阅读说明：本技术 一种提高复明速率的光致变色玻璃的制备方法 (Preparation method of photochromic glass for improving speed of renaturation ) 是由 彭寿 齐帅 魏晓俊 于浩 周文彩 王伟 曾红杰 张纲 于 2020-07-01 设计创作，主要内容包括：本发明提供一种复合光致变色玻璃,包括作为基层的光致变色玻璃,所述光致变色玻璃的迎光面和/或背光面由内至外依次设有相变层和吸热层。本发明进一步提供一种复合光致变色玻璃的制备方法及其在制备提高复明速率的光致变色玻璃中的用途。本发明提供的一种提高复明速率的光致变色玻璃的制备方法,能够提高光致变色玻璃的复明速率,并均有良好的可见光透光率,不会影响光色玻璃的透明度。(The invention provides composite photochromic glass, which comprises photochromic glass serving as a base layer, wherein a phase change layer and a heat absorption layer are sequentially arranged on a light facing surface and/or a backlight surface of the photochromic glass from inside to outside. The invention further provides a preparation method of the composite photochromic glass and application of the composite photochromic glass in preparing the photochromic glass for improving the speed of renaturation. The preparation method of the photochromic glass for improving the speed of the renaturation can improve the speed of the renaturation of the photochromic glass, has good visible light transmittance, and does not influence the transparency of the photochromic glass.)

1. The composite photochromic glass comprises photochromic glass serving as a base layer, wherein a phase change layer and a heat absorption layer are sequentially arranged on a light facing surface and/or a backlight surface of the photochromic glass from inside to outside.

2. The composite photochromic glass of claim 1, wherein the phase change layer comprises a polyvinyl alcohol film with a solid-solid phase change material uniformly distributed thereon.

3. The composite photochromic glass of claim 1 wherein the ratio of the thickness of the phase change layer to the base layer is from 0.05 to 5: 100-; in the phase change layer, the mass fraction of the solid-solid phase change material is 5-30 wt%.

4. The composite photochromic glass of claim 1 wherein the heat absorbing layer comprises a polyvinyl alcohol film having an infrared absorbing material uniformly distributed thereon.

5. The composite photochromic glass of claim 1 wherein the ratio of the thickness of the heat absorbing layer to the base layer is from 0.01 to 1: 100-; in the heat absorption layer, the mass fraction of the infrared absorption material is 1-20 wt%.

6. The method for preparing a composite photochromic glass according to any one of claims 1 to 5, comprising: and coating phase change slurry and heat absorption slurry on the light facing surface and/or the backlight surface of the photochromic glass from inside to outside in sequence to form a phase change layer and a heat absorption layer.

7. The method for preparing a composite photochromic glass according to claim 6 wherein the surface of the photochromic glass is subjected to hydroxylation treatment.

8. The method for preparing the composite photochromic glass according to claim 6, wherein the phase-change slurry takes a polyvinyl alcohol solution as a film-forming carrier and a solid-solid phase-change material solution is mixed in the film-forming carrier; including any one or more of the following conditions:

A1) the solid-solid phase change material solution is an aqueous solution of a solid-solid phase change material, and the mass fraction of the solid-solid phase change material in the aqueous solution of the solid-solid phase change material is 1-3 wt%;

A2) the solid-solid phase change material is selected from any one of polyethylene glycol PEG1000, polyethylene glycol PEG2000 or polyethylene glycol PEG 10000;

A3) the volume ratio of the solid-solid phase change material solution to the polyvinyl alcohol solution is 1-2: 0.5 to 5.

9. The method for preparing the composite photochromic glass according to claim 6, wherein the heat absorbing paste takes a polyvinyl alcohol solution as a film forming carrier and an infrared absorbing material solution is mixed in the film forming carrier; including any one or more of the following conditions:

B1) the infrared absorption material solution is an aqueous solution of an infrared absorption material, and the mass fraction of the infrared absorption material in the aqueous solution of the infrared absorption material is 5-30 wt%;

B2) the infrared absorption material is selected from any one or a mixture of more of tungsten bronze, indium tin oxide, copper sulfide or lanthanum boride;

B3) the volume ratio of the infrared absorption material solution to the polyvinyl alcohol solution is 1-2: 0.5 to 5.

10. The method for preparing composite photochromic glass according to any one of claims 8 or 9, wherein the polyvinyl alcohol solution is an aqueous solution of polyvinyl alcohol obtained by adding water to polyvinyl alcohol, performing ultrasonic dispersion and reflux heating; in the aqueous solution of the polyvinyl alcohol, the mass fraction of the polyvinyl alcohol is 5-15 wt%.

Technical Field

The invention belongs to the technical field of material science, relates to a preparation method of photochromic glass for improving the speed of renaturation, and particularly relates to a preparation method of photochromic glass for improving the speed of renaturation by using a photo-thermal material.

Background

Photochromic glass, referred to as photochromic glass for short, can be colored after light irradiation, and can be restored to the original state after a period of time after the light irradiation is stopped. The light transmittance of the air conditioner can be changed along with the change of the intensity of the radiation light, so that the air conditioner can control the sunlight to enter, and the indoor space always has proper brightness and temperature, thereby providing a good large-visual-field visual environment and effectively reducing the use of the air conditioner. However, the application of the photochromic glass is greatly limited because the renaming rate of the photochromic glass after discoloration is slow and an effective solution is lacked.

It is known that the heat radiation or the long-wave light can accelerate the brightening reaction of the photochromic glass, and the saturated light transmittance and the brightening speed of the photochromic glass are obviously improved at higher temperature. Therefore, it is necessary to study and investigate the above.

Disclosure of Invention

In view of the above disadvantages of the prior art, an object of the present invention is to provide a method for preparing photochromic glass capable of increasing the speed of renaturation, which overcomes the disadvantage of the prior photochromic glass that the speed of renaturation is slow, and reasonably collects and releases sunlight through a photo-thermal material, thereby increasing the speed of renaturation of photochromic glass by using the heat provided by sunlight.

In order to achieve the above and other related objects, a first aspect of the present invention provides a composite photochromic glass for improving a speed of vision recovery, which includes a photochromic glass as a base layer, wherein a light facing surface and/or a backlight surface of the photochromic glass are sequentially provided with a phase change layer and a heat absorption layer from inside to outside.

Preferably, the existing photochromic glass is selected from any one of inorganic photochromic glass or organic photochromic glass. The photochromic glass is conventionally used photochromic glass, and can be purchased from the market or prepared by the raw materials. Currently, there are two types of photochromic glasses, one inorganic photochromic glass and the other organic photochromic glass.

The inorganic photochromic glass is alkali-aluminoborosilicate glass which is obtained by melting under strong reducing atmosphere and contains a large amount of CdO silicate glass or contains trace silver halide (AgX), titanium halide (TiX), cadmium chloride (CdCl) and copper chloride (CuCl) crystals.

The organic photochromic glass is glass prepared from an organic material sensitive to heat. The heat-sensitive organic material is a spiropyran compound, an azobenzene compound, a diarylethene compound or a salicylaldehyde Schiff base compound.

More preferably, the preparation method of the inorganic photochromic glass is selected from any one of a sol-gel method, an ion exchange method or a crucible melting method. The sol-gel method, the ion exchange method or the crucible melting method are all methods which are used for preparing inorganic photochromic glass in the field.

Preferably, the phase change layer includes a polyvinyl alcohol film in which a solid-solid phase change material is uniformly distributed.

Preferably, the ratio of the thickness of the phase change layer to the thickness of the base layer is 0.05-5: 100-10000.

Preferably, in the phase change layer, the mass fraction of the solid-solid phase change material is 5-30 wt%.

Preferably, the heat absorbing layer comprises a polyvinyl alcohol film with an infrared absorbing material uniformly distributed.

Preferably, the ratio of the thickness of the heat absorbing layer to the base layer is 0.01-1: 100-10000.

Preferably, in the heat absorption layer, the mass fraction of the infrared absorption material is 1-20 wt%. More preferably, in the heat absorption layer, the mass fraction of the infrared absorption material is 5-10 wt%.

The invention provides a preparation method of composite photochromic glass for improving the speed of vision restoration, which comprises the following steps: and coating phase change slurry and heat absorption slurry on the light facing surface and/or the backlight surface of the photochromic glass from inside to outside in sequence to form a phase change layer and a heat absorption layer.

Preferably, the surface of the photochromic glass is subjected to a hydroxylation treatment. The hydroxylation treatment enables the light facing surface and/or the back light surface of the base layer to be fully hydroxylated to form polyhydroxy compounds, and due to the fact that the hydroxyl groups are hydrophilic groups, the subsequent hydrophilic phase change material coating is facilitated to form the phase change layer.

More preferably, the hydroxylation treatment is to clean the light facing surface and/or the back surface of the photochromic glass and then treat the photochromic glass by using a plasma device.

Further preferably, the cleaning is ultrasonic cleaning, and the ultrasonic cleaning is performed by sequentially using deionized water, ethanol and acetone as cleaning agents.

Still more preferably, the ultrasonic cleaning conditions are: the power is 150-250W, the frequency is 30-50 KHz, and the cleaning time of the deionized water, the ethanol and the acetone is 20-40 min respectively.

Most preferably, the conditions of the ultrasonic cleaning are: the power is 200W, the frequency is 40KHz, and the cleaning time of the deionized water, the ethanol and the acetone is respectively 30 min.

Further preferably, the plasma apparatus is a conventionally used plasma cleaning apparatus. Specifically, the plasma apparatus is a PLT-VM500 small rf plasma cleaner manufactured by puttler electrical technology (telepresence) limited. So that the surface of the substrate is sufficiently hydroxylated.

Further preferably, the processing power of the plasma equipment is 90-110W, and the processing frequency is 13-14 MHZ.

Still further preferably, the plasma apparatus has a processing power of 100W and a processing frequency of 13.56 MHz.

Preferably, the phase change slurry takes a polyvinyl alcohol solution as a film forming carrier, and a solid-solid phase change material solution is mixed in the film forming carrier.

More preferably, the solid-solid phase change material solution is an aqueous solution of a solid-solid phase change material, and the mass fraction of the solid-solid phase change material in the aqueous solution of the solid-solid phase change material is 1-3 wt%.

More preferably, the solid-solid phase change material is selected from any one of polyethylene glycol PEG1000, polyethylene glycol PEG2000 or polyethylene glycol PEG 10000.

More preferably, the volume ratio of the solid-solid phase change material solution to the polyvinyl alcohol solution is 1-2: 0.5 to 5.

More preferably, the mixing temperature is 80-100 ℃. Most preferably, the temperature of the mixing is 90 ℃.

More preferably, the mixing is performed for 1 to 5 hours. Most preferably, the mixing is carried out for a stirring time of 2 hours.

Preferably, the endothermic slurry takes polyvinyl alcohol solution as a film forming carrier and infrared absorption material solution is mixed in the film forming carrier.

More preferably, the infrared absorption material solution is an aqueous solution of an infrared absorption material, and the mass fraction of the infrared absorption material in the aqueous solution of the infrared absorption material is 5-30 wt%.

More preferably, the infrared absorbing material is selected from tungsten bronze (M)_xWO₃) Any one or more of indium tin oxide, copper sulfide or lanthanum boride.

The tungsten bronze (M)_xWO₃) In the formula, M is one of alkali metal ions, alkaline earth metal ions, ammonium ions or rare earth metal ions, and x is between 0 and 1.

More preferably, the volume ratio of the infrared absorption material solution to the polyvinyl alcohol solution is 1-2: 0.5 to 5.

More preferably, the mixing comprises ultrasonic dispersion and ball milling which are carried out sequentially.

Further preferably, the conditions of the ultrasonic dispersion are: the power is 150-250W, the frequency is 30-50 KHz, and the ultrasonic dispersion time is 1.5-2.5 h.

Most preferably, the conditions of the ultrasonic dispersion are: the power is 200W, the frequency is 40KHz, and the ultrasonic dispersion time is 2 h.

More preferably, the ball milling time is 1-10 hours, and the rotation speed of the ball milling is 500-1500 r/min.

Most preferably, the time of ball milling is 1 to 5 hours.

More preferably, the polyvinyl alcohol solution is an aqueous solution of polyvinyl alcohol obtained by adding water to polyvinyl alcohol, performing ultrasonic dispersion, and performing reflux heating. The aqueous solution of the polyvinyl alcohol is transparent and uniform.

More preferably, in the aqueous solution of polyvinyl alcohol, the mass fraction of the polyvinyl alcohol is 5 to 15 wt%.

Further preferably, the conditions of the ultrasonic dispersion are: the power is 150-250W, the frequency is 30-50 KHz, and the ultrasonic dispersion time is 30-180 min. Most preferably, the conditions of the ultrasonic dispersion are: the power is 200W, the frequency is 40KHz, and the ultrasonic dispersion time is 30-60 min. The ultrasonic dispersion causes the polyvinyl alcohol to fully swell in water.

Further preferably, the temperature of the reflux heating is 80-100 ℃. Most preferably, the temperature of the reflux heating is 90 ℃.

Further preferably, the time of the reflux heating is 0.5 to 10 hours. Most preferably, the time of reflux heating is 1 to 5 hours.

Preferably, the coating method is selected from any one of spin coating, knife coating, roll coating, curtain coating, spray coating, or pulling method. The spin coating method, the blade coating method, the roller coating method, the curtain coating method, the spray coating method or the pulling method are all conventional coating methods.

As described above, according to the method for preparing the photochromic glass capable of improving the speed of restoration provided by the invention, the composite photochromic glass with high speed of restoration can be obtained through the preferable materials and the processing steps thereof. The photochromic glass can change color when outdoor sunlight is strong, infrared light is fully absorbed through the characteristic that the heat absorption layer absorbs heat of the infrared light, the infrared light is converted into heat energy which is conducted to the phase change layer, and the phase change layer retains the heat through solid-solid phase change along with the temperature higher than the phase change point of the phase change material. When the outdoor sunlight is weakened, the heat stored in the phase change layer is released when the outdoor temperature is lower than the phase change point, so that the temperature of the photochromic glass is increased, the brightening reaction is further promoted, the brightening reaction is often an endothermic reaction, the temperature is increased, the reaction speed is increased, and the brightening rate is increased. Meanwhile, the film forming agent selected by the photochromic glass is as follows: the polyvinyl alcohol, the solid-solid phase change material and the infrared absorption material have good visible light transmittance, and the transparency of the photochromic glass is not influenced.

Drawings

FIG. 1 is a schematic diagram showing a three-layer structure of the composite photochromic glass of the present invention, wherein 1 is a base layer of the photochromic glass; 2 is a phase change layer of photochromic glass; and 3 is a heat absorption layer of photochromic glass.

Fig. 2 shows a spectrum of transmitted light after the photochromic glass is coated with the material of the heat absorbing layer in the present invention.

FIG. 3 is a DSC chart of the phase change layer material of the photochromic glass of the present invention.

FIG. 4 is a graph showing the temperature distribution of the composite structure of the photochromic glass under a thermal imager in accordance with the present invention.

Detailed Description

The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.

Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.