CN109628896B - Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof - Google Patents

Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof Download PDF

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CN109628896B
CN109628896B CN201910042017.6A CN201910042017A CN109628896B CN 109628896 B CN109628896 B CN 109628896B CN 201910042017 A CN201910042017 A CN 201910042017A CN 109628896 B CN109628896 B CN 109628896B
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coating
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aluminum
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CN109628896A (en
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鲜广
范洪远
赵海波
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Sichuan University
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Sichuan University
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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target

Abstract

The invention discloses a gradient structure TiAlSiYN multi-element nano coating which is composed of an inner layer, a middle layer and an outer layer, wherein the components of the inner layer, the middle layer and the outer layer are different, and the Al content of the sublayers from the inner layer to the outer layer is gradually reduced and is 15-20 at.%, 10-15 at.% and 7-10 at.% in sequence; the Ti content is increased progressively and is 28-32 at.%, 32-36 at.%, and 36-40 at.% in sequence; the Si content in each sublayer is 1-3 at.%, the Y content is <0.1at.%, and the remainder is N. The invention also discloses a preparation method thereof, which comprises the steps of firstly utilizing the titanium aluminum arc target with high aluminum content, the titanium silicon arc target and the yttrium sputtering target to deposit for a period of time; then closing the titanium aluminum target with high aluminum content, opening the titanium aluminum arc target with medium aluminum content, and continuing to deposit for a period of time; and finally closing the titanium-aluminum target with medium aluminum content, opening the titanium-aluminum arc target with low aluminum content, and depositing for a period of time. The gradient-structure TiAlSiYN multi-element nano coating is firmly combined with a substrate, has good toughness and antifriction performance, has good controllability and easy implementation, and is suitable for industrial production and application.

Description

Gradient structure TiAlSiYN multi-element nano coating and preparation method thereof
Technical Field
The invention belongs to the technical field of surface coatings of cutting tools, and particularly relates to a preparation method of a gradient structure TiAlSiYN multi-element nano coating.
Background
The preparation of a hard coating on the surface of a cutting tool not only can further enhance the hardness of the surface of the tool and resist abrasion, but also the coating can often hinder thermal diffusion and chemical diffusion. The TiAlSiN coating is a quaternary coating developed by adding a small amount of Si atoms on the basis of the TiAlN ternary coating. The Si element is usually in the form of net nc-Si in the coating4N3The continuous amorphous phase breaks through the mode that the coating grows according to a columnar structure, limits the growth of the wrapped TiAlN grains, refines the grains, and also serves as an interface phase to hinder dislocation motion and crack propagation, so that the TiAlSiN coating often has high hardness and even has a superhard effect. The TiAlSiN coating is also characterized in that Si element and O element are combined to generate compact SiO at high temperature2The oxide film can block and slow down the continuous diffusion of the O element in the environment to the coating, so the TiAlSiN coating also has good high-temperature oxidation resistance. The high hardness and the high oxidation resistance of the TiAlSiN coating make the TiAlSiN coating have potential application value, and the TiAlSiN coating is particularly suitable for high-speed cutting, dry cutting and precise cutting occasions, but the coating has large brittleness and internal stress,The disadvantage of low bonding strength limits the large area application.
Currently, the TiAlSiN coating is toughened and modified, so that the TiAlSiN coating has the comprehensive performance of being hard and tough and being well combined with a substrate, and the method is an important way for exerting the performance advantages of the TiAlSiN coating. Researches prove that other component elements are doped in the TiAlSiN quaternary coating, so that the toughness of the TiAlSiN coating can be effectively improved. J. Shi et al (doi: 10.1016/j. surfcoat.2011.12.027) report that a Cu block is embedded in a TiAlSi alloy target material, a Cu-doped TiAlSiCuN five-membered coating is prepared by co-sputtering TiAlSi alloy and Cu, after the Cu is doped, the coating is obviously softened, when about 1at.% of Cu is added into the coating, the hardness of the coating is reduced to 23GPa, and the hardness of the TiAlCuN five-membered coating is continuously reduced along with the increase of the content of the added Cu atoms; the Cu element can enhance the combination of the coating and the substrate, and compared with the critical load of 32N of the TiAlSiN coating, the critical load of the TiAlSiCuN coating can reach 50N. The report does not directly compare the change of the toughness of the coating before and after doping, and the Cu element has good toughening effect from the aspect of hardness change alone, but the sputtering coating method adopted by the report has low coating deposition efficiency, and the homogeneity and stability of the coating components are difficult to ensure by using the mosaic target. Y is a rare element with active chemical property, the high-temperature performance of the coating can be improved by doping the rare element in the coating, and T, Mori et al (doi: 10.1016/j. surfcoat.2012.10.050) utilize Ti63Al27Si10And Cr45Al53Y2The TiAlSiN/CrAlYN nano multilayer coating with different modulation periods is prepared by arc ion plating of two targets, and the hardness of the coating is about 37GPa, which is consistent with that of a TiAlSiN single-layer coating. Similarly, from the aspect of hardness change alone, no toughening phenomenon is found when the TiAlSiN coating is doped with two elements of Cr and Y.
Disclosure of Invention
The invention aims to provide a gradient structure TiAlSiYN multi-element nano coating aiming at the problems in the prior art.
The invention also aims to provide a preparation method of the gradient structure TiAlSiYN multi-component nano coating.
The gradient-structure TiAlSiYN multi-element nano coating provided by the invention is a five-element coating composed of five elements of Ti, Al, Si, Y and N, the coating structure is composed of three sublayers, namely an inner sublayer, a middle sublayer and an outer sublayer, the Al content in the sublayers from the inner sublayer to the outer sublayer is sequentially reduced, the Ti content is sequentially increased, the Al content in the inner sublayer is 15-20 at.%, the Ti content is 28-32 at.%, the Al content in the middle sublayer is 10-15 at.%, the Ti content is 32-36 at.%, the Al content in the outer sublayer is 7-10 at.%, the Ti content is 36-40 at.%, the contents of the elements Si, Y and N in the three sublayers are kept constant, the Si content is 1-3 at.%, the Y content is less than 0.1at.%, and the balance is N; the inner layer, the middle layer and the outer layer of the coating are formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the thickness of each modulation layer is within 30nm, and the thicknesses of the inner, middle and outer sub-layers are 0.6-1.2 um respectively.
In the coating, the average grain size of the coating is within 30nm, and the total thickness of the coating is 1.8-3.6 um.
The invention provides a preparation method of the gradient structure TiAlSiYN multi-element nano coating, which comprises the following steps:
A. loading the cleaned substrate into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the matrix;
C. depositing an inner layer with higher Al content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
D. depositing the intermediate layer by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
E. and depositing the outer layer with low Al content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering.
Wherein, in the step A, the step of vacuumizing and heating is to firstly vacuumize the back bottom to 5.8 multiplied by 10-2And when the pressure is lower than Pa, opening an auxiliary heating device on the furnace wall to heat the base body, simultaneously opening a rotating power supply to enable the base body to continuously rotate, and heating for 50-80 min until the temperature of the base body reaches 320-380 ℃.
In the step B of the method, the ion etching is to introduce argon into the vacuum chamber firstlyAdjusting the flow of argon gas to ensure that the pressure is 1.0-2.5 multiplied by 10-1Pa, then applying a direct current bias of-100 to-200V and a pulse bias of-200 to-400V to the substrate, and utilizing the ionized Ar+And etching the surface of the substrate for 30-80 min, and raising the temperature of the substrate to 360-420 ℃.
In the step C of the method, the inner layer with high Al content is deposited by sequentially closing the substrate bias voltage, closing argon and introducing nitrogen, adjusting the nitrogen flow to ensure that the working pressure is 1.9-2.6 Pa, and opening the high-alumina Ti100-xAlxAlloy target and Ti100-ySiyArc ion deposition of an alloy target, high-alumina Ti100-xAlxThe atomic content of the alloy target satisfies: x =60 to 67, Ti100-ySiyThe atomic content of the alloy target satisfies: y = 5-15, and high-aluminum Ti is adjusted100-xAlxAlloy target and Ti100-ySiyThe working power of each alloy target is 2-3 kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 1-2 kW, bias voltage of-80 to-120V is applied to the substrate, and deposition is performed for 20-40 min.
Wherein, in the step D of the method, the process of depositing the intermediate layer is to turn off the high-aluminum Ti100-xAlxAlloy target, open medium aluminum Ti100-xAlxAlloy target, medium Al Ti100-xAlxThe atomic content of the alloy target satisfies: x =50, medium aluminum Ti is adjusted100-xAlxThe working power of the alloy target is 2-3 kW, and Ti100-ySiyAnd keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and depositing for 20-40 min.
Wherein, in the step E of the method, the outer layer with lower Al element content is deposited by closing medium aluminum Ti100-xAlxAlloy target, open low-aluminum Ti100-xAlxAlloy target, low-Al Ti100-xAlxThe atomic content of the alloy target satisfies: x = 33-40, and low-aluminum Ti is adjusted100-xAlxThe working power of the alloy target is 2-3 kW, and Ti100-ySiyThe working power, Y target sputtering power, matrix bias voltage and working pressure of the alloy target are kept unchanged, and the alloy target is deposited for 20-40 minAnd (6) ending.
In the method, the coating equipment for preparing the gradient TiAlSiYN multi-element nano coating is a multi-target plasma enhanced cathodic arc plating and magnetron sputtering composite ion coating system, wherein the used deposition targets comprise 4 pairs of arc targets and 1 pair of sputtering targets, and the 4 pairs of arc targets are respectively high-aluminum Ti100-xAlxAlloy target, medium aluminum Ti100-xAlxAlloy target, low-aluminum Ti100-xAlxAlloy target and Ti100-ySiyAlloy targets, 1 pair of sputtering targets was a Y target, and 5 pairs of targets were controlled individually.
Compared with the prior art, the invention has the following advantages:
1) the gradient-structure TiAlSiYN multi-element nano coating provided by the invention is composed of an inner layer, a middle layer and an outer layer which are changed in components, firstly, the gradient structure is favorable for relieving internal stress in the coating, so that the toughness of the coating is increased, meanwhile, each sublayer is formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the crack expansion can be hindered by an interlayer interface in a multilayer structure, and the multilayer structure also breaks through a continuous columnar structure of the coating, so that the stress is released, and further the toughness of the coating is improved. The Y element in the coating can improve the high-temperature performance of the coating, and can purify grain boundaries or form YN with lower hardness, so that the toughness of the coating is further improved. In general, the TiAlSiYN multi-element nano coating with good toughness and hardness is obtained through the triple synergistic effect of the composition gradient structure, the interlayer interface and the rare earth Y element, so that the application range of the TiAlSiN coating is expanded.
2) The invention provides a preparation method of a gradient structure TiAlSiYN multi-element nano coating, which is a composite ion plating process mainly based on arc deposition and assisted by implanting trace elements through magnetron sputtering. The impurities adsorbed in the base material are released by heating before coating, and the ionized Ar + is adopted to carry out bombardment etching on the surface of the base body, so that the combination of the coating and the base body is enhanced, and the coating and the base body are combined well even if a transition layer process is not adopted. The cathode arc plating technology ensures high deposition rate, can save the time of the coating process, and is planted by the magnetron sputtering technologyThe trace elements can inhibit the component segregation phenomenon caused by using an excessively complicated arc alloy target to the maximum extent, ensure the stable components and performance of the coating, simultaneously, the sputtering has certain interference effect on the arc deposition process, so that the vertical growth rate of the coating is reduced, the transverse diffusion of deposited atoms is more sufficient, and the densification of the coating is facilitated. When coating, three groups of Ti with different Al contents are added100-xAlxThe preparation of the gradient component coating is easy to realize by the independent control and switching of the target, the operation process is simple and is easy to master and control.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 345 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 40min, and raising the temperature of the matrix to 397 ℃; closing the substrate bias voltage, closing argon gas, introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the high-aluminum Ti33Al67Alloy target and Ti85Si15The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti33Al67Alloy target and Ti85Si15The working power of each alloy target is 2.2kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 1.2kW, bias voltage of-100V is applied to the matrix, and deposition is performed for 30 min; shutting off high alumina Ti33Al67Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 2.2kW and Ti85Si15Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 30 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti67Al33Alloy target, adjusted low-aluminum Ti67Al33The working power of the alloy target is 2.2kW and Ti85Si15And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 30 min.
Through detection, in the embodiment, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating is 2.68um, the content of Al element in the innermost layer of the coating is 18.21at.%, the content of Ti element is 29.12at.%, the content of Si element is 1.88at.%, the content of Y element is 0.05at.%, and the content of N element is 50.74 at.%; the content of Al element in the intermediate layer was 13.82at.%, the content of Ti element was 34.48at.%, the content of Si element was 1.97at.%, the content of Y element was 0.05at.%, and the content of N element was 49.68 at.%; the outermost layer had an Al element content of 8.92at.%, a Ti element content of 38.88at.%, an Si element content of 1.92at.%, an Y element content of 0.06at.%, and an N element content of 50.22 at.%. The bonding strength of the coating and the substrate is 33N, the coating hardness is 28GPa, and the fracture toughness of the coating is 0.21 MPa.m1/2The friction coefficients of the coating at normal temperature and 400 ℃ are 0.63 and 0.65 respectively.
Example 2
Loading the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.0 × 10-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 325 ℃ after heating for 50 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.0 multiplied by 10-1Pa, then applying a DC bias of-100V and a pulsed bias of-200V to the substrate using ionized Ar+Etching the surface of the matrix for 30min, and raising the temperature of the matrix to 368 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 1.9Pa, and opening the high-aluminum Ti35Al65Alloy target and Ti95Si5The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti35Al65Alloy target and Ti95Si5The working power of each alloy target is 2kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 1kW, a bias voltage of-80V is applied to the substrate, and the deposition is performed for 20 min; shutting off high alumina Ti35Al65Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 2kW and Ti95Si5Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 20 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti65Al35Alloy target, adjusted low-aluminum Ti65Al35The working power of the alloy target is 2kW and Ti95Si5And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 20 min.
Through detection, in the embodiment, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating is 1.83um, the content of Al element in the innermost layer of the coating is 19.07at.%, the content of Ti element is 28.63at.%, the content of Si element is 1.21at.%, the content of Y element is 0.04at.%, and the content of N element is 51.05 at.%; the content of Al element in the intermediate layer was 14.67at.%, the content of Ti element was 32.59at.%, the content of Si element was 1.45at.%, the content of Y element was 0.04at.%, and the content of N element was 51.25 at.%; the outermost layer had an Al element content of 9.29at.%, a Ti element content of 37.03at.%, an Si element content of 1.42at.%, an Y element content of 0.04at.%, and an N element content of 52.22 at.%. The bonding strength of the coating and the substrate is 45N, the coating hardness is 26.7GPa, and the fracture toughness of the coating is 0.25 MPa-m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.65 and 0.69.
Example 3
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.5 multiplied by 10 after the back bottom is vacuumized-2When Pa is needed, the auxiliary heating device of the furnace wall is opened to heat the substrate, and the rotary power supply is turned on to heat the substrateThe body is ceaselessly rotated, and after heating for 80min, the temperature of the matrix reaches 377 ℃; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 2.5 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-400V to the substrate using ionized Ar+Etching the surface of the matrix for 80min, and raising the temperature of the matrix to 415 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.6Pa, and opening the high-aluminum Ti40Al60Alloy target and Ti85Si15The alloy target is subjected to arc ion deposition to adjust high-aluminum Ti40Al60Alloy target and Ti85Si15The working power of each alloy target is 3kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 2kW, a bias voltage of-80V is applied to the substrate, and the deposition is performed for 40 min; shutting off high alumina Ti40Al60Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 3kW and Ti85Si15Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 40 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti60Al40Alloy target, adjusted low-aluminum Ti60Al40The working power of the alloy target is 3kW and Ti85Si15And keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and finishing the deposition after 40 min.
Through detection, the total thickness of the gradient-structure TiAlSiYN multi-element nano coating in the embodiment is 3.47um, the content of Al element in the innermost layer of the coating is 15.86at.%, the content of Ti element is 31.53at.%, the content of Si element is 2.42at.%, the content of Y element is 0.07at.%, and the content of N element is 50.12 at.%; the content of Al element in the intermediate layer was 11.65at.%, the content of Ti element was 35.37at.%, the content of Si element was 2.61at.%, the content of Y element was 0.06at.%, and the content of N element was 50.31 at.%; the outermost layer had an Al element content of 7.39at.%, a Ti element content of 39.02at.%, an Si element content of 2.57at.%, an Y element content of 0.07at.%, and an N element content of 50.95 at.%. The bonding strength of the coating to the substrate was 32N, the coating hardness is 31.6GPa, and the coating fracture toughness is 0.19 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.59 and 0.62.
Example 4
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device on the furnace wall is opened to heat the matrix, a rotating power supply is turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 366 ℃ after heating for 70 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 2.0 multiplied by 10-1Pa, then applying a DC bias of-150V and a pulsed bias of-300V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 391 ℃; closing the substrate bias voltage, closing argon gas, introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.2Pa, and opening the high-aluminum Ti33Al67Alloy target and Ti90Si10Arc ion deposition of gold target to regulate high-alumina Ti33Al67Alloy target and Ti90Si10The working power of each alloy target is 2.5kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 2kW, a bias voltage of-90V is applied to the substrate, and the deposition is performed for 40 min; shutting off high alumina Ti33Al67Alloy target, open medium aluminum Ti50Al50Alloy target, adjusted medium Al Ti50Al50The working power of the alloy target is 2kW and Ti90Si10Keeping the working power of the alloy target, the sputtering power of the Y target, the bias voltage of the substrate and the working pressure unchanged, and depositing for 30 min; closing medium aluminum Ti50Al50Alloy target, open low-aluminum Ti67Al33Alloy target, adjusted low-aluminum Ti67Al33The working power of the alloy target is 3kW and Ti90Si10And continuously keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and depositing for 20 min.
Through detection, the total thickness of the gradient structure TiAlSiYN multi-element nano coating in the embodiment is 2.85um, and the innermost layer Al of the coatingThe element content was 17.72at.%, the Ti element content was 30.23at.%, the Si element content was 2.01at.%, the Y element content was 0.06at.%, and the N element content was 49.98 at.%; the content of Al element in the intermediate layer was 14.33at.%, the content of Ti element was 32.63at.%, the content of Si element was 2.76at.%, the content of Y element was 0.05at.%, and the content of N element was 50.23 at.%; the outermost layer had an Al element content of 7.86at.%, a Ti element content of 39.14at.%, an Si element content of 1.29at.%, an Y element content of 0.06at.%, and an N element content of 56.65 at.%. The bonding strength of the coating and the substrate is 37N, the coating hardness is 27.8GPa, and the fracture toughness of the coating is 0.23 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.61 and 0.65.
Comparative example 1
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device of the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 348 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 401 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the medium aluminum Ti50Al50Alloy target and Ti85Si15Alloy target, adjusted medium Al Ti50Al50Alloy target and Ti85Si15The working power of the alloy target is 2.2kW respectively, a bias voltage of-100V is applied to the substrate, and the deposition is finished after 90 min.
Through detection, the total thickness of the TiAlSiN multi-element nano coating in the comparative example is 3.3 microns, the content of Al element in the coating is 13.68at.%, the content of Ti element is 26.73at.%, the content of Si element is 2.26at.%, and the content of N element is 57.33 at.%. The bonding strength of the coating and the substrate is 30N, the coating hardness is 34.3GPa, and the fracture toughness of the coating is 0.09 MPa.m1/2The coating is at normal temperature and 400 DEG CThe coefficient of friction of (a) was 0.79 and 0.76.
Comparative example 2
Putting the cleaned substrate into a vacuum chamber of a multi-target plasma enhanced cathode arc plating and magnetron sputtering composite ion plating system, and vacuumizing the back to 5.7 multiplied by 10 when the back bottom is vacuumized-2When Pa is needed, an auxiliary heating device of the furnace wall is opened to heat the matrix, a rotating power supply is simultaneously turned on to enable the matrix to rotate ceaselessly, and the temperature of the matrix reaches 348 ℃ after heating for 60 min; then argon is introduced into the vacuum chamber, and the flow of the argon is adjusted to ensure that the pressure is 1.8 multiplied by 10-1Pa, then applying a DC bias of-200V and a pulsed bias of-350V to the substrate using ionized Ar+Etching the surface of the matrix for 60min, and raising the temperature of the matrix to 401 ℃; closing the substrate bias voltage, closing argon gas and introducing nitrogen gas in sequence, adjusting the nitrogen gas flow to ensure that the working pressure is 2.5Pa, and opening the medium aluminum Ti50Al50Alloy target and Ti85Si15Alloy target, adjusted medium Al Ti50Al50Alloy target and Ti85Si15The working power of the alloy target is 2.2kW respectively, a bias voltage of-100V is applied to the substrate, and the deposition is finished after 90 min.
Through detection, the total thickness of the TiAlSiYN multi-element nano coating in the comparative example is 2.7um, the content of Al element in the coating is 13.38at.%, the content of Ti element is 25.48at.%, the content of Si element is 2.58at.%, the content of Y element is 0.05at.%, and the content of N element is 58.51 at.%. The bonding strength of the coating and the substrate is 38N, the coating hardness is 26.6GPa, and the fracture toughness of the coating is 0.12 MPa.m1/2The friction coefficient of the coating at normal temperature and 400 ℃ is 0.67 and 0.74.

Claims (9)

1. The gradient-structure TiAlSiYN multielement nano coating is characterized in that the coating is a quinary coating composed of five elements of Ti, Al, Si, Y and N, the coating structure is composed of an inner sublayer, a middle sublayer and an outer sublayer which are different in components, the Al content of the sublayers from the inner sublayer to the outer sublayer is sequentially reduced, the Ti content is sequentially increased, the Al content of the inner sublayer is 15-20 at.%, the Ti content is 28-32 at.%, the Al content of the middle sublayer is 10-15 at.%, the Ti content is 32-36 at.%, the Al content of the outer sublayer is 7-10 at.%, the Ti content is 36-40 at.%, the contents of the Si, Y and N elements in the three sublayers are kept constant, the Si content is 1-3 at.%, the Y content is less than 0.1at.%, and the balance is N; the inner sublayer, the middle sublayer and the outer sublayer of the coating are formed by alternately depositing three modulation layers of TiSiN, TiAlN and YN, the thickness of each modulation layer is within 30nm, and the thickness of each of the inner sublayer, the middle sublayer and the outer sublayer is 0.6-1.2 mu m.
2. The gradient-structure TiAlSiYN multielement nano-coating according to claim 1, characterized in that the average grain size of the coating is within 30nm, and the total thickness of the coating is 1.8-3.6 μm.
3. The preparation method of the gradient structure TiAlSiYN multi-component nano coating according to any one of claims 1 to 2, characterized by comprising the following steps:
A. loading the cleaned substrate into a vacuum chamber of a coating device, vacuumizing and heating;
B. carrying out ion etching on the surface of the matrix;
C. depositing an inner layer with higher Al element content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
D. depositing the intermediate layer by using a composite ion plating technology of cathodic arc plating and magnetron sputtering;
E. and depositing the outer layer with low Al element content by using a composite ion plating technology of cathodic arc plating and magnetron sputtering.
4. The method for preparing the gradient-structured TiAlSiYN multi-component nano-coating according to claim 3, wherein in the step A, the vacuum-pumping and heating are performed by firstly vacuumizing the back substrate to 5.8 x 10-2And when the pressure is lower than Pa, opening an auxiliary heating device on the furnace wall to heat the base body, simultaneously opening a rotating power supply to enable the base body to continuously rotate, and heating for 50-80 min until the temperature of the base body reaches 320-380 ℃.
5. The method for preparing the gradient TiAlSiYN multi-component nano-coating according to claim 3, wherein in the step B,the ion etching is to introduce argon into a vacuum chamber firstly, and adjust the flow of the argon to ensure that the pressure is 1.0-2.5 multiplied by 10- 1Pa, then applying a direct current bias of-100 to-200V and a pulse bias of-200 to-400V to the substrate, and utilizing the ionized Ar+And etching the surface of the substrate for 30-80 min, and raising the temperature of the substrate to 360-420 ℃.
6. The method for preparing the gradient-structure TiAlSiYN multi-element nano coating according to claim 3, wherein the step C of depositing the inner layer with higher Al content comprises the steps of sequentially closing the substrate bias voltage, closing argon gas and introducing nitrogen gas, adjusting the nitrogen gas flow to ensure that the working pressure is 1.9-2.6 Pa, and opening high-aluminum Ti100-xAlxAlloy target and Ti100-ySiyArc ion deposition of an alloy target, high-alumina Ti100-xAlxThe atomic content of the alloy target satisfies: x =60 to 67, Ti100-ySiyThe atomic content of the alloy target satisfies: y = 5-15, and high-aluminum Ti is adjusted100-xAlxAlloy target and Ti100-ySiyThe working power of each alloy target is 2-3 kW, the Y target is started to perform sputtering deposition at the same time, the sputtering power is 1-2 kW, bias voltage of-80 to-120V is applied to the substrate, and deposition is performed for 20-40 min.
7. The method for preparing the gradient-structured TiAlSiYN multi-component nano-coating according to claim 3, wherein the intermediate layer is deposited in the step D by shutting off the high-aluminum Ti100-xAlxAlloy target, open medium aluminum Ti100-xAlxAlloy target, medium Al Ti100-xAlxThe atomic content of the alloy target satisfies: x =50, medium aluminum Ti is adjusted100-xAlxThe working power of the alloy target is 2-3 kW, and Ti100-ySiyAnd keeping the working power of the alloy target, the sputtering power of the Y target, the substrate bias voltage and the working pressure unchanged, and depositing for 20-40 min.
8. The method for preparing the gradient TiAlSiYN multi-component nano-coating according to claim 3, wherein in step E, Al component is depositedThe outer layer process with low element content is to close medium aluminum Ti100-xAlxAlloy target, open low-aluminum Ti100-xAlxAlloy target, low-Al Ti100-xAlxThe atomic content of the alloy target satisfies: x = 33-40, and low-aluminum Ti is adjusted100-xAlxThe working power of the alloy target is 2-3 kW, and Ti100-ySiyAnd keeping the working power, the Y target sputtering power, the matrix bias voltage and the working pressure of the alloy target unchanged, and finishing the deposition after 20-40 min.
9. The method for preparing the gradient-structure TiAlSiYN multi-component nano-coating according to any one of claims 3 to 8, characterized in that the coating equipment for preparing the gradient-structure TiAlSiYN multi-component nano-coating is a multi-target plasma enhanced cathodic arc plating and magnetron sputtering composite ion coating system, wherein the deposition targets used comprise 4 pairs of arc targets and 1 pair of sputtering targets, and the 4 pairs of arc targets are respectively high-alumina Ti100-xAlxAlloy target, medium aluminum Ti100-xAlxAlloy target, low-aluminum Ti100-xAlxAlloy target and Ti100-ySiyAlloy targets, 1 pair of sputtering targets was a Y target, and 5 pairs of targets were controlled individually.
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