A method for preparing a high-content titanium oxide hydrophobic film

Abstract

The present invention belongs to the technical field of hydrophobic film preparation methods, and specifically relates to a method for preparing a high-content titanium oxide hydrophobic film. The present invention adopts a multi-arc ion plating process to prepare TiO2. First, voltage breakdown is used to generate glow plasma, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The charged particles hit the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular level cleaning and improve the film-base bonding force; voltage breakdown is used again to generate glow plasma, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. At this time, oxygen plasma is used to bombard the workpiece surface, and the pure titanium atoms contained in the film layer are further oxidized to increase the proportion of the TiO2 component of the workpiece. The obtained titanium oxide film has extremely strong hydrophobicity.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrophobic film preparation methods, and in particular relates to a method for preparing a high-content titanium oxide hydrophobic film. Background Art

[0002] The wettability of a material surface is an important property of the material itself, usually characterized by the contact angle between a liquid and a solid surface. Generally, a surface with a contact angle of water greater than 150° is called a super-hydrophobic surface. Super-hydrophobic surfaces have a wide range of practical applications, such as anti-icing, oil-water separation, anti-fouling self-cleaning, corrosion resistance, etc., which has attracted the interest of researchers.

[0003] It is reported that the two factors for preparing super-hydrophobic surfaces are surface roughness and low surface energy. Therefore, people have designed a variety of methods to form super-hydrophobic surfaces, including sol-gel method, vapor deposition method, electrochemical method, etching method and plasma technology. By constructing a rough structure on a low-energy surface material or reducing the surface energy of the rough structure, a super-hydrophobic surface of a material can be achieved.

[0004] Titanium dioxide (TiO 2 ) is an important material that is used in many industrial fields, such as water photolysis, photocatalysis, photovoltaic devices, etc. Since 1997, hydrophilic TiO 2 Since the discovery of photoinduced superhydrophilicity (water contact angle CA < 10°) on surfaces, many studies have been devoted to exploring this photosensitizing mechanism, with the aim of using TiO 2 Good light, heat, and chemical stability as well as better biocompatibility than other organic or inorganic materials allow for manipulation of surface wettability to a greater extent. So far, only limited tuning of its wettability has been achieved. However, in the case of high TiO 2 Component coating technology is still limited.

[0005] Therefore, it is urgent to adopt a suitable technical strategy to obtain high TiO 2 Component coating to achieve an excellent super hydrophobic surface. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a high-content titanium oxide hydrophobic film. The present invention adopts multi-arc ion plating to prepare TiO 2The process first uses voltage breakdown to generate glow plasma, and generates an accelerating electric field between the vacuum chamber wall and the metal workpiece. The charged particles hit the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular level cleaning and improve the film-base bonding strength. The voltage breakdown is used again to generate glow plasma, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. At this time, oxygen plasma is used to bombard the workpiece surface to further oxidize the pure titanium atoms contained in the film layer, and the TiO content of the workpiece is increased as much as possible. 2 The proportion of ingredients.

[0007] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows: The present invention provides a method for preparing a high-content titanium oxide hydrophobic film, comprising the following steps: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) Heating the workpiece under a certain vacuum degree; (3) Close the throttle valve, introduce argon gas and maintain a certain vacuum degree, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown to clean the workpiece; (4) After the workpiece is cleaned in step (3), the throttle valve is opened to increase the vacuum to a certain degree to clean up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen and maintain a certain vacuum degree, turn on the small circular multi-arc target, arc current, arc voltage, and DC bias power supply, and perform coating treatment. The target material is titanium metal; (6) Close the throttle valve, and in a high-purity oxygen atmosphere and maintain a certain vacuum degree, turn on the DC bias power supply to generate glow plasma through voltage breakdown, generate an accelerating electric field between the vacuum chamber wall and the metal workpiece, and bombard the workpiece surface with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer to increase the TiO 2 The high-content titanium oxide hydrophobic film is obtained by adjusting the ratio of the components.

[0008] Preferably, the vacuum degree in step (2) is 2.0×10 -3 -6.0×10 -3 Pa.

[0009] Preferably, the heating temperature in step (2) is 100-300 °C / min.

[0010] Preferably, the heating rate in step (2) is 5°C / min.

[0011] Preferably, in step (3), the vacuum degree is increased to 2-5 Pa and the cleaning time is 5-15 minutes.

[0012] Preferably, the vacuum degree in step (4) is 2.0×10 -3 -6.0×10 -3 Pa.

[0013] Preferably, in step (5), the vacuum degree is 0.5-2 Pa, 2-3 small circular multi-arc targets are turned on, the arc current is 80-100 A, the arc voltage is 16-20 V, the DC bias voltage is -80 V ~ -100 V, and the working time is maintained for 5-10 minutes.

[0014] Preferably, in step (6), the vacuum degree is 0.5-2 Pa, the vacuum chamber is +0 V, the voltage is -800 V, and the coating time is 5-10 minutes.

[0015] The titanium oxide hydrophobic film is prepared by the above method.

[0016] The titanium oxide films obtained by the method of the present invention all have good hydrophobicity.

[0017] The technical effects achieved by the present invention are: 1. The multi-arc ion plating method used in the present invention to prepare TiO 2 The process is simple to operate and easy to mass produce.

[0018] 2. The present invention generates glow plasma by voltage breakdown to generate an accelerating electric field between the vacuum chamber wall and the metal workpiece, so that the pure titanium atoms contained therein are oxidized to obtain TiO 2 High in ingredients. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a contact angle photograph of the titanium oxide hydrophobic film prepared in Example 1 of the present invention; Figure 2 This is a contact angle photograph of the workpiece surface before treatment by the present invention; Figure 3 This is a schematic diagram of the capillary diffusion of water on the surface of the hydrophobic titanium oxide film; Figure 4 This is a water wetting diagram of the titanium oxide hydrophobic film prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0020] The present invention adopts multi-arc ion plating to prepare TiO 2The process obtains a hydrophobic film with a high content of titanium oxide. First, voltage breakdown is used to generate glow plasma, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The charged particles hit the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular level cleaning and improve the film-base bonding. Voltage breakdown is used again to generate glow plasma, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. At this time, oxygen plasma is used to bombard the workpiece surface to further oxidize the pure titanium atoms contained in the film layer, thereby increasing the TiO content of the workpiece as much as possible. 2 The proportion of ingredients.

[0021] In order to achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows: The present invention provides a method for preparing a high-content titanium oxide hydrophobic film, comprising the following steps: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) Heating the workpiece under appropriate vacuum conditions; (3) Close the throttle valve, introduce argon gas and maintain a certain vacuum degree, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown to clean the workpiece; (4) After the workpiece is cleaned in step (3), the throttle valve is opened to increase the vacuum to a certain degree to clean up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen and maintain a certain vacuum degree, turn on the small circular multi-arc target, arc current, arc voltage, and DC bias power supply, and perform coating treatment. The target material is titanium metal; (6) Close the throttle valve, and in a high-purity oxygen atmosphere and maintain a certain vacuum degree, turn on the DC bias power supply to generate glow plasma through voltage breakdown, generate an accelerating electric field between the vacuum chamber wall and the metal workpiece, and bombard the workpiece surface with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer to increase the TiO 2 The proportion of ingredients.

[0022] Example 1 A method for preparing a high-content titanium oxide hydrophobic film comprises the following steps: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) The whole system is vacuumed and the background vacuum is reduced to better than 6.0×10 -3 Pa, and the workpiece is heated to 200 °C at a heating rate of 5 °C / min; (3) Close the throttle valve, introduce argon gas until the vacuum degree is 3 Pa, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The charged particles collide with the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular level cleaning and improve the membrane-base bonding strength. The cleaning time is 10 min; (4) After step (3) is completed, open the throttle valve to increase the vacuum degree to 6.0×10 -3 Pa, cleans up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen until the vacuum degree is 1 Pa, turn on three small circular multi-arc targets, maintain the arc current at 90 A and the arc voltage at 18 V, and at the same time turn on the DC bias power supply, apply a voltage of -100 V for 5 minutes, and carry out coating treatment. The target material is titanium metal; (6) Close the throttle valve, maintain the vacuum degree of 1 Pa with high-purity oxygen, turn on the DC bias power supply, at this time the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The workpiece surface is bombarded with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer. The oxidation time is 5 minutes to obtain a workpiece containing TiO 2 Film of ingredients.

[0023] Figure 1 This is a contact angle photograph of the titanium oxide hydrophobic film prepared in Example 1 of the present invention; as can be seen from the figure, the contact angle of the obtained high-content titanium oxide hydrophobic film to water is 172°. The surface titanium oxide hydrophobic film has good super hydrophobic properties.

[0024] Figure 2 This is a contact angle photograph of the workpiece surface before treatment according to the present invention; as can be seen from the figure, the surface clearly exhibits hydrophilic properties.

[0025] Figure 3 The capillary diffusion principle diagram of water on the surface of the titanium oxide hydrophobic film; as shown in the figure, the present invention observes the wettability of water on the surface of the titanium oxide hydrophobic film through the capillary diffusion principle, performs high-precision observation through a visual recognition system, and deeply evaluates the super hydrophobic properties of the film.

[0026] Figure 4 This is a water wetting diagram of the titanium oxide hydrophobic film prepared in Example 1 of the present invention; as can be seen from the figure, after a wettability test lasting 120 s, the liquid level only dropped by 1.19 mm, indicating that the titanium oxide hydrophobic film has excellent super-hydrophobic properties.

[0027] Example 2 A method for preparing a high-content titanium oxide hydrophobic film comprises the following steps: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) The whole system is vacuumed and the background vacuum is reduced to better than 2.0×10 -3 Pa, and heat the workpiece to 100 °C at a heating rate of 5 °C / min; (3) Close the throttle valve, introduce argon gas to a vacuum degree of 2 Pa, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated through voltage breakdown, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The charged particles collide with the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular-level cleaning and improve the membrane-base bonding strength. The cleaning time is 10 min.

[0028] (4) After step (3) is completed, open the throttle valve to increase the vacuum degree to 2.0×10 -3 Pa, clean up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen until the vacuum degree is 0.5 Pa, turn on three small circular multi-arc targets, maintain the arc current at 80 A and the arc voltage at 16 V, and at the same time turn on the DC bias power supply, apply a voltage of -80 V for 5 minutes, and carry out coating treatment. The target material is titanium metal; (6) Close the throttle valve, maintain the vacuum degree of 0.5 Pa with high-purity oxygen, turn on the DC bias power supply, at this time the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The workpiece surface is bombarded with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer. The oxidation time is 10 minutes to obtain a workpiece containing low content of TiO 2 Film of ingredients.

[0029] Example 3 A method for preparing a high-content titanium oxide hydrophobic film comprises the following steps: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) The whole system is vacuumed and the background vacuum is reduced to better than 6.0×10 -3 Pa, and the workpiece is heated to 300 °C at a heating rate of 5 °C / min; (3) Close the throttle valve, introduce argon gas to a vacuum degree of 5 Pa, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated through voltage breakdown, and an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece. The charged particles collide with the workpiece at high speed under the acceleration of the electric field. This process is glow plasma cleaning, which can achieve molecular-level cleaning and improve the membrane-base bonding strength. The cleaning time is 15 min; (4) After step (3) is completed, open the throttle valve to increase the vacuum degree to 6.0×10 -3 Pa, cleans up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen until the vacuum degree is 2 Pa, turn on three small circular multi-arc targets, maintain the arc current at 100 A and the arc voltage at 20 V, and at the same time turn on the DC bias power supply, apply a voltage of -100 V for 10 minutes, and carry out coating treatment. The target material is titanium metal; (6) Close the throttle valve, maintain the vacuum degree at 2 Pa with high-purity oxygen, turn on the DC bias power supply, at this time the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown, an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece, and the workpiece surface is bombarded with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer. The oxidation time is 8 minutes to obtain a workpiece containing TiO 2 Film of ingredients.

[0030] The present invention obtains high-content TiO by a suitable process technology scheme. 2 The film has super hydrophobic properties in terms of water wettability.

[0031] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a high-content titanium oxide hydrophobic film, characterized in that: The following steps are involved: (1) Place the workpiece in a mechanical pump and molecular pump vacuum system; (2) Heating the workpiece under a certain vacuum degree; (3) Close the throttle valve, introduce argon gas and maintain a certain vacuum degree, turn on the DC bias power supply, the workpiece is the negative electrode, the vacuum chamber is +0 V, and the voltage is applied to -800 V. Glow plasma is generated by voltage breakdown to clean the workpiece; (4) After the workpiece is cleaned in step (3), the throttle valve is opened to increase the vacuum to a certain degree to clean up the impurities generated during the glow cleaning bombardment process to ensure the quality and purity of the film layer; (5) Close the throttle valve, introduce high-purity oxygen and maintain a certain vacuum degree, turn on the small circular multi-arc target, arc current, arc voltage, and DC bias power supply, and perform coating treatment. The target material is titanium metal; (6) The throttle valve is closed, and a DC bias power supply is turned on in a high-purity oxygen atmosphere while maintaining a certain vacuum degree. A glow plasma is generated by voltage breakdown, an accelerating electric field is generated between the vacuum chamber wall and the metal workpiece, and the workpiece surface is bombarded with oxygen plasma to further oxidize the pure titanium atoms contained in the film layer, thereby increasing the proportion of the TiO2 component of the workpiece and obtaining the high-content titanium oxide hydrophobic film.

2. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: The vacuum degree in step (2) is 2.0×10 -3 -6.0×10 -3 Pa.

3. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: The heating temperature in step (2) is 100-300 °C / min.

4. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: The heating rate in step (2) is 5°C / min.

5. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: In the step (3), the vacuum degree is increased to 2-5 Pa and the cleaning time is 5-15 minutes.

6. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: The vacuum degree in step (4) is 2.0×10 -3 -6.0×10 -3 Pa.

7. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: In the step (5), the vacuum degree is 0.5-2 Pa, 2-3 small circular multi-arc targets are turned on, the arc current is 80-100 A, the arc voltage is 16-20 V, the DC bias voltage is -80 V ~ -100 V, and the working time is maintained for 5-10 minutes.

8. The method for preparing a high-content titanium oxide hydrophobic film according to claim 1, characterized in that: In the step (6), the vacuum degree is 0.5-2 Pa, the vacuum chamber is +0 V, the voltage is -800 V, and the coating time is 5-10 minutes.

9. A high-content titanium oxide hydrophobic film prepared by the preparation method according to any one of claims 1 to 8.

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