Inorganic hydrophobic composite coating and preparation method and product thereof

Abstract

The invention discloses an inorganic hydrophobic composite coating as well as a preparation method and a product thereof. The inorganic hydrophobic composite coating is combined with a base material and located on the base material and comprises a transition layer 1 combined with the base material, a transition layer 2 located on the transition layer 1 and a hydrophobic layer located on the transition layer 2. The transition layer 1 is a metal layer; the transition layer 2 is a binary layer, and a material for preparing the transition layer 2 is selected from at least one of CrN, NiN, TiN and ZrN; the hydrophobic layer is a ternary-binary composite layer, and the material for preparing the hydrophobic layer is selected from at least one of NiCrN-Cr2N, AlCrN-Cr2N, TiCrN-Cr2N and ZrCrN-Cr2N. The coating is only composed of metal and metal nitride, does not contain organic components and has good hydrophobicity and abrasion resistance, meanwhile, organic solvent volatilization caused by an existing preparation process is avoided in the preparation process of the coating, and therefore the coating is more environmentally friendly.

Description

Technical Field

[0001] The present invention relates to material technology, and more particularly to an inorganic hydrophobic composite coating and a preparation method and product thereof. Background Art

[0002] Kitchen and bathroom hardware products (such as faucets, showers, pendants, toilet flush buttons, etc.) are prone to water stains and scale due to the humid and complex use environment. These water stains and scale are difficult to clean and affect product quality and appearance. Therefore, new technologies and processes for preparing long-lasting, easy-to-clean, and hydrophobic functional coatings on the surface of hardware products have emerged.

[0003] At present, there are two main methods to improve the easy-to-clean hydrophobic properties of the surface of hardware products: one is a low surface energy silicon-containing organic coating, such as the patent application number CN202410726891.2 (patent name: a method for preparing a super hydrophobic and oleophobic coating), which discloses a method for preparing a super hydrophobic and oleophobic coating, comprising the following steps: dispersing at least two nanoparticles with different surface energies in an alcohol solution, ultrasonically dispersing to form a solution A; then adding a silane coupling agent, tetraethyl orthosilicate and a fluorinated organic silane to react to form a solution B; spraying solution B onto a substrate and curing to obtain. The invention uses nanoparticles to construct a rough surface structure, and uses low surface energy substances such as fluorinated organic silanes for modification, and successfully prepares a coating with super hydrophobic and super oleophobic properties, which is hydrophobic and oleophobic. The other is vacuum evaporation AF film (high-transmittance anti-fingerprint, oil-stain film), such as the patent application number CN202310231621.X (patent name: A preparation process of AF film coating), which uses vacuum coating to coat the surface of the substrate with a silicon dioxide coating and an AF coating in sequence. The pill composition of the AF film is 15% nonafluorobutyl ethyl ether, 8% perfluoropolyether and 4% fluoroalkyl ether.

[0004] However, the above two methods have the following problems:

[0005] (1) Both methods essentially involve coating low surface energy organic matter onto the surface of metal products to form a low surface energy coating to achieve hydrophobic and easy-to-clean functions. However, due to the low bonding force between metal and organic matter, both methods have bottleneck problems, namely, the hydrophobic coating has poor durability and cannot meet the requirements of long-term and easy-to-clean products;

[0006] (2) Both methods cannot avoid the volatilization of solvents and the emission of volatile organic compounds (VOCs), which pollute the environment.

[0007] Therefore, there is an urgent need to develop an environmentally friendly inorganic long-lasting and easy-to-clean composite coating on the surface of a metal substrate. Summary of the invention

[0008] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0009] The conventional methods in the prior art include: pretreatment → organic spraying, while the present application mainly prepares an inorganic hydrophobic composite coating on the surface of a metal product by combining physical vapor deposition with vacuum sintering, that is, the process flow of the present application includes: pretreatment → PVD composite coating → vacuum sintering.

[0010] To achieve the purpose of this application, this application provides the following technical solutions:

[0011] The first aspect of the present application provides an inorganic hydrophobic composite coating, which is combined with a substrate and located on the substrate. The inorganic hydrophobic composite coating includes a transition layer combined with the substrate and a hydrophobic layer located on the transition layer.

[0012] In an exemplary embodiment, the transition layer has two or more layers.

[0013] In an exemplary embodiment, the number of the transition layers is 2, including transition layer 1 and transition layer 2. The larger the number of the transition layer, the farther it is from the surface of the substrate.

[0014] In an exemplary embodiment, the inorganic hydrophobic composite coating is combined with a substrate and located on the substrate, and includes a transition layer 1 combined with the substrate, a transition layer 2 located on the transition layer 1 , and a hydrophobic layer located on the transition layer 2 .

[0015] In an exemplary embodiment, the thickness of the transition layer 1 is 1-3 μm.

[0016] In an exemplary embodiment, the thickness of the transition layer 2 is 2-5 μm.

[0017] In an exemplary embodiment, the hydrophobic layer has a thickness of 0.5-1 μm.

[0018] In an exemplary embodiment, the transition layer 1 is a metal layer;

[0019] Optionally, the metal used to prepare the metal layer is selected from at least one of Cr, Ni, Ti, and Zr.

[0020] In an exemplary embodiment, the metal layer is a Cr layer.

[0021] In an exemplary embodiment, the transition layer 2 is a binary layer;

[0022] Optionally, the material for preparing the transition layer 2 is selected from at least one of CrN, NiN, TiN and ZrN.

[0023] In an exemplary embodiment, the transition layer 2 is a CrN layer.

[0024] In an exemplary embodiment, the hydrophobic layer is a ternary-binary composite layer.

[0025] Optionally, the material for preparing the hydrophobic layer is selected from at least one of NiCrN-Cr2N, AlCrN-Cr2N, TiCrN-Cr2N, and ZrCrN-Cr2N.

[0026] In an exemplary embodiment, the hydrophobic layer is a NiCrN-Cr2N layer or a TiCrN-Cr2N layer.

[0027] The second aspect of the present application provides a method for preparing the above-mentioned inorganic hydrophobic composite coating, comprising the following steps:

[0028] S100. Substrate pretreatment;

[0029] S200. Place the substrate after the treatment in step S100 into a coating machine for glow cleaning to remove impurities and grease on the surface of the substrate;

[0030] S300. Plating a transition layer 1 on the surface of the substrate after glow cleaning;

[0031] S400. A transition layer 2 is plated on the surface of the transition layer 1;

[0032] S500. Plating a hydrophobic layer on the surface of the transition layer 2.

[0033] In an exemplary embodiment, in step S100, the substrate pretreatment is a PVD cleaning process, the purpose of which is to remove grease, dirt, etc. on the surface of the metal substrate.

[0034] In an exemplary embodiment, the process conditions of glow cleaning in step S200 are:

[0035] The background vacuum is 6.5×10 -4 -3.5×10 -2 Pa; working gas: argon; working pressure: 1-2Pa; negative bias: 800V-1000V, duty cycle: 0.5%-2%, time: 10-20min;

[0036] Preferably, the background vacuum is 6.5×10 -3 Pa, working gas: argon, working pressure: 1.5Pa, negative bias: 800V, duty cycle: 1%, time: 10min.

[0037] In an exemplary embodiment, the process conditions for plating the transition layer 1 in step S300 are:

[0038] Working gas: argon; working pressure: 0.4-1Pa; negative bias: 100V-300V; arc current: 50-100A; duty cycle: 30%-50%; coating temperature: 50-150℃; time: 1-3min;

[0039] Preferably, the target material is Cr target, the working gas is argon, the working pressure is 1 Pa of argon pressure, the negative bias voltage is 200 V, the arc current is 70 A, the duty cycle is 50%, the coating temperature is 80° C., and the time is 1 min.

[0040] In an exemplary embodiment, the process conditions for plating the transition layer 2 in step S400 are:

[0041] Working gas: argon and nitrogen, the flow ratio of Ar and N2 is 1 to 3; working pressure: 0.4-1Pa; negative bias: 100V-300V; arc current: 50-100A; duty cycle is 30%-50%; coating temperature: 50-150℃; time: 3-5min;

[0042] Preferably, target material: Cr target, working gas: argon and nitrogen, the flow ratio of Ar and N2 is 2, working pressure: 1Pa, negative bias: 200V, arc current: 70A, duty cycle: 50%, coating temperature: 100℃, time: 3min.

[0043] In an exemplary embodiment, the process conditions for plating the hydrophobic layer in step S500 are:

[0044] The target material used is Ni x Cr y 、Al x Cr y 、Ti x Cr y 、Zr x Cr y At least one of the following, wherein 0.02≤x≤0.1, 0.9≤y≤0.98, x, y are the mass ratios of metal elements; working gas: argon / nitrogen / oxygen, wherein the flow ratio of Ar and N2 is 1 to 4, and O2 accounts for 0.5%-5% of the total gas flow; working pressure: 0.5-1.5Pa; negative bias voltage: 100V-200V; arc current: 30-80A; duty cycle: 50%-70%; coating temperature: 150-300℃; time: 5-8min.

[0045] In an exemplary embodiment, the process conditions for plating the hydrophobic layer in step S500 are: target material: Ni 0.05 Cr 0.95Target, working gas: argon / nitrogen / oxygen, where the flow ratio of Ar and N2 is 1, O2 accounts for 2% of the total gas flow, working pressure: 0.8Pa, negative bias: 100V, arc current: 50A, duty cycle: 60%, coating temperature: 250℃, time: 6min; or

[0046] Target: Ni 0.1 Cr 0.9 Target, working gas: argon / nitrogen / oxygen, where the flow ratio of Ar and N2 is 1, O2 accounts for 2% of the total gas flow, working pressure: 0.8Pa, negative bias: 100V, arc current: 50A, duty cycle: 60%, coating temperature: 250℃, time: 6min; or

[0047] Target: Ti 0.1 Cr 0.9 target, working gas: argon / nitrogen / oxygen, where the flow ratio of Ar and N2 is 1, O2 accounts for 5% of the total gas flow, working pressure: 0.8Pa, negative bias: 200V, arc current: 50A, duty cycle: 60%, coating temperature: 250℃, time: 6min.

[0048] In an exemplary embodiment, the method further includes: S600. placing the inorganic hydrophobic composite coating obtained in step S500 into a vacuum sintering furnace for vacuum sintering to further crystallize the film layer and enhance the hydrophobic performance of the film layer.

[0049] In an exemplary embodiment, the process conditions of step S600 are:

[0050] Background vacuum degree: 5×10 -2 -5×10 -1 Pa; sintering temperature: 500-800℃; sintering time: 30-60min; heating rate: 5℃ / min-10℃ / min.

[0051] In an exemplary embodiment, the process conditions of step S600 are:

[0052] Background vacuum degree: 9×10 -1 Pa, sintering temperature: 600℃, sintering time: 60min, heating rate: 5℃ / min.

[0053] The third aspect of the present application provides an inorganic hydrophobic composite coating prepared by the above method.

[0054] A fourth aspect of the present application provides a product having the above-mentioned inorganic hydrophobic composite coating, wherein the product comprises a substrate and an inorganic hydrophobic composite coating located on the substrate.

[0055] In an exemplary embodiment, the product is a household kitchen and bathroom hardware product, such as a faucet, a shower, a pendant, a toilet flush button, etc.

[0056] In an exemplary embodiment, the substrate is a metal substrate;

[0057] Optionally, the metal substrate is at least one of copper alloy, zinc alloy and stainless steel.

[0058] Compared with the related art, this application has the following technical effects:

[0059] The present application proposes an inorganic hydrophobic composite coating, which is composed only of metals and metal nitrides, does not contain any organic components, has good hydrophobicity and wear resistance, and at the same time, the coating avoids the volatilization of organic solvents caused by the existing preparation process during preparation, thereby being more environmentally friendly.

[0060] Other features and advantages of the present application will be described in the following description, and partly become apparent from the description, or be understood by implementing the present application. Other advantages of the present application can be realized and obtained by the schemes described in the description and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The accompanying drawings are used to provide an understanding of the technical solution of the present application and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solution of the present application and do not constitute a limitation on the technical solution of the present application.

[0062] Figure 1 This is a schematic diagram of the coating structure of this application.

[0063] Description of reference numerals:

[0064] 1. Substrate; 2. Transition layer 1; 3. Transition layer 2; 4. Hydrophobic layer. DETAILED DESCRIPTION

[0065] In order to make the purpose, technical solution and advantages of the present application more clear, the embodiments of the present application will be described in detail below. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other arbitrarily without conflict.

[0066] The present invention is further described in detail below in conjunction with specific examples, but the examples should not be construed as limiting the present invention. The raw materials of this application are all conventional products on the market.

[0067] Example 1

[0068] The preparation process of the inorganic hydrophobic composite coating of the present application is as follows:

[0069] S100, substrate pretreatment, metal substrate pretreatment is a cleaning process before PVD, the purpose of which is to remove grease, dirt, etc. on the surface of the metal substrate.

[0070] S200, place the pre-treated metal substrate in the vacuum coating machine, install the corresponding target material, and perform glow cleaning. The specific process parameters are as follows:

[0071] The background vacuum is 6.5×10 -3 Pa, working gas: argon, working pressure: 1.5Pa, negative bias: 800V, duty cycle: 1%, time: 10min.

[0072] S300, a Cr transition layer 1 is plated on the surface of the substrate after glow cleaning, and the specific parameters are as follows: target material: Cr target, working gas: argon, working pressure: argon pressure 1Pa, negative bias voltage: 200V, arc current: 70A, duty cycle 50%, coating temperature: 80°C, time: 1min; the thickness of the transition layer 1 is 1-3μm.

[0073] S400, a CrN transition layer 2 is plated on the surface of the transition layer 1, and the specific parameters are as follows: target material: Cr target, working gas: argon and nitrogen, the flow ratio of Ar and N2 is 2, working pressure: 1Pa, negative bias voltage: 200V, arc current: 70A, duty cycle is 50%, coating temperature: 100℃, time: 3min; the thickness of the transition layer 2 is 2-5μm.

[0074] S500, a NiCrN-Cr2N hydrophobic layer is plated on the surface of the transition layer 2, and the specific parameters are as follows: Target material: Ni 0.05 Cr 0.95 Target, working gas: argon / nitrogen / oxygen, wherein the flow ratio of Ar and N2 is 1, O2 accounts for 2% of the total gas flow, working pressure: 0.8Pa, negative bias: 100V, arc current: 50A, duty cycle: 60%, coating temperature: 250℃, time: 6min; the thickness of the hydrophobic layer is 0.5-1μm.

[0075] S600, after taking out the sample, put it into the vacuum sintering furnace for sintering. The working parameters are as follows: background vacuum degree: 9×10 - 1 Pa, sintering temperature: 600℃, sintering time: 60min, heating rate: 5℃ / min. After the sample is taken out, the sample is obtained.

[0076] The process parameters of Example 1 are shown in Table 1 below.

[0077] Table 1

[0078]

[0079]

[0080] Example 2

[0081] The preparation method is basically the same as that of Example 1, except that the hydrophobic layer is NiCrN-Cr2N and the target material is Ni 0.1 Cr 0.9 target.

[0082] Example 3

[0083] The preparation method is basically the same as that in Example 1, except that the hydrophobic layer is TiCrN-Cr2N. The specific parameters are as follows: Target material: Ti 0.1 Cr 0.9 target, working gas: argon / nitrogen / oxygen, where the flow ratio of Ar and N2 is 1, O2 accounts for 5% of the total gas flow, working pressure: 0.8Pa, negative bias: 200V, arc current: 50A, duty cycle: 60%, coating temperature: 250℃, time: 6min.

[0084] Example 4

[0085] The preparation method is basically the same as that of Example 1, except for the vacuum sintering step. The parameters are as follows: Background vacuum degree: 9×10- 1 P a , sintering temperature: 800℃, sintering time: 30min, heating rate: 5℃ / min.

[0086] Comparative Example 1

[0087] The preparation method is basically the same as that of Example 1, except that the hydrophobic layer plating step is not performed.

[0088] Comparative Example 2

[0089] The preparation method is basically the same as that of Example 1, except that the vacuum sintering step is not performed.

[0090] test:

[0091] The above examples 1-4 and comparative examples 1-2 were subjected to static contact angle and friction resistance tests. The specific test methods are as follows:

[0092] Static contact angle test: Grade 3 water that meets the requirements of GB / T 6682 is used as the reagent, and the reagent volume for each test is 5 μ L, according to the method in Appendix B of JC / T 2168-2013, 5 different positions are taken as test points for each piece, and the average value of the 5 test points is taken as the contact angle value of the piece.

[0093] Friction resistance test: repeated friction tester (following GB / T 9266-2009, using black pig brown and applying a weight of (0.45±0.01) kg vertically on the surface of the sample for repeated friction test), repeated friction 10,000 times, and then test the static contact angle.

[0094] The test results are shown in Table 2 below.

[0095] Table 2

[0096] sample Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Static contact angle 115° 120° 118° 123° 78° 103° Static contact angle after 10,000 frictions 112° 118° 115° 116° 75° 100°

[0097] According to Table 2, the sample without hydrophobic coating (Comparative Example 1) has no hydrophobic effect, and the sample without vacuum sintering (Comparative Example 2) has a hydrophobic effect that is not as good as that after vacuum sintering. The samples prepared by this application (Examples 1-4) have good hydrophobic effect and wear resistance.

[0098] Conclusion: The environmentally friendly inorganic hydrophobic composite coating prepared in this application is composed only of metals and metal nitrides, does not contain organic components, has good hydrophobicity and wear resistance, and at the same time, the coating avoids the volatilization of organic solvents caused by the existing preparation process during preparation, thus being more environmentally friendly.

[0099] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. An inorganic hydrophobic composite coating, characterized in that: The inorganic hydrophobic composite coating is combined with the substrate and is located on the substrate, and includes a transition layer 1 combined with the substrate, a transition layer 2 located on the transition layer 1, and a hydrophobic layer located on the transition layer 2; The transition layer 1 is a metal layer; The transition layer 2 is a binary layer, and the material for preparing the transition layer 2 is selected from at least one of CrN, NiN, TiN, and ZrN; The hydrophobic layer is a ternary-binary composite layer, and the material for preparing the hydrophobic layer is selected from at least one of NiCrN-Cr2N, AlCrN-Cr2N, TiCrN-Cr2N, and ZrCrN-Cr2N.

2. The inorganic hydrophobic composite coating according to claim 1, characterized in that: The thickness of the transition layer 1 is 1-3 μm; and / or The thickness of the transition layer 2 is 2-5 μm; and / or The thickness of the hydrophobic layer is 0.5-1 μm.

3. The inorganic hydrophobic composite coating according to claim 1 or 2, characterized in that: The metal used to prepare the metal layer is selected from at least one of Cr, Ni, Ti and Zr.

4. The inorganic hydrophobic composite coating according to claim 1 or 2, characterized in that: The metal layer is a Cr layer, the transition layer 2 is a CrN layer, and the hydrophobic layer is a NiCrN-Cr2N layer or a TiCrN-Cr2N layer.

5. A method for preparing the inorganic hydrophobic composite coating according to any one of claims 1 to 4, characterized in that: The following steps are involved: S100. Substrate pretreatment; S200. Place the substrate processed in step S100 into a coating machine for glow cleaning; S300. Plating a transition layer 1 on the surface of the substrate after glow cleaning; S400. Plating a transition layer 2 on the surface of the transition layer 1; S500. Plating a hydrophobic layer on the surface of the transition layer 2.

6. The method according to claim 5, characterized in that The process conditions of glow cleaning in step S200 are: the background vacuum degree is 6.5×10 -4 -3.5×10 -2 Pa; working gas: argon; working pressure: 1-2Pa; negative bias: 800V-1000V, duty cycle: 0.5%-2%, time: 10-20min; and / or The process conditions for plating the transition layer 1 in step S300 are: working gas: argon; working pressure: 0.4-1Pa; negative bias: 100V-300V; arc current: 50-100A; duty cycle: 30%-50%; coating temperature: 50-150°C; time: 1-3min; and / or The process conditions for plating the transition layer 2 in step S400 are: working gas: argon and nitrogen, the flow ratio of Ar and N2 is 1 to 3; working pressure: 0.4-1Pa; negative bias: 100V-300V; arc current: 50-100A; duty cycle is 30%-50%; coating temperature: 50-150°C; Time: 3-5 minutes; and / or Step S500 The process conditions for plating the hydrophobic layer are: the target material used is Ni x Cr y 、Al x Cr y 、Ti x Cr y 、Zr x Cr y At least one of the following, wherein 0.02≤x≤0.1, 0.9≤y≤0.98, x, y are the mass ratios of metal elements; working gas: argon / nitrogen / oxygen, wherein the flow ratio of Ar to N2 is 1 to 4, and O2 accounts for 0.5%-5% of the total gas flow; working pressure: 0.5-1.5Pa; negative bias voltage: 100V-200V; arc current: 30-80A; Duty cycle is 50%-70%; coating temperature: 150-300℃; time: 5-8min.

7. The method according to claim 5 or 6, characterized in that: The method further comprises: S600. placing the inorganic hydrophobic composite coating obtained in step S500 into a vacuum sintering furnace for vacuum sintering; Optionally, the process conditions of step S600 are: background vacuum degree: 5×10 -2 -5×10 -1 Pa; sintering temperature: 500-800℃; sintering time: 30-60min; heating rate: 5℃ / min-10℃ / min.

8. An inorganic hydrophobic composite coating prepared by the method according to any one of claims 5 to 7.

9. A product having the inorganic hydrophobic composite coating according to any one of claims 1 to 4 and 8, the product comprising a substrate and the inorganic hydrophobic composite coating located on the substrate; the product is a household kitchen and bathroom hardware product.

10. The product according to claim 9, characterized in that The substrate is a metal substrate; Optionally, the metal substrate is at least one of copper alloy, zinc alloy and stainless steel.

Images