阅读说明：本技术 一种在玻璃基底上形成超滑表面的方法及制得的具有超滑表面的玻璃片 (Method for forming super-smooth surface on glass substrate and prepared glass sheet with super-smooth surface ) 是由 符小艺 刘姜华 于 2020-06-23 设计创作，主要内容包括：本发明公开了一种在玻璃基底上形成超滑表面的方法及制得的具有超滑表面的玻璃片。该方法包括：先将玻璃片进行清洁处理,再在玻璃片上沉积蜡烛灰作为掩膜,然后用氢氟酸气体腐蚀玻璃,去除蜡烛灰得到具有多孔形貌,此玻璃经疏水处理后,灌注润滑油得到超滑表面。超滑表面上水滴接触角范围为111°-126.5°,滑动角范围为3.9°-5.6°,在可见光区域透明度为89%-92%。此外,还表现出良好的稳定性和耐水冲刷性。本发明提供的方法无需任何昂贵的设备与材料、操作简单、成本低廉,可以有效阻止水滴在材料表面的滞留。(The invention discloses a method for forming a super-smooth surface on a glass substrate and a prepared glass sheet with the super-smooth surface. The method comprises the following steps: firstly, cleaning a glass sheet, then depositing candle ash on the glass sheet as a mask, then corroding the glass with hydrofluoric acid gas, removing the candle ash to obtain a porous shape, and pouring lubricating oil into the glass after hydrophobic treatment to obtain an ultra-smooth surface. The contact angle of a water drop on the ultra-smooth surface ranges from 111 degrees to 126.5 degrees, the sliding angle ranges from 3.9 degrees to 5.6 degrees, and the transparency in a visible light region ranges from 89 percent to 92 percent. In addition, good stability and resistance to water scouring are exhibited. The method provided by the invention does not need any expensive equipment and materials, is simple to operate and low in cost, and can effectively prevent water drops from being retained on the surface of the material.)

1. A method of forming a super-smooth surface on a glass substrate, comprising the steps of:

(1) washing and drying the glass sheet to obtain a pretreated glass sheet;

(2) marking one surface of the pretreated glass sheet in the step (1) as an A surface; igniting a candle, horizontally placing the pretreated glass sheet in the step (1) in an outer flame of candle flame, wherein the surface A faces the candle, and performing candle ash super-hydrophobic coating deposition treatment on the surface A of the glass sheet to obtain the coated glass sheet; (3) carrying out oil bath heating treatment on the hydrofluoric acid solution to generate hydrofluoric acid steam, and enabling the surface A of the glass sheet with the coating in the step (2) to face the hydrofluoric acid solution so that the hydrofluoric acid steam corrodes the glass sheet to obtain a corroded glass sheet;

(4) putting the corroded glass sheet A in the step (3) into water with the surface facing upwards, and carrying out ultrasonic cleaning treatment to obtain a cleaned glass sheet;

(5) putting the cleaned glass sheet A in the step (4) into an ethanol solution of a hydrophobic modifier, soaking, washing and drying to obtain a modified glass sheet;

(6) and (3) dropwise adding lubricating oil on the surface A of the glass sheet modified in the step (5) until the surface A of the glass sheet is completely covered by the lubricating oil film, and then vertically placing the glass sheet and standing to obtain the glass sheet with the super-smooth surface.

2. The method of forming a super-smooth surface on a glass substrate of claim 1 wherein the washing of step (1) comprises: sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water; the drying temperature is 50-70 deg.C, and the drying time is 20-40 min.

3. The method for forming a super-smooth surface on a glass substrate as claimed in claim 1, wherein the time of the deposition treatment of the candle ash super-hydrophobic coating of step (2) is 10s to 10 min.

4. The method of claim 1, wherein the hydrofluoric acid solution of step (3) has a concentration of 30-40% by volume; the temperature of the oil bath heating treatment is 60-65 ℃.

5. The method for forming a super-smooth surface on a glass substrate according to claim 1, wherein the hydrofluoric acid vapor etching the glass sheet in the step (3) is performed for 1 to 30 min.

6. The method for forming an ultra-smooth surface on a glass substrate according to claim 1, wherein the number of times of the ultrasonic cleaning treatment in the step (4) is 2 to 5 times, and the time of each ultrasonic cleaning treatment is 10 to 15 min.

7. The method for forming a super-smooth surface on a glass substrate according to claim 1, wherein the ethanol solution of the hydrophobic modifier in the step (5) is a solution obtained by uniformly mixing the hydrophobic modifier with absolute ethanol; the concentration of the ethanol solution of the hydrophobic modifier is 1.5-15 mM; the soaking time is 6-12 h; the drying temperature is 40-60 deg.C, and the drying time is 20-40 min.

8. The method of forming a super-smooth surface on a glass substrate of claim 7 wherein the hydrophobic modification agent is a silane coupling agent containing a long hydrophobic chain; the hydrophobic modifier is more than one of dodecyl trimethoxy silane, octyl triethoxy silane, hexadecyl trimethoxy silane, octadecyl trichlorosilane, heptadecafluorodecyl trimethoxy silane and tridecafluorooctyl triethoxy silane.

9. The method for forming an ultra-smooth surface on a glass substrate according to claim 1, wherein the standing time of step (6) is 10 to 12 hours; the lubricating oil is more than one of silicone oil, perfluorinated silicone oil, phenyl silicone oil, palm oil and olive oil.

10. A glass sheet having a super-smooth surface produced by the method of any one of claims 1 to 9, wherein the surface of the glass sheet has a micro-porous structure with a pore size of 0.2 to 1 μm; the contact angle range is 111-126.5 degrees, the sliding angle range is 1.4-5.6 degrees, the sliding speed is 1.48-1.67mm/s, and the transparency is 89-92 percent.

Technical Field

The invention relates to the field of preparation of ultra-smooth surfaces, in particular to a method for forming an ultra-smooth surface on a glass substrate and a prepared glass sheet with the ultra-smooth surface.

Background

Liquid poured porous super-slip surface (SLIPS) (WONG, t.s.; KANG, s.h., TANG, s.k., et al, bioinsed self-reparingingslip surfaces with pressure-stable organic biology [ J ]. Nature, 2011, 477(7365): 443) for the first time in 2011 by Joanna ai zenberg of harvard university and its group members. The artificial surface constructed by pitcher plant in nature is simulated, and the essence of the surface lies in that a porous structure is filled with low-surface-energy liquid, a gas film in a porous solid is replaced by a liquid film to form a more stable solid/liquid composite film layer, so that liquid drops show a very low sliding angle on the surface of the liquid drops, and in addition, the problems of poor stability and the like existing on the surface of the solid/gas of a super-hydrophobic structure are solved. The super-smooth surface has the advantages of organic liquid resistance, low surface energy liquid (crude oil), biological liquid (blood and the like), ice and biological fouling resistance, good stability, self-repairing capability and the like, and shows good application prospect in various fields such as antifouling, anti-freezing, anti-fog, corrosion resistance and the like.

At present, the construction of an ultra-smooth surface on a glass substrate is complex, and a porous surface needs to be prepared by specific equipment or complex processes, such as photoetching, reactive ion etching, femtosecond laser direct writing, sol-gel, electrochemical deposition and the like. These methods are either complicated in preparation process, or use expensive materials or special equipment, and are difficult to really be popularized in a large scale in practice. For example, chinese patent CN 109320097 a (published japanese 2019.02.12) discloses a method for preparing a novel oil-impregnated super-smooth surface based on a sol-gel method, in which a sol formed by silane and silica is spin-coated on a glass sheet to construct a porous rough surface covered by a mesh structure, and perfluoropolyether oil is then added dropwise to prepare a super-smooth surface with lyophobic property. The method has the advantages of more reaction raw materials, long preparation period, ultraviolet irradiation treatment and higher-temperature heat treatment, and more operation steps.

Chinese patent CN 109627975 a (published japanese 2019.04.16) discloses a method for preparing a high-transmittance biomimetic super-smooth surface with self-repairing performance, which comprises mixing Polydimethylsiloxane (PDMS) oligomer with a curing agent to prepare a cross-linked PDMS network structure, and then immersing the PDMS network structure in n-alkane to form the biomimetic super-smooth surface. The anti-fouling transparent glass is applied to the field of underwater window antifouling, the transparency of the anti-fouling transparent glass can reach more than 88% in a visible light region, but the transparency is not uniform, and the transparency of a low-frequency region is lower.

The construction of a porous structure on the surface of glass is the key to the preparation of a transparent ultra-smooth surface. The etching process can build a porous structure on the glass surface. However, if the glass is directly etched with an etching solution (e.g., fluoride), the resulting pores are shallow or have low transparency, and it is not suitable for preparing a transparent and ultra-smooth surface.

Disclosure of Invention

In order to overcome the above-mentioned disadvantages of the prior art, the present invention provides a method for forming a super-smooth surface on a glass substrate and a glass sheet having a super-smooth surface.

The present invention provides a novel method for forming a transparent and durable ultra-smooth surface on glass. The method takes candle ash as a mask, uses hydrofluoric acid vapor to corrode a glass sheet to construct a porous surface, and then pours hydrophobic liquid into the glass sheet after hydrophobization to obtain a super-smooth surface. This ultra-smooth surface has good wetting properties: the contact angle range is 111-126.5 degrees, the sliding angle range is 1.4-5.6 degrees, the sliding speed is 1.48-1.67mm/s, the transparency is up to 92 percent, the durability is good, the material is simple, the cost is low, the operation is simple and convenient, the application prospect is wide, and the large-scale application is expected.

The purpose of the invention is realized by at least one of the following technical solutions.

The invention provides a novel method for preparing an ultra-smooth surface on glass, which comprises the following specific technical route:

the candle ash is used as a mask, hydrofluoric acid steam corrodes the glass sheet to obtain the surface appearance of the micron-sized porous reticular structure, and then the ultra-smooth surface is obtained after the surface appearance is modified by low surface energy substances and covered by lubricating oil in sequence.

The glass sheet with the super-smooth surface provided by the invention has the advantages that the glass surface is provided with the porous layer which is of a three-dimensional network structure, the inner wall of the pore channel and the glass surface are modified by hydrophobic organic matters, and the pore channel is filled with hydrophobic lubricating liquid. The size of the pore channel is 0.2-1 μm.

The method for forming the super-smooth surface on the glass substrate provided by the invention is characterized in that a porous structure is constructed on the glass substrate by adopting a candle gray mask method and a glass corrosion method, then the surface of the porous structure is subjected to hydrophobic treatment, and finally, hydrophobic lubricating oil is filled in a pore channel.

The invention provides a method for forming a super-smooth surface on a glass substrate, which comprises the following steps:

(1) washing and drying the glass sheet to obtain a pretreated glass sheet;

(2) preparation of porous surface morphology: marking one surface of the pretreated glass sheet in the step (1) as an A surface; igniting a candle, after the flame is stabilized, flatly placing the pretreated glass sheet obtained in the step (1) in the outer flame of the candle flame, wherein the surface A faces the candle, and performing candle ash super-hydrophobic coating deposition treatment (depositing candle ash as a mask) on the surface A of the glass sheet to obtain the coated glass sheet; (3) carrying out oil bath heating treatment on the hydrofluoric acid solution to generate hydrofluoric acid steam, and enabling the surface A of the glass sheet with the coating in the step (2) to face the hydrofluoric acid solution so that the hydrofluoric acid steam corrodes the glass sheet to obtain a corroded glass sheet;

(4) putting the corroded glass sheet A in the step (3) into deionized water with the surface facing upwards, and carrying out ultrasonic cleaning treatment (cleaning the glass sheet to remove candle ash) to obtain a cleaned glass sheet;

(5) modifying the surface with a surface modifier solution: putting the cleaned glass sheet A in the step (4) into an ethanol solution of a hydrophobic modifier in a culture dish, soaking, washing with absolute ethanol, and drying to obtain a modified glass sheet;

(6) pouring lubricating oil: and (3) dropwise adding lubricating oil on the surface A of the modified glass sheet in the step (5) until the surface A of the glass sheet is completely covered by the lubricating oil film, vertically placing the glass sheet (inclining for 90 degrees and forming a 90 degree angle with the horizontal direction), and standing to remove the excessive lubricating oil on the surface to obtain the glass sheet with the super-smooth surface.

Further, the washing of step (1) comprises: sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water; the drying temperature is 50-70 deg.C, and the drying time is 20-40 min.

Further, the time of the candle ash super-hydrophobic coating deposition treatment in the step (2) is 10s-10 min.

Preferably, in the step (2), in the process of depositing the candle ash super-hydrophobic coating, the glass sheet is moved at a constant speed for 10s-10min so that the candle ash generated by combustion is uniformly deposited on the glass sheet.

Further, the volume percentage concentration of the hydrofluoric acid solution in the step (3) is 30-40%; the temperature of the oil bath heating treatment is 60-65 ℃. At this temperature, hydrofluoric acid vapor is generated and the glass sheet is etched in this atmosphere.

Further, the time for etching the glass sheet by the hydrofluoric acid vapor in the step (3) is 1-30 min. To keep the hydrofluoric acid vapor generation constant, a solution of 30% -50% hydrofluoric acid may be added every half hour.

Further, the ultrasonic cleaning treatment in the step (4) is carried out for 2-5 times, the time of each ultrasonic cleaning treatment is 10-15min, deionized water is replaced after each ultrasonic cleaning treatment is finished, and candle ash is prevented from being contained in the solution. An ultrasonic cleaning treatment to remove candle ash. Usually, the candle ash can be completely cleaned for three times, and the cleaning times are increased if the candle ash is not completely cleaned.

Further, the ethanol solution of the hydrophobic modifier in the step (5) is a solution obtained by uniformly mixing the hydrophobic modifier and absolute ethanol; the concentration of the ethanol solution of the hydrophobic modifier is 1.5-15 mM; the soaking time is 6-12 h; the drying temperature is 40-60 deg.C, and the drying time is 20-40 min.

Preferably, the hydrophobic modifier is a silane coupling agent containing a hydrophobic long chain; the hydrophobic modifier is one or more of dodecyl trimethoxy silane, octyl triethoxy silane, hexadecyl trimethoxy silane, octadecyl trichlorosilane, heptadecafluorodecyl trimethoxy silane, tridecafluorooctyl triethoxy silane and the like.

Further, the standing time in the step (6) is 10-12 h.

Preferably, the lubricating oil is hydrophobic liquid oil immiscible with water, and the lubricating oil is more than one of silicone oil, perfluorinated silicone oil, phenyl silicone oil, palm oil, olive oil and the like.

Further preferably, the lubricating oil is silicone oil; the silicone oil is a silicone oil containing- (C)₂H₆OSi)_nThe normal temperature non-volatile liquid of (E). n is any integer.

The invention provides a glass sheet with an ultra-smooth surface, which is prepared by the method, wherein the surface of the glass sheet is of a micron-sized porous structure, and the size of a pore channel is 0.2-1 mu m; the contact angle range is 111-126.5 degrees, the sliding angle range is 1.4-5.6 degrees, the sliding speed is 1.48-1.67mm/s, and the transparency is 89-92 percent.

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

(1) in the preparation method provided by the invention, the material is simple, the cost is low, the operation is simple and convenient, and the prepared super-smooth surface has good lubricity, durability and transparency;

(2) in the preparation method provided by the invention, under the action of capillary action and Van der Waals force, the silicone oil can stably exist on the surface of the glass, so that a stable and continuous smooth liquid film is formed, and the ultra-smooth surface is prepared.

Drawings

FIG. 1 is an SEM image of candle ash;

FIGS. 2 to 11 show the surface appearance of the glass after the candle ash is used as a mask and the glass sheet is etched by hydrofluoric acid vapor for 1, 2, 3, 4, 5, 10, 15, 20, 25 and 30 min;

FIG. 12 is a schematic diagram showing the contact angles of water drops on an ultra-smooth surface with erosion times of 5, 10, 15, 20, 25, and 30min, respectively;

FIG. 13 is a graph showing the transparency of the ultra-smooth surface and the visible region of a common glass with an etching time of 1-4 min.

Detailed Description

The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.