阅读说明：本技术 一种防雾自清洁玻璃及其制备方法 (Antifogging self-cleaning glass and preparation method thereof ) 是由 崔洪涛 赵玉莹 马小惠 刘召超 闫惠刚 滕超 王鹏飞 郭钰 商怀帅 张纪刚 于 2021-09-02 设计创作，主要内容包括：本发明提出了一种防雾自清洁玻璃及其制备方法。所述防雾自清洁玻璃的制备方法为：在玻璃上沉积铝或硅中的至少一种材料的薄膜；激光扫描所述处理后的玻璃表面；将处理后的玻璃在空气中退火,获得所述防雾自清洁玻璃。本发明沉积方法使用磁控溅射或电子束蒸发等；退火条件真空或者氮气保护性气氛容易实现；对激光扫描的功率要求低,采用激光扫描设备的最大功率为20～50W,光纤激光打标机或紫外激光打标机即可满足功率需求；整个制备方法成本低廉,可使用工业化稳定成熟的设备完成,因此可直接用于改进大规模制备玻璃工艺,生产防雾自清洁玻璃,具有可规模化生产的优势。(The invention provides antifogging self-cleaning glass and a preparation method thereof. The preparation method of the antifogging self-cleaning glass comprises the following steps: depositing a thin film of at least one of aluminum or silicon on the glass; laser scanning the treated glass surface; and annealing the treated glass in the air to obtain the antifogging self-cleaning glass. The deposition method of the invention uses magnetron sputtering or electron beam evaporation, etc.; the annealing condition is easy to realize in vacuum or nitrogen protective atmosphere; the power requirement on laser scanning is low, the maximum power of the laser scanning equipment is 20-50W, and the power requirement can be met by the fiber laser marking machine or the ultraviolet laser marking machine; the whole preparation method is low in cost and can be completed by using industrial, stable and mature equipment, so that the method can be directly used for improving a large-scale glass preparation process to produce the antifogging self-cleaning glass, and has the advantage of large-scale production.)

1. A preparation method of antifogging self-cleaning glass is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) depositing a thin film of at least one of aluminum or silicon on the glass; the thickness of the film is 1-200 nm;

(2) scanning the glass surface treated in the step (1) by laser to form a micro-nano structure on the glass surface;

(3) and (3) introducing oxygen into the glass treated in the step (2) or annealing the glass in the air, wherein the annealing temperature is 500-700 ℃, and the antifogging self-cleaning glass is obtained.

2. The preparation method of the anti-fog self-cleaning glass as claimed in claim 1, wherein the step (1) is to deposit an aluminum film with a thickness of 10-200 nm or a silicon film with a thickness of 60-200 nm on the glass.

3. The method for preparing the anti-fog self-cleaning glass according to claim 1, wherein the contact angle of the glass in the step (1) is 20-70 °.

4. The method for preparing the anti-fog self-cleaning glass as claimed in claim 1, wherein the step (1) further comprises the step of placing the deposited glass in a nitrogen protective atmosphere or less than 1 x 10^-1Annealing in vacuum of Pa.

5. The preparation method of the antifogging self-cleaning glass as claimed in claim 4, wherein the annealing temperature is 300-650 ℃; the time is 1min to 1 h.

6. The method for preparing the anti-fog self-cleaning glass according to claim 1, wherein the deposition method of the step (1) is any one of magnetron sputtering, electron beam evaporation, thermal evaporation or electroplating.

7. The method for preparing the anti-fog self-cleaning glass according to claim 1, wherein the laser scanning device in the step (2) is any one of a fiber laser, a carbon dioxide laser and an ultraviolet laser.

8. The method for preparing the anti-fog self-cleaning glass as claimed in claim 1, wherein the power density of the laser scanning in the step (2) is less than or equal to 10000kW per square meter.

9. The preparation method of the anti-fog self-cleaning glass as claimed in claim 1, wherein the annealing time in the step (3) is 10 s-30 min.

10. The antifogging self-cleaning glass prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of antifogging glass preparation, and particularly relates to antifogging self-cleaning glass and a preparation method thereof.

Background

The antifogging self-cleaning characteristic can eliminate the trouble of daily cleaning of glasses and surface fogging, reduce the daily cleaning cost of the solar panel, and has wide application prospects in the fields of automobile windproof glass, high-rise building windows, sensor glass shells for automatic driving electric cars, photovoltaic building integration and the like. The self-cleaning anti-reflection nano structure is formed on the surface of the glass, and the etching cost of the traditional electron beam writing, photoetching, reactive ion etching and the like is higher; the low-cost hydrothermal method and sol-gel method have the problems that the process is difficult to control and the stability (including mechanical, high-temperature, environmental and other stability) of the generated structure is weak. The nano-imprinting method can relieve the preparation cost of an expensive nano-array structure master plate, and the prepared diffraction grating has self-cleaning property, but the anti-reflection performance is not ideal, so that the efficiency of the cell is deteriorated. Coating a layer of low surface energy material on the surface of glass tests the stability of the material under service conditions. The picosecond laser is directly adopted to induce the texture, and the transmission rate is reduced because the picosecond laser scanning groove is deep and only covers a small part of the surface and scattering loss still exists; and still require low surface energy coatings. The prior art is difficult to industrialize, and the development of related technologies which are easy to control and can be industrialized in a large scale is urgently needed. Until now there have been only direct applications in a few fields, such as in mars solar panels; or spectacle lenses, but the cost is higher, and the selling price of a pair of spectacles with the anti-fog function is additionally increased by about 100 yuan.

Disclosure of Invention

The technical scheme of the invention can enable the glass to have hydrophilicity and antifogging self-cleaning function, and the preparation method is simple and convenient for large-scale popularization and use.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the invention provides a preparation method of antifogging self-cleaning glass, which comprises the following steps:

(1) depositing a thin film of at least one of aluminum or silicon on the glass; the thickness of the film is 1-200 nm;

(2) scanning the glass surface treated in the step (1) by laser to form a micro-nano structure on the glass surface;

(3) and (3) introducing oxygen into the glass treated in the step (2) or annealing the glass in the air to obtain the antifogging self-cleaning glass.

Further, the step (1) is to deposit an aluminum film with the thickness of 40-200 nm or a silicon film with the thickness of 10-200 nm on the glass.

Further, the step (1) is to deposit an aluminum film with the thickness of 60-80 nm on the glass.

Further, the glass in the step (1) is soda-lime glass or borosilicate glass.

Further, the contact angle of the glass in the step (1) is 20-70 degrees.

Further, the step (1) also comprises the step of placing the deposited glass in a nitrogen protective atmosphere or less than 1 x 10^-1Annealing in vacuum of Pa.

Further, the annealing temperature is 300-650 ℃; the time is 1min to 1 h.

Further, the deposition method of the step (1) is any one of magnetron sputtering, electron beam evaporation, thermal evaporation or electroplating.

Further, the laser scanning device in the step (2) is any one of a fiber laser, a carbon dioxide laser and an ultraviolet laser.

Further, the power density of laser scanning in the step (2) is less than or equal to 10000 kW/square meter.

Further, the speed of laser scanning in the step (2) is 0.003-3.0 m/s; the laser scanning interval is less than or equal to 0.2 mm.

Further, the laser scanning conditions in the step (2) are as follows: the scanning speed is 0.003 to 3.0 m/s; the scanning pitch is less than 0.2 mm.

Further, the annealing time in the step (3) is 30 s-30 min.

The invention also provides the antifogging self-cleaning glass prepared by the preparation method.

Compared with the prior art, the invention has the advantages and beneficial effects that:

the existing preparation technology for forming the antifogging self-cleaning cannot meet the requirements on stability, uniformity and repeatability, and can not realize large-scale production; and the method of additional coating inevitably suffers from degradation of the coating. The invention adopts the reaction of silicon, aluminum and glass to bond to the glass network, and the process of laser processing the related materials generates a specific stable micro-nano structure, thereby overcoming the technical problem. Compared with common coating or filmed anti-fog glass, the anti-fog self-cleaning glass has a stable surface layer effect, and the formed local micro-nano structure not only has an anti-fog self-cleaning effect, but also enables the anti-fog self-cleaning glass to have a similar transmittance before being processed.

The preparation method of the invention obviously reduces the contact angle of the glass, can adapt to the glass of various materials by adjusting the thickness of the aluminum film or the silicon film, and ensures that the glass has super-hydrophilicity and antifogging self-cleaning function. In terms of process, the deposition method of the invention uses magnetron sputtering or electron beam evaporation and the like; the annealing condition is easy to realize in vacuum or nitrogen protective atmosphere; the power requirement on laser scanning is low, the maximum power of the laser scanning equipment is 20-50W, and the power requirement can be met by the fiber laser marking machine or the ultraviolet laser marking machine; the whole preparation method is low in cost and can be completed by using industrial, stable and mature equipment, so that the method can be directly used for improving a large-scale glass preparation process to produce the antifogging self-cleaning glass, and has the advantage of large-scale production.

Drawings

FIG. 1 is the wetting angle of the surface of the anti-fog self-cleaning glass according to the invention;

FIG. 2 is a microscopic photograph of the antifogging self-cleaning glass of the present invention with a depth of field of three-dimensional super;

FIG. 3 is a graded detail structure of the surface of the anti-fog self-cleaning glass of the invention;

FIG. 4 is a three-dimensional structural morphology of the anti-fog self-cleaning glass of the present invention;

FIG. 5 is the transmittance of the antifogging self-cleaning glass with the aluminum film of 60-80 nm thickness under different power treatments;

FIG. 6 shows the contact angle of glass with a silicon film of 10-60 nm thickness under ultraviolet laser treatment; wherein 50.752 ° is the contact angle of untreated borosilicate glass; 35.515 DEG is the contact angle of untreated soda-lime glass.

Detailed Description

The following embodiments better illustrate the present invention. However, the present invention is not limited to the following examples.

Example 1: preparation of antifogging self-cleaning glass

1. The preparation method of the antifogging self-cleaning glass comprises the following specific steps:

(1) depositing a thin film of pure aluminum (hereinafter referred to as "aluminum film") on glass; performing magnetron sputtering for 10min and 30s, wherein the thickness of the aluminum film is 60-80 nm; it can also be deposited by electron beam evaporation with a glass thickness of 3 a before depositionmm, contact angle 50.7 °; the glass after deposition is at 1X 10^-2Annealing in vacuum of Pa; the annealing temperature is 300 ℃; the time is 1 h.

The aluminum film deposition process comprises the following steps: a magnetron sputtering coating system is adopted, and an aluminum film is deposited on a glass substrate by vacuumizing through a turbo molecular pump, wherein the mode is changed into direct current sputtering. Final substrate pressures were all 10^-4 Pa, direct current sputtering water-cooled Al target (99.9995%) with diameter of 60 mm, pure Ar (99.9995%) sputtering gas, and working pressure of 1.6 Pa. The two substrates of soda-lime glass and borosilicate glass with the thickness of 3 mm are adopted for deposition, and the dimension specification is 100 mm multiplied by 100 mm. The argon flow is set to be 30 sccm, the starting voltage is about 250V, the sputtering voltage is controlled to be 280-290V, the current is about 0.2A, and the aluminizing time is 10min for 30 s.

(2) Scanning the glass surface treated in the step (1) by laser to form a micro-nano structure on the glass surface; carrying out laser scanning by adopting a fiber laser marking machine with the maximum power of 20W; the conditions of laser scanning were: 1%, 15%, 30%, 60% power; the scanning speed is 3.0 m/s; the scanning distance is 0.06 mm; the frequency is 30 khz.

(3) Annealing the glass treated in the step (2) in the air to obtain the antifogging self-cleaning glass; the annealing temperature is 550 ℃; the annealing time was 3 min.

2. Structure and performance test of antifog self-cleaning glass

The wetting angle test of the anti-fog self-cleaning glass prepared in example 1 shows that the contact angle of the anti-fog self-cleaning glass prepared in example 1 is 0 DEG and the anti-fog self-cleaning glass has super-hydrophilicity, and the result is shown in figure 1 (the straight line in the figure shows that the straight line is the interface). The preparation method of the invention obviously reduces the contact angle of the glass, and enables the glass to have super-hydrophilicity, thereby having the antifogging self-cleaning function.

The surface structure of the anti-fog self-cleaning glass prepared in the embodiment 1 is shown in fig. 2-4, and a three-dimensional super-depth-of-field microscope photo of the surface of the anti-fog self-cleaning glass is shown; FIG. 2 shows that the surface of the antifogging self-cleaning glass prepared in example 1 is composed of hierarchical cellular micro-nano structures, the peripheral period is about 100 microns, secondary structures with 20 micron periods are nested, and dense nano structures exist in the whole structure; the amplitude in the depth direction reaches 600 nm.

As shown in fig. 5, the curves from bottom to top are respectively 1%, 15%, 30% and 60% of the sample under the laser power, the transmittance detection is performed without annealing after the laser scanning, and the transmittance of the antifogging self-cleaning glass with the aluminum film thickness of 60-80 nm adopted in the embodiment is close to that of untreated glass; the transmittance map shows that the wetting angle is smaller and smaller to reach the super-hydrophilicity of 4.3 degrees along with the increase of the laser power; indicating that transmission is attenuated due to large microstructure scattering and that transmittance increases with increasing laser power, closer to that of untreated glass.

After the final annealing at 550 ℃ for 3min, the transmittance is obviously improved, and the contact angle is not obviously changed. The annealing treatment in the step (3) can improve the transmittance of the antifogging self-cleaning glass.

Example 2: effect of film thickness on contact Angle of antifogging self-cleaning glass

1. The preparation method of the antifogging self-cleaning glass based on the silicon film comprises the following specific steps:

(1) silicon films of different thickness were deposited on glass: adopting an electron beam evaporation coating system, and vacuumizing to 10 ℃ by a turbo-molecular pump^-4And depositing silicon films on the soda-lime glass substrate and the borosilicate glass substrate respectively in the Pa magnitude. The soda-lime glass and the borosilicate glass have the size specification of 100 mm multiplied by 100 mm and the thickness of 3 mm. High-purity silicon metal particles are put into a copper crucible, and aluminum wires are put into a graphite crucible. Manually adjusting the size of the light spot of the electron beam, and controlling the deposition rate to be 1-2A/s. The deposition thickness of the silicon film is set to be 10nm, 20 nm, 30 nm, 40 nm, 50 nm and 60 nm.

(2) And (2) laser scanning the surfaces of the soda-lime glass and the borosilicate glass processed in the step (1), processing the sample by adopting an ultraviolet laser marking machine, wherein all the surfaces are default parameter settings of the marking machine, and the scanning speed is still 3 m/s.

(3) Annealing the glass treated in the step (2) in air to obtain the antifogging self-cleaning glass; the annealing temperature is 550 ℃; the annealing time was 3 min.

2. Effect of film thickness on contact Angle of antifogging self-cleaning glass

The contact angle results of the anti-fog self-cleaning glass based on silicon film prepared in example 2 are shown in fig. 6, and the contact angles of the borosilicate glass and the soda lime glass used in the example before deposition are respectively 50.7 ° and 35.515 °. Deposition of silicon films of any thickness on soda-lime glass can result in a significant reduction in glass contact angle without protective atmosphere annealing or vacuum annealing during deposition of the silicon film. The borosilicate glass achieves super-hydrophilicity by changing the thickness of the silicon film, the contact angle of the borosilicate glass is obviously reduced along with the increase of the thickness of the deposited silicon film, and when the thickness of the borosilicate glass is 60nm, the contact angle is close to 5 degrees of super-hydrophilic contact angle, so that the antifogging self-cleaning function is realized. The soda-lime glass has a lower contact angle when the silicon film is thinner, and shows better hydrophilicity.

The preparation method provided by the invention combines the laser induced texture and the aluminum nanoparticle preparation technology to successfully prepare the anti-fog self-cleaning glass micro-nano structure. After the thin film is deposited, a nano-particle array can be formed on the glass by annealing in a selective nitrogen protective atmosphere or vacuum; this step may also be omitted. The aluminum/silicon film on the surface of the glass is melted and solidified or evaporated at a very high speed by adopting laser rapid scanning, and on one hand, a self-assembled local micro-nano structure is rapidly formed on the surface under the action of surface tension; on the other hand, because the aluminum and the glass react and bond in the network structure of the glass at high temperature, and the silicon is one of the main constituent elements of the glass, the silicon can easily permeate and diffuse into the loose glass structure to bond with the loose glass structure, and further a stable micro-nano structure is formed. Surface tension and physicochemical reactions will affect the resulting micro-nano structure. And finally, finishing the preparation of the anti-fog self-cleaning glass by adopting an in-air annealing mode, oxidizing possibly residual absorptive aluminum or silicon, and improving the transparency of the anti-fog self-cleaning glass.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.