Max phase coating with (110) plane preferred orientation and preparation method and application

Abstract

The application discloses a (110) plane preferred orientation MAX phase coating and a preparation method and application thereof. The preparation method comprises the following steps: adopting a double-target high-power pulse magnetron sputtering combined with a synchronous pulse bias technology, taking a metal target and a C target as target materials, and making the magnetic field between the metal target and the C target be a closed magnetic field with opposite magnet polarities or a mirror magnetic field with the same magnet polarities, so as to deposit the (110) plane preferred orientation MAX phase coating on the surface of a substrate; and the metal target is selected from a TiAl target, a CrAl target or a VAl target. The MAX phase coating provided by the application has the advantages of low deposition temperature, high purity, smooth surface, uniform composition, dense structure and the like, and has a good application prospect in the field of high-temperature oxidation resistance or corrosion resistance protection.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of material surface treatment, and particularly relates to a (110) surface preferentially oriented MAX phase coating and a preparation method and application thereof. BACKGROUND

[0002] M n+1 AX n MAX phase is a large class of thermodynamically stable, nano-layered metal carbide or nitride ceramic materials with a hexagonal structure, and the atomic structure is composed of M n+1 X n The A atom layers are alternately stacked in the c direction, and the X atoms are generally filled in the octahedral interstitial sites formed by the M atoms. Among them, M mainly represents IVB-VIB transition metals, A mainly comes from III or IV main group elements, and X represents C or N. Ti2AlC, Cr2AlC and V2AlC are typical representatives of MAX phase materials, which not only have excellent chemical corrosion resistance and high-temperature oxidation resistance, good thermal shock resistance, but also have excellent neutron irradiation stability. In addition, the unique layered structure and chemical bond characteristics also make Ti2AlC, Cr2AlC and V2AlC have good oxidation-induced self-healing ability; and they also have thermal physical properties matching materials such as stainless steel and high-performance Zr alloy. These excellent properties make Al-based Ti2AlC, Cr2AlC and V2AlC coatings as a zirconium alloy surface accident-resistant coating have been widely concerned at home and abroad.

[0003] Because MAX phase materials not only have strict chemical composition, but also have complex unit cell structure and large c-axis unit cell parameters (such as 211 system Cr2AlC c-axis length ), which leads to a narrow high-purity phase preparation window, a long atomic diffusion distance required for crystallization, and a high preparation temperature. In the common preparation methods of MAX phase coating materials, such as thermal spraying (including flame spraying, arc spraying and plasma spraying), cold spraying and physical vapor deposition (PVD), the synthesis temperature of MAX phase is above 500℃, the interface bonding strength is relatively low, and the synthesis product is often accompanied by phenomena such as powder oxidation and decarburization and impurity phase (TiC x , Ti3AlC, Zr x Al, CrC x or AlCr x compounds) generation, which reduces the high-temperature protection performance of the material.

[0004] For the Ti2AlC, Cr2AlC and V2AlC MAX phase protective coating materials of 211 system, the current preparation methods are mainly PVD technologies such as magnetron sputtering and cathodic arc ion plating, but the complete crystallization temperature is often in the range of 500-900℃, which is still higher than the final annealing temperature (450-600℃) of commonly used alloys and zirconium cladding materials, thereby limiting the surface protection application of the MAX phase coating in the key field of major technical equipment.

[0005] In summary, due to the large number of competing MAX phase materials, complex structure, high phase formation temperature, how to reduce the preparation temperature of the MAX phase coating and realize the high-purity low-temperature crystallization of the MAX phase coating is one of the bottleneck problems which need to be broken through to expand the application range of the MAX phase material in the temperature-sensitive substrate field, especially for the application in the harsh service environment of ATF zirconium alloy cladding, which has important research value and significance. SUMMARY

[0006] The main purpose of the present application is to provide a (110) surface preferentially oriented MAX phase coating and a preparation method and application thereof, so as to overcome the shortcomings of the prior art.

[0007] In order to achieve the above-mentioned purposes, the technical scheme adopted by the present application comprises:

[0008] The embodiment of the present application provides a preparation method of a (110) surface preferentially oriented MAX phase coating, which comprises:

[0009] The double-target high-power pulse magnetron sputtering is used to deposit the (110) surface preferentially oriented MAX phase coating on the surface of the substrate by using metal target and C target as target materials and making the magnetic field between the metal target and the C target be a closed magnetic field with opposite magnet polarities or a mirror magnetic field with the same magnet polarities.

[0010] The embodiment of the present application also provides a (110) surface preferentially oriented MAX phase coating prepared by the low-temperature preparation method, wherein the crystal in the MAX phase coating grows in a (110) crystal surface preferentially oriented manner, and the texture coefficient of the MAX phase coating is 2-3.

[0011] The embodiment of the present application also provides an application of the (110) surface preferentially oriented MAX phase coating in the field of high-temperature oxidation resistance or corrosion resistance protection of the substrate.

[0012] Compared with the prior art, the present application has the following beneficial effects:

[0013] (1) The application utilizes high-power pulse power to perform sputtering on the target material, the lower duty cycle and the higher peak power density in the high-power discharge of the target material improve the ionization rate of the sputtered material, enhance the kinetic energy of the particles incident on the substrate surface, and prolong the diffusion distance of the film-forming particles, thereby improving the growth kinetics of the coating and improving the accuracy of the component control of the film-forming particles; meanwhile, by adjusting the application time and voltage amplitude of the synchronous pulse bias, the migration energy of the deposited ion beam is improved, and the continuous bombardment of the charged particles on the film-forming surface is significantly enhanced, so as to improve the compactness of the coating and the film-substrate adhesion, thereby preparing the (110) plane preferred orientation MAX phase coating at a lower substrate heating temperature;

[0014] (2) The double-target high-power pulse magnetron sputtering combined with the synchronous pulse bias technology in the application combines the advantages of traditional magnetron sputtering low-temperature deposition, smooth surface, no large particle defects, high ionization rate of cathode material in arc ion plating, strong film-substrate adhesion, and dense coating, and improves the problems of low utilization rate of the target material, narrow runway area, and large internal stress in traditional magnetron sputtering, so that the prepared coating surface is free of large particle accumulation, the coating surface is smooth, the composition is uniform, and the structure is dense; meanwhile, the coating has good high-temperature oxidation resistance and corrosion resistance. BRIEF DESCRIPTION OF DRAWINGS

[0015] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments described in the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0016] Figure 1 is the discharge characteristic diagram of the double-target high-power pulse magnetron sputtering combined with the synchronous pulse bias in the (110) plane preferred orientation Cr2AlC MAX phase coating prepared in the embodiment 1 of the application;

[0017] Figure 2 is the XRD spectrum of the MAX phase coating prepared in the embodiment 1 and the comparative example 1 of the application;

[0018] Figure 3 is the Raman spectrum of the MAX phase coating prepared in the embodiment 1 and the comparative example 1 of the application;

[0019] Figure 4 is the surface morphology diagram of the (110) plane preferred orientation MAX phase coating prepared in the embodiment 1 of the application;

[0020] Figure 5 is the surface morphology diagram of the MAX phase coating prepared in the comparative example 1 of the application;

[0021] Figure 6 is the XRD spectrum of the MAX phase coating prepared in Example 2 and Comparative Example 2 of the present application;

[0022] Figure 7 is the Raman spectrum of the MAX phase coating prepared in Example 2 and Comparative Example 2 of the present application;

[0023] Figure 8 is the surface morphology of the (110) plane preferred orientation of the MAX phase coating prepared in Example 2 of the present application;

[0024] Figure 9 is the surface morphology of the MAX phase coating prepared in Comparative Example 2 of the present application;

[0025] Figure 10 is the XRD spectrum of the MAX phase coating prepared in Example 1 and Comparative Example 3 of the present application;

[0026] Figure 11 is the Raman spectrum of the MAX phase coating prepared in Example 1 and Comparative Example 3 of the present application;

[0027] Figure 12 is the electrochemical corrosion diagram of the MAX phase coating prepared in Example 1 and Comparative Example 1 of the present application and the Ti-6Al-4V substrate. DETAILED DESCRIPTION

[0028] In view of the defects of the prior art, the present inventors have long studied and practiced to propose the technical solution of the present application. The present application uses a double-target high-power pulsed magnetron sputtering combined with a synchronous pulsed bias technology to realize the high-purity phase low-temperature preparation of the MAX phase coating. The TiAl / CrAl / VAl target and the C target are sputtered by using a high-power pulse power supply. The lower duty cycle and the higher peak power density in the high-power discharge improve the ionization rate of the sputtered material, enhance the kinetic energy of the particles incident on the substrate surface, and improve the kinetic conditions of the coating growth. Secondly, the application time and the voltage amplitude of the synchronous pulsed bias are adjusted to enhance the energy of the Ar ions (Ar + and Ar 2+ ), Cr ions (Cr + and Cr 2+ ), Ti ions (Ti + and Ti 2+ ), V ions (V + and V 2+ ), and Al ions (Al + and Al 2+) to the film-forming surface, and can further improve the coupling efficiency of the pulsed bias, prolong the diffusion distance of the film-forming particles, improve the compactness of the coating and the film-base bonding strength, and further improve the oxidation corrosion resistance of the coating. Finally, the closed magnetic field discharge can further enhance the ionization rate of the film-forming atoms in the HiPIMS discharge, thereby facilitating the precise regulation of the film-forming particle composition control accuracy and kinetic energy by using the bias.

[0029] The technical solutions of the present application will be described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0030] Specifically, as one aspect of the technical solutions of the present application, a preparation method of a (110) plane preferred orientation MAX phase coating comprises:

[0031] A double-target high-power pulsed magnetron sputtering combined with a synchronous pulsed bias technology is used to deposit a (110) plane preferred orientation MAX phase coating on the surface of a substrate, using a metal target and a C target as target materials, and making the magnetic field between the metal target and the C target a closed magnetic field with opposite magnet polarities or a mirror magnetic field with the same magnet polarity; wherein the metal target is selected from a TiAl target, a CrAl target or a VAl target.

[0032] The present application applies a pulsed negative bias synchronized with the double-target high-power pulsed magnetron sputtering discharge pulse to the substrate, thereby achieving efficient acceleration of high-flux energetic ions, especially high-density target material ions (Ti + , Cr + , V + , Al + , C + ) and Ar + beam, realizing continuous ion bombardment, non-equilibrium atomic-level heating and introduction of residual stress (i.e. strain energy) to the film-forming surface, which can reduce the heating temperature required for coating crystallization while making the coating grow preferentially along the (110) plane.

[0033] Specifically, the MAX phase coating in the present application is obtained by sputtering high-purity TiAl / CrAl / VAl targets and C elemental targets. From the beginning of self-deposition, the TiAl target, the CrAl target or the VAl and the C target are sputtered by high-power pulsed magnetron sputtering technology. The parameters of the high-power pulsed magnetron sputtering power supply are set as follows: the frequency is 100-1000 Hz; the duty cycle is 2.5-10%; the pulse width is 25-1000 μs. Under a certain substrate preheating temperature, the crystalline Ti2AlC, Cr2AlC, V2AlC MAX phase coating is directly obtained.

[0034] As preferred, in the coating deposition of the present application, the duty cycle of the TiAl / CrAl / VAl target is preferably 2.5%, the pulse width is 50μs, and the pulse bias amplitude is -100V, so as to realize the high-purity phase low-temperature preparation of Ti2AlC, Cr2AlC and V2AlC MAX phase coatings.

[0035] In some preferred embodiments, the frequency of the pulse negative bias used in the double-target high-power pulsed magnetron sputtering combined with synchronous pulse bias technology is 100-1000Hz, the duty cycle is 10-15%, the pulse width is 150-1500μs, the delay time is 0-250μs, and the amplitude is 0-200V.

[0036] In some preferred embodiments, the deposition temperature is 320-600℃.

[0037] In some preferred embodiments, the preparation method specifically comprises:

[0038] placing the substrate in a reaction chamber, using a metal target and a C target as target materials, using a protective gas as working gas, and using the double-target high-power pulsed magnetron sputtering combined with synchronous pulse bias technology to apply a pulse negative bias to the substrate synchronously with the double-target high-power pulsed magnetron sputtering discharge pulse, so as to deposit a (110) plane preferred orientation MAX phase coating on the surface of the substrate;

[0039] In some preferred embodiments, the frequency of the power source used in the double-target high-power pulsed magnetron sputtering technology is 100-1000Hz, the period is 1000-10000μs, the power of the metal target is 75-150W, the duty cycle is 2.5-5%, and the pulse time is 25-500μs; the power of the C target is 90-180W, the duty cycle is 5-10%, and the pulse time is 50-1000μs; the working gas pressure is 0.2-1.0Pa, and the deposition time is 240-1200min.

[0040] In some preferred embodiments, the purity of the target material is above 99.99%, and the size is but not limited to the size of the cylindrical target, the rectangular target.

[0041] In some preferred embodiments, the working gas used in the formation of the MAX phase coating includes any one or a combination of two or more of neon, argon, krypton and xenon, and is not limited thereto.

[0042] In some preferred embodiments, the present application can pass a gaseous carbon source into the MAX phase coating, which acts together with the C target to finally form a MAX phase coating, and the gaseous carbon source includes methane and / or acetylene, and is not limited thereto.

[0043] Further, the flow rate of the methane is 0-5 sccm.

[0044] Further, the flow rate of the acetylene is 0-3 sccm.

[0045] In some preferred embodiments, the preparation method further comprises: placing the substrate in a reaction cavity, vacuumizing to 5x10 -4 Pa, heating the substrate and introducing a protective gas into the cavity, while turning on the power supply of the metal target and the C target, and performing self-cleaning treatment on the metal target and the C target by using a magnetron sputtering technology; wherein the substrate temperature is 320-600℃, the gas pressure in the reaction cavity is 0.2-2 Pa, the power of the metal target is 75-180 W, and the power of the C target is 75-180 W.

[0046] In some preferred embodiments, the preparation method further comprises: after completing the self-cleaning treatment, introducing Ar gas with a gas pressure of 0.2-2 Pa into the reaction cavity, and applying a synchronous pulsed negative bias to the substrate, so as to realize metal plasma etching treatment on the substrate.

[0047] Further, the process parameters of the metal plasma etching treatment include: the flow rate of the Ar gas is 20-50 sccm, the frequency of the negative bias of the substrate is 100-1000 Hz, the amplitude is 500-1000 V, the duty cycle is 5-20%, and the pulse width is 50-2000 μs; the frequency of the power supply of the metal target is 100-1000 Hz, the duty cycle is 2.5-10%, the pulse width is 25-1000 μs, and the power of the metal target is 75-150 W.

[0048] In some preferred embodiments, the preparation method further comprises: polishing and ultrasonic cleaning the substrate first, and then depositing the MAX phase coating on the surface of the substrate.

[0049] Further, the surface of the Ti-6Al-4V alloy sheet is polished by using SiC sandpaper with a grit of 400#-3000# in sequence, and then polished by using diamond polishing agent with a particle size of 2.5 μm for 20 min.

[0050] Further, the cleaning liquid used in the ultrasonic cleaning treatment includes acetone and / or ethanol.

[0051] In some preferred embodiments, the substrate includes Ti-6Al-4V or zirconium alloy, and is not limited thereto.

[0052] In some more specific embodiments, the preparation method of the MAX phase coating with the (110) plane preferentially oriented includes:

[0053] (1) Ti-6Al-4V alloy sheet is placed in acetone and alcohol for cleaning, dried, and then fixed on the rack using metal tablet for standby;

[0054] As preferred, the cleaning time is preferably 10 min using ultrasonic cleaning.

[0055] As preferred, after cleaning, deionized water is used for rinsing, and then high-purity N2 is used for blowing dry and placing on the rack.

[0056] (2) Ti-6Al-4V alloy sheet is placed in a deposition vacuum chamber, vacuumed to 5x10 -4 Pa, heated to 320-600℃, Ar gas is introduced into the vacuum chamber, TiAl / CrAl / VAl target and C target power is turned on, and the target material is cleaned by using magnetron sputtering.

[0057] As preferred, the Ar gas pressure is 0.2-1.0 Pa.

[0058] As preferred, the TiAl / CrAl / VAl target and C target power is 75-180 W.

[0059] As preferred, the cleaning time is 10-20 min.

[0060] (3) In the Ar gas atmosphere protection condition, TiAl / CrAl / VAl target HiPIMS power is turned on, the substrate is applied with synchronous pulse negative bias, and the high-energy metal plasma is used to clean and etch the substrate surface.

[0061] As preferred, the Ar gas pressure is 0.2-2 Pa.

[0062] As preferred, the pulse negative bias amplitude is 500-1000 V.

[0063] As preferred, the etching time is 15-30 min.

[0064] (4) In the working gas of Ar gas or Ar gas and methane / ethyne mixed gas atmosphere, the substrate is applied with synchronous pulse negative bias, TiAl / CrAl / VAl target and C target power is turned on, and the MAX phase coating is deposited on the substrate surface by using magnetron sputtering.

[0065] As preferred, the working gas pressure is 0.2-1.0 Pa.

[0066] As preferred, the pulse negative bias amplitude is 0-200 V.

[0067] As preferred, the TiAl / CrAl / VAl target power is 75-150 W, and the C target power is 90-180 W.

[0068] As preferred, the sputtering time is 240-1200 min.

[0069] As preferred, the substrate rotation speed during sputtering is 5-20 rpm.

[0070] As preferred, the crystallinity of the deposited MAX phase coating is controlled by controlling the frequency, duty cycle, substrate bias of the HiPIMS power source in step (4), so as to further reduce the crystallization temperature of the MAX phase coating.

[0071] The method for preparing the MAX phase coating provided by the application can reduce the deposition temperature by at least 50℃ or more than 50℃ compared with the conventional method when preparing the same MAX phase coating.

[0072] The application uses a high-power pulse power source to sputter a TiAl target, a CrAl target or a VAl target and a C target. The lower duty cycle and higher peak power density in the high-power discharge of the TiAl / CrAl / VAl target and the C target increase the ionization rate of the sputtered material, enhance the kinetic energy of the particles incident on the substrate surface, and prolong the diffusion distance of the film-forming particles. At the same time of improving the growth kinetics of the coating, the precision of the component control of the film-forming particles is improved. The application time and voltage amplitude of the synchronous pulse bias are controlled, which can significantly enhance the continuous bombardment of the Ar ions (Ar + and Ar 2+ ), Cr ions (Cr + and Cr 2+ ), Ti ions (Ti + and Ti 2+ ), V ions (V + and V 2+ ), and Al ions (Al + and Al 2+ ) on the film-forming surface, so as to improve the compactness of the coating and the film-substrate adhesion. Therefore, the high-purity Ti2AlC, Cr2AlC and V2AlC MAX phase coating can be prepared at a lower substrate heating temperature, the phase formation temperature required for the preparation of the MAX phase by the PVD technology is reduced, the high-purity (>90wt.%) MAX phase coating is prepared at 320-600℃ (the conventional temperature is 500-900℃), and a new idea is provided for the preparation of the MAX phase coating.

[0073] The double-target high-power pulsed magnetron sputtering combined with the synchronous pulsed bias technology in the application has the advantages of traditional magnetron sputtering low-temperature deposition, smooth surface, no large particle defects, high cathode material ionization rate of arc ion plating, strong film-base bonding, and dense coating, and simultaneously improves the problems of low utilization rate of target material, narrow runway area, and large internal stress in traditional magnetron sputtering, so that the prepared coating surface has no large particle accumulation phenomenon, and the coating surface is smooth, uniform in composition, and dense in structure.

[0074] Another aspect of the embodiment of the application also provides a (110) plane preferred orientation MAX phase coating prepared by the preparation method, wherein crystals in the MAX phase coating grow in (110) plane preferred orientation, and a texture coefficient of the MAX phase coating is 2-3.

[0075] Further, an atomic ratio in the MAX phase coating is 2:1:1, the MAX phase coating includes any one of Ti2AlC, Cr2AlC and V2AlC, and is not limited thereto.

[0076] Further, a crystallinity of the MAX phase coating is above 90%, and a surface roughness is 10-50 nm.

[0077] Further, a thickness of the MAX phase coating is 2-10 microns.

[0078] Another aspect of the embodiment of the application also provides application of the aforementioned (110) plane preferred orientation MAX phase coating in the field of high-temperature oxidation resistance or corrosion resistance protection of a substrate.

[0079] For example, the MAX phase coating prepared by the application is applied in high-temperature oxidation resistance or corrosion resistance protection of an outer surface of an accident tolerant fuel (ATF) zirconium alloy nuclear fuel cladding or a surface of a Ti-6Al-4V material of an aero-engine blade.

[0080] The MAX phase coating prepared by the application can effectively protect a substrate in a high-temperature, high-salt and high-humidity environment.

[0081] The technical solutions of the application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The embodiments are implemented on the premise of the technical solutions of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following embodiments.

[0082] In the following examples, the experimental materials used in the examples are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0083] Embodiment 1:

[0084] In this embodiment, the base material is a Ti-6Al-4V alloy sheet (TC4 alloy sheet), and the specific preparation steps of the base surface Cr2AlC MAX phase coating are as follows:

[0085] Step 1: sequentially polish the surface of the Ti-6Al-4V alloy sheet using 400#-3000# SiC sandpaper, and then polish using diamond polishing agent with a particle size of 2.5 μm for 20 min.

[0086] Step 2: ultrasonically clean the polished TC4 alloy sheet substrate in acetone and alcohol for 10 min, then rinse with deionized water, and then blow dry with high-purity N2. The substrate is fixed on the rack using a metal tablet for standby.

[0087] Step 3: place the rack in the deposition cavity chamber, and after the mechanical pump and molecular pump are vacuumed to 5 x 10 -4 After the pressure in the vacuum cavity is reduced to 5 x 10

[0088] Step 4: introduce high-purity Ar gas with a pressure of 0.5 Pa into the vacuum cavity, set the CrAl target HiPIMS power supply parameters as follows: frequency 500 Hz, duty cycle 2.5%, pulse width 50 μs, power 100 W, pulse negative bias power supply frequency 500 Hz, amplitude 900 V, duty cycle 5%, and perform Cr and Al metal ion etching cleaning on the Ti-6Al-4V alloy substrate for 20 min.

[0089] Step 5: introduce high-purity Ar gas with a pressure of 0.5 Pa into the vacuum cavity, and simultaneously open the high-power pulse sputtering power supply of the CrAl target and the C target under the closed magnetic field magnetic pole configuration of the CrAl target and the C target, with the power set to 100 W and 120 W respectively. The HiPIMS power supply parameters are set as follows: frequency 500 Hz, period 2000 μs, CrAl target duty cycle 2.5%, pulse time 50 μs, C target duty cycle 5%, pulse time 100 μs, and Cr2AlC MAX phase coating is deposited by using double-target high-power pulse magnetron co-sputtering combined with synchronous pulse bias technology. The pulse negative bias frequency of the substrate is 500 Hz, the amplitude is 100 V, the duty cycle is 12.5%, the pulse width is 250 μs, the delay is 10 μs (relative to the start of the metal target discharge pulse), and the deposition time is 360 min.

[0090] The bias waveform during deposition in this embodiment is as follows: Figure 1As shown in the figure, the peak current of the substrate is relatively large during the discharge of the CrAl target, indicating that when Ar ions bombard the substrate surface, a large number of Cr and Al metal ions are simultaneously incident on the substrate surface. The bias waveform during the deposition process is shown in the figure. Figure 1 As shown in the figure, both the CrAl and C targets are at relatively high peak power densities (400 W / cm²). 2 With 870W / cm 2 The sputtering was performed under the target. As for the synchronous pulse bias current, the peak current of the substrate was relatively large when the CrAl target was discharged, indicating that when Ar ions bombarded the substrate surface, a large number of Cr and Al metal ions were also injected into the substrate surface at the same time.

[0091] Comparative Example 1:

[0092] This embodiment is a comparative embodiment of Embodiment 1 described above.

[0093] In this embodiment, the substrate is exactly the same as in Example 1, and the polishing, cleaning, and surface metal plasma etching and cleaning processes of the substrate are also exactly the same. The difference is that in step 5, when the Cr2AlC MAX phase coating is deposited by dual-target high-power pulsed magnetron co-sputtering, no substrate bias is applied (the substrate is in a suspended state).

[0094] Figure 2 and Figure 3 As described in Example 1 above, the X-ray diffraction pattern and Raman spectrum of the coating were obtained in Comparative Example 1. Figure 2 and Figure 3 It can be seen that the deposited coating prepared by the dual-target high-power pulsed magnetron sputtering combined with synchronous pulsed bias technology in Example 1 is a crystalline Cr2AlC MAX phase coating with preferred orientation of the (110) plane, with a texture coefficient of about 3 and a crystallinity of >90%. In contrast, the deposited coating prepared by dual-target high-power pulsed magnetron sputtering in Comparative Example 1 is a non-preferred Cr2AlC MAX phase coating. The XRD pattern also shows some characteristic diffraction peaks originating from the matrix. Figure 4 and Figure 5 The figures show the surface morphology of the coatings prepared in Example 1 and Comparative Example 1, respectively. As can be seen from the figures, the surface of the deposited coating prepared by the dual-target high-power pulsed magnetron sputtering technology is relatively flat and uniform. The coating prepared by the composite synchronous pulsed bias technology has coarser grains and exhibits more obvious MAX phase layer growth characteristics compared to the coating without bias. Figure 12 The electrochemical test results of the (110) facet preferred growth coating prepared in Example 1, the non-preferred coating prepared in Comparative Example 1, and the TC4 substrate are shown in the figure. As can be seen from the figure, the corrosion current density of the prepared non-preferred coating is reduced to about 1 / 5 of that of the substrate, while the corrosion current density of the (110) facet preferred coating is reduced by one order of magnitude compared with the substrate, indicating that this preferred orientation coating has better corrosion resistance and protection performance.

[0095] Example 2:

[0096] In this embodiment, the base material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Cr2AlC MAX phase coating on the surface of the base are as follows:

[0097] Step 1: Use 400#-3000# SiC sandpaper to polish the surface of the Ti-6A1-4V alloy sheet in turn, and then use diamond polishing agent with a particle size of 2.5 μm for polishing for 20 min.

[0098] Step 2: After polishing, the TC4 alloy sheet substrate is placed in acetone and alcohol for ultrasonic cleaning for 10 min, then rinsed with deionized water, and then dried with high-purity N2. The substrate is fixed on the rack by metal pressing for standby.

[0099] Step 3: Place the rack in the deposition cavity chamber, and after the mechanical pump and molecular pump are pumped to a vacuum of 5×10 -4 Pa and the substrate heating temperature reaches 320℃, introduce high-purity Ar gas with a gas pressure of 0.5 Pa into the vacuum cavity, and under the closed magnetic field pole configuration of the CrAl target and the C target, simultaneously open the high-power pulse power supply of the CrAl target and the C target, and use magnetic control sputtering to clean each target.

[0100] Step 4: Introduce high-purity Ar gas with a gas pressure of 0.5 Pa into the vacuum cavity, set the CrAl target HiPIMS power supply parameters as follows: frequency 500 Hz, duty cycle 2.5%, pulse width 50 μs, power 100 W, pulse negative bias power supply frequency 500 Hz, amplitude 900 V, duty cycle 5%, and perform Cr, Al metal ion etching cleaning on the Ti-6Al-4V alloy substrate for 20 min.

[0101] Step 5: Introduce high-purity Ar gas with a gas pressure of 0.5 Pa into the vacuum cavity, and under the closed magnetic field pole configuration of the CrAl target and the C target, simultaneously open the high-power pulse sputtering power supply of the CrAl target and the C target, and set the power to 100 W and 120 W respectively. The HiPIMS power supply parameters are set as follows: frequency 500 Hz, period 2000 μs, CrAl target duty cycle 2.5%, pulse time 50 μs, C target duty cycle 5%, pulse time 100 μs, and Cr2AlC MAX phase coating is deposited by using double-target high-power pulse magnetron co-sputtering combined with synchronous pulse bias technology. The pulse negative bias frequency of the substrate is 500 Hz, the amplitude is 100 V, the duty cycle is 12.5%, the pulse width is 250 μs, the delay is 50 μs (relative to the start of the metal target discharge pulse), and the deposition time is 360 min.

[0102] Comparative Example 2:

[0103] This embodiment is a comparative example of the above-mentioned embodiment 2.

[0104] In this embodiment, the substrate is exactly the same as that in embodiment 2, and the polishing, cleaning treatment and surface Ar ion etching cleaning process of the substrate are also exactly the same, except that in step 5, the pulsed negative bias voltage of the substrate is a medium frequency bias voltage, the frequency is 350 kHz, the amplitude is 100 V, the duty cycle is 61.5%, and the pulse width is about 2.86 μs.

[0105] Figure 6 and Figure 7 The X-ray diffraction spectrum and the Raman spectrum of the coating prepared in the above-mentioned embodiment 2, comparative example 2 are shown in FIGS. 1 and 2. Figure 6 and Figure 7 As can be seen from FIGS. 1 and 2, the as-deposited coating prepared by the synchronous pulsed bias voltage technique is a (110) plane preferred orientation Cr2AlC MAX phase coating, and the texture coefficient is about 2, while the as-deposited coating prepared by the bias voltage technique in comparative example 2 is a Cr2AlC MAX phase coating. There are also some characteristic diffraction peaks from the substrate in the XRD spectrum. Figure 8 and Figure 9 The surface morphology diagrams of the coatings prepared in the above-mentioned embodiment 2, comparative example 2 are shown in FIGS. 3 and 4, respectively. The as-deposited coatings prepared by the two bias voltage techniques show certain MAX phase lamellar growth crystallization characteristics. As can be seen from the surface diagrams, the grain growth characteristics of embodiment 2 have been reduced to a certain extent compared with embodiment 1, and the surface of the coating prepared by the medium frequency bias voltage technique also shows certain bias voltage assisted ion bombardment effect, and the surface is also more flat, but the compactness is obviously not as good as that of the synchronous pulsed bias voltage technique.

[0106] Embodiment 3

[0107] In this embodiment, the substrate material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Cr2AlC MAX phase coating on the surface of the substrate are as follows:

[0108] Step 1: polish the surface of the Ti-6Al-4V alloy sheet successively using 400#-3000# SiC sandpaper, and then polish using diamond polishing agent with a particle size of 2.5 μm for 20 min.

[0109] Step 2: place the polished TC4 alloy sheet substrate in acetone and alcohol for ultrasonic cleaning for 10 min, then rinse with deionized water, and then blow dry using high-purity N2, and fix the substrate on the rack using a metal pressing sheet for standby.

[0110] Step 3: place the rack in the deposition cavity chamber, and wait until the mechanical pump and the molecular pump are vacuumed to 5×10 -4Pa and after the substrate heating temperature reaches 320℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are arranged in a magnetic pole configuration of a closed magnetic field, and the high-power pulse power supply of the CrAl target and the C target is turned on at the same time, and the targets are cleaned by the magnetic control sputtering.

[0111] Step 4: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 100 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%, and the Ti-6Al-4V alloy substrate is cleaned by Cr and Al metal ion etching for 20 min.

[0112] Step 5: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are arranged in a mirror magnetic field magnetic pole configuration, and the high-power pulse sputtering power supply of the CrAl target and the C target is turned on at the same time, and the power is set to 75 W and 90 W respectively, and the HiPIMS power supply parameters are set as follows: a frequency of 100 Hz, a period of 10000 μs, a CrAl target duty cycle of 2.5%, a pulse time of 250 μs, a C target duty cycle of 5%, a pulse time of 500 μs, and a Cr2AlC MAX phase coating is deposited by double-target high-power pulse magnetron sputtering combined with synchronous pulse bias deposition, the pulse negative bias frequency of the substrate is 100 Hz, the duty cycle is 10%, the pulse width is 1000 μs, the delay is 250 μs (relative to the start of the metal target discharge pulse), the substrate bias is -100 V, and the deposition time is 360 min.

[0113] Example 4

[0114] In this embodiment, the substrate material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Cr2AlC MAX phase coating on the substrate surface are as follows:

[0115] Step 1: the surface of the Ti-6Al-4V alloy sheet is polished in sequence using 400#-3000# SiC sandpaper, and then polished for 20 min using diamond polishing agent with a particle size of 2.5 μm.

[0116] Step 2: the polished TC4 alloy sheet substrate is ultrasonically cleaned in acetone and alcohol for 10 min, then rinsed with deionized water, and then dried with high-purity N2, and the substrate is fixed on the rack by metal pressing for standby use.

[0117] Step 3: the rack is placed in the deposition chamber, and the mechanical pump and the molecular pump are pumped to 5×10 -4Pa and after the substrate heating temperature reaches 320℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are arranged in a magnetic pole configuration of a closed magnetic field, and the high-power pulse power supply of the CrAl target and the C target is turned on at the same time, and the targets are cleaned by the magnetic control sputtering.

[0118] Step 4: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 100 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%, and the Ti-6Al-4V alloy substrate is cleaned by Cr and Al metal ion etching for 20 min.

[0119] Step 5: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are arranged in a mirror magnetic field magnetic pole configuration, and the high-power pulse sputtering power supply of the CrAl target and the C target is turned on at the same time, and the power is set to 150 W and 180 W respectively, and the HiPIMS power supply parameters are set as follows: a frequency of 1000 Hz, a period of 1000 μs, a CrAl target duty cycle of 2.5%, a pulse time of 25 μs, a C target duty cycle of 5%, a pulse time of 50 μs, and a Cr2AlC MAX phase coating is deposited by double-target high-power pulse magnetron sputtering combined with synchronous pulse bias deposition, the pulse negative bias frequency of the substrate is 1000 Hz, the duty cycle is 15%, the pulse width is 150 μs, the delay is 0 μs (relative to the start of the metal target discharge pulse), the substrate bias is -200 V, and the deposition time is 1200 min.

[0120] Example 5

[0121] In this embodiment, the substrate material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Cr2AlC MAX phase coating on the substrate surface are as follows:

[0122] Step 1: the surface of the Ti-6Al-4V alloy sheet is polished in sequence using 400#-3000# SiC sandpaper, and then polished for 20 min using diamond polishing agent with a particle size of 2.5 μm.

[0123] Step 2: the polished TC4 alloy sheet substrate is ultrasonically cleaned in acetone and alcohol for 10 min, then rinsed with deionized water, and then dried with high-purity N2, and the substrate is fixed on the rack by metal pressing for standby.

[0124] Step 3: the rack is placed in the deposition chamber, and the mechanical pump and the molecular pump are pumped to 5×10 -4Pa and the substrate heating temperature reaches 320℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse power supply of the CrAl target and the C target is turned on at the same time, and the targets are cleaned by the magnetic control sputtering.

[0125] Step 4: High-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 100 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%. The Ti-6Al-4V alloy substrate is cleaned by Cr and Al metal ion etching for 20 min.

[0126] Step 5: High-purity Ar and methane mixed gas atmosphere with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse sputtering power supply of the CrAl target and the C target is turned on at the same time, and the power is set to 100 W and 90 W respectively. The HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a period of 2000 μs, a CrAl target duty cycle of 2.5%, a pulse time of 50 μs, a C target duty cycle of 5%, a pulse time of 100 μs, and a double-target high-power pulse magnetron co-sputtering deposition Cr2AlC MAX phase coating is deposited by using a synchronous pulse bias technology. The pulse negative bias frequency of the substrate is 500 Hz, the amplitude is 100 V, the duty cycle is 12.5%, the pulse width is 250 μs, the delay is 50 μs (relative to the start of the metal target discharge pulse), and the deposition time is 360 min.

[0127] Example 6

[0128] In this embodiment, the substrate material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Cr2AlC MAX phase coating on the substrate surface are as follows:

[0129] Step 1: The surface of the Ti-6Al-4V alloy sheet is polished using 400#-3000# SiC sandpaper in sequence, and then polished using diamond polishing agent with a particle size of 2.5 μm for 20 min.

[0130] Step 2: The polished TC4 alloy sheet substrate is placed in acetone and alcohol for ultrasonic cleaning for 10 min, then rinsed with deionized water, and then dried with high-purity N2. The substrate is fixed on the rack by using metal pressing for standby.

[0131] Step 3: The rack is placed in the deposition chamber, and the mechanical pump and the molecular pump are pumped to 5×10 -4Pa and the substrate heating temperature reaches 320℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse power supply of the CrAl target and the C target is turned on at the same time, and the targets are cleaned by the magnetic control sputtering.

[0132] Step 4: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 100 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%. The Ti-6Al-4V alloy substrate is cleaned by Cr and Al metal ion etching for 20 min.

[0133] Step 5: high-purity Ar and acetylene mixed gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the CrAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse sputtering power supply of the CrAl target and the C target is turned on at the same time, and the power is set to 100 W and 90 W respectively. The HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a period of 2000 μs, a CrAl target duty cycle of 2.5%, a pulse time of 50 μs, a C target duty cycle of 5%, a pulse time of 100 μs, and a double-target high-power pulse magnetron co-sputtering deposition Cr2AlC MAX phase coating is deposited by using a synchronous pulse bias technology. The pulse negative bias frequency of the substrate is 500 Hz, the amplitude is 100 V, the duty cycle is 12.5%, the pulse width is 250 μs, the delay is 50 μs (relative to the start of the metal target discharge pulse), and the deposition time is 360 min.

[0134] Example 7

[0135] In this embodiment, the substrate material is a Ti-6Al-4V alloy sheet, and the specific preparation steps of the Ti2AlC MAX phase coating on the substrate surface are as follows:

[0136] Step 1: the surface of the Ti-6Al-4V alloy sheet is polished in sequence using 400#-3000# SiC sandpaper, and then polished for 20 min using diamond polishing agent with a particle size of 2.5 μm.

[0137] Step 2: the polished TC4 alloy sheet substrate is ultrasonically cleaned in acetone and alcohol for 10 min, then rinsed with deionized water, and then dried with high-purity N2. The substrate is fixed on the rack by using metal tabletting, and is ready for use.

[0138] Step 3: the rack is placed in the deposition chamber, and the mechanical pump and the molecular pump are pumped to 5×10 -4Pa and the substrate heating temperature reaches 600℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the TiAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse power supply of the TiAl target and the C target is turned on at the same time, and the targets are cleaned by the magnetic control sputtering.

[0139] Step 4: High-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the TiAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 150 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%. The Ti-6Al-4V alloy substrate is cleaned by Ti and Al metal ion etching for 30 min.

[0140] Step 5: High-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the TiAl target and the C target are in a closed magnetic field magnetic pole configuration. The high-power pulse sputtering power supply of the TiAl target and the C target is turned on at the same time, and the power is set to 150 W and 90 W, respectively. The HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a period of 2000 μs, a TiAl target duty cycle of 2.5%, a pulse time of 50 μs, a C target duty cycle of 2.5%, a pulse time of 50 μs, and a Ti2AlC MAX phase coating is deposited by double-target high-power pulse magnetron sputtering combined with synchronous pulse bias deposition. The pulse negative bias frequency of the substrate is 500 Hz, the duty cycle is 10%, the pulse width is 200 μs, the delay is 0 μs relative to the start of the metal target discharge pulse, the substrate bias is -100 V, and the deposition time is 360 min.

[0141] Example 8

[0142] In this embodiment, the substrate material is a zirconium alloy sheet, and the specific preparation steps of the V2AlC MAX phase coating on the surface of the substrate are as follows:

[0143] Step 1: The surface of the zirconium alloy sheet is polished with SiC sandpaper of 400#-3000# in sequence, and then polished with diamond polishing agent with a particle size of 2.5 μm for 20 min.

[0144] Step 2: The polished zirconium alloy sheet substrate is ultrasonically cleaned in acetone and alcohol for 10 min, then rinsed with deionized water, and then dried with high-purity N2. The substrate is fixed on the rack by metal pressing for standby use.

[0145] Step 3: The rack is placed in the deposition chamber, and the mechanical pump and the molecular pump are pumped to a vacuum degree of 5×10 -4Pa and the substrate heating temperature reaches 350℃, high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the VAl target and the C target are in a closed magnetic field magnetic pole configuration, and the high-power pulse power supply of the VAl target and the C target is turned on at the same time, and the magnetic control sputtering is used to clean the target material.

[0146] Step 4: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, the VAl target HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a duty cycle of 2.5%, a pulse width of 50 μs, a power of 100 W, a pulse negative bias power supply frequency of 500 Hz, an amplitude of 900 V, and a duty cycle of 5%, and the zirconium alloy sheet substrate is etched and cleaned by V and Al metal ions for 30 min.

[0147] Step 5: high-purity Ar gas with a gas pressure of 0.5 Pa is introduced into the vacuum chamber, and the VAl target and the C target are in a closed magnetic field magnetic pole configuration, and the high-power pulse sputtering power supply of the TiAl target and the C target is turned on at the same time, and the power is set to 100 W and 100 W respectively, and the HiPIMS power supply parameters are set as follows: a frequency of 500 Hz, a period of 2000 μs, a VAl target duty cycle of 2.5%, a pulse time of 50 μs, a C target duty cycle of 5%, a pulse time of 100 μs, a V2AlC MAX phase coating is deposited by double-target high-power pulse magnetron sputtering combined with synchronous pulse bias, a pulse negative bias frequency of the substrate is 500 Hz, a duty cycle is 10%, a pulse width is 200 μs, a delay is 0 μs relative to the start of the metal target discharge pulse, a substrate bias is -100 V, and a deposition time is 360 min.

[0148] Comparative Example 3

[0149] This example is a comparative example of the above-mentioned Example 1.

[0150] In this example, the substrate is completely the same as that in Example 1, the polishing, cleaning treatment and surface metal plasma etching cleaning process of the substrate are also completely the same, and the difference is that in Step 5, the CrAl target and the C target sputtering both use a conventional direct current power supply, not a high-power pulse power supply, and the direct current sputtering source is also set to a constant power of 100 W and 120 W during the deposition process.

[0151] Figure 10 and Figure 11 The X-ray diffraction spectrum and the Raman spectrum of the coating prepared in the above-mentioned Example 1 and Comparative Example 3 are shown in Figures 1 and 2. Figure 10 and Figure 11It can be seen that the as-deposited coating prepared by the double-target high-power pulsed magnetron sputtering is a crystalline Cr2AlC MAX phase coating with (110) plane preferred orientation, and the texture coefficient is 3, while the as-deposited coating prepared by the double-target direct current magnetron sputtering in Comparative Example 3 is a carbide (Cr2C) coating. There are also some characteristic diffraction peaks from the substrate in the XRD spectrum.

[0152] In addition, the inventors of the present application also carried out experiments with other raw materials, process operations and process conditions described in the specification with reference to the foregoing examples, and ideal results were obtained.

[0153] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.

Claims

1. A method for preparing a MAX phase coating with preferred orientation on the (110) plane, characterized in that, include: A dual-target high-power pulsed magnetron sputtering composite synchronous pulsed bias technology is adopted, using a metal target and a C target as the target materials, and making the magnetic field between the metal target and the C target a closed magnetic field with opposite magnet polarity or a mirror magnetic field with the same magnet polarity, thereby depositing a MAX phase coating with preferred orientation of (110) plane on the substrate surface; wherein, the metal target is selected from CrAl target; In the dual-target high-power pulsed magnetron sputtering composite synchronous pulsed bias technology, the frequency of the pulsed negative bias applied to the substrate is 100~1000 Hz, the duty cycle is 10~15%, the pulse width is 150~1500 μs, the delay is 0~250 μs, and the amplitude is 0~200V; the deposition temperature is 320~350 ℃.

2. The preparation method according to claim 1, characterized in that, Specifically, it includes: The substrate is placed in the reaction chamber, and a metal target and a C target are used as target materials. A protective gas is used as the working gas. A dual-target high-power pulsed magnetron sputtering composite synchronous pulse bias technology is used to apply a pulsed negative bias voltage synchronized with the discharge pulse of the dual-target high-power pulsed magnetron sputtering to the substrate. A MAX phase coating with preferred orientation of (110) plane is deposited on the surface of the substrate. The dual-target high-power pulsed magnetron sputtering technology uses a power supply with a frequency of 100~1000 Hz and a period of 1000~10000 μs. The power of the metal target is 75~150W, the duty cycle is 2.5~5%, and the pulse time is 25~500 μs. The power of the C target is 90~180W, the duty cycle is 5~10%, and the pulse time is 50~1000 μs. The working gas pressure is 0.2~1.0 Pa, and the deposition time is 240~1200 min.

3. The preparation method according to claim 1, characterized in that, Also includes: The matrix was placed in the reaction chamber and evacuated to a vacuum of 5 × 10⁻⁶. -4 Below Pa, the substrate is heated and a protective gas is introduced into the cavity. At the same time, the power supply to the metal target and the C target is turned on, and the metal target and the C target are self-cleaned using magnetron sputtering technology. The substrate temperature is 320~350 ℃, the gas pressure in the reaction cavity is 0.2~2 Pa, the power of the metal target is 75~180W, and the power of the C target is 75~180W.

4. The preparation method according to claim 3, characterized in that, Also includes: After the self-cleaning process is completed, Ar gas with a pressure of 0.2~2 Pa is introduced into the reaction chamber to apply a synchronous pulse negative bias voltage to the substrate, thereby realizing the metal plasma etching process of the substrate.

5. The preparation method according to claim 4, characterized in that, The process parameters for the metal plasma etching process include: Ar gas flow rate of 20~50 sccm, substrate negative bias frequency of 100~1000 Hz, amplitude of 500~1000 V, duty cycle of 5~20%, and pulse width of 50~2000 μs; metal target power supply frequency of 100~1000 Hz, duty cycle of 2.5~10%, pulse width of 25~1000 μs, and metal target power of 75~150 W.

6. The preparation method according to claim 1, characterized in that... Also includes: The substrate is first polished and ultrasonically cleaned, and then the MAX phase coating is deposited on the surface of the substrate; wherein the cleaning solution used for the ultrasonic cleaning process includes acetone and / or ethanol.

7. The preparation method according to claim 1, characterized in that: The matrix comprises Ti-6Al-4V or zirconium alloy.

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