CN111549322B - AlCrTiSiN/AlCrTiSiON multilayer composite coating and preparation process thereof - Google Patents

AlCrTiSiN/AlCrTiSiON multilayer composite coating and preparation process thereof Download PDF

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CN111549322B
CN111549322B CN202010558249.XA CN202010558249A CN111549322B CN 111549322 B CN111549322 B CN 111549322B CN 202010558249 A CN202010558249 A CN 202010558249A CN 111549322 B CN111549322 B CN 111549322B
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alcrtisin
alcrtision
coating
multilayer composite
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CN111549322A (en
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王铁钢
朱强
刘迁
张雅倩
刘艳梅
范其香
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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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • 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
    • C23C14/54—Controlling or regulating the coating process

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
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Abstract

The invention discloses an AlCrTiSiN/AlCrTiSiON multilayer composite coating and a preparation process thereof, belonging to the technical field of composite coating preparation. The AlCrTiSiN/AlCrTiSiON multilayer composite coating is formed by superposing single-layer AlCrTiSiN and AlCrTiSiON. The composite coating is prepared by adopting an arc ion coating technology, when in specific preparation, a target material is selected from a metal Cr target, an AlCrSi target and an AlTiSi target, a CrN transition layer is firstly deposited after glow discharge cleaning and ion bombardment cleaning, and finally, corresponding reaction gas is introduced to respectively prepare a working layer and a surface protection coating. The preparation process of the multilayer composite coating is simple and easy for industrial production. The prepared coating has good heat resistance, is suitable for high-speed cutting, and improves the processing efficiency.

Description

AlCrTiSiN/AlCrTiSiON multilayer composite coating and preparation process thereof
Technical Field
The invention relates to the technical field of composite coating preparation, in particular to a preparation process of an AlCrTiSiN/AlCrTiSiON multilayer composite coating.
Background
With the development of industry, high-strength and high-hardness materials such as high-speed steel and gray cast iron are increasingly widely applied, and the traditional coated cutting tool is more and more difficult to meet the process requirements of high-speed cutting, dry cutting and the like. In the actual processing process, a large amount of carbide hard particles in the material participate in the cutting process and generate abrasive wear with the cutter, so that the wear resistance and the high-temperature oxidation resistance of the coated cutter are greatly reduced. Compared with the common AlCrN, AlTiN and other coatings on the market, the high-entropy alloy coating AlCrTiSiN has the advantages that the hardness, the strength, the toughness and the high-temperature oxidation resistance are greatly improved, and the high-entropy alloy coating AlCrTiSiN is suitable for being processed and used under the conditions of high-speed cutting and dry cutting, and due to the addition of Si element, Si is formed inside the coating 3 N 4 Amorphous phase for strengthening fine grains, and (Al, Cr, Ti) N nano-crystalline grains embedded in amorphous Si 3 N 4 The nano composite structure is formed in the layer, and the mechanical and tribological properties of the coating are greatly improved. During cutting, dense (Al, Cr) is easily formed on the surface of the coating 2 O 3 The protective film has good heat insulation effect and can improveThe coated cutting tool has long service life.
In order to further improve the high-temperature oxidation resistance of the coating, the surface of the coating is subjected to pre-oxidation treatment to prepare a surface high-temperature protective layer, and an internal high-hardness and high-toughness working layer is combined, so that the coated cutting tool is suitable for ultrahigh-speed cutting, the cutting temperature can be greatly reduced, and the service life of the coated cutting tool is obviously prolonged. This patent adopts arc ion coating technique at metal or carbide substrate surface deposit AlCrTiSiN/AlCrTiSiON multilayer composite coating, and cutter and work piece can effectively be kept apart to this coating, have good thermal barrier and chemical barrier effect to improve the machining efficiency of coating cutter and make the labour life-span.
Disclosure of Invention
The invention aims to provide a preparation process of an AlCrTiSiN/AlCrTiSiON multilayer composite coating, and the prepared AlCrTiSiN/AlCrTiSiON multilayer composite coating has high hardness, high wear resistance and high heat resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the multilayer AlCrTiSiN/AlCrTiSiON composite coating is deposited on the surface of metal or hard alloy substrate and is formed by laminating AlCrTiSiN layers and AlCrTiSiON layers.
The AlCrTiSiN and AlCrTiSiON layers are both single layers, and the total deposition time is set to be 3 h.
The film/base bonding strength of the AlCrTiSiN/AlCrTiSiON multi-layer composite coating is greater than 60N, and the wear rate is lower than 6.26 multiplied by 10 -3 μm 3 /N·μm。
The preparation process of the AlCrTiSiN/AlCrTiSiON multilayer composite coating is characterized in that an AlCrTiSiN/AlCrTiSiON multilayer composite coating is deposited on the surface of a substrate by adopting an arc ion coating technology, and a target material is selected from a pure metal Cr target, an AlCrSi alloy target and an AlTiSi alloy target; when depositing AlCrTiSiN/AlCrTiSiON multilayer composite coating, firstly starting a Cr target, and carrying out ion bombardment cleaning and transition layer preparation. Then starting an AlCrSi target and an AlTiSi target together, depositing an AlCrTiSiN layer, finally introducing a certain amount of oxygen to prepare an AlCrTiSiON surface protective coating, and respectively controlling the deposition pressure, the reaction gas flow and the arc flow parameters of each target during coating to prepare the AlCrTiSiN/AlCrTiSiON multilayer composite coating.
When the AlCrTiSiN/AlCrTiSiON multilayer composite coating is deposited, arc flows are set to be 60-100A; when an AlCrSi target and an AlTiSi target are started to deposit an AlCrTiSiN coating, setting the bias voltage of a matrix to be-80 to-120V (the duty ratio is 60-90 percent), and introducing argon and nitrogen to adjust the deposition pressure to be 1.5-3.0 Pa; when the AlCrTiSiON coating is deposited, introducing oxygen for 5-15 min; the total coating time of the AlCrTiSiN/AlCrTiSiON multilayer composite coating is controlled to be 3h, and the opening time and the gas introduction time of different targets are set.
When the AlCrTiSiN coating is deposited, the flow of argon is 50sccm, the flow of nitrogen is 600sccm, and the total flow is 650 sccm; when the AlCrTiSiON coating is deposited, the flow of argon is introduced at 50sccm, the flow of nitrogen is introduced at 600sccm, the flow of oxygen is introduced at 20sccm, and the total flow is 670 sccm.
The preparation process of the AlCrTiSiN/AlCrTiSiON multilayer composite coating specifically comprises the following steps:
(1) fixing the cleaned hard alloy substrate, stainless steel sheet and silicon wafer on a rotating frame in a coating chamber, and pumping the vacuum degree to 3 × 10 -3 Pa; heating to 450 ℃;
(2) firstly, cleaning the substrate by adopting high negative bias glow discharge for 10-30 min, starting the Cr target after the glow discharge cleaning, adjusting the bias to-800V, -600V, -400V and-200V in sequence, and respectively carrying out ion bombardment cleaning on the surface of the substrate for 2min so as to remove a pollution layer and oxides on the surface of the substrate.
(3) Starting a Cr target, and introducing nitrogen and argon to prepare a CrN transition layer for 30min so as to improve the bonding strength of the working layer and the matrix
(4) Depositing AlCrTiSiN/AlCrTiSiON multilayer composite coating.
In the step (2), the glow discharge cleaning process includes: heating the furnace chamber to 200-500 ℃, introducing argon gas of 200-600 sccm, setting pulse bias voltage of-600-1000V, and performing glow discharge cleaning on the substrate. The ion bombardment cleaning process comprises the following steps: after glow discharge cleaning, starting a Cr target, adjusting the argon flow to be 50-100 sccm, and sequentially bombarding and cleaning for 2min under negative bias conditions of-800V, -600V, -400V and-200V.
In the step (3), the process of depositing the CrN transition layer is as follows: after glow discharge cleaning and ion bombardment cleaning, setting a bias voltage of-50 to-100V (duty ratio of 60-90%), starting a Cr target, introducing 50sccm of argon gas flow and 200sccm of nitrogen gas flow, adjusting the deposition pressure to 0.5-1.2 Pa, and depositing a CrN transition layer for 10-30 min.
The design mechanism of the invention is as follows:
the invention adopts the arc ion plating technology to deposit AlCrTiSiN/AlCrTiSiON multilayer composite film on hard alloy sheets, SUS304 stainless steel and single crystal Si sheets. A layer of AlCrTiSiON protective film is prepared on the surface of the AlCrTiSiN coating through a pre-oxidation experiment, so that the heat resistance of the coating is greatly improved on the premise of not obviously reducing the mechanical property and the tribological property of the AlCrTiSiN coating. The surface oxidation film can effectively prevent the interior of the working layer from being further oxidized, and has good thermal barrier and chemical barrier functions.
In the preparation process of the AlCrTiSiN/AlCrTiSiON multilayer composite coating, the deposition temperature has great influence on the performance of the coating, and when the temperature is lower, the kinetic energy of particles is smaller, so that the prepared coating is looser in structure; when the deposition temperature is too high, the kinetic energy of the particles is too high, the reverse sputtering phenomenon is serious, and the performance of the coating is reduced to some extent. In addition, the oxygen-containing coating has high brittleness, and when a surface oxidation film is prepared, the coating is easy to crack under the action of external load due to long oxygen introduction time, so that the service life of the coating is shortened; the heat barrier effect is not obvious when the surface oxide film is too thin. Therefore, the coating is prepared by changing the deposition temperature and the oxygen introduction time, and the AlCrTiSiN/AlCrTiSiON multilayer composite coating with the best performance is obtained through optimization.
The invention has the following advantages and beneficial effects:
1. the AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared by the method has high heat resistance and obvious heat insulation effect.
2. The AlCrTiSiN/AlCrTiSiON multilayer composite coating is formed by embedding AlN, CrN, TiN and other nanocrystals in Si 3 N 4 A nanocomposite structure formed in an amorphous layer and having high hardness and high durabilityGood grindability, stable chemical performance and the like.
3. The preparation process of the AlCrTiSiN/AlCrTiSiON multilayer composite coating is simple and has good repeatability, and the prepared coating has wide application prospect, is suitable for high-speed dry cutting of various difficult-to-process materials, and greatly improves the cutting efficiency and the service life of a cutter.
4. The AlCrTiSiN/AlCrTiSiON multilayer composite coating has excellent high-temperature oxidation resistance and good mechanical property and frictional wear property, and the coated cutter can be suitable for heavy-load intermittent machining.
Drawings
FIG. 1 is the X-ray diffraction spectrum of AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared by arc ion plating technology.
FIG. 2 is the surface morphology of AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared by arc ion plating technique.
FIG. 3 is a cross-sectional view of AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared by arc ion plating.
FIG. 4 is a loading-unloading curve for testing the nano hardness of AlCrTiSiN/AlCrTiSiON multilayer composite coating by using a nano indentation technology.
FIG. 5 is a scratch pattern of AlCrTiSiN/AlCrTiSiON multilayer composite coatings prepared by arc ion plating; wherein: (a) example 1; (b) example 2.
FIG. 6 is a graph of the coefficient of friction of AlCrTiSiN/AlCrTiSiON multilayer composite coatings prepared by arc ion plating.
FIG. 7 shows the wear scar morphology of AlCrTiSiN/AlCrTiSiON multilayer composite coatings prepared by arc ion plating; wherein: (a) example 1 oxygen was introduced for 10 min; (b) example 2 oxygen was introduced for 20 min.
Detailed Description
The present invention will be described in further detail by way of examples.
Example 1
In this example, AlCrTiSiN/AlCrTiSiON multilayer composite coatings were deposited on a single-crystal Si wafer (40 mm. times.40 mm. times.0.67 mm), a cemented carbide wafer (25 mm. times.25 mm. times.3.0 mm) and a stainless steel wafer (35 mm. times.35 mm. times.1.0 mm), and then the coating was carried out by arc ion plating. The specific operation steps are as follows:
(1) ultrasonic cleaning the substrate in acetone and alcohol solution for 30min, and treating with high purity N 2 (99.999%) and the substrate was mounted on a rotating frame in the coating chamber.
(2) Uniformly arranging a metal Cr target, an AlTiSi alloy target and an AlCrSi alloy target on the inner wall of a furnace body of arc ion plating equipment so as to ensure that the furnace cavity has higher plasma concentration in the deposition process; pumping the background vacuum degree of the vacuum chamber to 3.0 x 10 -3 Pa, heating to 450 ℃, then applying-800V bias voltage, introducing Ar (99.999%) into the vacuum chamber, controlling the flow rate to be 400sccm, adjusting the throttle valve to keep the working pressure at 1.0Pa, performing glow discharge cleaning for 20min, and removing the pollution layer and the oxide on the surface of the substrate.
(3) And starting a Cr target to carry out ion bombardment, maintaining the target current at 80-100A, introducing Ar with the flow rate of 350-450 sccm, keeping the working pressure at 0.8-1.5 Pa, and respectively carrying out ion bombardment cleaning on the surface of the substrate for 2min by sequentially adjusting the bias voltage to-800V, -600V, -400V and-200V so as to improve the coating film/substrate bonding strength.
(4) The bias voltage is reduced to-100V, the protective gas Ar is introduced, the flow rate is 50sccm, and N is adjusted 2 Flow rate of 200sccm, maintain Ar and N 2 The total flow is 250sccm, the working pressure is kept to be 1.0Pa by adjusting a throttle valve, and a CrN transition layer is deposited for 20 min; keeping the bias voltage at-100V and the Ar flow at 50sccm, starting AlTiSi and AlCrSi alloy targets to glow, setting the target currents to 80A and 100A respectively, and increasing N 2 The flow rate is up to 600sccm, the deposition pressure is kept at 2.8Pa, and 20sccm oxygen is continuously introduced for 10min before the coating is finished, so that the AlCrTiSiN/AlCrTiSiON multilayer composite coating is obtained.
The shape characterization and performance test of the alcrtiisin/AlCrTiSiON multilayer composite coating prepared in this example were specifically as follows:
the phase composition of the coating is analyzed by an X-ray diffractometer (XRD), data are collected in a step scanning mode, incident X-rays are radiated by a Cu target Ka characteristic spectral line (lambda is 0.154056nm), the tube voltage is 40kV, the tube current is 40mA, the scanning range of a diffraction angle (2 theta) is 20-80 degrees, the scanning step is 0.02 degree, and the counting time of each step is 0.2 s. The surface and cross-sectional morphology of the coating was observed using a field emission Scanning Electron Microscope (SEM) model S4800, and the chemical composition of the coating was analyzed using an electron probe (EPMA, Shimadzu, EPMA 1600).
The hardness and the elastic modulus of the coating are tested by adopting a nano indenter (Anton Paar, TTX-NHT-3), in order to eliminate the influence of the matrix effect on the measurement result, the pressing depth of the needle point is ensured not to exceed 1/10 of the thickness of the coating, and the average value is taken from 15 points. The bonding strength of the coating to the SUS304 stainless steel substrate was measured using a scratch tester (Anton Paar RST-3) with a diamond tip diameter of 200 μm and the following parameters: the loading speed is 6 mm/min; the scratch length is 3 mm; the load 120N was set and the experimental data was recorded by the computer in real time.
The coefficient of friction was measured on a friction and wear tester (Anton Paar THT) using 5.99mm diameter Al for the friction pair 2 O 3 The ball (hardness 22 + -1 GPa), sliding linear velocity 0.1m/s, normal load 2N, rotation radius 8mm, and sliding distance 110 m. The rubbing experiment was performed at room temperature 22 ± 3 ℃ and humidity 30%, each sample was tested 3 times, the coating wear rate W was calculated using the formula W ═ V/(F × S) (V is wear volume, F is normal load, S is sliding distance), and the morphology of the coating after wear was observed using a super depth of field microscope (VHX-1000C, Keyence).
FIG. 1 shows the X-ray diffraction spectrum of the AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared in this example, which mainly contains Al 2 O 3 AlN, CrN and (Al, Cr) 2 O 3 And (5) waiting for the hard phase, wherein no new phase appears in all coating diffraction patterns along with the change of oxygen introduction time. When the oxygen introduction time is 10min, the diffraction peak intensity of the coating is generally higher, which shows that the crystallinity of the coating is high, the hard phase is the most and is embedded in the amorphous layer to form a nano composite structure, and the hardness and the tribology performance of the coating can be effectively improved.
FIGS. 2 and 3 show the surface and cross-sectional morphology of the AlCrTiSiN/AlCrTiSiON multilayer composite coating, respectively. The surface appearance of the coating can be seen to distribute a certain amount of large particle defects on the surface of the coating, because in the arc ion plating process, a cathode arc spot generates charged particles and forms plasma, and simultaneously, a large amount of liquid drops are generated and deposited on the surface of the coating, which is the arc ion plating processThe drawbacks of the technology itself. As can be seen from FIG. 3, the coatings are CrN, AlCrTiSiN and AlCrTiSiON from inside to outside, and the transition layer is well bonded to the substrate and each layer. The CrN transition layer has an obvious columnar crystal structure, and amorphous Si is formed by introducing Si element 3 N 4 And the columnar crystal has obvious inhibiting effect, and the two layers of AlCrTiSiN and AlCrTiSiON have no obvious structural features.
FIG. 4 is a load-unload curve obtained by using a nanoindenter to test the nanometer hardness of the AlCrTiSiN/AlCrTiSiON multilayer composite coating, and the smooth curve shows that the coating has a compact structure and few defects. The maximum indentation depth is 252nm during loading, the coating rebounds to 142nm after unloading, and finally the coating hardness is measured to be 21.8 GPa.
FIG. 5(a) is the profile of the coating prepared in this example after scratch test. It can be seen that the coating bonds well to the substrate with a critical load L c2 Up to 63.2N, the propagation and propagation of microcracks is effectively suppressed due to the large number of two-phase interfaces in the nanocomposite coating.
FIG. 6 is a plot of the coefficient of friction of the coating after the fretting test. It can be seen from the figure that the pre-abrasion stage is shorter, and the fluctuation of the friction coefficient is smaller after entering the stable abrasion stage, which indicates that the coating is stable in friction, and the slight shake is accompanied by that the stripped coating fragments participate in the friction.
FIG. 7(a) is the AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared in this example and Al 2 O 3 The grinding trace appearance after the ball is rubbed for 110m is small in width, a small amount of micro furrows are distributed in the ball, and the coating shows good wear resistance.
Example 2:
in this example, AlCrTiSiN/AlCrTiSiON multilayer composite coatings were deposited on a cemented carbide sheet (25 mm. times.25 mm. times.3.0 mm), a single crystal Si sheet (40 mm. times.40 mm. times.0.67 mm), and a SUS304 stainless steel sheet (40 mm. times.40 mm. times.1.0 mm). The coating deposition is carried out by arc ion plating technology. The specific operation steps are as follows:
(1) sequentially ultrasonic cleaning the substrate in acetone and alcohol solution for 30min, and treating with high purity N 2 Drying and fixing the substrate on a rotating frame in the vacuum coating chamber.
(2) Uniformly arranging a metal Cr target, an AlTiSi alloy target and an AlCrSi alloy target on the inner wall of a furnace body of arc ion plating equipment so as to ensure that the furnace cavity has higher plasma concentration in the deposition process; pumping the background vacuum degree of the vacuum chamber to 3.0 x 10 -3 Pa, heating to 450 ℃, then applying-800V bias voltage, introducing Ar (99.999%) into the vacuum chamber, controlling the flow rate to be 400sccm, adjusting the throttle valve to keep the working pressure to be 1.0Pa, performing glow discharge cleaning for 20min, and removing the pollution layer and the oxide on the surface of the substrate.
(3) And starting a Cr target to carry out ion bombardment, maintaining the target current at 80-100A, introducing Ar with the flow rate of 350-450 sccm, keeping the working pressure at 0.8-1.5 Pa, and sequentially adjusting the bias voltage to-800V, -600V, -400V and-200V to respectively carry out ion bombardment cleaning on the surface of the substrate for 2min so as to improve the coating film/substrate bonding strength.
(4) The bias voltage is reduced to-100V, the protective gas Ar is introduced, the flow rate is 50sccm, and N is adjusted 2 Flow rate of 200sccm, maintain Ar and N 2 The total flow is 250sccm, the working pressure is kept to be 1.0Pa by adjusting a throttle valve, and a CrN transition layer is deposited for 20 min; keeping the bias voltage at-100V and the Ar flow at 50sccm, starting AlTiSi and AlCrSi alloy targets, setting the target currents to be 80A and 100A respectively, and increasing N 2 The flow rate is up to 600sccm, the deposition pressure is kept at 2.8Pa, and 20sccm oxygen is continuously introduced for 20min before the coating is finished, so that the AlCrTiSiN/AlCrTiSiON multilayer composite coating is obtained.
The shape observation and performance test of the alcrtiisin/AlCrTiSiON multilayer composite coating prepared in this example were specifically as follows:
the difference from the embodiment 1 is that: the final oxygen flow time was 20min when depositing AlCrTiSiN/AlCrTiSiON multilayer composite coatings, the other steps being the same as in example 1.
When the oxygen introducing time is 20min, the hardness of the prepared AlCrTiSiN/AlCrTiSiON multilayer composite coating is 20GPa, the brittle fracture phenomenon of the coating edge is serious during scratch test, and the critical load is 60N, which shows that the prepared oxide layer is thicker and has large brittleness, and the mechanical property of the coating is reduced to some extent.
The friction coefficient and the wear rate of the AlCrTiSiN/AlCrTiSiON multilayer composite coating prepared under the condition are both higher than those of the AlCrTiSiN/AlCrTiSiON multilayer composite coatingThe heights of example 1 were 0.75 and 6.26X 10, respectively -3 μm 3 /. mu.m. The wear scar morphology of the coating is shown in fig. 7(b), under the combined action of the normal load and the tangential load, a large amount of coating fragments are peeled off from the surface of the substrate, the amount of black abrasive dust is increased, a small amount of micro furrows are accompanied, and two wear mechanisms of abrasive wear and adhesive wear coexist.
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 (3)

1. An AlCrTiSiN/AlCrTiSiON multilayer composite coating is characterized in that: the coating is deposited on the surface of a hard alloy substrate, a stainless steel sheet or a silicon chip substrate, and the AlCrTiSiN/AlCrTiSiON multi-layer composite coating is formed by laminating an AlCrTiSiN layer and an AlCrTiSiON layer;
the preparation process of the AlCrTiSiN/AlCrTiSiON multilayer composite coating is characterized in that an AlCrTiSiN/AlCrTiSiON multilayer composite coating is deposited on a substrate by adopting an arc ion coating technology, and a target material is selected from a pure metal Cr target, an AlCrSi alloy target and an AlTiSi alloy target; when depositing AlCrTiSiN/AlCrTiSiON multilayer composite coating, firstly starting a Cr target to perform ion bombardment cleaning and deposit a CrN transition layer, then starting an AlCrSi target and an AlTiSi target together to deposit an AlCrTiSiN layer, and finally introducing a certain amount of oxygen to prepare an AlCrTiSiON surface protective coating; respectively controlling the deposition pressure, the reaction gas flow and the arc flow parameters of each target during film coating, and preparing an AlCrTiSiN/AlCrTiSiON multilayer composite coating on the surface of the substrate; the process specifically comprises the following steps:
(1) fixing the cleaned hard alloy substrate, stainless steel sheet or silicon wafer on a rotating frame in a coating chamber, and pumping the vacuum degree to 3 × 10 -3 Pa; heating to 450 ℃;
(2) firstly, cleaning a substrate by adopting high negative bias glow discharge for 10-30 min, starting a Cr target after the glow discharge cleaning, adjusting the argon flow to be 50-100 sccm, and adjusting the bias to-800V, -600V, -400V and-200V in sequence to respectively perform ion bombardment cleaning on the surface of the substrate for 2min so as to remove a pollution layer and oxides on the surface of the substrate; the glow discharge cleaning process comprises the following steps: heating the furnace chamber to 200-500 ℃, introducing argon gas with the flow of 200-600 sccm, setting pulse bias voltage to-600-1000V, and performing glow discharge cleaning on the substrate;
(3) depositing a CrN transition layer, wherein the process is as follows: after glow discharge cleaning and ion bombardment cleaning, setting a bias voltage of-50 to-100V, setting a duty ratio of 60 to 90 percent, starting a Cr target, introducing 50sccm of argon gas flow and 200sccm of nitrogen gas flow, adjusting the deposition pressure to 0.5 to 1.2Pa, and depositing a CrN transition layer for 10 to 30 min;
(4) depositing AlCrTiSiN/AlCrTiSiON multilayer composite coating;
when the AlCrTiSiN/AlCrTiSiON multilayer composite coating is deposited, arc flows are set to be 60-100A; when starting AlCrSi target and AlTiSi target to deposit AlCrTiSiN layer, setting bias voltage to-80-120V, duty ratio to 60-90%, and introducing argon and nitrogen to adjust deposition pressure to 1.5-3.0 Pa; when the AlCrTiSiON coating is deposited, introducing oxygen for 5-15 min; controlling the total coating time of the AlCrTiSiN/AlCrTiSiON multilayer composite coating to be 3h, and setting different target material starting times and gas introduction times;
when the AlCrTiSiN coating is deposited, the flow of argon is 50sccm, the flow of nitrogen is 600sccm, and the total flow is 650 sccm; when the AlCrTiSiON coating is deposited, the flow rate of introduced argon is 50sccm, the flow rate of introduced nitrogen is 600sccm, the flow rate of introduced oxygen is 20sccm, and the total flow rate is 670 sccm.
2. The AlCrTiSiN/AlCrTiSiON multilayer composite coating of claim 1, wherein: the AlCrTiSiN layer and the AlCrTiSiON layer are both single layers, and the total deposition time of the two layers is 3 h.
3. The AlCrTiSiN/AlCrTiSiON multilayer composite coating of claim 1, wherein: the bonding force between the AlCrTiSiN/AlCrTiSiON multilayer composite coating and the base material is more than 60N, and the wear rate is lower than 6.26 multiplied by 10 -3 μm 3 /N·μm。
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