CN115231827B

CN115231827B - Transparent glass with switchable wettability

Info

Publication number: CN115231827B
Application number: CN202211110343.4A
Authority: CN
Inventors: 李炜; 安阳; 王越
Original assignee: Changchun Institute of Optics Fine Mechanics and Physics of CAS
Current assignee: Changchun Institute of Optics Fine Mechanics and Physics of CAS
Priority date: 2022-09-13
Filing date: 2022-09-13
Publication date: 2023-06-02
Anticipated expiration: 2042-09-13
Also published as: CN115231827A

Abstract

The invention provides transparent glass with switchable wettability, the surface of the transparent glass is provided with micro-nano particles, the equivalent size of the micro-nano particles is d, d is less than or equal to 1 nanometer and less than 10 micrometers, the maximum of the clearance s of the micro-nano particles is 100 times of the equivalent size d, the filling rate of the micro-nano particles is a, a is more than or equal to 5% and less than 98%, and the visible light transmittance of the transparent glass is more than or equal to 40%. The invention can realize the conversion between the hydrophobicity and the hydrophilicity of the transparent glass without using a chemical coating, and has the advantages of low cost and environmental protection.

Description

Transparent glass with switchable wettability

Technical Field

The invention relates to the technical field of transparent glass manufacturing, in particular to transparent glass with switchable wettability.

Background

At present, the preparation of hydrophobic glass or hydrophilic glass is mainly realized by a sol-gel method or a chemical coating method, and partial technology is realized by a femtosecond laser matched chemical coating method or a nanosecond laser method, but the methods have certain defects.

The sol-gel method requires the consumption of chemicals to realize hydrophobic or hydrophilic glass, which can increase manufacturing costs as consumables. For example, in the chinese patent of publication No. CN102627410B, a three-layer sol-gel method is adopted, and silane, nano elastomer, sol and other structures are introduced to realize hydrophobic glass, or other hydrophilic glass is realized by hydrophilic chemicals, but because excessive chemical reagents are consumed, the combined action of macro-micro nano tertiary structures and greener low-surface energy substances are ignored, so that excessive waste of chemical reagents is caused, the product cost is increased, and meanwhile, environmental pollution is also caused.

The hydrophobic glass or hydrophilic glass realized by the chemical coating method also needs to consume chemical reagents, such as CN102643029B, and a large amount of silane coating is used, so that besides the cost is increased, the pollution to the environment is also an unavoidable problem. Furthermore, the hydrophobic properties and the time for maintaining the hydrophobicity are inferior to the present invention due to the instability of the chemical agent.

The hydrophobic or hydrophilic glass realized by the femtosecond laser and the chemical coating method ensures the hydrophobic or hydrophilic performance, such as CN 107500554A, but the cost of the hydrophobic or hydrophilic glass is increased due to the consumption of chemical reagents, and the environment is polluted.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides transparent glass with switchable wettability, which can realize hydrophobicity or hydrophilicity under the condition of not using a chemical coating.

In order to achieve the above purpose, the present invention adopts the following specific technical scheme:

the transparent glass with the switchable wettability has micro-nano particles on the surface, wherein the equivalent size of the micro-nano particles is d, d is less than or equal to 1 nanometer and less than 10 micrometers, the maximum clearance s of the micro-nano particles is 100 times of the equivalent size d, the filling rate of the micro-nano particles is a, a is more than or equal to 5% and less than 98%, and the visible light transmittance of the transparent glass is more than or equal to 40%.

Preferably, the micro-nano particles are oxide particles, metal particles or inorganic particles.

Preferably, the oxide particles are silica or titania, the metal particles are gold nanoparticles, silver nanoparticles or copper nanoparticles, and the inorganic particles are silicon and halogen compound particles.

Preferably, the micro-nano particles are etched on or applied to the glass body.

Preferably, the laser used for etching is a femtosecond laser, and the processing parameters of the femtosecond laser meet the following conditions: laser repetition frequency x line spacing = scan speed; the line spacing is any value between 0.2 and 20 times of the diameter of the light spot; the single pulse energy of the femtosecond laser is more than 20 micro-joules and less than 10 milli-joules.

Preferably, the micro-nano particles and the glass body are provided with an organic compound coating which does not contain silane and contains fluorine elements, the organic compound coating is used for introducing low-surface-energy substances in the air, and the transition between hydrophilicity and hydrophobicity of the transparent glass is realized by controlling the amount of the introduced low-surface-energy substances.

Preferably, a macro-scale structure is formed on the glass body, the size of the macro-scale structure is larger than 100 micrometers, the macro-scale structure is in a concave shape or a convex shape, the micro-nano particles are distributed on the surface of the macro-scale structure, and the macro-scale structure is used for preventing the micro-nano particles from being worn.

Preferably, the micro-nano particles comprise micro-scale solid particles and nano-scale solid particles, the nano-scale solid particles are arranged on the micro-scale solid particles, and the nano-scale solid particles and the micro-scale solid particles have a laminated relationship and a parallel relationship respectively.

Preferably, the partial area of the transparent glass is a hydrophobic area, and the micro-nano particles filled in the hydrophobic area are erased according to a preset path, so that the liquid drops move according to a prescribed path.

Preferably, the contact angle of the transparent glass with the liquid drop is θ; when the contact angle theta is more than or equal to 90 degrees and less than 180 degrees, the transparent glass shows hydrophobicity; when the contact angle theta is more than or equal to 0 degree and less than 80 degrees, the transparent glass shows hydrophilicity.

The invention can realize the conversion between the hydrophobicity and the hydrophilicity of the transparent glass without using a chemical coating, and has the advantages of low cost and environmental protection.

Drawings

Fig. 1 is a schematic diagram of measurement results of contact angle of transparent hydrophobic glass according to an embodiment of the present invention;

fig. 2 is a schematic view of transmittance of transparent hydrophobic glass according to an embodiment of the present invention.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, like modules are denoted by like reference numerals. In the case of the same reference numerals, their names and functions are also the same. Therefore, a detailed description thereof will not be repeated.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention.

The invention provides a transparent glass with switchable wettability, wherein the switchable wettability refers to the glass for realizing the switching between hydrophilicity and hydrophobicity. Whether the glass is hydrophilic or hydrophobic, micro-nano particles are required to be formed on the surface of the glass, but the micro-nano particles are required to meet a plurality of conditions to ensure the transparency of the glass.

The transparency in the present invention refers to the transmittance of the glass to visible light and near infrared light, and when the transmittance exceeds 40%, the transparency is defined in the present invention, and the specific measurement method is measured by using a spectrometer or a transmittance tester, which are well known in the art, and the average transmittance is described in the following examples.

The several conditions are respectively:

equivalent dimension d: the distance between two micro-nano particles farthest from each other in the three-dimensional space is the equivalent size of the micro-nano particles, and the equivalent size d of the micro-nano particles needs to satisfy that d is less than or equal to 1 nanometer and less than 10 micrometers.

Micro-nano particle gap s: the smallest distance of the micronano-particles from each other in the discontinuous condition is the micronano-particle gap s described in the present invention, which is calculated using a multiple of the equivalent dimension d. In the embodiment, the average micro-nano particle gaps are used for statistics, the micro-nano particle gaps s directly influence the transparency and the hydrophobicity of the glass, the micro-nano particle gaps s are in a direct proportion relation with the transparency, the larger the gaps are, the better the transparency is, the larger the gaps are, the inverse proportion relation between the micro-nano particle gaps and the hydrophobicity is, and the worse the hydrophobicity is. The micro-nano particle gap s is at most 100 times the equivalent dimension d.

Filling rate a: the micro-nano particles have better hydrophobicity without completely covering the glass surface in a certain area, the glass surface with high filling rate can obtain poorer transparency, the filling area is the area where micro-nano particles with small micro-nano particle gaps s are located, and the non-filling area is the area where micro-nano particles with large micro-nano particle gaps s are located or the area where no micro-nano particles are located. The larger the filling rate is, the better the hydrophobic performance is, the poorer the transparency is, the smaller the filling rate is, the worse the hydrophobic performance is, and the better the transparency is. The filling rate a is required to meet the requirement that a is more than or equal to 5% and less than 98%.

When the equivalent size d of the micro-nano particles, the gaps s of the micro-nano particles and the filling rate a meet the conditions, the glass has the necessary conditions for realizing hydrophilicity or hydrophobicity, and the glass is transparent, namely the transmittance of visible light and near infrared light exceeds 40 percent.

The conversion of the glass from hydrophilic to hydrophobic requires a heat treatment process to be performed on the surface on which the micro-nano particles are formed, and after the heat treatment, the glass is converted from hydrophilic to hydrophobic.

The micro-nano particles in the present invention include micro-scale solid particles and nano-scale solid particles, and the shape of the solid particles is not limited to a sphere, and may be any shape.

Because the actual micro-nano particles may not be in a single-layer state, the spatial relative position relationship among the micro-nano particles is a micro-nano particle lamination relationship, the micro-nano particles can be in a through-height parallel relationship, or in a different-height dislocation relationship, namely, the nano-scale solid particles are arranged on the micro-scale solid particles, the nano-scale solid particles and the micro-scale solid particles respectively have lamination relationship and parallel relationship, and the micro-nano particle lamination relationship depends on the size of the micro-nano particles, and the micro-nano particles generate strong field and surrounding field influence.

The relationship between the micron-sized solid particles and the nanometer-sized solid particles realizes the hydrophilicity or hydrophobicity of the glass.

The contact angle of the glass and the liquid drop is theta; when the contact angle theta is more than or equal to 90 degrees and less than 180 degrees, the glass shows hydrophobicity; when the contact angle theta is more than or equal to 0 degree and less than 80 degrees, the glass shows hydrophilicity.

In order to ensure the lasting hydrophobicity of the glass, a macroscopic structure is formed on the glass body, the macroscopic structure refers to a macroscopic structure with the size of more than 100 microns, the macroscopic structure can be macroscopic in both transverse and longitudinal three dimensions and can be unobvious to naked eyes, and the macroscopic structure has better micro-nano structure protection capability and can provide the durability improvement of transparent hydrophobic glass. The structure can be a concave structure, a convex structure or a concave-convex combined structure, and the structure shape can be any shape. The macro-scale structures may be any shape including, but not limited to, concave pyramids, convex pyramids, concave great wall shapes, convex great wall shapes, concave cubes, convex cubes, spirals, free curved shapes, and the like.

The macro-scale structures and micro-nano particles are collectively referred to as macro-micro nano structures.

The micro-nano particles can come from the glass body or be applied to the glass body by external means. Although the micro-nano particles may be externally applied, the present invention emphasizes that the micro-nano particles are derived from micro-nano particles generated by reattaching part of particles of the original material during the generation of the macro-micro nano structure, but are not limited thereto, and micro-nano particles of other materials additionally applied to satisfy a specific transparency may be included.

The glass can be divided into different types of glass, including glass such as microcrystalline glass, nano-calcium glass, fused quartz glass, coated glass and the like, and micro-nano particles composed of glass elements, such as silicon dioxide particles, silicon particles, metal particles, oxide particles, halide particles, inorganic particles and the like, can be generated in the etching process, and are derived from a body material, so that strong chemical bonds are easily formed with the body under the influence of strong fields.

Having a silane-free and fluorine-containing organic compound coating, such as C=C bonds, -CH in air, on the micro-nano particles and glass bodies ₃ Bond, -OH bond, etc., the above-mentioned substance does not need to rely on the excessive chemical substance to be coated, rely on the high surface energy that the strong field produced to absorb the above-mentioned substance directly in the air, can also absorb through the high Wen Jiasu, realize the organic compound coating that glass needs rapidly. The organic compound coating is used for introducing low-surface energy substances in air, and the conversion between hydrophilicity and hydrophobicity of the transparent glass is realized by controlling the amount of the introduced low-surface energy substances, so that the non-inhaled glass shows hydrophilicity, and the hydrophilicity is converted into hydrophobicity when a large amount of inhaled glass is inhaled.

The strong field in the invention refers to a strong physical field, a chemical field or a mixed field, and practical situations can include but are not limited to a plurality of methods such as high-energy laser, high-energy free electron laser, pulsed femtosecond laser, electron beam, ion beam and the like, and the method can provide the high-energy strong field to instantaneously strip the bulk material, and finally finish the generation of the macro-micro nano structure, and meanwhile, part of the bulk material falls back to generate micro-nano particles.

The surrounding field in the invention refers to other fields which generate macro-micro nano structures, such as an electric field, a magnetic field, a wind field, a gravity field and other various fields.

If the pulse femtosecond laser is adopted, the processing parameters of the pulse femtosecond laser meet the following conditions: laser repetition frequency x line spacing = scan speed; the line spacing is any value between 0.2 and 20 times of the diameter of the light spot; the single pulse energy of the femtosecond laser is more than 20 micro-joules and less than 10 milli-joules.

According to the invention, the durability of the hydrophobic glass is verified by adopting an ultrasonic mode and a sand paper scraping mode, the longer the ultrasonic time and the sand paper scraping times are, the better the durability is, and the shorter the ultrasonic time is, the worse the durability is.

Class a durability: after ultrasonic wave is carried out for 30 minutes and sand paper is scraped for 30 times, the hydrophobic attenuation is less than 5 percent,

b-stage durability: after the ultrasonic wave lasts for 20 minutes and the sand paper is scraped for 20 times, the hydrophobic attenuation is less than 5 percent,

c-stage durability: after the ultrasonic wave lasts for 10 minutes and the sand paper is scratched for 10 times, the hydrophobic attenuation is more than 5 percent.

Hereinafter, the present disclosure will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

The invention applies typical strong field means pulse femtosecond laser, nanosecond laser and thermal field to process a great amount of macro-micro nano structures on typical nano calcium glass, automobile glass and building glass, and performs transparency, hydrophobicity and durability characterization on processed samples.

The macro-micro nano particles can be regulated and controlled by adjusting the parameters of a strong field and a thermal field, wherein the laser strong field is taken as an example, when the laser power, the heavy frequency and the single pulse energy rise, larger-scale micro-nano particles and a larger number of micro-nano particles are generated, the movement track of the light spot of the laser on the surface of the glass determines the conditions of macro-scale and filling rate of the glass, when the light spot stays in a certain fixed area, the material of the glass body at the position is removed to form a macro-scale structure, the material of the body part can fall back around to form micro-nano particles, when the light spot stays near the certain fixed area, the material of the body part is removed to form a macro-scale structure, and then the material of the body part falls back onto the macro-scale structure to form micro-nano particles, and the macro-micro-nano structure jointly acts to influence the transparency and the hydrophobic performance of the glass. The strength and duration of the thermal field will affect the adsorption properties of the organic compound coating and will also affect the transparency and hydrophobic properties of the glass together.

The following relationship exists between the strong field parameter and the macro-micro nano structure:

in order to describe the correlation of strong fields with macro-micro nano structures and transparency and hydrophobicity, the following examples and comparative examples are abbreviated as follows: the pulse laser form Type, fs stands for femto seconds, ns stands for nanoseconds; the pulse laser power parameter is P (W); the single pulse energy parameter of the pulse laser is E (mu J); the pulse laser repetition frequency is F (kHz); the laser movement speed is S (mm/S); the laser scanning interval is D (μm); contact angle CA (°; the average transmittance is T (%); the thermal field temperature is Temp (deg.C); the thermal field duration is Time (h); micro-nano particle equivalent size d (nm); micro-nano particle gaps s (nm); the ratio s/d (dimensionless) of the micro-nano particle gap to the micro-nano particle equivalent size; filling rate a (%); macrostructure equivalent dimension m (mm).

Examples 1-10 present different strong field parameters and their corresponding macro-micro nano structure practical conditions, and compare in detail the requirements of micro-nano particle under-filling and over-filling that would result in failure to achieve wettability conversion or transparency by comparative example 1 and comparative example 2.

Example 6 is a preferred embodiment of the present invention, which can perfectly exhibit the transparency and hydrophobic properties of glass. The measurement result of the contact angle of the transparent hydrophobic glass can be presented by fig. 1. The transmittance effect of the transparent hydrophobic glass can be exhibited by fig. 2.

Example 9 hydrophilicity was achieved by further erasing with an S-shaped laser on the basis of example 6, the S-shaped laser erased area.

In example 10, hydrophilicity was achieved by applying an S-type heating electrode to the surface of the transparent glass of example 12 without using a heat treatment process on the whole transparent glass on the basis of example 6, and the heat treatment parameters of copper example 6 were used to achieve hydrophobicity in the S-type region, but hydrophilicity was achieved outside the S-type region.

Example 11 by combining the relevant parameters of example 6 on the basis of a glass substrate with a tetrahedral macrostructure having a side length of 0.5 mm and a tilt angle of 3 °, a class a durability is achieved in which the scratch resistance is significantly improved.

Example 12, by combining the related parameters of example 6 with a planar glass substrate, achieves a class B durability that can achieve class a ultrasonic cleaning resistance, but the scratch resistance can only achieve class B, which is combined to class B.

Example 13, by combining the parameters related to example 7 on a flat glass substrate, only class C durability was achieved, and both of its scratch resistance and ultrasonic cleaning resistance were only able to meet the class C durability criteria.

Examples 14, 15, 16, 17 and 18 realize the surrounding conditions of micro-nano particles, such as triangle, square, rectangle, circle and diamond by adopting different laser scanning routes based on the example 6, and the programmable conditions of transparency and wettability are very similar, and the result can be referred to as the related result of the example 6.

Examples 1-8 and comparative examples 3-10 illustrate the effect of different micronanoparticles on glass transparency, hydrophobicity. Comparative example 1 and comparative example 2 illustrate the effect of out-of-range micro-nano particles on glass transparency, hydrophobicity.

Example 9, example 10 illustrates the different methods of wettability transitions, and comparative examples 1-8 and comparative examples 3-10 illustrate the relative effects of different heat treatments on wettability transitions.

Examples 1-8 illustrate the different effects of preparing transparent wettability programmable glass by two typical macro-micro nano structures of femtosecond laser and nanosecond laser, and the femtosecond laser has better preparation effect.

The combined effect of macro-micro nano structures on glass transparency, wettability, durability is illustrated in examples 11, 12, 13.

Examples 14-17 illustrate the insensitivity of the overall form of macro-micro nanostructure application to glass transparency, wettability.

In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.

While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

The above embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.

Claims

1. The transparent glass with the switchable wettability is characterized in that micro-nano particles are arranged on the surface of the transparent glass, the equivalent size of the micro-nano particles is d, d is less than or equal to 1 nanometer and less than 8 micrometers, the gap s between the micro-nano particles is 10 times of the equivalent size d at the maximum, the filling rate of the micro-nano particles is a, a is more than or equal to 5% and less than 50%, and the visible light transmittance of the transparent glass is more than or equal to 40%; the micro-nano particles are generated by etching the glass body through pulsed femtosecond laser or pulsed nanosecond laser, and the surface forming the micro-nano particles is subjected to heat treatment, so that the surface of the glass body is converted from hydrophilicity to hydrophobicity.

2. The transparent glass with switchable wettability of claim 1, wherein the laser used for etching is a femtosecond laser, and the processing parameters of the femtosecond laser meet the following conditions:

laser repetition frequency x line spacing = scan speed;

the line spacing is any value between 0.2 and 20 times of the diameter of the light spot;

the single pulse energy of the femtosecond laser is greater than 20 microjoules and less than 10 millijoules.

3. The transparent glass with switchable wettability of claim 1, wherein a macro-scale structure is formed on the glass body, the macro-scale structure having a size greater than 100 microns, the macro-scale structure being concave or convex, the micro-nano particles being distributed on a surface of the macro-scale structure, the macro-scale structure being configured to prevent the micro-nano particles from being abraded.

4. The switchable wettability transparent glass of claim 1 wherein the micro-nano particles comprise micro-scale solid particles and nano-scale solid particles, the nano-scale solid particles being disposed on top of the micro-scale solid particles, the nano-scale solid particles and the micro-scale solid particles having a stacked relationship and a juxtaposed relationship, respectively.

5. A transparent glass with switchable wettability according to claim 3, wherein a portion of the surface of the transparent glass is hydrophobic regions, and wherein micro-nano particles filled in the hydrophobic regions are erased according to a predetermined path to cause the droplets to move according to a prescribed path.

6. The transparent glass with switchable wettability of claim 3, wherein the contact angle of the transparent glass with the droplet is θ; when the contact angle theta is more than or equal to 90 degrees and less than 180 degrees, the transparent glass shows hydrophobicity; when the contact angle theta is more than or equal to 0 degree and less than 80 degrees, the transparent glass shows hydrophilicity.