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The preparation method of the conductive wear-resistant self-lubricating carbon-based film is characterized by comprising the following steps of:
(1) Pretreatment of a matrix: placing the cleaned substrate in a vacuum environment, then introducing argon, applying negative bias voltage on the substrate, and generating plasma by glow discharge to carry out ion etching on the surface of the substrate;
(2) Depositing a gradient transition layer: introducing nitrogen and adjusting the power of a Cr target to 500-600W, depositing a metal CrN layer on the surface of the substrate after ion etching, then starting a high-power pulse power supply of a high-purity graphite target, gradient-lifting the power to 30kW, simultaneously reducing the power of the Cr target, and continuously depositing a metal carbide CrC on the deposited metal CrN layer x N y A layer; the deposition thickness of the metal CrN layer is 50-100 nm, and the metal carbide CrC x N y The deposition thickness of the layer is 100-200 nm, and the metal CrN layer and the metal carbide CrC x N y The total thickness of the layer is 150-300 nm;
(3) Depositing a functional carbon-based film: heating the substrate after the gradient transition layer is deposited in the step (2) to 300-350 ℃, controlling the negative bias voltage to 80-150V, starting a high-power pulse power supply of a high-purity graphite target embedded with metal Ni, introducing nitrogen at a flow of 30-50 sccm, and performing the CrC in the step (2) under the pressure of 0.35-0.5 Pa x N y Depositing a functional carbon-based film layer above the layer to obtain the conductive wear-resistant self-lubricating carbon-based film; the power of the high-purity graphite target high-power pulse power supply is 25-30 kW, the pulse width is 100-200 mu s, and the frequency is 100-200 Hz; the deposition thickness of the functional carbon-based film layer is 500-5000 nm.
2. The method of making a conductive, wear resistant, self-lubricating carbon-based film according to claim 1, wherein the substrate comprises at least one of a copper alloy, an aluminum alloy, a titanium alloy, a die steel, and a stainless steel.
3. The method for producing a conductive abrasion-resistant self-lubricating carbon-based film according to claim 1, wherein the air pressure of the vacuum atmosphere in the step (1) is not more than 5 x 10 -3 Pa。
4. The method for preparing the conductive wear-resistant self-lubricating carbon-based film according to claim 1, wherein in the pretreatment process of the substrate in the step (1), the air pressure after introducing argon is 1-1.5 Pa, negative bias voltage is not less than 800V on the substrate, and the ion etching time for the surface of the substrate is 20-30 min.
5. The method for preparing the conductive wear-resistant self-lubricating carbon-based film according to claim 1, wherein the negative bias voltage of the substrate is 100-200V and the nitrogen gas flow rate is 30-50 sccm when the metal CrN layer is deposited on the surface of the substrate in the step (2).
6. The conductive abrasion-resistant self-lubricating carbon-based film prepared by the method for preparing a conductive abrasion-resistant self-lubricating carbon-based film according to any one of claims 1 to 5.
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