In-rain and underwater high-definition glass and preparation method thereof

Abstract

The invention discloses in-rain and underwater high-definition glass and a preparation method thereof. The preparation method comprises the following steps: (1) depositing an inorganic film on glass; and (2) scanning the surface of the glass with the inorganic film deposited by laser to form a micro-nano structure on the surface of the glass so as to obtain the in-rain and underwater high-definition glass. The preparation method further comprises the step of directly scanning the surface of one side of the glass through laser to form a micro-nano structure, so as to obtain the in-rain and underwater high-definition glass. According to the invention, a simple process is adopted to achieve the excellent performance of high definition of glass running in rain and underwater for a long time. The prepared glass can be used for motor vehicle glass, train glass, airplane glass, medical endoscopes and underwater glass running in the rain. The preparation method disclosed by the invention is low in equipment requirement and low in cost, and has the advantage of large-scale production.

Description

Technical Field

[0001] The invention belongs to the technical field of preparing high-definition glass in rain and underwater, and achieves high-definition effect in rain and underwater by adjusting the process to prepare corresponding micro-nano structures. It specifically relates to high-definition glass in rain and underwater and a preparation method thereof. Background Art

[0002] At present, Fuyao Glass has launched hydrophobic glass to improve the clarity of cars driving in the rain. The sol-gel method is used to form a fluoride film layer on the glass surface. It is usually tetrafluorosilane, which is relatively expensive. It is not wear-resistant in dusty environments and has poor durability. From the video shown on its official website, it can be seen that this hydrophobic glass will still block part of the line of sight during the rolling of water, and may still block the field of vision in heavy rain. Currently, most rainproof films and rainproof agents on the market also use hydrophobic coating technology. The main problem is that the rolling process of water droplets blocks the line of sight.

[0003] Therefore, the glass prepared by the present invention is hydrophilic glass, which has a strong water spreading ability and forms a continuous water film, so that even the heaviest rainstorm does not affect the field of vision. At the same time, the surface material of the glass prepared by the present invention can be the glass itself, or can be a hard material such as diamond-like carbon film, silicon oxide, aluminum oxide, titanium oxide, silicon carbide, so the wear resistance and stability are better.

[0004] The present invention attempts to adopt a technology to solve the above-mentioned requirements of long-lasting, high-definition in rain and underwater by adjusting technical parameters. High-definition in rain and underwater is the core of the present invention. Summary of the invention

[0005] The present invention provides a high-definition glass in rain and underwater and a preparation method thereof. The purpose of high-definition in rain and underwater is achieved by changing the film thickness, composition and laser scanning parameters of the inorganic thin film to regulate the micro-nano structure array and its microscopic component composition.

[0006] 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 high-definition glass in rain and underwater, comprising the following steps: (1) Deposition of inorganic thin films on glass; (2) Laser scanning the glass surface after the inorganic thin film is deposited in step (1) to form a micro-nano structure on the glass surface, thereby obtaining high-definition glass in rain and underwater.

[0007] Furthermore, the glass includes all glass, glass that can be used in the rain, glass that can be used underwater, and glass that can be used inside the body.

[0008] Furthermore, the inorganic thin film includes at least one of a carbon film, a titanium film, a silicon film, a tungsten film, an aluminum film, a vanadium film, a silicon carbide film, a tungsten carbide film, a silicon nitride film, and a titanium nitride film; and the deposition thickness of the inorganic thin film is 0nm-3000nm.

[0009] Preferably, the deposition thickness of the inorganic thin film is 0 nm-1800 nm.

[0010] Furthermore, the deposition method includes magnetron sputtering, electron beam evaporation, thermal evaporation, and electroplating.

[0011] Furthermore, when the deposition method is magnetron sputtering, the typical settings are: DC sputtering of a water-cooled Al target with a diameter of 60 mm, the sputtering gas is pure Ar, the working gas pressure is 1.6 Pa, the argon gas flow rate is 30 sccm, the sputtering voltage is 290 V, the current is 0.2 A, and the deposition time is 10 min. Laser confocal microscopy shows that the test deposition thickness is 900 nm.

[0012] In the present invention, different equipment has different process parameters, which can be selected according to actual needs.

[0013] Furthermore, the laser includes at least one of an infrared laser, a visible light laser, an ultraviolet laser, a continuous laser, and a pulsed laser.

[0014] Furthermore, the laser energy density is greater than 10 mJ / cm 2 .

[0015] Preferably, the laser scanning uses a 30W rated power fiber laser.

[0016] Furthermore, the laser scanning speed is 0.01 m / s-500 m / s; and the scanning line spacing is ≤10 mm.

[0017] Preferably, the scanning speed of the laser scanning is 0.5 m / s-10 m / s; the scanning power is 1%-100% of the rated power; and the scanning line spacing is 0.02-0.1 mm.

[0018] When the thickness of the inorganic film is 0, that is, the laser directly scans the glass surface to form a micro-nano structure on the glass surface, thereby obtaining a super-hydrophilic, anti-fog, wide-spectrum anti-reflection glass.

[0019] Preferably, the laser scanning uses a 5W rated power ultraviolet laser with a wavelength of 355 nm. If the laser frequency is 30KHz and the laser spot diameter is 50 microns, the energy density at this time can be estimated to be 8.5 J / cm 2 .

[0020] Furthermore, the laser scanning speed is 0.01 m / s-500 m / s; and the scanning line spacing is ≤10 mm.

[0021] Preferably, the scanning speed of the laser scanning is 0.5 m / s-10 m / s; the scanning line spacing is 0.03 mm.

[0022] Furthermore, the inner surface of the high-definition glass in the rain or underwater can be used as the outer surface of the glass.

[0023] Compared with the prior art, the advantages and beneficial effects of the present invention are: 1. The present invention can achieve long-lasting high-definition performance in rain and underwater by using a simple process, which is superior to the existing technology. The existing technology uses the sol-gel method to deposit a layer of fluorosilane on the glass surface, which takes a long time, is costly, and is not durable. The present invention uses a hard film layer or the glass itself, so it has good durability; 2. The present invention forms a stable micro-nano structure on the glass surface, achieving a strong water spreading ability on the surface. Therefore, even a heavy rainstorm does not affect the field of vision. The existing technology uses hydrophobic glass, which will still block part of the vision during the rolling process of water, and is likely to block the field of vision in a heavy rainstorm; 3. In terms of technology, the deposition method of the present invention uses magnetron sputtering, electron beam evaporation, thermal evaporation, and electroplating; the requirements for laser scanning are low, and a fiber laser marker or an ultraviolet laser marker can meet the requirements; the entire preparation method is low-cost and can be completed using industrially stable and mature equipment, or even only using lasers. Therefore, it can be directly used to produce high-definition glass in the rain and underwater, and has the advantage of large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a comparison of the visual field of the treated glass and the reference glass in Example 1 after they were made into mirrors in heavy rain. Both the treated glass and the reference glass were made into mirrors by aluminum plating on the back. The visual field of the reference mirror was blurred in the rain.

[0025] Figure 2 This is a comparison of the transmitted vision of the treated glass and the reference glass after being sprayed with water in Example 1. The treated glass has been placed in the laboratory for one year and has accumulated dust and has been wiped with a paper towel. It still shows a clear vision.

[0026] Figure 3 This is a typical laser confocal microscope photo of the glass surface after treatment in Example 1.

[0027] Figure 4 This is a comparison of the visual field of the treated glass and the reference glass in Example 2 after they were made into mirrors in heavy rain. Both the treated glass and the reference glass were made into mirrors by aluminum plating on the back. The visual field of the reference mirror was blurred in the rain.

[0028] Figure 5 This is a comparison of the visual field of the treated glass and the reference glass in Example 3 after they were made into mirrors in heavy rain. The treated glass and the reference glass were both made into mirrors by aluminum plating on the back. The visual field of the reference mirror was blurred in the rain.

[0029] FIG. 6 is a scanning electron microscope (SEM) photograph of the glass surface processed by process 1 and process 2 in Example 3. Figure 6a It is the glass after process one; Figure 6b It is the glass processed by process 2.

[0030] Figure 7 This is a typical laser confocal microscope photo of the glass surface after process 1 in Example 3.

[0031] FIG8 is a perspective comparison diagram of the glass treated by process 2 in Example 3 and the reference glass in rain. Figure 8a Treat glass for process two; Figure 8b For reference glass.

[0032] FIG. 9 is a comparison diagram of the transmission field of view of the glass after process three treatment in Example 3 and the reference glass under a mist spraying environment. Figure 9a It is the glass after process three treatment; Figure 9b It is the reference glass.

[0033] Fig.10 This is a comparison of the visual field of the treated glass and the reference glass made into mirrors in Example 4 in heavy rain. Both the treated glass and the reference glass are made into mirrors by aluminum plating on the back. The visual field of the reference mirror is blurred in the rain.

[0034] Fig.11 This is a comparison of the visual field of the treated glass and the reference glass made into mirrors in Example 5 in heavy rain. Both the treated glass and the reference glass are made into mirrors by aluminum plating on the back. The visual field of the reference mirror is blurred in the rain.

[0035] Fig.12 This is a comparison of the visual field of the treated glass and the reference glass in Example 6 after they were made into mirrors in heavy rain. Both the treated glass and the reference glass were made into mirrors by aluminum plating on the back. The visual field of the reference mirror was blurred in the rain.

[0036] Fig. 13 is a comparison of the visual field in heavy rain after the treated glass and the reference glass are made into mirrors in Example 7. Both the treated glass and the reference glass are made into mirrors by aluminum plating on the back. Fig.13a The mirror is made of treated glass, and the view is clear in the rain; Fig.13b It is a reference mirror in the rain, and the vision is blurred in the rain.

[0037] Fig.14This is a comparison of the visual field of the treated glass and the reference glass in Example 8 after they were made into mirrors in heavy rain. Both the treated glass and the reference glass were made into mirrors by aluminum plating on the back. The visual field of the reference mirror was blurred in the rain.

[0038] Fig.15 This is a comparison of the visual field of the treated mirror and the reference mirror in the water spray test of Example 9. The water of the treated mirror spreads over the entire surface, and there is no water droplet scattering phenomenon. The visual field of the reference mirror is blurred in the water spray test. DETAILED DESCRIPTION

[0039] The following embodiments are used to better illustrate the present invention, but the present invention is not limited to the following embodiments.

[0040] The specific steps of the preparation method of the high-definition glass in rain and underwater based on carbon film are as follows: (1) A magnetron sputtering coating system was used to deposit carbon film on glass. The glass used was soda-lime glass or borosilicate glass. A water-cooled graphite target (99.999%) with a diameter of 60 mm was used for RF sputtering. The sputtering gas was pure Ar (99.9995%). The working gas pressure was 4 Pa, the argon gas flow rate was set to 80 sccm, the sputtering power was controlled at 180 W, and the carbon coating time was 10 min.

[0041] (2) Laser scanning: After the carbon film is deposited in step (1), the surface of the soda-lime glass or borosilicate glass is scanned with a 5W ultraviolet laser, 30KHz frequency, 8 microsecond pulse width, 3m / s scanning speed, and 0.03mm scanning line spacing; high-definition glass in the rain and underwater is obtained, and the glass has a certain wear resistance and still maintains high definition in the rain and underwater after wiping. A mirror is made by depositing an aluminum film on the back thereof. Compared with the reference glass mirror, the field of view of the treated glass mirror in the rain is still clear, while the reference mirror has many water droplets on its surface and the field of view is blurred. The results are shown in Figure 1 . Figure 2 After nearly a year of storage in the laboratory, the surface of the glass has accumulated dust. After washing with water and wiping with a paper towel, it still shows strong water spreading ability. When spraying water to simulate a rainy scene, the transmitted vision on the treated glass side is clear; while the vision on the reference glass side is blurred with many water droplets. In addition to the tolerance of carbon, its surface microstructure is an important reason for its clear vision in the rain. Figure 3 The micron-scale surface morphology and roughness information of the treated glass surface are shown. The surface has shallow stripes and widely distributed circular pits of varying depths with a diameter of about 40 microns. The stripes and circular pits show a quasi-periodic distribution.

[0042] The specific steps are as follows: (1) Silicon film was deposited on 3 mm soda-lime glass by electron beam evaporation; the thickness of the silicon film was about 400-1600 nm; Electron beam silicon plating process: back vacuum is 10-4 Pa level, high-purity silicon (99.9995%) particles are placed in a copper crucible, the electron beam spot size and brightness are manually adjusted, and the deposition rate is controlled at 1~2 nm / s until the target thickness is reached and the deposition is stopped.

[0043] Laser scanning the glass surface after the silicon film is deposited in step (1), forming a micro-nano structure on the glass surface; using a fiber laser marking machine with a rated power of 30W for laser scanning; the laser scanning conditions are: 100% power; scanning speed 0.5m / s; scanning line spacing 0.03mm; frequency 30KHz; obtaining high-definition glass in rain and underwater. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Figure 4 The mirror was shown to have a high-definition view in the rain and was not affected at all by heavy rain; whereas the reference sample had a blurred view.

[0044] Example 3: Laser direct scanning of glass to prepare high-definition glass in rain and underwater The specific steps are as follows: Ultraviolet laser is used to scan one side of soda-lime glass to form micro-nano structures on the glass surface; the laser rated power is 5W; three process parameters are used for laser scanning. The first is: scanning speed 3m / s; scanning line spacing 0.03mm; frequency 30KHz; pulse width 10 microseconds; the second is: scanning speed 10m / s; scanning line spacing is 0.06mm; frequency is 30KHz; pulse width is 1 microsecond; the third is: scanning speed 10m / s; scanning line spacing is 0.08mm; frequency is 30KHz; pulse width is 1 microsecond; process three is more efficient, so it is used to process large areas of glass of 0.5m*1m. At this time, it is assumed that the energy density is 5~8J / cm when the spot diameter is 50 microns 2 . Get high-definition glass in the rain and underwater. Depositing a layer of aluminum film on the back surface can make a rearview mirror or mirror. Figure 5 It was demonstrated that the mirror made from process one sample showed a high-definition field of view in the rain and was completely unaffected by heavy rain; while the reference sample had a blurred field of view. Figure 6a This is a SEM photo of the process surface. Figure 6b This is the SEM photo of the surface of process 2. It can be seen that nanoparticles of about 20-100 nm are widely distributed on the treated surface. Figure 7 This is a confocal microscope photo of the surface of process 1. It can be seen that there are shallow stripes on the surface and there are widely distributed round pits of varying depths with a diameter of about 25 microns. The stripes and round pits are quasi-periodic. This micro-nano structure promotes extremely strong water spreading ability, so it shows high clarity in the rain and underwater without obstructing the field of vision. Figure 5Figure 8 is a comparison of the performance of the glass treated by process 2 and the untreated glass in the rain. It can be seen that the treated glass still shows a clear view in the rain, while the reference glass has a blurred view. Figure 9 uses a sprayer for spraying pesticides to simulate a scene in the rain. Figure 9 shows that the large area of ​​glass treated by process 3 still shows a strong water spreading ability, and the transmitted field of view is basically unaffected. The reference glass obviously has a poor water spreading ability and a blurred transmitted field of view.

[0045] The specific steps are as follows: (1) Titanium film was deposited on soda-lime glass by magnetron sputtering. The deposition time was 5 min and the thickness of the titanium film was about 250 nm. The sputtering gas was argon with a flow rate of 30 sccm and an operating pressure of 1.6 Pa. The sputtering voltage was controlled at 300 V and the current was about 0.3 A.

[0046] (2) Laser scanning: After the titanium film is deposited in step (1), a micro-nano structure is formed on the glass surface; a fiber laser marking machine with a rated power of 30W is used for laser scanning; the laser scanning conditions are: 70% power; scanning speed 2m / s; scanning interval 0.03mm; frequency 30KHz; high-definition glass in rain and underwater is obtained. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Fig.10 The mirror was shown to have a high-definition view in the rain and was not affected at all by heavy rain; whereas the reference sample had a blurred view.

[0047] Example 5: Laser scanning of vanadium-plated film to prepare high-definition glass in rain and underwater The specific steps are as follows: (1) Magnetron sputtering deposition of vanadium film: DC sputtering of a water-cooled vanadium target (99.995%) with a diameter of 60 mm, the sputtering gas was pure Ar (99.9995%), the working gas pressure was 1.6 Pa; the argon gas flow rate was 30 sccm, the sputtering voltage was controlled at 279 V, the current was about 0.227 A, and the deposition thickness was about 500 nm.

[0048] (2) Laser scanning The glass surface after the vanadium film is deposited in step (1) is laser scanned by a fiber laser marking machine with a rated power of 30W: 100% of the rated power; scanning speed 2m / s; scanning line spacing 0.03mm; frequency 30KHz; to obtain high-definition glass in rain and underwater. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Fig.11 The mirror was shown to have a high-definition view in the rain and was not affected at all by heavy rain; whereas the reference sample had a blurred view.

[0049] Example 6: Laser scanning of silicon carbide film to prepare high-definition glass in rain and underwater The specific steps are as follows: (1) Magnetron sputtering deposition of silicon carbide film: DC sputtering of a water-cooled silicon carbide target (99.995%) with a diameter of 60 mm, the sputtering gas is pure Ar (99.9995%), the working gas pressure is 4 Pa; the argon gas flow rate is 80 sccm, the RF sputtering power is 150 W, and the deposition time is 10 min.

[0050] (2) Laser scanning The glass surface after the silicon carbide film is deposited in step (1) is laser scanned using a UV laser with a rated power of 5W: scanning speed 2m / s; scanning line spacing 0.05mm; frequency 20KHz; pulse width 6 microseconds, to obtain high-definition glass in rain and underwater. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Fig.12 The mirror was shown to have a high-definition view in the rain and was not affected at all by heavy rain; whereas the reference sample had a blurred view.

[0051] Example 7: Laser scanning of tungsten carbide film to prepare high-definition glass in rain and underwater The specific steps are as follows: (1) Magnetron sputtering deposition of tungsten carbide film: DC sputtering of a water-cooled tungsten carbide target (99.995%) with a diameter of 60 mm, the sputtering gas is pure Ar (99.9995%), the working gas pressure is 4 Pa; the argon gas flow rate is 80 sccm, the RF sputtering power is 150 W, and the deposition time is 10 min.

[0052] (2) Laser scanning The glass surface after the tungsten carbide film is deposited in step (1) is laser scanned using a UV laser with a rated power of 5W: scanning speed 2m / s; scanning line spacing 0.03mm; frequency 30KHz; pulse width 8 microseconds, to obtain high-definition glass in rain and underwater. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Fig.13a The mirror shows a high-definition view in the rain, which is not affected by heavy rain at all; while the reference mirror Fig.13b The vision becomes blurred.

[0053] Example 8: Laser scanning titanium nitride film to prepare high-definition glass in rain and underwater The specific steps are as follows: (1) Magnetron sputtering deposition of titanium nitride film: DC sputtering of a water-cooled titanium nitride target (99.995%) with a diameter of 60 mm, the sputtering gas is pure Ar (99.9995%), the working gas pressure is 4 Pa; the argon flow rate is 80 sccm, the RF sputtering power is 150 W, and the deposition time is 5-15 min.

[0054] (2) Laser scanning The glass surface after the titanium nitride film is deposited in step (1) is laser scanned using a UV laser with a rated power of 5W: scanning speed 2m / s; scanning line spacing 0.03mm; frequency 30KHz; pulse width 8 microseconds, to obtain high-definition glass in rain and underwater. A layer of aluminum film is deposited on the rear surface to make a rearview mirror or a mirror. Fig.14 It shows that the treated mirror shows a high-definition vision in the rain and is not affected by heavy rain at all; the two mirrors on the lawn are not affected by raindrops and are completely spread out, which are the mirrors obtained by the above process; while the rain on the reference mirror cannot completely spread on the surface, there are many raindrops, which will scatter light and affect the vision.

[0055] First, deposit about 1 micron aluminum film on one side of the glass to simulate a rearview mirror, and use it as a reference mirror without performing the following steps. The following steps are as follows.

[0056] (1) A titanium film was deposited on the reverse side of the aluminum film of the simulated rearview mirror by magnetron sputtering. The deposition time was 2 min and the thickness of the titanium film was about 100 nm. The sputtering gas was argon with a flow rate of 30 sccm and an operating pressure of 1.6 Pa. The sputtering voltage was controlled at 300 V and the current was about 0.3 A.

[0057] (2) Laser scanning: In the step (1), a micro-nano structure is formed on the glass surface after titanium film deposition; a femtosecond laser with a rated power of 20 W is used for laser scanning; the laser scanning conditions are: 30-40% power; scanning speed 5 m / s; scanning interval 0.05 mm; frequency 400 KHz; a high-definition mirror is obtained in the rain and underwater. Fig.15 It was shown that when the treated mirror was sprayed with water to simulate rainfall, the water spread completely on the surface, showing a high-definition field of view; while the water on the reference mirror could not spread completely on the surface, and there were many water droplets scattered, causing a blurred field of view.

[0058] The above embodiments illustrate that by using equipment that can be mass-produced and adjusting process parameters, a micro-nano structure is formed on the glass surface, thus having the advantage of being mass-produced. The glass obtained by the above preparation method of the present invention has the characteristics of high clarity in rain and underwater, and can be used to produce glass that can be used in rain and underwater, such as motor vehicle rearview mirrors, front windshields, train and aircraft glass, medical endoscopes, and other glass that can be used in rain and underwater.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.

Claims

1. A method for preparing high-definition glass in rain and underwater, characterized in that: The following steps are involved: (1) Deposition of inorganic thin films on glass; (2) Laser scanning the glass surface after the inorganic thin film is deposited in step (1) to form a micro-nano structure on the glass surface, thereby obtaining high-definition glass in rain and underwater.

2. The method for preparing high-definition glass in rain and underwater according to claim 1, characterized in that: The glass includes all glass, glass that can be used in rain, glass that can be used underwater, and glass that can be used in body fluids.

3. The method for preparing high-definition glass in rain and underwater according to claim 1, characterized in that: The inorganic thin film includes at least one of a carbon film, a titanium film, a silicon film, a tungsten film, an aluminum film, a vanadium film, a silicon carbide film, a tungsten carbide film, a silicon nitride film, and a titanium nitride film; the deposition thickness of the inorganic thin film is 0nm-2500nm. 0nm corresponds to no thin film deposition.

4. The method for preparing high-definition glass in rain and underwater according to claim 1, characterized in that: The deposition methods include magnetron sputtering, electron beam evaporation, thermal evaporation and electroplating.

5. According to the method for preparing high-definition glass in rain and underwater according to claim 1, the laser includes at least one of an infrared laser, a visible light laser, an ultraviolet laser, and a continuous laser and a pulsed laser.

6. The method for preparing the super-hydrophilic, anti-fog, wide-spectrum anti-reflection glass according to claim 1, characterized in that: The laser energy density is greater than 10 mJ / cm 2 .

7. The glass prepared according to claim 1 can be used for serving in rain, underwater, and in body fluids.

8. The high-definition glass in rain and underwater obtained by the preparation method according to any one of claims 1 to 7 and its application, characterized in that: The high-definition glass for use in rain or underwater can be used as the inner surface of glass, and can also be used as the outer surface of glass.

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