CN115074731A - Porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating and preparation method and application thereof - Google Patents

Abstract

The invention discloses a porous composite TiCN/TiAlXN wear-resistant and anti-oxidation coating, a preparation method and application thereof. The whole is composed of three sub-layers of the anti-oxidation layer. The order of the three sub-layers is from the inside to the outside, and the total thickness of the coating is 7-10 μm. The invention adopts the composite coating prepared by high temperature vapor deposition + cathodic arc + HiPIMS technology, has the advantages of chemical physical vapor deposition, and fully utilizes the advantages of arc and magnetron, by controlling nitrogen and argon flow, pulse peak current and deposition time, etc., deposit TiAlXN layer on the surface of the substrate; the multi-layer composite coating with organic combination of different functional sub-layers has high toughness, wear resistance, oxidation resistance and impact resistance, which is very suitable for intermittent cutting processing and wear and oxidation resistance. , Vibration-resistant scene, and the preparation process is simple, which is convenient for industrial production.

Description

A porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating and preparation method thereof, application

technical field

The invention relates to the technical field of surface coatings, in particular to a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating and a preparation method and application thereof.

Background technique

In recent years, the method of coating metal nitrides on tools, molds, mechanical parts and other products to improve the surface properties and service life of products has become a widely used surface modification technology. With the continuous development of coating technology, new high oxidation resistance, etc., meet the requirements of modern manufacturing for high hardness, high toughness, high wear resistance and high temperature performance of coatings.

Nitride coating is a widely used coating material for milling cutters, turning tools and other cutting tools, such as TiAlN, TiAlCrN, TiAlSiN, etc. The nitride coating has high hardness and good wear resistance. However, the nitride coating also has shortcomings: too high brittleness, insufficient bonding strength with the substrate, insufficient thermal stability under high temperature conditions, and poor impact resistance. In order to give play to the performance advantages of each coating, the multi-layer oxide/(carbon) nitride composite coating prepared by chemical vapor deposition method has excellent comprehensive properties and has been widely used in cutting tools. However, due to the high process temperature of chemical vapor deposition, the tool substrate material is prone to element diffusion and chemical reaction during the coating deposition process. The physical vapor deposition method has the characteristics of low deposition temperature, little influence on the properties of the substrate material, good surface quality, and flexible process. It is a more promising method for preparing complex structure composite coatings.

At present, arc ion plating and magnetron sputtering are the most widely used in physical vapor deposition (PVD). Among them, arc ion plating has higher ionization rate, stronger wear resistance and better film-base bonding force than magnetron sputtering, and is the mainstream choice for hard coating tools. However, the surface of the film deposited by traditional cathodic arc ion plating inevitably has large particles and a rough surface, which leads to high friction, more heat generation, and easier wear of the coated tool when cutting. The high temperature vapor deposition + cathodic arc + HiPIMS preparation method can generate higher density plasma, higher ionization rate and faster deposition rate. The large particles on the surface of the prepared thick film are significantly reduced, and the wear-resistant layer is organized into a porous structure, which has good impact resistance and anti-chipping effect.

There is no report on the method of preparing porous TiCN/TiAlXN wear-resistant coating by high temperature vapor deposition + cathodic arc + HiPIMS method. It is one of the important development directions of tool impact resistance, oxidation resistance and wear resistance.

SUMMARY OF THE INVENTION

In order to solve the problems existing in the prior art, the present invention provides a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating and its preparation method and application, which ensure the overall impact resistance, wear resistance and low stress of the coating. , high bonding strength, solve the problems mentioned in the above background technology.

In order to achieve the above purpose, the present invention provides the following technical solutions: a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating, the TiCN/TiAlXN wear-resistant and anti-oxidative coating is composed of 3 sub-layers, and the sub-layer order is from inside to outside The order is TiN bonding layer, TiCN porous wear-resistant layer, TiAlXN-based wear-resistant and anti-oxidation layer; the total thickness of the TiCN/TiAlXN wear-resistant and anti-oxidative coating is 7-10 μm, and the thickness of the TiN bonding layer is 0.05-0.1 μm, The thickness of the TiCN porous wear-resistant layer is 5-7 μm, and the thickness of the TiAlXN-based wear-resistant and anti-oxidation layer is 2-3 μm.

Preferably, the atomic percentage content of each element in the TiAlXN-based wear-resistant and oxidation-resistant layer is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%. %; wherein, X is C, Si, Zr, Mo, V, Cr and rare earth elements.

In addition, in order to achieve the above purpose, the present invention also provides the following technical solutions: a preparation method of a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating, comprising the following steps:

S1. Polish the surface of the substrate, and then put it into a solution in a 35°C hot water bath for ultrasonic cleaning; then spray fine-grained gravel for 3 to 5 times, each time for 2 to 5 seconds, and the blasting pressure is 0.8 to 1.3 Kg/cm ² , put it into the solution of the hot water bath again for 30min, and finally put it into the oven to bake;

S2, the sample obtained in step S1 is clamped into the furnace, and the temperature is vacuumed to start deposition to prepare the TiN bonding layer;

S3, on the basis of step S2, start to deposit and prepare the TiCN porous wear-resistant layer;

S4, take out the sample in step S3, repeat S1;

S5. Load the sample in step S4 into a furnace, perform intermediate frequency pulse etching at 300-500°C, pump the vacuum chamber to ^{3.0-10.0x10-3} Pa, pass in Ar gas for 350-550sccm, and set the workpiece bias to -600- -1000V, the frequency is 20~250k Hz, the rotation speed is 1.5~5.5 rev/min, the sample surface is subjected to pulse etching for 10~15min, and then the furnace cavity is cleaned with H ₂ ;

S6. Pour in Ar gas for 350-550 sccm, adjust the bias voltage to -100--200V, set the ion source current to 10-15A, and set the rotational speed to 1.5-5.5 r/min, and perform gas ion source DC etching on the sample in step S5 20 ~ 25min, then use H ₂ to clean the furnace cavity;

S7. For the sample in step S6, using cathodic arc combined with HiPIMS high-energy pulsed magnetron sputtering technology, by controlling nitrogen and argon gas flow, pulse peak current and deposition time parameters, a TiAlXN-based wear-resistant and anti-oxidation functional layer is deposited.

Preferably, the solution in the step S1 is acetone or alcohol; the fine-grained grit is corundum, zirconia or emery; and the baking is specifically baking at 60° C. for 20 minutes.

Preferably, in the deposition and preparation of the TiN bonding layer in the step S2, the deposition temperature is 850-900° C., the deposition pressure is 95-101 KPa, and the gases used include TiCl ₄ , H ₂ , N ₂ and Ar, wherein TiCl ₄ is composed of H ₂ Bring it into the reaction furnace, and the temperature of the water bath of TiCl ₄ is 45-48 ℃.

Preferably, in the preparation of the TiCN porous wear-resistant layer by deposition in step S3, the deposition temperature is 1000-1050° C., the deposition pressure is 6-50 KPa, and the gases used include TiCl ₄ , H ₂ , CH ₄ , N ₂ and Ar, which are mainly used for It is used to control the gas concentration and chemical balance, wherein, TiCl ₄ is brought into the reaction furnace by H, and the temperature of the water bath of TiCl ₄ is 45-48 ℃.

Preferably, the percentage of the flow rate of the CH ₄ gas is 3.5% to 4%, and the percentage of the flow rate of the TiCl ₄ gas is 1.5% to 3%.

Preferably, the cathode arc combined with HiPIMS high-energy pulsed magnetron sputtering technology is used in the step S7, and by controlling the flow rates of nitrogen and argon, the pulse peak current and the deposition time, specifically: adjusting the bias voltage to -100～-250V , pass 400～750sccm N ₂ gas, 400～750sccm Ar gas, ignite at least 2 Ti _a Al _b X _c rectangular magnetron targets, at least 4 Ti _a Al _b X _c cylindrical arc targets, adjust N ₂ The air pressure is 0.5～3.5Pa, the Ar air pressure is adjusted to 0.5～3.5Pa, the deposition temperature is 450～550℃, the deposition pressure is 9800～10500Mpa, the rotation speed is 1.5～5.5 rpm, the pulse arc power waveform is rectangular wave, and the average current 70～120A, bias voltage: -30～-500V, frequency: 20～250KHz, duty cycle: 5%～75%, output current of arc source electromagnetic coil: 0.3～5.2A, deposit TiAlXN layer for 100～300min.

Preferably, the atomic percentage in the Ti _a Al _b X _c target material is Ti: 10-50 at. %, Al: 30-67 at. %, X is C, Si, Zr, Mo, V or Cr; a+ b+c=100at.%.

In addition, in order to achieve the above purpose, the present invention also provides the following technical solution: the application of a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating in the field of surface protection of mechanical parts and tool molds.

The beneficial effects of the present invention are:

1) The porous wear-resistant composite coating provided by the present invention is composed of three sub-layers with different functions and components. First, the nano-TiN bonding layer has higher performance than the traditional Cr and Ti pure metal bonding layers. It can play a good bonding effect between the tool base material and the surface coating material, so that the coating and the base are combined firmly; secondly, when the coating is prepared at 850-900 ℃, it can ensure the coating The bonding strength prevents the diffusion of elements and avoids the formation of a brittle layer; once again, it provides a coherent growth condition for the nucleation and growth of the porous wear-resistant layer, and avoids excessive residual stress caused by lattice distortion. Finally, after the porous wear-resistant layer is prepared Sandblasting is then used to reduce the stress of the coating itself, which provides a support foundation for the subsequent preparation of the wear-resistant and oxidation-resistant layer, and ensures the overall impact resistance, wear resistance, low stress and high bonding strength of the coating.

2) The present invention has the advantages of chemical physical vapor deposition by using the composite coating prepared by high temperature vapor deposition + cathodic arc + HiPIMS technology (using high temperature vapor deposition to form coherent growth and form porous equiaxed crystals, ensuring that the coating resists The effect of impact energy absorption is to use physical vapor deposition to form fibrous crystals to ensure that the coating is hard enough, wear-resistant and anti-oxidative), and at the same time makes full use of the advantages of arc and magnetron, by controlling nitrogen and argon flow, pulse peak value Current and deposition time, etc., deposit a TiAlXN layer on the surface of the substrate. Compared with traditional arc ion plating, the pulsed arc ion plating of the present invention can generate higher density plasma, faster deposition rate, lower residual stress, higher coating hardness and more wear resistance.

Description of drawings

Figure 1 is a schematic diagram of the porous composite TiCN/TiAlXN wear-resistant and anti-oxidation coating;

Fig. 2 is the friction curve of the porous wear-resistant anti-oxidation coating prepared in Example 1;

Fig. 3 is the friction curve of the porous wear-resistant anti-oxidation coating prepared in Example 2;

FIG. 4 is the friction curve of the porous wear-resistant and oxidation-resistant coating prepared in Example 3. FIG.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Please refer to FIG. 1 , the present invention provides a technical solution: a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating, the TiCN/TiAlXN wear-resistant and anti-oxidative coating is composed of three sub-layers, as shown in FIG. 1 , The sub-layer sequence from inside to outside is TiN bonding layer, TiCN porous wear-resistant layer, TiAlXN-based wear-resistant and anti-oxidation layer; the total thickness of the TiCN/TiAlXN wear-resistant and anti-oxidative coating is 7-10 μm, and the TiN bonding layer is The thickness is 0.05-0.1 μm, the thickness of the TiCN porous wear-resistant layer is 5-7 μm, and the thickness of the TiAlXN-based wear-resistant and oxidation-resistant layer is 2-3 μm.

Further, the atomic percentage content of each element in the TiAlXN-based wear-resistant and oxidation-resistant layer is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.% %; wherein, X is C, Si, Zr, Mo, V, Cr and rare earth elements.

A preparation method of a porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating, comprising the following specific steps:

S1: Deposition of bonding layer: Polish the surface of the substrate to a mirror surface (Ra=0.2 μm), put it in ultrasonic waves and wash it in an acetone solution of 35°C in a hot water bath for 30 minutes, and spray it with fine-grained corundum three times, each time Spray for 2-5 seconds, sand blasting pressure 0.8-1.3Kg/cm ² , put it in the acetone solution of the hot water bath again for 30 minutes, then put it in the oven to bake at 60 ℃ for 20 minutes, put it into the furnace, and vacuumize The temperature rises to start the preparation of the bonding layer, the deposition temperature is 850-900°C, the deposition pressure is 95-101KPa, and the gases used include TiCl ₄ , H ₂ , N ₂ and Ar, wherein TiCl ₄ is brought into the reaction furnace by H ₂ , and the TiCl ₄ The temperature of the water bath is 45-48°C, and the coating thickness is 0.05-0.1 μm.

S2: TiCN porous wear-resistant layer: start to prepare the porous wear-resistant layer on the basis of step S1, the deposition temperature is 1000-1050°C, the deposition pressure is 6-50KPa, and the gases used include TiCl ₄ , H ₂ , CH ₄ , N ₂ and Ar, in which TiCl ₄ is brought into the reaction furnace by H ₂ , the water bath temperature of TiCl ₄ is 45-48 °C, and the coating thickness is 5-7 μm. The temperature and gas ratio are the keys to forming the porous wear-resistant layer. The percentage of _CH4 gas flow is 3.5%-4%, and the percentage of _TiCl4 gas flow is 1.5%-3%.

S3: TiAlXN-based functional coating: put the sample prepared by S2 into ultrasonic wave and wash it in acetone solution at 35°C in a hot water bath for 30min, put it in an oven and bake at 50°C for 20 minutes. HiPIMS vacuum system prepares TiAlXN-based coating and deposits TiAlXN-based functional layer: adjust the bias voltage to -100～-250V, pass N ₂ gas of 400～750sccm, Ar gas of 400～750sccm, and ignite at least 2 Ti _a Al _b X _c rectangular magnetron target, at least 4 Ti _a Al _b X _c cylindrical arc targets (the atomic percentage in the target Ti _a Al _b X _c is Ti: 10-50 at.%, Al: 30-67 at.% , X can be C, Si, Zr, Mo, V, Cr and rare earth metal elements, a+b+c=100at.%), adjust N ₂ pressure to 0.5~3.5Pa, adjust Ar pressure to 0.5~3.5Pa, The deposition temperature is 450～550℃, the deposition pressure is 9800～10500Mpa, the rotation speed is 1.5～5.5 rpm, the pulse arc power waveform is rectangular wave, the average current is 70～120A, the bias voltage: -30～-500V, the frequency: 20 ～250KHz, duty cycle: 5%～75%, output current of arc source electromagnetic coil: 0.3～5.2A, deposit TiAlXN functional layer for 100～300min, and obtain high-performance TiAlXN nanocomposite coating, coating thickness 2-3μm, The atomic percentage of each element in the TiAlXN-based coating is Ti: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%.

The application of a porous composite TiCN/TiAlXN wear-resistant and anti-oxidative coating in the field of surface protection of mechanical parts and tool molds.

Example 1

Deposition of this porous wear-resistant and oxidation-resistant coating on a TiCN-WC-MoC-Ni-Co cermet matrix

S1. Polish the cermet tool substrate to remove the oxide layer on the surface, put it into a solution in a 35°C hot water bath for ultrasonic cleaning for 30 minutes; then spray with fine-grained gravel for 5 times, each spray for 5 seconds, and the blasting pressure 1.3Kg/cm ² , put it into the solution of hot water bath again for 30min, then put it into the oven and bake it at 60℃ for 20min;

S2. Clamp the sample obtained in step S1 into the furnace, vacuumize and heat up to start the preparation of the bonding layer, the deposition temperature is 900°C, the deposition pressure is 101KPa, and the gases used include TiCl ₄ , H ₂ , N ₂ and Ar, among which TiCl ₄ The water bath temperature of _{TiCl 4 is} 48 ℃, and the coating thickness is 0.1 μm;

S3. On the basis of step S2, start to prepare the porous wear-resistant layer, the deposition temperature is 1050°C, the deposition pressure is 50KPa, and the gases used include TiCl ₄ , H ₂ , CH ₄ , N ₂ and Ar, wherein TiCl ₄ is carried by H ₂ Into the reaction furnace, the water bath temperature of TiCl ₄ is 48°C, and the coating thickness is 7 μm. The temperature and gas ratio are the keys to forming the porous wear-resistant layer. The percentage of CH ₄ gas flow is 4%, and the percentage of TiCl ₄ gas flow is 3%.

S4. Take out the sample in step S3, and repeat step S1.

S5. Load the sample in step S4 into a furnace, perform intermediate frequency pulse etching at 500°C, pump the vacuum chamber to 10.0x10 ^-3 Pa, pass in Ar gas for 550sccm, set the workpiece bias voltage to -1000V, the frequency to 250k Hz, and the rotation speed to 5.5 rev/min, pulse etching the sample surface for 15min, and then clean the furnace cavity with H ₂ ;

S6, DC direct current etching: pass Ar gas 550sccm, adjust the bias voltage to -200V, set the ion source current to 15A, and set the ion source current to 5.5 r/min, perform the gas ion source direct current etching on the sample in step S5 for 25min, and then use H ₂ to clean the oven cavity.

S7. Deposition of TiAlMoN functional layer: adjust the bias voltage to -250V, pass N ₂ gas of 750 sccm, Ar gas of 750 sccm, ignite at least 2 Ti _a Al _b Mo _c rectangular magnetron targets, at least 4 Ti _a Al _b Mo _c cylindrical arc target. For example: 3 Ti _a Al _b Mo _c rectangular magnetron targets, 6 Ti _a Al _b Mo _c cylindrical arc targets. (The atomic percentage in the target Ti _a Al _b Mo _c is Ti: 10-50 at. %, Al: 30-67 at. %, a+b+c=100 at. %), adjust the N ₂ gas pressure to 3.5Pa, adjust Ar pressure to 3.5Pa, temperature 550℃, rotation speed 5.5 rpm, pulse arc power waveform is rectangular wave, average current 120A, bias voltage: -500V, frequency: 250KHz, duty cycle: 70%, arc source electromagnetic coil Output current: 5.2A, deposit TiAlMoN functional layer for 100min, and obtain high-performance TiAlMoN nanocomposite coating with a coating thickness of 3μm, in which the atomic percentage of each element in the TiAlMoN-based coating is Ti: 30～50at.%, Al: 30 to 70 at.%, N: 10 to 50 at.%, Mo: 0 to 20 at.%.

The porous TiCN/TiAlMoN wear-resistant and anti-oxidation coating prepared in this example has a hardness of 45GPa, a residual stress of -0.3GPa, a surface roughness of 90nm, and an average friction coefficient of 0.36. The friction curve is shown in Figure 2.

Example 2:

Deposition of this porous wear-resistant and oxidation-resistant coating on WC-Co cemented carbide substrates

S1. Polish the cemented carbide substrate to remove the oxide layer on the surface, put it into a solution in a 35 ℃ hot water bath for ultrasonic cleaning for 30 minutes; then spray with fine-grained gravel for 3 times, each time for 2 seconds, and the blasting pressure 0.8Kg/cm ² , put it into the solution of hot water bath again for 30min, then put it into the oven and bake it at 60℃ for 20min;

S2. Clamp the sample obtained in step S1 into the furnace, vacuumize and heat up to start the preparation of the bonding layer, the deposition temperature is 850°C, the deposition pressure is 95KPa, and the gases used include TiCl ₄ , H ₂ , N ₂ and Ar, among which TiCl ₄ It is brought into the reaction furnace by H ₂ , the water bath temperature of TiCl ₄ is 45 °C, and the coating thickness is 0.05 μm;

S3. The porous wear-resistant layer is prepared on the basis of step S2. The deposition temperature is 1000° C. and the deposition pressure is 6KPa. The gases used include TiCl ₄ , H ₂ , CH ₄ , N ₂ and Ar, wherein TiCl ₄ is brought in by H ₂ In the reaction furnace, the water bath temperature of TiCl ₄ is 45°C, and the coating thickness is 5 μm. The temperature and gas ratio are the keys to forming the porous wear-resistant layer. The percentage of gas flow rate of CH ₄ is 3.5%, and the percentage of gas flow rate of TiCl ₄ is 1.5%. %.

S4, take out the sample in S3, and repeat S1.

S5. Load the S4 sample into the furnace, perform intermediate frequency pulse etching at 300°C, pump the vacuum chamber to 3.0x10 ^-3 Pa, pass in Ar gas for 350sccm, set the workpiece bias to -600V, the frequency to 20k Hz, and the rotation speed to 1.5 rpm /min, pulse etching the sample surface for 10min, and then clean the furnace cavity with H ₂ ;

S6, DC etching: pass Ar gas for 350sccm, adjust the bias voltage to -100, set the ion source current to 10A, and set the speed to 1.5 r/min, perform gas ion source DC etching on the S5 sample for 20min, and then use H ₂ Clean the oven cavity.

S7. Deposition of TiAlVN functional layer: adjust the bias voltage to -100V, pass N ₂ gas of 400 sccm, Ar gas of 400 sccm, ignite at least 2 Ti _a Al _b V _c rectangular magnetron targets, at least 4 Ti _a Al _b V _c cylindrical arc target (the atomic percentage in the target Ti _a Al _b V _c is Ti: 23 at. %, Al: 67 at. %, a+b+c=100 at. %), adjust the N ₂ gas pressure to 0.5Pa , adjust Ar pressure to 3Pa, temperature 450℃, speed 1.5 rpm, pulse arc power waveform is rectangular wave, average current 70A, bias voltage: -30V, frequency: 20KHz, duty cycle: 25%, arc source electromagnetic Coil output current: 0.3A, deposition of TiAlVN functional layer for 300min, to obtain high-performance TiAlVN nanocomposite coating, coating thickness 2-3μm, in which the atomic percentage of each element in the TiAlVN-based coating is Ti: 30～50at. %, Al: 30-70 at.%, N: 10-50 at.%, V: 0-20 at.%.

The porous TiCN/TiAlVN wear-resistant and oxidation-resistant coating prepared in this example has a hardness of 46GPa, a residual stress of -0.32GPa, a surface roughness of 85nm, and an average friction coefficient of 0.342. The friction curve is shown in Figure 3.

Example 3:

Deposition of this porous wear-resistant and oxidation-resistant coating on WC-TiC-Co cemented carbide substrates

S1. Polish the cemented carbide tool base to remove the oxide layer on the surface, put it into a solution in a 35 ℃ hot water bath for ultrasonic cleaning for 30 minutes; then spray with fine-grained gravel for 3 times, each time for 3 seconds, sandblasting The pressure is 1.2Kg/cm ² , put it into the solution of the hot water bath again for 30 minutes, and then put it into the oven and bake it at 60 ℃ for 20 minutes;

S2. Clamp the sample obtained in step S1 into the furnace, vacuumize and heat up to start the preparation of the bonding layer, the deposition temperature is 850°C, the deposition pressure is 95KPa, and the gases used include TiCl ₄ , H ₂ , N ₂ and Ar, among which TiCl ₄ The water bath temperature of _{TiCl 4 is} 45 °C, and the coating thickness is 0.06 μm;

S3. The porous wear-resistant layer is prepared on the basis of step S2. The deposition temperature is 1000°C and the deposition pressure is 20KPa. The gases used include TiCl ₄ , H ₂ , CH ₄ , N ₂ and Ar, wherein TiCl ₄ is brought in by H ₂ In the reaction furnace, the water bath temperature of TiCl ₄ is 45°C, and the coating thickness is 5.3 μm. The temperature and gas ratio are the keys to forming the porous wear-resistant layer. The percentage of CH ₄ gas flow is 3.5%, and the percentage of TiCl ₄ gas flow is 2%.

S4, take out the sample in S3, and repeat S1.

S5. Load the S4 sample into the furnace, perform intermediate frequency pulse etching at 400°C, pump the vacuum chamber to 5.0x10 ^-3 Pa, pass in Ar gas for 450sccm, set the workpiece bias to -800V, the frequency to 50k Hz, and the rotation speed to 5 rpm /min, pulse etching the sample surface for 12min, and then clean the furnace cavity with H ₂ ;

S6, DC Etching: Pass in Ar gas for 450sccm, adjust the bias voltage to -120V, set the ion source current to 12A, and set the speed to 5 r/min. Perform the gas ion source DC etching on the S5 sample for 22min, and then use H ₂ Clean the oven cavity.

S7. Deposition of TiAlYN functional layer: adjust the bias voltage to -200V, pass N ₂ gas of 450 sccm, Ar gas of 450 sccm, ignite at least 2 Ti _a Al _b Y _c rectangular magnetron targets, at least 4 Ti _a Al _b Y _c cylindrical arc target (the atomic percentage in the target Ti _a Al _b Y _c is Ti: 25 at. %, Al: 67 at. %, a+b+c=100 at. %), adjust the N ₂ gas pressure to 1Pa, Adjust the Ar pressure to 3Pa, the temperature to 480℃, the rotation speed to be 5 rpm, the pulse arc power waveform to be rectangular wave, the average current to be 90A, the bias voltage: -100V, the frequency: 100KHz, the duty cycle: 50%, the arc source electromagnetic coil Output current: 1.2A, deposition of TiAlYN functional layer for 150min, to obtain high-performance TiAlYN nanocomposite coating, coating thickness 2μm, in which the atomic percentage of each element in the TiAlYN-based coating is Ti: 30～50at.%, Al : 30 to 70 at.%, N: 10 to 50 at.%, Y: 0 to 20 at.%.

The porous TiCN/TiAlYN wear-resistant and oxidation-resistant coating prepared in this example has a hardness of 50GPa, a residual stress of -0.22GPa, a surface roughness of 80nm, and an average friction coefficient of 0.325. The friction curve is shown in Figure 4.

The multi-layer composite coating organically combined with different functional sub-layers has high toughness, wear resistance, oxidation resistance and impact resistance, and is very suitable for intermittent cutting processing and wear resistance, oxidation resistance and vibration resistance scenarios, and the preparation process is simple. , which is convenient for industrial production.

The present invention adopts the preparation method of high temperature vapor deposition + cathode arc + HiPIMS, which can generate higher density plasma, higher ionization rate and faster deposition rate. The large particles on the surface of the prepared thick film are significantly reduced, and the wear-resistant layer is organized into a porous structure, which has good impact resistance and anti-chipping effect.

Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still possible to modify the technical solutions described in the foregoing embodiments, or to perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. The porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is characterized by comprising 3 sublayers, wherein the sublayers sequentially comprise a TiN bonding layer, a TiCN porous wear-resistant layer and a TiAlXN-based wear-resistant and oxidation-resistant layer from inside to outside; the total thickness of the TiCN/TiAlXN wear-resistant and oxidation-resistant coating is 7-10 mu m, the thickness of the TiN bonding layer is 0.05-0.1 mu m, the thickness of the TiCN porous wear-resistant layer is 5-7 mu m, and the thickness of the TiAlXN-based wear-resistant and oxidation-resistant layer is 2-3 mu m.

2. The porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating of claim 1, wherein: the TiAlXN-based wear-resistant anti-oxidation layer comprises the following elements in atomic percent: 30-50 at.%, Al: 30-70 at.%, N: 10-50 at.%, X: 0-20 at.%; wherein X is C, Si, Zr, Mo, V or Cr.

3. A preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claims 1-2 is characterized in that: the method comprises the following steps:

s1, polishing the surface of the substrate, and then putting the substrate into a solution in a hot water bath at 35 ℃ for ultrasonic cleaning; spraying fine gravel for 3-5 times, wherein each time of spraying is 2-5 seconds, and the sand spraying pressure is 0.8-1.3Kg/cm ² Cleaning in hot water bath solution for 30min, and baking in oven;

s2, clamping the sample obtained in the step S1 into a furnace, vacuumizing, heating and starting to deposit to prepare a TiN bonding layer;

s3, starting to deposit and prepare a TiCN porous wear-resistant layer on the basis of the step S2;

s4, taking out the sample in the step S3, and repeating the step S1;

s5, charging the sample obtained in the step S4 into a furnace, performing medium-frequency pulse etching at 300-500 ℃, and pumping the vacuum chamber to 3.0-10.0 x10 ^-3 Pa, introducing Ar gas 350-550sccm, setting the workpiece bias voltage to-600-1000V, the frequency to 20-250 k Hz, the rotating speed to 1.5-5.5 r/min, performing pulse etching on the surface of the sample for 10-15 min, and then using H ₂ Cleaning the furnace chamber;

s6, introducing Ar gas of 350-550sccm, adjusting the bias voltage to-100-200V, setting the ion source current to 10-15A and the rotation speed to 1.5-5.5 rpm, performing gas ion source direct current etching on the sample obtained in the step S5 for 20-25 min, and then using H ₂ Cleaning the furnace chamber;

and S7, depositing the TiAlXN-based wear-resistant and oxidation-resistant functional layer on the sample obtained in the step S6 by adopting a cathodic arc combined HiPIMS high-energy pulse magnetron sputtering technology and controlling the flow of nitrogen and argon, the pulse peak current and the deposition time parameters.

4. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized in that: the solution in the step S1 is acetone or alcohol; the fine granular gravel is corundum, zirconia or carborundum; the baking is specifically baking at 60 ℃ for 20 min.

5. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized by comprising the following steps: in the step S2 of preparing the TiN bonding layer by deposition, the deposition temperature is 850-900 ℃, the deposition pressure is 95-101KPa, and the used gas comprises TiCl ₄ ，H ₂ ，N ₂ And Ar, wherein, TiCl ₄ From H ₂ Carried into a reaction furnace, TiCl ₄ The temperature of the water bath is 45-48 ℃.

6. According to the claimsThe preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating is characterized by comprising the following steps: in the step S3 of preparing the TiCN porous wear-resistant layer by deposition, the deposition temperature is 1000-1050 ℃, the deposition pressure is 6-50KPa, and the used gas comprises TiCl ₄ ，H ₂ ，CH ₄ ，N ₂ And Ar, wherein, TiCl ₄ From H ₂ Carried into a reaction furnace, TiCl ₄ The temperature of the water bath is 45-48 ℃.

7. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 6, characterized in that: the CH ₄ The gas flow percentage is 3.5 percent to 4 percent, TiCl ₄ The gas flow percentage is 1.5% -3%.

8. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 3, characterized in that: in the step S7, a cathodic arc and HiPIMS high-energy pulse magnetron sputtering technology is adopted, and the flow rate of nitrogen and argon, the pulse peak current and the deposition time are controlled, specifically: adjusting the bias voltage to-100 to-250V, and introducing N of 400 to 750sccm ₂ Igniting at least 2 Ti with Ar gas of 400-750 sccm _a Al _b X _c Rectangular magnetron target, at least 4 Ti _a Al _b X _c Cylindrical arc target, regulation N ₂ The pressure is 0.5-3.5 Pa, the Ar pressure is adjusted to 0.5-3.5 Pa, the deposition temperature is 450-550 ℃, the deposition pressure is 9800-10500Mpa, the rotating speed is 1.5-5.5 r/min, the waveform of a pulse arc power supply is rectangular wave, the average current is 70-120A, and the bias voltage is as follows: -30 to-500V, frequency: 20-250 KHz, duty cycle: 5% -75%, the output current of the arc source electromagnetic coil: 0.3-5.2A, depositing the TiAlXN layer for 100-300 min.

9. The preparation method of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to claim 8, characterized in that: the Ti _a Al _b X _c The atomic percentage of Ti in the target material is 10-50 at.%, and Al: 30-67 at.%, X is C, Si, Zr, Mo, V or Cr; a + b + c is 100at.％。

10. The application of the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating according to any one of claims 1-2 or the porous composite TiCN/TiAlXN wear-resistant and oxidation-resistant coating prepared by the preparation method according to any one of claims 3-9 in the field of surface protection of mechanical parts and cutting tools and dies.

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