AlTiSiMoVN multi-element nano composite coating as well as preparation method and application thereof

Abstract

The invention discloses an AlTiSiMoVN multi-element nano composite coating as well as a preparation method and application thereof. The preparation method comprises the following process steps: S1, ultrasonically cleaning a substrate; s2, the substrate is loaded to a sample holder and placed in a coating chamber, the temperature of the coating chamber is set to be 25-500 DEG C, and the vacuum degree is set to be 1.0 * 10 <-3 >-1.0 * 10 <-4 > Pa; s3, inert gas and nitrogen are introduced into the coating chamber, the flow ratio of the inert gas to the nitrogen is 1: 1-3: 1, the vacuum degree is set to be 0.5-2.0 Pa, and the bias voltage is set to be 0-200 V; and S4, an electric arc ion plating power supply and a magnetron sputtering power supply are started, an electric arc target AlTiSi target and a sputtering target MoV target are adopted, the current of the electric arc target is set to be 60-90 A, the power of the sputtering target is set to be 100-1000 W, and double-target co-deposition is conducted for 30-90 min. The AlTiSiMoVN multi-element nano composite coating is obtained by deposition according to the preparation method disclosed by the invention. The AlTiSiMoVN multi-element nano composite coating can be applied to a cutter coating or a surface lubricating coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating preparation, in particular to an AlTiSiMoVN multi-element nano-composite coating, a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the development of industrial manufacturing towards high efficiency, precision and green, the friction and wear scenarios such as cutting and die forming have put forward increasingly stringent requirements for coating materials. Although traditional liquid lubricants have a significant effect on reducing friction, their volatile and leaky characteristics not only pollute the environment, but also make it difficult to effectively apply in special working conditions such as high temperature, high speed or vacuum, and their use is greatly limited. Therefore, developing environmentally friendly, efficient and highly adaptable new dry solid lubricating coating materials has become an important direction to improve the performance of cutting tools, molds and wear-resistant parts and prolong their service life. Among many hard coating materials, transition metal nitrides such as TiN and CrN are widely used due to their good hardness, wear resistance and chemical stability. However, these coatings usually exhibit a high friction coefficient, and when working under no or little lubrication conditions, they still face serious wear problems, which limits their further application in high-precision and long-life processing fields. In order to improve this situation, researchers are constantly exploring new coating systems with self-lubricating properties.

[0003] Researchers have found that introducing multiple elements into a single nitride matrix to form a multi-element alloyed coating can significantly optimize the overall performance of the coating. For example, the incorporation of aluminum (Al) can further increase the hardness of the coating due to solid solution strengthening, and a thin and dense Al2O3 film can be easily formed on the surface at high temperatures, effectively improving the oxidation resistance and high-temperature wear resistance of the coating. In addition, the introduction of lubricating phase elements such as molybdenum (Mo) or vanadium (V) not only helps to improve the hardness of the coating, but also the Mo-O or V-O lubricating phase oxides formed on the friction surface have good self-lubricating effect, effectively reducing the friction coefficient of the coating. In order to further improve the overall performance of the coating, especially the synergistic effect of wear resistance and lubricity, the introduction of silicon (Si) element has become a promising exploration direction. The addition of silicon (Si) can bring many benefits: on the one hand, Si can promote the formation of nanocrystalline structure during the growth of the coating, or even form a nano-composite structure (such as nanocrystalline / amorphous structure), which can significantly improve the hardness and toughness of the coating and improve its wear resistance. On the other hand, Si may form silicon oxide (Si-O) with lubricating effect during the friction process of the coating surface, or interact with the oxides of Mo and V to form new composite oxide lubricating phases, thereby possibly widening the effective self-lubricating temperature range of the coating and possibly improving its lubricating stability in different temperature ranges.

[0004] Although the introduction of Si elements may bring potential advantages, the complex system of the coexistence of Al, Ti, Si, Mo, V, N six elements, the phase composition, microstructure, element distribution and the interaction between elements will be more complex. How to accurately control the ratio of each element, so that it forms an ideal nano composite structure in the coating, and ensures that the Si element can effectively promote the formation of a lubricating phase or structure with excellent comprehensive performance (high hardness, high wear resistance, wide temperature range self-lubricating), while avoiding the performance degradation caused by the possible harmful phase precipitation or element segregation, is still a technical problem to be solved.

[0005] Therefore, it is of important theoretical significance and application value to develop a technical scheme that can effectively regulate the Al, Ti, Si, Mo, V, N multi-element system and obtain an AlTiSiMoVN multi-element nano composite coating with excellent performance, which is also the key problem that the present application focuses on solving. SUMMARY

[0006] To solve at least one of the above technical problems, the present application provides an AlTiSiMoVN multi-element nano composite coating and a preparation method and application, and the technical scheme adopted is as follows.

[0007] The present application provides a preparation method of an AlTiSiMoVN multi-element nano composite coating, and the preparation method comprises the following process steps:

[0008] S1, ultrasonic cleaning the substrate;

[0009] S2, loading the substrate to the sample holder and putting it into the coating chamber, setting the temperature of the coating chamber to 25 to 500 DEG C, and setting the vacuum degree to 1.0*10 -3 to 1.0*10 -4 Pa;

[0010] S3, introducing inert gas and nitrogen into the coating chamber, the flow ratio of inert gas and nitrogen is 1:1 to 3:1, the vacuum degree is set to 0.5 to 2.0 Pa, and the bias voltage is set to 0 to-200 V;

[0011] S4, turn on the arc ion plating power supply and the magnetron sputtering power supply, use arc target AlTiSi target and sputtering target MoV target, set the current of the arc target to 60 to 90 A, set the power of the sputtering target to 100 to 1000 W, and co-deposit for 30 to 90 min.

[0012] In some embodiments of the present application, the rotation speed of the sample holder is set to 1 to 10 rpm, and the target base distance of the arc target and the sputtering target is set to 100 to 300 mm.

[0013] In some embodiments of the present application, the atomic ratio of the elements in the AlTiSi target is set to be Al:Ti:Si = 60:30:10 at.%.

[0014] In some embodiments of the present application, the atomic ratio of the elements in the MoV target is set to be Mo:V = 50:50 at.%.

[0015] In some embodiments of the present application, the substrate is high-speed steel or cemented carbide.

[0016] The AlTiSiMoVN multi-element nanocomposite coating provided by the present application is obtained by using the preparation method as described above.

[0017] In some embodiments of the present application, the atomic percentage of the elements in the AlTiSiMoVN multi-element nanocomposite coating is respectively Al: 15-25 at.%, Ti: 7-15 at.%, Si: 5-10 at.%, Mo: 0-10 at.%, V: 0-10 at.%, and N: 50-65 at.%.

[0018] In some embodiments of the present application, the hardness of the AlTiSiMoVN multi-element nanocomposite coating is 30-40 GPa.

[0019] In some embodiments of the present application, the thickness of the AlTiSiMoVN multi-element nanocomposite coating is 1.0-3.0 μm.

[0020] The AlTiSiMoVN multi-element nanocomposite coating provided by the present application can be applied to tool coating or surface lubricating coating.

[0021] Compared with the prior art, the present application has at least the following beneficial effects: the AlTiSiMoVN multi-element nanocomposite coating utilizes the composite and synergistic effect of multi-element, while maintaining high hardness and excellent wear resistance, introduces Si, Mo, V and other elements into the coating by precisely controlling the ratio of each element, and realizes the synergistic optimization of wide temperature range self-lubrication and wear resistance of the coating. The AlTiSiMoVN multi-element nanocomposite coating has excellent wear resistance and wide temperature range self-lubrication, and can adapt to more harsh working environments, greatly expanding its application potential.

[0022] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0023] The present application will be further illustrated below in conjunction with the drawings and examples. It should be noted that the examples embodied in the following drawings are exemplary and are used to explain the present application, and cannot be understood as a limitation of the present application.

[0024] Figure 1 Figure 1 is a schematic diagram of a structure inside a coating chamber, where L1 and L2 are target-substrate distances.

[0025] Figure 2 Figure 2 is a SEM surface image of a coating layer in each embodiment, where the Mo+V content is: (a) 1.4 at.%; (b) 3.8 at.%; (c) 6.8 at.%; (d) 10.6 at.%.

[0026] Figure 3 Figure 3 is a SEM cross-sectional image of a coating layer in each embodiment, where the Mo+V content is: (a) 1.4 at.%; (b) 3.8 at.%; (c) 6.8 at.%; (d) 10.6 at.%.

[0027] Figure 4 Figure 4 is a graph of the friction coefficient of a coating layer in each embodiment. DETAILED DESCRIPTION

[0028] The embodiments of the present application will be described below in conjunction with Figures 1 to 4 The embodiments of the present application will be described below in conjunction with

[0029] In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "center", "middle", "lengthwise", "widthwise", "thickness", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "axial", "radial", "circumferential" and the like are based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the device or element indicated must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0030] In the description of the present application, if the meaning of several is more than one, the meaning of multiple is more than two, greater than, less than, more than, etc. are understood as not including the number, above, below, within, etc. are understood as including the number. If it is described as first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features or the sequence of indicated technical features.

[0031] In the description of the application, unless otherwise explicitly specified and limited, the terms "arrangement", "installation", "connected", "connected" should be understood broadly, for example: it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium, or it can be connected inside two elements. For those skilled in the art, the specific meaning of the above terms in this application can be understood according to the specific circumstances.

[0032] In the description of the application, if the description of the terms "one embodiment", "some embodiments", "one example", "some examples", "some embodiments", "illustrative embodiments", "example", "specific example", "some examples" appears, it means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the application. In this specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0033] The application relates to an AlTiSiMoVN multi-element nanocomposite coating, which is prepared by adopting the composite deposition of arc ion plating technology and magnetron sputtering technology.

[0034] The atomic percentage content of elements in the AlTiSiMoVN multi-element nanocomposite coating is as follows: Al: 15-25 at.%, Ti: 7-15 at.%, Si: 5-10 at.%, Mo: 0-10 at.%, V: 0-10 at.%, and N: 50-65 at.%. The AlTiSiMoVN multi-element nanocomposite coating is obtained by optimizing the element ratio, and has a coating structure with good wear resistance and wide-temperature-range self-lubricating property, which can significantly reduce the friction coefficient of the coating in the friction process and improve the comprehensive tribological property.

[0035] It can be understood that the AlTiSiMoVN multi-element nanocomposite coating is designed by carefully designing the combination and ratio of Al, Ti, Si, Mo, V and N elements, aiming to utilize the synergistic effect between elements, effectively introduce or promote the formation of phases or structures with self-lubricating function while maintaining high hardness and excellent wear resistance of the coating. Specifically, the solid solution strengthening effect of Al and the Al2O3 film formed at high temperature can improve the hardness and high-temperature oxidation resistance of the coating. The introduction of Si can not only promote the formation of nanocrystalline or nanocomposite structure to enhance the hardness and toughness of the coating, but also form silicon oxide with lubricating effect or synergistically act with Mo and V oxides. Mo and V can form Mo-O and V-O lubricating phases on the friction surface of the coating to provide self-lubricating effect in different temperature ranges.

[0036] In some examples, the AlTiSiMoVN multi-element nanocomposite coating has a hardness of 30 to 40 GPa.

[0037] In some examples, the AlTiSiMoVN multi-element nanocomposite coating has a thickness of 1.0 to 3.0 μm.

[0038] The present application relates to the application of an AlTiSiMoVN multi-element nanocomposite coating, which can be applied to tool coatings or surface lubrication coatings, especially suitable for working conditions sensitive to friction and wear, requiring low friction coefficient and long service life, improving processing or running accuracy and efficiency. Specific application scenarios include but are not limited to: high-speed cutting tools such as drills, milling cutters, turning tools, etc., to improve cutting efficiency and tool life; wear-resistant molds such as stamping molds, injection molds, etc., to reduce mold wear, improve product precision and mold service life; precision mechanical parts such as bearings, gears, piston rings, etc., to reduce running friction, reduce energy consumption, and improve equipment running efficiency and reliability.

[0039] The present application relates to a preparation method of an AlTiSiMoVN multi-element nanocomposite coating, which uses arc ion plating technology and magnetron sputtering technology to deposit the AlTiSiMoVN multi-element nanocomposite coating.

[0040] The preparation method comprises the following process steps.

[0041] S1, ultrasonic cleaning of the substrate;

[0042] S2, loading the substrate into the sample holder and placing it in the coating chamber, setting the temperature of the coating chamber to 25 to 500℃, and setting the vacuum degree to 1.0*10 -3 to 1.0*10 -4 Pa;

[0043] S3, introducing inert gas and nitrogen into the coating chamber, the flow ratio of inert gas and nitrogen being 1:1 to 3:1, the vacuum degree being set to 0.5 to 2.0 Pa, and the bias voltage being set to 0 to -200 V;

[0044] S4, turning on the arc ion plating power supply and the magnetron sputtering power supply, using an arc target AlTiSi target and a sputtering target MoV target, setting the current of the arc target to 60 to 90 A, setting the power of the sputtering target to 100 to 1000 W, and co-depositing for 30 to 90 min.

[0045] It should be noted that in step S1, the substrate is made of high-speed steel or hard alloy. The mirror-polished substrate is placed in an ultrasonic cleaner and ultrasonically cleaned with acetone and anhydrous ethanol for 10 to 20 min, and then dried and fixed on the sample holder in the coating chamber.

[0046] In the process of starting deposition in steps S3 and S4, the rotation speed of the sample holder is set to 1 to 10 rpm, and the target base distance of the arc target and the sputtering target is set to 100 to 300 mm.

[0047] In step S4, the atomic ratio of the elements in the AlTiSi target is set to Al:Ti:Si = 60:30:10 at.%. The atomic ratio of the elements in the MoV target is set to Mo:V = 50:50 at.%.

[0048] After the deposition is completed, the arc ion plating power supply, the magnetron sputtering power supply, the bias power supply, the temperature control power supply, the gas flow valve, and the like are turned off, and the sample is taken out after the temperature of the film deposition chamber is reduced to room temperature.

[0049] It can be understood that the preparation method of the present application aims to accurately control the process parameters, adopt the arc ion plating and magnetron sputtering composite deposition technology, accurately control the input ratio of each element by designing a multi-element composite target or adopting multi-target co-deposition, and optimize the deposition process parameters such as power, gas pressure, bias voltage, chamber temperature, etc., to accurately control the chemical composition, microstructure (such as promoting the formation of nanocrystalline or amorphous composite structure) and stress state of the coating. Through process control, it is ensured that the prepared coating can realize effective combination and synergy of each element, and obtain the excellent comprehensive performance required by the target, that is, a good balance of high hardness, high wear resistance and wide temperature range self-lubricity.

[0050] Compared with the prior art, the scheme of the present application has at least the following beneficial effects.

[0051] The synergy optimization of wear resistance and wide temperature range self-lubricity is achieved: during the deposition process, the combination and synergy effect of multi-element is ingeniously utilized, the ratio of each element is accurately controlled, not only the high hardness and excellent wear resistance of the coating are maintained, but also multi-element is introduced. The introduction of Si element not only helps to form a nanocomposite structure, improve the hardness and toughness of the coating, but also forms a Si-O phase with lubricating effect, and produces a synergistic effect with Mo-O, V-O and other lubricating phases, so that the friction coefficient can be kept low and stable in a wider temperature range (from low temperature to high temperature), effectively solving the problem of poor lubricating effect of existing single or binary lubricating phases in a specific temperature range, and significantly improving the comprehensive tribological performance of the coating under complex working conditions.

[0052] The application range of the coating material is widened: due to the excellent wear resistance and wide temperature range self-lubricity of the AlTiSiMoVN multi-element nanocomposite coating, it can adapt to more severe working environments such as high temperature, high speed, dry friction and even partial vacuum conditions, overcoming the shortcomings that traditional liquid lubricants are easy to fail under these conditions and the limitation that single solid lubricating coating has a narrow applicable temperature range, greatly expanding the application potential of the coating.

[0053] The content of the present application will be described in detail below in conjunction with specific examples. It should be noted that the following description is only exemplary and is not a specific limitation on the present application.

[0054] Example 1

[0055] The preparation method comprises the following process steps.

[0056] S1, ultrasonic cleaning of the mirror-polished substrate.

[0057] S2, the substrate is loaded into a sample holder and placed into a coating chamber, the temperature of the coating chamber is set to 200°C, and the vacuum degree is set to 9.0*10 -4 Pa, the rotation speed of the sample holder is set to 5rpm;

[0058] S3, argon and nitrogen are introduced into the coating chamber, the flow rate ratio of argon and nitrogen is set to 1:1, the vacuum degree is set to 1.0Pa, and the bias voltage is set to -100V;

[0059] S4, turn on the arc ion plating power supply and the magnetron sputtering power supply, use an arc target AlTiSi target and a sputtering target MoV target, the current of the arc target is set to 80A, the power of the sputtering target is set to 200W, and the deposition time is 30min.

[0060] An AlTiSiMoVN multi-element nanocomposite coating is obtained by deposition, and the coating thickness is 1.4μm. The atomic percentage content of each element in the coating is Al: 20.4at.%, Ti: 8.3at.%, Si: 7.5at.%, Mo: 0.8at.%, V: 0.6at.%, and N: 62.4at.%.

[0061] Example 2

[0062] Compared with Example 1, the difference of Example 2 is that the power of the sputtering target in step S4 is set to 300W.

[0063] An AlTiSiMoVN multi-element nanocomposite coating is obtained by deposition, and the coating thickness is 1.4μm. The atomic percentage content of each element in the coating is Al: 20.4at.%, Ti: 8.3at.%, Si: 7.5at.%, Mo: 0.8at.%, V: 0.6at.%, and N: 62.4at.%.

[0064] Example 3

[0065] Compared with Example 1, the difference of Example 3 is that the power of the sputtering target in step S4 is set to 400W.

[0066] The AlTiSiMoVN multi-element nanocomposite coating is obtained by deposition, and the thickness of the coating is 1.5 μm. The atomic percentage content of each element in the coating is Al: 21.5 at.%, Ti: 9.2 at.%, Si: 8.0 at.%, Mo: 3.5 at.%, V: 3.3 at.%, and N: 54.5 at.%.

[0067] Example 4

[0068] Compared with Example 1, the difference of Example 4 is that the power of the sputtering target in step S4 is set to 500 W.

[0069] The AlTiSiMoVN multi-element nanocomposite coating is obtained by deposition, and the thickness of the coating is 1.6 μm. The atomic percentage content of each element in the coating is Al: 20.5 at.%, Ti: 8.7 at.%, Si: 7.7 at.%, Mo: 5.5 at.%, V: 5.1 at.%, and N: 52.5 at.%.

[0070] The AlTiSiMoVN multi-element nanocomposite coating obtained in each example is subjected to structural characterization and performance testing.

[0071] Figure 2 The SEM surface images of the coatings in each example are shown in FIG. 1. Figure 2 It can be seen that the coating surface presents obvious large particles, and the particle defects on the coating surface gradually decrease with the increase of the Mo+V content.

[0072] Figure 3 The SEM cross-sectional images of the coatings in each example are shown in FIG. 2. Figure 3 It can be seen that the coating presents a dense fine-grained structure.

[0073] Figure 4 The friction coefficient diagrams of the coatings in each example are shown in FIG. 3. Figure 4 It can be seen that with the increase of the Mo+V content, the friction coefficient of the coating at room temperature RT and high temperature 800℃ both presents a gradually decreasing trend, which indicates that the coating exhibits excellent tribological performance in a wide temperature range.

[0074] The embodiments of the present application are described in detail above with reference to the accompanying drawings, but the present application is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A method for preparing AlTiSiMoVN multi-element nanocomposite coating, characterized in that: comprising S1, ultrasonic cleaning the substrate; S2, the substrate is loaded to the sample holder and put into the coating chamber, the temperature of the coating chamber is set to 25 to 500℃, the vacuum degree is set to 1.0*10 -3 Pa; the coating process is carried out. -4 Pa; the coating process is carried out. S3, the film coating chamber is connected with inert gas and nitrogen gas, the flow ratio of the inert gas and the nitrogen gas is 1:1 to 3:1, the vacuum degree is set to 0.5 to 2.0 Pa, and the bias voltage is set to 0 to -200 V; S4, the arc ion plating power supply and the magnetron sputtering power supply are turned on, an arc target AlTiSi target and a sputtering target MoV target are used, the current of the arc target is set to 60 to 90 A, the power of the sputtering target is set to 100 to 1000 W, and the double targets are co-deposited for 30 to 90 min.

2. The method for preparing the AlTiSiMoVN multi-element nanocomposite coating according to claim 1, characterized in that: The rotation speed of the sample holder is set to 1 to 10 rpm, and the target-substrate distance of the arc target and the sputtering target is set to 100 to 300 mm.

3. The method for preparing the AlTiSiMoVN multi-element nanocomposite coating according to claim 1, characterized in that: The atomic ratio of the elements in the AlTiSi target is set to Al:Ti:Si=60:30:10 at.%.

4. The method for preparing the AlTiSiMoVN multi-element nanocomposite coating according to claim 1, characterized in that: The atomic ratio of the elements in the MoV target is set to Mo:V=50:50 at.%.

5. The method for preparing the AlTiSiMoVN multi-element nanocomposite coating according to claim 1, characterized in that: The substrate is high-speed steel or cemented carbide.

6. An AlTiSiMoVN multi-element nanocomposite coating, characterized by: The AlTiSiMoVN multi-element nanocomposite coating is deposited by the preparation method according to any one of claims 1 to 5.

7. The AlTiSiMoVN multicomponent nanocomposite coating according to claim 6, characterized in that: The atomic percentage of the elements in the AlTiSiMoVN multi-element nanocomposite coating is 15 to 25 at.% for Al, 7 to 15 at.% for Ti, 5 to 10 at.% for Si, 0 to 10 at.% for Mo, 0 to 10 at.% for V, and 50 to 65 at.% for N.

8. The AlTiSiMoVN multi-element nanocomposite coating according to claim 6, characterized in that: The hardness of the AlTiSiMoVN multi-element nanocomposite coating is 30 to 40 GPa.

9. The AlTiSiMoVN multi-element nanocomposite coating according to claim 6, characterized in that: The thickness of the AlTiSiMoVN multi-element nanocomposite coating is 1.0 to 3.0 μm.

10. Use of an AlTiSiMoVN multinary nanocomposite coating, characterized in that: The AlTiSiMoVN multi-element nanocomposite coating according to any one of claims 6 to 9 can be applied to a cutting tool coating or a surface lubricating coating.

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