CN111908803B - Super-hydrophilic and high-wear-resistance film layer and preparation method thereof - Google Patents
Super-hydrophilic and high-wear-resistance film layer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The invention relates to a super-hydrophilic and high-wear-resistance film layer and a preparation method thereof. The preparation method comprises the following steps: cleaning and drying a glass substrate to obtain a glass substrate, and placing the glass substrate in an inner cavity of coating equipment; selecting high-purity Si, SnSb alloy and TiO 2 And conductive ZrO x The source of Si, Sn, Sb, Ti and Zr is used and is arranged in the inner cavity of the coating equipment; vacuumizing the inner cavity, heating the cavity and the glass substrate, introducing argon after the heating is finished, and performing glow cleaning on the cavity and the target material; introducing oxygen, and sputtering Si and TiO on the surface of the glass substrate in sequence after the air pressure in the cavity reaches a set value 2 SnSb alloy, TiO 2 And conductive ZrO x Obtaining a multilayer composite film; and after sputtering is finished, releasing the vacuum pressure, and taking out the coated glass. The target, the coating method and the film structure provided by the invention can obtain a film with strong wear resistance, high transmittance and super-hydrophilicity.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a super-hydrophilic and high-wear-resistance film layer and a preparation method thereof.
Background
The process of replacing a gas on a solid surface with a liquid becomes wetting, and the degree of wetting exhibited by water on a solid surface, generally expressed as a contact angle (θ), can be classified into four broad categories: superhydrophobic surfaces (theta >150 deg.), hydrophobic surfaces (theta >90 deg.), hydrophilic surfaces (theta <90 deg.) and superhydrophilic surfaces (theta <5 deg.). Both the super-hydrophobic surface and the super-hydrophilic surface have antifogging and self-cleaning properties, so that the super-hydrophobic surface and the super-hydrophilic surface are greatly concerned by people. The glass can be applied to automobile glass, bathroom antifogging glass, solar panels, optical lenses and displays of other electronic products in daily life.
Currently, there are two main approaches to making superhydrophilic films, one is via photocatalysis, such as TiO 2 The film layer can be changed from hydrophobic to super-hydrophilic after being irradiated by ultraviolet light, thereby achieving the effects of antifogging and self-cleaning. However, the membrane layer has certain application limitation because the membrane layer achieves a super-hydrophilic effect by utilizing ultraviolet rays or visible light and is changed from super-hydrophilic to hydrophobic in a non-illumination or dark environment. Another approach is to change the surface roughness and densification of the hydrophilic material. At present, the second method mostly utilizes a chemical vapor deposition mode to deposit and generate a film on the surface of the substrate, but the process is complicated, the manufacturing cost is high, and the abrasion resistance of the film is poor.
Disclosure of Invention
The invention provides a vacuum sputtering coating method for obtaining a film with strong wear resistance, compact and smooth film layer and high light transmittance, aiming at the problems of large water contact angle and short service life caused by large surface roughness and low wear resistance of a super-hydrophilic film.
The invention provides a preparation method of a super-hydrophilic and high-wear-resistance film layer, which comprises the following steps:
(1) cleaning and drying the glass substrate to obtain a glass substrate, and placing the glass substrate in a chamber inside coating equipment;
(2) selecting high-purity Si target material, SnSb alloy target material and TiO 2 Target material and conductive ZrO x The target material is used as a source of Si, Sn, Sb, Ti and Zr and is arranged in an inner cavity of the coating equipment;
(3) vacuumizing a chamber in the coating equipment, heating the chamber and the glass substrate, introducing argon after the heating, and performing glow cleaning on the chamber and the target;
(4) introducing oxygen, and sputtering Si target and TiO target on the surface of the glass substrate in sequence after the air pressure in the chamber reaches a set value 2 Target material, SnSb alloy target material and TiO 2 Target material and conductive ZrO x The target material is used for obtaining the coated glass with the surface provided with the multilayer composite film;
(5) and (5) after sputtering is finished, taking out the coated glass obtained in the step (4) to obtain the super-hydrophilic and high-wear-resistant film layer finished by vacuum sputtering coating.
The invention adopts magnetron sputtering coating equipment to prepare the super-hydrophilic and high-wear-resistance film layer.
Preferably, in the step (1), the glass substrate is an ultra-white glass substrate.
Preferably, in the step (2), the high-purity Si target material with the purity of 99.99% is prepared by adopting a vacuum plasma thermal spraying method; preparing the TiO with the purity of 99.9% by adopting a plasma thermal spraying method 2 A target material; preparing the SnSb alloy target with the antimony content of 2-20% by adopting a fusion casting method; preparing the conductive ZrO with the purity of 99.9% by adopting a plasma spraying method x A target material.
Preferably, in step (3), the vacuum is applied to 10 -4 ～10 -3 Pa; heating to 80-250 ℃; when the vacuum pressure of argon is 10 -1 ～10 -3 At Pa, glow cleaning was started.
Preferably, in the step (4), the volume percentage of the oxygen is 10-60%; the set value of the air pressure is 0.1-0.5 Pa.
It should be noted that the use of high purity argon as the ionized gas ensures an efficient glow discharge process, and the use of high purity oxygen as the reactant gas ionizes and reacts with Si, SnSb, TiO targets 2 And conductive ZrO x The elements in the target are combined, and uniform silicon oxide, tin antimony oxide, titanium oxide and zirconium oxide films are deposited on the surface of the glass substrate.
Preferably, in the step (4), the specific operations of sequentially sputtering the target material are as follows: turning on a Si target control power supply, adjusting the power supply to 2-6 kW, and depositing for 50-250 s to obtain a silicon oxide film; the Si target is closed to control the power supply, the oxygen gas flow is adjusted, and the TiO is opened 2 Control power supply of target material, and mixing TiO 2 Adjusting the power supply of the target material to 2-6 kW, and obtaining a titanium oxide film with the deposition time of 50-150 s; turning off TiO 2 Controlling a power supply of the target material, adjusting the flow of oxygen gas, turning on the SnSb alloy target material to control the power supply, adjusting the power supply to 80-150W, and depositing for 50-250 s to obtain the target materialTo tin antimony oxide films; the SnSb target is closed to control the power supply, the oxygen gas flow is adjusted, and the TiO is opened 2 Controlling a power supply of the target material, adjusting the power supply to 2-6 kW, and depositing for 50-250 s to obtain a titanium oxide film; turn off TiO 2 The target material controls the power supply, adjusts the oxygen gas flow and opens the conductive ZrO x And controlling a power supply of the target material, adjusting the power supply to 2-6 kW, and depositing for 50-250 s to obtain the zirconium oxide film.
Preferably, in the step (5), after the sputtering is finished, the coated glass is taken out when the temperature in the chamber is reduced to 25-80 ℃.
Based on the same technical concept, the invention further provides the super-hydrophilic and high-wear-resistance film layer obtained by the preparation method.
Preferably, the film layer has 5 layers, the bottommost layer is directly contacted with the glass substrate, and SiO is arranged from the bottommost layer to the top layer in sequence 2 Film layer, TiO x Thin film layer, SnSbO x Film layer, TiO 2 Film layer and ZrO 2 A thin film layer.
Preferably, the SiO 2 The thickness of the film layer is 20-40 nm, and TiO 2 Film layer and TiO x The thickness of the film layer is 8-30 nm, and SnSbO x The thickness of the thin film layer is 50-100 nm, ZrO 2 The thickness of the thin film layer is 10-50 nm.
The invention has the beneficial effects that:
1. according to the preparation method, the target material atoms have strong moving capability by heating the cavity and the substrate and preserving heat for a long time, so that the mobility in the film layer is improved, and meanwhile, sufficient time is provided for diffusion, so that loose cavities with shadow effects collapse, the surface of the film layer is smoother and more continuous, and the compactness is good. And by SnSbO x The film layer is added to enable the film layer and the glass substrate to be combined more tightly through ZrO 2 The film layer is added, so that the film layer has higher wear resistance.
2. SiO obtained by the invention 2 -TiO x -SnSbO x -TiO 2 -ZrO 2 A composite super-hydrophilic and high-wear-resistance film layer made of TiO 2 And SnSbO x High light transmittance characteristic of (2), SiO 2 High adhesion to glass surfaces and ZrO 2 The wear resistance of the glass substrate can be changed after the comprehensive action, so that when the glass substrate is contacted with water mist or the surface of the glass substrate is condensed to form small water drops when the temperature of the surface of the glass substrate is lower than the ambient temperature, the small water drops are coated with SiO 2 -TiO x -SnSbO x -TiO 2 -ZrO 2 The surface of the glass substrate of the composite film layer is easier to spread, the contact angle is 0 degree, the super-hydrophilicity of the surface is realized, and the atomization phenomenon is avoided, so that the light transmittance of the glass substrate is ensured to reach more than 91%, and the pencil hardness of the surface of the film layer reaches 6H.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view of the layered structure of the superhydrophilic highly abrasion-resistant film layer of the present invention.
FIG. 2 is a schematic structural diagram of the magnetron sputtering coating equipment of the present invention.
The reference numbers in the figures are:
1-a vacuum chamber; 2-heating a rod; 3-sample holder rotating table; 4-a sample holder; 5-a first Si target; 6-a second Si target site; 7-TiO 2 A target site; 8-conductive ZrO x A target site; 9-SnSb planar target.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a super-hydrophilic and high-wear-resistance film layer, which comprises the following steps:
(1) immersing an ultra-white glass substrate into absolute ethyl alcohol for ultrasonic cleaning for 10min, then drying at the ambient temperature of 60 ℃ to obtain a glass substrate, and then placing the glass substrate on a sample rack in a vacuum chamber of magnetron sputtering coating equipment, wherein the sample rack is positioned at the upper part of a rotating platform of the sample rack, has a rotating function and can ensure the uniformity of a film layer in the coating process;
(2) high-purity Si target material with the purity of 99.99 percent is prepared by adopting a vacuum plasma thermal spraying method, and TiO with the purity of 99.9 percent is prepared by adopting a plasma thermal spraying method 2 The target material is SnSb alloy target material with 2% antimony content prepared through fusion casting process and conductive ZrO material with 99.9% purity prepared through plasma spraying process x The target material is correspondingly used as the source of Si, Sn, Sb, Ti and Zr and is arranged at the corresponding target position of the inner cavity of the coating equipment (the Si target material is arranged at the first Si target position and the second Si target position, and the TiO target material is arranged at the first Si target position and the second Si target position 2 The target material is arranged on the TiO 2 Target position, conductive ZrO x The target material is arranged in the conductive ZrO x A target position, wherein the SnSb alloy target material is placed at a SnSb plane target position); the target material adopts a phi 155/135x300mm rotary target material as a source of Si, Ti and Zr elements, and the sputtering rate of each target material is controlled by adjusting the power of a medium-frequency power supply; 3-inch plane targets are used as Sn and Sb element sources, and the power of a direct-current power supply is adjusted to control the sputtering rate of the SnSb target material;
(3) vacuum chamber is pumped to 10 -4 Pa, starting a heating system, heating the chamber and the glass substrate by using a heating rod until the temperature is 80 ℃, introducing argon at the flow rate of 20sccm after the heating is finished, starting each target position power supply, setting the power to be 2kW, and when the vacuum pressure of the argon is 10 -3 When Pa is needed, the chamber and the target substrate are bombarded and cleaned one by one, and the power supply is turned off after glow cleaning is finished;
(4) introducing oxygen with the volume percentage of 10 percent, setting the rotation speed of the sample holder to be 2rpm, turning on the Si target material control power supply when the air pressure of the vacuum chamber reaches 0.1Pa, adjusting the power supply to 2kW, and ensuring that the deposition time is 50 percents, obtaining a silicon oxide film; the Si target material control power supply is closed, the oxygen percentage is adjusted to be 20 percent, and TiO is opened 2 Control power supply of target material, and mixing TiO 2 Adjusting the power supply of the target material to 2kW, and obtaining a titanium oxide film with the deposition time of 50 s; turn off TiO 2 Controlling a power supply by the target, adjusting the oxygen percentage to be 50%, turning on the SnSb alloy target to control the power supply, adjusting the power supply to 80W, and depositing for 50s to obtain the tin antimony oxide film; the SnSb target material control power supply is closed, the oxygen percentage is adjusted to be 30 percent, and the TiO target material control power supply is opened 2 Controlling a power supply of the target material, adjusting the power supply to 2kW, and obtaining a titanium oxide film with the deposition time of 50 s; turn off TiO 2 Controlling a power supply by the target material, adjusting the oxygen percentage to be 20%, and opening the conductive ZrO x Controlling a power supply by the target material, adjusting the power supply to 2kW, and depositing for 50s to obtain a zirconium oxide film;
(5) and after the sputtering is finished, taking out the coated glass when the temperature in the chamber is reduced to 25 ℃, and obtaining the super-hydrophilic and high-wear-resistant film layer after the coating is finished.
Example 2
The embodiment provides a preparation method of a super-hydrophilic and high-wear-resistance film layer, which comprises the following steps:
(1) immersing an ultra-white glass substrate into absolute ethyl alcohol for ultrasonic cleaning for 8min, then drying at the ambient temperature of 50 ℃ to obtain a glass substrate, and then placing the glass substrate on a sample rack in a vacuum chamber of magnetron sputtering coating equipment, wherein the sample rack is positioned on the upper part of a sample rack rotating table and can ensure the uniformity of a film layer in the coating process;
(2) preparing high-purity Si target material with the purity of 99.99 percent by adopting a vacuum plasma thermal spraying method, and preparing TiO target material with the purity of 99.9 percent by adopting the plasma thermal spraying method 2 The target material is SnSb alloy target material with 20% of antimony content prepared by a fusion casting method, and the conductive ZrO material with 99.9% of purity prepared by a plasma spraying method x The target material is correspondingly used as the source of Si, Sn, Sb, Ti and Zr and is arranged at the corresponding target position of the inner cavity of the coating equipment (the Si target material is arranged at the first Si target position and the second Si target position, and the TiO target material is arranged at the first Si target position and the second Si target position 2 The target material is arranged on the TiO 2 Target position, conductive ZrO x The target material is arranged in the conductive ZrO x Target site, SnSb alloy targetThe material is placed at a SnSb plane target position); the target material adopts a phi 155/135x300mm rotary target material as a source of Si, Ti and Zr elements, and the sputtering rate of each target material is controlled by adjusting the power of a medium-frequency power supply; a 3-inch plane target is used as a source of Sn and Sb elements, and the power of a direct-current power supply is adjusted to control the sputtering rate of the SnSb target material;
(3) vacuum chamber is pumped to 10 -3 Pa, starting a heating system, heating the chamber and the glass substrate by using a heating rod until the temperature is 250 ℃, introducing argon at the flow rate of 40sccm after the heating is finished, starting each target position power supply, setting the power to be 6kW, and when the vacuum pressure of the argon is 10 -1 When Pa is needed, the chamber and the target substrate are bombarded and cleaned one by one, and the power supply is turned off after cleaning is finished;
(4) introducing oxygen, wherein the volume percentage of the oxygen is 60%, setting the rotating speed of the sample holder to be 10rpm, turning on a Si target material control power supply when the air pressure of the vacuum chamber reaches 0.5Pa, adjusting the power supply to 6kW, and depositing for 250s to obtain a silicon oxide film; the Si target material control power supply is closed, the oxygen percentage is adjusted to be 20 percent, and TiO is opened 2 Control power supply of target material, and mixing TiO 2 Adjusting the power supply of the target material to 6kW, and obtaining a titanium oxide film with the deposition time of 150 s; turn off TiO 2 Controlling a power supply by the target, adjusting the oxygen percentage to be 50%, turning on the SnSb alloy target, adjusting the power supply to be 150W, and depositing for 250s to obtain a tin antimony oxide film; the SnSb target material control power supply is closed, the oxygen percentage is adjusted to be 30 percent, and the TiO target material control power supply is opened 2 Controlling a power supply of the target material, adjusting the power supply to 6kW, and obtaining a titanium oxide film with the deposition time of 250 s; turn off TiO 2 Controlling a power supply by the target material, adjusting the oxygen percentage to be 20%, and opening the conductive ZrO x Controlling a power supply of the target material, adjusting the power supply to 6kW, and depositing for 250s to obtain a zirconium oxide film;
(5) and after the sputtering is finished, taking out the coated glass when the temperature in the chamber is reduced to 80 ℃, and obtaining the super-hydrophilic and high-wear-resistant film layer after the coating is finished.
Example 3
The embodiment provides a preparation method of a super-hydrophilic and high-wear-resistance film layer, which comprises the following steps:
(1) immersing an ultra-white glass substrate into absolute ethyl alcohol for ultrasonic cleaning for 9min, then drying at the ambient temperature of 55 ℃ to obtain a glass substrate, and then placing the glass substrate on a sample rack in a vacuum chamber of magnetron sputtering coating equipment, wherein the sample rack is positioned at the upper part of a rotating platform of the sample rack, so that the uniformity of a film layer in the coating process can be ensured;
(2) high-purity Si target material with the purity of 99.99 percent is prepared by adopting a vacuum plasma thermal spraying method, and TiO with the purity of 99.9 percent is prepared by adopting a plasma thermal spraying method 2 The target material is SnSb alloy target material with 10% Sb content and prepared through smelting casting process and plasma spraying process to obtain conductive ZrO material with 99.9% purity x The target material is correspondingly used as a source of Si, Sn, Sb, Ti and Zr and is arranged at a corresponding target position of an inner cavity of the coating equipment (the Si target material is arranged at a first Si target position and a second Si target position, and the TiO target material is arranged at a first Si target position and a second Si target position 2 The target material is arranged on the TiO 2 Target position, conductive ZrO x The target material is arranged in the conductive ZrO x A target position, wherein the SnSb alloy target material is placed at a SnSb plane target position); the target material adopts a phi 155/135x300mm rotary target material as a source of Si, Ti and Zr elements, and the sputtering rate of each target material is controlled by adjusting the power of a medium-frequency power supply; a 3-inch plane target is used as a source of Sn and Sb elements, and the power of a direct-current power supply is adjusted to control the sputtering rate of the SnSb target material;
(3) vacuum chamber is evacuated to 5 × 10 -4 Pa, starting a heating system, heating the chamber and the glass substrate by using a heating rod until the temperature is 50 ℃, introducing argon at the flow rate of 30sccm after the heating is finished, starting each target position power supply, setting the power to be 3.5kW, and when the vacuum pressure of the argon is 10 DEG -2 When Pa is needed, the chamber and the target substrate are bombarded and cleaned one by one, and the power supply is turned off after cleaning is finished;
(4) introducing oxygen with the volume percentage of 35%, setting the rotation speed of the sample frame at 6rpm, turning on a Si target material control power supply when the air pressure of the vacuum chamber reaches 0.3Pa, adjusting the power supply to 4kW, and depositing for 150s to obtain a silicon oxide film; the Si target material control power supply is closed, the oxygen percentage is adjusted to be 20 percent, and TiO is opened 2 Control power supply of target material, and mixing TiO 2 The power supply of the target material is adjusted to 4kW, the deposition time is 100s, and oxygen is obtainedTitanium film is formed; turning off TiO 2 Controlling a power supply by the target, adjusting the oxygen percentage to be 50%, turning on the SnSb alloy target, adjusting the power supply to be 110W, and depositing for 150s to obtain a tin antimony oxide film; the SnSb target material control power supply is closed, the oxygen percentage is adjusted to be 30 percent, and the TiO target material control power supply is opened 2 Controlling a power supply of the target material, adjusting the power supply to 4kW, and obtaining a titanium oxide film with the deposition time of 150 s; turn off TiO 2 Controlling a power supply by the target material, adjusting the oxygen percentage to be 20%, and opening the conductive ZrO x Controlling a power supply by the target, adjusting the power supply to 4kW, and depositing for 150s to obtain a zirconium oxide film;
(5) and after the sputtering is finished, taking out the coated glass when the temperature in the chamber is reduced to 55 ℃, and thus obtaining the super-hydrophilic and high-wear-resistant film layer after the coating is finished.
In order to verify the technical indexes of the super-hydrophilic and highly wear-resistant film layer, the film layer obtained in example 3 was tested, and the results are shown in table 1.
TABLE 1 technical test standards
| Detecting items | Example 3 |
| Contact angle | 0° |
| Whether the atomization phenomenon appears or not | Whether or not |
| Light transmittance | 91％ |
| Pencil hardness on film surface | 6H |
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (4)
1. A preparation method of a super-hydrophilic and high-wear-resistance film layer is characterized by comprising the following steps:
(1) cleaning and drying the glass substrate to obtain a glass substrate, and placing the glass substrate in a chamber inside coating equipment; wherein the glass substrate is an ultra-white glass substrate;
(2) selecting high-purity Si target material, SnSb alloy target material and TiO 2 Target material and conductive ZrO x The target material is used as a source of Si, Sn, Sb, Ti and Zr and is arranged in an inner cavity of the coating equipment; wherein the high-purity Si target material is prepared by adopting a vacuum plasma thermal spraying method; the TiO is prepared by adopting a plasma thermal spraying method 2 A target material; preparing the SnSb alloy target by adopting a fusion casting method; the conductive ZrO is prepared by adopting a plasma spraying method x A target material;
(3) vacuumizing a chamber in the coating equipment, heating the chamber and the glass substrate, introducing argon after the heating, and performing glow cleaning on the chamber and the target; wherein the vacuum is up to 10 -4 ～10 -3 Pa; heating to 80-250 ℃; when the vacuum pressure of argon is 10 -1 ～10 -3 When Pa, starting glow cleaning;
(4) introducing oxygen, and sputtering Si target and TiO target on the surface of the glass substrate in sequence after the air pressure in the cavity reaches a set value 2 Target material, SnSb alloy target material and TiO 2 Target material and conductive ZrO x The target material is used for obtaining the coated glass with the surface provided with the multilayer composite film; wherein the volume percentage of the oxygen is 10-60%; the set value of the air pressure is 0.1-0.5 Pa; the specific operation of sputtering the target material in sequence is as follows:turning on a Si target control power supply, adjusting the power supply to 2-6 kW, and depositing for 50-250 s to obtain a silicon oxide film; the Si target is closed to control the power supply, the oxygen gas flow is adjusted, and TiO is opened 2 Control power supply of target material, and mixing TiO 2 Adjusting the power supply of the target material to 2-6 kW, and obtaining a titanium oxide film with the deposition time of 50-150 s; turn off TiO 2 Controlling a power supply by the target, adjusting the flow of oxygen gas, turning on the SnSb alloy target to control the power supply, adjusting the power supply to 80-150W, and depositing for 50-250 s to obtain a tin antimony oxide film; the SnSb target is closed to control the power supply, the oxygen gas flow is adjusted, and the TiO is opened 2 Controlling a power supply by the target, adjusting the power supply to 2-6 kW, and obtaining a titanium oxide film with the deposition time of 50-250 s; turn off TiO 2 The target controls the power supply, adjusts the oxygen gas flow, and turns on the conductive ZrO x Controlling a power supply of the target material, adjusting the power supply to 2-6 kW, and depositing for 50-250 s to obtain a zirconium oxide film;
(5) after sputtering is finished, taking out the coated glass obtained in the step (4) to obtain a super-hydrophilic and high-wear-resistance film layer finished by vacuum sputtering coating; and after the sputtering is finished, taking out the coated glass when the temperature in the chamber is reduced to 25-80 ℃.
2. The super-hydrophilic and high-wear-resistant film layer obtained by the preparation method of claim 1.
3. The superhydrophilic highly abrasion resistant film layer of claim 2, wherein the film layer comprises 5 layers, wherein the lowermost layer is in direct contact with the glass substrate and the SiO layer is sequentially disposed from the lowermost layer to the top layer 2 Film layer, TiO x Thin film layer, SnSbO x Film layer, TiO 2 Film layer and ZrO 2 A thin film layer.
4. The superhydrophilic, highly abrasion resistant film layer of claim 3, wherein the SiO 2 The thickness of the film layer is 20-40 nm, and TiO 2 Film layer and TiO x The thickness of the film layer is 8-30 nm, and SnSbO x The thickness of the thin film layer is 50-100 nm, ZrO 2 The thickness of the thin film layer is 10-50 nm.
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