Composite material, functional glass and preparation method

Abstract

The invention relates to the field of nano coating material preparation, and discloses a composite material, functional glass and a preparation method.The composite material comprises a sol main body and doping elements doped in the sol main body, the sol main body comprises sol of a core-shell structure, the core-shell structure comprises an inner core and an outer shell, the inner core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements are doped in the sol main body; the doping elements at least comprise Ag, K, Na and Li; or, the core is zinc oxide, the shell is silicon dioxide, and the doping element at least comprises Mg. The composite material can improve the self-cleaning performance, the transmittance, the friction resistance, the salt spray corrosion resistance, the water soaking resistance, the alcohol wiping resistance and the like of the functional glass.

Description

Technical Field

[0001] The present application relates to the field of nano-coating material preparation, and in particular to a composite material, functional glass and a preparation method thereof. Background Art

[0002] Glass serves as the window of cameras, display screens, cars, etc. It has important functions of protection, light transmission, and lighting for the products, and plays a key role in the clarity of imaging and display. However, the self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, blister resistance, and alcohol wiping resistance of current functional glass cannot meet actual needs. Summary of the invention

[0003] In view of this, the main technical problem to be solved by this application is the poor self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, blister resistance, alcohol wiping resistance and other properties of functional glass, thereby providing a composite material, functional glass and a preparation method, which will help to improve the self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, blister resistance, alcohol wiping resistance and other properties of functional glass.

[0004] In order to solve the above technical problems, a technical solution adopted in the present application is: to provide a composite material, including a sol main body and doping elements doped in the sol main body, wherein the sol main body includes a sol with a core-shell structure, the core-shell structure includes an inner core and an outer shell, the inner core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or, the inner core is zinc oxide, the outer shell is silicon dioxide, and the doping elements include at least Mg.

[0005] Furthermore, Ag element is doped into titanium dioxide particles; K element, Na element and Li element are doped into silicon dioxide particles.

[0006] Furthermore, the average particle size of titanium dioxide is 50 to 80 nm; and the thickness of the shell is 20 to 50 nm.

[0007] The present application also includes a second technical solution, a method for preparing a composite material, comprising:

[0008] A sol body is provided, the sol body includes a sol having a core-shell structure, the core-shell structure includes a core and an outer shell, the core is titanium dioxide, and the outer shell is silicon dioxide;

[0009] adding silver nitrate solution to the main body of the sol to obtain an intermediate solution;

[0010] In the intermediate solution, lithium silicate, potassium silicate and sodium silicate are added in sequence to form a composite material.

[0011] Furthermore, the step of providing a sol body includes:

[0012] mixing a base-catalyzed silica sol and an acid-catalyzed silica sol to obtain a first mixed sol;

[0013] The titanium dioxide sol is added dropwise to the first mixed sol to form a sol main body.

[0014] Furthermore, the mass ratio of the base-catalyzed silica sol to the acid-catalyzed silica sol is (3.8-4.2):(0.8-1.2).

[0015] Further, the preparation method of the acid-catalyzed silica sol comprises:

[0016] Mixing (C2H5O)4Si and CH3CH2OH to form a first solution;

[0017] The HNO3 solution is added dropwise to the first solution to react and form an acid-catalyzed silica sol.

[0018] Furthermore, the molar ratio of (C2H5O)4Si, CH3CH2OH, HNO3, and H2O is (0.8-1.2):(3.8-4.2):(0.08-0.12):(5.8-6.2).

[0019] Further, the step of adding the HNO3 solution dropwise to the first solution to react and form an acid-catalyzed silica sol comprises:

[0020] Under stirring, add HNO3 solution dropwise to the first solution for 30 to 50 minutes;

[0021] After the dropwise addition, the mixed solution is stirred at 25° C. to 30° C. for 2 h to 2.5 h to form an acid-catalyzed silica sol.

[0022] Further, the preparation method of the base-catalyzed silica sol comprises:

[0023] Mixing (C2H5O)4Si and CH3CH2OH to form a second solution;

[0024] The NH3 solution is added dropwise to the second solution to react and form a base-catalyzed silica sol.

[0025] Furthermore, the molar ratio of (C2H5O)4Si, CH3CH2OH, NH3, and H2O is (0.8-1.2):(3.8-4.2):(0.04-0.06):(5.8-6.2).

[0026] Further, the step of adding the NH3 solution dropwise to the second solution to react and form a base-catalyzed silica sol comprises:

[0027] Under stirring, add the NH3 solution dropwise to the second solution for 30 to 50 minutes;

[0028] After the dropwise addition, the mixed solution is stirred at 60° C. to 65° C. for 4 h to 5 h to form a base-catalyzed silica sol.

[0029] Furthermore, the preparation method of titanium dioxide sol comprises:

[0030] Anhydrous ethanol, water, hydrochloric acid, and tetrabutyl titanate are mixed in a molar ratio of (49.75-50.25):(3.55-4.0):(0.22-0.3):(0.8-1.2) to form a third solution;

[0031] The third solution is reacted at 20° C. to 35° C. for 2 h to 2.5 h, and aged at 30° C. to 35° C. for 3 d to 4 d to form a titanium dioxide sol.

[0032] Furthermore, the mass ratio of the first mixed sol to the titanium dioxide sol is (19-21): (0.8-1.2).

[0033] Furthermore, the step of adding the titanium dioxide sol dropwise into the first mixed sol to form a sol main body includes:

[0034] Under stirring at 25°C to 30°C, adding the titanium dioxide sol dropwise to the first mixed sol at a rate of 0.8 ml / min to 1.2 ml / min;

[0035] After the dropwise addition is completed, stirring is continued for 2 h to 3 h, and aging is carried out at 30° C. to 35° C. for 7 days to 10 days to form a sol main body.

[0036] Furthermore, the concentration of the silver nitrate solution is 0.2-0.4 mol / L.

[0037] Furthermore, the mass ratio of the silver nitrate solution to the sol main body is (0.8-1.2):(99.2-98.8).

[0038] Furthermore, the mass ratio of lithium silicate, potassium silicate and sodium silicate satisfies the following relationship:

[0039] Potassium silicate: sodium silicate: lithium silicate = (2.8~3.2): (1.9~2.3): (0.8~1.2).

[0040] Further, the modulus of potassium silicate is 3.2-3.4; and / or the modulus of sodium silicate is 3.0-3.3; and / or the modulus of lithium silicate is 4.8-5.

[0041] Further, the step of sequentially adding lithium silicate, potassium silicate and sodium silicate to the intermediate solution comprises:

[0042] Add water and surfactant to the intermediate solution and continue stirring;

[0043] Add lithium silicate dropwise and continue stirring until the solution becomes clear and transparent;

[0044] Add potassium silicate dropwise and continue stirring until the solution becomes clear and transparent;

[0045] Add sodium silicate dropwise and continue stirring until the solution becomes clear and transparent to obtain a first precursor solution;

[0046] A stabilizing agent is added to the first precursor solution to obtain a second precursor solution.

[0047] Furthermore, the surfactant includes at least one of fatty alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and fatty alcohol polyoxyethylene ether phosphate.

[0048] Furthermore, the stabilizing aid includes at least one of tetraethylammonium perfluorooctane sulfonate, dodecyl alcohol ester, and 2-amino-2-methyl-1-propanol.

[0049] Furthermore, the mass ratio of the intermediate solution, surfactant, water, potassium silicate, sodium silicate, lithium silicate and stabilizing agent = (8-12): (1.0-1.6): (20-26): (56-64): (38-46): (16-24): (0.5-0.9).

[0050] Furthermore, after the step of adding the stabilizing agent, the method further includes: adding a pH regulator to control the pH of the second precursor solution to be 7 to 9 to form a composite material; the pH regulator includes at least one of sodium bicarbonate solution, sodium tetraborate, and sodium acetate.

[0051] Furthermore, the NaHCO3 solution is a NaHCO3 solution with a mass concentration of 4%, and the mass ratio of the NaHCO3 solution with a mass concentration of 4% to the second precursor solution is (4-6.5):(93.5-96).

[0052] The present application also includes a third technical solution, a functional glass, including a glass substrate and a functional film layer arranged on the surface of the glass substrate, the functional film layer including a film layer body and doping elements, the film layer body including a core-shell structure, the core-shell structure including an inner core and an outer shell, the inner core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or, the inner core is zinc oxide, the outer shell is silicon dioxide, and the doping elements include at least Mg.

[0053] Furthermore, the thickness of the functional film layer is 100 nm to 150 nm, and the uniformity of the film thickness is 5% to 10%.

[0054] Furthermore, the average particle size of titanium dioxide is 50 to 80 nm; and the thickness of the shell is 20 to 50 nm.

[0055] Furthermore, Ag element is doped into titanium dioxide particles; K element, Na element and Li element are doped into silicon dioxide particles.

[0056] The present application also includes a fourth technical solution, a method for preparing functional glass, comprising:

[0057] Providing a glass substrate;

[0058] Arranging a composite material on a glass substrate, wherein the composite material comprises any of the composite materials described above or a composite material prepared by any of the methods for preparing a composite material described above;

[0059] The glass substrate provided with the composite material is heat treated, and the composite material forms a functional film layer.

[0060] Furthermore, the heat treatment process includes a drying stage and a curing stage. The temperature of the drying stage is 60-85°C and the time is 10-30 minutes. The temperature of the curing stage is 180-200°C and the time is 30 minutes to 60 minutes.

[0061] The beneficial effects of the present application are as follows: the composite material of the present application includes a sol body and doping elements doped in the sol body, wherein the sol body includes a sol with a core-shell structure, the core-shell structure includes a core and an outer shell, the core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or the core is zinc oxide, the outer shell is silicon dioxide, and the doping elements include at least Mg. The present application uses silicon dioxide to coat titanium dioxide or zinc oxide to improve the salt spray resistance of functional glass, improve the self-cleaning ability and super-hydrophilic performance of functional glass, and the composite material of the present application can improve the self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, blister resistance, alcohol wiping resistance and other properties of functional glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, among which:

[0063] Figure 1 This is a schematic diagram of a model in which a plurality of silicon dioxide particles are coated on titanium dioxide particles in the present application;

[0064] Figure 2 It is a flowchart of the steps of a first embodiment of a method for preparing a composite material of the present application;

[0065] Figure 3 This is a diagram of the silanol condensation reaction process of the present application;

[0066] Figure 4 is a scanning electron microscope image of the nanopapilla of the present application;

[0067] Figure 5 is another scanning electron microscope image of the nanopapilla of the present application;

[0068] Figure 6 is another scanning electron microscope image of the nanopapilla of the present application;

[0069] Figure 7 is a transmission electron microscope image of the core-shell structure of the present application;

[0070] Figure 8 is a flow chart of steps of a second embodiment of a method for preparing a composite material of the present application;

[0071] Fig. 9 is a flowchart of the steps of a third embodiment of a method for preparing a composite material of the present application;

[0072] Fig.10 is a flowchart of the steps of a fourth embodiment of a method for preparing a composite material of the present application;

[0073] Fig.11 This is a flow chart of steps of an embodiment of a method for preparing functional glass of the present application;

[0074] Fig.12 This is the EDS data graph of the first area of ​​the finished window of the present application before repeated rubbing;

[0075] Fig.13 This is the EDS data graph of the second area of ​​the finished window of the present application before repeated rubbing;

[0076] Fig.14 This is the EDS data graph of the third area of ​​the finished window of the present application before repeated rubbing;

[0077] Fig.15 This is the EDS data graph of the first area of ​​the finished window of the present application after repeated rubbing;

[0078] Fig.16 This is the EDS data graph of the fourth area of ​​the finished window of the present application after repeated rubbing;

[0079] Fig.17 This is the EDS data graph of the fifth area of ​​the finished window of the present application after repeated rubbing;

[0080] Fig.18 This is the EDS data graph of the sixth area of ​​the finished window of the present application after repeated rubbing;

[0081] Fig.19 This is a self-cleaning test diagram of an embodiment of the present application. DETAILED DESCRIPTION

[0082] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0083] It should be noted that the terms "first" and "second" in this application are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first" and "second" can explicitly or implicitly include at least one of the features. In the description of this application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not limited to the listed steps or units, but optionally also includes steps or units that are not listed, or optionally also includes other steps or units inherent to these processes, methods, products or devices.

[0084] In one embodiment of the present application, a composite material is provided, comprising a sol body and a doping element dispersed in the sol body, wherein the sol body comprises a sol having a core-shell structure, such as Figure 1 The core-shell structure includes a core and a shell, 100 is the core, 200 is the shell, 300 is the sol body, the core 100 is titanium dioxide, the shell 200 is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or, the core 100 is zinc oxide, the shell 200 is silicon dioxide, and the doping elements include at least Mg.

[0085] By coating titanium dioxide with silicon dioxide, the optical transmittance of functional glass can be improved. The optical transmittance of the core-shell structure can reach 3.5%. At the same time, it can protect titanium dioxide from long-term use in the natural environment and ensure that titanium dioxide is not corroded by salt spray, which is beneficial to improving the salt spray corrosion resistance of the film layer formed by the composite material.

[0086] The sol body 300 is used as a filler. The sol body 300 includes a sol with a core-shell structure of titanium dioxide and silicon dioxide. Silica and titanium dioxide are inorganic nanoparticles with different low refractive indices. The composite structure of titanium dioxide sol and silicon dioxide sol regulates the composite refractive index to achieve increased transmittance in the visible light band. The film thickness of the composite material formed on the functional glass can be controlled to greatly reduce surface light reflection and increase transmittance. It should be noted that if the titanium dioxide sol and the silicon dioxide sol are simply mixed without forming a core-shell structure, the effect of increasing transmittance cannot be achieved. On the contrary, due to the high refractive index of titanium dioxide, the transmittance of some areas will be low.

[0087] In addition, the silica shell 200 has a certain degree of light transmittance, and sunlight can pass through the silica shell 200 to reach titanium dioxide. Titanium dioxide generates electron-hole pairs under ultraviolet light irradiation, and the electrons and holes migrate to the surface of silica. Electrons have strong reducing properties, and holes have strong oxidizing properties. The two active substances, electrons and holes, can react with water molecules, oxygen, etc. adsorbed on the surface of silica to generate highly oxidizing hydroxyl radicals. Hydroxyl radicals can effectively degrade organic pollutants and kill bacteria and viruses, and can clean pollutants and bacteria on the surface of the film layer formed by the composite material, thereby realizing self-cleaning of functional glass. In addition, the high activity of hydroxyl radicals can greatly increase the surface energy of the functional glass. The higher the surface energy, the easier it is for the molecules on the solid surface to interact with the liquid molecules, thereby making it easier for the liquid to form a wetting effect on the surface of the functional glass, thereby improving the anti-fog and anti-frost properties of the functional glass.

[0088] By doping Ag elements, such as silver nitrate, in the sol body 300, the bandgap width of titanium dioxide can be reduced, so that titanium dioxide can be photocatalyzed under the irradiation of the visible light blue light band of 400-450nm, and produce highly reactive free radicals, thereby decomposing organic pollutants and improving the self-cleaning ability of the functional glass after coating the composite material. It can be understood that by doping Ag elements, titanium dioxide can be photocatalyzed in both the ultraviolet light band and the blue light band, expanding the wavelength range of titanium dioxide photocatalysis.

[0089] By doping K element, for example, potassium silicate, into the sol body 300, the film layer formed by the composite material 0 has strong hydrophilicity and hygroscopicity, as well as high transmittance. Specifically, the potassium ions in the composite material can absorb moisture in the air and generate more hydroxyl groups on the surface, thereby greatly improving the hydrophilic effect of the film layer formed by the composite material. At the same time, the potassium ions can greatly reduce the crystallization tendency of the film layer, reduce the bubbles and impurities in the film layer, make the film layer higher in quality and more transparent, and help improve the transmittance.

[0090] By doping Na element, for example, sodium silicate, into the sol body 300, the film layer formed by the composite material has strong impact resistance and high transmittance. Specifically, the sodium ions in the composite material have a good optical refractive index, which prevents light scattering, makes the film layer highly transparent, and is conducive to improving transmittance.

[0091] By doping Li elements, such as lithium silicate, into the sol body 300, the film layer formed by the composite material has high strength and smoothness, which is beneficial to improving the friction resistance of the film layer. Specifically, the volume of lithium ions in the composite material is small, and the lithium ions on the surface diffuse into the silicon oxide film layer, which can cause permanent compressive stress on the surface of the film layer. At the same time, lithium has a strong attraction to oxygen and has the effect of tightening the free space of the silicate structure, making the silicon oxide film layer denser, thereby enhancing the strength of the film layer and improving the surface smoothness.

[0092] By coating zinc oxide with silicon dioxide, the performance of functional glass can be improved. The silicon dioxide shell has a certain transmittance, and sunlight can pass through the silicon dioxide shell to reach zinc oxide. Zinc oxide generates electron-hole pairs under ultraviolet irradiation, and electrons and holes migrate to the surface of silicon dioxide. Electrons have strong reducing properties, while holes have strong oxidizing properties. The two active substances, electrons and holes, can react with water molecules, oxygen, etc. adsorbed on the surface of silicon dioxide to generate highly oxidizing hydroxyl radicals. Hydroxyl radicals can effectively degrade organic pollutants and kill bacteria and viruses, and can clean pollutants and bacteria on the surface of the film layer formed by the composite material, thereby realizing the self-cleaning of functional glass; in addition, the high activity of hydroxyl radicals can greatly increase the surface energy of functional glass. The higher the surface energy, the easier it is for molecules on the solid surface to interact with liquid molecules, thereby making it easier for liquid to form a wetting effect on the surface of functional glass, thereby improving the anti-fog and anti-frost performance of functional glass. By doping Mg element in the main body of the sol, the band gap width of zinc oxide can be reduced, the band range of zinc oxide photocatalysis can be increased, and the self-cleaning ability of functional glass after coating with composite materials can be improved.

[0093] In one embodiment, Ag elements are doped into the lattice of titanium dioxide particles through silicon dioxide particles. Doping with Ag elements can reduce the band gap of titanium dioxide, so that it can generate electron-hole pairs by photocatalysis under the irradiation of visible light blue light band 400-450nm, and the electrons and holes migrate to the surface of silicon dioxide to generate highly reactive hydroxyl radicals, thereby decomposing organic pollutants and improving the self-cleaning ability of the functional glass after coating the composite material.

[0094] In one embodiment, K element, Na element and Li element are doped into the silicon dioxide particles.

[0095] In one embodiment of the present application, the average particle size of silicon dioxide is 10 to 25 nm; for example, 10 nm, 12 nm, 15 nm, 16 nm, 18 nm, 25 nm, etc., or a range consisting of any two of the above values, for example, 16 to 25 nm, 18 to 25 nm, etc. The average particle size of titanium dioxide is 50 to 80 nm; for example, 50 nm, 52 nm, 55 nm, 66 nm, 78 nm, 80 nm, etc., or a range consisting of any two of the above values, for example, 50 to 66 nm, 52 to 78 nm, etc. The thickness of the shell 200 formed by silicon dioxide is 20 to 50 nm; for example, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, etc., or a range consisting of any two of the above values, for example, 20 to 25 nm, 30 to 50 nm, etc. It should be noted that the average particle size of silicon dioxide is nanometer-level, the particle size is small, and it exhibits good light transmittance.

[0096] By performing the above configuration on the shell 200, the shell 200 is nanometer-scale, so that the doped element silver ions can pass through silicon dioxide into titanium dioxide, thereby expanding the wavelength range of titanium dioxide for photocatalysis.

[0097] This application also includes a second technical solution, such as Figure 2 , Figure 3 , Figure 4 , Figure 5 , Figure 6 , Figure 7 , a method for preparing a composite material, which can be used to prepare the composite material provided in the above embodiment. The method for preparing a composite material comprises:

[0098] S200: providing a sol body 300, the sol body 300 includes a sol having a core-shell structure, the core-shell structure includes a core 100 and an outer shell 200, the core 100 is titanium dioxide, and the outer shell 200 is silicon dioxide;

[0099] S210: adding silver nitrate solution to the sol body 300 to obtain an intermediate solution;

[0100] S220: In the intermediate solution, lithium silicate, potassium silicate and sodium silicate are added in sequence to form a composite material.

[0101] Lithium silicate, potassium silicate and sodium silicate are used as film-forming substances. When the pH in the system reaches a suitable value, any two silanol groups (-Si-OH) of the monosilicate will undergo a condensation reaction, that is, the monosilicate ion will form a dimer, and the dimer can continue to condense with the monosilicate ion or dimer to form a trimer / tetramer. The polymerization reaction continues to form a highly cross-linked three-dimensional grid. Figure 6 As shown, Figure 6The protruding white substance in the is a papillary structure, some of which are single white spheres or spheroids, some of which are aggregates of multiple white spheres or spheroids, and a single white sphere or spheroid is a core-shell structure, that is, the papillary structure is formed by the core-shell structure of silicon dioxide and titanium dioxide completely exposed on the surface of the three-dimensional network layer or half embedded in the three-dimensional network membrane layer, and several core-shell structures are aggregated to form a nano-papillary structure protruding from the three-dimensional network; and the papillary structure is cross-linked with the three-dimensional network formed by lithium silicate, potassium silicate and sodium silicate. According to Casses-Wenzel's theory of special wettability, silicate chemical components with high surface energy hydrophilicity plus micro-nano level roughness (nanopapillary structure forms nano-level roughness) can obtain surface super-hydrophilic properties; such as Figure 4 , Figure 5 , Figure 6 As shown, Figure 4 , Figure 5 The dots in the middle are papillary structures. Figure 6 The white substance in the glass is a papillary structure, and multiple papillary structures are arranged unevenly, thereby improving the super-hydrophilic properties of the functional glass surface.

[0102] A composite film layer with super hydrophilic surface and anti-reflection is prepared using lithium silicate, potassium silicate and sodium silicate as film-forming materials and inorganic nanoparticles of TiO2 and SiO2 with different low refractive indices as fillers. The film thickness formed by the composite material can be controlled to greatly reduce surface light reflection and increase transmittance.

[0103] like Figure 7 As shown, the middle part of the particle in the figure is titanium dioxide sol, and the edge part is silicon dioxide sol. For example, A in the figure is titanium dioxide sol, and B is silicon dioxide sol. Figure 7 The test method of the core-shell structure shown is: prepare the core-shell structure into a dispersion liquid, drip the dispersion liquid on the surface of the carbon mesh, and then seal it with carbon tetrachloride and observe it using a transmission electron microscope. Figure 7 It can be seen that the silica sol is coated around the titanium dioxide sol, and the coating effect is good. Titanium dioxide produces electron-hole pairs under the irradiation of ultraviolet and blue light bands. The electrons and holes migrate to the surface of silica to produce highly reactive hydroxyl radicals. Hydroxyl radicals can effectively degrade organic pollutants and kill bacteria and viruses. They can clean pollutants and bacteria on the surface of the film layer formed by the composite material, thereby realizing self-cleaning of functional glass.

[0104] The doping of Ag element enables titanium dioxide to continuously provide highly active hydroxyl radicals to the film system under the action of blue light and ultraviolet light, and work together with the high surface energy potassium silicate partially doped in it to continuously generate chemically adsorbed water and form a continuous super hydrophilic surface.

[0105] In one embodiment of the present application, Figure 8 , in the step of providing a sol body 300, comprising:

[0106] S100: mixing a base-catalyzed silica sol and an acid-catalyzed silica sol to obtain a first mixed sol;

[0107] S110 : adding titanium dioxide sol dropwise into the first mixed sol to form a sol main body 300 .

[0108] The mixing of the first mixed sol and the titanium dioxide sol is physical mixing. The silicon dioxide in the first mixed sol and the titanium dioxide in the titanium dioxide sol repel each other, and the stability of the system can still be maintained after mixing together. The core-shell structure is formed at this time, and the sol body 300 is still in a sol state after the core-shell structure is formed.

[0109] It should be noted that the morphology of the base-catalyzed silica sol is roughly spherical and porous, which is conducive to penetration. For example, it is conducive to silver ions passing through silica to be doped in titanium dioxide. For another example, it is conducive to the migration of electron-hole pairs generated by titanium dioxide under the action of ultraviolet and blue light to the surface of silica. The morphology of the acid-catalyzed silica sol is linear, roughly strip-shaped, which is conducive to adhesion. By mixing the base-catalyzed silica sol with the acid-catalyzed silica sol, the formed sol body 300 has a strong adhesion. At the same time, silver ions can easily pass through silica to be doped in titanium dioxide, and the electron-holes generated by titanium dioxide under the action of ultraviolet and blue light can easily pass through silica to the surface of silica.

[0110] In one embodiment, the mass ratio of base-catalyzed silica sol to acid-catalyzed silica sol is (3.8-4.2):(0.8-1.2); for example, 3.8:0.8, 3.8:1, 3.8:1.2, 4:0.8, 4:1, 4:1.2, 4.2:0.8, 4.2:1, 4.2:1.2, etc.

[0111] Optionally, the base-catalyzed silica sol and the acid-catalyzed silica sol are mixed and stirred for 2 h to 3 h in a mass ratio of (3.8 to 4.2): (0.8 to 1.2) to obtain a first mixed sol. The stirring time can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h, 3 h, etc., or can be a range consisting of any two of the above values.

[0112] In one embodiment, the preparation method of the acid-catalyzed silica sol includes: mixing (C2H5O)4Si (tetraethyl orthosilicate, TEOS) and CH3CH2OH (anhydrous ethanol, EtOH) to form a first solution; adding HNO3 solution dropwise to the first solution to react and form an acid-catalyzed silica sol.

[0113] Optionally, the concentration of the HNO3 solution is 4 mol / L to 6 mol / L. The concentration of the HNO3 solution can be 4 mol / L, 4.2 mol / L, 4.5 mol / L, 4.7 mol / L, 5 mol / L, 5.3 mol / L, 5.5 mol / L, 5.6 mol / L, 5.9 mol / L, 6 mol / L, etc., or can be a range consisting of any two of the above values.

[0114] Optionally, the molar ratio of (C2H5O)4Si, CH3CH2OH, HNO3, and H2O is (0.8-1.2):(3.8-4.2):(0.08-0.12):(5.8-6.2); for example, 0.8:3.8:0.08:5.8, 0.8:4:0.1:5.9, 0.8:4.2:0.12:6.2, 0.9:3.8:0.08:5.8, 0.9:4.2:0.09:5.9, 1:4:0.1:6, etc.

[0115] Optionally, the step of adding HNO3 solution dropwise to the first solution to react to form an acid-catalyzed silica sol includes: adding HNO3 solution dropwise to the first solution under stirring, the dropping time being 30 min to 50 min; after the dropwise addition is completed, the mixed solution is stirred at 25°C to 30°C for 2h to 2.5h to form an acid-catalyzed silica sol.

[0116] The dropping time can be 30min, 35min, 40min, 45min, 50min, etc., or a range consisting of any two of the above numbers. The stirring time after the dropping is completed can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, etc., or a range consisting of any two of the above numbers; the stirring temperature can be 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., or a range consisting of any two of the above numbers.

[0117] Under stirring, the HNO3 solution is added dropwise to the first solution, and the stirring speed is 1200 rpm to 1500 rpm; the stirring speed can be 1200 rpm, 1300 rpm, 1400 rpm, 1500 rpm, etc., or a range consisting of any two of the above values. By controlling the stirring speed, the full reaction of the HNO3 solution and the first solution is promoted.

[0118] By controlling the ratio of (C2H5O)4Si, CH3CH2OH, HNO3, and H2O and the dropping time, the first solution and the HNO3 solution are kept to fully react; after the dropping is completed, stirring is continued at 25°C to 30°C for 2h to 2.5h to further keep the first solution and the HNO3 solution fully react to form an acid-catalyzed silica sol; the morphology of the acid-catalyzed silica sol is linear.

[0119] In one embodiment, the preparation method of base-catalyzed silica sol includes: mixing (C2H5O)4Si (tetraethyl orthosilicate, TEOS) and CH3CH2OH (anhydrous ethanol, EtOH) to form a second solution; adding NH3 solution (ammonia solution) dropwise to the second solution to react and form base-catalyzed silica sol.

[0120] Optionally, the concentration of the NH3 solution is 1 mol / L to 2 mol / L. The concentration of the NH3 solution can be 1 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L, 2 mol / L, etc.

[0121] Optionally, the molar ratio of (C2H5O)4Si, CH3CH2OH, NH3, and H2O is (0.8-1.2):(3.8-4.2):(0.04-0.06):(5.8-6.2); for example, 0.8:3.8:0.04:5.8, 0.8:4:0.05:5.9, 0.8:4.2:0.06:6.2, 0.9:3.8:0.04:5.8, 0.9:4.2:0.06:5.9, 1:4:0.05:6, etc.

[0122] Optionally, the step of adding NH3 solution dropwise to the second solution to react to form base-catalyzed silica sol includes: adding NH3 solution dropwise to the second solution under stirring, the dropping time being 30 min to 50 min; after the dropwise addition is completed, the mixed solution is stirred at 60°C to 65°C for 4h to 5h to form base-catalyzed silica sol.

[0123] The dropping time can be 30min, 35min, 40min, 45min, 50min, etc., or a range consisting of any two of the above numbers. The stirring time after the dropping is completed can be 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h, 5h, etc., or a range consisting of any two of the above numbers; the temperature can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, etc., or a range consisting of any two of the above numbers.

[0124] Under stirring, the NH3 solution is added dropwise to the second solution, and the stirring speed is 1200 rpm to 1500 rpm; the stirring speed can be 1200 rpm, 1300 rpm, 1400 rpm, 1500 rpm, etc., or a range consisting of any two of the above values. By controlling the stirring speed, the full reaction of the NH3 solution and the second solution is promoted.

[0125] By controlling the ratio of (C2H5O)4Si, CH3CH2OH, NH3, and H2O and the dropping time, the second solution and the NH3 solution are kept to fully react; after the dropping is completed, stirring is continued at 60°C to 65°C for 4h to 5h to further keep the second solution and the NH3 solution fully react to form a base-catalyzed silica sol, and the morphology of the formed base-catalyzed silica sol is roughly spherical.

[0126] It should be noted that, in the process of preparing acid-catalyzed silica sol and base-catalyzed silica sol, using ethyl orthosilicate as the silicon source can reduce the influence of the silicon source on step S220 and affect the transmittance of the composite material, compared with using other materials such as sodium silicate as the silicon source. In the process of preparing acid-catalyzed silica sol, using nitric acid, compared with other acids such as sulfuric acid, the acidity of nitric acid meets the requirements, and can reduce the reaction with sodium silicate, potassium silicate, and lithium silicate in step S220. In the process of preparing base-catalyzed silica sol, using ammonia water can reduce the introduction of impurity elements compared with using other weak bases or weak alkaline salts.

[0127] In one embodiment, the preparation method of titanium dioxide sol includes: mixing anhydrous ethanol, water, hydrochloric acid, and tetrabutyl titanate in a molar ratio of (49.75-50.25): (3.55-4.0): (0.22-0.3): (0.8-1.2) to form a third solution; reacting the third solution at 20°C-35°C for 2h-2.5h, and aging at 30°C-35°C for 3d-4d to form a titanium dioxide sol.

[0128] Among them, the molar ratio of anhydrous ethanol, water, hydrochloric acid, and tetrabutyl titanate can be 49.75:3.55:0.22:1, 49.75:4.0:0.28:1, 49.75:3.60:0.26:1.2, 50.25:3.70:0.25:0.9, 50.10:3.75:0.24:1, etc. The reaction temperature of the third solution can be 20°C, 25°C, 30°C, 35°C, etc., or it can be a range composed of any two of the above numbers. The reaction time of the third solution can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, etc., or it can be a range composed of any two of the above values. The aging temperature of the third solution can be 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, etc., or it can be a range composed of any two of the above values. The aging time of the third solution can be 3 days, 3.5 days, 4 days, etc., or can be a range consisting of any two of the above values. Aging refers to the process of allowing the sol formed by the reaction of the third solution to be left for a period of time to evolve naturally in a relatively static state.

[0129] By selecting tetrabutyl titanate as the titanium source for preparing titanium dioxide sol, the introduction of impurity elements can be reduced, and the reaction with sodium silicate, potassium silicate, and lithium silicate in step S220 can be reduced.

[0130] Optionally, the third solution is reacted at 20° C. to 35° C. for 2 h to 2.5 h, and then placed in a sealed glass container and aged at 30° C. to 35° C. for 3d to 4d to form a titanium dioxide sol.

[0131] In one embodiment, the mass ratio of the first mixed sol to the titanium dioxide sol is: (19-21): (0.8-1.2); for example, 19:0.8, 19:1.2, 20:1, 20:1.2, 21:0.8, 21:1.2, etc.

[0132] In one embodiment, the step of adding titanium dioxide sol to the first mixed sol to form the sol body 300 includes: adding titanium dioxide sol to the first mixed sol at a rate of 0.8 ml / min to 1.2 ml / min under stirring at 25°C to 30°C; after the addition is completed, stirring is continued for 2h to 3h, and aging is carried out at 30°C to 35°C for 7d to 10d to form the sol body 300.

[0133] Titanium dioxide sol is added drop by drop into the silica mixed sol (i.e., the first mixed sol), and the temperature and the dropping speed are controlled. When the titanium dioxide particles enter the silica mixed sol, the silica nanoparticles will immediately surround the titanium dioxide. Due to the pure and high surface energy of the titanium dioxide surface and the hydrogen bonds on the silica surface, the silica is adsorbed on the titanium dioxide surface, thereby forming a core-shell structure.

[0134] The stirring speed is 1200 rpm to 1500 rpm; the stirring speed can be 1200 rpm, 1300 rpm, 1400 rpm, 1500 rpm, etc., or a range consisting of any two of the above values. By controlling the stirring speed, the first mixed sol and the titanium dioxide sol are fully reacted.

[0135] The dropping temperature can be 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., or a range consisting of any two of the above values. The dropping speed can be 0.8ml / min, 0.9ml / min, 1.0ml / min, 1.1ml / min, 1.2ml / min, etc., or a range consisting of any two of the above values. The stirring time after the dropwise addition is completed can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h, etc., or a range consisting of any two of the above values. The aging temperature can be 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, etc., or a range consisting of any two of the above values. The aging time can be 7d, 8d, 9d, 10d, etc., or a range consisting of any two of the above values.

[0136] In one embodiment, the concentration of the silver nitrate solution is 0.2-0.4 mol / L, for example, 0.2 mol / L, 0.3 mol / L, or 0.4 mol / L.

[0137] In one embodiment, the mass ratio of the silver nitrate solution to the sol body 300 is (0.8-1.2):(99.2-98.8), for example, 0.8:99.2, 0.9:99.5, 1.0:99.0, 1.2:98.8.

[0138] In one embodiment, the mass ratio of lithium silicate, potassium silicate and sodium silicate satisfies the following relationship: potassium silicate: sodium silicate: lithium silicate = (2.8-3.2): (1.9-2.3): (0.8-1.2), for example, potassium silicate: sodium silicate: lithium silicate = 2.8: 1.9: 0.8, potassium silicate: sodium silicate: lithium silicate = 2.9: 2.0: 1.0, potassium silicate: sodium silicate: lithium silicate = 3.0: 2.2: 1.1, potassium silicate: sodium silicate: lithium silicate = 3.2: 2.3: 1.2. It should be noted that, when the proportion of potassium silicate is set as above, the moisture absorption of the surface of the film layer is suitable, and it is not easy to crack the surface, and the hydrophilic effect is better; when the proportion of lithium silicate is set as above, the film layer has higher strength and smoothness, which is conducive to improving the friction resistance of the film layer; when the proportion of sodium silicate is set as above, the film layer has stronger impact resistance and higher transmittance.

[0139] In one embodiment, the modulus of potassium silicate is 3.2 to 3.4; and / or the modulus of sodium silicate is 3.0 to 3.3; and / or the modulus of lithium silicate is 4.8 to 5. For example, the modulus of potassium silicate may be 3.2, 3.3, 3.4, etc.; the modulus of sodium silicate may be 3.0, 3.1, 3.2, 3.3, etc.; the modulus of lithium silicate may be 4.8, 4.9, 5, etc.

[0140] The modulus of potassium silicate indicates the ratio of potassium oxide (K2O) to silicon dioxide (SiO2) in potassium silicate. The modulus of sodium silicate indicates the ratio of potassium oxide (Na2O) to silicon dioxide (SiO2) in potassium silicate. The modulus of lithium silicate indicates the ratio of lithium oxide (Li2O) to silicon dioxide (SiO2) in potassium silicate.

[0141] By setting the modulus of potassium silicate, sodium silicate and lithium silicate as above, the alkalinity and viscosity of the solution are appropriate, and the formed composite material has good hydrophilicity and high transmittance.

[0142] In one embodiment of the present application, Fig. 9 , the step of sequentially adding lithium silicate, potassium silicate and sodium silicate to the intermediate solution comprises:

[0143] S221: adding water and surfactant to the intermediate solution and continuing stirring;

[0144] S222: Add lithium silicate dropwise and continue stirring until the solution becomes clear and transparent;

[0145] S223: Add potassium silicate dropwise and continue stirring until the solution becomes clear and transparent;

[0146] S224: adding sodium silicate dropwise and stirring continuously until the solution becomes clear and transparent to obtain a first precursor solution;

[0147] S225: Adding a stabilizing agent to the first precursor solution to obtain a second precursor solution.

[0148] In one embodiment, the speed of dropping lithium silicate is 5ml / min to 6ml / min, the speed of dropping potassium silicate is 5ml / min to 6ml / min, and the speed of dropping sodium silicate is 5ml / min to 6ml / min. By setting the dropping speed as above, the sufficiency of the reaction is maintained, and the K element, the Li element, and the Na element are well doped. The speeds of dropping lithium silicate, potassium silicate, and sodium silicate can be 5ml / min, 5.2ml / min, 5.5ml / min, 5.7ml / min, 5.9ml / min, 6ml / min, etc., respectively, or can be a range consisting of any two of the above values.

[0149] It should be noted that when potassium silicate, lithium silicate or sodium silicate is dropped, the area where the sol is dropped appears milky white, and stirring until the solution becomes clear and transparent means stopping stirring when the solution is in the initial state of an intermediate solution.

[0150] In one embodiment of the present application, the surfactant includes at least one of fatty alcohol polyoxyethylene ether phosphate (AEO-9P), fatty alcohol polyoxyethylene ether sodium sulfate (AES), and fatty alcohol polyoxyethylene ether (POE).

[0151] In one embodiment of the present application, the stabilizing aid includes at least one of tetraethylammonium perfluorooctane sulfonate, dodecyl alcohol ester, and 2-amino-2-methyl-1-propanol.

[0152] In one embodiment, the mass ratio of the intermediate solution, surfactant, water, potassium silicate, sodium silicate, lithium silicate and stabilizing agent is (8-12): (1.0-1.6): (20-26): (56-64): (38-46): (16-24): (0.5-0.9), for example, the intermediate solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent = 8: 1.0: 20: 60: 39: 17: 0.5, the intermediate solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent = 8: 1.0: 20: 60: 39: 17: 0.5 Solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent = 9: 1.2: 22: 68: 40: 20: 0.7, intermediate solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent = 11: 1.4: 24: 64: 46: 24: 0.8, intermediate solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent = 10: 1.3: 22: 60: 40: 20: 0.6, etc.

[0153] In a specific embodiment, water and 0.1% AEO-9P are added to the intermediate solution and stirred for 6 minutes; a certain amount of lithium silicate is slowly added to the solution under continuous stirring and stirred for 10 minutes until the solution becomes clear and transparent; a certain amount of potassium silicate is slowly added and stirred for 10 minutes until the solution becomes clear and transparent; a certain amount of sodium silicate is slowly added and stirred for 10 minutes until the solution becomes clear and transparent, a stabilizing agent (tetraethylammonium perfluorooctanesulfonate) is added and stirred for 10 minutes and then allowed to stand for 30 minutes to obtain a second precursor solution.

[0154] In one embodiment of the present application, Fig.10 , after the step of adding the stabilizing agent, further comprising:

[0155] S226: adding a pH regulator to control the pH of the second precursor solution to be 7-9 to form a composite material; the pH regulator includes at least one of sodium bicarbonate solution, sodium tetraborate, and sodium acetate.

[0156] Adding a pH regulator can lower the pH value of the system, reduce the alkalinity of the system, and cause a condensation reaction among lithium silicate, potassium silicate and sodium silicate.

[0157] In one embodiment of the present application, the NaHCO3 solution is a NaHCO3 solution with a mass concentration of 4%, and the mass ratio of the 4% mass concentration NaHCO3 solution to the second precursor solution is (4-6.5):(93.5-96), for example 4.0:93.5, 5:94.0, 6.5:96.0.

[0158] It should be noted that the core of the composite material is zinc oxide, the shell is silicon dioxide, and the doping element includes at least Mg. The preparation method thereof can refer to the preparation method of the composite material whose core is titanium dioxide and whose shell is silicon dioxide, and will not be repeated. Exemplarily, the preparation method of the composite material whose core is zinc oxide, whose shell is silicon dioxide, and whose doping element includes at least Mg includes: providing a sol body, the sol body includes a sol having a core-shell structure, the core-shell structure includes a core and a shell, the core is zinc oxide, and the shell is silicon dioxide; adding a magnesium nitrate solution to the sol body to obtain a composite material.

[0159] The present application also includes a third technical solution, a functional glass, including a glass substrate and a functional film layer arranged on the surface of the glass substrate, the functional film layer including a film layer body and doping elements, the film layer body including a core-shell structure, the core-shell structure including a core 100 and a shell 200, the core 100 is titanium dioxide, the shell 200 is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or, the core 100 is zinc oxide, the shell 200 is silicon dioxide, and the doping elements include at least Mg. It should be noted that the functional film layer can be formed by the composite material provided in the above embodiment or by a composite material prepared by the preparation method of the composite material provided in the above embodiment.

[0160] In one embodiment of the present application, the thickness of the functional film layer is 100nm to 150nm, such as 100nm, 120nm, 140nm, 150nm, and the uniformity of the film thickness is 5% to 10%, such as 5%, 6%, 7%, 9%, 10%. By setting the thickness of the functional film layer to 100nm to 150nm, which is 1 / 4 of the visible light wavelength of 400nm to 700nm, it is beneficial to enhance the transmittance of the functional film layer.

[0161] In one embodiment, the average particle size of silicon dioxide is 10-25 nm, 10 nm, 12 nm, 15 nm, 16 nm, 18 nm, 25 nm, etc., or a range consisting of any two of the above values, for example, 16-25 nm, 18-25 nm, etc. The average particle size of titanium dioxide is 50-80 nm, for example, 50 nm, 52 nm, 55 nm, 66 nm, 78 nm, 80 nm, etc., or a range consisting of any two of the above values, for example, 50-66 nm, 52-78 nm, etc. The thickness of the shell 200 formed by silicon dioxide is 20-50 nm; for example, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, etc., or a range consisting of any two of the above values, for example, 20-25 nm, 30-50 nm, etc.

[0162] In one embodiment, Ag element is doped into the titanium dioxide particles.

[0163] In one embodiment, K element, Na element and Li element are doped into the silicon dioxide particles.

[0164] This application also includes a fourth technical solution, such as Fig.11 , a method for preparing functional glass, comprising:

[0165] S300: providing a glass substrate;

[0166] S310: Arranging a composite material on a glass substrate, wherein the composite material includes the composite material described above or a composite material prepared by the method for preparing the composite material described above;

[0167] S320: heat-treating the glass substrate provided with the composite material, so that the composite material forms a functional film layer.

[0168] The surface of the glass substrate forming the composite material is mostly a silicon dioxide surface. The silicon dioxide surface can absorb more water to form surface hydroxyl groups that are symmetrical to the silicon atoms on the silicon dioxide surface and have strong stability. In addition, the physical adsorption of water by silicon dioxide can stabilize the Ti-OH structure on the titanium dioxide surface, thereby enhancing the hydrophilicity of the functional glass and prolonging the duration of the hydrophilicity, ultimately achieving continuous super-hydrophilicity and self-cleaning of the functional glass surface.

[0169] The contact angle of the surface of the glass substrate formed with the composite material is in the range of 8 to 11 degrees; the transmittance is 95%, of which the transmittance of the glass substrate without the composite material is 91%; the salt spray resistance time is 240 hours; the ultraviolet resistance time is 2000 hours; and the water bubble resistance time is 200 hours.

[0170] In one embodiment, the heat treatment process includes a drying stage and a curing stage. The temperature of the drying stage is 60-85°C, for example, 60°C, 65°C, 70°C, 79°C, 83°C, and the time is 10-30 minutes, for example, 10 minutes, 15 minutes, 20 minutes, 28 minutes, 30 minutes. The temperature of the curing stage is 180-200°C, for example, 180°C, 183°C, 187°C, 190°C, 199°C, and the time is 30 minutes to 60 minutes, for example, 30 minutes, 35 minutes, 40 minutes, 58 minutes, 60 minutes.

[0171] The present application also applies the composite material provided in the above embodiment to the surface of a glass substrate by roller coating, and then rubs the glass coated with the composite material. EDS tests are performed before and after rubbing. The specific test results are as follows: Figure 12-Figure 18 shown.

[0172] Before rubbing the glass, EDS tests are performed on the first area, the second area, and the third area of ​​the glass, respectively. The first area, the second area, and the third area do not overlap and are independent of each other. The test results before rubbing are as follows: Figure 12-14 After the glass is rubbed, EDS tests are performed on the first area, the fourth area, the fifth area, and the sixth area of ​​the glass, respectively. The first area, the fourth area, the fifth area, and the sixth area do not overlap and are independent of each other. The test structure after rubbing is shown in FIG. Figure 15-18 It should be noted that the first area before friction and the first area after friction are the same area of ​​the glass, and the first area, the fourth area, the fifth area, and the sixth area after friction are all within the friction treatment range of the glass; the first area, the second area, and the third area before friction are randomly selected areas, and the fourth area, the fifth area, and the sixth area after friction are randomly selected areas of the friction-treated glass.

[0173] like Figure 12-14 As shown in Figure 2, there is no peak of Ti element before friction; Figure 15-18 As shown in the figure, there is a peak of Ti element after friction. SiO2 is partially rubbed off, and Ti element is exposed due to friction, which further illustrates that silica sol covers titanium dioxide sol to form a core-shell structure. By randomly selecting different areas of the glass before friction for EDS testing, no Ti element was detected; and by randomly selecting different areas of the glass after friction for EDS testing, Ti element was detected in all of them, ensuring the accuracy of the test results.

[0174] It should be noted that the instrument used to test the EDS image is: Zeiss, model SIGMA-300. The EDS test is used to verify the core-shell structure composed of silicon dioxide and titanium dioxide; Figure 12-Figure 18The fact that no peaks of Li and Ag were detected does not mean that there are no Li and Ag elements in the composite material. This is due to the limitation of the detection instrument. The content of Ag element is relatively small, so Figure 12-Figure 18 There is no peak of Ag element in the graph; the atomic radius of Li element is small, the X-ray energy generated by electron transition is low, and the signal intensity generated in the energy spectrum is relatively weak, so Figure 12-Figure 18 There is no peak of Li element.

[0175] To facilitate understanding of the embodiments of the present application, the present application provides the following non-limiting embodiments to further explain the present application in detail.

[0176] Embodiment 1:

[0177] Thoroughly mix tetraethyl orthosilicate (TEOS) and anhydrous ethanol (EtOH), and add a mixture of deionized water and nitric acid (HNO3) dropwise under stirring at 1200 rpm with a magnetic stirrer for 30 min. After completion, stir the reaction mixture at 30°C for 2 h. After the sol is cooled, an acid-catalyzed SiO2 sol is obtained, wherein TEOS:EtOH:HNO3:H2O=1:4:0.1:6 (molar ratio).

[0178] Thoroughly mix tetraethyl orthosilicate (TEOS) and anhydrous ethanol (EtOH), and add a mixture of deionized water and aqueous ammonia (NH3) dropwise under stirring at 1200 rpm with a magnetic stirrer for 30 min. After completion, stir the reaction mixture at 60°C for 4 h. After the sol is cooled, a base-catalyzed SiO2 sol is obtained, wherein TEOS:EtOH:NH3:H2O=1:4:0.05:6 (molar ratio).

[0179] The base-catalyzed silica sol and the acid-catalyzed silica sol were mixed and stirred at a mass ratio of 4:1 for 2 hours to obtain a first mixed sol.

[0180] Anhydrous ethanol, deionized water, concentrated hydrochloric acid and butyl titanate were added into a flat-bottom flask in a molar ratio of 49.75:3.55:0.22:1 in sequence, reacted at 30°C for 2 hours, taken out, placed in a sealed glass container, and aged in a 30°C constant temperature bath for 3 days to obtain TiO2 sol.

[0181] 1000 ml of the first mixed sol was stirred in a magnetic stirrer at 1200 rpm, and 100 ml of the TiO2 sol was added dropwise to the SiO2 sol at a rate of 1 ml / min using a burette at room temperature of 25°C. After the addition was completed, the mixture was stirred for 2 hours, and then aged in a constant temperature bath at 30°C for 7 days to obtain a sol body 300 having a core-shell structure.

[0182] Silver nitrate is added to the sol body 300 to obtain an intermediate solution, and the mass ratio of the silver nitrate solution to the sol body 300 is 0.8:99.2; water, surfactant, lithium silicate, potassium silicate and sodium silicate are added to the intermediate solution in sequence to obtain a first precursor solution; a stabilizing agent is added to the first precursor solution to obtain a second precursor solution, and the mass ratio of the intermediate solution: surfactant: water: potassium silicate: sodium silicate: lithium silicate: stabilizing agent is 10:1.2:24:70:40:20:0.7, wherein the surfactant is 0.1% AEO-9P and the stabilizing agent is tetraethylammonium perfluorooctanesulfonate; a pH regulator is added to the second precursor solution to control the pH of the second precursor solution to 7, wherein the pH regulator is a sodium bicarbonate solution with a mass concentration of 4%, and the mass ratio of the sodium bicarbonate solution with a mass concentration of 4% to the second precursor solution is 4:96, to obtain a composite material. The composite material is coated on a glass substrate and heat-treated to obtain a functional glass.

[0183] Comparative Example 1A

[0184] The parameters of Comparative Example 1A are substantially the same as those of Comparative Example 1, except that the composite material used in Comparative Example 1A does not include a silver nitrate solution.

[0185] Comparative Example 1B

[0186] The parameters of Comparative Example 1B are substantially the same as those of Comparative Example 1, except that the composite material used in Comparative Example 1B does not include a surfactant.

[0187] Comparative Example 1C

[0188] The parameters of Comparative Example 1C are substantially the same as those of Example 1, except that the composite material used in Comparative Example 1C does not include lithium silicate.

[0189] Comparative Example 1D

[0190] The parameters of Comparative Example 1D are substantially the same as those of Example 1, except that the composite material used in Comparative Example 1D does not include potassium silicate.

[0191] Comparative Example 1E

[0192] The parameters of Comparative Example 1E are substantially the same as those of Example 1, except that the composite material used in Comparative Example 1E does not include sodium silicate.

[0193] Table 1

[0194]

[0195]

[0196] In Example 1, the self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, water bubble resistance, alcohol wiping resistance and other properties of the functional glass obtained are the best. Among them, the comparative example 1A cannot achieve self-cleaning under blue light conditions, indicating that the band gap of titanium dioxide is too large and no electron-hole pairs are generated to oxidize and reduce oil stains. Self-cleaning test: The coated glass is placed on a 100ml beaker containing 30g of vegetable oil. Fig.19 As shown, the film was baked on a baking table at 30°C for 2 days, and the haze and transmittance were tested. Transmittance test: tested using a UV-visible spectrophotometer. Hydrophilicity: the water drop angle of the film layer was tested using a water drop angle. Smoothness: the surface was observed through a 600x magnifying glass. Pit impact performance test: refer to GB / T 20138-2006 / IEC 62262; 2002, using 0.5J energy for impact.

[0197] It should be noted that since most of the surface of the glass substrate is a silicon dioxide surface, the action of silicate ions is similar to the action principle of ions in glass.

[0198] Since lithium ions are small in size, the lithium ions on the surface can easily diffuse into the silicon oxide film at high temperature, replacing some of the potassium ions and sodium ions inside. In the process of replacement, permanent compressive stress can be generated on the surface of the film (this is also the principle of chemical strengthening of glass). At the same time, lithium has a strong attraction to oxygen, which has the effect of tightening the free space of the silicate structure, making the silicon oxide film more dense, thereby enhancing the strength of the film and improving the surface finish. Therefore, the lack of lithium ions in Comparative Example 1C will reduce the strength of the film and reduce the finish.

[0199] Since potassium silicate has strong hygroscopicity, after the sodium potassium ion and lithium potassium ion exchange, the potassium ions on the surface absorb moisture in the air and produce more hydroxyl groups on the surface, thus greatly improving the hydrophilic effect of the film layer. At the same time, potassium ions can greatly reduce the crystallization tendency of the film layer, reduce bubbles and impurities in the film layer, and make the film layer higher in quality and more transparent. Therefore, the lack of potassium silicate in comparative example 1D will greatly weaken or even eliminate the hydrophilic effect of the film layer, and reduce the transmittance.

[0200] Since the optical refractive index of sodium ions is good, the scattering of light is prevented, making the film layer highly transparent. At the same time, the lack of sodium ions will lead to an increase in potassium ions, reducing the sodium-potassium ion exchange process of the film layer, reducing the surface compressive stress, thereby reducing the strength and impact resistance of the film layer. Therefore, Comparative Example 1E lacks sodium silicate, and the transmittance of the film layer is reduced, and the impact resistance is reduced.

[0201] Example 2

[0202] The parameters of Example 2 are basically the same as those of Example 1, except that the mass ratio of the silver nitrate solution and the sol body 300 used in Example 2 is different, wherein they are respectively marked as Example 2-1, Example 2-2, Example 2-3, and Example 2-4 according to the different mass ratios.

[0203] The results of the above examples are shown in Table 2. The transmittance of Examples 2-3 and 2-4 is lower than that of Example 1, but still has an anti-reflection effect compared to Examples 2-1 and 2-2.

[0204] Table 2

[0205]

[0206] Example 3

[0207] The parameters of Example 3 are basically the same as those of Example 1, except that Example 3 uses a mass ratio of the intermediate solution to the surfactant, wherein the intermediate solutions are respectively marked as Example 3-1, Example 3-2, Example 3-3, and Example 3-4 according to the different mass ratios of the intermediate solution to the surfactant.

[0208] The results of the above examples are shown in Table 3. The whitening and granularity of the film surface are determined by visual observation. The anti-reflection effects of Examples 3-2 and 3-3 are lower than those of Example 1, but are better than those of Examples 3-1 and 3-4.

[0209] Table 3

[0210]

[0211] The composite material provided by the present application includes a sol body 300 and doping elements doped in the sol body 300, wherein the sol body 300 includes a sol having a core-shell structure, the core-shell structure includes a core 100 and a shell 200, the core 100 is titanium dioxide, the shell 200 is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or, the core 100 is zinc oxide, the shell 200 is silicon dioxide, and the doping elements include at least Mg. The composite material of the present application can improve the self-cleaning, transmittance, friction resistance, salt spray corrosion resistance, blister resistance, alcohol wiping resistance and other properties of functional glass.

[0212] The above description is only an embodiment of the present application and does not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly used in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A composite material, characterized in that: It includes a sol body and doping elements doped in the sol body, wherein the sol body includes a sol with a core-shell structure, the core-shell structure includes an inner core and an outer shell, the inner core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements include at least Ag, K, Na and Li; or the inner core is zinc oxide, the outer shell is silicon dioxide, and the doping elements include at least Mg.

2. The composite material according to claim 1, characterized in that The Ag element is doped into titanium dioxide particles; the K element, the Na element and the Li element are doped into silicon dioxide particles.

3. The composite material according to claim 1, characterized in that The average particle size of the titanium dioxide is 50 to 80 nm; and / or the thickness of the shell is 20 to 50 nm.

4. A method for preparing a composite material, characterized in that: include: Providing a sol body, the sol body comprising a sol having a core-shell structure, the core-shell structure comprising a core and an outer shell, the core being titanium dioxide, and the outer shell being silicon dioxide; adding silver nitrate solution to the main body of the sol to obtain an intermediate solution; Lithium silicate, potassium silicate and sodium silicate are sequentially added into the intermediate solution to form a composite material.

5. The method for preparing a composite material according to claim 4, characterized in that: The step of providing a sol body includes: mixing a base-catalyzed silica sol and an acid-catalyzed silica sol to obtain a first mixed sol; The titanium dioxide sol is added dropwise to the first mixed sol to form the sol main body.

6. The method for preparing a composite material according to claim 5, characterized in that: The mass ratio of the base-catalyzed silica sol to the acid-catalyzed silica sol is (3.8-4.2):(0.8-1.2).

7. The method for preparing a composite material according to claim 5, characterized in that: The method for preparing the acid-catalyzed silica sol comprises: Mixing (C2H5O)4Si and CH3CH2OH to form a first solution; The HNO3 solution is added dropwise into the first solution to react and form the acid-catalyzed silica sol.

8. The method for preparing a composite material according to claim 7, characterized in that: The molar ratio of (C2H5O)4Si, CH3CH2OH, HNO3 and H2O is (0.8~1.2):(3.8~4.2):(0.08~0.12):(5.8~6.2).

9. The method for preparing a composite material according to claim 7 or 8, characterized in that: The step of adding the HNO3 solution dropwise to the first solution to react and form the acid-catalyzed silica sol comprises: Under stirring, the HNO3 solution is added dropwise to the first solution, and the adding time is 30min to 50min; After the dropwise addition, the mixed solution is stirred at 25° C. to 30° C. for 2 h to 2.5 h to form an acid-catalyzed silica sol.

10. The method for preparing a composite material according to claim 5, characterized in that: The preparation method of the base-catalyzed silica sol comprises: Mixing (C2H5O)4Si and CH3CH2OH to form a second solution; The NH3 solution is added dropwise to the second solution to react and form the base-catalyzed silica sol.

11. The method for preparing a composite material according to claim 10, characterized in that: The molar ratio of (C2H5O)4Si, CH3CH2OH, NH3, and H2O is (0.8~1.2):(3.8~4.2):(0.04~0.06):(5.8~6.2).

12. The method for preparing a composite material according to claim 10 or 11, characterized in that: The step of adding the NH3 solution dropwise into the second solution to react and form the base-catalyzed silica sol comprises: Under stirring, adding the NH3 solution dropwise into the second solution, the adding time being 30 min to 50 min; After the dropwise addition, the mixed solution is stirred at 60° C. to 65° C. for 4 h to 5 h to form a base-catalyzed silica sol.

13. The method for preparing a composite material according to claim 5, characterized in that: The preparation method of the titanium dioxide sol comprises: Anhydrous ethanol, water, hydrochloric acid, and tetrabutyl titanate are mixed in a molar ratio of (49.75-50.25):(3.55-4.0):(0.22-0.3):(0.8-1.2) to form a third solution; The third solution is reacted at 20° C. to 35° C. for 2 h to 2.5 h, and aged at 30° C. to 35° C. for 3 d to 4 d to form the titanium dioxide sol.

14. The method for preparing a composite material according to claim 5, characterized in that: The mass ratio of the first mixed sol to the titanium dioxide sol is (19-21): (0.8-1.2).

15. The method for preparing a composite material according to claim 5 or 14, characterized in that: The step of adding the titanium dioxide sol dropwise into the first mixed sol to form the sol main body comprises: Under stirring at 25° C. to 30° C., adding the titanium dioxide sol dropwise to the first mixed sol at a rate of 0.8 ml / min to 1.2 ml / min; After the dropwise addition is completed, stirring is continued for 2 h to 3 h, and aging is carried out at 30° C. to 35° C. for 7 d to 10 d to form the sol main body.

16. The method for preparing a composite material according to claim 4, characterized in that: The concentration of the silver nitrate solution is 0.2-0.4 mol / L.

17. The method for preparing a composite material according to claim 4 or 16, characterized in that: The mass ratio of the silver nitrate solution to the sol main body is (0.8-1.2):(99.2-98.8).

18. The method for preparing a composite material according to claim 4, characterized in that: The mass ratio of the lithium silicate, the potassium silicate and the sodium silicate satisfies the following relationship: Potassium silicate: sodium silicate: lithium silicate = (2.8~3.2): (1.9~2.3): (0.8~1.2).

19. The method for preparing a composite material according to claim 4, characterized in that: The modulus of the potassium silicate is 3.2-3.4; and / or the modulus of the sodium silicate is 3.0-3.3; and / or the modulus of the lithium silicate is 4.8-5.

20. The method for preparing a composite material according to claim 4, characterized in that: The step of sequentially adding lithium silicate, potassium silicate and sodium silicate to the intermediate solution comprises: Adding water and surfactant to the intermediate solution and stirring continuously; Add lithium silicate dropwise and continue stirring until the solution becomes clear and transparent; Add potassium silicate dropwise and continue stirring until the solution becomes clear and transparent; Add sodium silicate dropwise and continue stirring until the solution becomes clear and transparent to obtain a first precursor solution; A stabilizing agent is added to the first precursor solution to obtain a second precursor solution.

21. The method for preparing a composite material according to claim 20, characterized in that: The surfactant includes at least one of fatty alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and fatty alcohol polyoxyethylene ether phosphate.

22. The method for preparing a composite material according to claim 20, characterized in that: The stabilizing aid includes at least one of tetraethylamine perfluorooctane sulfonate, dodecyl alcohol ester, and 2-amino-2-methyl-1-propanol.

23. The method for preparing a composite material according to claim 20, characterized in that: The mass ratio of the intermediate solution, the surfactant, the water, the potassium silicate, the sodium silicate, the lithium silicate and the stabilizing agent is (8-12):(1.0-1.6):(20-26):(56-64):(38-46):(16-24):(0.5-0.9).

24. The method for preparing a composite material according to claim 20, characterized in that: After the step of adding the stabilizing aid, the method further includes: adding a pH regulator to control the pH of the second precursor solution to be 7-9 to form the composite material; the pH regulator includes at least one of sodium bicarbonate solution, sodium tetraborate, and sodium acetate.

25. The method for preparing a composite material according to claim 24, characterized in that: The sodium bicarbonate solution is a sodium bicarbonate solution with a mass concentration of 4%, and the mass ratio of the sodium bicarbonate solution with a mass concentration of 4% to the second precursor solution is (4-6.5):(93.5-96).

26. A functional glass, characterized in that: The invention comprises a glass substrate and a functional film layer arranged on the surface of the glass substrate, wherein the functional film layer comprises a film layer body and doping elements, wherein the film layer body comprises a core-shell structure, wherein the core-shell structure comprises an inner core and an outer shell, wherein the inner core is titanium dioxide, the outer shell is silicon dioxide, and the doping elements comprise at least Ag, K, Na and Li; or wherein the inner core is zinc oxide, the outer shell is silicon dioxide, and the doping elements comprise at least Mg.

27. The functional glass according to claim 26, characterized in that: The film thickness of the functional film layer is 100nm-150nm, and the film thickness uniformity is 5%-10%.

28. The functional glass according to claim 26, characterized in that: The average particle size of the titanium dioxide is 50-80 nm; the thickness of the shell is 20-50 nm.

29. The functional glass according to claim 26, characterized in that: The Ag element is doped into titanium dioxide particles; the K element, the Na element and the Li element are doped into silicon dioxide particles.

30. A method for preparing functional glass, characterized in that: include: Providing a glass substrate; Disposing a composite material on the glass substrate, wherein the composite material comprises the composite material according to any one of claims 1 to 3 or a composite material prepared by the method for preparing a composite material according to any one of claims 4 to 25; The glass substrate provided with the composite material is subjected to heat treatment, and the composite material forms a functional film layer.

31. The method for preparing functional glass according to claim 30, characterized in that: The heat treatment process includes a drying stage and a curing stage. The temperature of the drying stage is 60-85°C and the time is 10-30 minutes. The temperature of the curing stage is 180-200°C and the time is 30 minutes to 60 minutes.

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