CN110670038A - AlCrN/MoS with self-lubricating and wear-resisting properties2Nano composite film and preparation method thereof - Google Patents

AlCrN/MoS with self-lubricating and wear-resisting properties2Nano composite film and preparation method thereof Download PDF

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CN110670038A
CN110670038A CN201911093858.6A CN201911093858A CN110670038A CN 110670038 A CN110670038 A CN 110670038A CN 201911093858 A CN201911093858 A CN 201911093858A CN 110670038 A CN110670038 A CN 110670038A
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mos
alcrn
film
lubricating
composite film
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王铁钢
蒙德强
许人仁
刘艳梅
阎兵
尹照星
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Tianjin University of Technology and Education China Vocational Training Instructor Training Center
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Tianjin University of Technology and Education China Vocational Training Instructor Training 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
    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses an AlCrN/MoS with self-lubricating and wear-resisting properties2A nano composite film and a preparation method thereof belong to the technical field of films. The AlCrN/MoS is prepared on a cutter substrate by adopting a high-power pulse and pulse direct-current magnetic control composite coating technology2The nano composite film is deposited by adjusting the bias voltage to-50 to-150V and then introducing N2And Ar; the working air pressure is kept at 0.5-1.0 Pa, the AlCr target power is kept at 0.5-1.0 kW, and MoS2The target power is 0.05-0.3 kW, and the AlCrN/MoS is obtained after deposition2A nanocomposite film. Prepared AlCrN/MoS2The composite film has excellent lubricating property, can obviously enhance the abrasion resistance of a matrix, has better chemical stability, and easily transfers abrasive dust to a friction interface to form a lubricating film.

Description

AlCrN/MoS with self-lubricating and wear-resisting properties2Nano composite film and preparation method thereof
Technical Field
The invention relates to the technical field of thin films, in particular to AlCrN/MoS with self-lubricating and wear-resisting properties2A nano composite film and a preparation method thereof.
Background
With the rapid development of modern industry, various difficult-to-machine materials are increasing, higher requirements are continuously put on the cutting performance of the cutter, and the coating applied to the surface of the cutter is a method for effectively prolonging the service life of the cutter. The traditional double-bed nitride coating cutter has the defects of high cutting temperature, large friction coefficient, easy abrasion of the cutter and the like during cutting, and the application of the traditional double-bed nitride coating cutter is severely limited. At present, the components of the cutter coating gradually develop to multiple components, and the multi-component hard coating has the advantages of high hardness, good wear resistance and the like, so that the service life of the cutter and the surface processing quality of a workpiece can be obviously improved. For example, Al element added into CrN coating can form (Al, Cr) N solid solution phase to play a role of solid solution strengthening, and the coating surface can be formed during friction (Al2,Cr2)O3The protective layer can prevent external O element from diffusing into the coating, obviously improves the thermal stability and oxidation resistance of the coating, and has the highest heat-resistant temperature of 900 ℃.
The AlCrN coating has the advantages of high hardness, good wear resistance, strong heat resistance and the like, but when cutting materials which are difficult to process, such as high-temperature alloy and the like, the cutting temperature is increased due to serious friction, and the service life of a cutter is shortened. Solid lubricant MoS2The laminated material has a typical laminated structure, atoms in the layers are bonded through strong covalent bonds, and the layers are bonded through Van der Waals force, so that slippage is easily generated between the layers, and the friction coefficient is low. If appropriate amount of MoS2Doping into AlCrN coating to prepare AlCrN/MoS2Composite coating capable of giving full play to two materialsThe self-lubricating cutting tool has the advantages that the self-lubricating function is expected to be realized, the self-lubricating cutting tool can meet the working conditions of dry cutting, high temperature, high-speed cutting and the like when being applied to the surface of the cutting tool, and the service life and the processing efficiency of the cutting tool are improved.
MoS2The common preparation methods of the film include an ion plating method, an organic bonding method, composite plating and infiltration, but the methods have certain limitations. In recent years, the emerging high-power pulse magnetron sputtering (HiPIMS) technology depends on the fact that the instantaneous current density is high (0.5-10 kW/cm)2) And the high metal ionization rate (more than 50%) is realized by the advantages of low duty ratio (0.5-5%) and the like, and a high-quality coating with a smooth and compact surface can be prepared. However, the problems of serious discharge in the vacuum chamber and low deposition rate (generally 30-80% of pulse diameter) still remain unsolved by the HiPIMS technology, and if the composite pulse direct current magnetron sputtering technology is adopted, the defects can be effectively compensated, and the film with excellent performance is prepared.
The invention adopts the high-power pulse and pulse direct current magnetron sputtering composite coating technology to deposit AlCrN/MoS2The self-lubricating composite film endows the cutter with higher hardness, good heat resistance and wear resistance, is suitable for the field of modern high-speed dry cutting, and further improves the service life and the processing efficiency of the cutter.
Disclosure of Invention
The invention aims to provide AlCrN/MoS with self-lubricating and wear-resisting properties2Nano composite film and preparation method thereof, and prepared AlCrN/MoS2The composite film has excellent lubricating property, can obviously enhance the wear resistance of the base material, has good chemical stability, and easily transfers abrasive dust to a friction interface to form a lubricating film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
AlCrN/MoS with self-lubricating and wear-resisting properties2The preparation method of the nano composite film adopts the high-power pulse and pulse direct current magnetron sputtering composite coating technology to deposit AlCrN/MoS2The nano composite film specifically comprises the following steps:
(1) fixing the substrate on a rotating frame in a vacuum chamber, and vacuumizing the background to 3 × 10-3Pa below; the AlCr alloy target is loaded to a high-power pulse power supply, MoS2The target is loaded to a pulsed dc power supply;
(2) firstly, glow cleaning is carried out on a substrate to remove surface impurities; then, ion bombardment is carried out to improve the film/base binding force;
(3) deposition of AlCrN/MoS2Nano composite film:
after the ion bombardment is carried out on the matrix, the bias voltage is reduced to-50 to-150V, and then N is introduced2And Ar, wherein the total flow rate is kept to be 50-150 sccm, wherein the reaction gas N2The flow rate is 20-40 sccm, and the Ar flow rate is 30-110 sccm; the working pressure is kept at 0.5-1.0 Pa, the AlCr target power is kept at 0.5-1.0 kW, and MoS is started simultaneously2Adjusting the target power to 0.05-0.3 kW, and obtaining the AlCrN/MoS after depositing for a certain time2A nanocomposite film.
The substrate material is a stainless steel sheet or a monocrystalline silicon piece.
In the step (1), the substrate is fixed on the rotating frame after being pretreated, and the pretreatment process comprises the following steps: ultrasonic cleaning the substrate in acetone for 10-30 min, then ultrasonic cleaning in ethanol solution for 10-30 min, and then adopting high-purity N2And (5) carrying out drying treatment.
In the step (2), the glow cleaning process includes: introducing Ar with the flow rate of 50-200 sccm under the bias action of-780-800V, maintaining the working pressure of 0.5-1.5 Pa by adjusting a throttle valve, performing glow discharge for 5-15 min, and cleaning the surface of the substrate to remove surface impurities.
In the step (2), the ion bombardment process is as follows: starting a high-power AlCr target to carry out ion bombardment, maintaining the target power at 0.5-1.0 kW, introducing Ar with the flow rate of 50-100 sccm, and keeping the working pressure at (1.0-8.0) x 10-1Pa, and the bombardment time is 5-15 min.
In the step (3), the deposition time is determined according to the technical requirements and the film deposition rate.
The AlCrN/MoS with self-lubricating and good wear-resisting properties is prepared by the method2A composite film comprising an AlN nanocrystalline phase,CrN nanocrystal phase, Mo2N nanocrystalline phase and MoS2A nanocomposite structure of an amorphous phase; calculated by atomic percentage, the AlCrN/MoS2The chemical components of the composite film are as follows: 18.97-33.95% of Al, 7.8-15.5% of Cr, 49.03-54.49% of N, 1.78-5.58% of S and 7.18-18.62% of Mo.
The design mechanism of the invention is as follows:
the invention adopts the high-power pulse and pulse direct current magnetron sputtering composite coating technology to deposit AlCrN/MoS on the surface of SUS304 stainless steel and monocrystal Si substrate for the first time2Composite film due to MoS2The interlayer is combined by weak van der Waals force, has low shear strength and low friction coefficient (as low as 0.01) in vacuum, so that proper amount of MoS is added2The lubricating phase is in contact with the AlCrN film to improve the coating performance. In AlCrN/MoS2In the nano composite film, Mo element exists in the following modes: a part of Mo atoms are dissolved in CrN crystal lattices in a solid solution manner to play a solid solution strengthening role; the other part is in MoS2The amorphous phase form is uniformly distributed in the film, and a wear mechanism is converted into abrasive wear under a lubricating condition in a friction process. By regulating and controlling parameters such as gas flow, target power and the like in the coating process, the film has the advantages of high hardness, good wear resistance, low friction coefficient and the like.
In the invention, AlCrN/MoS is prepared2In the process of compounding the film, parameters such as reaction gas flow, sputtering target power and the like have great influence on the film performance. When N is present2When the deposition rate of the film is too much, the target material is easy to be passivated; and N is2Less, the metal elements in the film are not sufficiently reacted, resulting in a decrease in hardness. Meanwhile, the MoS in the film can be changed by adjusting the sputtering power of the target material2Content, which in turn affects the film properties, if MoS2Excessive film mechanical properties are weakened, such as film hardness and film/base bonding force are reduced; and MoS2Too little of the phases will result in an insignificant lubricating effect of the film. Therefore, the invention controls the gas flow and MoS2The target power and other parameters are used to regulate and control the components and structure of the film, and the AlCrN/MoS with the best performance is prepared after the process optimization2A self-lubricating film.
The invention has the following advantages and beneficial effects:
1. AlCrN/MoS prepared by the invention2The film has good lubricating property, can obviously enhance the wear resistance of a matrix, has good chemical stability, and easily transfers abrasive dust to a friction interface to form a lubricating film.
2. The AlCrN/MoS2The film is made of AlN, CrN and Mo2The nanocrystalline such as N and the like is embedded in the amorphous layer to form a nano composite structure, and the nano composite structure has the advantages of high hardness, good wear resistance, stable chemical performance and the like.
3. AlCrN/MoS of the invention2The film has smooth surface, compact structure, high bonding strength with the matrix, low friction coefficient and good toughness; the critical load of the film tested by the scratching method is more than 40N, the friction coefficient is as low as 0.21, and the wear rate is about 4.4 multiplied by 10-3μm3/N·μm。
4、AlCrN/MoS2The film has good repeatability of the preparation process, has wider application prospect, can be used for cutting various difficult-to-process materials at high speed, and has unique advantages.
5. The self-lubricating film prepared by the invention is suitable for the fields of high-speed cutting, dry cutting and the like, and can obviously improve the service life and the processing efficiency of a cutter; the special working conditions that fluid lubrication cannot be implemented, such as high temperature, high load, ultralow temperature, ultrahigh vacuum, strong oxidation, strong radiation and the like, can be met, and the application prospect on high-speed cutting tools is wide.
Drawings
FIG. 1 shows AlCrN/MoS2XRD pattern of the film.
FIG. 2 shows AlCrN/MoS2Surface topography of the film.
FIG. 3 shows AlCrN/MoS2The cross-sectional morphology of the film.
FIG. 4 shows AlCrN/MoS2Scratch morphology of the film.
FIG. 5 shows AlCrN/MoS2Coefficient of friction curve of the film.
FIG. 6 shows MoS2AlCrN/MoS deposited with target power of 0.1kW2And (3) grinding trace appearance of the film.
FIG. 7 shows MoS2Target workAlCrN/MoS deposited at a rate of 0.5kW2And (3) grinding trace appearance of the film.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Example 1
In the embodiment, a high-power pulse magnetron sputtering and pulse direct-current magnetron sputtering composite coating system is adopted to deposit AlCrN/MoS on the surfaces of a single crystal Si sheet (40mm multiplied by 0.67mm) and a stainless steel sheet (35mm multiplied by 1.0mm)2A film. The specific operation steps are as follows:
(1) ultrasonic cleaning the substrate in acetone and alcohol solution for 30min, and treating with high purity N2(purity is 99.999 percent) and then the substrate is fixed on a rotating frame in a coating chamber.
(2) The AlCr alloy target is connected with a high-power pulse magnetron sputtering power supply, MoS2The target is connected with a pulse direct current magnetron sputtering power supply; pumping the background vacuum degree to 3.0X 10-3And Pa above, heating the substrate to 300 ℃, applying-780V bias voltage, introducing Ar (with the purity of 99.999%) into the vacuum chamber, controlling the flow rate to be 110sccm, controlling the throttle valve to keep the working pressure at 1.1Pa, performing glow discharge cleaning for 10min, and removing impurities on the surface of the substrate.
(3) And (3) regulating the Ar flow to 65sccm, maintaining a bias voltage of-780V, reducing the working pressure to 0.45Pa, starting a high-power pulse magnetron sputtering AlCr target to carry out ion bombardment, maintaining the target power at 0.8kW, and bombarding and cleaning for 5min to improve the film/substrate binding force of the film.
(4) The bias voltage is reduced to-50V, and the reaction gas N is introduced2The flow rate is 38sccm, the flow rate of Ar is adjusted to 36sccm, and Ar and N are maintained2The total flow is 74sccm, the working pressure is kept at 0.7Pa, the AlCr target power is maintained at 0.8kW, and the MoS is started2Target, holding MoS2The target power is 0.1kW, and the deposition is continued for 240min to obtain AlCrN/MoS2And (3) compounding the film.
For the AlCrN/MoS prepared in this example2The film is subjected to morphology characterization and performance test, and the method specifically comprises the following steps:
the surface and cross-sectional morphology of the film were observed by a field emission Scanning Electron Microscope (SEM) model S4800, and the chemical composition was analyzed by an electron probe (EPMA, Shimadzu, EPMA 1600). The method comprises the steps of utilizing an X-ray diffractometer (XRD, D8-discovery Brucker) to analyze the phase of a film, collecting X-ray diffraction data in a step scanning mode, selecting a Cu target Ka characteristic spectral line (lambda is 0.154056nm) for radiation of incident X-rays, selecting a 2 theta mode for scanning, wherein the scanning range is 20-80 degrees, the scanning step size is 0.02 degree, and the counting time of each step is 0.2 s.
Measuring the residual Stress of the Film by using a Film Stress meter (SuPro Instruments, Film Stress tester FST-150), testing the front and rear curvature radius of the coated Si sheet by using the optical lever curvature amplification principle, and calculating the residual Stress by using a Stoney formula; the hardness and the elastic modulus of the film are tested by adopting a nanoindenter (Anton Paar, TTX-NHT-3), in order to avoid the influence of the matrix effect on the measurement result, the pressing depth of the needle point is ensured to be 1/10 of the thickness of the film, and the average value of 15 test points is selected as the hardness and the elastic modulus of the film. The bonding strength of the film and the stainless steel substrate is measured by adopting a scratch tester (Anton Paar RST-3), the cone apex angle and the radius of the diamond needle point are respectively 120 degrees and 100 mu m, the normal load is set to be 60N in the testing process, the loading speed is 6mm/min, the scratch length is 3mm, and the experimental data is recorded by a computer in real time.
The friction coefficient is tested on a friction wear tester (Anton Paar THT), and Al with the diameter of 5.99mm is selected as a friction pair2O3The ball (hardness 22 + -1 GPa), the sliding linear velocity of 0.1m/s, the normal load of 2N, the rotation radius of 8mm and the sliding distance of 80 m. The rubbing experiment was performed at room temperature of 22 ± 3 ℃ and humidity of 30 ± 5%, each group of sample pieces was repeatedly tested 3 times, and the film wear rate W was calculated using the formula W ═ V/(F × S) (V is wear volume, F is load, S is sliding distance), and the wear scar morphology of the film was observed using a super depth of field microscope (VHX-1000C, Keyence).
FIG. 1 shows AlCrN/MoS2XRD pattern of the composite film. The visible film mainly comprises NaCl type (Al, Cr) N phase with a face-centered cubic structure and Mo2And (4) N-phase composition. fcc-Mo grown along the (111), (200), and (220) crystal planes was detected in the vicinity of 37.9 °, 43.9 °, and 63.8 ° 2 θ, respectively2Diffraction peaks for N and fcc- (Al, Cr) N phases. Fcc- (Al, Cr) N phase grown along (111) crystal plane at 37.9 DEG 2 theta2The N-phase diffraction peak is shifted to a low angle. Since Mo atoms (0.139) having a large atomic radius replace Cr (0.127) atoms in the CrN lattice to form a (Cr, Mo) N-replaced solid solution based on the fcc-CrN phase, the lattice distortion and the lattice constant increase, and the diffraction peak shifts to a low angle. Meanwhile, at 43.9 ° and 63.8 ° 2 θ, fcc- (Al, Cr) N phase and fcc-Mo in the film2The intensity of N phase diffraction peak reaches the strongest, because of Mo2N has lower binding energy, and N element is easy to react with Mo to generate more Mo2N crystal grains, thereby improving crystallinity; in addition, proper target power improves the diffusion capability of sputtered particles, promotes the increase of particle nucleation sites, contributes to grain refinement, and leads to broadening of diffraction peaks. In AlCrN/MoS2No MoS was detected in the film2Phase diffraction peaks, indicating MoS2Possibly in the form of an amorphous phase.
FIG. 2 shows AlCrN/MoS2Surface topography of the film. As can be seen from the figure, spherical clusters composed of nano-unit cells began to appear on the surface of the thin film, and a dense morphology was exhibited. The high-energy ion beam generated by the high-power pulse magnetron sputtering can improve the diffusion capacity of sputtered particles on the surface of the film, promote the repeated nucleation and recrystallization of the particles and improve the uniformity and compactness of the film. In addition, amorphous MoS2Will fill in the (Al, Cr) N crystal grain gap to refine the crystal grain to nanometer level. FIG. 3 shows AlCrN/MoS2The cross-sectional profile of the film, with a film thickness of about 5.8 μm, has a typical columnar crystal structure, a through growth mode with the top corresponding to the unit cell in the surface profile. When high-density ion beam current is continuously injected into the film-substrate interface, the local epitaxial growth of the coating is promoted, and a good chemical bond bonding interface can be obtained to ensure the compactness of the film-substrate interface. The film hardness was tested to be 14 GPa.
FIG. 4 is a graph of the scratch topography of a thin film. When the normal load is gradually increased to 10.6N, micro-cracks (marked as L) begin to appear on the surface of the filmc1) (ii) a As the load continues to increase, the crack zone becomes progressively wider and deeper, and local film spalling begins from the substrate surface (denoted as L)c2) The critical load is 44.8N, definedIs the membrane/base bonding force of the thin film; when the normal load reached 60N, the film was completely peeled from the substrate. Under the combined action of normal load and tangential load, cracks begin to grow at the internal defects of the film, then the internal defects of the film are sharply expanded, and finally the internal defects of the film fail. Due to AlCrN/MoS2The film has a nano composite structure, and a large number of two-phase interfaces effectively inhibit the expansion and the propagation of microcracks, so that the toughness and the film/base binding force of the film are improved.
FIG. 5 shows AlCrN/MoS2Coefficient of friction curve of the film. The friction test initial stage is in a pre-grinding stage, and the friction coefficient rapidly rises; as the friction distance is continuously increased, the friction coefficient is slightly reduced, because Mo element in the coating is easily oxidized into layered MoO in the friction process3And the lubricating phase is transferred to a friction interface to form a lubricating film, so that the antifriction effect is realized, and the final friction coefficient value is stabilized at 0.21. FIG. 6 shows AlCrN/MoS2And (3) grinding trace appearance of the composite film. The surface of the grinding scar is relatively flat and has light abrasion, and fine cracks are densely distributed on the surface, and the abrasion mechanism is micro-furrow abrasion. The film wear rate is measured to be 4.36 multiplied by 10-3μm3and/N.mu.m, showing good wear resistance.
Example 2:
in the embodiment, a high-power pulse magnetron sputtering and pulse direct current magnetron sputtering composite coating system is adopted to deposit AlCrN/MoS on the surfaces of a single crystal Si sheet (40mm multiplied by 0.67mm) and an SUS304 stainless steel sheet (40mm multiplied by 1.0mm)2A film. The specific operation steps are as follows:
(1) ultrasonic cleaning the substrate in acetone and alcohol solution for 30min, and then cleaning with high-purity N2Drying, and then fixing the substrate on a rotating frame in a vacuum coating chamber.
(2) Connecting an AlCr alloy target with a high-power pulse magnetron sputtering power supply, MoS2The target is connected with a pulse direct current magnetron sputtering power supply; background vacuum higher than 3.0 x 10-3Pa, heating the substrate to 300 ℃, applying-785V bias voltage, introducing Ar into the vacuum chamber at the flow rate of 150sccm, regulating and controlling the throttle valve to keep the working pressure at 1.2Pa, glow-cleaning for 10min, and removing impurities on the surface of the substrate.
(3) And regulating the Ar flow to 65sccm, maintaining a bias voltage of-785V, reducing the working pressure to 0.45Pa, starting a high-power pulse magnetron sputtering power supply, starting the AlCr target to carry out ion bombardment, maintaining the target power to be 0.8kW, and bombarding and cleaning for 5min to improve the film/substrate binding force.
(4) Reducing the bias voltage to-60V, and introducing a reaction gas N2The flow rate is 35sccm, the flow rate of Ar is adjusted to 50sccm, and Ar and N are maintained2The total flow is 85sccm, the throttle valve is adjusted to keep the working pressure at 0.7Pa, the sputtering power of the AlCr alloy target is maintained at 0.75kW, and the MoS is opened simultaneously2Target with sputtering power of 0.15kW and AlCrN/MoS deposition2Film 240 min.
For the AlCrN/MoS prepared in this example2The film is subjected to morphology characterization and performance test, and the method specifically comprises the following steps:
through testing, AlCrN/MoS2The thickness of the composite film is 4.23 mu m; the chemical components of the film are as follows: 21.71 percent of Al, 43 percent of Cr, 54.49 percent of N, 11.98 percent of Mo and 2.39 percent of S, which are all atomic percentages; the film hardness is 12.7 GPa; the critical load of the film is 18.9N by a scratch method; the friction coefficient and the wear rate are respectively 0.24 and 6.72 multiplied by 10-3μm3The abrasion mechanism is mainly adhesive abrasion,/N.mu.m.
Comparative example 1:
the difference from the embodiment 1 is that: deposition of AlCrN/MoS2When thin film, MoS2The target power was 0.5kW, and the rest was the same as in example 1.
When MoS2When the target sputtering power is 0.5kW, AlCrN/MoS2Cracks in the scratch appearance of the composite film are obviously increased, the hardness of the film is reduced to 10.1GPa, the critical load is only 15.7N, and the fact that too much soft phase in the film has negative influence on the mechanical performance is shown.
AlCrN/MoS prepared under the condition2The friction coefficient and the wear rate of the composite film are both high and are respectively 0.32 and 8.17 multiplied by 10-3μm3/. mu.m. The appearance of the grinding marks of the film is shown in FIG. 7, and it can be seen that under the combined action of the normal load and the tangential load, a large amount of block fragments are peeled off from the surface of the film and are ground, so that the amount of black grinding dust is increased greatly, and a small amount of micro-furrowing phenomenon is accompanied, and the wear mechanism is thatAbrasive wear coexists with adhesive wear.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (9)

1. AlCrN/MoS with self-lubricating and wear-resisting properties2The preparation method of the nano composite film is characterized by comprising the following steps: the method is to adopt the high-power pulse and pulse direct current composite magnetic control coating technology to prepare AlCrN/MoS on a cutter substrate2The preparation method of the nano composite film specifically comprises the following steps:
(1) the cutter base body is fixed on a rotating frame in a vacuum chamber, and then the background vacuum degree of the vacuum chamber is pumped to 3 multiplied by 10-3Pa below; the AlCr target is connected to a high-power pulse power supply, MoS2The target is connected to a pulse direct current power supply;
(2) firstly, glow cleaning is carried out on a cutter matrix to remove surface impurities; then, ion bombardment is carried out to improve the film/base binding force;
(3) deposition of AlCrN/MoS2Nano composite film:
after the ion bombardment is carried out on the matrix, the bias voltage is reduced to-50 to-150V, and then N is introduced2And Ar; the total flow rate of the mixed gas is maintained to be 50-150 sccm, wherein the reaction gas N2The flow rate is 20-40 sccm, and the Ar flow rate is 30-110 sccm; the working pressure is kept at 0.5-1.0 Pa, the AlCr target power is kept at 0.5-1.0 kW, and MoS is started simultaneously2The target power is 0.05-0.3 kW, and the AlCrN/MoS is obtained after deposition for a certain time2A nanocomposite film.
2. AlCrN/MoS with self-lubricating and wear resistant properties according to claim 12The preparation method of the nano composite film is characterized by comprising the following steps: the substrate is a stainless steel sheet or a monocrystalline silicon piece.
3. According to the rightAlCrN/MoS with self-lubricating and wear-resistant properties according to claim 12The preparation method of the nano composite film is characterized by comprising the following steps: in the step (1), the cutter substrate is fixed on a rotating frame after being pretreated, and the pretreatment process comprises the following steps: ultrasonic cleaning the substrate in acetone for 10-30 min, then ultrasonic cleaning in ethanol solution for 10-30 min, and then adopting high-purity N2And (5) drying.
4. AlCrN/MoS with self-lubricating and wear resistant properties according to claim 12The preparation method of the nano composite film is characterized by comprising the following steps: in the step (2), the glow cleaning process comprises the following steps: introducing Ar with the flow rate of 50-200 sccm under the bias action of-780-800V, adjusting the angle of a throttle valve to keep the working pressure of 0.5-1.5 Pa, performing glow discharge for 5-15 min, and cleaning the surface of the substrate to remove surface impurities.
5. AlCrN/MoS with self-lubricating and wear resistant properties according to claim 12The preparation method of the nano composite film is characterized by comprising the following steps: in the step (2), the ion bombardment process comprises: starting a high-power AlCr target to carry out ion bombardment, maintaining the target power at 0.5-1.0 kW, introducing Ar with the flow rate of 50-100 sccm, and keeping the working pressure at (1.0-8.0) x 10-1Pa, and the bombardment time is 5-15 min.
6. AlCrN/MoS with self-lubricating and wear resistant properties according to claim 12The preparation method of the nano composite film is characterized by comprising the following steps: in the step (3), the deposition time is determined according to the technical requirements and the film deposition rate.
7. AlCrN/MoS with self-lubricating and wear-resistant properties prepared by the method of claim 12A nanocomposite film.
8. AlCrN/MoS with self-lubricating and wear resistant properties according to claim 72A nanocomposite film characterized by: the AlCrN/MoS2The nano composite film comprises AlN nanocrystalline phase, CrN nanocrystalline phase and Mo2N nanocrystalline phase and MoS2Amorphous nanocomposite structures.
9. AlCrN/MoS with self-lubricating and wear-resistant properties according to claim 7 or 82A nanocomposite film characterized by: calculated by atomic percentage, the AlCrN/MoS2The chemical composition of the nano composite film is as follows: 18.97-33.95% of Al, 7.8-15.5% of Cr, 49.03-54.49% of N, 1.78-5.58% of S and 7.18-18.62% of Mo.
CN201911093858.6A 2019-01-21 2019-11-11 AlCrN/MoS with self-lubricating and wear-resisting properties2Nano composite film and preparation method thereof Pending CN110670038A (en)

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