A physical vapor deposition process applied to amorphous alloys

Abstract

The application provides a physical vapor deposition process applied to amorphous alloy, which comprises the following steps: taking a zirconium-based amorphous alloy as a base layer, physically vapor depositing an Hf target material on the base layer, preparing an HfO2 thin film with a thickness of 0.5-3 microns on the base layer to obtain a first intermediate product; physically vapor depositing again on the second intermediate product to prepare a deposition layer with a thickness of 6-8 microns to obtain a third intermediate product; and heat treating the third intermediate product in a vacuum environment at 150-170 DEG C for 20-30 minutes and cooling with the furnace to obtain a final product. The application aims to provide a physical vapor deposition process applied to amorphous alloy, and aims to solve the technical problem of single appearance effect of amorphous alloy products, and can further enhance the surface strength, wear resistance and corrosion resistance of the amorphous alloy products.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloy surface treatment technology, specifically relating to a physical vapor deposition process applied to amorphous alloys. Background Technology

[0002] Physical vapor deposition (PVD) technology is often used to deposit high-adhesion coatings on substrates to obtain high-strength surface layers, high-wear-resistant surface layers, or surface layers with special colors, thereby enhancing the surface properties or appearance of the substrate.

[0003] Amorphous alloy materials have become a research hotspot in the field of new materials in recent years, and have already achieved mass production in fields such as 3C electronics, sporting goods, and medical devices. Although products made from amorphous alloy materials have characteristics such as high strength, high hardness, and high corrosion resistance, these very advantages make it difficult to perform surface treatments on amorphous products like traditional metal materials (stainless steel, aluminum alloys, etc.). Existing surface treatment processes such as electroplating, chemical plating, and anodizing cannot be applied to amorphous alloys, resulting in the drawback of amorphous alloy products having a limited range of aesthetic appeal. Summary of the Invention

[0004] The purpose of this invention is to provide a physical vapor deposition process for amorphous alloys, which aims to solve the technical problem of monotonous appearance of amorphous alloy products, while also further enhancing the surface strength, wear resistance and corrosion resistance of amorphous alloy products.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0006] A physical vapor deposition process for amorphous alloys includes the following steps:

[0007] Using a zirconium-based amorphous alloy as the substrate, a Hf target is physically vapor-deposited on the substrate to obtain an HfO2 thin film with a thickness of 0.5~3μm, thus obtaining the first intermediate product.

[0008] The first intermediate product is heat-treated in a vacuum environment at 280~420℃ for 3~5 minutes and then rapidly cooled to obtain the second intermediate product;

[0009] Physical vapor deposition was performed again on the second intermediate product, and the deposited layer was composed of Nb. a Cr b Al c Ti d a, b, c, and d are atomic percentages, where a+b+c+d=100, 20≤a≤30, 20≤b≤30, 20≤c≤30, and 20≤d≤30. The thickness of the deposited layer is 6~8μm, and the third intermediate product is obtained.

[0010] The third intermediate product is heat-treated in a vacuum environment at 150~170℃ for 20~30 minutes, and then cooled in the furnace to obtain the final product.

[0011] This invention employs a two-stage coating process to treat the surface of a zirconium-based amorphous alloy. First, an intermediate product with a light golden hue is obtained by coating an HfO2 thin film, followed by heating and rapid cooling to fix the color. Then, a second layer of mixed metal coating is deposited, giving the amorphous alloy surface a brighter metallic luster while simultaneously enhancing its surface strength, wear resistance, and corrosion resistance.

[0012] Preferably, the rapid cooling rate of the first intermediate product after heat treatment is 35~40℃ / second. The treatment temperature of the first intermediate product should not exceed 420℃, otherwise there is a risk of crystallization of the zirconium-based amorphous alloy material. Rapid cooling is also to prevent the amorphous material from crystallizing, thereby affecting the overall mechanical properties of the product.

[0013] Preferably, the physical vapor deposition can be any one of vacuum evaporation, arc plasma deposition, sputtering deposition, or ion deposition, as long as it meets the requirements.

[0014] Preferably, the zirconium-based amorphous alloy substrate layer has a thickness of 0.1~2 mm. Before processing, it is baked in an oven at 100~120℃ for 1~2 hours, and then ion-cleaned for 2~5 minutes under a vacuum of less than 0.5 Pa. Before physical vapor deposition, the substrate material must be clean and free of contaminants, and moisture must be strictly removed. The physical vapor deposition process provided in this invention is more suitable for surface treatment of thin-walled amorphous alloy parts, especially for thin-walled parts with curved surfaces, and can obtain colored amorphous thin-walled parts with a soft luster.

[0015] Preferably, the first intermediate product is prepared using magnetron sputtering. The vapor deposition process for preparing the first intermediate product is as follows: a film is deposited using magnetron sputtering in a magnetron sputtering instrument, wherein the sputtering current is 300~400mA, the voltage is 600~800V, and the sputtering time is 12~15 minutes.

[0016] Preferably, the third intermediate product is prepared using a plasma deposition method. The vapor deposition process conditions for preparing the third intermediate product are as follows: applying a pulsed bias voltage of -60V to -380V to the second intermediate product through an arc plasma deposition process, controlling the duty cycle to be 12% to 15%, and the pulse bias frequency to be 12 to 14Hz.

[0017] Preferably, to prevent the surface layer from combining with free oxygen in the air and causing excess oxides to form on the surface, the vacuum level of the vacuum environment during the heat treatment of the first intermediate product is 0.05 Pa to 0.5 Pa.

[0018] Preferably, the thickness ratio of all deposited layers to the substrate layer is 1:(20~200). The achievable deposited layer thickness is limited because the first deposited oxide layer is more porous than the second deposited alloy layer. Structurally, the second deposited alloy layer fills and solidifies the first deposited oxide layer. If the first deposited layer is too thick, the overall adhesion between the deposited layer and the substrate will decrease, failing to achieve the desired enhanced surface strength and wear resistance. Conversely, if the second deposited layer is too thick, it will affect the resulting surface morphology, preventing the attainment of a glossy appearance. Therefore, the thickness of the two deposited layers must be strictly controlled within permissible limits to obtain the desired surface appearance.

[0019] Preferably, the zirconium-based amorphous alloy is an amorphous alloy with zirconium as the main element, and the atomic percentage of zirconium in the alloy is ≥55%. The process method provided in this invention is more suitable for zirconium-based amorphous surfaces with zirconium as the absolute main element, and can achieve good technical results.

[0020] Preferably, the process also includes cleaning and drying the final product.

[0021] This invention provides a two-step physical vapor deposition process for amorphous alloys, aiming to solve the technical problem of monotonous appearance in amorphous alloy products. When applied to the surface of zirconium-based amorphous alloy products, it achieves a bright color and a soft metallic luster. Furthermore, the deposited layer can further enhance the surface strength, wear resistance, and corrosion resistance of the amorphous alloy products, thus broadening their applications. The amorphous alloy products prepared by this physical vapor deposition process are suitable for fields requiring both aesthetic appeal and strength, wear resistance, and corrosion resistance, such as wearable devices with various curved surfaces and lightweight AR / VR / MR hardware. Detailed Implementation

[0022] To make the objectives, technical solutions, and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. The embodiments described below are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art in conjunction with the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed; where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0023] It should be understood that the weights of the relevant components mentioned in the embodiments of this invention can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this invention is within the scope of this invention. Specifically, the weights mentioned in the embodiments of this invention can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg.

[0024] Furthermore, unless the context explicitly uses it otherwise, the singular form of a word should be understood as including the plural form of that word. The terms "comprising" or "having" are intended to specify the presence of a feature, quantity, step, operation, element, part, or combination thereof, but are not intended to exclude the presence or possible addition of one or more other features, quantities, steps, operations, elements, parts, or combinations thereof.

[0025] This invention provides a physical vapor deposition process for amorphous alloys. Example 1

[0026] The substrate material used in Example 1 is a zirconium-based amorphous material with a composition of Z. r58 Cu 18 Ni 10 Nb8Al6, where the number after the element symbol represents the atomic percentage of each element. The amorphous raw material with the above composition is weighed and melted in a vacuum melting furnace (suction casting furnace). The melting is repeated three times to make the melt uniform, and then it is suction-cast into a copper mold to make a sample with a length of 100mm, a width of 20mm, and a thickness of 1mm.

[0027] After cleaning the surface of the prepared substrate strip with anhydrous alcohol to remove residual dirt, it was baked in an oven at 100°C for 2 hours, and then ion-cleaned for 5 minutes under a vacuum of 0.1 Pa.

[0028] The cleaned substrate sample was placed in a magnetron sputtering apparatus, and Hf target material was deposited using magnetron sputtering. The sputtering current was 400 mA, the voltage was 800 V, and the sputtering time was 15 minutes. An HfO2 film with an average thickness of 2.367 μm was obtained on the substrate layer, which is the first intermediate product. The film thickness was measured using a laser height gauge. Five test points were evenly selected on the prepared first intermediate product sample, and the average of the five test values ​​was taken.

[0029] The first intermediate product was heat-treated in a vacuum muffle furnace at 380℃ for 3 minutes, then removed and rapidly air-cooled to room temperature within 10 seconds to prevent changes in the amorphous morphology, thus obtaining the second intermediate product. During the heat treatment of the first intermediate product, the vacuum level should ideally be controlled within the range of 0.05Pa to 0.5Pa; a lower vacuum level reduces the risk of surface oxidation and discoloration of the intermediate product. The treatment temperature of the first intermediate product should not exceed 420℃, otherwise the zirconium-based amorphous alloy material may crystallize. Rapid cooling is also to prevent crystallization of the amorphous material, which would affect the overall mechanical properties of the product.

[0030] After cleaning and drying the surface of the second intermediate product, physical vapor deposition was performed again. Using an arc plasma deposition process, a -300V pulsed bias voltage was applied to the second intermediate product, with a duty cycle controlled at 13% and a pulsed bias frequency of 13Hz. The deposited layer consisted of Nb. 30 Cr 25 Al 25 Ti 20 The thickness of the prepared deposited layer was measured to be 7.054 μm, and the method for measuring the thickness of the deposited layer was the same as that used for testing the film thickness on the first intermediate product. This step then yielded the third intermediate product.

[0031] The aforementioned third intermediate product was heat-treated at 150°C and a vacuum of 0.5Pa for 20 minutes, and then cooled in the furnace. After cooling, the product was cleaned and dried to obtain the final desired product.

[0032] In another set of embodiments, the zirconium-based amorphous substrate material used has a composition of Z0. r60 Cu 18 Ni 10 Nb8Al4、Z r60 Cu 20 Ni8Nb8Al4、Z r60 Cu 18 Ni 12 Nb6Al4, Z r60 Cu 18 Ni8Nb8Al6、Z r61 Cu 16 Ni 10 Nb8Al5, Z r62 Cu 15 Ni 10 Nb8Al5, Z r65 Cu 15 Ni 10 Nb5Al5, Z r65 Cu 13 Ni 12 Nb5Al5, Z r70 Cu10 Ni 10 Nb5Al5. In the process of preparing the physical vapor deposition layer, the same technical parameters as in Example 1 can be used, or adaptive adjustments can be made within the range of technical parameters set in this invention.

[0033] For example, the thickness ratio of the deposited layer to the substrate layer should preferably be controlled within the range of 1:(20~200). If the HfO2 thin film layer is too thick, the thickness of the alloy deposited layer should be appropriately increased, or the bias voltage and pulse bias frequency should be increased in the alloy deposited layer processing. Conversely, if the HfO2 thin film layer is too thin, the thickness of the alloy deposited layer should be appropriately reduced to avoid insufficient surface color development.

[0034] In addition to the physical vapor deposition method mentioned in the embodiments, any one of vacuum evaporation, arc plasma deposition, sputtering deposition, or ion deposition can be used in the physical vapor deposition process of the present invention, as long as the required thickness of the coating surface can be obtained.

[0035] As can be seen from the above embodiments, the two-step physical vapor deposition process for amorphous alloys provided by the present invention solves the technical problem of the monotonous appearance of amorphous alloy products. When applied to the surface of zirconium-based amorphous alloy products, it can obtain a surface with bright color and soft metallic luster. Furthermore, the deposited layer can further enhance the surface strength, wear resistance and corrosion resistance of amorphous alloy products, thus further broadening the application of amorphous alloy products.

[0036] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A physical vapor deposition process for amorphous alloys, characterized in that, Includes the following steps, Using a zirconium-based amorphous alloy as the substrate, Hf target material is physically vapor-deposited on the substrate to obtain an HfO2 thin film with a thickness of 0.5~3μm, thus obtaining a first intermediate product. The vapor deposition process for preparing the first intermediate product is as follows: the film is deposited using magnetron sputtering in a magnetron sputtering instrument, wherein the sputtering current is 300~400mA, the voltage is 600~800V, and the sputtering time is 12~15 minutes. The first intermediate product is heat-treated in a vacuum environment at 280~420℃ for 3~5 minutes and then rapidly cooled to obtain the second intermediate product; Physical vapor deposition was performed again on the second intermediate product, and the deposited layer was composed of Nb. a Cr b Al c Ti d a, b, c, and d represent atomic percentages, where a+b+c+d=100, 20≤a≤30, 20≤b≤30, 20≤c≤30, and 20≤d≤30. The thickness of the deposited layer is 6~8μm, yielding the third intermediate product. The vapor deposition process conditions for preparing the third intermediate product are as follows: applying a pulse bias voltage of -60V~-380V to the second intermediate product using an arc plasma coating process, controlling the duty cycle at 12%~15%, and the pulse bias frequency at 12~14Hz. The thickness ratio of all deposited layers to the base layer is 1:(20~200); The third intermediate product is heat-treated in a vacuum environment at 150~170℃ for 20~30 minutes, and then cooled in the furnace to obtain the final product.

2. The physical vapor deposition process for amorphous alloys according to claim 1, characterized in that, The rapid cooling rate of the first intermediate product after heat treatment is 35~40℃ / second.

3. The physical vapor deposition process for amorphous alloys according to claim 2, characterized in that, The zirconium-based amorphous alloy substrate layer has a thickness of 0.1~2mm. Before processing, it is baked in an oven at 100~120℃ for 1~2 hours, and then ion cleaned for 2~5 minutes under a vacuum of less than 0.5Pa.

4. The physical vapor deposition process for amorphous alloys according to claim 1, characterized in that, During the heat treatment of the first intermediate product, the vacuum level of the vacuum environment is 0.05 Pa to 0.5 Pa.

5. The physical vapor deposition process for amorphous alloys according to claim 1, characterized in that, The zirconium-based amorphous alloy is an amorphous alloy with zirconium as the main element, and the atomic percentage of zirconium in the alloy is ≥55%.

6. The physical vapor deposition process for amorphous alloys according to claim 1, characterized in that, It also includes cleaning and drying the final product.