Composite film layer and method for producing same, and sanitary article

Abstract

The application provides a composite film layer and a preparation method thereof and a bathroom product. The composite film layer comprises a substrate, a transition metal layer located on the substrate and formed by an ion plating method based on a first target material in a vacuum environment containing an inert gas, an AlFeCrNiCo high-entropy alloy layer located on the transition metal layer and formed by a sputtering plating method based on a second target material in a vacuum environment containing the inert gas, and an AlFeCrNiCo high-entropy alloy oxide layer located on the AlFeCrNiCo high-entropy alloy layer and formed by the sputtering plating method based on the second target material in a vacuum environment containing the inert gas and oxygen. The composite film layer of the application presents blue color and has significantly enhanced wear resistance, scratch resistance and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to, but is not limited to, the field of materials, and in particular to a composite film layer and a preparation method thereof, and a bathroom product. BACKGROUND

[0002] The existing market kitchen and bathroom hardware products, such as faucets, shower heads, etc. Physical vapor deposition (PVD) coating generally uses zirconium, titanium and other metal target materials to react with nitrogen, acetylene or methane to deposit decorative films of various colors such as gold, rose gold, imitation stainless steel color, etc.

[0003] However, there are many deficiencies in the current technology for obtaining a blue decorative layer. For example, when preparing a blue coating layer by TiO2, the thickness range of the coating layer is usually controlled to utilize the light transmission and light interference phenomenon to present a blue color tone within a specific range of coating layer thickness, but such technology has the disadvantage of narrow interference thickness range window and is difficult to operate to achieve mass production. In addition, the existing preparation of blue coating layer often uses spraying and other methods to spray high-entropy alloy powder onto the substrate, which has a complex process, poor coating adhesion, and a greater impact on the environment.

[0004] Therefore, there is a need for a composite film layer for displaying blue and a preparation method thereof, and a bathroom product, which at least overcome the above problems. SUMMARY

[0005] 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.

[0006] In one aspect, the present application provides a composite film layer, comprising:

[0007] a substrate;

[0008] a transition metal layer located above the substrate and formed by an ion plating method based on a first target material in a vacuum environment containing an inert gas;

[0009] an AlFeCrNiCo high-entropy alloy layer located above the transition metal layer and formed by a sputtering plating method based on a second target material in a vacuum environment containing an inert gas; and

[0010] an AlFeCrNiCo high-entropy alloy oxide layer located above the AlFeCrNiCo high-entropy alloy layer and formed by a sputtering plating method based on the second target material in a vacuum environment containing an inert gas and oxygen;

[0011] wherein the first target material is formed by one or more of the metals Zr, Ti and Cr;

[0012] The second target is formed by metal powders of Al, Fe, Cr, Ni and Co in atomic percentage of 0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1 via a powder metallurgy method.

[0013] In an embodiment, the second target is formed by metal powders of Al, Fe, Cr, Ni and Co in atomic percentage of 1:1:1:1:1 via a powder metallurgy method.

[0014] In an embodiment, the thickness of the transition metal layer is in the range of 10-50 nm, the thickness of the AlFeCrNiCo high-entropy alloy layer is in the range of 50-100 nm, and the thickness of the AlFeCrNiCo high-entropy alloy oxide layer is in the range of 50-100 nm.

[0015] In an embodiment, the LAB values of the AlFeCrNiCo high-entropy alloy oxide layer are L=23±4, a=-3±1 and b=-24±2. Thus, in the present application, the composite film layer can also be referred to as a blue composite film layer.

[0016] In another aspect, the present application provides a method for preparing a composite film layer, the method comprising the following steps:

[0017] 1) setting a pretreated substrate, at least one first target and at least one second target in a coating machine;

[0018] 2) vacuumizing the coating machine and continuously feeding inert gas, turning on a first power source corresponding to the first target, and generating a metal transition layer on the substrate by ion plating;

[0019] 3) turning off the first power source and turning on a second power source corresponding to the second target, and generating an AlFeCrNiCo high-entropy alloy layer on the metal transition layer by sputtering;

[0020] 4) continuously feeding oxygen into the coating machine, and generating an AlFeCrNiCo high-entropy alloy oxide layer on the AlFeCrNiCo high-entropy alloy layer by sputtering, thereby obtaining the composite film layer;

[0021] wherein the first target is formed by one or more of the metals Zr, Ti and Cr;

[0022] The second target is formed by metal powders of Al, Fe, Cr, Ni and Co in atomic percentage of 0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1 via a powder metallurgy method.

[0023] In an embodiment, step 2) can further comprise setting the vacuum degree in the range of 8x10 -4 ~ 6x10 -3 Pa, setting the flow rate of the inert gas in the range of 20~60sccm, and maintaining the pressure in the film coating machine in the range of 8x10 -2 ~ 7x10 -1 Pa.

[0024] In an embodiment, step 4) can further comprise applying a bias voltage of -100~ -200V to the substrate, the metal transition layer and the AlFeCrNiCo high-entropy alloy layer, maintaining the pressure in the film coating machine in the range of 8x10 -2 ~ 7x10 -1 Pa, setting the film coating temperature in the range of 100~200℃, setting the film coating time in the range of 600~1800s, setting the voltage in the range of 350~600V, setting the current in the range of 2~5A, filling the argon gas in the flow rate of 20~60sccm and the oxygen gas in the flow rate of 20~60sccm.

[0025] In other embodiments, step 2) can further comprise applying a bias voltage of -100~ -300V to the substrate, setting the film coating temperature in the range of 100~150℃, setting the film coating time in the range of 60~120s, setting the voltage in the range of 20~40V, and setting the current in the range of 50~150A.

[0026] In other embodiments, step 3) can further comprise setting the film coating temperature in the range of 100~150℃, and setting the film coating time in the range of 600~1800s.

[0027] In other embodiments, step 3) can further comprise applying a bias voltage of -50~ -150V to the substrate and the metal transition layer, setting the voltage in the range of 350~600V, and setting the current in the range of 2~5A.

[0028] In another aspect, the present application provides a sanitary ware with a composite film layer, wherein the composite film layer is the composite film layer described above or prepared by the method described above.

[0029] In the present application, the term "sanitary ware" can refer to an article whose surface is coated or otherwise decorated with the blue composite film layer of the present application, including but not limited to a faucet, a shower, a bath cabinet, a shower head, a shower nozzle, a spray gun, and a floor drain.

[0030] The application can realize a composite film layer including a metal transition layer, an AlFeCrNiCo high-entropy alloy layer and an AlFeCrNiCo high-entropy alloy oxide layer closely connected between each layer on a substrate by using various physical vapor deposition technologies, and the composite film layer can exhibit blue color. The application reduces the use of organic coating by using physical vapor deposition technology, reduces VOC gas emission, and achieves the purpose of environmental protection and pollution-free.

[0031] The application solves the shortcomings of narrow interference thickness range window and difficulty in operation to realize mass production when preparing a blue coating by conventional PVD plating TiO2, and avoids color changes of optical films caused by uneven plating.

[0032] The AlFeCrNiCo high-entropy alloy layer and the AlFeCrNiCo high-entropy alloy oxide layer in the composite film layer of the application have excellent properties such as high strength / hardness, high toughness, high wear resistance, scratch and scratch resistance, high corrosion resistance, high temperature oxidation resistance, etc., which improves the comprehensive performance of the composite film layer.

[0033] Other features and advantages of the application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the application. Other advantages of the application can be realized and obtained by the solutions described in the specification. BRIEF DESCRIPTION OF DRAWINGS

[0034] The accompanying drawings are used to provide an understanding of the technical solutions of the application, and constitute a part of the specification, and are used together with embodiments of the application to explain the technical solutions of the application, and do not constitute a limitation on the technical solutions of the application.

[0035] Figure 1 A cross-sectional schematic view of a composite film layer provided for an exemplary embodiment of the present disclosure;

[0036] Figure 2 An appearance photo of a composite film layer provided for embodiment 1 of the present disclosure; and

[0037] Figure 3 An SEM photo of a composite film layer provided for embodiment 1 of the present disclosure. DETAILED DESCRIPTION

[0038] In order to make the purposes, technical solutions and advantages of the application more clear, the embodiments of the application are described in detail below. It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other arbitrarily without conflict.

[0039] REFERENCES Figure 1The application provides a composite film layer, which comprises a substrate 10, a transition metal layer 20 located on the substrate 10, a wear-resistant hard AlFeCrNiCo high-entropy alloy layer 30 located on the transition metal layer 20, and an AlFeCrNiCo high-entropy alloy oxide layer 40 located on the AlFeCrNiCo high-entropy alloy layer 30.

[0040] In the application, the transition metal layer 20 can be formed by an ion plating method based on a first target material in a vacuum environment containing an inert gas.

[0041] The ion plating method can be carried out by a multi-arc ion plating method or the like. The multi-arc ion plating method directly generates plasma by arc discharge, has a high ionization rate, a high deposition rate and good adhesion, and is suitable for forming a transition layer between the substrate and other film layers in the application.

[0042] The AlFeCrNiCo high-entropy alloy layer 30 can be formed by a sputtering plating method based on a second target material in a vacuum environment containing an inert gas.

[0043] The AlFeCrNiCo high-entropy alloy oxide layer 40 can be formed by a sputtering plating method based on a second target material in a vacuum environment containing an inert gas and oxygen.

[0044] The sputtering plating method can be a planar target sputtering method.

[0045] In the application, the substrate suitable for the application can include, but is not limited to, stainless steel, aluminum alloy, zinc alloy, copper alloy, electroplatable plastic coated with copper, nickel and chromium.

[0046] In the application, the first target material can be formed by one or more of metals Zr, Ti and Cr. The second target material can be formed by metal powders of Al, Fe, Cr, Ni and Co with an atomic percentage of 0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1. In other embodiments, the second target material is formed by metal powders of Al, Fe, Cr, Ni and Co with an atomic percentage of 1:1:1:1:1.

[0047] In the application, the second target material can be formed by a powder metallurgy method.

[0048] In the application, the pretreatment can adopt a conventional pretreatment method in the art, for example, including polishing, oil removal by acetone and anhydrous ethanol, ultrasonic cleaning, acid solution cleaning, alkaline solution neutralization, deionized water rinsing, preservative rinsing and the like.

[0049] The application also provides a method for preparing a composite film layer, comprising the following steps: 1) arranging a pretreated substrate, at least one first target material and at least one second target material in a coating machine; 2) vacuumizing the coating machine and continuously supplying inert gas, turning on a first power source corresponding to the first target material, and generating a metal transition layer on the substrate by ion coating; 3) turning off the first power source and turning on a second power source corresponding to the second target material, and generating an AlFeCrNiCo high-entropy alloy layer on the metal transition layer by sputtering coating; and 4) continuously supplying oxygen into the coating machine, and generating an AlFeCrNiCo high-entropy alloy oxide layer on the high-entropy alloy layer by sputtering coating, thereby obtaining the composite film layer.

[0050] In the application, the number of targets arranged in the coating machine varies with the size of the coating machine. For example, in the application, 2 first target materials in 1 column and 1 second target material in 1 column can be arranged in the coating machine.

[0051] The following examples specifically describe the method for preparing the composite film layer of the application.

[0052] Example 1

[0053] 1. The first target material is formed of Zr metal; Al, Fe, Cr, Ni and Co metal powders are uniformly mixed in a proportion of 1:1:1:1:1 in atomic percentage, and an alloy with a specific shape prepared by powder metallurgy is used as the second target material.

[0054] 2. Pretreatment of the substrate: the substrate is made of 304 stainless steel; the surface of the substrate is polished, then washed by ultrasonic with acetone, deionized water and alcohol, and dried.

[0055] 3. The substrate, the first target material and the second target material are installed in the vacuum coating machine, wherein the first target material for multi-arc ion coating includes 2 zirconium targets in 1 column, and the second target material for sputtering coating includes 1 high-entropy alloy target in 1 column.

[0056] 4. Preparation of the metal transition layer: the Zr target is used for bottoming, the vacuum is pre-pumped to a vacuum degree of 6x10 -3 Pa, argon gas with a flow rate of 25 sccm is filled, and the pressure in the coating machine is maintained at 3.5x10 -1 Pa; the multi-arc ion coating power source is turned on, the voltage is 21 V, the current is 70 A, and the coating time is 120 s; the negative bias voltage during coating is -200 V, and the coating temperature is 130℃.

[0057] 5. Preparation of the AlFeCrNiCo high-entropy alloy layer: the multi-arc ion coating power source for preparing the metal transition layer in step 4 is turned off, the planar target sputtering coating power source is turned on, the voltage is 450 V, the current is 2.5 A, and the coating time is 1200 s; the negative bias voltage during coating is -100 V, and the coating temperature is 130℃.

[0058] 6. Preparation of AlFeCrNiCo high-entropy alloy oxide layer: simultaneously inject argon flow rate of 22 sccm and oxygen flow rate of 20 sccm, turn on the planar target sputtering power supply, the voltage is 450 V, the current is 2.5 A, the coating time is 1200 s; the negative bias voltage is -100 V during coating, and the coating temperature is 130°C.

[0059] The wear-resistant blue composite film layer is obtained.

[0060] In this embodiment, the metal transition layer is 23 nm, the AlFeCrNiCo high-entropy alloy layer is 78 nm, and the AlFeCrNiCo high-entropy alloy oxide layer is 65 nm.

[0061] Figure 2 It is shown that the composite film layer prepared in this embodiment presents blue. It is determined that in this embodiment, the LAB value of the AlFeCrNiCo high-entropy alloy oxide layer is L: 23.89, a: -3.89 b: -24.29.

[0062] Figure 3 The scanning electron microscope photos of the AlFeCrNiCo high-entropy alloy oxide layer of the composite film layer prepared in this embodiment are shown. It is shown that the AlFeCrNiCo high-entropy alloy oxide layer of the composite film layer prepared in this embodiment is dense and wear-resistant. Figure 3 It can be seen that due to the different atomic radii of cobalt, chromium, iron, nickel and aluminum, the film layer deposited on the substrate after sputtering forms the effect of "green beans filling yellow beans", thereby giving the film layer density and wear resistance.

[0063] In addition, the atomic percentage of each element in the AlFeCrNiCo high-entropy alloy oxide layer is obtained through the SEM photos. Among them, Al is 10.1%, Fe is 9.26%, Cr is 15.5%, Ni is 11.8%, Co is 10.3%, O is 29.2%, and other elements such as C is 13.6%, Si is 0.27%.

[0064] Example 2

[0065] The preparation method is basically the same as that of Example 1, except that the argon flow rate is 22 sccm, the oxygen flow rate is 60 sccm, the planar target sputtering power supply is turned on, the voltage is 350 V, the current is 2.0 A, the coating time is 1800 s; the negative bias voltage is -100 V during coating, and the coating temperature is 100°C.

[0066] It is determined that in this embodiment, the LAB value of the AlFeCrNiCo high-entropy alloy oxide layer is L: 19.30, a: -2.89 b: -25.07. This also shows that the AlFeCrNiCo high-entropy alloy oxide layer in this embodiment presents blue.

[0067] Example 3

[0068] The preparation method is substantially the same as that in Example 1, except that the argon flow rate is 22 sccm, the oxygen flow rate is 30 sccm, the planar target sputtering power is turned on, the voltage is 600 V, the current is 5.0 A, and the film deposition time is 600 s; the negative bias voltage is -200 V, and the film deposition temperature is 200 °C.

[0069] It is determined that the LAB values of the AlFeCrNiCo high-entropy alloy oxide layer in this example are L: 26.39, a: -3.27, and b: -23.21. This also indicates that the AlFeCrNiCo high-entropy alloy oxide layer in this example is blue.

[0070] Comparative Example 1

[0071] A TiO2 blue optical film layer is prepared by using a conventional physical vapor deposition process.

[0072] 1. Pretreatment of the substrate

[0073] The pretreatment process includes polishing the surface of the substrate, and then ultrasonic washing with acetone, deionized water, and alcohol and drying.

[0074] 2. Preparation of the TiO2 blue optical film layer

[0075] The target material is installed in the PVD film deposition chamber, and a multi-arc ion plating is performed on 1 row of 2 titanium targets. The pretreated substrate is placed in the vacuum film deposition machine, and a metal Ti transition layer and a TiO2 blue optical film layer are sputtered in sequence.

[0076] Preparation of the metal titanium transition layer:

[0077] The titanium target is used to pre-evacuate the film deposition chamber to a vacuum degree of 6 x 10 -3 Pa, and argon gas is filled at a flow rate of 20 sccm, and the gas pressure is maintained at 3 x 10 -1 Pa; the multi-arc ion film deposition power is turned on, the voltage is 23 V, the current is 75 A, and the film deposition time is 120 s; the negative bias voltage is -200 V, and the film deposition temperature is 130 °C.

[0078] Preparation of the TiO2 blue optical film layer:

[0079] The titanium target is used to pre-evacuate the film deposition chamber to a vacuum degree of 6 x 10 -3 Pa, and oxygen gas is filled at a flow rate of 90 sccm, and the gas pressure is maintained at 4.5 x 10 -1 Pa; the multi-arc ion film deposition power is turned on, the voltage is 23 V, the current is 75 A, and the film deposition time is 120 s; the negative bias voltage is -200 V, and the film deposition temperature is 150 °C.

[0080] Comparative Example 2

[0081] 1. Pretreatment of the substrate:

[0082] The substrate was cleaned with double distilled water at room temperature for 480 s, and then the substrate was cleaned with ultrasonic waves to remove oil, wherein the concentration of the oil removal powder was 55±5 g / L, the temperature was 60±10 °C, the time was 480-600 s, and the ultrasonic current was 2±1 A. Finally, the substrate was cleaned again with quintuple distilled water at room temperature for 1200 s.

[0083] 2. Preparation of a blue organic coating

[0084] The blue organic coating was prepared. The primer: main agent (white epoxy primer) + epoxy reactive diluent (alcohol-ether solvent) + epoxy resin curing agent (acid anhydride curing agent) = 10:1:(11±1); the topcoat: main agent (Lantuo high-concentration pure white LT-01-1 topcoat 95% + paint foreman C-120 1K standard blue 5%) + diluent (alcohol-ether solvent) + curing agent (acid anhydride curing agent) = 4:1:(3±1).

[0085] The substrate was sprayed with the obtained blue organic coating. The spraying process conditions were as follows: voltage 80 KV, air pressure 6 kg / cm, paint amount 25 cc / min; leveling: linear speed 1.5 m / min, 25 min; curing: temperature 80 °C, linear speed 1.5 m / min, 60 min.

[0086] Performance detection

[0087] The test was carried out according to the provisions of Appendix D in QB / T 5419-2019, and the test results are shown in Table 1 below:

[0088] Table 1

[0089]

[0090] As can be seen from the results in Table 1, the abrasion resistance tests of Examples 1-3 of the present application are all greater than 5000 cycles, indicating that the prepared coating is dense and wear-resistant, and fully plays the excellent performance of high-entropy alloy, such as high strength / hardness, high toughness, and high wear resistance, thereby improving various performances of the coating. The adhesion strength test can meet the standard requirements. As can be seen from the LAB values of the sample appearance, the color change is small, the color difference is small, the process window is stable, and it is suitable for mass production.

[0091] Although the embodiments disclosed in the present application are as above, the content described is only the embodiments adopted for the purpose of facilitating the understanding of the present application, and is not intended to limit the present application. Any person skilled in the art without departing from the spirit and scope of the present application can make any modification and change in the form and details, but the protection scope of the present application shall be subject to the scope defined by the appended claims.

Claims

1. A composite film layer, characterized by, It comprises: a substrate; a transition metal layer formed on the substrate by ion plating based on a first target material in a vacuum environment containing inert gas; an AlFeCrNiCo high-entropy alloy layer formed on the transition metal layer by sputter plating based on a second target material in a vacuum environment containing inert gas; and an AlFeCrNiCo high-entropy alloy oxide layer formed on the AlFeCrNiCo high-entropy alloy layer by sputter plating based on the second target material in a vacuum environment containing inert gas and oxygen; wherein the first target material is formed of one or more of metals Zr, Ti, and Cr; the second target material is formed of metal powders of Al, Fe, Cr, Ni, and Co in atomic percentage of 0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1 via powder metallurgy.

2. The composite film layer of claim 1, wherein the second target material is formed of metal powders of Al, Fe, Cr, Ni, and Co in atomic percentage of 1:1:1:1:1 via powder metallurgy.

3. The composite film layer according to claim 1 or 2, characterized in that, The thickness of the transition metal layer is in the range of 10-50 nm, the thickness of the AlFeCrNiCo high-entropy alloy layer is in the range of 50-100 nm, and the thickness of the AlFeCrNiCo high-entropy alloy oxide layer is in the range of 50-100 nm.

4. The composite film layer according to claim 1 or 2, characterized by, The LAB value of the AlFeCrNiCo high-entropy alloy oxide layer is L=23±4, a=-3±1, and b=-24±2.

5. A method of preparing a composite membrane layer, characterized by, The method comprises the following steps: 1) setting a pretreated substrate, at least one first target material, and at least one second target material in a plating machine; 2) vacuumizing the plating machine and continuously supplying inert gas, turning on a first power source corresponding to the first target material, and generating a metal transition layer on the substrate by ion plating; 3) turning off the first power source and turning on a second power source corresponding to the second target material, and generating an AlFeCrNiCo high-entropy alloy layer on the metal transition layer by sputter plating; and 4) continuously supplying oxygen to the plating machine, and generating an AlFeCrNiCo high-entropy alloy oxide layer on the AlFeCrNiCo high-entropy alloy layer by sputter plating, to obtain the composite film layer; wherein the first target material is formed of one or more of metals Zr, Ti, and Cr; the second target material is formed of metal powders of Al, Fe, Cr, Ni, and Co in atomic percentage of 0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1:0.9-1.1 via powder metallurgy.

6. The method of claim 5, wherein, Step 2) further includes setting the vacuum degree in the range of 8 x 10 -4 ~ 6 x 10 -3 Pa, setting the flow rate of the inert gas in the range of 20 ~ 60 seem, and maintaining the pressure in the film coater in the range of 8 x 10 -2 ~ 7 x 10 -1 Pa.

7. The method of claim 5, wherein, Step 4) further comprises applying a bias voltage of -100 to -200 V to the substrate, the metal transition layer, and the AlFeCrNiCo high-entropy alloy layer, maintaining a pressure in the range of 8 x 10 -2 ~ 7 x 10 -1 Pa in the plating machine, setting a plating temperature in the range of 100 to 200 °C, setting a plating time in the range of 600 to 1800 s, setting a voltage in the range of 350 to 600 V, setting a current in the range of 2 to 5 A, and charging an argon flow of 20 to 60 seem and an oxygen flow of 20 to 60 seem.

8. A sanitary ware having a composite film layer, characterized by, The composite film layer is the composite film layer according to any one of claims 1-4 or prepared by the method according to any one of claims 5-7.

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