Coated glass

Abstract

The utility model provides coated glass, which relates to the technical field of coated glass and comprises a glass substrate, and a first titanium oxide coating layer, a zinc oxide aluminum coating layer and a second titanium oxide coating layer which are sequentially stacked on the surface of the glass substrate, wherein the first titanium oxide coating layer is made of anatase type titanium oxide, and the second titanium oxide coating layer is made of anatase type titanium oxide. The coated glass provided by the utility model can accelerate the fading of methyl blue and degrade pollutants such as formaldehyde under the irradiation of ultraviolet light.

Description

Technical Field

[0001] This utility model relates to the field of coated glass technology, and in particular to a coated glass. Background Technology

[0002] After interior decoration, the formaldehyde concentration caused by building materials and paints has attracted increasing attention. How to degrade indoor formaldehyde, improve indoor air quality, and protect human health has become an important industry issue. Utility Model Content

[0003] The purpose of this invention is to provide a coated glass that expands the new functions of coated glass, enabling the coated glass to accelerate the fading of methyl blue and degrade formaldehyde under ultraviolet light.

[0004] To achieve the above-mentioned utility model objectives, this utility model proposes a coated glass, which includes a glass substrate and a first titanium oxide coating layer, a zinc oxide aluminum coating layer, and a second titanium oxide coating layer sequentially stacked on the surface of the glass substrate; wherein, the material of the first titanium oxide coating layer is anatase titanium oxide, and the material of the second titanium oxide coating layer is anatase titanium oxide.

[0005] In one embodiment, the thickness of the second titanium oxide coating layer is 100–500 nm.

[0006] In one embodiment, the thickness of the zinc oxide aluminum coating layer is 30-80 nm.

[0007] In one embodiment, the thickness of the first titanium dioxide coating layer is 20–40 nm.

[0008] In one embodiment, the thickness of the second titanium oxide coating layer is 200–400 nm.

[0009] In one embodiment, the thickness of the zinc oxide aluminum coating layer is 50–78 nm.

[0010] In one embodiment, the thickness of the first titanium dioxide coating layer is 30–38 nm. Attached Figure Description

[0011] To more clearly illustrate the technical solutions in the embodiments of this utility model or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this utility model. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0012] Figure 1This is a schematic diagram of the structure of an embodiment of the coated glass proposed in this utility model.

[0013] Explanation of icon numbers:

[0014] 100. Coated glass; 1. Glass substrate; 2. First titanium dioxide coating layer; 3. Zinc oxide aluminum coating layer; 4. Second titanium dioxide coating layer.

[0015] The realization of the purpose, functional features and advantages of this utility model will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0016] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the described embodiments are only some embodiments of the present utility model, and not all embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present utility model.

[0017] It should be noted that, unless specific conditions are specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available products. Furthermore, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, solution B, or a solution that simultaneously satisfies A and B. In addition, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. If the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this utility model. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this utility model.

[0018] After interior decoration, the formaldehyde concentration caused by building materials and paints has attracted increasing attention. How to degrade indoor formaldehyde, improve indoor air quality, and protect human health has become an important industry issue.

[0019] With increasing emphasis on environmental protection and health, a trend of formaldehyde removal has quietly emerged in building materials, including formaldehyde-removing paints, curtains, films, equipment, and items. Photocatalytic formaldehyde removal is currently a relatively effective technology, utilizing sunlight to decompose formaldehyde with remarkable results. Glass, as a carrier constantly exposed to sunlight, can effectively degrade indoor formaldehyde levels if photocatalysis is organically combined with it.

[0020] To resolve the above issues, please refer to Figure 1 This utility model proposes a coated glass 100, which includes a glass substrate 1 and a first titanium oxide coating layer 2, a zinc oxide aluminum coating layer 3 and a second titanium oxide coating layer 4 sequentially stacked on the surface of the glass substrate 1; wherein the material of the first titanium oxide coating layer 2 is anatase titanium oxide, and the material of the second titanium oxide coating layer 4 is anatase titanium oxide.

[0021] In the technical solution of this utility model, a sandwich structure is formed by sequentially stacking a first titanium dioxide coating layer 2, a zinc oxide aluminum coating layer 3, and a second titanium dioxide coating layer 4 on a glass substrate 1, which promotes the catalytic purification effect on pollutants in the air environment. The second titanium dioxide coating layer 4 is in contact with air. Under light irradiation, ultraviolet light excites electrons in the valence band of the anatase titanium dioxide semiconductor to jump to the conduction band, forming conduction band electrons. At the same time, corresponding holes are generated in the valence band, forming highly active photogenerated electron-hole pairs on the surface. The excited electron and hole pairs are effectively separated and migrate from the interior to the surface. The photogenerated holes have strong oxidizing properties and can capture electrons from adsorbed substances or solvents on the surface, such as hydroxyl radicals obtained by oxidation of hydroxyl groups and water on the surface. The conduction band electrons have strong reducing properties and can form superoxide radicals from adsorbed oxygen. The hydroxyl radicals and superoxide radicals generated in this process have strong oxidizing properties and can attack the unsaturated bonds in the pollutants adsorbed on the titanium dioxide surface, causing redox reactions, thereby achieving photocatalytic oxidation to remove pollutants. Subsequently, desorption and re-adsorption occur on the titanium dioxide surface. The zinc oxide aluminum oxide coating layer 3 has a band gap of 3.37 eV between its band and conduction band, enabling it to absorb light with wavelengths less than or equal to 370 nanometers. This absorption range is wider than that of titanium dioxide. Therefore, it works synergistically with titanium dioxide to jointly promote the catalytic degradation of pollutants such as formaldehyde by the coated glass 100. Thus, the coated glass 100 provided by this invention can accelerate the fading of methylene blue and degrade pollutants such as formaldehyde under ultraviolet light irradiation.

[0022] Energy bands refer to the range of possible energy values ​​for electrons in a solid material. In solids, due to the interactions between atoms, electrons are no longer confined to a single atom but move throughout the entire crystal. The energy states of electrons change, forming a series of discrete energy bands. The highest energy state in the bands is called the valence band, which represents the highest energy level of electrons in the solid. In the valence band, electrons are bound and do not participate in electrical conduction. The conduction band is an energy band higher than the valence band, where electrons are free and can participate in electrical conduction. When electrons transition from the valence band to the conduction band, they become free electrons and can move freely in the solid, thus forming an electric current. The region between the conduction band and the valence band is called the band gap (or band barrier), and the size of the band gap has a decisive influence on the electrical properties of the material.

[0023] Anatase titanium dioxide has a band gap of 3.2 eV, and according to Planck's relation, it can be calculated that it can only absorb ultraviolet light with wavelengths less than 400 nm. Since ultraviolet light constitutes a relatively small proportion of sunlight, the large band gap limits the absorption efficiency of titanium dioxide. The first step in the photocatalytic process is light absorption, so the size of the band gap directly affects the photocatalytic performance of titanium dioxide.

[0024] However, while a smaller band gap can improve light absorption efficiency, an excessively small band gap can lead to an increased recombination probability of photogenerated electron-hole pairs, which is detrimental to improving photocatalytic quantum efficiency. In titanium dioxide, the 3.2 eV band gap strikes a balance between these two factors, ensuring a certain level of light absorption efficiency while reducing the recombination probability of photogenerated electron-hole pairs. Therefore, titanium dioxide can convert light energy into usable chemical energy, thereby promoting the synthesis or degradation of compounds.

[0025] Ultraviolet light excites electrons in the inner valence band of titanium dioxide semiconductors to transition to the conduction band, forming conduction band electrons (ep). - At the same time, corresponding holes (h) are generated in the valence band. + The photogenerated electron-hole pairs are formed on the surface, exhibiting high reactivity. After excitation, the electrons and holes effectively separate and migrate from the interior to the surface. The photogenerated holes possess strong oxidizing properties, capable of capturing electrons from adsorbed substances or solvents on the surface, such as hydroxyl groups (OH groups). - ) and water (H2O) are oxidized to hydroxyl radicals (OH) - The conduction band electrons have strong reducing properties, which can form superoxide radicals (-O2) from adsorbed oxygen. The hydroxyl radicals and superoxide radicals generated in this process have strong oxidizing properties, which can attack the unsaturated bonds of pollutants adsorbed on the surface of titanium dioxide, causing redox reactions, thereby achieving photocatalytic oxidation to remove pollutants. Subsequently, desorption and re-adsorption occur on the surface of titanium dioxide.

[0026] In some embodiments, the thickness of the second titanium dioxide coating layer 4 is 100–500 nm. Specifically, the thickness of the second titanium dioxide coating layer 4 can be any value between 100 and 500 nm, such as 100 nm, 117 nm, 246.4 nm, or 389.4 nm. The thicker the titanium dioxide, the larger the anatase crystals and the better the photocatalytic effect. However, excessively thick titanium dioxide coating layers are difficult to process. Therefore, when the thickness of the second titanium dioxide coating layer 4 is 100–500 nm, a better photocatalytic effect can be obtained. More preferably, the thickness of the second titanium dioxide coating layer 4 is 200–400 nm.

[0027] Doping the zinc-aluminum oxide coating layer 3 between the first titanium dioxide coating layer 2 and the second titanium dioxide coating layer 4 can improve the photocatalytic activity and enhance the color of the film. It should be noted that the zinc-aluminum oxide coating layer 3 is composed of zinc oxide and aluminum oxide. The zinc-aluminum oxide coating layer 3 can be prepared using a zinc-aluminum alloy target via magnetron sputtering. The zinc-aluminum target is oxidized in an oxygen environment to generate a mixture of zinc oxide and aluminum oxide, resulting in the zinc-aluminum oxide coating layer 3. The mass fraction of aluminum in the zinc-aluminum target is 1-10%.

[0028] The first titanium dioxide coating layer 2 and the second titanium dioxide coating layer 4 are high-refractive-index titanium dioxide coating layers. The refractive index of the titanium dioxide aluminum coating layer satisfies the following: when incident light with a wavelength of 400-800 nm is incident, the real part of the refractive index n is 2.3-2.5, and the extinction coefficient k is 55-5*10. -5 .

[0029] The refractive index is the ratio of the speed of light in a vacuum to the speed of light in the medium. It reflects the ability of light to refract in the medium. The higher the refractive index of a material, the stronger its ability to refract incident light.

[0030] The zinc oxide aluminum coating layer 3 is a medium refractive index zinc oxide aluminum coating layer 3. The refractive index of the zinc oxide aluminum coating layer 3 satisfies the following: when incident light with a wavelength of 400-800 nm is incident, the real part n of the refractive index of the zinc oxide layer is 2.3-2.5, and the extinction coefficient k is 10-1*10. -5 .

[0031] In some embodiments, the thickness of the zinc-aluminum oxide coating layer 3 is 30–80 nm. Specifically, the thickness of the second titanium oxide coating layer 4 can be any value between 20 and 40 nm, such as 30 nm, 35 nm, 50 nm, 77.6 nm, or 80 nm. The zinc-aluminum oxide coating layer 3 can absorb ultraviolet light and some violet light, and in conjunction with the second titanium oxide coating layer 4, utilizes natural light with a wider wavelength range to obtain a better photocatalytic effect. The zinc-aluminum oxide coating layer 3 with the above-mentioned thickness not only has a better photocatalytic effect but also a better appearance. More preferably, the thickness of the zinc-aluminum oxide coating layer 3 is 50–78 nm.

[0032] In some embodiments, the thickness of the first titanium dioxide coating layer 2 is 20–40 nm. Specifically, the thickness of the first titanium dioxide coating layer 2 can be any value between 20 and 40 nm, such as 20 nm, 25 nm, 30 nm, 37.7 nm, or 40 nm. When the thickness of the first titanium dioxide coating layer 2 is 20–40 nm, a better photocatalytic effect can be obtained. More preferably, the thickness of the first titanium dioxide coating layer is 30–38 nm.

[0033] Therefore, the coated glass 100 provided by this utility model has the following effects:

[0034] 1. The coated glass 100 provided by this utility model can be prepared by using conventional target materials and magnetron sputtering combined with tempering process, and the process is controllable.

[0035] 2. The film system structure adopted in this invention is reasonable, possessing excellent adhesion while producing products with good optical parameters. The film structure is stable, free from defects such as cracking, oxidation, and delamination, and is resistant to high temperature and humidity, with strong processability.

[0036] 3. The coated glass 100 provided by this utility model can accelerate the fading of methyl blue and degrade formaldehyde under ultraviolet light.

[0037] This utility model also provides a method for preparing the above-mentioned coated glass 100:

[0038] Using metallic titanium as the target material, the first titanium oxide coating layer 2 is prepared on a glass substrate 1 by magnetron sputtering in an oxidizing gas environment;

[0039] Using zinc-aluminum alloy as the target material, the zinc-aluminum oxide coating layer 3 is prepared by magnetron sputtering on the first titanium oxide coating layer 2 in an oxidizing gas environment;

[0040] Using metallic titanium as the target material, the second titanium oxide coating layer 4 is prepared on the zinc oxide aluminum coating layer 3 by magnetron sputtering in an oxidizing gas environment;

[0041] The glass substrate 1 with the second titanium oxide coating layer 4 is oxidized in air and then annealed at 600℃~700℃ for 12~14min to obtain coated glass 100.

[0042] When the first titanium dioxide coating layer 2 is prepared on the glass substrate 1 by magnetron sputtering, the main process parameters of magnetron sputtering are as follows: the working gas is argon and oxygen, and the flow rate ratio of argon to oxygen is 1200 sccm: 200 sccm; the sputtering power is 20-50 kW; and the sputtering pressure is (3.5-4) x 10⁻⁶. -3 mbar.

[0043] When preparing the second titanium oxide coating layer 4 on the zinc oxide aluminum coating layer 3 by magnetron sputtering, the main process parameters of magnetron sputtering are as follows: the working gas is argon and oxygen, and the flow rate ratio of argon to oxygen is 600 sccm:800 sccm; the sputtering power is 20-50 kW; and the sputtering pressure is (3.5-4) x 10⁻⁶. -3 mbar.

[0044] When preparing the second titanium oxide coating layer 4 on the zinc oxide aluminum coating layer 3 by magnetron sputtering, the main process parameters of magnetron sputtering are as follows: the working gas is argon and oxygen, and the flow rate ratio of argon to oxygen is 1200 sccm: 200 sccm; the sputtering power is 20-50 kW; and the sputtering pressure is (3.5-4) x 10⁻⁶. -3 mbar.

[0045] Magnetron sputtering offers advantages in controlling process conditions, thus facilitating the control of film structure and properties. It also enables the deposition of large-area, uniform, high-quality TiO2 and zinc oxide films. During magnetron sputtering, the working gases, argon and oxygen, must have a purity greater than 99.99%; the sputtering pressure needs to be stable, the molecular mean free path relatively stable, and the target sputtering stable, resulting in a denser film and thus better performance.

[0046] The growth process of titanium dioxide thin films is roughly as follows: gaseous particles collide with the substrate and are adsorbed onto the substrate surface. Particles with a certain energy migrate on the film surface, reaching suitable lattice sites for nucleation and growth. Initially, island-like structures are formed, and then these islands connect to create a continuous thin film material. The deposited titanium dioxide is amorphous. Annealing can reduce or remove internal stress in the material, causing the titanium dioxide to exhibit a specific crystal form. If the annealing temperature is too low, anatase titanium dioxide cannot be obtained; if the annealing temperature is too high, rutile titanium dioxide will form. Therefore, an annealing temperature of 600℃~700℃ can yield a high-quality anatase titanium dioxide coating.

[0047] The coated glass 100 prepared by the above method can have the above refractive index and light absorption rate, the film structure is stable and will not have defects such as cracking, oxidation, or delamination. It is resistant to high temperature and high humidity, has strong processability, not only has good appearance performance, but can also accelerate the fading of methyl blue and degrade formaldehyde under ultraviolet light.

[0048] The technical solution of this utility model will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain this utility model and are not intended to limit this utility model.

[0049] Example 1

[0050] A coated glass is provided, the coated glass comprising a 6mm glass substrate and a 25nm first titanium dioxide coating layer, a 35nm zinc-aluminum oxide coating layer and a 117nm second titanium dioxide coating layer sequentially formed on the surface of the glass substrate.

[0051] Example 2

[0052] A coated glass is provided, the coated glass comprising a 6mm glass substrate and a 30nm first titanium dioxide coating layer, a 50nm zinc-aluminum oxide coating layer and a 246.4nm second titanium dioxide coating layer sequentially formed on the surface of the glass substrate.

[0053] Example 3

[0054] A coated glass is provided, the coated glass comprising a 6 mm glass substrate and a 37.7 nm first titanium oxide coating layer, a 77.6 nm zinc oxide aluminum coating layer and a 389.4 nm second titanium oxide coating layer sequentially formed on the surface of the glass substrate.

[0055] Performance testing

[0056] 1. Lab tests and color observations were performed on the coated glass provided in Examples 1 to 3 from three angles: front, side, and through the glass. The results are shown in Tables 1, 2, and 3. Table 1 shows the test results of the coated glass provided in Example 1; Table 2 shows the test results of the coated glass provided in Example 2; and Table 3 shows the test results of the coated glass provided in Example 3.

[0057] Table 1. Test results of the coated glass provided in Example 1

[0058]

[0059]

[0060] Table 2 Test results of the coated glass provided in Example 2

[0061] Observation angle L a b color front 49.59 0.19 -35.16 blue side 53.98 16.52 -24.28 Purple Through 78.44 -2.47 22.81 yellow

[0062] Table 3 shows the test results of the coated glass provided in Example 3.

[0063] Observation angle L a b color front 64.17 17.99 0.17 red side 66.35 -9.92 12.91 grass green Through 62.82 -16.18 1.94 green

[0064] As can be seen from Tables 1-3, the coated glass provided in Examples 1-3 has bright and vivid colors when viewed from the front, side and through the glass, and has a good decorative effect.

[0065] 2. The coated glasses obtained in Examples 1-3 were subjected to photocatalytic degradation of methylene blue solution.

[0066] The coated glass provided in Examples 1-3 was cut into small pieces and placed in containers containing methylene blue solution of the same concentration. The containers were then left to stand in sunlight for 72 hours. Meanwhile, a control group consisting only of methylene blue solution of the same concentration was also left to stand in sunlight for 72 hours. The results are as follows:

[0067] Control group: The methylene blue solution remained essentially unchanged in color;

[0068] Example 1: The blue color in the solution lightened;

[0069] Example 2: The blue color in the solution lightened;

[0070] Example 3: The solution changed from blue to white.

[0071] As can be seen from the above, the control group container contained only methylene blue solution, and after being placed in sunlight, the methylene blue solution remained essentially unchanged in color. However, when the container contained the coated glass provided in Examples 1-3 in addition to the methylene blue solution, the methylene blue solution exhibited varying degrees of color change after being placed in sunlight. Therefore, the coated glass provided by this invention can catalyze the degradation of methylene blue under light conditions.

[0072] When the container contains the coated glass provided in Example 3 in addition to the methylene blue solution, the solution changes from blue to white after being placed in sunlight, indicating that the methylene blue in the solution is basically completely degraded. Therefore, the coated glass provided in Example 3 has the best effect on catalytic degradation of methylene blue under light conditions. When the container contains the coated glass provided in Example 1 or Example 2 in addition to the methylene blue solution, the blue color of the solution becomes lighter after being placed in sunlight, indicating that the methylene blue in the solution is partially degraded.

[0073] The solution containing the coated glass provided in Example 2 was lighter in color than the solution containing the coated glass provided in Example 1 after placement, indicating that the methylene blue in the solution faded more. Therefore, compared with Example 1, the coated glass provided in Example 2 has a thicker coating layer and a better effect on catalytic degradation of methylene blue under light conditions.

[0074] The above are merely preferred embodiments of this utility model and do not limit the patent scope of this utility model. Various modifications and variations can be made to this utility model by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this utility model should be included within the patent protection scope of this utility model.

Claims

1. A coated glass, characterized in that, The coated glass includes a glass substrate and a first titanium oxide coating layer, a zinc aluminum oxide coating layer and a second titanium oxide coating layer sequentially stacked on the surface of the glass substrate. Wherein, the material of the first titanium oxide coating layer is anatase titanium oxide, and the material of the second titanium oxide coating layer is anatase titanium oxide; The thickness of the second titanium dioxide coating layer is 100~500nm; The thickness of the zinc oxide aluminum coating layer is 30~80nm; The thickness of the first titanium dioxide coating layer is 20~40nm.

2. The coated glass as described in claim 1, characterized in that, The thickness of the second titanium dioxide coating layer is 200~400nm.

3. The coated glass as described in claim 1, characterized in that, The thickness of the zinc oxide aluminum coating layer is 50~78nm.

4. The coated glass as described in claim 1, characterized in that, The thickness of the first titanium oxide coating layer is 30~38nm.

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