A corrosion resistant coating and method of making the same

Abstract

The application provides a kind of corrosion-resistant coating and its preparation method, it is related to corrosion-resistant coating technical field.The corrosion-resistant coating includes: at least one group of dense composite unit layers arranged in turn from inside to outside starting from the surface of substrate;Wherein, in a group of dense composite unit layers, including metal primer layer, transition layer and glassy dense silicon oxide layer arranged in turn from inside to outside.The application is coated by at least one group of dense composite unit layers arranged in turn from inside to outside on the surface of substrate with easy corrosion and / or rough surface;Wherein, metal primer layer is used to increase the bonding force with metal substrate;Transition layer formed on the surface of metal primer layer can improve the bonding strength of coating and substrate, which is conducive to improving the corrosion resistance of coating;Glassy dense silicon oxide layer formed on the surface of the transition layer can achieve strong coating of substrate, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of corrosion-resistant coating, and more particularly to a corrosion-resistant coating and a preparation method thereof. BACKGROUND

[0002] With the demand for lightweight and cost reduction of mobile phones, light metals such as aluminum alloy and copper alloy are increasingly widely used in the 3C electronic industry; iron-based materials are also increasingly used in wearable devices due to their magnetic properties and other functional characteristics.

[0003] However, compared with stainless steel materials, aluminum, copper alloy and iron-based materials have poorer corrosion resistance, and the corrosion-resistant coatings originally developed on the surface of stainless steel cannot meet the corrosion resistance requirements when applied to aluminum, copper alloy and iron-based materials. Especially in some small holes or rough surfaces of special-shaped parts, the corrosion-resistant coating has higher requirements.

[0004] Therefore, a coating with more excellent corrosion resistance is needed to protect the rough and loose substrates of aluminum alloy, copper alloy and iron-based materials. Physical vapor deposition method can control the deposition of metal ions to form a metal and metal compound transition layer to enhance the adhesion to the substrate, but the metal and metal compound transition layer formed by the PVD method on the rough surface has insufficient wrapping to the substrate, has a certain directional growth, and is prone to form defects such as nodules, pinholes and micro-cracks during the growth process. These defects make it easy for corrosive electrolyte to penetrate into the channel, resulting in local corrosion. SUMMARY

[0005] Therefore, the present application provides a corrosion-resistant coating applied to the coating of a substrate surface with easy corrosion and / or rough outer surface, comprising:

[0006] at least one group of dense composite unit layers arranged in order from inside to outside starting from the substrate surface;

[0007] Among the dense composite unit layers in a group, a metal primer layer, a transition layer and a glassy dense silicon oxide layer are arranged in order from inside to outside.

[0008] Preferably, the metal primer layer comprises one or a combination of two of elemental metals or alloy target materials;

[0009] Preferably, the elemental metal comprises one of Cr, Ti, Al, Nb and Ta;

[0010] Preferably, the alloy target material comprises one of TiAl, CrAl and TiCr.

[0011] Preferably, the transition layer is a transition layer formed by covering the surface of the metal primer layer and merging with the metal primer layer.

[0012] Preferably, the transition layer comprises a metal fusion layer and a carbide layer; and the transition layer is a transition layer from the metal fusion layer to the carbide layer.

[0013] Preferably, the metal fusion layer is one or a combination of metal nitride and metal oxynitride after the metal fusion with the surface of the metal primer layer.

[0014] Preferably, the glassy dense silicon oxide layer is a glassy dense silicon oxide layer containing SiO x C y .

[0015] Preferably, the glassy dense silicon oxide layer is a glassy dense silicon oxide layer containing SiO x C y formed by the Si-DLC coating layer after oxygen is introduced.

[0016] Preferably, it further comprises a functional composite layer.

[0017] The functional composite layer is a functional composite layer deposited on the outer surface of the dense composite unit layer of the outermost layer and having a color decoration function and / or a wear resistance function: a metal primer layer and a functional outer layer arranged in order from inside to outside; or a metal primer layer, a transition layer and a functional outer layer arranged in order from inside to outside.

[0018] In addition, to solve the above problems, the application also provides a preparation method of the corrosion-resistant coating as described above, which is applied to coating the surface of a substrate with easy corrosion and / or rough surface, comprising:

[0019] Depositing at least one dense composite unit layer on the surface of the substrate;

[0020] Preferably, the dense composite unit layer comprises a metal primer layer, a transition layer and a glassy dense silicon oxide layer arranged in order from inside to outside.

[0021] The depositing at least one dense composite unit layer on the surface of the substrate comprises:

[0022] Starting from the surface of the substrate, performing at least one deposition process of the dense composite unit layer from inside to outside;

[0023] Preferably, the starting from the surface of the substrate, performing at least one deposition process of the dense composite unit layer from inside to outside comprises:

[0024] Depositing a metal primer layer;

[0025] Forming a transition layer fused with the surface of the metal primer layer on the surface of the metal primer layer;

[0026] forming a layer of glassy dense silicon oxide on the surface of the transition layer;

[0027] Preferably, before depositing the metal primer layer, the method further comprises:

[0028] when the inner layer of the metal primer layer is a substrate surface, performing a gas plasma cleaning on the substrate surface under vacuum by introducing an inert gas;

[0029] Preferably, the gas plasma cleaning is one of a plasma source ion cleaning, a bias assisted glow ion cleaning, and an AEDG arc discharge enhanced assisted ionization ion cleaning.

[0030] Preferably, the thickness of the metal primer layer is 10-300 nm.

[0031] Preferably, the thickness of the transition layer is 100-500 nm.

[0032] Preferably, the thickness of the layer of glassy dense silicon oxide is 30-300 nm.

[0033] Preferably, the inert gas is any one of argon, helium, neon, krypton, and xenon.

[0034] Preferably, depositing the metal primer layer comprises:

[0035] under an inert gas environment, depositing a layer of the metal primer layer on the surface by a magnetron sputtering cathode source or an arc discharge sputtering source.

[0036] Preferably, the transition layer comprises a metal fusion layer and a carbide layer.

[0037] forming the transition layer on the surface of the metal primer layer, which is fused with the metal primer layer, comprises:

[0038] under an inert gas environment, introducing nitrogen or oxygen to form a layer of the metal fusion layer on the surface of the metal primer layer, which is fused with the metal primer layer; the metal fusion layer comprises metal nitride or metal oxide.

[0039] reducing the content of nitrogen or oxygen and increasing the content of a carbon-containing gas source to form the carbide layer on the surface of the metal fusion layer, thereby forming a transition layer covering the surface of the metal primer layer and transitioning from the metal fusion layer to the carbide layer.

[0040] Preferably, forming a layer of glassy dense silicon oxide on the surface of the transition layer comprises:

[0041] Turning off the magnetron sputtering cathode source, and introducing inert gas and silicon-containing carbon organic gas source, a Si-DLC coating layer is prepared by PECVD method;

[0042] On the basis of the Si-DLC coating layer, O2 is introduced to form a glassy dense SiO x C y layer;

[0043] Preferably, the silicon-containing carbon organic gas source is siloxane gas or silane gas.

[0044] Preferably, the PECVD method is one of the following: AEGD arc electron enhanced auxiliary ionization ion source combined with pulsed bias method, radio frequency auxiliary ionization RF-PECVD method, and microwave auxiliary ionization PECVD method.

[0045] Preferably, after the deposition of at least one dense composite unit layer on the surface of the substrate, the method further comprises:

[0046] On the surface of the dense composite unit layer of the outermost layer, a functional composite layer with color decoration function and / or wear resistance function is deposited by PVD magnetron sputtering method; the functional composite layer comprises: a metal primer layer and a functional outer layer arranged in sequence from inside to outside; or a metal primer layer, a transition layer and a functional outer layer arranged in sequence from inside to outside.

[0047] The present application provides a kind of corrosion-resistant coating and preparation method thereof, wherein the corrosion-resistant coating is applied to the coating of substrate surface with easy corrosion and / or rough outer surface, comprising: at least one group of dense composite unit layers arranged in sequence from inside to outside from the substrate surface;Wherein, in a group of the dense composite unit layers, it comprises metal primer layer, transition layer and glassy dense silicon oxide layer arranged in sequence from inside to outside.The present application is coated by at least one group of dense composite unit layers arranged in sequence from inside to outside on the substrate surface with easy corrosion and / or rough outer surface;Wherein, metal primer layer is used to increase the adhesion with metal substrate;Transition layer formed on the surface of metal primer layer can improve the bonding strength of coating and substrate, and is conducive to improving the corrosion resistance of coating;Glassy dense silicon oxide layer formed on the surface of the transition layer can realize strong coating of substrate, block the penetration of corrosive atoms and ions to substrate, and improve the overall corrosion resistance of coating. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 It is the overall structure schematic diagram of the corrosion-resistant coating of the present application;

[0049] Figure 2 It is the film layer structure schematic diagram of the first embodiment of the present application;

[0050] Figure 3 Schematic diagram of the membrane structure of the second embodiment of the present invention;

[0051] Figure 4 Schematic diagram of the film structure of the comparative example of the present invention;

[0052] Figure 5 Graph showing the corrosion polarization test results of Example 1, Example 2 and the comparative example of the present invention.

[0053] Reference numerals:

[0054] 100, substrate surface; 200, dense conformal unit layer; 210, metal base layer; 220, transition layer; 230, glassy dense silicon oxide layer; 300, functional composite layer; 310, metal base layer; 320, transition layer; 330, functional outer layer.

[0055] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0056] The embodiments of the present invention are described in detail below, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions.

[0057] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature identified as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, "plurality" means two or more, unless otherwise specifically defined.

[0058] In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "connect," "fixed," etc. should be understood broadly. For example, they may refer to fixed connection, detachable connection, or integration; mechanical connection or electrical connection; direct connection or indirect connection through an intermediate medium; internal communication between two components or interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0059] It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0060] This embodiment provides a corrosion-resistant coating, the overall structure of which can be referred to Figure 1 , Applications: Coating of substrates with corrosion-prone and / or rough outer surfaces, including:

[0061] at least one group of dense composite unit layers arranged in sequence from inside to outside starting from the surface of the substrate; wherein in one group of the dense composite unit layers, a metal primer layer, a transition layer and a glassy dense silicon oxide layer are arranged in sequence from inside to outside.

[0062] In this embodiment, the material to be coated is a substrate surface with a tendency to corrode and / or a rough surface, and the provided corrosion-resistant coating is used to coat the surface of this kind of substrate to avoid or reduce the occurrence of corrosion phenomena on the surface.

[0063] The above-mentioned corrosion-resistant coating includes at least one group of dense composite unit layers. If there is only one group of dense composite unit layers, the dense composite unit layer is directly coated on the surface of the substrate; if there are multiple groups of dense composite unit layers, for example, three groups, the coating or arrangement order is "substrate surface-dense composite unit layer 1-dense composite unit layer 2-dense composite unit layer 3".

[0064] The above-mentioned metal primer layer is a metal primer layer formed by metal etching and deposited on the surface of the substrate, which is used to increase the adhesion of the metal primer layer to the metal substrate.

[0065] The above-mentioned transition layer is coated on the metal primer layer, which can improve the adhesion of the coating to the substrate and is beneficial to improve the corrosion resistance of the coating.

[0066] The above-mentioned glassy dense silicon oxide layer has the characteristics of glassy state to achieve strong wrapping of the substrate, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating.

[0067] The present embodiment coats at least one group of dense composite unit layers on the surface of a substrate with a tendency to corrode and / or a rough surface from inside to outside; wherein the metal primer layer is used to increase the adhesion to the metal substrate; the transition layer formed on the surface of the metal primer layer can improve the adhesion of the coating to the substrate and is beneficial to improve the corrosion resistance of the coating; the glassy dense silicon oxide layer formed on the surface of the transition layer can achieve strong wrapping of the substrate, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating.

[0068] Further, the metal primer layer includes one or a combination of elemental metal or alloy target material;

[0069] Further, the elemental metal includes one of Cr, Ti, Al, Nb and Ta;

[0070] Further, the alloy target material includes one of TiAl, CrAl and TiCr.

[0071] Further, the transition layer is a transition layer formed by covering the surface of the metal primer layer and fusing with the metal primer layer.

[0072] Further, the transition layer comprises a metal fusion layer and a carbide layer; and the transition layer is a transition layer from the metal fusion layer to the carbide layer.

[0073] Further, the metal fusion layer is one or a combination of the other of metal nitride and metal oxynitride after fusing with the metal on the surface of the metal primer layer.

[0074] The transition layer is used for the transition of the metal primer layer, which is composed of a metal fusion layer and a carbide layer, and the metal fusion layer and the carbide layer are deposited on the surface of the material by different deposition methods.

[0075] Further, the glassy dense silicon oxide layer is a glassy dense silicon oxide layer containing SiO x C y .

[0076] Further, the glassy dense silicon oxide layer is a glassy dense silicon oxide layer containing SiO x C y formed by the Si-DLC coating layer after oxygen is introduced.

[0077] The Si-DLC coating layer is first coated on the transition layer of the inner layer, and a glassy dense silicon oxide layer containing SiO x C y is formed after oxygen is introduced.

[0078] Further, it further comprises a functional composite layer.

[0079] The functional composite layer is a functional composite layer deposited on the outer surface of the dense composite unit layer of the outermost layer and having a color decoration function and / or a wear-resistant function; the functional composite layer comprises: a metal primer layer and a functional outer layer arranged in sequence from inside to outside; or a metal primer layer, a transition layer and a functional outer layer arranged in sequence from inside to outside.

[0080] The functional layer is used to form a material surface with a certain color decoration function and to form a wear-resistant surface.

[0081] In addition, to solve the above problems, the application also provides a preparation method of the corrosion-resistant coating as described above, which is applied to coating the surface of a substrate with easy corrosion and / or rough surface, comprising:

[0082] Depositing at least one dense composite unit layer on the surface of the substrate;

[0083] Further, the dense composite unit layer comprises a metal primer layer, a transition layer and a glassy dense silicon oxide layer arranged in order from inside to outside.

[0084] In the above, the dense composite unit layer has a certain arrangement order when coating, which is arranged in order from inside to outside as follows: 1, a metal primer layer, 2, a transition layer and 3, a glassy dense silicon oxide layer.

[0085] In the above, one or more dense composite unit layers are deposited on the substrate surface. For example, if there are two dense composite unit layers, according to the arrangement order, they can be as follows:

[0086] Substrate surface-metal primer layer 1-transition layer 1-glassy dense silicon oxide layer 1-metal primer layer 2-transition layer 2-glassy dense silicon oxide layer 2.

[0087] The deposition of at least one dense composite unit layer on the substrate surface comprises:

[0088] The deposition process of the dense composite unit layer from inside to outside is carried out at least once from the substrate surface.

[0089] Further, the deposition process of the dense composite unit layer from inside to outside is carried out at least once from the substrate surface, which comprises:

[0090] 1. Depositing a metal primer layer;

[0091] 2. Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer;

[0092] 3. Forming a glassy dense silicon oxide layer on the surface of the transition layer;

[0093] Further, before depositing the metal primer layer, it further comprises:

[0094] When the inner layer of the metal primer layer is the substrate surface, inert gas is introduced in a vacuum state to clean the substrate surface by gas plasma.

[0095] In the above, only when the dense composite unit layer is directly deposited on the substrate surface, the cleaning of the substrate surface is required first.

[0096] Further, the gas plasma cleaning is one of plasma source ion cleaning, bias auxiliary glow ion cleaning and AEDG arc discharge enhanced auxiliary ionization ion cleaning.

[0097] Further, the thickness of the metal primer layer is 10-300 nm.

[0098] Further, the thickness of the transition layer is 100-500 nm.

[0099] Further, the thickness of the glassy dense silicon oxide layer is 30-300nm.

[0100] Preferably, the inert gas is any one of argon, helium, neon, krypton and xenon.

[0101] Further, the deposition of the metal primer layer includes:

[0102] The metal primer layer is deposited on the surface by a magnetron sputtering cathode source or an arc discharge sputtering source in an inert gas environment.

[0103] Further, the transition layer includes a metal fusion layer and a carbide layer.

[0104] The formation of the transition layer on the surface of the metal primer layer includes:

[0105] The metal fusion layer is formed on the surface of the metal primer layer by introducing nitrogen or oxygen in an inert gas environment; the metal fusion layer includes metal nitride or metal oxide.

[0106] The content of nitrogen or oxygen is reduced and the content of carbon-containing gas source is increased to form the carbide layer on the surface of the metal fusion layer, thereby forming the transition layer covering the surface of the metal primer layer and transitioning from the metal fusion layer to the carbide layer.

[0107] Further, the formation of the glassy dense silicon oxide layer on the surface of the transition layer includes:

[0108] The magnetron sputtering cathode source is closed, inert gas and silicon-containing carbon organic gas source are introduced, and a Si-DLC coating layer is prepared by a PECVD method.

[0109] O2 is introduced on the basis of the Si-DLC coating layer to form a glassy dense SiO x C y layer.

[0110] Further, the silicon-containing carbon organic gas source is siloxane gas or silane gas.

[0111] Further, the PECVD method is one of an AEGD arc electron enhanced auxiliary ionization ion source combined with a pulsed bias method, a radio frequency auxiliary ionization RF-PECVD method, and a microwave auxiliary ionization PECVD method.

[0112] Further, after the deposition of at least one dense composite unit layer on the surface of the substrate, the method further includes:

[0113] On the surface of the dense composite unit layer in the outermost layer, a functional composite layer with color decoration function and / or wear resistance function is deposited by a PVD magnetron sputtering method; the functional composite layer comprises: a metal primer layer and a functional outer layer arranged in sequence from inside to outside; or a metal primer layer, a transition layer and a functional outer layer arranged in sequence from inside to outside.

[0114] In summary, the preparation method of the corrosion-resistant coating provided in the embodiment deposits a metal etching and primer layer by PVD, forms a transition layer of metal nitride and carbide on the surface to increase the bonding force with the substrate, deposits a Si-DLC coating by PVD, and forms a glassy dense SiOxCy layer on the basis to achieve dense coating of the substrate, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating.

[0115] A metal primer layer is deposited by PVD to increase the bonding force with the metal substrate, and a transition layer of metal nitride and carbide is formed to improve the bonding strength of the coating with the substrate, which is conducive to improving the corrosion resistance of the coating. A SiOx-DLC coating is deposited by PVD, and a glassy dense silicon oxide layer is formed on the basis to achieve strong coating of defects in the PVD layer, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating. A surface functional layer is prepared by PVD to protect the dense silicon oxide layer.

[0116] By realizing the PVD layer with high bonding force and the PECVD glassy dense layer with strong coating performance in the same vacuum chamber, the corrosion-resistant protection of the surface of the easily corroded rough substrate is achieved.

[0117] Example 1:

[0118] Reference Figure 2 In the embodiment, an aluminum alloy is selected as the substrate, an arc discharge assisted ionization device described in the patent (CN114481071A) is selected as the device, the aluminum alloy is ultrasonically cleaned with acetone and ethanol, and after drying, the aluminum alloy is placed in a vacuum chamber and fixed on a workpiece holder. The vacuum chamber is pumped to a pressure of 5x10 -3 Pa, and heated to 200℃;

[0119] (1) When the inner layer of the metal primer layer is the substrate surface, inert gas is introduced under vacuum to clean the substrate surface with gas plasma: AEGD gas plasma etching and cleaning of the workpiece.

[0120] Argon gas is introduced into the vacuum chamber until the vacuum pressure reaches 0.8 Pa, the arc target current is 80 A, the anode current is 30 A, the pulse bias voltage is 150-300 V, and the gas ion etching and cleaning time is 20 min;

[0121] (2) Depositing a metal primer layer: sputtering a metal Cr primer layer

[0122] The vacuum chamber was filled with argon gas, the pressure was maintained at 0.3-0.5 Pa, a Cr target was selected as the magnetron sputtering source, the current was set to 5 A, the rotor bias was set to 200-600 V, a metal Cr primer layer was deposited on the workpiece, the sputtering time was 10 min, and the thickness was 100 nm.

[0123] (3) Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer: sputtering a CrC transition layer (metal fusion layer) and a CrC layer (carbide layer).

[0124] Gradually, C2H2 was filled, and the flow rate of C2H2 was gradually increased, the vacuum degree was maintained at 0.5-0.8 Pa, the flow rate ratio of Ar:C2H2 was gradually changed from 1:0 to 2:1, and the workpiece bias was gradually reduced to 120-80 V, the CrC transition layer deposition time was 15 min, and the thickness was about 200 nm; the CrC sputtering parameters were kept unchanged, the CrC layer deposition time was 10 min, and the thickness was 100 nm;

[0125] (4) Turn off the magnetron sputtering cathode source, introduce inert gas and silicon-containing carbon organic gas source, and prepare a Si-DLC coating layer by PECVD method: deposit a SiOx-DLC layer.

[0126] The SiOx-DLC layer was deposited on the surface of the transition layer CrC by auxiliary anode enhanced arc electron glow ionization of C2H2 and HMDSO gas; the Cr target power supply was turned off, the arc target current was set to 80 A, the anode current was 30 A, the pulse bias was increased to 600-800 V, the Ar gas flow rate was kept unchanged, the vacuum chamber was gradually filled with HMDSO gas, and the C2H2 gas flow rate was gradually reduced until it was turned off, the flow rate ratio of Ar:HMDSO in the chamber was finally 3:1, and the pressure in the chamber was maintained at 1-2 Pa, the deposition time was 10 min, and the total thickness of the transition and SiOx-DLC layer was 100 nm;

[0127] (5) On the basis of the Si-DLC coating layer, O2 was introduced to form a glassy dense SiO x C y layer: deposit a SiOxCy dense layer.

[0128] The equipment power supply parameters were kept unchanged, the HMDSO flow rate was kept unchanged, the Ar gas flow rate was gradually reduced until it was turned off, the O2 gas flow rate was gradually introduced, the flow rate ratio of O2:HMDSO was finally 3-5, the transition layer deposition time was 5 min; finally, the reaction gas ratio was maintained, the SiOxCy dense layer was deposited to a thickness of 100 nm, and the deposition time was 10 min;

[0129] (6) Depositing a metal primer layer: sputtering a metal Cr primer layer

[0130] Turning off the O2 and HMDSO inlets, filling the vacuum chamber with argon gas, maintaining the gas pressure at 0.3-0.5 Pa, turning on the power supply of the other rotating magnetron Cr target, setting the current at 1-3 A, the bias voltage at 400-600 V, etching and cleaning the workpiece with metal Cr ions for 5 min; increasing the target current to 6-12 A and reducing the bias voltage to 200-60 V, and depositing a metal Cr layer with a thickness of 50 nm;

[0131] (7) Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer: sputtering a CrC transition layer (metal fusion layer) and a CrC layer (carbide layer).

[0132] Gradually filling C2H2 and gradually increasing the flow rate of C2H2, maintaining the vacuum degree at 0.5-0.8 Pa, and gradually reducing the workpiece bias voltage to 120-80 V, with the flow rate ratio of Ar:C2H2 gradually changing from 1:0 to 2:1, and the CrC transition layer deposition time being 15 min and the thickness being about 200 nm; keeping the CrC sputtering parameters unchanged, depositing a CrC layer for 10 min and the thickness being 100 nm;

[0133] (8) Turning off the magnetron sputtering cathode source, introducing inert gas and silicon-containing carbon organic gas source, and preparing a Si-DLC coating layer by PECVD method: depositing a SiOx-DLC layer.

[0134] Depositing a SiOx-DLC layer on the surface of the transition layer CrC by auxiliary anode enhanced arc electron glow ionization of C2H2 and HMDSO gas; turning off the Cr target power supply, setting the arc target current at 80 A, the anode current at 30 A, increasing the pulse bias voltage to 600-800 V, keeping the Ar inlet flow rate unchanged, gradually filling HMDSO gas into the vacuum chamber, and gradually reducing the C2H2 gas flow rate until it is turned off, finally making the flow rate ratio of Ar:HMDSO in the chamber 3:1 while ensuring the gas pressure in the chamber at 1-2 Pa, and the deposition time being 10 min, and the total thickness of the transition and SiOx-DLC layers being 100 nm;

[0135] (9) On the basis of the Si-DLC coating layer, introducing O2 to form a glassy dense SiO x C y layer: depositing a SiOxCy dense layer.

[0136] Keeping the power parameters of the equipment unchanged, keeping the HMDSO flow unchanged, gradually reducing the Ar flow until it is turned off, gradually introducing the O2 flow, and finally making the O2:HMDSO flow ratio 3-5, the transition layer deposition time is 5 min; finally, keeping the reaction gas ratio, depositing a SiOxCy dense layer with a thickness of 100 nm, and the deposition time is 10 min;

[0137] (10) Depositing a metal primer layer: sputtering a metal Cr primer layer

[0138] Turning off the O2 and HMDSO inlets, filling argon into the vacuum chamber to maintain a gas pressure of 0.3-0.5 Pa, turning on another rotating magnetic control Cr target power source, setting the current to 1-3 A, and the bias voltage to 400-600 V, using metal Cr ion etching to clean the workpiece for 5 min; increasing the target current to 6-12 A and reducing the bias voltage to 200-60 V, depositing a metal Cr layer with a thickness of 50 nm;

[0139] (11) Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer: sputtering a CrC transition layer (metal fusion layer) and a CrC layer (carbide layer).

[0140] Gradually, fill in C2H2 and gradually increase the flow of C2H2, maintain the vacuum degree at 0.5-0.8 Pa, finally make the Ar:C2H2 flow ratio gradually from 1:0 to 2:1, and gradually reduce the workpiece bias voltage to 120-80 V, the CrC transition layer deposition time is 15 min, the thickness is about 200 nm; keeping the CrC sputtering parameters unchanged, the CrC layer deposition time is 10 min, and the thickness is 100 nm;

[0141] (12) On the surface of the outermost dense composite unit layer, a functional layer with color decoration function and / or wear resistance function is deposited by PVD magnetic sputtering method: depositing a DLC wear-resistant functional layer.

[0142] Turn off the Cr target power, set the arc target current to 80 A, the anode current to 20 A, increase the pulse bias to 400-600 V, continue to gradually fill C2H2 gas into the vacuum chamber, finally make the C2H2:Ar flow ratio in the chamber 3:1, while ensuring the gas pressure in the chamber 1-2 Pa, the deposition time is 20 min, and the deposition thickness is 200 nm.

[0143] Example 2:

[0144] Reference Figure 3In this embodiment, FeNi alloy is selected as the substrate, and hot wire electron enhanced glow discharge technology is selected. Reference: Li Canmin, et al. Plasma Enhanced Magnetron Sputtering Deposition of New Type of Nanocomposite Coating. China Outstanding Master Degree Thesis Database Engineering and Technology Series. 2013, (No. 01)

[0145] The aluminum alloy is cleaned with acetone and ethanol by ultrasonic cleaning, and then dried and placed in a vacuum chamber. The workpiece is fixed on the workpiece holder, and the vacuum degree is extracted to 5x10 -3 Pa, and heated to 150°C.

[0146] 1) When the inner layer of the metal primer layer is the substrate surface, inert gas is introduced under vacuum conditions, and the substrate surface is cleaned by gas plasma: gas plasma etching cleaning of the workpiece.

[0147] Argon gas is introduced into the vacuum chamber until the vacuum pressure reaches 0.8 Pa. Electrons are emitted by a hot tungsten wire electron emission device, the tungsten wire current is maintained at 20-45 A, the hot wire and the vacuum chamber are negatively biased at 120 V. The workpiece rotating frame pulse negative bias is 150-250 V, and the gas ion etching cleaning time is 10-20 min.

[0148] 2) Depositing a metal primer layer: sputtering a metal Cr primer layer

[0149] The tungsten wire current is turned off, the amount of argon gas is adjusted, the gas pressure is maintained at 0.3-0.5 Pa, a Cr target is selected as the magnetron sputtering source, the current is set to 5 A, the rotating frame bias is set to 200-600 V, and a metal Cr primer layer is deposited on the workpiece. The sputtering time is 5-10 min, and the thickness is 50-100 nm.

[0150] 3) Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer: sputtering a CrAlN / CrAlCN transition layer.

[0151] The tungsten wire current is turned on to 20-45 A, and the hot wire and the vacuum chamber are negatively biased at 120 V. Gradually, N2 is filled to maintain a vacuum degree of 0.5-0.8 Pa, the sputtering CrAl target is turned on, the atomic percentage of the target material is Cr: Al = 7:3, the current is set to 5-8 A, the CrAlN layer is formed, and the deposition time is 10 min. Gradually reduce the N2 flow, and simultaneously gradually increase the C2H2 flow, sputter to form a CrAlCN layer, and the deposition time is 10 min. The workpiece bias is gradually reduced from 200 V to 60-80 V in steps.

[0152] 4) Turn off the magnetron sputtering cathode source, introduce inert gas and silicon-containing carbon organic gas source, and prepare a Si-DLC coating layer by PECVD method: deposit a SiOx-DLC layer.

[0153] Depositing SiOx-DLC layer on CrAlCN transition layer by hot filament electron enhanced ionization of C2H2 and HMDSO gas; turning off CrAl target power, maintaining tungsten filament current and negative bias, increasing pulse bias to 600-800 V, gradually filling HMDSO gas into the vacuum chamber, gradually reducing C2H2 gas flow until it is turned off, finally making the flow ratio of Ar:HMDSO in the chamber 3:1, while ensuring the gas pressure in the chamber is 1-2 Pa, the deposition time is 10 min, and the total thickness of the transition and SiOx-DLC layer is 100 nm;

[0154] 5) On the basis of the Si-DLC coating, O2 is introduced to form a glassy dense SiO x C y layer: depositing a dense SiOxCy layer.

[0155] Keeping the device power parameters unchanged and the HMDSO flow unchanged, gradually reducing the Ar gas flow until it is turned off, gradually introducing O2 gas flow, finally making the flow ratio of O2:HMDSO 3-5, the transition layer deposition time is 5 min; finally keeping the reaction gas ratio, depositing a dense SiOxCy layer with a thickness of 100 nm, and the deposition time is 10 min;

[0156] 6) Depositing a metal primer layer: sputtering a metal Cr primer layer.

[0157] Turning off the tungsten filament current, turning off O2 and HMDSO gas, filling argon gas into the vacuum chamber, maintaining the gas pressure at 0.3-0.5 Pa, turning on the magnetron Cr target power, setting the current to 1-3 A, and the bias voltage to 400-600 V, using metal Cr ion etching to clean the workpiece for 5 min; increasing the target current to 6-12 A and reducing the bias voltage to 200-60 V, depositing a metal Cr layer with a thickness of 50 nm;

[0158] 7) Forming a transition layer fused with the metal primer layer on the surface of the metal primer layer: sputtering CrAlN / CrAlCN transition layer.

[0159] Turning on the tungsten filament current to 20-45 A and the hot filament with a negative bias of 120 V; gradually, filling N2, maintaining the vacuum degree at 0.5-0.8 Pa, turning on the sputtering CrAl target again, setting the current to 5-8 A, forming a CrAlN layer, and the deposition time is 10 min; gradually reducing the N2 flow, synchronously gradually increasing the C2H2 flow, sputtering to form a CrAlCN layer, and the deposition time is 10 min;

[0160] 8) Turning off the magnetron sputtering cathode source, introducing inert gas and silicon-containing carbon organic gas source, and preparing a Si-DLC coating layer by PECVD method: depositing SiOx-DLC layer.

[0161] Deposition of SiOx-DLC layer on transition layer CrAlCN by hot filament electron enhanced ionization of C2H2 and HMDSO gas; turn off CrAl target power, maintain tungsten filament current and negative bias, increase pulse bias to 600-800 V, gradually fill HMDSO gas into the vacuum chamber, and gradually reduce C2H2 gas flow until it is turned off, finally make the flow ratio of Ar:HMDSO in the chamber 3:1, while ensuring the gas pressure in the chamber is 1-2 Pa, the deposition time is 10 min, and the total thickness of the transition and SiOx-DLC layer is 100 nm;

[0162] 9) On the basis of the Si-DLC coating, O2 is introduced to form a glassy dense SiO x C y layer: deposition of SiOxCy dense layer.

[0163] Keep the device power parameters unchanged, keep the HMDSO flow unchanged, gradually reduce the Ar gas flow until it is turned off, gradually introduce O2 gas flow, finally make the flow ratio of O2:HMDSO 3-5, the transition layer deposition time is 5 min; finally keep the reaction gas ratio, deposit SiOxCy dense layer thickness 100 nm, deposition time is 10 min;

[0164] 10) Deposition of metal primer layer: sputtering of metal Cr primer layer

[0165] Turn off the tungsten filament current, turn off the O2 and HMDSO gas, fill argon gas into the vacuum chamber, maintain the gas pressure at 0.3-0.5 Pa, turn on the magnetron Cr target power, set the current to 1-3 A, the bias value to 400-600 V, use metal Cr ion etching to clean the workpiece, the time is 5 min; increase the target current to 6-12 A, reduce the bias to 200-60 V, deposit a metal Cr layer with a thickness of 50 nm;

[0166] 11) On the surface of the dense composite unit layer of the outermost layer, a functional layer with color decoration function and / or wear resistance function is deposited by PVD magnetron sputtering method: sputtering of CrAlCN color layer.

[0167] Gradually, fill N2, maintain the vacuum degree at 0.5-0.8 Pa, turn on the sputtering CrAl target again, set the current to 5-8 A, form a CrAlN layer, the deposition time is 10 min; simultaneously gradually increase the C2H2 flow, sputter to form a CrAlCN layer, the deposition time is 10-30 min, and a decorative layer with a specific color is prepared.

[0168] Comparative example:

[0169] Reference Figure 4, the comparative example of example 1 is provided, using the same substrate and the same process, without step (5) and step (9), without SiO x C y dense layer, the rest of the process parameters and film layer structure are the same.

[0170] The experimental results (reference Figure 5 ):

[0171] 1. The sample of example 1 was tested for corrosion current density in a 5wt% NaCl solution, and the test result was 3.5x10 -5 mA / cm 2 ;

[0172] 2. The surface color value of the comparative example had almost no difference compared with example 1, and the same was tested for corrosion current density in a 5wt% NaCl solution, and the test result was 9x10 -3 mA / cm 2 ;

[0173] 3. The sample of example 2 was tested for corrosion current density in a 5wt% NaCl solution, and the test result was 9x10 -5 mA / cm 2 ;

[0174] In summary, the corrosion current densities of example 1 and example 2 were in the order of 10 -5 mA / cm 2 , and the comparative example 1 did not contain SiO x C y dense layer, and the corrosion current density was in the order of 10 -3 mA / cm 2 , which was two orders of magnitude higher than the corrosion current densities of the samples of example 1 and example 2.

[0175] In summary, the experimental results show that:

[0176] 1. Depositing a metal etching and primer layer by PVD to increase the adhesion to the metal substrate, and then forming a transition layer of metal nitride and carbide to improve the adhesion between the coating and the substrate, is beneficial to improving the corrosion resistance of the coating. Depositing a SiOx-DLC coating by PECVD, and then forming a glassy dense silicon oxide layer, to achieve strong encapsulation of the substrate, block the penetration of corrosive atoms and ions to the substrate, and improve the overall corrosion resistance of the coating. The surface functional layer is prepared by PVD to protect the dense silicon oxide layer.

[0177] 2. By realizing high adhesion PVD layer and strong encapsulation PECVD glassy dense layer in the same vacuum chamber, the corrosion resistance of the surface of the easily corroded rough substrate is achieved.

[0178] The above-mentioned embodiment numbers of the present application are only for description, and do not represent the advantages and disadvantages of the embodiments.

[0179] Through the above description of the embodiments, those skilled in the art can clearly understand that the above-mentioned embodiment methods can be realized by means of software and the necessary general hardware platform, of course, they can also be realized by hardware, but in many cases the former is a better embodiment. Based on such understanding, the technical solutions of the present application can be embodied in the form of a software product, which is stored in a storage medium (such as a ROM / RAM, a magnetic disk, an optical disk) as described above, and includes a plurality of instructions for causing a terminal device (which can be a mobile phone, a computer, a server, or a network device, etc.) to execute the methods described in the various embodiments of the present application. The above is only the preferred embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent flow transformation made by using the content of the specification and drawings, or directly or indirectly applied to other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A corrosion-resistant coating for coating a substrate surface having a corrosion-prone and / or rough outer surface, characterized in that: include: At least one group of dense composite unit layers is arranged sequentially from the inside to the outside starting from the substrate surface; Wherein, in a group of said dense composite unit layers, it includes a metal base layer, a transition layer and a glassy dense silicon oxide layer arranged in sequence from the inside to the outside; The metal base layer includes a single metal or an alloy target material or a combination of two; the single metal includes one of Cr, Ti, Al, Nb and Ta; The alloy target material includes one of TiAl, CrAl and TiCr; The transition layer is a transition layer formed by covering the surface of the metal base layer and integrating with the metal base layer; The transition layer includes a metal fusion layer and a carbide layer; and the transition layer is a transition layer transitioning from the metal fusion layer to the carbide layer; The metal fusion layer is one or a combination of metal nitride and metal oxynitride fused with the metal on the surface of the metal base layer; The glassy dense silicon oxide layer contains SiO x C y A glassy dense silicon oxide layer; The glassy dense silicon oxide layer is formed by the Si-DLC coating after oxygen is introduced. x C y A glassy dense silicon oxide layer.

2. The corrosion-resistant coating according to claim 1, wherein: Also includes a functional composite layer; The functional composite layer is a functional composite layer deposited on the outer surface of the outermost dense composite unit layer and has color decoration function and / or wear resistance function; the functional composite layer includes: a metal base layer and a functional outer layer arranged in sequence from the inside to the outside; or, a metal base layer, a transition layer and a functional outer layer arranged in sequence from the inside to the outside.

3. A method for preparing a corrosion-resistant coating according to claim 1 or 2, which is applied to coating a substrate surface having a corrosive and / or rough outer surface, characterized in that: include: At least one dense composite unit layer is deposited on the surface of the substrate.

4. The method for preparing the corrosion-resistant coating according to claim 3, wherein: The dense composite unit layer includes a metal base layer, a transition layer and a glassy dense silicon oxide layer arranged in sequence from the inside to the outside; Depositing at least one dense composite unit layer on the substrate surface comprises: Starting from the substrate surface, a deposition process of the dense composite unit layer is performed from the inside to the outside at least once.

5. The method for preparing the corrosion-resistant coating according to claim 3, wherein: The process of depositing the dense composite unit layer from the substrate surface at least once from the inside out comprises: Depositing metal base layer; forming a transition layer on the surface of the metal base layer to be fused with the metal base layer; A glassy dense silicon oxide layer is formed on the surface of the transition layer.

6. The method for preparing the corrosion-resistant coating according to claim 5, wherein: Before depositing the metal base layer, the method further comprises: When the inner layer of the metal primer layer is the surface of the substrate, an inert gas is introduced under a vacuum state to perform gas plasma cleaning on the surface of the substrate.

7. The method for preparing the corrosion-resistant coating according to claim 6, wherein: The gas plasma cleaning is one of plasma source ion cleaning, bias assisted glow ion cleaning and AEDG arc discharge enhanced assisted ionization ion cleaning.

8. The method for preparing the corrosion-resistant coating according to claim 5, wherein: The thickness of the metal primer layer is 10-300 nm.

9. The method for preparing the corrosion-resistant coating according to claim 5, wherein: The thickness of the transition layer is 100-500 nm.

10. The method for preparing the corrosion-resistant coating according to claim 5, wherein: The thickness of the glassy dense silicon oxide layer is 30-300 nm.

11. The method for preparing the corrosion-resistant coating according to claim 6, wherein: The inert gas is any one of argon, helium, neon, krypton and xenon.

12. The method for preparing the corrosion-resistant coating according to claim 3, wherein: The deposited metal base layer comprises: In an inert gas environment, a layer of the metal primer layer is deposited on the surface by a magnetron sputtering cathode source or an arc discharge sputtering source.

13. The method for preparing the corrosion-resistant coating according to claim 5, wherein: The transition layer includes a metal fusion layer and a carbide layer; A transition layer is formed on the surface of the metal base layer to be fused therewith, comprising: In an inert gas environment, nitrogen or oxygen is introduced to form a metal fusion layer on the surface of the metal base layer, which is fused with the metal base layer; the metal fusion layer includes metal nitride or metal oxide; The nitrogen or oxygen content is reduced, and the carbon-containing gas source is increased to form the carbide layer on the surface of the metal fusion layer, constituting the transition layer covering the surface of the metal base layer and transitioning from the metal fusion layer to the carbide layer.

14. The method for preparing the corrosion-resistant coating according to claim 12, wherein: The step of forming a glassy dense silicon oxide layer on the surface of the transition layer comprises: The magnetron sputtering cathode source is turned off, an inert gas and a silicon-carbon organic gas source are introduced, and a Si-DLC coating layer is prepared by a PECVD method; On the basis of the Si-DLC coating, O2 is introduced to form a layer of glassy dense SiO x C y layer.

15. The method for preparing the corrosion-resistant coating according to claim 14, wherein: The silicon-carbon-containing organic gas source is siloxane gas or silane gas.

16. The method for preparing the corrosion-resistant coating according to claim 14, wherein: The PECVD method is: selecting one of an AEGD arc electron enhanced ionization assisted ion source combined with a pulse bias method, a radio frequency assisted ionization RF-PECVD method and a microwave assisted ionization PECVD method.

17. The method for preparing a corrosion-resistant coating according to claim 3, wherein: After depositing at least one dense composite unit layer on the substrate surface, the method further comprises: On the surface of the outermost dense composite unit layer, a functional composite layer with color decoration function and / or wear resistance function is deposited by the PVD magnetron sputtering method; the functional composite layer includes: a metal base layer and a functional outer layer arranged in sequence from the inside to the outside; or, a metal base layer, a transition layer and a functional outer layer arranged in sequence from the inside to the outside.

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