Imitation titanium film layer, preparation method thereof and composite structure

Abstract

The present invention relates to the field of film layer technology, and in particular to a titanium-imitation film layer, a preparation method thereof, and a composite structure. The titanium-imitation film layer comprises a laminated inner base layer and a decorative outer layer; the inner base layer is used to connect to a substrate to be processed, and the material of the inner base layer comprises a transition metal element; the material of the decorative outer layer comprises tungsten and carbon, and the mass ratio of tungsten to carbon is (80-98): (2-20). The titanium-imitation film layer of the present invention has high surface hardness, good wear resistance, and strong scratch resistance, which is conducive to improving the customer experience in using watches, jewelry, and consumer electronic products.

Description

Technical Field

[0001] The present invention relates to the technical field of film layers, in particular to a titanium-imitation film layer and a preparation method and a composite structure thereof. Background Art

[0002] Products made of titanium and titanium alloys have a metallic luster, which can significantly enhance the product's appearance and appeal. They have great application potential in watches, jewelry and consumer electronics.

[0003] Imitation titanium coatings have a color similar to that of titanium and titanium alloys, offering attractive appearance. Currently, industry research has identified methods for creating imitation titanium coatings on aluminum or magnesium through anodizing, electrolytic coloring, or metallic paint combined with vacuum stainless steel plating. However, these methods often suffer from low surface hardness, poor wear resistance, and poor scratch resistance, resulting in a poor user experience with watches, jewelry, and consumer electronics. Summary of the Invention

[0004] Based on this, the present invention provides a titanium-imitation film layer, a preparation method thereof, and a composite structure.

[0005] The first aspect of the present invention provides a titanium-imitation film layer. The technical solution is as follows:

[0006] A titanium-imitation film layer comprises a laminated inner base layer and a decorative outer layer;

[0007] The inner base layer is used to connect with the substrate to be processed, and the material of the inner base layer includes transition metal elements;

[0008] The material of the decorative outer layer includes tungsten and carbon, and the mass ratio of the tungsten to carbon is (80-98): (2-20).

[0009] In some embodiments, the material of the inner primer layer includes chromium.

[0010] In some embodiments, an intermediate hardening layer is further included, wherein the intermediate hardening layer is located between the inner base layer and the decorative outer layer.

[0011] In some embodiments, the material of the intermediate hardening layer includes one or more of tungsten, carbon, and chromium.

[0012] In some embodiments, the intermediate hardening layer includes a stacked tungsten-carbon composite layer and a chromium-carbon composite layer.

[0013] In some embodiments, one or more of the following features are included:

[0014] 1) The thickness of the inner base layer is 0.1μm to 0.2μm; 2) The thickness of the middle hardening layer is 0.6μm to 0.8μm; 3) The thickness of the decorative outer layer is 0.3μm to 0.5μm.

[0015] The second aspect of the present invention provides a method for preparing a titanium-imitation film layer. The technical solution is as follows:

[0016] A method for preparing a titanium-imitation film layer comprises the following steps:

[0017] Forming an inner base layer by a first physical vapor deposition method for connecting with a substrate to be processed, wherein the target material of the first physical vapor deposition method includes a transition metal target;

[0018] A decorative outer layer is formed on the inner base layer through a second physical vapor deposition method, wherein the target material of the second physical vapor deposition method includes a tungsten target, and the reaction gas includes a carbon-containing gas. By controlling the parameters of the second physical vapor deposition method, the mass ratio of tungsten element to carbon element in the decorative outer layer is (80~98): (2~20).

[0019] In some embodiments, the transition metal target comprises a chromium target.

[0020] In some embodiments, before the second physical vapor deposition method, a third physical vapor deposition method is further included to form an intermediate hardening layer on the inner base layer.

[0021] In some embodiments, the target material for the third physical vapor deposition includes a chromium target and a tungsten target, and the reaction gas includes a carbon-containing gas.

[0022] The third aspect of the present invention provides a composite structure, which includes a substrate and a titanium-imitation film layer provided on the substrate. The titanium-imitation film layer is as described above, and the inner primer layer of the titanium-imitation film layer is connected to the substrate.

[0023] Compared with the traditional solution, the present invention has the following beneficial effects:

[0024] The titanium-like film layer of the present invention comprises an inner base layer and a decorative outer layer. The inner base layer serves as a connecting layer between the substrate to be processed and the decorative outer layer, improving the bonding strength between the titanium-like film layer and the substrate to be processed. The decorative outer layer serves as a titanium-like color layer. By controlling the mass ratio of tungsten and carbon in the decorative outer layer, the titanium-like color is achieved. The titanium-like film layer of the present invention has high surface hardness, excellent wear resistance, and strong scratch resistance, which can enhance the user experience of watches, jewelry, and consumer electronics products. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application and to more fully understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present application. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0026] Figure 1 A schematic structural diagram of a composite structure according to an embodiment of the present invention;

[0027] Figure 2 It is a coordinate diagram of the original color value of the titanium layer, the color value of each embodiment and the comparative example. DETAILED DESCRIPTION

[0028] The present invention will be further described in detail below with reference to specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the present disclosure.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0030] the term

[0031] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0032] In the present invention, "plurality", "multiple", "multiple times", "multiple", etc., unless otherwise specified, refer to a number greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0033] In the present invention, "combinations thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0034] In the present invention, “preferred”, “better”, “more preferred” and “suitable” are only used to describe implementation methods or examples with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of the present invention.

[0035] In the present invention, the terms “further”, “further”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of the present invention.

[0036] In this disclosure, the terms "optionally," "optional," and "optional" are optional and refer to either option, i.e., to the selection of either option from the two parallel options of "optional" or "optional." If multiple "optional" terms appear in a technical solution, each "optional" term is independent unless otherwise specified and there are no conflicts or constraints.

[0037] In the present invention, in the "first aspect," "second aspect," "third aspect," "fourth aspect," etc., the terms "first," "second," "third," "fourth," etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the technical features indicated. Furthermore, "first," "second," "third," "fourth," etc. serve only as non-exhaustive enumeration and description and should be understood not to constitute a closed-ended limitation on quantity.

[0038] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0039] In the present invention, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution is considered continuous within the above numerical interval and includes the two numerical endpoints of the numerical range (i.e., the minimum value and the maximum value), as well as each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as each integer between the two endpoints. In this article, it is equivalent to directly listing each integer, such as t is an integer selected from 1 to 10, indicating that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges included therein.

[0040] The temperature parameters in the present invention, unless otherwise specified, may be either constant temperature or fluctuating within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the precision range of the instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0041] In the present invention, when it comes to percentage content, unless otherwise specified, for solid-liquid mixing and solid-solid mixing, it refers to mass percentage, and for liquid-liquid mixing, it refers to volume percentage.

[0042] In the present invention, when referring to percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the percentage of the added component in the system after the addition of the component.

[0043] In the present invention, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass volume percentage.

[0044] See Figure 1 One embodiment of the present invention provides a composite structure 01, which includes a substrate 40 and a titanium-imitation film layer arranged on the substrate 40, wherein the titanium-imitation film layer includes a stacked inner base layer 10, an intermediate hardening layer 30 and a decorative outer layer 20.

[0045] The inner base layer 10 is connected to the substrate 40. The material of the inner base layer 10 includes transition metal elements.

[0046] In this embodiment, the material of the inner base layer 10 includes chromium. As a transition metal element, chromium is more easily bonded to the surface of the substrate 40, forming surface crystal nuclei, which serve as a connecting layer between the substrate 40 and the decorative outer layer 20, thereby improving the bonding strength between the titanium-imitation film layer and the substrate.

[0047] Optionally, the thickness of the inner primer layer 10 is 0.1 μm to 0.2 μm.

[0048] In this embodiment, the intermediate hardening layer 30 is located between the inner base layer 10 and the decorative outer layer 20. The intermediate hardening layer can further increase the hardness of the titanium-imitation film. In other embodiments, the intermediate hardening layer 30 may not be present, in which case the decorative outer layer 20 is directly connected to the inner base layer 10.

[0049] Optionally, the material of the intermediate hardening layer 30 includes one or more of tungsten, carbon and chromium.

[0050] Preferably, the intermediate hardened layer 30 is made of a laminated tungsten-carbon composite layer and a chromium-carbon composite layer. This provides a higher hardness. Furthermore, the tungsten-carbon composite layer in the intermediate hardened layer 30 is closer in material to the decorative outer layer 20, making it easier to bond with the decorative outer layer 20, forming a dense film.

[0051] Optionally, the thickness of the intermediate hardening layer 30 is 0.6 μm to 0.8 μm.

[0052] The decorative outer layer 20 serves as a titanium-imitation color layer, and its materials include tungsten and carbon, and the mass ratio of the tungsten element to the carbon element is (80-98): (2-20). By controlling the mass ratio of the tungsten element and the carbon element in the decorative outer layer 20, the titanium-imitation color is achieved. It can be understood that the mass ratio of tungsten to carbon includes but is not limited to 80:20, 85:15, 87:13, 90:10, 91:9, 91.3:8.7, 91.5:8.5, 91.8:8.2, 92:8, 93:7, 94:6, 95:5, and 98:2. Preferably, the mass ratio of tungsten to carbon is (87-95): (5-13). More preferably, the mass ratio of tungsten to carbon is (91-93): (7:9).

[0053] Optionally, the thickness of the decorative outer layer 20 is 0.3 μm to 0.5 μm.

[0054] The substrate of this embodiment can be made of aluminum, magnesium, stainless steel, or titanium or titanium alloy.

[0055] The density of titanium or titanium alloy is generally 4.5g / cm 3 About 60% of steel, it is light and high in strength. In order to reduce the weight of watches, jewelry and consumer electronics and improve consumer experience, titanium or titanium alloys have become the favored materials of product designers. However, the surface hardness of titanium or titanium alloys is low, with a Vickers hardness of only about HV280 to 340, and the surface is easily scratched during wear and use.

[0056] When the titanium-imitation film layer of this embodiment is applied to a titanium or titanium alloy surface, the surface color of the titanium-imitation film layer is similar to that of titanium, and the surface hardness is high. Compared with the titanium or titanium alloy substrate, the hardness can be increased by about 2 times to approximately HV1000. The wear resistance and scratch resistance are also greatly improved, which is conducive to enhancing the customer experience of watches, jewelry, and consumer electronics products. This achieves both the appearance and color of the product and the improvement of the surface hardness, thereby enhancing the product's competitiveness.

[0057] One embodiment of the present invention provides a method for forming a titanium-imitation film layer on a substrate to be processed, comprising the following steps:

[0058] S1. Take the substrate to be processed and clean it to remove dirt, oil stains, and other residual foreign matter from the surface. Dry it after cleaning. After drying it using a support fixture, the substrate to be processed is assembled into the vacuum furnace of the physical vapor deposition equipment. Evacuation and heating are performed to remove moisture and impurities. The surface of the substrate to be processed is then cleaned using target ion bombardment to further remove impurities and activate the substrate surface.

[0059] Optionally, the cleaning includes one or more of cleaning with a degreasing agent solution, cleaning with a dewaxing agent solution, and cleaning with water.

[0060] Further optionally, when cleaning with a degreaser solution, the substrate to be processed is immersed in a degreaser solution with a volume concentration of 5% to 10%, and ultrasonically cleaned at 60°C to 80°C for more than 10 minutes to remove oil stains on the surface of the substrate to be processed.

[0061] Further optionally, when cleaning with a wax remover solution, the substrate to be processed is immersed in a wax remover solution with a volume concentration of 3% to 5%, and ultrasonically cleaned at 60°C to 80°C for more than 10 minutes to remove the wax and stains on the surface of the substrate to be processed.

[0062] Further optionally, during water cleaning, the substrate to be processed is immersed in deionized water and ultrasonically cleaned for more than 5 minutes to 10 minutes to remove foreign matter remaining on the surface.

[0063] Optionally, the drying can be carried out in an oven, for example, in an industrial oven, at 60° C. to 120° C. for more than 20 minutes.

[0064] Optionally, vacuum the furnace to a background vacuum pressure no higher than 8.0×10 -3 Pa. Heat until the furnace temperature reaches 60℃~120℃.

[0065] Optionally, the parameters for target ion bombardment cleaning the surface of the substrate to be processed include: the target is a Cr arc target, the target is connected to a DC power supply, the working gas Ar is introduced, the flow rate is 600sccm~900sccm, the bias voltage is 300V~800V, the duty cycle is 20%~80%, the target bombardment current is 60A~90A, and the bombardment time is 3min~5min.

[0066] S2. Forming an inner base layer on the substrate to be processed by a first physical vapor deposition method, and connecting the inner base layer to the substrate to be processed.

[0067] The target material of the first physical vapor deposition method includes a transition metal target. In this embodiment, the transition metal target includes a Cr target, and the inner bottom layer is a Cr layer.

[0068] Optionally, the first physical vapor deposition parameters include: a Cr target connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 20 kHz to 60 kHz, an Ar working gas with a flow rate of 200 sccm to 800 sccm, a bias voltage of 50 V to 200 V, a duty cycle of 20% to 80%, and a Cr target deposition power of 3 kW to 12 kW. The film formation time is adjusted according to different parameter settings to achieve a target film thickness. Optionally, the inner base layer is deposited with a thickness of 0.1 μm to 0.2 μm.

[0069] S3. After forming the inner base layer, a middle hardening layer is formed on the inner base layer by a third physical vapor deposition method.

[0070] Optionally, the target material of the third physical vapor deposition includes a Cr target and a W target, and the reaction gas includes a carbon-containing gas. In this embodiment, the carbon-containing gas is C2H2.

[0071] Optionally, the parameters for the third physical vapor deposition process include: both the Cr target and the W target are connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 20kHz to 60kHz, a working gas Ar with a flow rate of 200sccm to 800sccm, a reactive gas C2H2 with a flow rate of 100sccm to 200sccm, a bias voltage of 100V to 200V, a duty cycle of 20% to 80%, and deposition powers of 3kW to 12kW for both the Cr target and the W target. The film formation time is adjusted to the target film thickness according to different parameter settings. Optionally, the deposition thickness of the intermediate hardening layer is 0.6μm to 0.8μm, and the deposition thickness can be increased according to the hardness requirements.

[0072] In this embodiment, the intermediate hardening layer is a stacked Cr.C layer and a WC layer.

[0073] In this embodiment, an intermediate hardening layer is formed on the inner base layer. In other embodiments, the intermediate hardening layer may not be formed.

[0074] S4. Forming a decorative outer layer on the inner base layer by a second physical vapor deposition method. In this embodiment, the decorative outer layer is formed on the intermediate hardening layer.

[0075] The target material of the second physical vapor deposition method includes a W target, and the reaction gas includes a carbon-containing gas. In this embodiment, the carbon-containing gas is C2H2, and the decorative outer layer is a WC layer.

[0076] By controlling the parameters of the second physical vapor deposition method, the mass ratio of W to C in the decorative outer layer is adjusted to (80-98):(2-20). For example: 80:20, 85:15, 87:13, 90:10, 91:9, 91.3:8.7, 91.5:8.5, 91.8:8.2, 92:8, 93:7, 94:6, 95:5, 98:2. Preferably, the mass ratio of W to C in the decorative outer layer is adjusted to (87-95):(5-13). More preferably, the mass ratio of W to C in the decorative outer layer is adjusted to (91-93):(7:9).

[0077] Optionally, the second physical vapor deposition parameters include: a W target connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 20 kHz to 60 kHz, a working gas Ar flow rate of 200 sccm to 800 sccm, a reactant gas C₂H₂ flow rate of 200 sccm to 400 sccm, a bias voltage of 50 V to 100 V, a duty cycle of 20% to 80%, and a W target deposition power of 3 kW to 12 kW. The film formation time is adjusted according to different parameter settings to achieve the target film thickness, followed by cooling and removal from the furnace. Optionally, the deposited thickness of the decorative outer layer is 0.3 μm to 0.5 μm.

[0078] Optionally, the mixture is cooled to a temperature of 60°C to 80°C.

[0079] The industry's methods of forming a titanium-like color layer through anodizing, electrolytic coloring, or metallic paint + vacuum plating of stainless steel, in addition to the problems of low surface hardness, poor wear resistance, and poor scratch resistance of the titanium-like color layer, also have the following problems: 1) The problem of large chemical pollution and high environmental protection costs. The waste liquid and waste gas generated by metallic paint or chemical solution can be easily inhaled into the human body during the processing, which is harmful to the health of practitioners and has poor safety. 2) Anodizing and electrolytic coloring require the addition of relevant configuration solutions and other tanks. The differences in solution pH, temperature and other conditions have a greater impact on the color. 3) When the substrate is titanium or titanium alloy, due to the poor electrical and thermal conductivity of titanium or titanium alloy, it is more sensitive to hydrogen and hot salt stress corrosion. When forming a titanium-like color layer through anodizing, electrolytic coloring, or metallic paint + vacuum plating of stainless steel, the solution, paint and drying temperature will affect the bonding strength of the titanium-like coating on the surface of the product and even affect the appearance, resulting in appearance defects such as pinholes and corrosion.

[0080] Relatively speaking, the method for preparing the titanium-like film layer in this embodiment has at least the following advantages: (1) high preparation efficiency, suitable for large-scale mass production, and the whole process working time is 6 hours to 10 hours; (2) the titanium-like film layer has a consistent color, stability, and good repeatability, and does not produce uneven appearance caused by chemical dyeing; (3) due to the use of vacuum coating, no chemical strong alkaline or strong acid solution is used, which will not corrode the product; (4) the production process is green and environmentally friendly. In a vacuum environment, the film layer is deposited by PVD and physical magnetron sputtering, and no waste gas or waste liquid is generated. The cleaning process is simple, environmentally friendly, and pollution-free.

[0081] The following is further described in conjunction with specific examples and comparative examples. Unless otherwise specified, the raw materials involved in the following specific examples and comparative examples can be sourced from commercial sources. The instruments used can be sourced from commercial sources unless otherwise specified. The processes involved can be selected conventionally by those skilled in the art unless otherwise specified.

[0082] Example 1

[0083] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0084] Step 1: Take the Ti2 titanium substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the Ti2 titanium substrate into the vacuum furnace of the physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities, and then use Cr arc target ion bombardment to clean the surface of the Ti2 titanium substrate, further remove impurities on the surface of the Ti2 titanium substrate, and activate the substrate surface.

[0085] Step 2: Form a Cr layer on the Ti2 titanium substrate by a first physical vapor deposition method as an inner base layer. The parameters of the first physical vapor deposition method are: the Cr target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced with a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 75%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.1 μm.

[0086] Step 3: Form a stacked Cr.C layer and WC layer on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: both the Cr target and the W target are connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, a working gas Ar flow rate of 400 sccm, a reactive gas C2H2 flow rate of 200 sccm, a bias voltage of 100 V, a duty cycle of 50%, a deposition power of 8 kW for both the Cr target and the W target, and a deposition thickness of 0.8 μm.

[0087] Step 4: A WC layer (with a mass ratio of W to C of 91.5:8.5) is formed on the intermediate hardening layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: a W target is connected to a medium-frequency pulsed sputtering power supply at a power frequency of 40 kHz, a working gas Ar is introduced at a flow rate of 400 sccm, a reaction gas C2H2 is introduced at a flow rate of 260 sccm, a bias voltage of 100 V, a duty cycle of 50%, a W target deposition power of 8 kW, a deposition thickness of 0.5 μm, the vacuum furnace is cooled to 70°C, the furnace is filled with air, and the composite structure with a titanium-like film layer on the substrate is obtained.

[0088] Example 2

[0089] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0090] Step 1: Take the Ti5 titanium substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the Ti5 titanium substrate into the vacuum furnace of the physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities, and then use Cr arc target ion bombardment to clean the surface of the Ti5 titanium substrate, further remove impurities on the surface of the Ti5 titanium substrate, and activate the substrate surface.

[0091] Step 2: Form a Cr layer as an inner base layer on the Ti5 titanium substrate by a first physical vapor deposition method. The parameters of the first physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced with a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 75%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.1 μm.

[0092] Step 3: Form a stacked Cr.C layer and WC layer on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: both the Cr target and the W target are connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, a working gas Ar flow rate of 400 sccm, a reactive gas C2H2 flow rate of 200 sccm, a bias voltage of 100 V, a duty cycle of 50%, a deposition power of 8 kW for both the Cr target and the W target, and a deposition thickness of 0.8 μm.

[0093] Step 4: A WC layer (mass ratio of W element to C element is 91.8:8.2) is formed on the intermediate hardening layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: the W target is connected to a medium-frequency pulse sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced with a flow rate of 400 sccm, the reaction gas C2H2 is introduced with a flow rate of 260 sccm, the bias voltage is 100 V, the duty cycle is 50%, the W target deposition power is 8 kW, the deposition thickness is 0.5 μm, the vacuum furnace is cooled to 70°C, the vacuum furnace is filled with air and the furnace is removed, resulting in a composite structure with a titanium-like film layer on the substrate.

[0094] Example 3

[0095] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0096] Step 1: Take a stainless steel substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the stainless steel substrate into a vacuum furnace of a physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities. Then use Cr arc target ion bombardment to clean the surface of the stainless steel substrate, further remove impurities on the surface of the stainless steel substrate, and activate the substrate surface.

[0097] Step 2: Form a Cr layer on the stainless steel substrate as an inner base layer by a first physical vapor deposition method. The parameters for the first physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply at a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 75%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.1 μm.

[0098] Step 3: Form a stacked Cr.C layer and WC layer on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: both the Cr target and the W target are connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, a working gas Ar flow rate of 400 sccm, a reactive gas C2H2 flow rate of 200 sccm, a bias voltage of 100 V, a duty cycle of 50%, a deposition power of 8 kW for both the Cr target and the W target, and a deposition thickness of 0.8 μm.

[0099] Step 4: A WC layer (with a mass ratio of W to C of 91.3:8.7) is formed on the intermediate hardening layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: a W target is connected to a medium-frequency pulsed sputtering power supply at a power frequency of 40 kHz, a working gas Ar is introduced at a flow rate of 400 sccm, a reaction gas C2H2 is introduced at a flow rate of 260 sccm, a bias voltage of 100 V, a duty cycle of 50%, a W target deposition power of 8 kW, a deposition thickness of 0.5 μm, the vacuum furnace is cooled to 70°C, the furnace is filled with air, and the composite structure with a titanium-like film layer on the substrate is obtained.

[0100] Example 4

[0101] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0102] Step 1: Take a stainless steel substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the stainless steel substrate into a vacuum furnace of a physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities. Then use Cr arc target ion bombardment to clean the surface of the stainless steel substrate, further remove impurities on the surface of the stainless steel substrate, and activate the substrate surface.

[0103] Step 2: Form a Cr layer on the stainless steel substrate as an inner base layer by a first physical vapor deposition method. The parameters for the first physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply at a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 75%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.1 μm.

[0104] Step 3: A WC layer (mass ratio of W to C element: 91.3:8.7) is formed on the inner base layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: the W target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 400 sccm, the reaction gas C2H2 is introduced at a flow rate of 260 sccm, the bias voltage is 100 V, the duty cycle is 50%, the W target deposition power is 8 kW, the deposition thickness is 0.5 μm, the vacuum furnace is cooled to 70°C, the vacuum furnace is filled with air and the substrate is removed from the furnace, resulting in a composite structure with a titanium-like film layer on the substrate.

[0105] Example 5

[0106] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0107] Step 1: Take a stainless steel substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the stainless steel substrate into a vacuum furnace of a physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities. Then use Cr arc target ion bombardment to clean the surface of the stainless steel substrate, further remove impurities on the surface of the stainless steel substrate, and activate the substrate surface.

[0108] Step 2: Form a Cr layer on the stainless steel substrate as an inner base layer by a first physical vapor deposition method. The parameters for the first physical vapor deposition method are: a Cr target connected to a medium-frequency pulsed sputtering power supply at a power frequency of 40 kHz, an Ar working gas at a flow rate of 600 sccm, a bias voltage of 100 V, a duty cycle of 75%, a W target deposition power of 8 kW, and a deposition thickness of 0.1 μm.

[0109] Step 3: Form a stacked Cr.C layer and WC layer on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: both the Cr target and the W target are connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, a working gas Ar flow rate of 400 sccm, a reactive gas C2H2 flow rate of 200 sccm, a bias voltage of 100 V, a duty cycle of 50%, a deposition power of 8 kW for both the Cr target and the W target, and a deposition thickness of 0.8 μm.

[0110] Step 4: A WC layer (W to C mass ratio of 87:13) is formed on the intermediate hardening layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: the W target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 400 sccm, the reaction gas C2H2 is introduced at a flow rate of 260 sccm, the bias voltage is 100 V, the duty cycle is 50%, the W target deposition power is 8 kW, the deposition thickness is 0.5 μm, the vacuum furnace is cooled to 70°C, the vacuum furnace is filled with air and the furnace is removed, resulting in a composite structure with a titanium-like film layer on the substrate.

[0111] Example 6

[0112] This embodiment provides a titanium-imitation film layer and a preparation method and composite structure thereof, and the steps are as follows:

[0113] Step 1: Take a stainless steel substrate, clean it, remove dirt, oil stains and other residual foreign matter on the surface, dry it after cleaning, and assemble the stainless steel substrate into a vacuum furnace of a physical vapor deposition equipment after drying. Vacuum and heat it to remove water vapor and impurities. Then use Cr arc target ion bombardment to clean the surface of the stainless steel substrate, further remove impurities on the surface of the stainless steel substrate, and activate the substrate surface.

[0114] Step 2: Form a Cr layer on the stainless steel substrate as an inner base layer by a first physical vapor deposition method. The parameters for the first physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply at a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 75%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.1 μm.

[0115] Step 3: A Cr.C layer is formed on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 400 sccm, the reaction gas C2H2 is introduced at a flow rate of 200 sccm, the bias voltage is 100 V, the duty cycle is 50%, the Cr target deposition power is 8 kW, and the deposition thickness is 0.8 μm.

[0116] Step 4: A WC layer (with a mass ratio of W to C of 91.3:8.7) is formed on the intermediate hardening layer by a second physical vapor deposition method as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: a W target is connected to a medium-frequency pulsed sputtering power supply at a power frequency of 40 kHz, a working gas Ar is introduced at a flow rate of 400 sccm, a reaction gas C2H2 is introduced at a flow rate of 260 sccm, a bias voltage of 100 V, a duty cycle of 50%, a W target deposition power of 8 kW, a deposition thickness of 0.5 μm, the vacuum furnace is cooled to 70°C, the furnace is filled with air, and the composite structure with a titanium-like film layer on the substrate is obtained.

[0117] Comparative Example 1

[0118] This comparative example provides a film layer, a preparation method thereof, and a composite structure, which are basically the same as Example 1, except that the mass ratio of W element to C element in step 4 is 74:26. ​​Step 4 is as follows:

[0119] Step 4: A second physical vapor deposition method is used to form a WC layer (the mass ratio of W element to C element is 74:26) on the intermediate hardening layer as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: the W target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 400 sccm, the reaction gas C2H2 is introduced at a flow rate of 600 sccm, the bias voltage is 100 V, the duty cycle is 50%, the W target deposition power is 8 kW, the deposition thickness is 0.5 μm, the vacuum furnace is cooled to 70°C, the furnace is filled with air and the substrate is removed from the furnace to obtain a composite structure with a film layer on the substrate.

[0120] Comparative Example 2

[0121] This comparative example provides a film layer, a preparation method thereof, and a composite structure, which are basically the same as those in Example 1, with the main difference being that in step 4, the W element is replaced with Cr, and in step 3, no WC layer is formed. Step 4 is as follows:

[0122] Step 3: A Cr.C layer is formed on the inner base layer by a third physical vapor deposition method as an intermediate hardening layer. The parameters of the third physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply with a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 500 sccm, the reactive gas C2H2 is introduced at a flow rate of 185 sccm, the bias voltage is 200 V, the duty cycle is 60%, the Cr target and the target deposition power are both 8 kW, and the deposition thickness is 0.8 μm.

[0123] Step 4: A second physical vapor deposition method is used to form a Cr.C layer (with a mass ratio of Cr to C of 87.2:12.8) on top of the intermediate hardened layer as a decorative outer layer. The parameters of the second physical vapor deposition method are as follows: the Cr target is connected to a medium-frequency pulsed sputtering power supply at a power supply frequency of 40 kHz, the working gas Ar is introduced at a flow rate of 500 sccm, the reactive gas C2H2 is introduced at a flow rate of 220 sccm, the bias voltage is 60 V, the duty cycle is 40%, the target deposition power is 7 kW, the deposition thickness is 0.5 μm, the vacuum furnace is cooled to 70°C, the vacuum furnace is filled with air and the furnace is removed, resulting in a composite structure with a film layer on the substrate.

[0124] The composite structures prepared in the examples and comparative examples were tested according to the following items.

[0125] Project 1 Visual Effect

[0126] Use a standard color matching light box with AC220V 50HZ and 180W power supply to match the color. Visually inspect the composite structure sample from the side of the decorative outer layer to observe the color effect. If it is close to the color requirement of the titanium substrate before plating, it is judged to be OK.

[0127] Project 2 Color Value Measurement

[0128] Visually inspect the surface condition of the composite structure sample from the decorative outer layer side, ensure the sample and jig are clean, and adjust the jig to the appropriate position and size. Place the sample in the cleaned jig. Place the loaded sample steadily on the measuring workbench and secure it. Gently place the measuring jig on the measuring base jig and secure it. Place the CM-700d spectrometer on the measuring base, ensuring the instrument is in the appropriate position. Then manually press the measurement button on the side of the instrument to start the measurement and record the color value.

[0129] Project 3 Hardness Test

[0130] Clean the surface of the composite sample to ensure it is clean, flat, and smooth. Place the sample in a fixture on the measuring table. Select the load force measurement and adjust the measuring lens until the display is clear. Press the LOAD key to automatically load the measurement. Adjust the eyepiece until the loaded indentation diamond is clear. Measure the diagonal line of the indentation diamond to obtain the Vickers hardness value. If the hardness value is greater than 1000 HV, the hardness is considered to meet the standard.

[0131] Project 4 Hundred Grid Test

[0132] Wipe the surface of the composite sample with a clean cotton cloth. Remove any dirt or dust from the surface. Use a ruler and a razor blade to draw six lines horizontally and vertically on the sample surface, spacing each line 1mm apart. Clean away any debris left from drawing the lines. Apply a piece of 3M-610 adhesive tape to the grid and flatten it with your fingers. After 10 seconds, peel back the tape in one quick, continuous motion. Observe the entire tape and the sample under test using a 4x or 8x magnifying glass. After testing, observe if there is a small amount of film shedding at the intersection of the drawn lines. If less than 5% to 15% of the area is affected, the test is considered acceptable.

[0133] Project 5: Artificial sweat test

[0134] Refer to ISO 3160 / 2, using artificial sweat solution at 25°C and pH 4.7. Composite sample quantity: at least one. Visually inspect the sample before testing to ensure it is normal. Place the test sample in a test dish. Each cycle consists of 48 cycles (24 hours total). After testing, rinse, dry, visually inspect the sample, and perform a tape test. Test duration: 24 hours. Additional test cycles may be performed if necessary. After testing, observe the presence of 1-3 minor corrosion pits / holes, a slight color change in the coating, and the absence of crystals. This indicates a pass.

[0135] Project 6 Salt spray test

[0136] Refer to ISO9227, temperature: 35±1℃, relative humidity: ≧95%, number of composite structure samples: at least 1. Visually inspect the sample before testing. Place the test sample in the testing machine and spray the solution on the sample. Each spray should last for 15 minutes and the temperature should be set at +35℃. After the spraying is completed, place the test sample in an environment with a relative humidity of 95% and a temperature of +35℃ and store it for 15 minutes as one stage. 48 stages (a total of 24 hours) are one cycle. After the test is completed, wash, dry, visually inspect the sample and perform a tape test. Test cycle: The test cycle is 24 hours. If necessary, the number of test cycles can be increased. If there are 1-3 tiny corrosion pits / holes, the color of the coating changes slightly, and there are no crystals, it is judged to be OK.

[0137] Project 7 Thermal shock test

[0138] Before testing, observe and record the composite structure sample. Place the sample in an electric oven heated to 250±10°C for 15 minutes. Remove the sample from the oven and quickly cool it in room temperature DI water. After 10 minutes, remove the sample, dry it, and observe it. If the coating shows no blisters, cracks, detachment, or color change, it is considered acceptable.

[0139] The test results are shown in Table 1 and Table 2, wherein the original color value of the titanium layer, the color value coordinates of Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 are shown in Table 1 and Table 2. Figure 2 .

[0140] Table 1

[0141]

[0142]

[0143] Table 2

[0144]

[0145]

[0146]

[0147] Table 3

[0148]

[0149] In Tables 1 and 2, since the color differences of different titanium substrates after polishing are small, the chromaticity values ​​(L: 75.5, a: 0.5, b: 3.5) are uniformly used to represent the original color values ​​of the titanium layer.

[0150] From Table 1, Table 2 and Figure 2 As can be seen from the figure, under standard light box inspection, Examples 1, 2, and 3 meet visual standards, with color values ​​close to the original color of the titanium layer. The surface hardness is all below 1000 HV. The titanium-like film layers show no obvious abnormalities in the 100-grid, artificial sweat, salt spray, and thermal shock tests, performing well and are all judged to be acceptable.

[0151] Examples 4 and 6 were inspected under a standard light box and met the visual standards, with color values ​​close to the original color of the titanium layer. However, the surface hardness of both samples did not reach 1000 HV, and the 100-grid test was acceptable. However, the artificial sweat, salt spray, and thermal shock tests failed to meet the standards.

[0152] When inspected under a standard light box, Example 5 meets the visual standards, but its color value is not as close to the original color value of the titanium layer as that of Example 3.

[0153] The color of comparative example 1 is darker, the Lab values ​​are far from the target, and the hardness is also low, only 596HV, which does not reach the target hardness. Although there are no abnormalities in other tests, it cannot meet the requirements of imitation titanium and hardening.

[0154] The color of comparative example 2 is lighter and the L value is far from the target. The hardness is also lower, only 882HV, which does not reach the target hardness. Although there are no abnormalities in other tests, it cannot meet the requirements of imitation titanium and hardening.

[0155] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0156] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A titanium-like film layer, characterized in that: including a laminated inner base layer and a decorative outer layer; The inner base layer is used to connect with the substrate to be processed, and the material of the inner base layer includes transition metal elements; The decorative outer layer is made of tungsten and carbon, and the mass ratio of tungsten to carbon is (80-98): (2-20); The titanium-imitation film layer further includes an intermediate hardening layer, and the intermediate hardening layer is located between the inner base layer and the decorative outer layer; The intermediate hardening layer includes a stacked tungsten-carbon composite layer and a chromium-carbon composite layer.

2. The titanium-imitation film layer according to claim 1, characterized in that: The material of the inner primer layer includes chromium element.

3. The titanium-imitation film layer according to any one of claims 1 to 2, characterized in that: Include one or more of the following characteristics: 1) The thickness of the inner base layer is 0.1μm~0.2μm; 2) The thickness of the middle hardening layer is 0.6μm~0.8μm; 3) The thickness of the decorative outer layer is 0.3μm~0.5μm.

4. A method for preparing the titanium-imitation film according to any one of claims 1 to 3, characterized in that: The following steps are involved: Forming an inner base layer by a first physical vapor deposition method for connecting with a substrate to be processed, wherein the target material of the first physical vapor deposition method includes a transition metal target; A decorative outer layer is formed on the inner base layer by a second physical vapor deposition method, wherein the target material of the second physical vapor deposition method includes a tungsten target, the reaction gas includes a carbon-containing gas, and by controlling the parameters of the second physical vapor deposition method, the mass ratio of tungsten element to carbon element in the decorative outer layer is (80~98):(2~20).

5. The method for preparing the titanium-imitation film according to claim 4, wherein: The transition metal target includes a chromium target.

6. The method for preparing the titanium-imitation film according to claim 4 or 5, characterized in that: Before the second physical vapor deposition method, the method further includes forming an intermediate hardening layer on the inner base layer through a third physical vapor deposition method.

7. The method for preparing the titanium-imitation film according to claim 6, wherein: The target materials for the third physical vapor deposition include a chromium target and a tungsten target, and the reaction gas includes a carbon-containing gas.

8. A composite structure, characterized in that The invention comprises a substrate and a titanium-imitation film layer arranged on the substrate, wherein the titanium-imitation film layer is as described in any one of claims 1 to 3, and an inner primer layer of the titanium-imitation film layer is connected to the substrate.

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