TiVCrZrWAg high-entropy alloy thin film material, and preparation method and application thereof

Abstract

This invention provides a TiVCrZrWAg high-entropy alloy thin film material, its preparation method, and its application, comprising the following steps: cleaning and drying a silicon substrate; placing the cleaned and dried silicon substrate in the vacuum chamber of a magnetron sputtering apparatus, and mounting TiVCrZrW and Ag targets on the target positions of the magnetron sputtering apparatus; introducing Ar gas into the vacuum chamber as the sputtering gas and adjusting the working pressure in the chamber; bombarding the TiVCrZrW and Ag targets, with both targets starting sputtering simultaneously and achieving equal sputtering thicknesses; and cooling the chamber to room temperature after sputtering to obtain the TiVCrZrWAg high-entropy alloy thin film. The TiVCrZrWAg high-entropy alloy thin film material, its preparation method, and its application provided by this invention introduce silver into the TiVCrZrW high-entropy alloy, refining the grain structure of the film, improving its density, and significantly enhancing its friction and corrosion resistance properties, which is of great significance for improving the performance of high-performance mechanical components.

Description

Technical Field

[0001] This invention belongs to the field of protective materials technology, specifically relating to a TiVCrZrWAg high-entropy alloy thin film material, its preparation method, and its application. Background Technology

[0002] With the rapid development of science and technology, thin film materials play a crucial role in aerospace engine components, precision mechanical components, and biomedical implants. However, in these applications, the high coefficient of friction and insufficient wear resistance of thin film materials remain major bottlenecks affecting component performance. Therefore, improving the self-lubricating properties and wear resistance of thin film materials has become an urgent scientific research topic.

[0003] High-entropy alloys differ from traditional alloys such as nickel-based alloys, titanium alloys, iron-based alloys, and aluminum alloys. Traditional alloys are based on one or two metallic elements, with different alloying elements added to improve their properties. High-entropy alloys, on the other hand, are defined as being composed of five or more elements in equimolar ratios (or near-equimolar ratios).

[0004] In high-entropy alloys, the atoms of various elements are randomly distributed across the crystal lattice, and this unique crystal structure provides the alloy with superior properties, including high strength and toughness, high wear resistance, high hardness, high plasticity, corrosion resistance, magnetic properties, and excellent stability at high temperatures. The research focus of domestic and international scholars on academic exchange websites clearly demonstrates the enormous potential of high-entropy alloys and high-entropy alloy coatings as novel materials, which are expected to become leaders in the next generation of materials. This scheme explores the introduction of silver into a TiVCrZrW high-entropy alloy to investigate its tribological and corrosion resistance properties. Summary of the Invention

[0005] The purpose of this invention is to provide a TiVCrZrWAg high-entropy alloy thin film material, its preparation method, and its application. By introducing silver into the TiVCrZrW high-entropy alloy, the grain structure of the thin film is refined, its density is improved, and its friction performance and corrosion resistance are significantly improved, which is of great significance for improving the performance of high-performance mechanical components.

[0006] A method for preparing a TiVCrZrWAg high-entropy alloy thin film material specifically includes the following steps:

[0007] Step S1: Clean and dry the silicon substrate;

[0008] Step S2: Place the cleaned and dried silicon substrate in the vacuum chamber of the magnetron sputtering apparatus. Install the TiVCrZrW and Ag targets on the target positions of the magnetron sputtering apparatus, with the distance between the two targets and the silicon substrate set to 10cm-12cm. Evacuate to a vacuum level of 1×10⁻⁶.-4 Pa ~ 1.2 × 10 -4 Pa;

[0009] Step S3: Introduce Ar gas into the vacuum chamber as sputtering gas, and adjust the working pressure in the chamber to 0.7 Pa to 0.8 Pa;

[0010] After bombarding the TiVCrZrW and Ag targets, the TiVCrZrW and Ag targets started sputtering simultaneously, and the sputtering thickness of the two targets was equal, both ranging from 0.8 μm to 1.0 μm.

[0011] Step S4: After sputtering, the cavity is cooled to room temperature to obtain a TiVCrZrWAg high-entropy alloy thin film.

[0012] In step S1, the silicon substrate is ultrasonically cleaned sequentially with anhydrous ethanol, acetone and deionized water for 15 min to 20 min each, and finally dried at 70°C.

[0013] In step S2, the vacuum level of the cavity is evacuated to 1×10⁻⁶ using a turbomolecular pump. -4 Pa ~ 1.2 × 10 -4 Pa.

[0014] In step S3, the TiVCrZrW target is set to use a DC current with a sputtering current of 0.2A, and the Ag target is set to use a DC current with sputtering currents of 0, 0.08, 0.12, and 0.16A, respectively.

[0015] In step S3, the flow rate of Ar is 60 sccm.

[0016] In step S3, the deposition temperature is set to room temperature.

[0017] The deposition temperature is an experimental condition, and the experiment was conducted by sputtering at room temperature; the silicon substrate described in this scheme is single-crystal silicon (100).

[0018] A method for preparing TiVCrZrWAg high-entropy alloy thin film material.

[0019] Application of a TiVCrZrWAg high-entropy alloy thin film material in biomedical orthopedic implants.

[0020] This proposal suggests a novel thin film material based on the introduction of Ag elements into the TiVCrZrW high-entropy alloy. This material is mainly composed of titanium, vanadium, chromium, zirconium, tungsten, and silver. By introducing interstitial Ag atoms into the TiVCrZrW lattice structure, a significant improvement in the microstructure of the material is achieved.

[0021] Ag atoms, acting as interstitial elements, enter the TiVCrZrW lattice in the form of a solid solution, increasing lattice distortion. This distortion enhances the friction and corrosion resistance of the TiVCrZrW high-entropy alloy thin film material.

[0022] The addition of Ag significantly improves the performance of TiVCrZrW high-entropy alloy thin film materials, and its low coefficient of friction and corrosion resistance make it particularly suitable for application in biomedical orthopedic implants.

[0023] This invention achieves the following significant effects:

[0024] (1) The magnetron sputtering deposition technology used in this invention is used to prepare the above-mentioned TiVCrZrWAg high-entropy alloy thin film material. The process is simple, low-cost, and has a high yield, and can be mass-produced industrially.

[0025] (2) This invention proposes a method for constructing TiVCrZrWAg high-entropy alloy thin films with excellent tribological and corrosion-resistant properties using magnetron sputtering. Attached Figure Description

[0026] Figure 1 The image shows the XRD pattern of the sputtered product.

[0027] Figure 2 This is a graph showing the friction coefficient data.

[0028] Figure 3 This is an electrochemical corrosion polarization curve. Detailed Implementation

[0029] To more clearly illustrate the technical features of this solution, the following detailed implementation method will be used to explain the solution.

[0030] Example 1

[0031] This embodiment describes a method for preparing a TiVCrZrWAg high-entropy alloy thin film with excellent tribological and corrosion resistance properties, specifically carried out according to the following steps:

[0032] 1. The substrate is cleaned and dried sequentially; the substrate is a silicon-based material.

[0033] 2. Place the cleaned and dried substrate from step one into the vacuum chamber of the magnetron sputtering apparatus. Install the TiVCrZrW and Ag targets at two target positions on the magnetron sputtering apparatus, respectively, with a distance of 12cm to 13cm between the two targets and the substrate. Evacuate the chamber to a vacuum level of 1×10⁻⁶. -4 Pa ~ 1.2 × 10 -4 Pa;

[0034] 3. At room temperature, Ar gas is introduced into the cavity as the sputtering gas; a DC current is used for the TiVCrZrW target, and the sputtering current of the TiVCrZrW target is set to 0.2A; a DC current is used for the Ag target, and the sputtering current of the Ag target is set to 0, 0.08A, 0.12A, and 0.16A; the target window is closed; the TiVCrZrW target and the Ag target are sputtered simultaneously, and the sputtering thickness of the two targets is equal, both ranging from 0.9μm to 1.1μm, to obtain a TiVCrZrW high-entropy alloy thin film on the silicon substrate; the flow rate of Ar is 60 sccm;

[0035] IV. After sputtering, a TiVCrZrWAg high-entropy alloy thin film was obtained.

[0036] More preferably, in step one, anhydrous ethanol, acetone and deionized water are used sequentially to ultrasonically clean the substrate for 10 min to 15 min each, and finally the substrate is placed in a drying oven and dried at 60°C.

[0037] More preferably, in step two, the vacuum level of the cavity is evacuated to 1×10⁻⁶ using a turbomolecular pump. -4 Pa.

[0038] The invention was verified using the following experiments:

[0039] Experiment 1: This experiment demonstrates a method for preparing a TiVCrZrWAg high-entropy alloy thin film with excellent tribological and corrosion resistance properties. The specific steps are as follows:

[0040] 1. The substrate is ultrasonically cleaned sequentially with anhydrous ethanol, acetone and deionized water for 15 minutes each. Finally, the substrate is placed in a drying oven and dried at 60°C. The substrate is a silicon substrate.

[0041] 2. Place the cleaned and dried substrate from step one into the vacuum chamber of the magnetron sputtering apparatus. Install the TiVCrZrW and Ag targets at two target positions on the magnetron sputtering apparatus, respectively, with a distance of 12 cm between each target and the substrate. Then, use a turbomolecular pump to evacuate the chamber to a vacuum level of 1 × 10⁻⁶. -4 Pa;

[0042] 3. Ar gas is introduced into the cavity as the sputtering gas; a DC current is used for the TiVCrZrW target, and the sputtering current of the TiVCrZrW target is set to 0.2A; a DC current is used for the Ag target, and the sputtering current of the Ag target is set to 0.08A; the target window is closed; the TiVCrZrW and Ag targets are sputtered simultaneously, and the sputtering thickness of the two targets is equal, both being 1μm, to obtain a TiVCrZrWAg high-entropy alloy thin film on the silicon substrate; the flow rate of the Ar is 60 sccm;

[0043] IV. After sputtering, a TiVCrZrWAg high-entropy alloy thin film was obtained, denoted as TA1.

[0044] The friction coefficient of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 1 was measured to be 0.09 under dry friction conditions using a ball-and-disc tribometer (see...). Figure 2 ).

[0045] Experiment 2: The difference between this experiment and Experiment 1 is that the current of the Ag target is set to 0.12A in step 3, and the TiVCrZrWAg high-entropy alloy film obtained in step 4 of Experiment 1 is denoted as TA2. The rest is the same as Experiment 1.

[0046] The coefficient of friction of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 2 was measured to be 0.13 under dry friction conditions using a ball-and-disc tribometer (see...). Figure 2 ).

[0047] Experiment 3: This experiment differs from Experiment 1 in that the current of the Ag target is set to 0.16A in step 3, and the TiVCrZrWAg high-entropy alloy film obtained in step 4 is denoted as TA3. The rest is the same as Experiment 1.

[0048] The coefficient of friction of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 3 was measured to be 0.12 under dry friction conditions using a ball-and-disc tribometer (see...). Figure 2 ).

[0049] Experiment 4: This experiment is a comparative experiment. No Ag element was added. The specific process differs from Experiment 1 in that no Ag target was installed in step 2. The TiVCrZrW thin film obtained in step 4 is denoted as TA0. Everything else is the same as Experiment 1.

[0050] The friction coefficient of the TiVCrZrW high-entropy alloy film prepared in Experiment 4 was measured to be 0.251 under dry friction conditions using a ball-and-disc tribometer (see...). Figure 2 ).

[0051] Experiments one through four involved measuring friction.

[0052] Example 2

[0053] The difference between this embodiment and Example 1 is that the substrate in step one is MgO; anhydrous ethanol and acetone are used sequentially for ultrasonic cleaning of the substrate.

[0054] Experiment 5: This experiment demonstrates a method for preparing a TiVCrZrWAg high-entropy alloy thin film with excellent tribological and corrosion resistance properties. The specific steps are as follows:

[0055] 1. The substrate was ultrasonically cleaned sequentially with anhydrous ethanol and acetone for 15 minutes each time. Finally, the substrate was placed in a drying oven and dried at 60°C. The substrate was MgO.

[0056] 2. Place the cleaned and dried substrate from step one into the vacuum chamber of the magnetron sputtering apparatus. Install the TiVCrZrW and Ag targets at two target positions on the magnetron sputtering apparatus, respectively, with a distance of 12 cm between each target and the substrate. Then, use a turbomolecular pump to evacuate the chamber to a vacuum level of 1 × 10⁻⁶. -4 Pa;

[0057] 3. Ar gas is introduced into the cavity as the sputtering gas; a DC current is used for the TiVCrZrW target, and the sputtering current of the TiVCrZrW target is set to 0.2A; a DC current is used for the Ag target, and the sputtering current of the Ag target is set to 0.08A; the target window is closed; the TiVCrZrW and Ag targets are sputtered simultaneously, and the sputtering thickness of the two targets is equal, both being 1μm, to obtain a TiVCrZrWAg high-entropy alloy thin film on the silicon substrate; the flow rate of the Ar is 60 sccm;

[0058] IV. After sputtering, a TiVCrZrWAg high-entropy alloy film was obtained, denoted as TA1-Mg.

[0059] The self-corrosion current density of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 5 was measured to be 5.33E-7 A / cm² under simulated body fluid conditions (simulated body fluid is a supersaturated solution of apatite containing calcium and phosphate ions, thus simulating the environment in the human body). 2 The self-corrosion potential is -0.275V (see...). Figure 3 ).

[0060] Experiment Six: This experiment differs from Experiment Five in that the current of the Ag target is set to 0.12A in step three, and the TiVCrZrWAg high-entropy alloy film obtained in step four is denoted as TA2-Mg. The rest is the same as Experiment Five.

[0061] The self-corrosion current density of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 6 was measured to be 2.49E-6 A / cm² under simulated body fluid conditions using an electrochemical workstation. 2 The self-corrosion potential is -0.486V (see...). Figure 3 ).

[0062] Experiment 7: This experiment differs from Experiment 5 in that the current of the Ag target is set to 0.16A in step 3, and the TiVCrZrWAg high-entropy alloy film obtained in step 4 is denoted as TA3-Mg. The rest is the same as Experiment 5.

[0063] The self-corrosion current density of the TiVCrZrWAg high-entropy alloy film prepared in Experiment 7 was measured to be 3.47E-6 A / cm² under simulated body fluid conditions using an electrochemical workstation. 2 The self-corrosion potential is -0.502V (see...). Figure 3 ).

[0064] Tests five through eight were for corrosion testing.

[0065] Experiment 8: This experiment is a comparative experiment and no Ag element was added. The specific process differs from that of Experiment 5 in the following ways:

[0066] In step two, no Ag target was installed. The TiVCrZrW film obtained in step four is denoted as TA0-Mg. Everything else is the same as in experiment five.

[0067] The TA0-Mg, TA1-Mg, TA2-Mg, and TA3-Mg mentioned in this scheme are compared with TA0, TA1, TA2, and TA3. They all use the same thin film material, but different substrates.

[0068] The self-corrosion current density of the TiVCrZrW high-entropy alloy film prepared in Experiment 8 was measured to be 2.51E-6 A / cm² under simulated body fluid conditions using an electrochemical workstation. 2 The self-corrosion potential is -1.568V (see...). Figure 3 ).

[0069] Figure 1 The image shows the XRD pattern of the sputtered product. It can be seen from the image that the addition of Ag causes the peak position to shift to a lower angle. The peak positions of the silver-added samples TA1, TA2, and TA3 are between the Ag peak position and the undoped sample TA0, indicating that the doping process caused a change in the phase structure, changing the preferred orientation from BCC(110) to BCC(111), thereby altering the properties of the material.

[0070] This solution actually provides two types of substrates: silicon substrate and MgO. Specifically, magnesium oxide (MgO) is an excellent single-crystal substrate and is widely used in the fabrication of ferroelectric thin films, magnetic thin films, optoelectronic thin films and high-temperature superconducting thin films. Because it has a very low dielectric constant and loss in the microwave band and can produce large-area substrates (2 inches in diameter and larger), it is one of the important high-temperature superconducting thin film single-crystal substrates for current industrialization.

[0071] It should be noted that in this scheme, the Ag content is limited by controlling the current intensity, and the Ag content changes accordingly, that is, the sputtering concentration changes. Therefore, this scheme only studies the change of sputtering current of Ag target material to measure the corresponding properties of thin film material.

[0072] The technical features of this invention not described can be implemented by or using existing technology, and will not be repeated here. Of course, the above description is not a limitation of this invention, and this invention is not limited to the examples above. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of this invention should also be within the protection scope of this invention.

Claims

1. A method for preparing a TiVCrZrWAg high-entropy alloy thin film material, characterized in that, Specifically, the steps include the following: Step S1: Clean and dry the silicon substrate; Step S2: Place the cleaned and dried silicon substrate in the vacuum chamber of the magnetron sputtering apparatus. Install the TiVCrZrW and Ag targets on the target positions of the magnetron sputtering apparatus, with the distance between the two targets and the silicon substrate set to 10cm-12cm. Evacuate to a vacuum level of 1×10⁻⁶. -4 Pa ~ 1.2 × 10 -4 Pa; Step S3: Introduce Ar gas into the vacuum chamber as sputtering gas, and adjust the working pressure in the chamber to 0.7 Pa to 0.8 Pa; After bombarding the TiVCrZrW and Ag targets, the TiVCrZrW and Ag targets started sputtering simultaneously, and the sputtering thickness of the two targets was equal, both ranging from 0.8 μm to 1.0 μm. Step S4: After sputtering, the cavity is cooled to room temperature to obtain a TiVCrZrWAg high-entropy alloy thin film.

2. The method for preparing a TiVCrZrWAg high-entropy alloy thin film material according to claim 1, characterized in that, In step S1, the silicon substrate is ultrasonically cleaned sequentially with anhydrous ethanol, acetone and deionized water for 15 min to 20 min each, and finally dried at 70°C.

3. The method for preparing a TiVCrZrWAg high-entropy alloy thin film material according to claim 1, characterized in that, In step S2, the vacuum level of the cavity is evacuated to 1×10⁻⁶ using a turbomolecular pump. -4 Pa ~ 1.2 × 10 -4 Pa.

4. The method for preparing a TiVCrZrWAg high-entropy alloy thin film material according to claim 1, characterized in that, In step S3, the TiVCrZrW target is set to use a DC current with a sputtering current of 0.2A, and the Ag target is set to use a DC current with sputtering currents of 0.08, 0.12, and 0.16A, respectively.

5. The method for preparing a TiVCrZrWAg high-entropy alloy thin film material according to claim 1, characterized in that, In step S3, the flow rate of Ar is 60 sccm.

6. The method for preparing a TiVCrZrWAg high-entropy alloy thin film material according to claim 1, characterized in that, In step S3, the deposition temperature is set to room temperature.

7. A TiVCrZrWAg high-entropy alloy thin film material prepared by the preparation method according to any one of claims 1-6.

8. The application of the TiVCrZrWAg high-entropy alloy thin film material according to claim 7 in biomedical orthopedic implants.

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