Preparation method of intelligent glass based on cerium oxide-vanadium dioxide-PVA film

Abstract

The invention discloses a preparation method of intelligent glass based on a cerium oxide-vanadium dioxide-PVA film, cerium oxide-vanadium dioxide composite nanoparticles are synthesized through a double in-situ hydrothermal method, the cerium oxide-vanadium dioxide-PVA film is prepared by mixing the cerium oxide-vanadium dioxide composite nanoparticles with PVA, and finally the intelligent glass is prepared by taking glass as a substrate. The whole process is simple and easy to industrialize, and the prepared cerium oxide-vanadium dioxide composite nanoparticles not only have higher visible light transmittance and excellent thermochromism performance, but also are good in ultraviolet resistance and aging resistance and good in effect.

Description

Technical Field

[0001] The invention relates to the technical field of glass, and in particular to a method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film. Background Art

[0002] As greenhouse gas emissions become increasingly serious, energy conservation and emission reduction have gradually become the common development goals of all countries. Building energy consumption is particularly prominent, and glass materials account for 13% of the total building area, and heat dissipation reaches 70%. Among them, ordinary glass has poor insulation effect against infrared and ultraviolet rays.

[0003] Vanadium dioxide (VO2) is a transition metal oxide that undergoes a reversible insulating-metal phase transition at 68°C, from a semiconductor monoclinic phase (M phase) to a metallic state (R phase), and the optical properties undergo a sudden change along with the phase transition. At low temperatures, VO2 is in an insulating state with high infrared transmittance. At high temperatures, it is in a metallic state with low infrared transmittance, but the visible light transmittance remains almost unchanged. Therefore, VO2 can automatically adjust the heat generated by sunlight according to the temperature, and is an ideal intelligent energy-saving window material. At the same time, nano-cerium oxide is an excellent ultraviolet absorber, and its application in glass coatings can effectively improve the anti-ultraviolet and anti-aging properties.

[0004] At present, in the research and application of smart glass, vanadium dioxide is used and studied more, while nano cerium oxide is used and studied less, and smart glass based on cerium oxide-vanadium dioxide-PVA film has not been reported. Therefore, it is very necessary to develop a smart glass based on cerium oxide-vanadium dioxide-PVA film with excellent thermochromic performance and UV protection performance, which has very important practical value. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film, and the prepared smart glass has excellent thermochromic performance and anti-ultraviolet performance.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The preparation method of smart glass based on cerium oxide-vanadium dioxide-PVA film comprises the following steps:

[0008] S1, synthesizing cerium oxide-vanadium dioxide composite nanoparticles by dual in-situ hydrothermal method;

[0009] S2, fully mixing the cerium oxide-vanadium dioxide composite nanoparticles and the PVA dissolved in hot water to prepare a cerium oxide-vanadium dioxide-PVA film;

[0010] S3. Smart glass is prepared using glass as a substrate and cerium oxide-vanadium dioxide-PVA film as an interlayer.

[0011] Preferably, the step S1 is specifically as follows:

[0012] S11. Preparation of cerium oxide precursor:

[0013] A certain amount of NaOH aqueous solution is measured and gradually added dropwise to a certain amount of Ce(NO3)36H2O aqueous solution under magnetic stirring to prepare a cerium oxide precursor;

[0014] S12, preparing vanadium dioxide precursor:

[0015] A certain amount of vanadium pentoxide, citric acid and deionized water are measured and stirred in a water bath to obtain a tetravalent vanadium ion aqueous solution, an activator is added, and after mixing under magnetic stirring, a certain amount of NaOH aqueous solution is gradually added dropwise, and finally heated and cooled to room temperature to obtain a vanadium dioxide precursor;

[0016] S13, preparing nanocomposite particles:

[0017] A cerium oxide precursor and a vanadium dioxide precursor are placed in a high-pressure reactor, and then a dry SO2 gas flow is filled into the high-pressure reactor, and stirred at 80-90°C for 0.5-2h, and then allowed to stand at 300-500°C for 2-8h. After cooling, washing and drying, cerium oxide-vanadium dioxide nanocomposite particles with excellent thermochromic properties and UV protection properties are obtained.

[0018] Preferably, the molar ratio of Ce in step S11 to vanadium pentoxide in step S12 is 100:(20-100).

[0019] Preferably, the S11 step is specifically as follows: measure a certain amount of Ce(NO3)36H2O and a certain amount of deionized water and place them in beaker A, and stir them magnetically for 10 minutes; then, in beaker B, measure a certain amount of NaOH and dissolve it in a certain amount of deionized water; finally, gradually drip the dissolved NaOH aqueous solution in beaker B into the Ce(NO3)36H2O aqueous solution in beaker A at a constant rate of 10-20mL / min, and stir beaker A magnetically at 70-80°C for 20-30 minutes, thereby obtaining a cerium oxide precursor.

[0020] Preferably, the molar ratio of Ce(NO3)36H2O to NaOH in beaker A is 1:3.

[0021] Preferably, in step S12, the activating agent is toluene, hexanol and hexadecyltrimethylammonium bromide.

[0022] Preferably, in step S12, the molar ratio of vanadium pentoxide to citric acid is 1:(2-5)

[0023] Preferably, the S2 step is specifically as follows: measure a certain amount of deionized water and PVA, heat and dissolve them at 80-90°C to obtain a polyvinyl alcohol aqueous solution, then add the prepared cerium oxide-vanadium dioxide composite nanoparticles, continue to stir at a constant temperature until mixed, and finally cool to prepare a cerium oxide-vanadium dioxide-PVA film.

[0024] Preferably, the mass ratio of the cerium oxide-vanadium dioxide composite nanoparticles to PVA is (0.1-0.5):1.

[0025] The beneficial effects of the present invention are:

[0026] The invention discloses a method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film. Cerium oxide-vanadium dioxide composite nanoparticles are synthesized by a double in-situ hydrothermal method, and the process is simple and easy to industrialize. The prepared cerium oxide-vanadium dioxide composite nanoparticles are mixed with PVA to prepare a cerium oxide-vanadium dioxide-PVA film. Finally, glass is used as a substrate to prepare the smart glass, which not only has high visible light transmittance and excellent thermochromic performance, but also has good anti-ultraviolet performance and aging resistance, and has a good effect. DETAILED DESCRIPTION

[0027] The present invention is further described below in conjunction with the embodiments. It should be noted that these are merely examples and illustrations of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should be deemed to fall within the protection scope of the present invention.

[0028] Embodiment 1:

[0029] The preparation method of smart glass based on cerium oxide-vanadium dioxide-PVA film comprises the following steps:

[0030] S1. Synthesize cerium oxide-vanadium dioxide composite nanoparticles using a dual in-situ hydrothermal method.

[0031] S11. Preparation of cerium oxide precursor:

[0032] 0.1 mol of Ce(NO3)36H2O and a certain amount of deionized water were placed in beaker A, and magnetically stirred for 10 minutes to mix well. Then, in beaker B, 0.3 mol of NaOH was dissolved in a certain amount of deionized water, and stirred to form a NaOH aqueous solution.

[0033] Finally, the dissolved NaOH aqueous solution in beaker B is gradually dripped into the Ce(NO3)36H2O aqueous solution in beaker A at a constant rate of 10-20 mL / min, and beaker A is magnetically stirred at 70-80° C. for 20-30 min to obtain a cerium oxide precursor.

[0034] S12, preparing vanadium dioxide precursor:

[0035] Measure 0.02 mol of vanadium pentoxide, 0.04 mol of citric acid, and 50 ml of deionized water, stir and dissolve completely in a 70-80°C water bath, then add activating agents such as toluene, hexanol, and hexadecyltrimethylammonium bromide, mix under magnetic stirring, and gradually drop a certain amount of NaOH aqueous solution to make the solution neutral; finally, heat the mixed solution to 100°C for 2 hours, and then cool to room temperature to obtain a vanadium dioxide precursor.

[0036] S13, preparing nanocomposite particles:

[0037] A cerium oxide precursor and a vanadium dioxide precursor are placed in a high-pressure reactor, and then a dry SO2 gas flow is introduced into the high-pressure reactor, and stirred at 80-90°C for 0.5-2h, and then allowed to stand at 300-500°C for 2-8h. After cooling, washing and drying, cerium oxide-vanadium dioxide nanocomposite particles with excellent thermochromic properties and UV protection properties are obtained.

[0038] S2, the cerium oxide-vanadium dioxide composite nanoparticles and the PVA dissolved in hot water are fully mixed and uniformly prepared to form a cerium oxide-vanadium dioxide-PVA film. The details are as follows:

[0039] 200 g of deionized water and 10 g of PVA were measured and heated to dissolve at 80-90° C. to obtain a polyvinyl alcohol aqueous solution, and 5 g of the prepared cerium oxide-vanadium dioxide composite nanoparticles were added. The mixture was stirred at a constant temperature until uniformly mixed. Finally, the cerium oxide-vanadium dioxide-PVA film was prepared by cooling and spin coating.

[0040] S3. Using glass as a substrate and cerium oxide-vanadium dioxide-PVA film as an interlayer, a smart glass is prepared. The prepared smart glass has at least three layers, wherein the substrate glass has at least two layers and the cerium oxide-vanadium dioxide-PVA film interlayer has at least one layer.

[0041] Embodiment 2:

[0042] The preparation method of the smart glass based on cerium oxide / vanadium dioxide-PVA film is basically the same as that in Example 1, except that:

[0043] In step S12, the amounts of vanadium pentoxide, citric acid, and deionized water are 0.1 mol, 0.3 mol, and 100 ml, respectively; in step S2, the amounts of deionized water are 200 g, the amounts of PVA are 10 g, and the amounts of cerium oxide-vanadium dioxide composite nanoparticles are 1 g.

[0044] Embodiment 3:

[0045] The preparation method of the smart glass based on cerium oxide / vanadium dioxide-PVA film is basically the same as that in Example 1, except that:

[0046] In step S12, the amounts of vanadium pentoxide, citric acid, and deionized water are 0.04 mol, 0.04 mol, and 100 ml, respectively; in step S2, the amounts of deionized water are 200 g, the amounts of PVA are 10 g, and the amounts of cerium oxide-vanadium dioxide composite nanoparticles are 2 g.

[0047] Embodiment 4:

[0048] The preparation method of the smart glass based on cerium oxide / vanadium dioxide-PVA film is basically the same as that in Example 1, except that:

[0049] In step S12, the amounts of vanadium pentoxide, citric acid, and deionized water are 0.05 mol, 0.15 mol, and 100 ml, respectively; in step S2, the amounts of deionized water are 200 g, the amounts of PVA are 10 g, and the amounts of cerium oxide-vanadium dioxide composite nanoparticles are 3 g.

[0050] Embodiment 5:

[0051] The preparation method of the smart glass based on cerium oxide / vanadium dioxide-PVA film is basically the same as that in Example 1, except that:

[0052] In step S12, vanadium pentoxide, citric acid, and deionized water are 0.07 mol, 0.2 mol, and 120 ml, respectively; in step S2, deionized water is 200 g, PVA is 10 g, and cerium oxide-vanadium dioxide composite nanoparticles are 4 g.

[0053] Embodiment 6:

[0054] The preparation method of the smart glass based on cerium oxide / vanadium dioxide-PVA film is basically the same as that in Example 1, except that:

[0055] In step S12, the amounts of vanadium pentoxide, citric acid, and deionized water are 0.05 mol, 0.2 mol, and 120 ml, respectively; in step S2, the amounts of deionized water are 150 g, the amounts of PVA are 10 g, and the amounts of cerium oxide-vanadium dioxide composite nanoparticles are 3.5 g.

[0056] The three-layer smart glass prepared in Examples 1-6 was tested, and the phase change temperatures were 41°C, 49°C, 42°C, 46°C, 44°C, and 47°C, respectively; the visible light transmittances were 76.6%, 79.5%, 78.7%, 78.2%, 77.3%, and 77.8%, respectively; and the ultraviolet light transmittances were 17.6%, 21.7%, 20.5%, 19.6%, 18.4%, and 18.8%, respectively.

[0057] In summary, the preparation method of the smart glass based on the cerium oxide-vanadium dioxide-PVA film of the present invention synthesizes cerium oxide-vanadium dioxide composite nanoparticles by a double in-situ hydrothermal method, and the process is simple and easy to industrialize; the prepared cerium oxide-vanadium dioxide composite nanoparticles are mixed with PVA to prepare a cerium oxide-vanadium dioxide-PVA film, and finally the smart glass is prepared with glass as the substrate, and its phase transition temperature is below 50°C, the visible light transmittance is above 76%, and the ultraviolet light transmittance is below 20%. It not only has a high visible light transmittance and excellent thermochromic performance, but also has good anti-ultraviolet performance and aging resistance, and has a good effect.

[0058] The above is an exemplary description of the invention. Obviously, the specific implementation of the present invention is not limited to the above-mentioned method. As long as such non-substantial improvements are made by adopting the method concept and technical solution of the present invention, or the concept and technical solution of the invention are directly applied to other occasions without improvement, they are all within the protection scope of the present invention.

Claims

1. A method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film, characterized in that: The steps include: S1, synthesizing cerium oxide-vanadium dioxide composite nanoparticles by dual in-situ hydrothermal method; S2, fully mixing the cerium oxide-vanadium dioxide composite nanoparticles and the PVA dissolved in hot water to prepare a cerium oxide-vanadium dioxide-PVA film; S3. Smart glass is prepared using glass as a substrate and cerium oxide-vanadium dioxide-PVA film as an interlayer.

2. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 1, characterized in that: The S1 step is specifically as follows: S11. Preparation of cerium oxide precursor: A certain amount of NaOH aqueous solution is measured and gradually added dropwise to a certain amount of Ce(NO3)36H2O aqueous solution under magnetic stirring to prepare a cerium oxide precursor; S12, preparing vanadium dioxide precursor: A certain amount of vanadium pentoxide, citric acid and deionized water are weighed and dissolved in a water bath, and then an activator is added. After mixing under magnetic stirring, a certain amount of NaOH aqueous solution is gradually added dropwise, and finally heated and cooled to room temperature to obtain a vanadium dioxide precursor. S13, preparing nanocomposite particles: A cerium oxide precursor and a vanadium dioxide precursor are placed in a high-pressure reactor, and then a dry SO2 gas flow is filled into the high-pressure reactor, and stirred at 80-90°C for 0.5-2h, and then allowed to stand at 300-500°C for 2-8h. After cooling, washing and drying, cerium oxide-vanadium dioxide nanocomposite particles with excellent thermochromic properties and UV protection properties are obtained.

3. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 2, characterized in that: The molar ratio of Ce in step S11 to vanadium pentoxide in step S12 is 100:(20-100).

4. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 2, characterized in that: The S11 step is specifically as follows: A certain amount of Ce(NO3)36H2O and a certain amount of deionized water are measured and placed in beaker A, and magnetically stirred for 10 minutes; then, in beaker B, a certain amount of NaOH is measured and dissolved in a certain amount of deionized water; finally, the dissolved NaOH aqueous solution in beaker B is gradually dripped into the Ce(NO3)36H2O aqueous solution in beaker A at a constant rate of 10-20mL / min, and beaker A is magnetically stirred at 70-80°C for 20-30 minutes, thereby obtaining a cerium oxide precursor.

5. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 4, characterized in that: The molar ratio of Ce(NO3)36H2O to NaOH in beaker A is 1:

3.

6. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 2, characterized in that: In step S12, the activating agent is toluene, hexanol and hexadecyltrimethylammonium bromide.

7. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 2, characterized in that: In step S12, the molar ratio of vanadium pentoxide to citric acid is 1:(2-5).

8. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 1, characterized in that: The S2 step is specifically as follows: A certain amount of deionized water and PVA were measured, heated and dissolved at 80-90°C to obtain a polyvinyl alcohol aqueous solution, and then the prepared cerium oxide-vanadium dioxide composite nanoparticles were added, and constant temperature stirring was continued until mixed, and finally cooled to prepare a cerium oxide-vanadium dioxide-PVA film.

9. The method for preparing smart glass based on cerium oxide-vanadium dioxide-PVA film according to claim 1, characterized in that: The mass ratio of the cerium oxide-vanadium dioxide composite nanoparticles to PVA is (0.1-0.5):1.