CN113774347A - Superhard and tough nano composite coating, preparation method and use equipment - Google Patents

Superhard and tough nano composite coating, preparation method and use equipment Download PDF

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Publication number
CN113774347A
CN113774347A CN202111072554.9A CN202111072554A CN113774347A CN 113774347 A CN113774347 A CN 113774347A CN 202111072554 A CN202111072554 A CN 202111072554A CN 113774347 A CN113774347 A CN 113774347A
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target
power supply
doms
nano composite
tough
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欧伊翔
王浩琦
罗长维
周茜
华青松
欧阳晓平
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BEIJING RADIATION CENTER
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BEIJING RADIATION CENTER
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0664—Carbonitrides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target

Abstract

The invention provides a superhard and tough nano composite coating, a preparation method and a using device, which comprise the following steps: one target position is added in the center of a vacuum chamber of a traditional four-target closed field to form a five-target closed field, and full high-density plasma can be generated in the vacuum chamber. The specific experimental steps are as follows: firstly, preprocessing a workpiece; and secondly, placing the workpiece pretreated in the first step on a sample table of a vacuum chamber of target sputtering equipment, generating a high-density plasma beam by utilizing a multi-target deep oscillation magnetron sputtering technology, and performing sputtering deposition to obtain the superhard and tough multilayer nano composite coating. The room temperature preparation process is adopted, the high-efficiency continuous controllable preparation of the superhard and tough multilayer nano composite coating can be realized under the room temperature condition, the defects of incompact structure, large surface particles, overhigh hardness, insufficient toughness, poor bonding force and the like of the nano composite coating prepared by the existing preparation method are overcome, and the nano composite coating can be widely applied to mechanical parts, cutters, molds, hydrogen fuel bipolar plates and the like.

Description

Superhard and tough nano composite coating, preparation method and use equipment
Technical Field
The invention relates to the technical field of surface modification, in particular to a preparation method of a super-hard and tough nano composite coating and corresponding equipment.
Background
Nitride and carbide hard coatings have excellent wear resistance, corrosion resistance, fatigue resistance, oxidation resistance and the like, and are often used as surface protective coatings for machining various tools and mechanical parts to improve service performance and prolong service life. The hard coating is required to have the composite properties of high compactness, high surface integrity, high strength and toughness and the like under complex and harsh service working conditions such as high temperature, corrosion, abrasion, variable load and the like.
Generally, the hardness and the toughness of the coating are difficult to obtain simultaneously, and the current research on the hard coating mainly focuses on the direction of improving the hardness of the coating, however, the hard coating prepared by adopting the design idea is low in toughness, and is easy to crack in the using process to cause early failure, so that the application range of the hard coating is limited. In addition, in the conventional hard coating preparation process, due to the limitation of process conditions, the prepared hard coating often has structural defects of poor coating surface quality, such as particles, pores, coarse grains, uneven distribution of nano-crystals and non-crystals, insufficient compactness and the like, so that ideal composite performance is difficult to obtain. The prepared coating has the problems of low toughness, large stress, insufficient binding force and the like while having high hardness, which limits the wide application of the coating in the industrial field.
Therefore, it is an urgent need to solve the above-mentioned shortcomings of the existing preparation methods by improving the preparation method of the super-hard and tough nitride and carbide nano composite coating.
The super-hard and tough nano composite coating provided by the invention has the advantages of super-high hardness, high toughness, high film-substrate binding force and excellent corrosion-resistant and wear-resistant composite properties, can inhibit the initiation and expansion of microcracks in the service process, remarkably improves the service performance of the coating, and is the development direction of a new-generation high-performance coating.
Disclosure of Invention
The invention provides a preparation method of a superhard and tough nitride and carbide nano composite coating, which abandons the traditional high-temperature deposition process, adopts a room-temperature preparation process, can realize the preparation of a composite material under the room-temperature condition and overcomes the defects of the nano composite material prepared by the existing preparation method.
In order to solve the technical problem, the invention provides a preparation method of a superhard and tough nano composite coating workpiece, which comprises the following steps:
firstly, preprocessing a workpiece;
and secondly, placing the workpiece pretreated in the first step on a sample table of a vacuum chamber of target sputtering equipment, and performing target sputtering by using a multi-target deep oscillation magnetron sputtering technology to obtain the nano composite coating.
Wherein the nano composite layer is a Ti-TiAlSiCN multi-layer nano composite coating.
The first step is to sequentially perform ultrasonic cleaning on a workpiece to be coated in acetone, ethanol and deionized water.
The target sputtering equipment comprises a cylindrical target positioned at the center E, a sample table capable of rotating and revolving, a rectangular target A, a rectangular target B, a rectangular target C, a rectangular target D, a DOMS power supply, a C DOMS power supply, a D DOMS power supply and an E DOMS power supply which are positioned at the periphery, 4 movable baffles positioned in front of the target A, the target B, the target C and the target D, and a bias power supply.
The second step is further embodied as follows:
step 1, mounting a TiAlSi target on four different target positions of target sputtering equipment, mounting a Ti target on a central target position of the target sputtering equipment, vacuumizing, introducing argon, and starting a sample table to rotate;
step 2, cleaning the surface of the sample by a high-current ion beam, and activating the surface/interface of the sample;
step 3, preparing a metal Ti binding force layer;
step 4, deposition;
step 5, preparing a metal Ti layer on the surface of the TiAlSiCN coating again;
step 6, repeating the step 4 and the step five to prepare a multilayer nano composite coating;
and 7, cooling and taking out the workpiece.
The 2 nd step specifically comprises the steps of starting a DOMS power supply corresponding to the E target, setting the macro pulse width to be 1-3 ms, setting the micro pulse width on/off time to be 2-10 mus/8-40 mus, setting the average power to be 0.4-2 kW, and carrying out bias voltage to be-100 to-300V, cleaning the surface of a sample by using a high-current ion beam, and activating the surface/interface of the sample for 10-30 min.
The step 3 is to provide a bias voltage of 0-minus 80V by a bias voltage power supply, prepare a metal Ti binding force layer for 1-10 min, and obtain a thickness of 10 nm-2 μm.
The step 4 is that nitrogen N is introduced2The flow is 10-60 sccm, the Ar flow is 60-150sccm, the working air pressure is adjusted to be 0.3-1.7 Pa, a DOMS power supply corresponding to the target A, the target B, the target C and the target D is started, the macro pulse width is set to be 1-3 ms, the micro pulse width on/off time is 2-10 mus/8-40 mus, the average power is 4-8 kW, the bias voltage is-100V-300V, a baffle plate in front of the target is moved after the plasma discharge is stable, and the deposition time is 20-60 min.
The superhard and tough nano composite coating workpiece prepared by the method is provided.
The invention also provides target sputtering equipment for preparing the superhard and tough nano composite coating workpiece, which comprises a cylindrical target positioned at the center E, a sample table capable of rotating and revolving, an A-target rectangular target positioned at the periphery, a B-target rectangular target, a C-target rectangular target, a D-target rectangular target, an A DOMS power supply, a B DOMS power supply, a C DOMS power supply, a D DOMS power supply, an E DOMS power supply, 4 movable baffles positioned in front of the A-target position, the B-target position, the C-target position and the D-target position, and a bias power supply, wherein the A DOMS power supply, the B DOMS power supply, the C DOMS power supply, the E DOMS power supply, the 4 movable baffles and the bias power supply are correspondingly connected with each target position.
The invention has the advantages of
The preparation method has the advantages of high efficiency, simple and convenient operation, low cost and the like, can be suitable for surface protective coatings of various machining tools and parts, and greatly improves the performance of the tools and the parts.
Drawings
FIG. 1 is a schematic structural diagram of a superhard and tough TiAlSiCN nanocomposite coating prepared by the present invention; wherein 100 is a workpiece substrate, 110 is a Ti transition layer, 120 is a TiAlSi transition layer, and 130 is a TiAlSiCN functional layer.
FIG. 2 is a schematic diagram of a target sputtering apparatus for preparing a superhard and tough TiAlSiCN nano composite coating.
FIG. 3A cross-sectional structure (TEM) of a TiAlSiCN nanocomposite coating.
FIG. 4 is a High Resolution Transmission Electron Microscope (HRTEM) photograph and a selected area electron diffraction photograph of the TiAlSiCN nano composite coating.
FIG. 5 hardness, Young's modulus, H/E and H of TiAlSiCN coating3/E2Trend plot with DOMS target power.
FIG. 6 micro-indentation morphology of TiAlSiCN coating.
Detailed Description
The invention provides a preparation method of a sputtering superhard and tough nitride and carbide nano composite coating workpiece, which comprises the following steps:
firstly, preprocessing a workpiece;
and secondly, placing the workpiece pretreated in the first step on a sample table of a vacuum chamber of target sputtering equipment, and performing target sputtering by using a multi-target deep oscillation magnetron sputtering technology to obtain the nano composite coating.
The first step is to sequentially perform ultrasonic cleaning on the workpiece to be deposited with the coating in acetone, ethanol and deionized water, wherein the ultrasonic power is 100-300W, the ultrasonic time is 15-30min, and then dry the workpiece with dry nitrogen for later use.
The second step is further embodied as
Step 1, mounting a TiAlSi target material on four different target positions of a target material sputtering device, namely an A target position, a B target position, a C target position and a D target position, mounting a Ti target material on a central E target position of the target material sputtering device, and vacuumizing a vacuum chamber to 5 multiplied by 10- 3Pa, introducing argon and argonThe gas flow is 50-200sccm, the sample stage is started to rotate, the rotation is set to be 0.5-2rpm, the revolution is 1-3rpm, the working air pressure is 0.3-2Pa, the revolution target sputtering equipment is connected with a deep oscillation magnetron sputtering power supply (DOMS) power supply corresponding to the A target position, the B target position, the C target position and the D target position, a magnetron power supply corresponding to the E target position is connected with a corresponding DOMS power supply, and the movable baffle blocks the A target position, the B target position, the C target position and the D target position;
step 2, starting a DOMS power supply corresponding to the E target, setting the macro pulse width to be 1-3 ms, the micro pulse width on/off time to be 2-10 mus/8-40 mus, the average power to be 0.4-2 kW, and the bias voltage to be-100-300V, cleaning the surface of the sample by using a high-current ion beam, and activating the sample surface/interface for 10-30 min;
step 3, providing a bias voltage of 0 to minus 80V by a bias voltage power supply, and starting to prepare a metal Ti binding force layer for 1 to 10min with the thickness of 10nm to 2 mu m;
step 4, introducing nitrogen N2Flow rate of 10-60 sccm, argon Ar flow rate of 60-150sccm, acetylene C2H2The flow is 10-50sccm, the working air pressure is adjusted to be 0.3-1.7 Pa, DOMS power supplies corresponding to the target A, the target B, the target C and the target D are started, the macro pulse width is set to be 1-3 ms, the micro pulse width on/off time is 2-10 mus/8-40 mus, the average power is 4-8 kW, the bias voltage is-100V-300V, a baffle plate in front of the target position is moved after the plasma discharge is stable, and the deposition time is 20-60 min;
step 5, closing nitrogen and DOMS power supplies corresponding to the target position A, the target position B, the target position C and the target position D, only keeping the DOMS power supply for stacking the target position E to be started, and preparing a metal Ti layer on the surface of the TiAlSiCN coating again;
step 6, repeating the step 4 and the step 5 for 0-10 times to prepare a Ti-TiAlSi-TiAlSiCN-Ti-TiAlSiCN multi-layer nano composite coating;
and 7, turning off all DOMS power supplies, bias power supplies and nitrogen switches, and taking out the workpiece after cooling in the Ar atmosphere (less than 50 ℃).
The invention also provides equipment for preparing the superhard and tough nitride and carbide nano composite coating by adopting the method.
The invention also provides target sputtering equipment which comprises a cylindrical target positioned at the center E, a sample table capable of rotating and revolving, a rectangular target positioned at the periphery of the target A, a rectangular target positioned at the target B, a rectangular target positioned at the target C, a rectangular target positioned at the target D, a DOMS power supply A, a DOMS power supply B, a DOMS power supply C, a DOMS power supply D and an EDOMS power supply which are correspondingly connected with each target, and 4 movable baffles and a bias power supply which are positioned in front of the target A, the target B, the target C and the target D.
The superhard and tough nano composite coating provided by the invention adopts a metal Ti bonding layer + transition layer TiAlSi + TiAlSiCN multilayer composite structure design, realizes the regulation and control of the energy and density of deposited ions through the width control of macro/micro pulses and negative bias waveforms, pulse widths, frequency and voltage, and finally controls the size, distribution and orientation of nanocrystalline grains in the nano composite structure of the coating. According to the method and the equipment for efficiently preparing the superhard and tough nano composite coating, a multi-target co-sputtering mode is carried out by utilizing a deep oscillation magnetron sputtering technology, a plasma beam with high target ionization rate, high density and low energy is generated, a workpiece in a vacuum chamber is completely immersed in the high density plasma, and the superhard and tough nano composite coating on the surface of the workpiece is efficiently prepared.
The following embodiments are described in detail to solve the technical problems by applying technical means to the present invention, and the implementation process of achieving the technical effects can be fully understood and implemented.
Examples
In order to more clearly understand the invention, a multi-target deep oscillation pulse magnetron sputtering technology is adopted, a Ti cylindrical target, a TiAlSi rectangular target, high-purity nitrogen, acetylene and argon (the gas purity is more than or equal to 99.99 at.%) are utilized to prepare the Ti/TiAlSi/TiAlSiCN multi-layer nano composite coating, and the coating has super-hard and tough high composite performance. The Ti/TiAlSi/TiAlSiCN multilayer nano composite coating is prepared by adopting a multi-target deep oscillation pulse magnetron sputtering technology, and comprises the following steps:
a. workpiece pretreatment: sequentially ultrasonically cleaning a workpiece in deionized water, acetone and absolute ethyl alcohol, drying the workpiece by using dry nitrogen, and then placing the workpiece into a vacuum chamber;
b. cleaning a gas path: to-be-coated equipmentThe air pressure in the vacuum chamber is pumped to 5 x 10-3Introducing argon into a vacuum chamber below Pa, wherein the flow of the argon is 120sccm, and cleaning a gas path for 1-5 min;
c. cleaning by strong current ion beams: starting the sample table to rotate and revolve; starting a bias power supply, wherein the negative bias is 800V, and the duty ratio is 90%; starting an E target DOMS power supply, setting the macro pulse width to be 2ms, setting the micro pulse on/off time to be 5 mus/20 mus, carrying out high-current ion sputtering cleaning on the surface of the workpiece with the average power of 1kW, activating the surface/interface of the workpiece, and carrying out bombardment cleaning for 5-15 min;
ti bond layer deposition: confirming A, B, C, D that the front baffle of the target is closed, and changing the power supply parameter of the E target DOMS to deposit the Ti binding force layer; setting the parameters of the E target DOMS power supply as 2.5ms of macro-pulse width, 5 mus/20 mus of micro-pulse on/off time and 2kW of average power; the bias power supply parameter is negative bias 100V, and the duty ratio is 90%; and depositing the Ti transition layer for 5-15 minutes to obtain the Ti transition layer with the thickness of 400-1500 nm.
e. Depositing a gradient transition layer, namely setting the DOMS power supply parameters corresponding to A, B, C and the D target as 3ms of macropulse width, 6 mus/30 mus of micropulse switching time and 4-8 kW of average power, starting the A, B, C, D target and opening A, B, C and a front baffle of the D target; gradually reducing the power of the E target, reducing the power of the E target by 0.5kW every 1min, closing the E target 1min after the power of the E target is reduced to 1KW, and continuously depositing the TiAlSi transition layer for 5-10 min to obtain the TiAlSi transition layer with the thickness of 250-450 nm and the Ti-TiAlSi gradient layer with the thickness of 20-50 nm.
f. Depositing a TiAlSiCN nano composite layer, namely gradually introducing acetylene and nitrogen into a vacuum chamber at the flow rate of every 30s, increasing the flow rate of the acetylene and the nitrogen by 5sccm respectively on the basis of keeping the DOMS power supply corresponding to A, B, C and a D target on, finally depositing a coating until the flow rate of the acetylene is 15sccm and the flow rate of the nitrogen is 30sccm, and depositing for 60-120 min to obtain a TiAlSiCN coating with the thickness of 3-5 mu m;
g. cooling and discharging: and after the coating deposition is finished, cooling the workpiece to below 50 ℃ along with the furnace in the argon atmosphere, and taking out the workpiece.
A structural workpiece with a superhard and tough TiAlSiCN nano composite coating is shown in figure 1, wherein 100 is a workpiece substrate, 110 is a Ti transition layer, 120 is a TiAlSi transition layer, and 130 is a TiAlSiCN nano composite.
Fig. 2 shows a schematic diagram of a target sputtering apparatus, which includes a cylindrical target located at the center E, a sample stage capable of rotating and revolving, a rectangular target located at the periphery a, a rectangular target located at the center B, a rectangular target located at the target C, a rectangular target located at the target D, a DOMS power supply a, a DOMS power supply B, a DOMS power supply C, a DOMS power supply D and an EDOMS power supply correspondingly connected to each target, and 4 movable baffles and bias power supplies located in front of the target a, the target B, the target C and the target D.
As can be seen from the TEM cross-section of the TiAlSiCN coating in FIG. 3, the coating has a multi-layer structure with gradient bonding, and the bonding between the layers is dense.
As shown in the high resolution TEM photograph and the selective electron diffraction photograph of FIG. 4, the TiAlSiCN nano composite coating has dense nanocrystalline nc-TiAl (C) N/a-Si3N4The amorphous structure and the nanocrystalline form a single FCC structure.
Hardness, Young's modulus, H/E and H of TiAlSiCN coating from FIG. 53/E2The TiAlSiCN coating prepared by adopting a multi-target deep oscillation pulse magnetron sputtering technology has the hardness of 43GPa, the highest H/E of 0.121 and the highest H of 0.633/E2。
The microhardness morphology of the TiAlSiCN coating in figure 6 shows that no visible crack is initiated at the indentation edge, which indicates that the coating has excellent crack initiation and expansion resistance, and the fracture toughness K of the coating is further calculated according to the figureICIs 3.22MPa · m1/2And the calculation result further confirms that the coating has super-hard and tough performance.
Please supplement different parameters of nanocrystalline grain size, distribution and orientation of coating structures prepared under different macro/micro pulse widths, proving that the required superhard and tough composite coating of the present application can be obtained only under the pulse width of the present application.
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (10)

1. A method for preparing a superhard and tough nano composite coating workpiece is characterized by comprising the following steps:
firstly, preprocessing a workpiece;
and secondly, placing the workpiece pretreated in the first step on a sample table of a vacuum chamber of target sputtering equipment, and performing target sputtering by using a multi-target deep oscillation magnetron sputtering technology to obtain the nano composite coating.
2. The method of making an ultra-hard and tough nanocomposite coated workpiece according to claim 1, wherein: the nano composite layer is a Ti-TiAlSi-TiAlSiCN multi-layer nano composite coating.
3. A method of making a superhard and tough nanocomposite coated workpiece according to claim 1 or 2, wherein: the first step is to carry out ultrasonic cleaning on the workpiece to be deposited with the coating in acetone, ethanol and deionized water in sequence.
4. The method of making an ultra-hard and tough nanocomposite coated workpiece according to claim 1, wherein: the target sputtering equipment comprises a cylindrical target positioned at the center E, a sample table capable of rotating and revolving, a rectangular target positioned at the periphery A, a rectangular target positioned at the B, a rectangular target positioned at the C, a rectangular target positioned at the D, an A DOMS power supply, a B DOMS power supply, a C DOMS power supply, a D DOMS power supply and an E DOMS power supply which are correspondingly connected with each target, 4 movable baffles positioned in front of the A, B, C and D targets, and a bias power supply.
5. A method of making a superhard and tough nanocomposite coated workpiece according to claim 1 or 2, wherein: the second step is further embodied in that,
step 1, mounting a TiAlSi target on four different target positions of target sputtering equipment, mounting a Ti target on a central target position of the target sputtering equipment, vacuumizing, introducing argon, and starting a sample table to rotate;
step 2, cleaning the surface of the sample by a high-current ion beam, and activating the surface/interface of the sample;
step 3, preparing a metal Ti binding force layer;
step 4, deposition;
step 5, preparing a metal Ti layer on the surface of the TiAlSiCN coating again;
step 6, repeating the step 4 and the step five to prepare a multilayer nano composite coating;
and 7, cooling and taking out the workpiece.
6. The method of making an ultra-hard and tough nanocomposite coated workpiece according to claim 5, wherein: the 2 nd step specifically comprises the steps of starting a DOMS power supply corresponding to the E target, setting the macro pulse width to be 1-3 ms, setting the micro pulse width on/off time to be 2-10 mus/8-40 mus, setting the average power to be 0.4-2 kW, and carrying out bias voltage to be-100 to-300V, cleaning the surface of a sample by using a high-current ion beam, and activating the surface/interface of the sample for 10-30 min.
7. The method of making an ultra-hard and tough nanocomposite coated workpiece according to claim 5, wherein: the step 3 is to provide a bias voltage of 0-minus 80V by a bias voltage power supply, prepare a metal Ti binding force layer for 1-10 min, and obtain a thickness of 10 nm-2 μm.
8. The method of making an ultra-hard and tough nanocomposite coated workpiece according to claim 5, wherein: the step 4 is specifically that in the step 4,introducing nitrogen N2The flow is 10-60 sccm, the Ar flow is 60-150sccm, the working air pressure is adjusted to be 0.3-1.7 Pa, a DOMS power supply corresponding to the target A, the target B, the target C and the target D is started, the macro pulse width is set to be 1-3 ms, the micro pulse width on/off time is 2-10 mus/8-40 mus, the average power is 4-8 kW, the bias voltage is-100V-300V, a baffle plate in front of the target is moved after the plasma discharge is stable, and the deposition time is 20-60 min.
9. An ultra-hard and tough nanocomposite coated workpiece produced by the method of any one of claims 1 to 8.
10. A target sputtering apparatus for preparing the superhard and tough nanocomposite coated workpiece of claim 9, characterized by: the device comprises a cylindrical target positioned at a center E, a sample platform capable of rotating and revolving, a rectangular target positioned at a peripheral A target, a rectangular target positioned at a B target, a rectangular target positioned at a C target, a rectangular target positioned at a D target, an A DOMS power supply, a B DOMS power supply, a C DOMS power supply, a D DOMS power supply, an E DOMS power supply, 4 movable baffles positioned in front of the A target, the B target, the C target and the D target, and a bias power supply.
CN202111072554.9A 2021-09-14 2021-09-14 Superhard and tough nano composite coating, preparation method and use equipment Pending CN113774347A (en)

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