Ti / TiCrAlSiN nano multilayer film and preparation method and application thereof

Abstract

The invention discloses a Ti / TiCrAlSiN nano multilayer film as well as a preparation method and application thereof. The Ti / TiCrAlSiN nano multi-layer thin film comprises a plurality of periodic units which are sequentially arranged on the surface of a base body in a stacked mode in the thickness direction, and each periodic unit comprises a Ti layer and a TiCrAlSiN layer. The Ti layers in the periodic units adjacent to the base body are arranged adjacent to the base body, and the top end of the Ti / TiCrAlSiN nanometer multilayer film is a TiCrAlSiN layer. The preparation method comprises the following steps: depositing a Ti layer on the surface of a substrate by adopting a magnetron sputtering technology; and depositing a TiCrAlSiN layer on the Ti layer by adopting a magnetron sputtering technology to form periodic units, and repeatedly preparing a plurality of periodic units to prepare the Ti / TiCrAlSiN nano multilayer film. The Ti / TiCrAlSiN nano multilayer film disclosed by the invention has good mechanical property, friction property and long-term corrosion resistance, and can be widely applied to the field of matrix surface protection in a marine environment.

Description

Technical Field

[0001] This invention belongs to the field of substrate surface treatment technology, specifically relating to a Ti / TiCrAlSiN nanolayered thin film, its preparation method, and its application. Background Technology

[0002] Key components of marine engineering and equipment suffer severe brittle fracture, spalling, and pitting corrosion under conditions of high salinity, high humidity, friction, and impact, significantly reducing the reliability and service life of the engineering and equipment. Currently, nitride films prepared using physical vapor deposition (PVD) technology are widely used in machining, mold making, aerospace, and other fields. However, nitride protective films exhibit a distinct columnar crystal structure, with numerous wide grain boundaries and voids existing between the columnar crystals in traditional nitride coatings, making them prone to failure under the multi-factory marine environment.

[0003] Due to the unique working environment of marine engineering and equipment, the surface protection of critical components requires membranes with high hardness, as well as excellent wear and corrosion resistance. For example, load-bearing structural connectors, fasteners, and transmission components of key equipment such as top drive systems, blowout preventers, and plug valves used in marine drilling are subjected to high loads and the high-salt and high-humidity environment of the ocean for extended periods, requiring membranes with good friction properties and long-term corrosion resistance.

[0004] While the hardness of nitride films can be improved through single-element doping and process parameter optimization, it is difficult to achieve a synergistic improvement in wear resistance and other properties, especially good corrosion resistance, under humid, hot, salt spray, and high-load operating conditions. This is insufficient to meet the long-term protection requirements of critical components in marine engineering and equipment operating in harsh marine environments. Therefore, developing surface protective films with high hardness, excellent wear resistance, and corrosion resistance is of great significance. It is key to achieving highly reliable protection and extended service life of critical components in marine environments, and will solve a series of problems such as difficulty in comprehensive performance design and control, poor structural performance stability, and severely insufficient service life under multiple factors including high salt, high humidity, high heat, friction, and impact. Summary of the Invention

[0005] The main objective of this invention is to provide a Ti / TiCrAlSiN nanolayered thin film, its preparation method, and its application, in order to overcome the shortcomings of the prior art.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes: The first aspect of the present invention provides a Ti / TiCrAlSiN nanomultilayer film, comprising a plurality of periodic units sequentially stacked on the surface of a substrate in the thickness direction, each periodic unit comprising a Ti layer and a TiCrAlSiN layer; the Ti layer in the periodic unit adjacent to the substrate is disposed adjacent to the substrate, and the top of the Ti / TiCrAlSiN nanomultilayer film is a TiCrAlSiN layer.

[0007] A second aspect of the present invention provides a method for preparing the Ti / TiCrAlSiN nanolayered thin film, comprising: A Ti layer is deposited on the substrate surface using magnetron sputtering technology; A TiCrAlSiN layer was deposited on the Ti layer using magnetron sputtering technology to form a periodic unit. Multiple periodic units were repeatedly prepared to obtain a Ti / TiCrAlSiN nanomultilayer film.

[0008] A third aspect of the invention provides the application of the Ti / TiCrAlSiN nanolayered film in the protection of substrate surfaces in marine environments, the substrate surfaces including the surfaces of marine engineering and equipment components.

[0009] A fourth aspect of the invention provides a corrosion-resistant protective component comprising a substrate and the Ti / TiCrAlSiN nanolayer film deposited on the surface of the substrate.

[0010] Compared with the prior art, the present invention has at least the following beneficial effects: (1) The present invention designs the thin film located on the substrate surface as consisting of alternating Ti layers and TiCrAlSiN layers, with the outermost layer being a TiCrAlSiN layer. The TiCrAlSiN layer, as a ceramic layer, provides high hardness and directly contacts the working load; Ti, as a stress-absorbing layer, absorbs energy during friction and synergistically improves the friction performance of the thin film; the present invention is designed with 3 to 5 multi-periodic units, which can improve the overall deformation coordination ability and suppress crack generation and propagation; moreover, by precisely controlling the interface between the Ti layer and the TiCrAlSiN layer through deposition time, the TiCrAlSiN layer has a stronger preferred orientation, and the relationship between the columnar crystals is a tight grain boundary. This grain boundary replaces a large number of wide grain boundaries, greatly improving the quality of the TiCrAlSiN layer and enhancing the overall corrosion resistance of the thin film; in addition, the thin film of the present invention also has good mechanical properties and friction properties.

[0011] (2) Compared with traditional nitride protective films (such as TiN, CrN, TiAlN films), the Ti / TiCrAlSiN nanomultilayer film provided by the present invention uses a Ti layer as an intermediate layer. Under the premise that the TiCrAlSiN layer provides high hardness and lubrication phase, the deformation coordination ability of the overall film is improved, thereby improving fatigue life. At the same time, the Ti / TiCrAlSiN interlayer interface has an effective blocking effect on crack propagation, which greatly improves the friction performance of the film. Attached Figure Description

[0012] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0013] Figure 1 This is a cross-sectional view of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of the present invention; Figure 2 This is a tribological test curve of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of this invention; Figure 3 These are Bode plots of electrochemical impedance spectroscopy on day 1 and day 70 of the immersion test of the Ti / TiCrAlSiN nanolayered film prepared in Example 1 of this invention. Figure 4 This is a comparison of the surface morphology of the Ti / TiCrAlSiN nanolayered film prepared in Example 1 of this invention before immersion testing and after 70 days of immersion testing. Figure 5 This is a TEM image of the surface position of the Ti / TiCrAlSiN nanolayered thin film prepared in Comparative Example 2 of this invention; Figure 6 This is a TEM image of the surface position of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of this invention; Figure 7 This is a TEM image of the interface position of the Ti / TiCrAlSiN nanolayered thin film prepared in Comparative Example 2 of this invention. Figure 8 This is a TEM image of the interface position of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of this invention. Detailed Implementation

[0014] In view of the problems existing in the prior art, the inventors of this invention have conducted extensive and in-depth research and have provided a Ti / TiCrAlSiN nanolayered thin film, its preparation method and application. The main feature is that the thin film located on the substrate surface is designed to consist of alternating Ti layers and TiCrAlSiN layers. By precisely controlling the interlayer interface between the Ti layers and TiCrAlSiN layers, this thin film possesses high hardness, excellent wear resistance, and especially long-term corrosion resistance. The aim is to provide a protective film that can meet the long-term service requirements of key components in engineering and equipment under harsh marine environments.

[0015] The following will provide a further explanation of the technical solution, its implementation process, and its principles.

[0016] The first aspect of the present invention provides a Ti / TiCrAlSiN nanomultilayer film, comprising a plurality of periodic units sequentially stacked on the surface of a substrate in the thickness direction, each periodic unit comprising a Ti layer and a TiCrAlSiN layer; the Ti layer in the periodic unit adjacent to the substrate is disposed adjacent to the substrate, and the top of the Ti / TiCrAlSiN nanomultilayer film is a TiCrAlSiN layer.

[0017] In some embodiments, the thickness ratio of the Ti layer to the TiCrAlSiN layer is (0.1~0.4):1. In this invention, the thickness ratio of the Ti layer to the TiCrAlSiN layer is closely related to the tribological and corrosion resistance of the nano-multilayer film. If the thickness is too low, the corrosion resistance will decrease significantly; if the thickness ratio is too high, the tribological performance will decrease significantly.

[0018] In some embodiments, the Ti / TiCrAlSiN nanolayered film comprises 3 to 5 periodic units. In this invention, the Ti layer and the TiCrAlSiN layer form an alternating cycle, and the interface between the Ti layer and the TiCrAlSiN layer is precisely controlled according to the relative relationship between the grain sizes of the two layers. The precise control method is to precisely control the thickness of the Ti layer. The result of this precise control is a significant improvement in the quality of the TiCrAlSiN layer, manifested as a transformation from numerous wide grain boundaries to numerous dense grain boundaries, which greatly improves the overall corrosion resistance of the film.

[0019] In some implementations, the thickness of the Ti layer is 200~340 nm.

[0020] In some embodiments, the thickness of the TiCrAlSiN layer is 960 nm to 1100 nm.

[0021] In some embodiments, the TiCrAlSiN layer has a tight grain boundary structure.

[0022] In some embodiments, the total thickness of the Ti / TiCrAlSiN nanolayer film is 4~7 μm.

[0023] In some implementations, the substrate is made of 304 stainless steel.

[0024] In some embodiments, the Ti / TiCrAlSiN nanolayer film has a nanohardness of 30~40 GPa and a modulus of 300~500 GPa.

[0025] In some embodiments, the average dry friction coefficient of the Ti / TiCrAlSiN nanolayer film after stabilization in an atmospheric environment is 0.2~0.6.

[0026] A second aspect of the present invention provides a method for preparing the Ti / TiCrAlSiN nanolayered thin film, comprising: A Ti layer is deposited on the substrate surface using magnetron sputtering technology; A TiCrAlSiN layer was deposited on the Ti layer using magnetron sputtering technology to form a periodic unit. Multiple periodic units were repeatedly prepared to obtain a Ti / TiCrAlSiN nanomultilayer film.

[0027] In some embodiments, the preparation method of the Ti / TiCrAlSiN nanolayered thin film specifically includes: Using magnetron sputtering technology, a Ti target is used as the target material. A target current is applied to the Ti target in a vacuum environment, and a negative bias voltage is applied to the substrate to deposit the Ti layer on the substrate surface.

[0028] Furthermore, the sputtering power applied to the Ti target is 150~250 W, the negative bias voltage is -100~-200 V, the pressure of the vacuum environment is 0.1~1.0 Pa, and the deposition time is 1800~3000 s.

[0029] Furthermore, the Ti target includes a high-purity Ti target.

[0030] In some embodiments, the preparation method of the Ti / TiCrAlSiN nanolayered thin film specifically includes: Using magnetron sputtering technology, Ti, Cr, Al, and Si targets are used as targets. Target currents are applied to the Ti, Cr, Al, and Si targets respectively in a vacuum environment. A negative bias voltage is applied to the substrate containing the Ti layer, and nitrogen gas is introduced to deposit the TiCrAlSiN layer on the surface of the Ti layer, forming the periodic unit. This process is repeated to prepare 3 to 5 periodic units to obtain the Ti / TiCrAlSiN nanomultilayer thin film.

[0031] Furthermore, the sputtering power applied to the Ti target is 150~250 W; the sputtering power of the Cr target is 50~150 W; the sputtering power of the Al target is 150~250 W; the sputtering power of the Si target is 50~150 W; the negative bias voltage is -100~-200 V; the pressure of the vacuum environment is 0.1~1.0 Pa; the nitrogen flow rate is 5~15 sccm; and the deposition time is 5800~6600 s.

[0032] Furthermore, the Ti target includes a high-purity Ti target, the Cr target includes a high-purity Cr target, the Al target includes a high-purity Al target, and the Si target includes a high-purity Si target.

[0033] In some embodiments, the preparation method of the Ti / TiCrAlSiN nanolayered thin film further includes a pretreatment, which includes: before performing the magnetron sputtering process, in an environment with a temperature of less than 2 × 10⁻⁶ ppm. -2 Under a vacuum environment of Pa, the surface of the substrate is etched for 10-20 minutes using plasma technology.

[0034] In some more specific embodiments, the preparation method of the Ti / TiCrAlSiN nanolayered thin film specifically includes the following steps: (1) Pretreatment: After cleaning the substrate surface, it is placed in a closed-field magnetron sputtering vacuum chamber, and the vacuum chamber is pre-evacuated to less than 2×10⁻⁶. -2 For Pa below, plasma etching is used to etch the substrate surface for 10-20 minutes; (2) Deposition of Ti layer: High-purity Ti target is selected as the target material. Turn on the power supply of Ti target gun, the sputtering power of Ti target is 150~250 W, the bias voltage is -100~-200 V, the working pressure is 0.1~1.0 Pa, the deposition time is 1800~3000s, and turn off all power supply after the Ti layer is deposited on the substrate surface. (3) Deposition of TiCrAlSiN layer: High-purity Ti target, high-purity Cr target, high-purity Al target, and high-purity Si target are selected. The power supply of Ti, Cr, Al, and Si target guns is turned on. The sputtering power of Ti target is 150~250 W, the sputtering power of Cr target is 50~150 W, the sputtering power of Al target is 150~250 W, and the sputtering power of Si target is 50~150 W. The bias voltage is -100~-200 V. Nitrogen gas is introduced. The nitrogen flow rate is 5~15 sccm, the working pressure is 0.1~1.0 Pa, and the deposition time is 5800~6600s. A TiCrAlSiN layer is deposited on the surface of Ti layer. (4) Repeat the preparation of 3 to 5 periodic units to obtain the Ti / TiCrAlSiN nano multilayer film.

[0035] A third aspect of the invention provides the application of the Ti / TiCrAlSiN nanolayered film in the protection of substrate surfaces in marine environments, the substrate surfaces including the surfaces of marine engineering and equipment components.

[0036] A fourth aspect of the invention provides a corrosion-resistant protective component comprising a substrate and the Ti / TiCrAlSiN nanolayer film deposited on the surface of the substrate.

[0037] In summary, the Ti / TiCrAlSiN nanolayered thin film provided by this invention has excellent mechanical properties, friction properties, and corrosion resistance. It can meet the high reliability and long service life protection requirements of key components of equipment and engineering in marine environments under conditions of high salt, high humidity, and multiple factors such as friction and impact, and has excellent application value.

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Modifications or equivalent substitutions made by those skilled in the art based on their understanding of the technical solutions of this invention, without departing from the spirit and scope of the invention, should be covered within the protection scope of this invention.

[0039] For experiments not specifically described in the examples, the procedures or conditions can be performed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available. Other unmentioned raw materials and instruments are all conventionally chosen and do not involve the core technical means of this invention.

[0040] Example 1

[0041] In this embodiment, the substrate material is 304 stainless steel, and the preparation method of the Ti / TiCrAlSiN nanolayered film on the surface of the substrate includes the following steps:

[0042] S1. Cleaning and degreasing the substrate surface: Place the acetone-washed parts in an acetone solution for ultrasonic cleaning for 30 minutes, dry with nitrogen, then transfer to anhydrous ethanol for cleaning for 30 minutes, and dry with nitrogen.

[0043] S2, Magnetron sputtering deposition of Ti layer: The substrate treated in step S1 is placed in a closed-field magnetron sputtering vacuum chamber and pre-evacuated to 2×10⁻⁶. -3 Below Pa, after plasma treatment for 15 minutes, the Ti target gun power supply was turned on, the titanium target sputtering power was 200W, the bias voltage was -160 V, the working gas pressure was 0.1 Pa, the deposition time was 1800s, and a 200 nm Ti layer was deposited on the substrate surface. After completion, the Ti target gun power supply was turned off.

[0044] S3. Magnetron sputtering deposition of TiCrAlSiN layer: Turn on the power supplies of Ti, Cr, Al, and Si target guns. The sputtering power of Ti target is 200W, the sputtering power of Cr target is 100W, the sputtering power of Al target is 200W, and the sputtering power of Si target is 100W. The bias voltage is -160V, nitrogen gas is introduced, the nitrogen flow rate is 5 sccm, the working pressure is 0.2 Pa, and the deposition time is 6600s. A TiCrAlSiN layer is deposited on the substrate surface.

[0045] S4. Repeat steps S2 and S3 four times to obtain Ti / TiCrAlSiN nanolayered films.

[0046] In this embodiment, the thin film on the substrate surface has a nano-multilayer structure, consisting of alternating layers of Ti and TiCrAlSiN from the substrate surface. The outermost layer is a TiCrAlSiN layer, with a Ti layer thickness of 200 nm and a TiCrAlSiN layer thickness of 1100 nm. The thickness ratio of the Ti layer to the TiCrAlSiN layer is approximately 0.18:1. Each Ti layer and each TiCrAlSiN layer constitutes one alternation cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0047] Example 2

[0048] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this embodiment differs from that in Example 1 only in that: S2, Magnetron sputtering deposition of Ti layer: deposition time is 2400s; S3, Magnetron sputtering deposition of TiCrAlSiN layer: deposition time is 6200s.

[0049] In this embodiment, the Ti / TiCrAlSiN nanolayer film has a Ti layer thickness of 270 nm and a TiCrAlSiN layer thickness of 1030 nm, with a thickness ratio of approximately 0.26:1. One Ti layer and one TiCrAlSiN layer form an alternating cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0050] The Ti / TiCrAlSiN nanolayered film of this embodiment has a nanohardness of approximately 35.2 GPa and a modulus of approximately 327.3 GPa. The average dry friction coefficient under atmospheric conditions is 0.43, and after 20,000 cycles, no surface cracks or peeling were observed; the wear rate is 1.07 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance showed no significant decrease, indicating excellent corrosion resistance.

[0051] Example 3

[0052] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this embodiment differs from that in Example 1 only in that: S2, Magnetron sputtering deposition of Ti layer: deposition time is 3000s; S3, Magnetron sputtering deposition of TiCrAlSiN layer: deposition time is 5800s.

[0053] In this embodiment, the Ti / TiCrAlSiN nanolayer film has a Ti layer thickness of 340 nm and a TiCrAlSiN layer thickness of 960 nm, with a thickness ratio of approximately 0.35:1. One Ti layer and one TiCrAlSiN layer form an alternating cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0054] The Ti / TiCrAlSiN nanolayered film of this embodiment has a nanohardness of approximately 30.8 GPa, a modulus of approximately 313.3 GPa, an average dry friction coefficient of 0.54 under atmospheric conditions, and exhibits no surface cracks or peeling after 20,000 cycles; the wear rate is 1.17 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance showed no significant decrease, indicating excellent corrosion resistance.

[0055] Example 4

[0056] The only difference between the preparation method of Ti / TiCrAlSiN nanolayered thin film provided in this embodiment and that in Example 1 is that the thickness of the Ti layer and the TiCrAlSiN layer in this embodiment is the same as that in Example 1. One Ti layer and one TiCrAlSiN layer are used as an alternating cycle, with a total of five cycle units and a total thickness of 6.5 μm.

[0057] The Ti / TiCrAlSiN nanolayered film of this embodiment has a nanohardness of approximately 32.5 GPa and a modulus of approximately 342.1 GPa. The average dry friction coefficient under atmospheric conditions is 0.31, and after 20,000 cycles, no surface cracks or peeling were observed; the wear rate is 1.05 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance showed no significant decrease, indicating excellent corrosion resistance.

[0058] Example 5

[0059] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this embodiment differs from that in Example 1 only in that the thickness of the Ti layer and the TiCrAlSiN layer in this embodiment is the same as that in Example 1. One Ti layer and one TiCrAlSiN layer are used as an alternating cycle, with a total of three cycle units and a total thickness of 3.9 μm.

[0060] The Ti / TiCrAlSiN nanolayered film of this embodiment has a nanohardness of approximately 37.4 GPa and a modulus of approximately 344.3 GPa. The average dry friction coefficient under atmospheric conditions is 0.28, and after 20,000 cycles, no surface cracks or peeling were observed; the wear rate is 9.3 × 10⁻⁶. -7 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance showed no significant decrease, indicating excellent corrosion resistance.

[0061] Comparative Example 1

[0062] The difference between the thin film preparation method provided in this comparative example and Example 1 is that: The thin film in this comparative example has no multi-period units, only a single TiCrAlSiN layer and a Ti layer. The thickness of the TiCrAlSiN layer is 5100 nm. Before depositing the TiCrAlSiN layer, a 100 nm Ti layer is deposited on a 304 substrate to improve the adhesion.

[0063] The TiCrAlSiN nanolayer film in this comparative example has a nanohardness of 46.2 GPa and a modulus of approximately 439.3 GPa. Its average dry friction coefficient under atmospheric conditions is 0.41. After 20,000 cycles, surface cracks and peeling occurred; the wear rate was 2.59 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance decreased, indicating only moderate corrosion resistance.

[0064] Comparative Example 2

[0065] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this comparative example differs from that in Example 1 only in that: S2, Magnetron sputtering deposition of Ti layer: deposition time is 600s; S3, Magnetron sputtering deposition of TiCrAlSiN layer: deposition time is 7400s.

[0066] In this comparative example, the Ti / TiCrAlSiN nanolayer film has a Ti layer thickness of 60 nm and a TiCrAlSiN layer thickness of 1240 nm. One Ti layer and one TiCrAlSiN layer form an alternating cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0067] The Ti / TiCrAlSiN nanolayered film in this comparative example exhibits a nanohardness of approximately 37 GPa and a modulus of approximately 381.2 GPa. Under atmospheric conditions, the average dry friction coefficient is 0.28. After 20,000 cycles, surface cracks appear, but no peeling occurs; the wear rate is 1.02 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance decreased significantly, indicating poor corrosion resistance.

[0068] Comparative Example 3

[0069] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this comparative example differs from that in Example 1 only in that: S2, Magnetron sputtering deposition of Ti layer: deposition time is 1200s; S3, Magnetron sputtering deposition of TiCrAlSiN layer: deposition time is 7000s.

[0070] In this comparative example, the Ti / TiCrAlSiN nanolayer film has a Ti layer thickness of 130 nm and a TiCrAlSiN layer thickness of 1170 nm. One Ti layer and one TiCrAlSiN layer form an alternating cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0071] The Ti / TiCrAlSiN nanolayered film in this comparative example exhibits a nanohardness of approximately 32.6 GPa and a modulus of approximately 352.1 GPa. Under atmospheric conditions, the average dry friction coefficient is 0.32, and after 20,000 cycles, no surface cracks or peeling were observed; the wear rate is 7.85 × 10⁻⁶. -7 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance decreased, indicating only moderate corrosion resistance.

[0072] Comparative Example 4

[0073] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this comparative example differs from that in Example 1 only in that the thickness of the Ti layer and the TiCrAlSiN layer in this comparative example is the same as that in Example 1. One Ti layer and one TiCrAlSiN layer are used as an alternating cycle, with a total of two cycle units and a total thickness of 3.9 μm.

[0074] The Ti / TiCrAlSiN nanolayered film in this comparative example exhibits a nanohardness of approximately 37.9 GPa and a modulus of approximately 348.6 GPa. Under atmospheric conditions, the average dry friction coefficient is 0.35. After 20,000 cycles, surface cracks and peeling occur; the wear rate is 2.3 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance decreased significantly, indicating only average corrosion resistance.

[0075] Comparative Example 5

[0076] The method for preparing a Ti / TiCrAlSiN nanolayered thin film provided in this comparative example differs from that in Example 1 only in that: S2, Magnetron sputtering deposition of Ti layer: deposition time is 3100s; S3, magnetron sputtering deposition of TiCrAlSiN layer: deposition time is 5110s.

[0077] In this comparative example, the thickness of the Ti / TiCrAlSiN nanolayered film is 450 nm, the thickness of the Ti layer is 850 nm, and the thickness ratio of the Ti layer to the TiCrAlSiN layer is approximately 0.53:1. One Ti layer and one TiCrAlSiN layer constitute one alternating cycle, with a total of four cycles and a total thickness of 5.2 μm.

[0078] The Ti / TiCrAlSiN nanolayered film in this comparative example exhibits a nanohardness of approximately 29.6 GPa and a modulus of approximately 289.1 GPa. Under atmospheric conditions, the average dry friction coefficient is 0.56. After 20,000 cycles, surface cracks and peeling occur; the wear rate is 8.97 × 10⁻⁶. -6 mm 3 (Nm) -1 After 70 days of immersion testing, the impedance showed no significant decrease, indicating excellent corrosion resistance.

[0079] Structural and performance testing

[0080] The Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of this invention was subjected to various performance tests. The test process and results are as follows: (1) Structural testing: Test results: The thin film on the component surface is grayish-white, dense and glossy. The cross-sectional view is shown below. Figure 1 As shown, its cross-section exhibits a clear multi-layered structural feature.

[0081] (2) Mechanical property testing

[0082] The nanohardness and modulus of the Ti / TiCrAlSiN nanolayered thin film of the present invention were tested using a KLA nanoindentation system. Test results: The nanohardness of the Ti / TiCrAlSiN nanolayer film of the present invention is about 35.2 GPa, and the modulus is 346.1 GPa.

[0083] (3) Tribological and wear performance test

[0084] The dry friction coefficient and wear life of the Ti / TiCrAlSiN nanolayered thin film of the present invention under atmospheric conditions were evaluated using an Anton Paar tribometer. The specific experimental conditions were as follows: reciprocating sliding mode was used, the friction pair ball was a Φ6mm ZrO2 ball, the sliding amplitude was 5 mm, the sliding frequency was 4 Hz, the load was 2 N, the total sliding distance was 200 m, and the total number of cycles was 20,000. The wear rate was calculated using an UP-Lambda3D profilometer.

[0085] Test results: The Ti / TiCrAlSiN nanolayered film of this invention has an average dry friction coefficient of 0.22 under atmospheric conditions. After 20,000 cycles, no surface cracks or peeling were observed. The test results are as follows: Figure 2 As shown; the wear rate is 5.53 × 10⁻⁶. -7 mm 3 (Nm) -1 .

[0086] (4) Corrosion resistance test

[0087] Long-term impedance (EIS) monitoring of Ti / TiCrAlSiN nanolayered films was conducted using a Gamry electrochemical workstation. Specifically, the substrate sample with the Ti / TiCrAlSiN nanolayered film was sealed on one side and immersed in an open beaker containing 3.5 wt.% NaCl solution at room temperature. A three-electrode method was used for long-term impedance monitoring for 70 days.

[0088] Test results: The impedance of the Ti / TiCrAlSiN nanolayered film of the present invention did not decrease significantly after the immersion experiment. The test results are as follows: Figure 3 As shown.

[0089] The surface morphology comparison of the Ti / TiCrAlSiN nanolayer film before and after 70-day immersion test is shown in the figure below. Figure 4 As shown, there is basically no obvious corrosion on the surface.

[0090] (5) Precise control of Ti / TiCrAlSiN nano multilayer films: The interface between the Ti layer and the TiCrAlSiN layer is precisely controlled according to the relative relationship between the grain sizes of the two layers. The precise control method is to precisely control the thickness of the Ti layer.

[0091] TEM images of the surface positions of the Ti / TiCrAlSiN nanolayered thin film prepared in Comparative Example 2 of this invention are shown below. Figure 5 The TEM image of the surface location of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of this invention is shown below. Figure 6 As shown.

[0092] Compared with Comparative Example 2, Example 1 achieved precise control over the deposition time of the Ti layer, resulting in a film with numerous tight boundaries. In Comparative Example 2, it can be seen that there are obvious wide grain boundaries between the columnar crystals, indicating that the overall quality of the film in Example 1 is better than that in Comparative Example 2.

[0093] Figure 7 This is a TEM image of the interface position of the Ti / TiCrAlSiN nanolayered film prepared in Comparative Example 2 of this invention. It can be seen that there are a large number of wide grain boundaries between the columnar crystals of the TiCrAlSiN layer, and the overall quality is poor.

[0094] Figure 8 This is a TEM image of the interface position of the Ti / TiCrAlSiN nanolayered thin film prepared in Example 1 of the present invention. It can be seen that the interface between the Ti layer and the TiCrAlSiN layer after regulation is relatively flat, which can provide a good basal surface for the growth of the next TiCrAlSiN layer, reduce the competitive growth relationship between the columnar crystals of the TiCrAlSiN layer, and thus make the overall TiCrAlSiN layer change from high-density wide grain boundaries to high-density tight grain boundaries, resulting in high interface quality.

Claims

1. A Ti / TiCrAlSiN nanolayered thin film, characterized in that, The film includes multiple periodic units stacked sequentially on the surface of a substrate in the thickness direction. Each periodic unit includes a Ti layer and a TiCrAlSiN layer. The Ti layer in the periodic unit adjacent to the substrate is disposed adjacent to the substrate, and the top of the Ti / TiCrAlSiN nanolayer film is a TiCrAlSiN layer.

2. The Ti / TiCrAlSiN nanolayered thin film according to claim 1, characterized in that: The thickness ratio of the Ti layer to the TiCrAlSiN layer is (0.1~0.4):1; And / or, the thickness of the Ti layer is 200~340 nm; And / or, the thickness of the TiCrAlSiN layer is 960 nm to 1100 nm; And / or, the total thickness of the Ti / TiCrAlSiN nanolayer film is 4~7 μm; And / or, the Ti / TiCrAlSiN nanolayered film comprises 3 to 5 periodic units; And / or, the TiCrAlSiN layer has a tight grain boundary structure; And / or, the material of the substrate includes 304 stainless steel.

3. The Ti / TiCrAlSiN nanolayered thin film according to claim 1 or 2, characterized in that: The nanohardness of the Ti / TiCrAlSiN nanolayer film is 30~40 GPa, and the modulus is 300GPa~500 GPa. And / or, the average dry friction coefficient of the Ti / TiCrAlSiN nanolayer film is 0.2~0.6 under atmospheric conditions.

4. The method for preparing Ti / TiCrAlSiN nanolayered thin films according to any one of claims 1-3, characterized in that, include: A Ti layer is deposited on the substrate surface using magnetron sputtering technology; A TiCrAlSiN layer was deposited on the Ti layer using magnetron sputtering technology to form a periodic unit. Multiple periodic units were repeatedly prepared to obtain a Ti / TiCrAlSiN nanomultilayer film.

5. The preparation method according to claim 4, characterized in that, Specifically, it includes: Using magnetron sputtering technology, a Ti target is used as the target material. A target current is applied to the Ti target in a vacuum environment, and a negative bias voltage is applied to the substrate to deposit the Ti layer on the substrate surface.

6. The preparation method according to claim 5, characterized in that: The sputtering power applied to the Ti target is 150~250 W, the negative bias voltage is -100~-200 V, the pressure of the vacuum environment is 0.1~1.0 Pa, and the deposition time is 1800~3000 s; And / or, the Ti target includes a high-purity Ti target.

7. The preparation method according to claim 4, characterized in that, Specifically, it includes: Using magnetron sputtering technology, Ti, Cr, Al, and Si targets are used as targets. Target currents are applied to the Ti, Cr, Al, and Si targets respectively in a vacuum environment. A negative bias voltage is applied to the substrate containing the Ti layer, and nitrogen gas is introduced to deposit the TiCrAlSiN layer on the surface of the Ti layer, forming the periodic unit. This process is repeated to prepare 3 to 5 periodic units to obtain the Ti / TiCrAlSiN nanomultilayer thin film.

8. The preparation method according to claim 7, characterized in that: The sputtering power applied to the Ti target is 150~250 W; the sputtering power of the Cr target is 50~150 W; the sputtering power of the Al target is 150~250 W; the sputtering power of the Si target is 50~150 W; the negative bias voltage is -100~-200 V; the pressure of the vacuum environment is 0.1~1.0 Pa; the nitrogen flow rate is 5~15 sccm; and the deposition time is 5800~6600 s. And / or, the Ti target includes a high-purity Ti target, the Cr target includes a high-purity Cr target, the Al target includes a high-purity Al target, and the Si target includes a high-purity Si target; And / or, the preparation method further includes a pretreatment, the pretreatment comprising: before performing the magnetron sputtering process, in an environment with a temperature of less than 2 × 10⁻⁶ ppm. -2 Under a vacuum environment of Pa, the surface of the substrate is etched for 10-20 minutes using plasma technology.

9. The application of the Ti / TiCrAlSiN nanolayered thin film according to any one of claims 1-3 in the protection of substrate surfaces in marine environments, wherein the substrate surface includes the surface of marine engineering and equipment components.

10. A corrosion-resistant protective component, characterized in that, The Ti / TiCrAlSiN nanolayered film according to any one of claims 1-3 includes a substrate and a Ti / TiCrAlSiN nanolayered film deposited on the surface of the substrate.

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