VMoSiN tough wear-resistant coating as well as preparation method and application thereof

Abstract

The invention provides a VMoSiN tough wear-resistant coating as well as a preparation method and application thereof, and particularly relates to the technical field of functional coating materials. The VMoSiN tough and wear-resistant coating is of a uniform nanocrystalline structure, and the VMoSiN tough and wear-resistant coating comprises a VMoSiN phase, a VN phase, a V2N phase and a MoN phase. Compared with the prior art, the preparation method disclosed by the invention has the advantages that the collaborative optimization of the coating performance is realized by constructing a multi-phase composite nanocrystalline structure of VMoSiN, VN, V2N and MoN. The high hardness and wear resistance of the coating are jointly ensured by multiple hard phases; and a multiphase interface can effectively passivate cracks and deflect microcracks, so that the toughness and the bearing capacity of the coating are remarkably enhanced. The uniform nanocrystalline structure further strengthens the effect, so that the coating has excellent hardness, toughness, wear resistance and structural stability at the same time, and the inherent contradiction that the obdurability of a traditional single-phase or ternary coating is difficult to consider at the same time is overcome.

Description

Technical Field

[0001] This invention relates to the field of functional coating materials technology, and more specifically, to a VMoSiN tough and wear-resistant coating, its preparation method, and its application. Background Technology

[0002] Traditional transition metal nitride coatings such as titanium nitride (TiN) and chromium nitride (CrN) have been widely used as surface protective layers for critical components such as cutting tools and molds due to their high hardness, good chemical stability, and wear resistance, effectively improving their service life and machining accuracy. However, with the increasing demand for machining difficult-to-machine materials (such as nickel-based superalloys and titanium alloys) in aerospace, precision manufacturing, and other fields, these traditional coatings are gradually revealing their limitations under extreme cutting conditions such as high speed, high temperature, and heavy load. On the one hand, their inherent brittleness and insufficient toughness make the coating prone to microcracks and peeling under impact loads, leading to premature tool failure. On the other hand, their poor high-temperature wear resistance and lubrication performance, along with their high coefficient of friction, easily generate a large amount of frictional heat during dry or semi-dry high-speed cutting, exacerbating tool wear and making it difficult to meet the stringent requirements of modern high-efficiency machining for the comprehensive performance of cutting tools.

[0003] To improve the toughness and high-temperature tribological properties of coatings, researchers have attempted to introduce various alloying elements for composite modification. Among them, vanadium (V) and molybdenum (Mo) have attracted widespread attention due to their unique properties. Studies have shown that oxides of V and Mo (such as V₂O₅ and MoO₃) can form a lubricating film with a Magnéli phase during high-temperature friction, which can significantly reduce the coefficient of friction of the coating and endow it with excellent high-temperature self-lubricating properties. Incorporating V and Mo into nitride coatings can form complex (V,Mo)N solid solutions or composite phase structures. By constructing a mixed network of strong and weak covalent-metallic bonds, high hardness can be maintained while effectively improving the coating's toughness, crack propagation resistance, and thermal stability.

[0004] Furthermore, the introduction of silicon (Si) has proven to be an effective means of further optimizing the performance of nitride coatings. Si doping can significantly refine the coating grains, promote the formation of amorphous Si3N4 grain boundary phases, thereby encapsulating the nanocrystals, inhibiting grain boundary slip and crack propagation, and enhancing the toughening effect of the coating. Simultaneously, the presence of the amorphous phase can also improve the high-temperature oxidation resistance of the coating and help form a denser lubricating oxide film at the friction interface.

[0005] Although V-Mo-N based coatings have shown promising application potential, most current research still focuses on ternary systems. How to prepare a nanocrystalline composite coating that simultaneously possesses high hardness, high toughness, excellent high-temperature wear resistance, and self-lubricating properties through multi-component synergistic design, particularly by introducing Si into the V-Mo-N system and precisely controlling the atomic ratios and phase composition of each element, remains a pressing technical challenge in this field. Existing preparation techniques often struggle to achieve precise control over the proportions of multiple elements and the nanocrystalline structure in a one-step deposition process, or require subsequent heat treatment, which can introduce adverse effects such as grain coarsening and increased internal stress.

[0006] Therefore, developing a V-Mo-Si-N quaternary tough and wear-resistant coating with controllable composition and structure and more comprehensive performance, as well as its efficient and stable preparation method, is of great significance for promoting the development of next-generation high-performance tool coating technology. Summary of the Invention

[0007] To overcome the shortcomings of the prior art, the present invention provides a VMoSiN tough and wear-resistant coating, its preparation method and application.

[0008] The first aspect of the present invention provides a VMoSiN tough and wear-resistant coating, wherein the VMoSiN tough and wear-resistant coating has a uniform nanocrystalline structure and comprises a VMoSiN phase, a VN phase, a V2N phase and a MoN phase.

[0009] Compared with existing technologies, this invention achieves synergistic optimization of coating performance by constructing a multiphase composite nanocrystalline structure of VMoSiN, VN, V2N, and MoN. Multiple hard phases collectively ensure the coating's high hardness and wear resistance; while the multiphase interface effectively passivates cracks and deflects microcracks, significantly enhancing the coating's toughness and load-bearing capacity. The uniform nanocrystalline structure further strengthens these effects, enabling the coating to simultaneously possess excellent hardness, toughness, wear resistance, and structural stability, overcoming the inherent contradiction of traditional single-phase or ternary coatings that struggle to balance strength and toughness.

[0010] In one possible implementation, the VMoSiN tough and wear-resistant coating contains, by atomic percentage, 1-10% Si and 40-55% N; the atomic ratio of V to Mo is (0.8-1.2):1.

[0011] Compared to existing technologies, this composition design, by controlling the Si content at 1-10 at%, leverages its advantages in fine-grain toughening and amorphous interface formation while avoiding excessive hardness reduction due to excessive Si. Maintaining the N content at 40-55 at% ensures sufficient nitride formation, while strictly limiting the V / Mo atomic ratio to 0.8-1.2 allows V and Mo to form a stable coherent solid solution structure, fully utilizing their synergistic effect in building a strong and tough network and high-temperature self-lubricating properties, which is key to achieving the coating's core performance.

[0012] In one possible implementation, the thickness of the VMoSiN tough and wear-resistant coating is 0.1-10 μm.

[0013] Compared to existing technologies, the coating thickness range of 0.1-10 μm offers superior engineering applicability and reliability. This thickness ensures the formation of a continuous, dense protective layer, providing sufficient wear life, while also effectively controlling deposition stress to guarantee excellent adhesion between the coating and the substrate. This prevents peeling due to excessive thickness or premature failure due to insufficient thickness, meeting the stringent requirements of most cutting tools for coating thickness and overall performance.

[0014] The second objective of this invention is to provide a method for preparing a VMoSiN tough and wear-resistant coating, the method specifically comprising the following steps: S1. Perform plasma glow etching on the substrate; S2. In an argon and nitrogen working atmosphere, a VMo alloy target is used as a high-power pulse sputtering target and a Si target is used as a DC sputtering target. A DC composite high-power pulse magnetron sputtering method is used to deposit a VMoSiN tough and wear-resistant coating on the substrate surface treated by plasma glow etching in step S1.

[0015] Compared with existing technologies, this preparation method has the advantage of employing a one-step in-situ synthesis of multiphase composite structures. By combining high-power pulse and DC technologies, the high ionization rate sputtering of the VMo alloy target and the stable doping of the Si target are independently optimized, achieving precise and synergistic control of the multi-element composition. Combined with the efficient cleaning and activation of the substrate by plasma glow etching in the early stage, excellent film-substrate adhesion of the coating is ensured. This process eliminates the need for subsequent heat treatment, avoids grain coarsening, and directly obtains a dense, high-performance nanocrystalline coating. The process is simple, efficient, and highly controllable.

[0016] In one possible implementation, the parameters for the plasma glow etching process in step S1 are as follows: vacuum degree ≤ 5 × 10⁻⁶. -6 For Torr etching, the substrate temperature is 100-500 ℃, the argon flow rate is 20-80 sccm, the substrate bias voltage is -600 to -300 V, and the etching time is 10-60 min.

[0017] Compared to existing technologies, this parameter combination effectively avoids impurity contamination through an ultra-high vacuum environment, providing a clean environment for subsequent deposition. The substrate temperature is controlled within the aforementioned range, promoting surface atomic activation without causing changes in the substrate structure. A moderate argon flow rate combined with a high negative bias generates high-energy argon ions to bombard and clean the substrate surface, effectively removing oxide layers and contaminants while simultaneously creating microscopic defects. The etching time described above ensures atomic-level surface cleanliness and the formation of an activated layer, providing an excellent bonding foundation for the coating and fundamentally solving the industry problem of insufficient film-substrate adhesion.

[0018] In one possible implementation, in step S1, the substrate is selected from one of titanium alloys, nickel-based superalloys, cemented carbides, stainless steel, and high-speed steel.

[0019] Compared to existing technologies, the above selections cover mainstream cutting tool and key component materials such as titanium alloys, nickel-based superalloys, cemented carbide, stainless steel, and high-speed steel, demonstrating the broad applicability of this technology. In particular, for difficult-to-machine nickel-based superalloys and titanium alloys, this coating effectively provides surface protection; its application on cemented carbide and high-speed steel can directly improve the performance of traditional cutting tools. This multi-substrate adaptability greatly expands the application scenarios of this technology, meeting the surface strengthening requirements of cutting tools made from different materials in fields such as aerospace and precision manufacturing.

[0020] In one possible implementation, in step S2, the VMo alloy target and the Si target are respectively fixed to two magnetron cathodes, and the surface of the substrate is parallel to the line connecting the center of the target surface of the two magnetron cathodes.

[0021] Compared to existing technologies, the innovative design of independently mounting VMo alloy and Si targets on two magnetron cathodes enables precise control of multi-element co-deposition. The arrangement of the substrate surface parallel to the center line connecting the two target surfaces ensures uniform mixing of the two sputtered particle streams on the substrate surface, avoiding component segregation and concentration gradients. This configuration provides the necessary conditions for forming a VMoSiN composite coating with uniform composition and consistent structure, and is a key guarantee for achieving repeatable coating performance.

[0022] In one possible implementation, the magnetron cathode is a circular planar magnetron cathode with an included angle of 120°.

[0023] Compared to existing technologies, the optimized cathode angle ensures a uniform distribution of plasma regions generated by the two magnetron cathodes within the cavity. This angular configuration guarantees sufficient target utilization while allowing the sputtered particle stream to uniformly cover the substrate surface, ensuring the uniformity of coating thickness and composition on the three-dimensionally complex substrate. The choice of a circular planar magnetron cathode further enhances plasma stability, providing a reliable guarantee for large-scale industrial production.

[0024] In one possible implementation, the distance between the substrate surface and the line connecting the center of the target surface of the two magnetron cathodes is 5-12 cm.

[0025] Compared to existing technologies, the aforementioned distance range has been carefully optimized to achieve the best balance between deposition rate and film quality. This distance ensures that sputtered particles have sufficient kinetic energy to complete the migration process before reaching the substrate surface, forming a dense coating structure, while avoiding thermal effects and stress concentration problems caused by excessively close distances. This parameter setting is crucial for obtaining nanocrystalline coatings with good crystallinity and interfacial bonding.

[0026] In one possible implementation, the parameters of the DC-DC composite high-power pulsed magnetron sputtering method in step S2 are as follows: working gas pressure is 2-10 mTorr, the pulse bias voltage of the substrate is -150 to -20 V, the argon flow rate is 10-40 sccm, the nitrogen flow rate is 5-30 sccm, the DC sputtering power is 10-100 W, and the average power of the high-power pulsed magnetron sputtering is 100-200 W.

[0027] Compared with existing technologies, the above deposition parameters enable precise control of the film formation process: the working gas pressure optimizes plasma characteristics; the pulsed bias voltage controls the energy of the deposited particles; the dual gas flow ratio regulates the degree of reaction; and the dual power supply parameters independently control the deposition rates of VMo and Si. The synergistic effect of these parameters ensures that the VMoSiN coating can form an ideal multiphase nanocrystalline structure in situ, avoiding the need for subsequent heat treatment.

[0028] In one possible implementation, the duty cycle of the pulse bias is 1-10%, and the frequency is 300-1000 Hz.

[0029] Compared to existing technologies, the aforementioned pulsed bias scheme with a duty cycle and a frequency of 3 achieves a "soft bombardment" effect on the deposited particles. This intermittent energy input can generate sufficient bombardment on the growing coating, refining the grains and increasing density, while avoiding overheating and defect accumulation problems caused by continuous bias. This technology effectively controls the internal stress state of the coating, maintaining good film-substrate adhesion while improving coating performance.

[0030] The third objective of this invention is to provide an application of a VMoSiN tough and wear-resistant coating in high-performance cutting tools. Attached Figure Description

[0031] Figure 1 The XRD diffraction pattern of the VMoSiN coating prepared in Example 1 of this invention; Figure 2 The surface morphology and cross-sectional morphology of the VMoSiN coating prepared in Example 1 of this invention; Figure 3 The XRD diffraction pattern of the VMoN coating prepared in Comparative Example 1 of this invention; Figure 4 The nanoindentation load-displacement curves are shown for the VMoSiN coating prepared in Example 1 of this invention and the VMoN coating prepared in Comparative Example 1. Figure 5 The hardness and elastic modulus of the VMoSiN coating prepared in Example 1 of the present invention and the VMoN coating prepared in Comparative Example 1 are compared. Figure 6 The coefficient of friction is the VMoSiN coating obtained in Example 1 of this invention and the VMoN coating obtained in Comparative Example 1. Detailed Implementation

[0032] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the present invention.

[0033] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventional meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents, and instruments shall be performed according to the manufacturer's instructions and parameters.

[0035] Example 1 This embodiment provides a VMoSiN tough and wear-resistant coating, which is prepared by the following method: (1) The Inconel 718 nickel-based superalloy substrate was subjected to mechanical polishing, ultrasonic cleaning, and plasma glow etching in sequence. The plasma glow etching specifically included the following steps: heating the substrate to 500 °C and the chamber pressure to 5.0 × 10⁻⁶. -6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoSiN coating was deposited on the surface of a nickel-based alloy after plasma glow discharge etching using DC composite high-power pulsed magnetron sputtering technology. High-purity argon gas (16 sccm) and high-purity nitrogen gas (12 sccm) were introduced into the chamber at a pressure of 4 mTorr and a substrate bias of -70 V. The target material was a vanadium-molybdenum alloy target (atomic ratio 1:1) and a silicon target, both fixed to two magnetron cathodes. The angle between the two magnetron cathodes was 120°. The angle between the substrate surface and the center of the target surface of the magnetron cathode was 20°, and the distance between the substrate surface and the center of the target surface of the magnetron cathode was 10 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W, the pulse duty cycle was 3%, and the frequency was 606 Hz. The DC power supply connected to the silicon target had a power of 40 W.

[0036] Figure 1 The XRD diffraction pattern of the VMoSiN coating prepared in this embodiment is shown below. Figure 1 It can be seen that the main phase of the VMoSiN coating prepared in this embodiment is the VMoSiN phase.

[0037] Figure 2 These are surface and cross-sectional morphology images of the VMoSiN coating prepared in this embodiment. Figure 2 As can be seen, the VMoSiN coating deposited in this embodiment has a uniform, dense, and continuous surface, with no cracks at the cross-sectional interface and good adhesion.

[0038] Example 2 This embodiment provides a VMoSiN tough and wear-resistant coating, which is prepared by the following method: (1) The M2 high-speed steel substrate was subjected to mechanical polishing, ultrasonic cleaning and plasma glow etching in sequence. The plasma glow etching specifically included the following steps: heating the substrate to 100 °C and the chamber pressure to 5.0 × 10⁻⁶. -6When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2.1 Pa, a bias voltage of -450V is applied to the substrate, and the etching time is 30 min. (2) A VMoSiN coating was deposited on the surface of high-speed steel using high-power pulsed magnetron sputtering and DC magnetron sputtering techniques. High-purity argon gas (16 sccm) and high-purity nitrogen gas (14 sccm) were introduced into the chamber, with a chamber pressure of 3.8 mTorr and a substrate bias of -70 V. The targets were vanadium-molybdenum alloy targets (atomic ratio 1:1) and silicon elemental targets, respectively fixed to two magnetron cathodes. The included angle between the two magnetron cathodes was 120°, the included angle between the substrate surface and the center of the magnetron cathode target was 20°, and the distance between the substrate surface and the center of the magnetron cathode target was 10 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W, the pulse duty cycle was 3%, and the frequency was 606 Hz. The power of the DC power supply connected to the silicon target was 30 W.

[0039] Example 3 This embodiment provides a VMoSiN tough and wear-resistant coating, which is prepared by the following method: (1) The TC4 titanium alloy substrate was subjected to mechanical polishing, ultrasonic cleaning and plasma glow etching in sequence. The plasma glow etching specifically included the following steps: heating the substrate to 200 ℃ and the chamber pressure to 5.0 × 10 -6 When the Torr is below 1, 50 sccm of 99.99% pure argon gas is introduced, the plasma glow etching gas pressure is set to 1.9 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoSiN coating was deposited on the surface of a titanium alloy using high-power pulsed magnetron sputtering and DC magnetron sputtering techniques. High-purity argon gas (15 sccm) and high-purity nitrogen gas (13 sccm) were introduced into the chamber. The chamber pressure was 4 mTorr, and the substrate bias was -70 V. The target material was a vanadium-molybdenum alloy target (atomic ratio 1:1) and a silicon elemental target, both fixed to two magnetron cathodes. The angle between the two magnetron cathodes was 120°. The angle between the substrate surface and the center of the target surface of the magnetron cathode was 20°, and the distance between the substrate surface and the center of the target surface of the magnetron cathode was 10 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W, the pulse duty cycle was 3%, and the frequency was 606 Hz. The power of the DC power supply connected to the silicon target was 20 W.

[0040] Example 4 This embodiment provides a VMoSiN tough and wear-resistant coating, which is prepared by the following method: (1) The WC-Co cemented carbide substrate was subjected to mechanical polishing, ultrasonic cleaning, and plasma glow etching in sequence. The plasma glow etching specifically included the following steps: heating the substrate to 400 °C, and the chamber pressure to 5.0 × 10⁻⁶. -6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2.5 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoSiN coating was deposited on the surface of a cemented carbide using high-power pulsed magnetron sputtering and DC magnetron sputtering techniques. High-purity argon gas (16 sccm) and high-purity nitrogen gas (13 sccm) were introduced into the chamber, with a chamber pressure of 4.5 mTorr and a substrate bias of -70 V. The targets were vanadium-molybdenum alloy targets (atomic ratio 1:1) and silicon elemental targets, respectively fixed to two magnetron cathodes. The angle between the two magnetron cathodes was 120°. The angle between the substrate surface and the center of the magnetron cathode target was 20°, and the distance between the substrate surface and the center of the magnetron cathode target was 10 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W, the pulse duty cycle was 3%, and the frequency was 606 Hz. The DC power supply connected to the silicon target had a power of 40 W.

[0041] Comparative Example 1 This comparative example provides a VMoN coating, which is prepared by the following method: (1) The Inconel 718 nickel-based superalloy substrate was subjected to mechanical polishing, ultrasonic cleaning and plasma etching in sequence. The plasma etching process specifically included the following steps: heating the substrate to 500 °C and the chamber pressure to 5.0 × 10⁻⁶. - 6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoN coating is deposited on the surface of a nickel-based alloy after plasma glow discharge etching using high-power pulsed magnetron sputtering technology. 16 sccm of high-purity argon and 12 sccm of high-purity nitrogen are introduced into the chamber. The chamber pressure is 4 mTorr and the substrate bias is -70 V. The target material is a vanadium-molybdenum alloy target (atomic percentage 1:1), which is fixed to the magnetron cathode. The angle between the substrate surface and the center of the target surface of the magnetron cathode is 20° and the distance between the substrate surface and the center of the target surface of the magnetron cathode is 10 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target is 150 W, the pulse duty cycle is 3%, and the frequency is 606 Hz.

[0042] Comparative Example 2 This comparative example provides a VMoN coating, which is prepared by the following method: (1) The M2 high-speed steel substrate was subjected to mechanical polishing, ultrasonic cleaning, and plasma etching treatment in sequence. The plasma etching treatment specifically included the following steps: heating the substrate to 100 ℃, and the chamber pressure was 5.0 × 10⁻⁶. -6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoN coating was deposited on the surface of M2 high-speed steel using high-power pulsed magnetron sputtering technology. 12 sccm of high-purity argon and 1.6 sccm of high-purity nitrogen were introduced into the chamber. The chamber pressure was 4 mTorr and the substrate bias was -70 V. The target material was a vanadium-molybdenum alloy target (atomic percentage 1:1), which was fixed to the magnetron cathode. The angle between the substrate surface and the center of the target surface of the magnetron cathode was 20° and the distance between the substrate surface and the center of the target surface of the magnetron cathode was 5 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W and the pulse duty cycle was 10%. The frequency was 2000 Hz.

[0043] Comparative Example 3 This comparative example provides a VMoN coating, which is prepared by the following method: (1) The TC4 titanium alloy substrate was subjected to mechanical polishing, ultrasonic cleaning, and plasma etching treatment in sequence. The plasma etching treatment specifically included the following steps: heating the substrate to 200 ℃, and the chamber pressure to 5.0 × 10⁻⁶. -6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoN coating was deposited on the surface of TC4 titanium alloy using high-power pulsed magnetron sputtering technology. 20 sccm of high-purity argon and 15 sccm of high-purity nitrogen were introduced into the chamber. The chamber pressure was 4 mTorr and the substrate bias was -70 V. The target material was a vanadium-molybdenum alloy target (atomic percentage 1:1), which was fixed to the magnetron cathode. The angle between the substrate surface and the center of the target surface of the magnetron cathode was 20° and the distance between the substrate surface and the center of the target surface of the magnetron cathode was 12 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target was 150 W, the pulse duty cycle was 5%, and the frequency was 1000 Hz.

[0044] Comparative Example 4 This comparative example provides a VMoN coating, which is prepared by the following method: (1) The WC-Co cemented carbide substrate was subjected to mechanical polishing, ultrasonic cleaning, and plasma etching treatment in sequence. The plasma etching treatment specifically included the following steps: heating the substrate to 400 ℃, and the chamber pressure to 5.0 × 10⁻⁶. -6 When the Torr is below 50 sccm, argon gas with a purity of 99.99% is introduced, the plasma glow etching gas pressure is set to 2 Pa, a bias voltage of -450 V is applied to the substrate, and the etching time is 30 min. (2) A VMoN coating is deposited on the surface of WC-Co hard alloy using high-power pulsed magnetron sputtering technology. 24 sccm of high-purity argon and 18 sccm of high-purity nitrogen are introduced into the chamber. The chamber pressure is 4 mTorr and the substrate bias is -70 V. The target material is a vanadium-molybdenum alloy target (atomic percentage 1:1), which is fixed to the magnetron cathode. The angle between the substrate surface and the center of the target surface of the magnetron cathode is 20° and the distance between the substrate surface and the center of the target surface of the magnetron cathode is 15 cm. The average power of the pulsed DC power supply connected to the vanadium-molybdenum alloy target is 150 W, the pulse duty cycle is 7%, and the frequency is 1400 Hz.

[0045] Figure 3 The XRD diffraction pattern of the VMoN coating prepared in Comparative Example 1 is shown below. Figure 1 As can be seen from the comparison, Si exists in the VMoSiN coating prepared in the embodiments of the present invention in the form of a doped V-Mo-N phase, and does not form an independent silicon nitride phase.

[0046] Figure 4 The figures show the nanoindentation load-displacement curves of the VMoSiN coating prepared in Example 1 and the VMoN coating prepared in Comparative Example 1. Figure 4 The load-displacement curve can be obtained by calculating using the Oliver-Pharr method. Figure 5 ,from Figure 5 It can be seen that the VMoSiN coating prepared in Example 1 has a hardness of 32.0 GPa and an elastic modulus of 385.6 GPa; the VMoN coating prepared in Comparative Example 1 has a hardness of 23.0 GPa and an elastic modulus of 326.0 GPa.

[0047] Figure 6 The coefficient of friction of the VMoSiN coating prepared in Example 1 and the VMoN coating prepared in Comparative Example 1 is given by... Figure 6 It can be seen that the VMoSiN coating obtained in Example 1 has a friction coefficient of 0.43 at 600°C, while the VMoN coating obtained in Comparative Example 1 has a friction coefficient of 0.61 at 600°C. The friction coefficient of Example 1 is 29.5% lower than that of Comparative Example 1. This proves that the VMoSiN coating of the present invention has excellent wear resistance.

[0048] All aspects, embodiments, features, and examples of this invention are to be regarded as illustrative in all respects and are not intended to limit the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0049] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0050] While the disclosure is as stated above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of this disclosure, and all such changes and modifications will fall within the protection scope of this invention.

Claims

1. A VMoSiN tough and wear-resistant coating, characterized in that, The VMoSiN tough and wear-resistant coating has a uniform nanocrystalline structure and includes VMoSiN phase, VN phase, V2N phase and MoN phase.

2. The VMoSiN tough and wear-resistant coating as described in claim 1, characterized in that, In the VMoSiN tough and wear-resistant coating, the Si content is 1-10% and the N content is 40-55% by atomic percentage; the atomic ratio of V to Mo is (0.8-1.2):

1.

3. The VMoSiN tough and wear-resistant coating as described in claim 1, characterized in that, The thickness of the VMoSiN tough and wear-resistant coating is 0.1-10 μm.

4. A method for preparing a VMoSiN tough and wear-resistant coating as described in any one of claims 1-3, characterized in that, The preparation method specifically includes the following steps: S1. Perform plasma glow etching on the substrate; S2. In an argon and nitrogen working atmosphere, a VMo alloy target is used as a high-power pulse sputtering target and a Si target is used as a DC sputtering target. A DC composite high-power pulse magnetron sputtering method is used to deposit a VMoSiN tough and wear-resistant coating on the substrate surface treated by plasma glow etching in step S1.

5. The preparation method according to claim 4, characterized in that, In step S1, the parameters for plasma glow etching are as follows: vacuum degree ≤ 5 × 10⁻⁶ -6 For Torr etching, the substrate temperature is 100-500 ℃, the argon flow rate is 20-80 sccm, the substrate bias voltage is -600 to -300 V, and the etching time is 10-60 min.

6. The preparation method according to claim 4, characterized in that, In step S1, the matrix is ​​selected from one of titanium alloy, nickel-based high-temperature alloy, cemented carbide, stainless steel and high-speed steel.

7. The preparation method according to claim 4, characterized in that, In step S2, the VMo alloy target and the Si target are respectively fixed to two magnetron cathodes, and the surface of the substrate is parallel to the line connecting the center of the target surface of the two magnetron cathodes.

8. The preparation method according to claim 7, characterized in that, The magnetron cathode is a circular planar magnetron cathode with an included angle of 120°; And / or, the distance between the surface of the substrate and the line connecting the center of the target surface of the two magnetron cathodes is 5-12 cm.

9. The preparation method according to claim 7, characterized in that, In step S2, the parameters of the DC composite high-power pulsed magnetron sputtering method are as follows: working gas pressure is 2-10 mTorr, the pulse bias voltage of the substrate is -150 to -20 V, the flow rate of argon is 10-40 sccm, the flow rate of nitrogen is 5-30 sccm, the DC sputtering power is 10-100 W, and the average power of high-power pulsed magnetron sputtering is 100-200 W. And / or, the duty cycle of the pulse bias voltage is 1-10%, and the frequency is 300-1000 Hz.

10. The application of a VMoSiN tough and wear-resistant coating as described in any one of claims 1-3 in high-performance cutting tools.

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