CN112195452B - Methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film and preparation method thereof - Google Patents

Methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film and preparation method thereof Download PDF

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CN112195452B
CN112195452B CN202011294438.7A CN202011294438A CN112195452B CN 112195452 B CN112195452 B CN 112195452B CN 202011294438 A CN202011294438 A CN 202011294438A CN 112195452 B CN112195452 B CN 112195452B
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lanthanum hexaboride
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CN112195452A (en
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张斌
赖振国
张俊彦
贾倩
高凯雄
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • 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
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • 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
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • 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
    • 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
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    • 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
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/0641—Nitrides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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

Abstract

The invention provides a methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film, which is formed by sequentially depositing a Cr layer, a CrN layer, a CrC layer and a CrC layer on the surface of a substrate by adopting a multi-target magnetron sputtering deposition systemx(LaB6)y、Cx(LaB6)yAnd obtaining the product. According to the invention, rare earth elements Cr and La are introduced to the surface of the substrate, so that an amorphous nanocrystalline composite structure can be formed, the amorphous nanocrystalline composite structure and the multi-interface of the gradient same-layer structure can act together, and the corrosion resistance of the substrate is improved; the multi-electron generation performance of lanthanum hexaboride improves the plasma ionization rate, promotes the graphitization of a carbon structure, and improves the conductivity of the composite film; a multi-interface barrier layer is formed through a multi-layer structure design, so that cracks caused by multiple impact abrasion are prevented, the possibility of providing an ion channel for corrosive liquid is provided, and the bearing capacity of the substrate is improved; and a high-power pulse magnetron sputtering technology is utilized to endow Cr with higher ionization rate and ion energy, so that high-strength bonding of a multilayer structure and a substrate is formed.

Description

Methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film and preparation method thereof
Technical Field
The invention relates to a preparation method of a lanthanum hexaboride-based composite carbon film, in particular to a methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride-based composite carbon (Cr/CrN/CrCx (LaB)6)y/Cx(LaB6)y) The film preparation method is mainly used for key parts such as methanol internal combustion engines, fuel cell bipolar plates and the like, and belongs to the fields of vacuum coating and surface engineering.
Background
The direct methanol fuel cell is one of the key directions for the development of clean energy. The existing fuel cell adopts a graphite bipolar plate, has large volume in mass ratio, and limits the energy density and the endurance capacity of the fuel cell. Although light weight can be achieved by using metal bipolar plates, the life of the bipolar plates of methanol fuel cells is limited by formic acid generated in chemical processes. Therefore, to improve the service life of the bipolar plate, the development of a high-performance membrane of the bipolar plate of the methanol fuel cell is required.
Disclosure of Invention
The invention aims to provide a preparation method of a methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film.
Composite carbon film of lanthanum hexaboride
The invention relates to a methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film, which is prepared by sequentially depositing a Cr bonding layer, a CrN layer, a CrC layer and a CrC layer on the surfaces of a titanium alloy and a stainless steel substratex(LaB6)y、Cx(LaB6)yAnd is given as (Cr/CrN/CrC)x(LaB6)y/Cx(LaB6)y）。
The preparation method of the lanthanum hexaboride composite carbon film comprises the following process steps:
(1) symmetrically placing a Cr target material, a lanthanum hexaboride target material and a pair of graphite target materials in a vacuum cavity of a multi-target magnetron sputtering deposition system;
(2) cleaning a workpiece to be plated by hydrocarbon to remove oil stains and rust spots, putting the workpiece into a rotary tool of a film plating vacuum chamber, and keeping the workpiece rotatable for 360 degrees;
(3) vacuumizing the vacuum chamber of the coating film to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute; opening a high-voltage pulse power supply, introducing argon and hydrogen, and controlling the flow ratio of the argon to the hydrogen to be 1: 1; regulating and controlling the air pressure to be 2-3 Pa, bias voltage of 3000V, frequency of 500 Hz and duty ratio of 5%, and cleaning for 25-30 minutes;
(4) closing the hydrogen and the high-voltage pulse power supply, and keeping 1.0-1.2 Pa of argon; turning on a direct current pulse power supply, regulating and controlling bias voltage to be 500-650V, duty ratio to be 40-80%, and frequency to be 20 KHz; opening a Cr target, and depositing a Cr bonding layer at the voltage of 550-700V and the pulse frequency of 0.5-1 Hz; the deposition time is 25-30 minutes, and the thickness of the Cr bonding layer is 400-500 nm;
(5) keeping the conditions unchanged, adjusting a bias voltage power supply to 80-120V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1.0-1.2 Pa, and depositing a CrN layer; the deposition time is 5-10 minutes; the thickness of the CrN layer is 100-150 nm;
(6) closing nitrogen and opening a graphite target, controlling the current to be 10-12A, the duty ratio to be 80% and the frequency to be 40 KHz, keeping other conditions unchanged, and depositing a CrC layer; the deposition time is 20-25 minutes, and the thickness of the CrC layer is 300-400 nm;
(7) starting a lanthanum hexaboride target, controlling the current to be 2-3A, keeping other conditions unchanged, and depositing CrCx(LaB6)yA film; depositing for 20-25 min, CrCx(LaB6)yThe thickness of the film is 300-400 nm;
(8) closing the Cr target, keeping other conditions unchanged, and depositing Cx(LaB6)yA film; deposition time is 55-60 min, Cx(LaB6)yThe thickness of the film is 700-800 nm;
(9) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining the lanthanum hexaboride composite carbon film Cr/CrN/CrCx (LaB) on the surface of the substrate6)y/Cx(LaB6)yThe thickness of the film is 1700 to 1900 nm.
Cr/CrN/CrCx (LaB) prepared by the method6)y/Cx(LaB6)yThe structure of the film is shown in FIG. 2. In the figure: sequentially comprises a Cr bonding layer, a CrN layer, a CrC layer and a CrC layer from bottom to topx(LaB6)y、Cx(LaB6)yAnd (3) compounding a carbon film.
II, Cr/CrN/CrCx (LaB)6)y/Cx(LaB6)yProperties of the film
1. Contact resistance
Using under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ and air) and an average corrosion current density of 0.51 to 0.73 muA/cm2(potentiostatic polarization 0.6V). The contact resistance of the interface of the modified polar plate is 5.43-7.34 m omega cm by using a surface resistance contact tester2(at a pressure of 1.4 MPa).
2. Friction performance in methanol environment
Testing Cr/CrN/CrCx (LaB) in a methanol environment6)y/Cx(LaB6)yThe reciprocating friction performance of the film. And (3) testing conditions are as follows: the friction coefficient of the alloy is about 0.05 compared with Cx (LaB) measured by a csm friction tester in an atmospheric environment6)yThe wear-resisting life of the film is prolonged by about 10 times (6000-6500 min).
In conclusion, the rare earth elements Cr and La are introduced into the surface of the metal substrate, so that an amorphous nanocrystalline composite structure can be formed, the amorphous nanocrystalline composite structure and the multi-interface of the gradient same-layer structure can act together, and the corrosion resistance of the metal is improved; in addition, the multi-electron generation performance of lanthanum hexaboride can improve the ionization rate of plasma, promote the graphitization of a carbon structure and improve the conductivity of the composite film; through the design of a multilayer structure, a multi-interface barrier layer is formed, cracks caused by multiple times of impact abrasion are prevented, the possibility of providing an ion channel for corrosive liquid is provided, and the bearing capacity of the substrate is improved; and a high-power pulse magnetron sputtering technology is utilized to endow Cr with higher ionization rate and ion energy, so that high-strength bonding of a multilayer structure and a substrate is formed.
Drawings
FIG. 1 is a schematic diagram of a vacuum chamber of a multi-target magnetron sputtering deposition system used in the present invention. Wherein 1 is a tool rotating frame (loading valve sealing body); 2 is a metal C target; 3 is a Cr target; 4 is LaB6A target; and 5 is a vacuum cavity.
FIG. 2 shows Cr/CrN/CrCx (LaB) of the present invention6)y/Cx(LaB6)yThe structure of the film is shown schematically.
Detailed Description
The invention of Cr/CrN/CrCx (LaB) is described in detail below with reference to the accompanying drawings6)y/Cx(LaB6)yThe preparation and properties of the films are further illustrated.
A multi-target magnetron sputtering deposition system is adopted for coating, and a Cr target material, a lanthanum hexaboride target material and a pair of graphite target materials are symmetrically arranged in a vacuum cavity. The rotary tool is arranged at the central part of the film coating vacuum chamber and can rotate 360 degrees.
The plated piece is made of Tang alloy and 316L stainless steel sheets, and is cleaned by hydrocarbon to remove oil stains, rust spots and the like.
Example 1
(1) Putting the cleaned workpiece into a vacuum chamber for coating, and vacuumizing the vacuum chamber to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute;
(2) opening a high-voltage pulse power supply, introducing argon and hydrogen (the airflow ratio is 1: 1), keeping the air pressure at 3 Pa, biasing at 3000V, the frequency at 500 Hz, the duty ratio at 5%, and cleaning for 30 minutes;
(3) closing hydrogen and a high-voltage pulse power supply, keeping argon gas at 1 Pa, opening a direct-current pulse power supply, adjusting the bias voltage to be 500V, keeping the duty ratio to be 50 percent, and keeping the frequency to be 20 KHz; opening a Cr target, keeping the voltage at 700V, the pulse frequency at 0.5 Hz and the duty ratio at 80%, and depositing for 30 minutes to obtain a Cr bonding layer;
(4) keeping the conditions unchanged, adjusting a bias voltage power supply to 80V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1 Pa, and depositing for 10 minutes to obtain a CrN layer;
(5) closing nitrogen, starting a graphite target, adjusting the current to be 12A, keeping the duty ratio to be 80 percent and the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 20 minutes to obtain a CrC layer;
(6) starting a lanthanum hexaboride target, adjusting the current to be 2A, the duty ratio to be 80 percent, the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 25 minutes to obtain CrCx (LaB)6)yA layer;
(7) closing the chromium target, keeping other conditions unchanged, and continuing to deposit for one hour to obtain Cx (LaB)6)yA layer;
(8) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining Cr/CrN/CrCx (LaB) on the surface of the plated piece6)y/Cx(LaB6)yA film.
Using under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ with air), an average corrosion current density of 0.51. mu.A/cm2(potentiostatic polarization 0.6V). Testing modified polar plate interface contact electricity by using surface resistance contact testerThe resistance is 7.34 m omega cm2(at a pressure of 1.4 MPa). The reciprocating friction coefficient is about 0.055 and the wear-resistant life is prolonged by 10 times (6000-6300 min.) when the test is carried out in a methanol environment
EXAMPLE 2
(1) Putting the cleaned workpiece into a vacuum chamber for coating, and vacuumizing the vacuum chamber to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute;
(1) opening a high-voltage pulse power supply, introducing argon and hydrogen (the airflow ratio is 1: 1), keeping the air pressure at 2Pa, biasing at 3000V, the frequency at 500 Hz, the duty ratio at 5%, and cleaning for 30 minutes;
(2) closing hydrogen and a high-voltage pulse power supply, keeping argon gas at 1 Pa, opening a direct-current pulse power supply, adjusting the bias voltage to 650V, keeping the duty ratio to 50 percent and keeping the frequency to be 20 KHz; opening a Cr target, enabling the voltage to be 550V, enabling the pulse frequency to be 1 Hz and the duty ratio to be 40%, and depositing for 30 minutes to obtain a Cr bonding layer;
(4) keeping the conditions unchanged, adjusting a bias voltage power supply to 120V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1 Pa, and depositing for 5 minutes to obtain a CrN layer;
(5) closing nitrogen, starting a graphite target, adjusting the current to be 10A, the duty ratio to be 80 percent, the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 25 minutes to obtain a CrC layer;
(6) starting a lanthanum hexaboride target, adjusting the current to be 3A, the duty ratio to be 80 percent, the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 20 minutes to obtain CrCx (LaB)6)yA layer;
(7) closing the chromium target, keeping other conditions unchanged, and continuing to deposit for one hour to obtain Cx (LaB)6)yA layer;
(8) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining Cr/CrN/CrCx (LaB) on the surface of the plated piece6)y/Cx(LaB6)yA film.
Using under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ with air), an average corrosion current density of 0.73. mu.A/cm2(constant potential polarization)0.6V). The interface contact resistance of the modified polar plate is 5.43 m omega cm by using a surface resistance contact tester2(at a pressure of 1.4 MPa). The reciprocating friction coefficient is about 0.053 when tested in a methanol environment, and the wear-resisting service life is prolonged by 10 times (6100-6500 min).
EXAMPLE 3
(1) Putting the cleaned workpiece into a vacuum chamber for coating, and vacuumizing the vacuum chamber to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute;
(2) opening a high-voltage pulse power supply, introducing argon and hydrogen (the airflow ratio is 1: 1), keeping the air pressure at 2.5Pa, biasing at 3000V, frequency at 500 Hz, duty ratio at 5%, and cleaning for 30 minutes;
(3) closing hydrogen and a high-voltage pulse power supply, keeping argon gas at 1 Pa, opening a direct-current pulse power supply, adjusting bias voltage to 600V, keeping the duty ratio at 50% and keeping the frequency at 20 KHz; opening a Cr target, enabling the voltage to be 600V, the pulse frequency to be 0.7 Hz and the duty ratio to be 60%, and depositing for 30 minutes to obtain a Cr bonding layer;
(4) keeping the conditions unchanged, adjusting a bias voltage power supply to 100V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1 Pa, and depositing for 8 minutes to obtain a CrN layer;
(5) closing nitrogen, starting a graphite target, adjusting the current to be 11A, keeping the duty ratio to be 80% and the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 22 minutes to obtain a CrC layer;
(6) starting a lanthanum hexaboride target, adjusting the current to be 2.5A, the duty ratio to be 80 percent, the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 22 minutes to obtain CrCx (LaB)6)yA layer;
(7) closing the chromium target, keeping other conditions unchanged, and continuing to deposit for one hour to obtain Cx (LaB)6)yA layer;
(8) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining Cr/CrN/CrCx (LaB) on the surface of the plated piece6)y/Cx(LaB6)yA film.
Using under simulated PEMFC cathode environment (1M H)2SO4 + 5ppm HF，70 °C，Air) was passed, and the average corrosion current density was 0.59. mu.A/cm2(potentiostatic polarization 0.6V). The interface contact resistance of the modified polar plate is 6.84 m omega cm by using a surface resistance contact tester2(at a pressure of 1.4 MPa). The reciprocating friction coefficient is about 0.048 in a methanol environment, and the wear-resisting service life is prolonged by 10 times (6150-6400 min).
EXAMPLE 4
(1) Putting the cleaned workpiece into a vacuum chamber for coating, and vacuumizing the vacuum chamber to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute;
(2) opening a high-voltage pulse power supply, introducing argon and hydrogen (the airflow ratio is 1: 1), keeping the air pressure at 3 Pa, biasing at 3000V, the frequency at 500 Hz, the duty ratio at 5%, and cleaning for 30 minutes;
(3) closing hydrogen and a high-voltage pulse power supply, keeping argon gas at 1 Pa, opening a direct-current pulse power supply, adjusting the bias voltage to 650V, keeping the duty ratio to 50 percent and keeping the frequency to be 20 KHz; opening a Cr target, enabling the voltage to be 550V, enabling the pulse frequency to be 0.7 Hz and the duty ratio to be 50%, and depositing for 30 minutes to obtain a Cr bonding layer;
(4) keeping the conditions unchanged, adjusting a bias voltage power supply to 90V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1 Pa, and depositing for 10 minutes to obtain a CrN layer;
(5) closing nitrogen, starting a graphite target, adjusting the current to be 12A, keeping the duty ratio to be 80 percent and the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 22 minutes to obtain a CrC layer;
(6) starting a lanthanum hexaboride target, adjusting the current to be 3A, the duty ratio to be 80 percent, the frequency to be 40 KHz, keeping other conditions unchanged, and depositing for 22 minutes to obtain CrCx (LaB)6)yA layer;
(7) closing the chromium target, keeping other conditions unchanged, and continuing to deposit for one hour to obtain Cx (LaB)6)yA layer;
(8) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining Cr/CrN/CrCx (LaB) on the surface of the plated piece6)y/Cx(LaB6)yA film.
Is utilized atSimulation PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ with air), an average corrosion current density of 0.65. mu.A/cm2(potentiostatic polarization 0.6V). The interface contact resistance of the modified polar plate is 6.34 m omega cm by using a surface resistance contact tester2(at a pressure of 1.4 MPa). The reciprocating friction coefficient is about 0.046 when tested in a methanol environment, and the wear-resistant service life is prolonged by 10 times (6300-6500 min).

Claims (7)

1. A methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film is prepared by sequentially depositing a Cr bonding layer, a CrN layer, a CrC layer and a CrC layer on the surfaces of a titanium alloy and a stainless steel substratex(LaB6)yLayer, Cx(LaB6)yObtaining a layer; the CrCx(LaB6)yLayer, Cx(LaB6)yIn the layer, the values of x and y do not include 0.
2. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 1, comprising the following process steps:
(1) symmetrically placing a Cr target material, a lanthanum hexaboride target material and a pair of graphite target materials in a vacuum cavity of a multi-target magnetron sputtering deposition system;
(2) cleaning a workpiece to be plated by hydrocarbon to remove oil stains and rust spots, putting the workpiece into a rotary tool of a film plating vacuum chamber, and keeping the workpiece rotatable for 360 degrees;
(3) vacuumizing the vacuum chamber of the coating film to 10 DEG-4 Pa, opening the rotating tool to rotate at the speed of 2 circles per minute; opening a high-voltage pulse power supply, introducing argon and hydrogen, and controlling the flow ratio of the argon to the hydrogen to be 1: 1; regulating and controlling the air pressure to be 2-3 Pa, bias voltage of 3000V, frequency of 500 Hz and duty ratio of 5%, and cleaning for 25-30 minutes;
(4) closing the hydrogen and the high-voltage pulse power supply, and keeping 1.0-1.2 Pa of argon; turning on a direct current pulse power supply, regulating and controlling bias voltage to be 500-650V, duty ratio to be 40-80%, and frequency to be 20 KHz; opening a Cr target, and depositing a Cr bonding layer at the voltage of 550-700V and the pulse frequency of 0.5-1 Hz;
(5) keeping the conditions unchanged, adjusting a bias voltage power supply to 80-120V, introducing nitrogen, controlling the flow ratio of argon to nitrogen to be 3:1, keeping the air pressure to be 1.0-1.2 Pa, and depositing a CrN layer;
(6) closing nitrogen and opening a graphite target, controlling the current to be 10-12A, the duty ratio to be 80% and the frequency to be 40 KHz, keeping other conditions unchanged, and depositing a CrC layer;
(7) starting a lanthanum hexaboride target, controlling the current to be 2-3A, keeping other conditions unchanged, and depositing CrCx(LaB6)yA film;
(8) closing the Cr target, keeping other conditions unchanged, and depositing Cx(LaB6)yA film;
(9) closing the power supply and the gas, naturally cooling for 40 minutes, filling nitrogen to atmospheric pressure, taking out the plated piece, and obtaining the lanthanum hexaboride composite carbon film Cr/CrN/CrCx (LaB) on the surface of the substrate6)y/Cx(LaB6)y。
3. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 2, wherein the method comprises the following steps: the deposition time of the Cr bonding layer is 25-30 minutes, and the thickness of the Cr bonding layer is 400-500 nm.
4. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 2, wherein the method comprises the following steps: the deposition time of the CrN layer is 5-10 minutes; the thickness of the CrN layer is 100-150 nm.
5. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 2, wherein the method comprises the following steps: the deposition time of the CrC layer is 20-25 minutes, and the thickness of the CrC layer is 300-400 nm.
6. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 2, wherein the method comprises the following steps: CrCx(LaB6)yThe deposition time of the film is 20-25 minutes, and CrCx(LaB6)yThe thickness of the film is 300 to 400 nm.
7. The method for preparing the methanol environment corrosion-resistant wear-resistant conductive lanthanum hexaboride composite carbon film as claimed in claim 2, wherein the method comprises the following steps: cx(LaB6)yThe deposition time of the film is 55-60 min, Cx(LaB6)yThe thickness of the film is 700-800 nm.
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US7589047B1 (en) * 2006-06-08 2009-09-15 Los Alamos National Security, Llc Composite materials and method of making
CN102931421A (en) * 2012-11-06 2013-02-13 上海交通大学 Fuel cell metal bipolar plate with conductive and anti-corrosion plating and preparation method thereof
JP2013142187A (en) * 2012-01-12 2013-07-22 Sumitomo Osaka Cement Co Ltd Lanthanum hexaboride film and organic semiconductor device
CN111926302A (en) * 2020-08-13 2020-11-13 江苏金晟元特种阀门股份有限公司 Deposition method and corrosion-resistant application of lanthanum hexaboride composite carbon film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7589047B1 (en) * 2006-06-08 2009-09-15 Los Alamos National Security, Llc Composite materials and method of making
JP2009123376A (en) * 2007-11-12 2009-06-04 Taiyo Stainless Spring Kk Metal separator for polymer electrolyte fuel cell
JP2013142187A (en) * 2012-01-12 2013-07-22 Sumitomo Osaka Cement Co Ltd Lanthanum hexaboride film and organic semiconductor device
CN102931421A (en) * 2012-11-06 2013-02-13 上海交通大学 Fuel cell metal bipolar plate with conductive and anti-corrosion plating and preparation method thereof
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