Corrosion-resistant thin film and method of making and use thereof

Abstract

The present application relates to the technical field of decorative plating, and particularly relates to a corrosion-resistant film, a preparation method and application thereof. The corrosion-resistant film comprises a substrate, a primer layer arranged on one side of the substrate, a transition layer arranged on the primer layer, and a color layer arranged on the transition layer. The primer layer is a Cr layer, a Ti layer or a TiCr layer. The transition layer is a SiCrC layer or a SiTiC layer. The color layer is a WC layer. The WC layer is obtained by using a skip air mode for deposition. The film can meet the requirements of high-end decoration industry companies on blackness, and has excellent corrosion resistance and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of decorative plating, in particular to a corrosion-resistant film and a preparation method and application thereof. BACKGROUND

[0002] PVD film coating is generally divided into three technologies of evaporation plating, sputtering plating and ion plating. Evaporation plating has the disadvantages of low particle energy, difficulty in evaporation of high-melting-point film material and poor diffraction performance of the film, which makes it difficult to ensure the uniformity of the film thickness of each surface of a three-dimensional workpiece, and the deposited film generally cannot meet the requirements of color consistency, wear resistance, scratch resistance and corrosion resistance in the field of decorative plating. Ion plating has a high ionization rate of target material or film material, but the existing ion plating technology has a low deposition rate and a relatively complex device structure, which cannot meet the manufacturing cost requirements of the field of decorative plating. The magnetron sputtering plating is a kind of sputtering plating method, which can be used to prepare a coating with excellent properties such as dense film layer, scratch resistance, corrosion resistance and good film-substrate adhesion. In addition, the magnetron sputtering plating is an energy-saving and environmentally friendly film coating technology, and the entire film forming process is completed by target sputtering deposition under vacuum conditions without pollution to the environment. Therefore, the magnetron sputtering is the most widely used PVD film coating technology in the field of decorative plating.

[0003] Black color tone has visual characteristics such as being steady, low-key and rich in technological sense, so it is favored by customers and the market. It is usually prepared by magnetron sputtering of different proportions of Ti, Cr and W single-element metal or alloy target material and C2H2 and / or CH4, and the color of the film layer is controlled by adjusting the metal target sputtering rate and the flow rate of C-containing gas and adjusting the film thickness. In this process, if the brightness of the film layer needs to be reduced, the metal target sputtering rate must be reduced or the flow rate of C-containing gas must be increased, so that the proportion of compounds on the surface of the target will inevitably increase, and the sputtering rate will be significantly lower than the reaction rate, which is the phenomenon of target poisoning. After the target is poisoned, the surface resistance of the metal target will become higher and higher, causing unstable glow, even arc extinction (termination of glow discharge), and ultimately making the film layer unable to continue to deposit. Therefore, under the existing technical conditions, in order to prevent the occurrence of unstable glow due to target poisoning, the metal target sputtering rate and the flow rate of C-containing reaction gas must be controlled within a certain limit to avoid target poisoning. In this way, the brightness of the deposited black film layer is always high, and its blackness is difficult to meet the increasingly high requirements of high-end decorative industry companies. In addition, the traditional sputtering deposition of black film layer uses single-element metal target material or alloy target material, which is prone to columnar crystal gaps during the deposition process, thereby reducing the corrosion resistance and failing to meet the existing requirements of decorative film layer corrosion resistance.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] An object of the present application is to provide a corrosion-resistant film to solve the technical problems in the prior art that the blackness and corrosion resistance of the film layer cannot meet the requirements.

[0006] In order to achieve the above object of the present application, the technical scheme is as follows:

[0007] The corrosion-resistant film comprises a substrate;

[0008] A primer layer arranged on one side of the substrate;

[0009] A transition layer arranged on the primer layer; and

[0010] A color layer arranged on the transition layer.

[0011] The primer layer is a Cr layer, a Ti layer or a TiCr layer; the transition layer is a SiCrC layer or a SiTiC layer; and the color layer is a WC layer.

[0012] In the embodiment of the present application, a color connecting layer is arranged between the transition layer and the color layer. Further, the color connecting layer is a CrWC layer or a TiWC layer.

[0013] In the embodiment of the present application, the WC layer is deposited by using a skip gas mode. Further, in the skip gas mode, the flow of the reaction gas C2H2 is instantaneously increased to 450-650 sccm when the WC layer is deposited.

[0014] In the embodiment of the present application, the SiCrC layer comprises CrC layers and SiC layers arranged alternately and in layers; and the SiTiC layer comprises TiC layers and SiC layers arranged alternately and in layers.

[0015] In the embodiment of the present application, the Lab color value of the corrosion-resistant film satisfies: L is 25-30, a is -1-1, and b is -2-1.

[0016] Another object of the present application is to provide a preparation method of the corrosion-resistant film.

[0017] The preparation method of the corrosion-resistant film comprises the following steps:

[0018] The primer layer, the transition layer and the color layer are sequentially deposited on one side surface of the substrate by using a medium-frequency magnetron sputtering method.

[0019] In the embodiment of the present application, the method further comprises: depositing a color connecting layer between the transition layer and the color layer.

[0020] In the specific embodiment of the present application, when the transition layer is deposited, the substrate with the primer layer circulates through the Cr target and the Si target, and the CrC layer and the SiC layer are alternately and sequentially formed on the primer layer; or, when the transition layer is deposited, the substrate with the primer layer circulates through the Ti target and the Si target, and the TiC layer and the SiC layer are alternately and sequentially formed on the primer layer.

[0021] In the specific embodiment of the present application, when the color layer is deposited, the flow of the reaction gas C2H2 is increased to 450-650 sccm within <1 s.

[0022] Another object of the present application is to provide the application of the corrosion-resistant film in the field of 3C products or high-end decoration.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] (1) The corrosion-resistant film of the present application is provided with a primer layer, a transition layer, a color transition layer and a color layer, and the CrC (or TiC) and SiC layers are alternately and sequentially arranged to avoid the generation of columnar crystal gaps and improve the corrosion resistance of the film layer; the color transition layer solves the problem of the bonding force between the color layer and the transition layer; the color layer adjusts the final L value of the film layer, and the final L value of the film layer is reduced to the appropriate range by controlling the W target current and the flow of C2H2; thus, the film of the present application not only meets the requirements of the high-end decoration industry for blackness, but also has excellent corrosion resistance.

[0025] (2) The present application uses intermediate frequency magnetron sputtering to prepare a film with corrosion resistance and consistent color on the surface of the workpiece by reacting the target materials with C2H2 and other reaction gases, and by using appropriate modes and parameter conditions, a film layer with blackness meeting the requirements is prepared, and at the same time, since the film layer meeting the blackness requirements is deposited in a short time, the phenomenon of palladium poisoning caused by long-term work of the metal target surface, which leads to unstable glow, is avoided. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the specific embodiments of the present application or the prior art, the drawings needed in the specific embodiment or prior art description will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0027] Figure 1 The structural schematic diagram of the corrosion-resistant film provided by some embodiments of the present application is shown in the following figure:

[0028] Figure 2Structural schematic diagram of the corrosion-resistant film provided for some embodiments of the present application.

[0029] Reference signs:

[0030] 1 - substrate; 2 - primer layer; 3 - transition layer;

[0031] 4 - color matching layer; 5 - color layer. DETAILED DESCRIPTION

[0032] The technical solutions of the present application will be described clearly and completely in combination with the drawings and specific embodiments, but those skilled in the art will understand that the following described embodiments are part of the embodiments of the present application, not all the embodiments, and are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts are within the scope of protection of the present application. The specific conditions are not specified in the embodiments, and are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0033] It should be noted that the chemical formula "TiCr", "SiCrC", "SiTiC", "CrWC", "TiWC", "WC" and the like used in the present application represent that the corresponding layer contains the elements listed in the formula, and the ratio between the elements is not limited. Taking TiCr as an example, when the primer layer is a TiCr layer, the primer layer contains both Ti elements and Cr elements, and the molar ratio of the two can be 1:1, or can be adjusted to other ratios.

[0034] Figure 1 Structural schematic diagram of the corrosion-resistant film provided for some embodiments of the present application; as Figure 1 shown, the corrosion-resistant film provided by some embodiments of the present application comprises:

[0035] a substrate 1;

[0036] a primer layer 2 arranged on one side of the substrate 1;

[0037] a transition layer 3 arranged on the primer layer 2; and

[0038] a color layer 5 arranged on the transition layer 3.

[0039] The primer layer 2 is a Cr layer, a Ti layer or a TiCr layer; the transition layer 3 is a SiCrC layer or a SiTiC layer; and the color layer 5 is a WC layer.

[0040] The corrosion-resistant film of the present application can meet the requirements of high-end decoration industry companies on blackness and has excellent corrosion resistance through the arrangement of the layer structure and materials.

[0041] Figure 2 The structure diagram of the corrosion-resistant film provided by some other embodiments of the present application is shown in the figure; the embodiment is an improvement on the above-mentioned embodiment, and the content disclosed in the above-mentioned embodiment will not be described repeatedly and also belongs to the content disclosed by the embodiment. Figure 2 As shown in the figure, the corrosion-resistant film provided by some embodiments of the present application is further provided with a color transition layer 4 between the transition layer 3 and the color layer 5. Further, the color transition layer 4 is a CrWC layer or a TiWC layer.

[0042] In the specific embodiment of the present application, the WC layer is obtained by using a jump gas mode. Further, in the jump gas mode, the flow of the reaction gas C2H2 is instantaneously increased to 450-650 sccm when the WC layer is deposited.

[0043] The color layer of the present application uses a jump gas mode, and the reaction gas C2H2 is instantaneously added to the gas amount required by the process, rather than a step-by-step gas addition mode. This jump gas mode can quickly make the metal target surface reach the super-black deposition state, and the ultra-low L value film layer can be deposited in a short time, avoiding the phenomenon of target poisoning caused by long-time work of the metal target surface, which leads to unstable glow.

[0044] At the same time, the remaining layers use a step-by-step gas addition mode; since the thickness of the remaining layers is relatively thick, the stress is large, and if the jump gas mode is used, obvious interlayer interfaces are easy to appear, and then stress differences exist between the layers, which can lead to poor adhesion.

[0045] In the specific embodiment of the present application, the SiCrC layer includes CrC layers and SiC layers arranged alternately and stacked; and the SiTiC layer includes TiC layers and SiC layers arranged alternately and stacked.

[0046] Through the CrC layer (or TiC layer) and SiC layer arranged alternately and stacked, the generation of columnar crystal gaps can be avoided, and the SiC material itself has strong corrosion resistance. The arrangement of the film layer structure of the transition layer 3 and the selection of the material effectively improve the corrosion resistance of the film.

[0047] In the specific embodiment of the present application, the thickness of a single CrC layer or a single SiC layer in the SiCrC layer is 2-10 nm; and the thickness of a single TiC layer or a single SiC layer in the SiTiC layer is 2-10 nm.

[0048] As in different embodiments, the thickness of the SiCrC layer, single CrC layer or single SiC layer can be exemplarily 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc.; the thickness of the SiTiC layer, single TiC layer or single SiC layer can be exemplarily 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc.

[0049] In the specific embodiment of the present application, the thickness of the primer layer 2 is 0.1-0.3μm; the thickness of the transition layer 3 is 0.6-1μm; the thickness of the color connection layer 4 is 0.1-0.5μm; the thickness of the color layer 5 is 0.04-0.06μm.

[0050] With the above range of proportions, the matching, uniformity, bonding performance and corrosion resistance between the layers can be ensured.

[0051] As in different embodiments, the thickness of the primer layer 2 can be exemplarily 0.1μm, 0.15μm, 0.2μm, 0.25μm, 0.3μm, etc.; the thickness of the transition layer 3 can be exemplarily 0.6μm, 0.7μm, 0.8μm, 0.9μm, 1μm, etc.; the thickness of the color connection layer 4 can be exemplarily 0.3μm, 0.35μm, 0.4μm, 0.45μm, 0.5μm, etc.; the thickness of the color layer 5 can be exemplarily 0.04μm, 0.045μm, 0.05μm, 0.055μm, 0.06μm, etc.

[0052] In the specific embodiment of the present application, the substrate 1 includes metal substrate, plastic substrate, ceramic substrate, glass substrate, etc. The type of the substrate 1 can be adjusted and selected according to the requirements of the workpiece, such as stainless steel substrate, etc.

[0053] In the specific embodiment of the present application, the Lab color value of the corrosion-resistant film satisfies: L is 25-30, a is -1-1, b is -2-1. Further, the Lab color value of the corrosion-resistant film satisfies: L is 26-30, a is -1-1, b is -1.8-1.

[0054] In different embodiments, the L in the Lab color value of the corrosion-resistant film can be exemplarily 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, etc., the a can be exemplarily -1, -0.8, -0.6, -0.5, -0.4, -0.2, 0, 0.2, 0.4, 0.6, 0.8, 1, etc., and the b can be exemplarily -2, -1.8, -1.6, -1.5, -1.4, -1.2, -1, -0.8, -0.6, -0.5, -0.4, -0.2, 0, 0.2, 0.4, 0.6, 0.8, 1, etc.

[0055] In the existing conventional black film, the L in the Lab color value is usually > 32. Through the film layer structure setting of the present application, the blackness of the corrosion-resistant film obtained meets the blackness requirement (L is 26-29) of the high-end decoration industry on the decoration plating.

[0056] The present application also provides a preparation method of any one of the corrosion-resistant films, comprising the following steps:

[0057] The base layer 2, the transition layer 3 and the color layer 5 are sequentially deposited on one side surface of the substrate 1 by using a medium-frequency magnetron sputtering method.

[0058] In the specific embodiment of the present application, the preparation method further comprises: depositing a color connection layer 4 between the transition layer 3 and the color layer 5.

[0059] In the specific embodiment of the present application, when the base layer 2 is deposited, the sputtering working gas Ar flow is 200-800 sccm, the bias voltage is 50-400 V, the duty cycle is 20%-80%, and the target material power is 3-12 kW.

[0060] In different embodiments, when the base layer 2 is deposited, the sputtering working gas Ar flow can be exemplarily 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, etc.; the bias voltage can be exemplarily 50 V, 100 V, 200 V, 300 V, 400 V, etc.; the duty cycle can be exemplarily 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; and the target material power can be exemplarily 3 kW, 4 kW, 5 kW, 6 kW, 7 kW, 8 kW, 9 kW, 10 kW, 11 kW, 12 kW, etc.

[0061] In actual operation, the element of the primer layer 2 can be Cr or Ti, or a mixture of Cr and Ti. The Cr and / or Ti target is connected to a medium-frequency magnetron sputtering power source, and then Ar is introduced, the flow rate, bias voltage, duty cycle, target power, etc. are set, and the deposition time is adjusted according to the parameter settings until the target deposition thickness is reached.

[0062] In the specific embodiments of the present application, when depositing the transition layer 3, the sputtering working gas Ar flow rate is 200-800 sccm, the reaction gas C2H2 flow rate is 50-150 sccm, the bias voltage is 50-400 V, the duty cycle is 20%-80%, and the target power is 3-12 kW. Among them, the power of the Cr target or Ti target is 3-12 kW, and the power of the Si target is 3-12 kW.

[0063] Further, when depositing the transition layer 3, the reaction gas C2H2 flow rate is increased from 50-60 sccm to 140-150 sccm within 18-22 min. For example, the reaction gas C2H2 flow rate is increased from 50 sccm to 150 sccm within 20 min.

[0064] As in different embodiments, when depositing the transition layer 3, the sputtering working gas Ar flow rate can be exemplarily 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, etc.; the reaction gas C2H2 flow rate can be exemplarily 50 sccm, 60 sccm, 80 sccm, 100 sccm, 120 sccm, 140 sccm, 150 sccm, etc.; the bias voltage can be exemplarily 50 V, 100 V, 200 V, 300 V, 400 V, etc.; the duty cycle can be exemplarily 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; and the target power can be exemplarily 3 kW, 4 kW, 5 kW, 6 kW, 7 kW, 8 kW, 9 kW, 10 kW, 11 kW, 12 kW, etc.

[0065] In actual operation, the transition layer 3 is a SiCrC layer or a SiTiC layer, and a Si target and a Cr target or a Si target and a Ti target are used. The Cr target (or Ti target) and the Si target are connected to a medium-frequency magnetron sputtering power source, and then Ar and the reaction gas C2H2 are introduced, the flow rate, bias voltage, duty cycle, target power, etc. are set, and the deposition time is adjusted according to the parameter settings until the target deposition thickness is reached.

[0066] In the specific embodiment of the present application, when depositing the color transition layer 4, the sputtering working gas Ar flow rate is 200-800 sccm, the reaction gas C2H2 flow rate is 150-300 sccm, the bias voltage is 50-400 V, the duty cycle is 20%-80%, and the target power is 3-12 kW. Among them, the power of the Cr target or Ti target is 3-12 kW, and the power of the W target is 3-12 kW.

[0067] Further, when depositing the color transition layer 4, the reaction gas C2H2 flow rate is increased from 150-160 sccm to 240-250 sccm within 8-12 min. For example, the reaction gas C2H2 flow rate is increased from 150 sccm to 250 sccm within 10 min.

[0068] As in different embodiments, when depositing the color transition layer 4, the sputtering working gas Ar flow rate can be exemplarily 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, etc.; the reaction gas C2H2 flow rate can be exemplarily 150 sccm, 180 sccm, 200 sccm, 220 sccm, 250 sccm, 280 sccm, 300 sccm, etc.; the bias voltage can be exemplarily 50 V, 100 V, 200 V, 300 V, 400 V, etc.; the duty cycle can be exemplarily 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; and the target power can be exemplarily 3 kW, 4 kW, 5 kW, 6 kW, 7 kW, 8 kW, 9 kW, 10 kW, 11 kW, 12 kW, etc.

[0069] In actual operation, the color transition layer 4 is a CrWC layer or a TiWC layer, and a Cr target and a W target or a Ti target and a W target are used respectively. The Cr target (or Ti target) and the W target are connected to a medium-frequency magnetron sputtering power source, and then Ar and the reaction gas C2H2 are introduced, and the flow rate, bias voltage, duty cycle, target power, etc. are set. The deposition time is adjusted according to the parameter setting until the target deposition thickness is reached.

[0070] In the specific embodiment of the present application, when depositing the color layer 5, the sputtering working gas Ar flow rate is 200-800 sccm, the reaction gas C2H2 flow rate is 450-650 sccm, the bias voltage is 50-200 V, the duty cycle is 20%-80%, and the target power is 3-8 kW.

[0071] Further, when depositing the color layer 5, the reaction gas C2H2 flow rate is increased to 450-650 sccm within <1 s, without a gas addition step.

[0072] As in different embodiments, when depositing the color layer 5, the sputtering working gas Ar flow rate can be exemplarily 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, etc.; the reaction gas C2H2 flow rate can be exemplarily 450 sccm, 480 sccm, 500 sccm, 520 sccm, 550 sccm, 580 sccm, 600 sccm, 620 sccm, 650 sccm, etc.; the bias voltage can be exemplarily 50 V, 80 V, 100 V, 120 V, 150 V, 180 V, 200 V, etc.; the duty cycle can be exemplarily 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; and the target power can be exemplarily 3 kW, 4 kW, 5 kW, 6 kW, 7 kW, 8 kW, etc.

[0073] In actual operation, the color layer 5 is a WC layer, a W target is connected to a medium-frequency magnetron sputtering power source, and then Ar and the reaction gas C2H2 are introduced, the flow rate, bias voltage, duty cycle, target power, etc. are set, and the deposition time is adjusted according to the parameter setting until the target deposition thickness is reached.

[0074] In the present application, when depositing the WC layer, the W target power and the C2H2 flow rate are controlled to reduce the final L value of the film layer to about 26. Specifically, the gas switching mode is adopted, the reaction gas C2H2 is instantaneously added to the gas amount required by the process, the metal target surface rapidly reaches the super-black deposition state, and the ultra-low L value film layer can be deposited in a short time, avoiding the target poisoning caused by the long-time work of the metal target surface, which leads to the instability of the glow. At the same time, if the palladium poisoning time is longer, it will cause the color layer to be loose, which greatly affects the wear resistance and the like.

[0075] In the specific embodiments of the present application, when depositing the transition layer 3, the substrate 1 deposited with the primer layer 2 circulates through the Cr target and the Si target to form the CrC layer and the SiC layer alternately and stacked on the primer layer 2; or, when depositing the transition layer 3, the substrate 1 deposited with the primer layer 2 circulates through the Ti target and the Si target to form the TiC layer and the SiC layer alternately and stacked on the primer layer 2.

[0076] In actual operation, the transition layer 3 can be deposited in the following manner: when depositing the transition layer 3, the Cr target (or Ti target) and the Si target are respectively installed on opposite sides, and after the film layer deposition starts, the substrate 1 deposited with the primer layer 2 circulates through the Cr target (or Ti target) and the Si target, respectively, so that the CrC (or TiC) and SiC nanometer thin films are sequentially stacked, avoiding the generation of columnar crystal gaps, and the SiC material itself has strong corrosion resistance, so that the film layer structure and material selection of the transition layer 3 improve the corrosion resistance of the super-black film layer.

[0077] In the detailed description of the present application, the method further comprises: pretreating the substrate 1 before depositing the primer layer 2. The pretreatment comprises: cleaning the substrate 1 to remove dirt, oil stains and other residual foreign matter on the surface of the substrate 1; and then preheating the cleaned substrate 1 in a vacuum chamber. Further, the method further comprises: performing arc target bombardment treatment on the preheated substrate 1.

[0078] In actual operation, in the preheating, the base vacuum degree of the vacuum chamber is not higher than 8x10 -3 Pa, and the preheating temperature is 100-150℃, such as 120℃.

[0079] The arc target bombardment treatment comprises: the flow rate of working gas Ar is 200-800sccm, the bias voltage is 200-600V, the duty cycle is 20%-80%, the arc current is 40-100A, and the time is 1-10min. The arc target bombardment treatment is used to activate the surface of the substrate 1 and further remove residual foreign matter on the surface of the substrate 1.

[0080] In the detailed description of the present application, the substrate 1 is a metal material. In different embodiments, the substrate 1 can be stainless steel, magnesium alloy, aluminum or aluminum alloy, zinc alloy, etc., and is preferably stainless steel, aluminum alloy or magnesium alloy.

[0081] The present application also provides the application of the above-mentioned any one of the corrosion-resistant films in the field of 3C products or high-end decoration.

[0082] Example 1

[0083] This embodiment provides a corrosion-resistant film, which has the structure as shown in Figure 1 The corrosion-resistant film comprises a substrate 1 and a primer layer 2, a transition layer 3 and a color layer 5 which are sequentially stacked on one side surface of the substrate 1.

[0084] The substrate 1 is stainless steel; the primer layer 2 is a Cr layer with a thickness of 0.2μm; the transition layer 3 is a SiCrC layer with a thickness of 0.8μm; and the color layer 5 is a WC layer with a thickness of 0.05μm. In the transition layer 3, the SiCrC layer comprises CrC layers and SiC layers which are alternately stacked, and the thickness of a single CrC layer is 5nm and the thickness of a single SiC layer is 5nm.

[0085] The preparation method of the corrosion-resistant film of this embodiment comprises the following steps:

[0086] (1) The substrate is pre-cleaned to remove dirt, oil stains and other residual foreign matter on the surface of the substrate.

[0087] (2) Put the cleaned substrate into the vacuum chamber, and vacuumize and preheat it. The base vacuum pressure is 8.0x10 -3 Pa, and the preheating temperature is 120℃.

[0088] (3) Perform arc target bombardment treatment. Introduce working gas Ar at a flow rate of 600sccm, and apply a bias voltage of 300V / 80% (duty cycle) to the workpiece. The arc current is 70A, and the time is 5min. The surface of the workpiece is activated, and the residual foreign matter on the surface of the substrate can be further removed.

[0089] (4) Deposit a Cr primer layer. Introduce working gas Ar at a flow rate of 400sccm, and apply a bias voltage of 100V / 75% (duty cycle). The Cr target power is 8kW, and the deposition time is 20min.

[0090] (5) Deposit a SiCrC transition layer. Introduce working gas Ar at a flow rate of 400sccm, and introduce reaction gas C2H2 at a flow rate of 50sccm to 150sccm within 20min. Apply a bias voltage of 80V / 50% (duty cycle). The Cr target power is 8kW, the Si target power is 8kW, and the reaction gas is stable at 150sccm for 30min.

[0091] (6) Deposit a WC color layer. Introduce working gas Ar at a flow rate of 400sccm, and introduce reaction gas C2H2 at a flow rate of 600sccm (instantaneous to position, no gas step length). Apply a bias voltage of 100V / 50% (duty cycle). The W target power is 6kW, and the deposition time is 5min.

[0092] (7) Cool down and discharge.

[0093] Example 2

[0094] The corrosion-resistant film provided in this example has a structure as shown in Figure 2 which includes a substrate 1 and a primer layer 2, a transition layer 3, a color transition layer 4, and a color layer 5 which are sequentially stacked on one side surface of the substrate 1.

[0095] The substrate 1 is stainless steel. The primer layer 2 is a Cr layer with a thickness of 0.2μm. The transition layer 3 is a SiCrC layer with a thickness of 0.8μm. The color transition layer 4 is a CrWC layer with a thickness of 0.4μm. The color layer 5 is a WC layer with a thickness of 0.05μm. In the transition layer 3, the SiCrC layer includes CrC layers and SiC layers which are alternately stacked. The thickness of a single CrC layer is 5nm, and the thickness of a single SiC layer is 5nm.

[0096] The preparation method of the corrosion-resistant film provided in this example includes the following steps:

[0097] Steps (1) to (3) are the same as in Example 1.

[0098] (4) Deposit Cr as the bottom layer. Connect the Cr target to the medium frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 400 sccm, bias voltage of 100V / 75% (duty cycle), Cr target power of 8kW, and deposition time of 20min.

[0099] (5) Deposit SiCrC transition layer. Cr target and Si target are connected to a medium-frequency magnetron sputtering power supply. Ar working gas is introduced with a flow rate of 400 sccm. The flow rate of C2H2 reaction gas increases from 50 sccm to 150 sccm within 20 min. Bias voltage is 80V / 50% (duty cycle). Cr target power is 8kW and Si target power is 8kW. The reaction gas is deposited at a stable 150 sccm for 30 min.

[0100] (6) Deposit CrWC color bonding layer. Cr target and W target are connected to a medium-frequency magnetron sputtering power supply. Ar working gas is introduced at a flow rate of 400 sccm. The flow rate of C2H2 reaction gas increases from 150 sccm to 250 sccm within 10 min. The bias voltage is 100V / 50% (duty cycle). The power of Cr target is 8kW and the power of W target is 6kW. The reaction gas is deposited at a stable flow rate of 250 sccm for 20 min.

[0101] (7) Deposit WC color layer, W target connected to medium frequency magnetron sputtering power supply, introduce working gas Ar with a flow rate of 400 sccm, reactant gas C2H2 with a flow rate of 600 sccm (instantaneous arrival, no gas addition step), bias voltage 100V / 50% (duty cycle), W target power 6kW, deposition time 5min.

[0102] (8) Cool and remove from the furnace.

[0103] Example 3

[0104] This embodiment refers to the corrosion-resistant film and preparation method of Embodiment 2, with the only difference being: in step (7), the flow rate of the reaction gas C2H2 is 450 sccm (instantaneous arrival, no gas addition step); the deposition time is adjusted according to the target deposition thickness.

[0105] Example 4

[0106] This embodiment refers to the corrosion-resistant film and preparation method of Embodiment 2, the only difference being: in step (7), the flow rate of the reaction gas C2H2 is 650 sccm (instantaneous arrival, no gas addition step).

[0107] Example 5

[0108] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that in step (7) the flow of the reaction gas C2H2 is 400 seem (instantaneous to position, without gas steps).

[0109] Example 6

[0110] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the transition layer 3 is different.

[0111] In this example the thickness of the transition layer 3 is 0.5 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0112] Example 7

[0113] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the transition layer 3 is different.

[0114] In this example the thickness of the transition layer 3 is 1.1 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0115] Example 8

[0116] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the color transition layer 4 is different.

[0117] In this example the thickness of the color transition layer 4 is 0.6 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0118] Example 9

[0119] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the color transition layer 4 is different.

[0120] In this example the thickness of the color transition layer 4 is 0.08 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0121] Example 10

[0122] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the color layer 5 is different.

[0123] In this example the thickness of the color layer 5 is 0.03 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0124] Example 11

[0125] This example refers to the corrosion-resistant film and the method of preparation of example 2, the difference being that the thickness of the color layer 5 is different.

[0126] The thickness of the color layer 5 in this embodiment is 0.07 μm; the deposition time of this layer is adjusted according to the target deposition thickness.

[0127] Embodiment 12

[0128] This embodiment refers to the corrosion-resistant film and the preparation method of Embodiment 2, with the difference that the base layer 2 is a Ti layer with a thickness of 0.2 μm; the transition layer 3 is a SiTiC transition layer with a thickness of 0.8 μm; and the color connection layer 4 is a TiWC layer with a thickness of 0.4 μm. In the transition layer 3, the SiTiC layer comprises TiC layers and SiC layers arranged alternately, with a thickness of 5 nm for each TiC layer and a thickness of 5 nm for each SiC layer.

[0129] In the preparation, the Cr target in the base layer 2, the transition layer 3 and the color connection layer 4 is replaced by a Ti target in steps (4)-(6).

[0130] Embodiment 13

[0131] This embodiment refers to the corrosion-resistant film and the preparation method of Embodiment 2, with the difference that in step (7), the flow rate of the reaction gas C2H2 is increased from 250 sccm to 600 sccm within 30 min using the conventional stepwise gas feeding mode.

[0132] Embodiment 14

[0133] This embodiment refers to the corrosion-resistant film and the preparation method of Embodiment 2, with the difference that in the transition layer 3, the SiCrC layer comprises CrC layers and SiC layers arranged alternately, with a thickness of 12.5 nm for each CrC layer and a thickness of 12.5 nm for each SiC layer.

[0134] Comparative Example 1

[0135] Comparative Example 1 refers to the corrosion-resistant film and the preparation method of Embodiment 2, with the difference that the film does not comprise a transition layer, and the color connection layer and the color layer are deposited on the base layer.

[0136] Experimental Example

[0137] In order to compare the properties of the films prepared in different embodiments and comparative examples, the color and properties of the films prepared in different embodiments and comparative examples are tested, and the test results are shown in Tables 1-2.

[0138] The test method is as follows:

[0139] 1. Color value test: the sample after plating is tested for L, a and b values according to the CIE-94 standard, with D65 as the standard illuminant.

[0140] 2. Crosshatch test: After the completion of the film, a small grid of 1 mm x 1 mm is drawn on the surface of the sample using a cutting tool, then a model of adhesive tape is pasted on the grid, the tape is pulled off with force at a vertical angle to the surface of the sample, and the process of pasting and tearing is repeated 3 times. The sample is qualified if the adhesion reaches or exceeds 4B.

[0141] Among them, the crosshatch test is divided into six grades: 5B, 4B, 3B, 2B, 1B, and 0B, with 5B being the best and 0B being the worst.

[0142] 3. Boiling crosshatch test: After the completion of the film, the sample is placed in a constant temperature pure water at 80℃±2℃ for 30 minutes, then the crosshatch test is performed. The sample is qualified if there is no abnormality in appearance, no obvious change (such as rusting, film peeling, etc.), and the adhesion reaches or exceeds 4B.

[0143] 4. Vibration wear test: The sample after completing the film is placed in a vibration wear tester together with ceramic particles, plastic particles, etc. and tested for 2H. The sample is qualified if there is no coating peeling and only slight scratches.

[0144] Among them, the vibration wear test result is divided into three grades: excellent, good, and poor; excellent - the protective layer of the sample with film does not fall off and is not significantly worn, and the substrate without film does not have obvious wear; good - normal exposure, such as edge exposure, high exposure, or slight exposure; poor - the protective layer of the sample with film is blistering, peeling, or abnormally exposed, and the substrate without film has cracks, chipping, or breakage.

[0145] 5. 24H vibration test: The sample after completing the film is placed in a vibration test machine together with ceramic particles and tested for 24H. The sample is qualified if there is no coating peeling and only slight scratches.

[0146] Among them, the 24H vibration test result is divided into three grades: excellent, good, and poor; excellent - the protective layer of the sample with film does not fall off and is not significantly worn, and the substrate without film does not have obvious wear; good - normal exposure, such as edge exposure, high exposure, or slight exposure; poor - the protective layer of the sample with film is blistering, peeling, or abnormally exposed, and the substrate without film has cracks, chipping, or breakage.

[0147] 6. DMGO test: After the completion of the film, the sample is wiped with dimethylglyoxime (DMGO) solution on its surface. The sample is qualified if it does not change color to pink after the test.

[0148] 7. 72H salt spray test: The sample after completing the film is placed in a salt spray test box with a salt concentration of 5% and a test temperature of 35℃±1℃ for 72H. The sample is qualified if there is no corrosion, no spots, no discoloration, no color change, no cracks, and no swelling on the surface after the test.

[0149] The 72H salt spray test result is divided into five grades, excellent, good, general, poor and very poor. Excellent: no coating peeling, no corrosion pits / pores, no blistering, no discoloration, no red rust; Good: 1-3 small corrosion pits / pores, or slight change in coating color and no crystalline; General: sparse and slight corrosion pits / pores on the surface, with a small amount of rust stains (in a ring shape) around the corrosion pits / pores; Poor: surface corrosion pits / pores, rust / crystalline, and corrosion or peeling of the coating, blistering; Very poor: the sample surface has various corrosion problems.

[0150] 8. 72H chlorinated water immersion test: the sample after coating is immersed in a mixture of salt water and bleach solution for 72 hours to test the surface of the sample after coating without corrosion, no spots, no discoloration, no cracks, no swelling.

[0151] 9. 72H high temperature and humidity test: the sample after coating is placed in a constant temperature and humidity chamber with a temperature of 85°C and a humidity of 95% for 72 hours to test the surface of the sample after coating without corrosion, no spots, no discoloration, no cracks, no swelling.

[0152] Among them, the above-mentioned 4B requirement: small pieces of peeling at the intersection of the cut, the actual damage in the grid area does not exceed 5%.

[0153] Table 1 Performance test results of different films

[0154]

[0155] From the above test results, it can be seen that compared with Example 2, the adhesion of the corresponding film is relatively poor when there is no color transition layer; compared with Examples 2-5, when the color layer is deposited in the jump gas mode, the color of the film will be significantly affected when the instantaneous value of the reaction gas flow changes, and the color blackness is better when the reaction gas flow reaches 600 sccm or more; compared with Example 2, when the color layer is deposited in the stepwise gas addition mode, the metal palladium poisoning time is longer, which leads to loose color layer and significantly poor wear resistance; compared with Comparative Example 1, the film adhesion is poor because there is no transition layer in Comparative Example 1.

[0156] Table 2 Performance test results of different films

[0157]

[0158]

[0159] From the test results, it can be seen that, compared with Example 2, the thickness of the transition layer of Example 6 is reduced, the 72H salt spray test result is good, and the corrosion resistance of the film is poor; compared with Example 2, the thickness of the transition layer of Example 7 is increased, the film stress is increased, and the crosshatch test result is 4B; compared with Example 2, the thickness of the transition layer of Example 8 is increased, the vibration wear and 24H vibration disc results are good, and the bonding force is poor; compared with Example 2, the thickness of the transition layer of Example 9 is reduced, and the transition effect is not effective, which affects the wear resistance; compared with Example 2, the color layer of Examples 10-11 is too thick or too thin, which affects the color and the wear resistance of the film; too thin directly affects the wear resistance, and when too thick, the film forming time is increased, which further aggravates the palladium poisoning, the surface layer is loose, and the wear resistance is also affected; compared with Example 2, when the thickness of the alternating single layer in the transition layer of Example 14 is too thick, the corrosion resistance is affected.

[0160] From the above, it can be seen that, by adopting the specific film layer structure and the appropriate thickness, the corrosion resistant film of the present application can ensure the matching, uniformity, bonding performance and corrosion resistance between the layers while ensuring the blackness of the film.

[0161] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the above examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A corrosion resistant film, characterized by, The film comprises: a substrate; a primer layer disposed on one side of the substrate; a transition layer disposed on the primer layer; and a color layer disposed on the transition layer; the primer layer is a Cr layer, a Ti layer or a TiCr layer; the transition layer is a SiCrC layer or a SiTiC layer; and the color layer is a WC layer; a color transition layer is disposed between the transition layer and the color layer; the color transition layer is a CrWC layer or a TiWC layer; the WC layer is deposited by a skip air mode; the Lab color value of the corrosion-resistant film satisfies: L is 25-30, a is -1-1, and b is -2-1.

2. The corrosion resistant film according to claim 1, wherein The SiCrC layer comprises CrC layers and SiC layers alternately stacked; and the SiTiC layer comprises TiC layers and SiC layers alternately stacked.

3. The corrosion resistant film of claim 1, wherein The thickness of the primer layer is 0.1-0.3 μm; the thickness of the transition layer is 0.6-1 μm; the thickness of the color transition layer is 0.1-0.5 μm; and the thickness of the color layer is 0.04-0.06 μm.

4. The method of producing a corrosion-resistant film according to any one of claims 1 to 3, characterized by, comprising the following steps: depositing a primer layer, a transition layer and a color layer on one side of the substrate in sequence by a medium frequency magnetron sputtering method; and depositing a color transition layer between the transition layer and the color layer.

5. The method of claim 4, wherein the corrosion resistant film is formed by a process selected from the group consisting of sputtering, vacuum deposition, and plasma deposition. when depositing the transition layer, the substrate with the primer layer circulates through a Cr target and a Si target to form CrC layers and SiC layers alternately stacked on the primer layer; or when depositing the transition layer, the substrate with the primer layer circulates through a Ti target and a Si target to form TiC layers and SiC layers alternately stacked on the primer layer; when depositing the color layer, the flow rate of the reaction gas C2H2 is increased to 450-650 sccm within <1 s.

6. Application of the corrosion-resistant film according to any one of claims 1-3 in the field of 3C products or high-end decoration.

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