CN114686821A - Wear-resistant TiSiCN nano composite multilayer coating and preparation method thereof - Google Patents

Wear-resistant TiSiCN nano composite multilayer coating and preparation method thereof Download PDF

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CN114686821A
CN114686821A CN202210256154.1A CN202210256154A CN114686821A CN 114686821 A CN114686821 A CN 114686821A CN 202210256154 A CN202210256154 A CN 202210256154A CN 114686821 A CN114686821 A CN 114686821A
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pulse
vacuum chamber
power supply
gas
tisicn
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马英鹤
杨建国
朱剑豪
贺艳明
郑文健
李华鑫
闾川阳
任森栋
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Zhejiang University of Technology ZJUT
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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
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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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • 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
    • C23C14/0641—Nitrides
    • 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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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon

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Abstract

The invention discloses a wear-resistant TiSiCN nano-composite multilayer coating and a preparation method thereof, wherein Ar ion glow cleaning and Ti ion cleaning are firstly carried out on a substrate in a vacuum chamber of a coating device, then a transition layer is deposited on the substrate, and finally the nano-composite TiSiCN nano-composite multilayer coating is alternately and periodically coated on the transition layer, so that the TiSiCN nano-composite multilayer coating deposited on the substrate is greatly improved in mechanical wear resistance and high-temperature oxidation resistance, can meet the requirement of modern industry on better material performance, has huge market potential and use value, and has the advantages of simple process, high deposition speed, low cost, high film-substrate bonding strength and the like.

Description

Wear-resistant TiSiCN nano composite multilayer coating and preparation method thereof
Technical Field
The invention relates to the technical field of hard coating preparation, in particular to a wear-resistant TiSiCN nano composite multilayer coating and a preparation method thereof.
Background
The physical vapor deposition method is adopted to deposit the hard coating on the surface of the material, the structural performance of the material is not influenced, the hardness, the wear resistance and the high-temperature oxidation resistance of the material can be effectively improved, and the service life of the material is greatly prolonged. The early coating mainly comprises TiN and TiC coatings, has higher mechanical wear resistance, abrasive wear resistance and lower friction coefficient, but has lower high-temperature oxidation resistance.
At present, elements such as Cr, Al and the like are added into a TiN coating to form a multi-component coating, such as a TiCrN coating and a TiAlN coating, the mechanical wear resistance is higher than that of the TiN coating and the TiCN coating, the application temperature of the coating is also improved to be more than 800 ℃, but the requirement of modern industry on better performance of materials cannot be met, recently, coatings with Si-added nano structures such as TiSiN, TiSiCN, AlTiSiN and the like have the characteristics of high hardness, high-temperature oxidation resistance and the like, and are one of the development directions of material coatings, and if the coatings are of multi-layer structures, the hardness and the toughness of the coatings can be further improved.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a wear-resistant TiSiCN nano-composite multilayer coating and a preparation method thereof, and the prepared nano-composite multilayer TiSiCN coating can improve the film-substrate bonding strength, inhibit the crack initiation and propagation and further improve the performance of the TiSiCN coating so as to meet the requirement of modern industry on better materials.
The technical scheme of the invention is as follows:
a wear-resistant TiSiCN nano composite multilayer coating is characterized in that a transition layer Ti/TiN/TiCN, Ti/TiN, Ti/TiC or Ti/TiCN is coated on the surface of stainless steel or a high-temperature alloy material by adopting a pulse multi-arc ion plating technology, and then the nano composite TiSiCN multilayer coating is alternately and periodically coated;
the thickness of the transition layer is 0.1-0.6 mu m, the thickness of the single layer of the nano composite TiSiCN multi-layer coating is 8-100 nm, and the nano composite TiSiCN multi-layer coating with a multi-layer structure is formed by repeating the steps for many times.
A preparation method of a wear-resistant TiSiCN nano composite multilayer coating comprises the following steps:
1) removing oil on the surface of the substrate, polishing, ultrasonic cleaning in acetone, cleaning with alcohol, blow-drying with nitrogen, placing on a rotating frame of a vacuum chamber of a coating device, and pumping the vacuum chamber until the vacuum degree is less than 5 × 10-4Pa, and simultaneously heating to 300-500 ℃;
2) performing Ar ion glow cleaning and Ti ion cleaning on the substrate in the step 1), and obtaining a workpiece to be plated for later use after cleaning;
3) applying a pulse enhanced multi-arc ion plating technology or a traditional direct current multi-arc ion plating technology to two titanium targets which are oppositely arranged, and depositing a transition layer on the workpiece to be plated in the step 2) to obtain a workpiece sample containing the transition layer;
4) and (3) coating the workpiece sample containing the transition layer obtained in the step 3) with a TiSiCN nano multilayer coating by adopting a pulse-enhanced multi-arc ion plating technology to obtain the wear-resistant TiSiCN nano composite multilayer coating.
Further, the specific process of step 2) is as follows:
firstly, introducing Ar gas into a vacuum chamber, regulating the flow of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 0.3-1.0 Pa, then starting a bias voltage power supply, regulating the bias voltage value to-600 to-1000V, regulating the duty ratio to 10-80%, and carrying out Ar glow cleaning on a workpiece for 5-100 min; then, simultaneously starting a Ti target power supply, adopting a direct-current multi-arc ion plating technology, keeping the air pressure of a vacuum chamber at 0.3-1.0 Pa, adjusting the bias voltage value of a bias power supply to-600 to-1000V, the duty ratio at 10-80 percent, and carrying out ion cleaning on the workpiece for 1-20 min to obtain the workpiece to be plated; wherein the substrate is stainless steel, high-speed steel or titanium alloy.
Further, the transition layer in step 3) includes a first transition sublayer and a second transition sublayer, and the specific preparation processes of the first transition sublayer and the second transition sublayer are as follows:
starting a first pulse multi-arc power supply and a second pulse multi-arc power supply, firstly introducing Ar gas into a vacuum chamber, maintaining the air pressure in the vacuum chamber to be 0.5-3.0Pa, adjusting the bias voltage value to be-50 to-500V, depositing a Ti layer of a first transition sublayer, after the deposition is finished, then closing the Ar gas, introducing N from a gas inlet2And C2H2And (3) maintaining the air pressure in the vacuum chamber to be constant, depositing a second transition sublayer TiN, TiC or TiCN layer, and obtaining a transition layer Ti/TiN, Ti/TiC or Ti/TiCN after the deposition is finished.
Further, when depositing the second transition sublayer, only N is introduced from the gas inlet2Meanwhile, the transition layer also comprises a third transition sublayer, and the preparation process is as follows:
after the deposition of the second transition sublayer is finished, N is continuously introduced2Then introducing C into the vacuum chamber from the gas inlet2H2And (3) gas, maintaining the air pressure of the vacuum chamber at 0.5-3.0Pa, depositing a third transition sublayer, and obtaining the Ti/TiN/TiCN transition layer after the third transition sublayer is deposited.
Further, when the pulse enhanced multi-arc ion plating technology is adopted in the step 3), the direct current end and the pulse end of the first pulse multi-arc power supply and the second pulse multi-arc power supply are simultaneously started, the current of the direct current end is set to be 30-150A, the average current of the pulse end is set to be 30-200A, the pulse discharge current is set to be 50-400A, the frequency is 10-20000Hz, and the pulse width is 5-1000 mus; when the traditional direct-current multi-arc ion technology is adopted, the first pulse multi-arc power supply and the second pulse multi-arc power supply only start the direct-current end, and the current of the direct-current end is set to be 30-110A.
Further, the preparation process parameters of the first transition sublayer Ti are as follows: introducing Ar gas with the flow rate of 100-500 sccm for deposition time of 10-60 min; the preparation process parameters of the second transition sublayer are as follows: introduction of N2And C2H2The flow rate of one or two gases is 100-.
Further, the preparation process parameters of the third transition sublayer are as follows: introduction of C2H2The flow rate of the gas is 20-200 sccm, and the deposition time is 10-60 min.
Further, in the step 4), the specific process of coating the workpiece sample containing the transition layer obtained in the step 3) with the TiSiCN nano multilayer coating is as follows:
keeping the first pulse multi-arc power supply and the second pulse multi-arc power supply on, starting the direct current end and the pulse end of the two multi-arc power supplies, wherein the current of the direct current end is 50-130A, the average current of the pulse end is 50-130A, the pulse discharge current is 100 plus 400A, the frequency is 100 plus 20000Hz, the pulse width is 5-1000 mu s, respectively introducing organic silicon gas in front of a first Ti multi-arc target source and a second Ti multi-arc target source which are arranged in opposite directions from a first air inlet pipe and a second air inlet pipe, N2And C2H2Mixing the gases, introducing the gases into a vacuum chamber through an air inlet, maintaining the air pressure of the vacuum chamber at 0.1-4.0 Pa, adjusting the bias voltage value of a bias voltage power supply to-50 to-400V, the duty ratio to 20-80%, adjusting the rotating speed of a workpiece rotating stand to 5-20 rpm, and the deposition time to 60-180 min, and after the deposition is finished, closing N2And C2H2And (3) closing and maintaining the first pulse multi-arc power supply and the second pulse multi-arc power supply, cooling the mixed gas in the vacuum chamber to 150-200 ℃, taking out the mixed gas, and continuously cooling the mixed gas to room temperature to obtain the TiSiCN nano composite multilayer coating deposited on the substrate.
Further, the organic silicon is one or more of silane, trimethylsilane, tetramethylsilane, hexamethylsilane and methylsilane; the pulse end currents of the two titanium targets are different from the corresponding organosilicon gas flow rate at least at one position.
Compared with the prior art, the invention has the beneficial effects that:
1) by adopting the preparation method, Ar ion glow cleaning and Ti ion cleaning are firstly carried out on the matrix in a vacuum chamber of the coating equipment, then a transition layer is deposited on the matrix, and finally the nanometer composite TiSiCN multilayer coating is alternately and periodically coated on the transition layer, so that the TiSiCN nanometer composite multilayer coating deposited on the matrix is obtained, the mechanical wear resistance and the high-temperature oxidation resistance of the TiSiCN nanometer composite multilayer coating are greatly improved, the requirement of modern industry on better performance of materials can be met, and the TiSiCN nanometer composite multilayer coating has huge market potential and use value;
2) the microstructure and microhardness performance of the coating are adjusted by changing the thickness of a single-layer film in the wear-resistant nano composite TiSiCN multi-layer coating and the coating period so as to adapt to different processing objects and working conditions;
3) in the cathode arc process, the proportion of plasma can be controlled by adjusting the flow of nitrogen and organic silicon gas, the ionization rate of reaction gas is improved by utilizing the discharge-enhanced cathode arc technology, and the discharge stability of the cathode arc is improved, so that the regulation and control of the components and the structure of the coating are realized;
4) the preparation process is simple and easy to control, and the organosilicon is adopted, so that the production cost is low; meanwhile, the coating preparation structure is simple, and the production cost is low;
5) the invention has the characteristics of high deposition rate, low cost, low energy consumption and suitability for industrial production.
Drawings
FIG. 1 is a transmission electron micrograph of the nanocomposite TiSiCN multilayer coating obtained in example 1;
FIG. 2 is an indentation morphology of the nanocomposite TiSiCN multilayer coating obtained in example 2;
FIG. 3 is a schematic structural view of a coating apparatus according to the present invention.
In the figure: 1. a vacuum chamber; 2. a first pulsed multi-arc power supply; 3. a second pulsed multi-arc power supply; 4. a first electromagnetic coil; 5. a second electromagnetic coil; 8. a first flow meter; 9. a second flow meter; 10. a first Ti multi-arc target source; 11. a second Ti multi-arc target source; 12. a first intake pipe; 13. a second intake pipe; 14. an air inlet; 15. rotating the frame; 16. a bias power supply.
Detailed Description
The invention will be further described with reference to the following figures and examples, to which, however, the scope of protection of the invention is not limited.
Example 1:
1) degreasing the surface of stainless steel, polishing, placing the stainless steel into acetone for ultrasonic cleaning, cleaning the cleaned matrix by using alcohol, blow-drying the cleaned matrix by using nitrogen, placing the dried matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) firstly, introducing Ar gas into a vacuum chamber, regulating the flow rate of the inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 1.0Pa, then starting a bias voltage power supply, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the ion cleaning time of the workpiece at 10min to obtain the workpiece to be plated;
3) depositing a transition layer Ti/TiN/TiCN: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 simultaneously start a direct current end and a pulse end, the current of the direct current end in a pulse enhancement mode is 40A, the average current of the pulse end is 100A, the pulse discharge current is 300A, the frequency is 1000 Hz, and the pulse width is 330 mus; introducing Ar gas into the vacuum chamber 1 from the second gas inlet pipe 13 with the flow rate of 200 sccm, maintaining the gas pressure of the vacuum chamber 1 at 1.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio of 50 percent and the deposition time of 30min, and preparing a Ti transition layer; then, the Ar gas is turned off, and N is introduced into the vacuum chamber 1 through the gas inlet 142Gas with the flow of 200 sccm, maintaining the pressure of the vacuum chamber 1 at 1.0Pa, and depositing for 30min to prepare a TiN transition layer; introducing C into the vacuum chamber 1 from the gas inlet 142H2Gas with the flow of 50 sccm, the vacuum chamber 1 with the pressure of 1.5 Pa, and the deposition time of 30min, and a TiCN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating:
keeping a titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 50A, the average current of a pulse end is 100A, the pulse discharge current is 300A, the frequency is 1000 Hz, and the pulse width is 330 mus; tetramethylsilane (TMS) gas is respectively introduced from a first air inlet pipe 12 and a second air inlet pipe 13 in front of two Ti targets which are arranged in opposite directions, and the TMS gas flow is regulated and controlled through a first flowmeter 8 and a second flowmeter 9; the TMS gas flow before the Ti target I is 30 sccm, the TMS gas flow before the Ti target II is 10 sccm, and the nitrogen gas and the acetylene gas flow are respectively adjusted at the same time to obtain a flow ratio of 4: 1, mixing and then introducing the mixture into a vacuum chamber, and maintaining the air pressure of the vacuum chamber to be 1.5 Pa; adjusting bias voltage value of bias power supplyis-200V, duty ratio is 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 120 min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 150 ℃, then the gas is taken out and is continuously cooled to room temperature, and the TiSiCN nano composite multilayer coating deposited on the substrate is obtained.
And detecting the thickness of the obtained wear-resistant nano composite TiSiCN multilayer coating by using a scanning electron microscope instrument, wherein the whole thickness of the coating is about 5 mu m.
FIG. 1 shows the results of the detection of the obtained nanocomposite TiSiCN multilayer coating by a high resolution transmission electron microscope, wherein the monolayer thickness of the coating is about 11 nm.
Example 2
1) Degreasing and polishing the surface of stainless steel, putting the stainless steel into acetone for ultrasonic cleaning for 5-10 min, cleaning the cleaned matrix with alcohol, blow-drying the cleaned matrix with nitrogen, putting the dried matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber 1 until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) introducing Ar gas into a vacuum chamber, regulating the flow of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 1.0Pa, then starting a bias voltage power supply, regulating the bias voltage value to-600V, and performing Ar glow cleaning on a workpiece for 5-10 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 0.3 Pa, keeping the bias voltage value at-600V, and keeping the ion cleaning time of the workpiece at 1 min to obtain the workpiece to be plated;
3) and (3) depositing a transition layer Ti/TiN/TiCN: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 only start a direct current end, and the current of the direct current end is set to be 30A; introducing Ar gas into the vacuum chamber 1 from the second gas inlet pipe 13 with the flow rate of 100 sccm, maintaining the gas pressure of the vacuum chamber 1 at 0.5Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-50V, the duty ratio of 50 percent and the deposition time of 10min, and preparing a Ti transition layer; then, the Ar gas is turned off, and N is introduced into the vacuum chamber 1 through the gas inlet 142Gas with the flow of 100 sccm, maintaining the air pressure of the vacuum chamber 1 at 0.5Pa, and depositing for 10min to prepare a TiN transition layer; introducing C into the vacuum chamber 1 from the gas inlet 142H2Gas with the flow of 100 sccm, the pressure of the vacuum chamber 1 is maintained at 0.5Pa, the deposition time is 10min, and a TiCN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating:
keeping a titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 50A, the average current of a pulse end is 50A, the pulse discharge current is 100A, the frequency is 100 Hz, and the pulse width is 5 mus; TMS gas is respectively introduced into the front of two Ti targets which are oppositely arranged from a first air inlet pipe 12 and a second air inlet pipe 13, and the flow of the Tetramethylsilane (TMS) gas is regulated and controlled by a first flowmeter 8 and a second flowmeter 9; the TMS gas flow before the Ti target I is 30 sccm, the TMS gas flow before the Ti target II is 10 sccm, and the nitrogen gas and the acetylene gas flow are respectively adjusted at the same time to obtain a flow ratio of 4: 1, mixing, introducing into a vacuum chamber, and maintaining the air pressure of the vacuum chamber at 0.1 Pa; adjusting the bias voltage value of the bias voltage power supply to-50V, and the duty ratio is 20%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 60min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 150 ℃, then the gas is taken out and is continuously cooled to room temperature, and the TiSiCN nano composite multilayer coating deposited on the substrate is obtained.
The bonding strength grade of the wear-resistant nano composite TiSiCN multilayer coating obtained by the method is detected by adopting a Rockwell hardness indentation instrument, and as can be seen from figure 2, the bonding strength grade of the coating is HF1, which indicates that the film-substrate bonding of the nano composite TiSiCN multilayer coating prepared by the method is good.
Example 3
1) The method comprises the steps of carrying out surface oil removal and polishing treatment on high-speed steel, then placing the high-speed steel into acetone for ultrasonic cleaning for 5-10 min, cleaning a cleaned matrix with alcohol, then blow-drying the matrix with nitrogen, placing the matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber 1 until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) introducing Ar gas into a vacuum chamber, regulating the flow of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 0.8 Pa, then starting a bias voltage power supply, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the ion cleaning time of the workpiece at 10min to obtain the workpiece to be plated;
3) depositing a transition layer Ti/TiCN: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 simultaneously start a direct current end and a pulse end, the current of the direct current end is 40A, the average current of the pulse end is 100A, the pulse discharge current is 300A, the frequency is 1000 Hz, and the pulse width is 330 mus; introducing Ar gas into the vacuum chamber 1 from the gas inlet 14 with the flow rate of 200 sccm, maintaining the gas pressure of the vacuum chamber 1 at 1.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio of 50 percent and the deposition time of 30min, and preparing a Ti transition layer; then, the Ar gas is turned off, and C is introduced into the vacuum chamber 1 through the gas inlet 142H2The flow is 50 sccm, the air pressure of the vacuum chamber 1 is maintained to be 1.5 Pa, the deposition time is 60min, and a TiCN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating:
keeping a titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 40A, the average current of a pulse end is 100A, the pulse discharge current is 350A, the frequency is 1000 Hz, and the pulse width is 300 mus; tetramethylsilane (TMS) gas is respectively introduced from a first air inlet pipe 12 and a second air inlet pipe 13 in front of two Ti targets which are arranged in opposite directions, and the TMS gas flow is regulated and controlled through a first flowmeter 8 and a second flowmeter 9; the TMS gas flow before the Ti target I is 30 sccm, the TMS gas flow before the Ti target II is 10 sccm, and the nitrogen gas flow and the acetylene gas flow are respectively adjusted at the same time, so that the flow ratio is 4: 1, mixing and then introducing the mixture into a vacuum chamber, and maintaining the air pressure of the vacuum chamber to be 1.5 Pa; adjusting the bias voltage value of the bias voltage power supply to-100V and the duty ratio to 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 120 min, and closing N after the deposition is finished2And C2H2The mixed gas of (2) closing the first pulseAnd (3) punching the multi-arc power supply 2 and the second pulse multi-arc power supply 3, cooling the inside of the vacuum chamber 1 to 180 ℃, taking out, and continuously cooling to room temperature to obtain the TiSiCN nano composite multilayer coating deposited on the substrate.
Example 4
1) Degreasing and polishing the surface of stainless steel, putting the stainless steel into acetone for ultrasonic cleaning for 5-10 min, cleaning the cleaned matrix with alcohol, blow-drying the cleaned matrix with nitrogen, putting the dried matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber 1 until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) introducing Ar gas into a vacuum chamber, regulating the flow of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 1.0Pa, then starting a bias voltage power supply 16, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of the vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the workpiece ion cleaning time at 20 min to obtain a workpiece to be plated;
3) and (3) depositing a transition layer Ti/TiN/TiCN:
starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 simultaneously start a direct current end and a pulse end, the current of the direct current end in a pulse enhancement mode is 150A, the average current of the pulse end is 200A, the pulse discharge current is 400A, the frequency is 20000Hz, and the pulse width is 1000 mus; introducing Ar gas into the vacuum chamber 1 from the second gas inlet pipe 13 at a flow rate of 500 sccm, maintaining the gas pressure of the vacuum chamber 1 at 3.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio to be 50%, and the deposition time to be 60min, thereby preparing a Ti transition layer; then, the Ar gas is turned off, and N is introduced into the vacuum chamber 1 through the gas inlet 142Gas with the flow of 500 sccm, maintaining the air pressure of the vacuum chamber 1 at 3.0Pa, and depositing for 60min to prepare a TiN transition layer; introducing C into the vacuum chamber 1 from the gas inlet 142H2Gas with the flow of 500 sccm, the vacuum chamber 1 with the pressure of 3.0Pa, and the deposition time of 60min, and a TiCN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating: keeping the power supply of the titanium target on and adoptingA pulse enhancement mode, wherein the current of a direct current end is 130A, the average current of a pulse end is 130A, the pulse discharge current is 400A, the frequency is 20000Hz, and the pulse width is 1000 mus; silane gas is respectively introduced from a first gas inlet pipe 12 and a second gas inlet pipe 13 in front of two Ti targets which are arranged in opposite directions, and the flow rate of the silane gas is regulated and controlled through a first flowmeter 8 and a second flowmeter 9; the TMS gas flow before the Ti target I is 30 sccm, the silane gas flow before the Ti target II is 10 sccm, and the nitrogen gas flow and the acetylene gas flow are respectively adjusted at the same time, so that the flow ratio is 4: 1, mixing and then introducing the mixture into a vacuum chamber, and maintaining the air pressure of the vacuum chamber to be 4.0 Pa; adjusting the bias voltage value of the bias voltage power supply to-100V and the duty ratio to 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 180 min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 200 ℃, then the gas is taken out, and the gas is continuously cooled to room temperature, thus obtaining the TiSiCN nano composite multilayer coating deposited on the substrate.
Example 5
1) Degreasing and polishing the surface of a titanium alloy, then putting the titanium alloy into acetone for ultrasonic cleaning, cleaning a cleaned matrix by using alcohol, then blowing the matrix by using nitrogen, then placing the matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber 1 until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) firstly, introducing Ar gas into a vacuum chamber, regulating the flow rate of the inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 1.0Pa, then starting a bias voltage power supply, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the ion cleaning time of the workpiece at 10min to obtain the workpiece to be plated;
3) depositing a transition layer Ti/TiN/TiCN: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 simultaneously start a direct current end and a pulse end, the current of the direct current end in a pulse enhancement mode is 40A, the average current of the pulse end is 100A, and pulse discharge is carried outThe current is 300A, the frequency is 1000 Hz, and the pulse width is 330 mus; introducing Ar gas into the vacuum chamber 1 from the second gas inlet pipe 13 with the flow rate of 200 sccm, maintaining the gas pressure of the vacuum chamber 1 at 1.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio of 50 percent and the deposition time of 30min, and preparing a Ti transition layer; then, the Ar gas is turned off, and N is introduced into the vacuum chamber 1 through the gas inlet 142Gas with the flow of 200 sccm, maintaining the pressure of the vacuum chamber 1 at 1.0Pa, and depositing for 30min to prepare a TiN transition layer; introducing C into the vacuum chamber 1 from the gas inlet 142H2Gas with the flow of 300sccm, the pressure of the vacuum chamber 1 maintained at 1.5 Pa, and the deposition time 30min, and a TiCN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating: keeping a titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 40A, the average current of a pulse end is 100A, the pulse discharge current is 350A, the frequency is 1000 Hz, and the pulse width is 300 mus, wherein the average current of the first pulse end of the Ti target is 50A, the pulse discharge current is 200A, the pulse frequency is 500Hz, the pulse width is 500 mus, the average current of the second pulse of the Ti target is 100A, the pulse discharge current is 400A, the pulse frequency is 500Hz, and the pulse width is 500 mus;
introducing methyl silane gas respectively before two opposite Ti targets from first intake pipe 12 and second intake pipe 13, methyl silane gas flow before the Ti target is 20sccm with methyl silane gas flow before the Ti target is two, adjust nitrogen gas and acetylene gas flow respectively simultaneously to flow ratio 4: 1, mixing, introducing into a vacuum chamber, and maintaining the air pressure of the vacuum chamber at 1.5 Pa; adjusting the bias voltage value of the bias voltage power supply to-400V and the duty ratio to 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 120 min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 175 ℃, then the gas is taken out, and the gas is continuously cooled to room temperature, thus obtaining the TiSiCN nano composite multilayer coating deposited on the substrate.
Example 6
1) Degreasing and polishing the surface of stainless steel, putting the stainless steel into acetone for ultrasonic cleaning for 5-10 min, and cleaning the cleaned matrix by using alcoholWashing, drying with nitrogen, placing on a rotary frame 15 of a vacuum chamber 1 of a coating device, and vacuumizing the vacuum chamber 1 to a vacuum degree of less than 5 × 10-4Pa, and simultaneously heating to 400 ℃;
2) firstly, introducing Ar gas into a vacuum chamber, regulating the flow rate of the inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 0.8 Pa, then starting a bias voltage power supply, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the ion cleaning time of the workpiece at 10min to obtain the workpiece to be plated;
3) depositing a transition layer Ti/TiC: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 simultaneously start a direct current end and a pulse end, the current of the direct current end is 40A, the average current of the pulse end is 100A, the pulse discharge current is 300A, the frequency is 1000 Hz, and the pulse width is 330 mus; introducing Ar gas into the vacuum chamber 1 from the gas inlet 14 with the flow rate of 200 sccm, maintaining the gas pressure of the vacuum chamber 1 at 1.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio of 50 percent and the deposition time of 30min, and preparing a Ti transition layer; then, the Ar gas is turned off, and C is introduced into the vacuum chamber 1 through the gas inlet 142H2The flow is 50 sccm, the air pressure of the vacuum chamber 1 is maintained to be 1.5 Pa, the deposition time is 60min, and a TiC transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating:
keeping a titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 40A, the average current of a pulse end is 100A, the pulse discharge current is 350A, the frequency is 1000 Hz, and the pulse width is 300 mus; introducing trimethylsilane gas into the front of two Ti targets arranged in opposite directions from a first gas inlet pipe 12 and a second gas inlet pipe 13 respectively, and regulating and controlling the flow rate of the trimethylsilane gas through a first flowmeter 8 and a second flowmeter 9; the flow rate of trimethylsilane gas in front of the Ti target I is 30 sccm, the flow rate of trimethylsilane gas in front of the Ti target II is 10 sccm, and the flow rates of nitrogen gas and acetylene gas are respectively adjusted at the same time, wherein the flow rate ratio is 4: 1, mixing, introducing into a vacuum chamber, and maintaining the air pressure of the vacuum chamber at 1.5 Pa;adjusting the bias voltage value of the bias voltage power supply to-100V and the duty ratio to 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 120 min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 180 ℃, then the gas is taken out, and the gas is continuously cooled to room temperature, thus obtaining the TiSiCN nano composite multilayer coating deposited on the substrate.
Example 7
1) Degreasing and polishing the surface of a titanium alloy, putting the titanium alloy into acetone for ultrasonic cleaning for 5-10 min, cleaning a cleaned matrix by using alcohol, blow-drying the cleaned matrix by using nitrogen, putting the dried matrix on a rotating frame 15 of a vacuum chamber 1 of coating equipment, and pumping the vacuum chamber 1 until the vacuum degree is less than 5 multiplied by 10-4Pa, and simultaneously heating to 400 ℃;
2) introducing Ar gas into a vacuum chamber, regulating the flow of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 1.0Pa (out of range), then starting a bias voltage power supply, regulating the bias voltage value to-1000V, and performing Ar glow cleaning on a workpiece for 10-20 min; then, simultaneously starting a Ti target power supply, adopting a direct current mode, keeping the air pressure of a vacuum chamber at 1.0Pa, keeping the bias voltage value at-1000V, and keeping the ion cleaning time of the workpiece at 10min to obtain the workpiece to be plated;
3) depositing a transition layer Ti/TiN: starting a first pulse multi-arc power supply 2 and a second pulse multi-arc power supply 3, wherein the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 only start a direct current end, and the current of the direct current end is set to be 90A; introducing Ar gas into the vacuum chamber 1 from the gas inlet 14 with the flow rate of 200 sccm, maintaining the gas pressure of the vacuum chamber 1 at 1.0Pa, adjusting the bias voltage value of the bias voltage power supply 16 to-400V, the duty ratio of 50 percent and the deposition time of 30min, and preparing a Ti transition layer; then, the Ar gas is turned off, and N is introduced into the vacuum chamber 1 through the gas inlet 142The flow is 50 sccm, the air pressure of the vacuum chamber 1 is maintained to be 1.5 Pa, the deposition time is 60min, and a TiN transition layer is prepared;
4) depositing a nano composite TiSiCN multilayer coating:
keeping the titanium target power supply on and adopting a pulse enhancement mode, wherein the current of a direct current end is 40A, and the average current of a pulse end100A, pulse discharge current 350A, frequency 1000 Hz, pulse width 300 mus; introducing hexamethylsilane gas in front of two Ti targets arranged in opposite directions from a first gas inlet pipe 12 and a second gas inlet pipe 13 respectively, and regulating and controlling the flow of the hexamethylsilane gas through a first flowmeter 8 and a second flowmeter 9; the flow rate of the hexamethylsilane gas before the first Ti target is 30 sccm, the flow rate of the hexamethylsilane gas before the second Ti target is 10 sccm, and the flow rates of the nitrogen gas and the acetylene gas are respectively adjusted to obtain a flow rate ratio of 4: 1, mixing, introducing into a vacuum chamber, and maintaining the air pressure of the vacuum chamber at 1.5 Pa; adjusting the bias voltage value of the bias voltage power supply to-100V and the duty ratio to 50%; adjusting the rotating speed of the workpiece rotating frame to be 5-20 rpm, keeping the deposition time at 120 min, and closing N after the deposition is finished2And C2H2The first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3 are closed, the temperature in the vacuum chamber 1 is reduced to 180 ℃, then the gas is taken out, and the gas is continuously cooled to room temperature, thus obtaining the TiSiCN nano composite multilayer coating deposited on the substrate.
As shown in fig. 3, the coating apparatus of the present invention comprises a vacuum chamber 1, a first pulse multi-arc power supply 2, a second pulse multi-arc power supply 3, a first Ti multi-arc target source 10 and a second Ti multi-arc target source 11, wherein a rotating frame 15 for placing a substrate is arranged in the vacuum chamber 1, an air inlet 14 is arranged at the bottom of the rotating frame 15, the rotating frame 15 is rotatably connected with the vacuum chamber 1, the first Ti multi-arc target source 10 and the second Ti multi-arc target source 11 are arranged on the inner wall of the vacuum chamber 1, the two metal multi-arc target sources are fixedly connected with the vacuum chamber 1, the first pulse multi-arc power supply 2 is connected between the first Ti multi-arc target source 10 and the vacuum chamber 1, and the second pulse multi-arc power supply 3 is connected between the second Ti multi-arc target source 11 and the vacuum chamber 1; a bias power supply 16 is connected between the rotating frame 15 and the vacuum chamber 1, a first electromagnetic coil 4 and a second electromagnetic coil 5 are respectively arranged outside the vacuum chamber 1 and close to the first pulse multi-arc power supply 2 and the second pulse multi-arc power supply 3, and the two electromagnetic coils are insulated by enameled copper wires.
The device comprises a first air inlet pipe 12 and a second air inlet pipe 13, wherein the first air inlet pipe 12 and the second air inlet pipe 13 are respectively arranged beside a first Ti multi-arc target source 10 and a second Ti multi-arc target source 11.
The first flowmeter 8 and the second flowmeter 9 are included, and the first flowmeter 8 and the second flowmeter 9 are respectively arranged on a first air inlet pipe 12 and a second air inlet pipe 13.
The electric connection end of the first Ti multi-arc target source 10 is electrically connected with the cathode of the first pulse multi-arc power supply 2, and the anode of the first pulse multi-arc power supply 2 is electrically connected with the vacuum chamber 1; the electric connection end of the second Ti multi-arc target source 11 is electrically connected with the cathode of the second pulse multi-arc power supply 3, and the anode of the second pulse multi-arc power supply 3 is electrically connected with the vacuum chamber 1; the negative pole of the bias power supply 16 is electrically connected to the electrical connection terminal of the turret 15, the positive pole of the bias power supply 16 is electrically connected to the electrical connection terminal of the vacuum chamber 1, and the vacuum chamber 1 is grounded.
The rotating frame 15, the first Ti multi-arc target source 10 and the second Ti multi-arc target source 11 are insulated from the vacuum chamber 1; the first air inlet pipe 12 is insulated with the first Ti multi-arc target source 10 and the vacuum chamber 1; the second gas inlet pipe 13 is insulated from the second Ti multi-arc target source 11 and the vacuum chamber 1.
The first Ti multi-arc target source 10 and the second Ti multi-arc target source 11 are arranged oppositely, and the first Ti multi-arc target source 10 and the second Ti multi-arc target source 11 are both fixedly connected with the vacuum chamber 1 through flanges.

Claims (10)

1. A wear-resistant TiSiCN nano composite multilayer coating is characterized in that the wear-resistant TiSiCN nano composite multilayer coating is formed by firstly coating a transition layer Ti/TiN/Tacna, Ti/TiN, Ti/TiC or Ti/TiCN on the surface of stainless steel or high-temperature alloy material by adopting a pulse multi-arc ion plating technology, and then alternately and periodically coating the nano composite TiSiCN multilayer coating;
the thickness of the transition layer is 0.1-0.6 mu m, the thickness of the single layer of the nano composite TiSiCN multi-layer coating is 8-100 nm, and the nano composite TiSiCN multi-layer coating with a multi-layer structure is formed by repeating the steps for many times.
2. A method for preparing a wear resistant TiSiCN nanocomposite multilayer coating according to claim 1, characterized in that it comprises the following steps:
1) the method comprises the steps of degreasing and polishing the surface of a substrate, then placing the substrate into acetone for ultrasonic cleaning, cleaning the cleaned substrate with alcohol, then blow-drying the substrate with nitrogen, placing the substrate on a rotating frame (15) of a vacuum chamber (1) of coating equipment, and pumping the vacuum chamber (1) to vacuumDegree less than 5 x 10-4Pa, and simultaneously heating to 300-500 ℃;
2) performing Ar ion glow cleaning and Ti ion cleaning on the substrate in the step 1), and obtaining a workpiece to be plated for later use after cleaning;
3) applying a pulse enhanced multi-arc ion plating technology or a traditional direct current multi-arc ion plating technology to two titanium targets arranged oppositely, and depositing a transition layer on the workpiece to be plated in the step 2) to obtain a workpiece sample containing the transition layer;
4) and (3) coating the workpiece sample containing the transition layer obtained in the step 3) with a TiSiCN nano multilayer coating by adopting a pulse-enhanced multi-arc ion plating technology to obtain the wear-resistant TiSiCN nano composite multilayer coating.
3. The method for preparing a wear-resistant TiSiCN nanocomposite multilayer coating according to claim 2, wherein the specific process of the step 2) is as follows:
firstly, introducing Ar gas into a vacuum chamber, regulating the flow rate of inlet gas through a flowmeter, keeping the air pressure of the vacuum chamber at 0.3-1.0 Pa, then starting a bias voltage power supply (16), regulating the bias voltage value to-600 to-1000V, regulating the duty ratio to 10-80%, and carrying out Ar glow cleaning on a workpiece for 5-100 min; then, simultaneously starting a Ti target power supply, adopting a direct-current multi-arc ion plating technology, keeping the air pressure of a vacuum chamber at 0.3-1.0 Pa, adjusting the bias voltage value of a bias power supply to-600 to-1000V, the duty ratio at 10-80 percent, and carrying out ion cleaning on the workpiece for 1-20 min to obtain the workpiece to be plated; wherein the substrate is stainless steel, high-speed steel or titanium alloy.
4. The method for preparing a wear-resistant TiSiCN nanocomposite multilayer coating according to claim 2, wherein the transition layer in the step 3) comprises a first transition sublayer and a second transition sublayer, and the first transition sublayer and the second transition sublayer are prepared by the following specific steps:
starting a first pulse multi-arc power supply (2) and a second pulse multi-arc power supply (3), firstly introducing Ar gas into a vacuum chamber (1), maintaining the air pressure in the vacuum chamber (1) at 0.5-3.0Pa, adjusting the bias voltage value to-50 to-500V,depositing a first transition sublayer Ti layer, closing Ar gas after the deposition is finished, and introducing N from a gas inlet (14)2And C2H2And (2) maintaining the air pressure in the vacuum chamber (1) to be constant, depositing a second transition sublayer TiN, TiC or TiCN layer, and obtaining a transition layer Ti/TiN, Ti/TiC or Ti/TiCN after the deposition is finished.
5. The method of claim 2, wherein the second transition sublayer is deposited by passing only N through the gas inlet (14)2Meanwhile, the transition layer also comprises a third transition sublayer, and the preparation process is as follows:
after the deposition of the second transition sublayer is finished, N is continuously introduced2Then introducing C into the vacuum chamber (1) through the gas inlet (14)2H2And (3) gas, maintaining the air pressure of the vacuum chamber (1) at 0.5-3.0Pa, depositing a third transition sublayer, and obtaining the Ti/TiN/TiCN transition layer after the third transition sublayer is deposited.
6. The method for preparing a wear-resistant TiSiCN nanocomposite multilayer coating according to any one of claims 2 to 5, wherein when the pulse enhanced multi-arc ion plating technique is adopted in the step 3), the direct current terminals and the pulse terminals of the first pulse multi-arc power supply (2) and the second pulse multi-arc power supply (3) are simultaneously turned on, the direct current terminal current is set to be 30 to 150A, the pulse terminal average current is 30 to 200A, the pulse discharge current is 50 to 400A, the frequency is 10 to 20000Hz, and the pulse width is 5 to 1000 μ s; when the traditional direct-current multi-arc ion technology is adopted, the first pulse multi-arc power supply (2) and the second pulse multi-arc power supply (3) only start a direct-current end, and the current of the direct-current end is set to be 30-110A.
7. The method for preparing a wear-resistant TiSiCN nanocomposite multilayer coating according to claim 4, wherein the preparation process parameters of the first transition sublayer Ti are as follows: introducing Ar gas with the flow rate of 100-500 sccm for deposition time of 10-60 min; the preparation process parameters of the second transition sublayer are as follows: introduction of N2And C2H2One or two ofThe gas flow is 100-.
8. The method for preparing a wear-resistant TiSiCN nanocomposite multilayer coating according to claim 5, wherein the preparation process parameters of the third transition sublayer are as follows: introduction of C2H2The flow rate of the gas is 20-200 sccm, and the deposition time is 10-60 min.
9. The method for preparing the TiSiCN nano composite multilayer coating with wear resistance as claimed in claim 2, wherein the specific process of coating the work piece sample containing the transition layer obtained in the step 3) with the TiSiCN nano multilayer coating in the step 4) is as follows:
keeping a first pulse multi-arc power supply (2) and a second pulse multi-arc power supply (3) on, respectively introducing organic silicon gas in front of a first Ti multi-arc target source (10) and a second Ti multi-arc target source (11) which are oppositely arranged from a first air inlet pipe (12) and a second air inlet pipe (13), and N2And C2H2Gas enters from the gas inlet (14) after being mixed, the air pressure of the vacuum chamber (1) is maintained to be 0.1-4.0 Pa, the bias voltage value of the bias voltage power supply (16) is adjusted to be-50-400V, the duty ratio is 20-80%, the rotating speed of the workpiece rotating frame (15) is adjusted to be 5-20 rpm, the deposition time is 60-180 min, and N is closed after the deposition is finished2And C2H2And (3) closing the mixed gas, keeping the first pulse multi-arc power supply (2) and the second pulse multi-arc power supply (3), cooling the interior of the vacuum chamber (1) to 150-200 ℃, taking out, and continuously cooling to room temperature to obtain the TiSiCN nano composite multilayer coating deposited on the substrate.
10. The method of claim 9, wherein the organosilicon is one or more of silane, trimethylsilane, tetramethylsilane, hexamethylsilane, and methylsilane; the pulse end currents of the two titanium targets are different from the corresponding organic silicon gas flow rate at least in one position; wherein the current at the DC end is 50-130A, the average current at the pulse end is 50-130A, the pulse discharge current is 100-400A, the frequency is 100-20000 Hz, and the pulse width is 5-1000 μ s.
CN202210256154.1A 2022-03-16 2022-03-16 Wear-resistant TiSiCN nano composite multilayer coating and preparation method thereof Pending CN114686821A (en)

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