Modified tungsten bronze, preparation method thereof, slurry composition, coating and application

Abstract

The invention discloses modified tungsten bronze and a preparation method thereof, a slurry composition, a coating and application. The chemical formula of the modified tungsten bronze is (AxMyW1-yO3). Z (TiO2), A is selected from one or more of Na, K, Rb and Cs, and M is selected from one or more of Hf, Mo, Ta and Nb; 0.25 < = x < = 0.4, 0 < y < 0.1, and 0 < z < = 0.04. When the modified tungsten bronze provided by the invention is applied to a coating, the modified tungsten bronze has excellent infrared barrier property and relatively low haze; and further, under the aging conditions of damp, high temperature and strong ultraviolet rays, the optical stability is excellent, and the service life is long.

Description

Technical Field

[0001] The present invention relates to a modified tungsten bronze, a preparation method thereof, a slurry composition, a coating, and an application thereof. Background Art

[0002] Tungsten bronze is a non-stoichiometric compound containing tungsten, which can be expressed as M x WO 3 , where M is usually an alkali metal, an alkaline earth metal, an ammonium ion, a rare earth metal ion, etc., and x ranges from 0 to 1. The crystal structure of tungsten bronze is similar to that of bronze in minerals, which endows them with unique physical and chemical properties and makes them attract much attention due to their excellent electrical and optical properties.

[0003] By introducing a third element or increasing oxygen vacancies in the lattice, free electrons can be injected into tungsten bronze, thereby enhancing its conductivity and improving its absorption ability for near-infrared (NIR) light. The modified tungsten bronze not only has excellent NIR shielding performance but also can maintain a high visible light transmittance, making it an ideal choice for energy-saving windows and other intelligent building technologies.

[0004] However, although the modified tungsten bronze thin film can work stably under conventional environments, its optical stability will be affected when facing strong ultraviolet rays or humid and high-temperature conditions, resulting in a decrease in NIR shielding performance. This is because the oxidation effect affects the absorption of small polarons and the local surface plasmon resonance (LSPR) effect inside the material, thereby shortening the service life of the material.

[0005] The stability problem greatly restricts the commercial application of tungsten bronze materials. Therefore, developing a modified tungsten bronze material with stability and durability is the key to expanding the application scope and technical potential of tungsten bronze materials. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects in the prior art that under strong ultraviolet rays, humid and high-temperature conditions, the optical stability of tungsten bronze materials is reduced, resulting in a decrease in near-infrared shielding performance and a short service life, and to provide a modified tungsten bronze, a preparation method thereof, a slurry composition, a coating, and an application thereof. The modified tungsten bronze provided by the present invention has excellent infrared barrier performance and low haze when applied to a coating; further, it has excellent optical stability and a long service life under the aging conditions of humid high temperature and strong ultraviolet rays.

[0007] The present invention solves the above technical problem through the following technical solutions:

[0008] The present invention provides a modified tungsten bronze, and the chemical formula of the modified tungsten bronze is (A x M y W 1-y O3 )·z(TiO 2 ), wherein A is selected from one or more of Na, K, Rb, and Cs, and M is selected from one or more of Hf, Mo, Ta, and Nb; and 0.25 ≤ x ≤ 0.4, 0 < y < 0.1, 0 < z ≤ 0.04.

[0009] In the present invention, A can be Cs or Na.

[0010] In the present invention, M can be Hf.

[0011] In the present invention, x can be 0.30 - 0.38, such as 0.33, 0.35, or 0.37.

[0012] In the present invention, y can be 0.04 - 0.09, such as 0.05, 0.07, or 0.08.

[0013] In the present invention, z can be 0.01 - 0.04, such as 0.01, 0.03, or 0.04.

[0014] In the present invention, preferably, in the modified tungsten bronze, TiO 2 nanoparticles are uniformly dispersed in the lattice structure of tungsten bronze or form a composite structure with tungsten bronze. It is not just the physically doped on the surface or in the pores obtained by traditional methods.

[0015] In the present invention, the primary particle size of the modified tungsten bronze can be 20 - 30 nm.

[0016] The present invention also provides a method for preparing a modified tungsten bronze, which includes the following steps: mixing a tungsten salt, an M metal salt, and a complex, and then mixing with an A metal salt to obtain a mixed solution; adding TiO2 to the mixed solution to obtain a modified tungsten bronze precursor; and obtaining the modified tungsten bronze after hydrothermal reaction and calcination of the modified tungsten bronze precursor;

[0017] wherein M in the M metal salt is selected from one or more of Hf, Mo, Ta, and Nb; A in the A metal salt is selected from one or more of Na, K, Rb, and Cs;

[0018] the molar ratio of M in the M metal salt to the metal W in the tungsten salt is (0 - 0.10):1; the molar sum of the metal W in the tungsten salt and M in the M metal salt and the molar ratio of A in the A metal salt is 1:(0.25 - 0.4); the TiO 2 accounts for the mass concentration of the modified tungsten bronze of 0 - 0.4% and is not 0%.

[0019] In the present invention, the tungsten salt can be selected from WCl 6 and / or Na2 WO 3 。

[0020] In the present invention, the M metal salt may be selected from HfCl 4 , MoCl 6 , TaCl 5 and NbCl 5 one or more of them, such as HfCl 4 . The selected M metal salt in the present invention can interact with the ions or lattice in tungsten bronze and enter the lattice interior to achieve doping, thereby reducing the photochromic phenomenon of tungsten bronze under ultraviolet light irradiation.

[0021] In the present invention, the molar ratio of M in the M metal salt to the metal W in the tungsten salt may be (0.04 - 0.09):1, such as 0.05:1, 0.08:1 or 0.09:1.

[0022] In the present invention, the complex may be a weak acid and / or a saccharide. The weak acid is preferably citric acid monohydrate and / or oxalic acid. The saccharide is preferably glucose and / or sucrose. The preferred complex in the present invention can not only form a complex with tungsten ions to promote the dissolution and dispersion of the tungsten salt, but also play a certain reduction role during the reaction to assist in controlling the valence state of tungsten.

[0023] In the present invention, the molar ratio of the complex to the metal W in the tungsten salt may be (0.7 - 1.3):1, preferably (0.8 - 1.1):1, such as 0.95:1, 1:1 or 1.05:1.

[0024] In the present invention, the A metal salt may be selected from Cs 2 CO 3 , CsOH, Na 2 CO 3 and NaOH one or more of them, preferably Cs 2 CO 3 and / or CsOH. In the present invention, mixing the M metal salt with the tungsten salt before the A metal salt can ensure that the metal M can be doped into the material.

[0025] In the present invention, the molar ratio of the total of M in the M metal salt and W in the tungsten salt to A in the A metal salt may be 1:(0.30 - 0.38), such as 1:0.33, 1:0.35 or 0.37.

[0026] In the present invention, the mixed solution may further include a solvent. The solvent is preferably deionized water and / or absolute ethanol.

[0027] In the present invention, the TiO 2The particle size of 2 can be 10 - 100 nm, preferably 10 - 50 nm. The preferred TiO

[0028] in the present invention 2 is added dropwise to the mixed solution in the form of a suspension. The dropping speed is preferably 0.5 - 2 mL / min.

[0029] In the present invention, if TiO 2 is added in advance, it may affect the nucleation and growth process of tungsten bronze, resulting in changes in properties such as the crystallinity and particle size distribution of the product, and may even reduce key performance indicators such as the visible light transmittance and near-infrared shielding performance of tungsten bronze itself. A further preferred dropping speed can promote the full mixing of the TiO 2 suspension and the mixed solution, avoiding the influence of too high or too low local concentration on the reaction effect.

[0030] Among them, the mass fraction of the suspension can be 3 - 8%, such as 5%.

[0031] Among them, preferably, the suspension is prepared by dispersing TiO 2 in water. The dispersion temperature is preferably 70 - 90 °C, such as 80 °C.

[0032] In the present invention, the mass concentration of TiO 2 in the modified tungsten bronze can be 0.1 - 0.4%, such as 0.1%, 0.35% or 0.4%.

[0033] In the present invention, in the modified tungsten bronze precursor, the mass concentration ratio of the materials can be 40 - 60%, such as 50%. %, refers to the mass percentage of the total mass of tungsten salt, M metal salt, complex, A metal salt and TiO 2 in the modified tungsten bronze precursor.

[0034] In the present invention, the temperature of the hydrothermal reaction can be 230 - 260 °C, such as 230 °C.

[0035] In the present invention, the time of the hydrothermal reaction can be 12 - 48 h, such as 24 h.

[0036] In the present invention, after the hydrothermal reaction and before calcination, an operation of drying may also be included. The drying is preferably spray drying. The inlet temperature of the spray drying is preferably 180 - 220 °C, such as 200 °C. The outlet temperature of the spray drying is preferably 80 - 100 °C, such as 90 °C. The feeding speed of the spray drying is preferably 10 - 20 mL / min, such as 15 mL / min.

[0037] In the present invention, the calcination temperature can be 500 - 600 °C, such as 500 °C.

[0038] In the present invention, the calcination time can be 4 - 8 h, such as 6 h.

[0039] In the present invention, preferably, the calcination is carried out in an inert atmosphere. The inert atmosphere is preferably argon or nitrogen.

[0040] The present invention also provides a modified tungsten bronze, which is prepared by the above preparation method.

[0041] In the present invention, the primary particle size of the modified tungsten bronze can be 20 - 30 nm.

[0042] The present invention also provides a slurry composition, which comprises the above modified tungsten bronze and an auxiliary agent.

[0043] In the present invention, the content of the modified tungsten bronze can be 10 - 40%, such as 30%.

[0044] In the present invention, the pH value of the slurry composition can be 5 - 6.

[0045] In the present invention, the primary particle size of the slurry composition can be 20 - 30 nm.

[0046] In the present invention, the auxiliary agent can be selected from one or more of a dispersant, an ultraviolet absorber, a photo-oxidation stabilizer, and a pH value regulator.

[0047] Among them, the dispersant can be selected from one or more of BYK2070, BYK7410, and TEGO245.

[0048] Among them, the content of the dispersant can be 1 - 10%, such as 10%.

[0049] Among them, the ultraviolet absorber can be selected from UV-531.

[0050] Among them, the content of the ultraviolet absorber can be 0.1 - 0.5%, such as 0.1%.

[0051] Among them, the photo-oxidation stabilizer can be selected from siloxane photo-oxidation stabilizers, preferably benzotriazole siloxane photo-oxidation stabilizers.

[0052] Among them, the content of the photo-oxidation stabilizer can be 0.1 - 0.5%, such as 0.1%.

[0053] Among them, the pH value regulator can be selected from triethanolamine. When triethanolamine is used as the pH value regulator, it can further avoid the oxidation of the valence state of W and improve the product quality.

[0054] Among them, the content of the pH regulator can be 1-5%, such as 2%.

[0055] In the present invention, the slurry composition may further include an organic solvent.

[0056] Among them, the organic solvent can be one or more of methanol, ethanol, isopropanol, tert-butanol, pentane, hexane, octane, benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, acetone, methyl butanone, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, acetonitrile, pyridine, dichloromethane, chlorobenzene, dichlorobenzene, ether, and petroleum ether, such as xylene.

[0057] Among them, the content of the organic solvent can be 54-83.8%, such as 57.8%.

[0058] The above percentages are all mass percentages of each material in the slurry.

[0059] The present invention also provides a coating, which comprises the above modified tungsten bronze or the above slurry composition.

[0060] The present invention also provides an application of the above modified tungsten bronze, the above slurry composition, or the above coating in the field of heat insulation materials.

[0061] On the basis of conforming to common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0062] The reagents and raw materials used in the present invention are all commercially available.

[0063] The positive and progressive effects of the present invention are as follows:

[0064] The modified tungsten bronze provided by the present invention has excellent infrared barrier performance and low haze when applied to a coating; further, it has excellent optical stability and a long service life under the aging conditions of high humidity and high temperature and strong ultraviolet rays. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 XRD pattern of the modified tungsten bronze prepared in Example 1.

[0066] Figure 2 SEM image of the modified tungsten bronze prepared in Example 1.

[0067] Figure 3 Particle size distribution diagram of the heat insulation slurry prepared in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0068] The present invention will be further illustrated by way of examples below, but the present invention is not limited to the scope of the examples described herein.

[0069] Example 1

[0070] (1)Prepare modified tungsten bronze (Cs 0.33 M 0.05 W 0.95 O 3 )·0.01(TiO 2 )

[0071] 1) Dissolve tungsten hexachloride WCl 6 in deionized water. After complete dissolution, add citric acid monohydrate C 6 H 8 O 7 •H 2 O and stir to dissolve to obtain a mixed solution A; where n(C 6 H 8 O 7 •H 2 O):n(W)=1:1.

[0072] 2) Dissolve hafnium tetrachloride HfCl 4 in absolute ethanol. After complete dissolution, add it to the mixed solution A and stir evenly to obtain a mixed solution B; where n(Hf):n(W)=0.05:1.

[0073] 3) Dissolve cesium carbonate Cs 2 CO 3 in deionized water. After complete dissolution, add it to the mixed solution B and stir thoroughly in a glass reaction kettle to obtain a mixed liquid, which is a pale yellow slurry; where n(Hf + W):n(Cs)=1:0.33.

[0074] 4) Disperse nano-titanium dioxide TiO 2 with a particle size of 10 - 50 nm in deionized water and stir at 80 °C to obtain a suspension with a mass fraction of 5%; under stirring, add the nano-titanium dioxide suspension dropwise to the mixed liquid at a rate of 0.5 - 2 mL / min to prepare a modified tungsten bronze precursor solution; where the mass of TiO 2 accounts for 0.1% of the product modified tungsten bronze.

[0075] In the modified tungsten bronze precursor solution, tungsten hexachloride WCl 6 , hafnium tetrachloride HfCl 4 , citric acid monohydrate C 6 H 8 O 7 •H 2 O, cesium carbonate Cs 2 CO 3 and TiO 2The total concentration is 50%, where "%" refers to the mass percentage of the total material in the modified tungsten bronze precursor solution.

[0076] 5) Heat the above-mentioned modified tungsten bronze precursor solution at 230 °C for 24 h. After the reaction is completed, cool it to room temperature to obtain a light blue solution; spray-dry the light blue solution to obtain a light blue powder; among them, the inlet air temperature for spray drying is 200 °C, the outlet air temperature is 90 °C, and the feeding rate is 15 mL / min. Place the light blue powder in a tubular furnace and calcine it at 500 °C for 6 h under an argon atmosphere.

[0077] The prepared modified tungsten bronze is in powder form, and its primary particle size is 20 - 30 nm.

[0078] (2) Preparation of heat-insulating slurry

[0079] Add 57.8% xylene to 10% TEGO245. After dissolution, add 0.1% ultraviolet absorber UV-531, 0.1% benzotriazole-based siloxane-based photo-oxidation stabilizer, and 2% triethanolamine. After dissolution, add 30% modified tungsten bronze powder, where "%" is the mass percentage; the pH value of the heat-insulating slurry is 5 - 6.

[0080] (3)Preparation of heat-insulating coating

[0081] Mix and stir according to the ratio of heat-insulating slurry: polyurethane: xylene = 1:3:3 to obtain a coating solution. Scrape the coating solution on a glass plate (50 mm × 50 mm) and dry it in an oven at 130 °C for 5 min to obtain a glass plate with a coating.

[0082] Example 2

[0083] (1)Preparation of modified tungsten bronze (Cs 0.35 M 0.07 W 0.93 O 3 )·0.03(TiO 2 )

[0084] 1) Dissolve tungsten hexachloride WCl 6 in deionized water. After complete dissolution, add citric acid monohydrate C 6 H 8 O 7 •H 2 O, and stir to dissolve to obtain a mixed solution A; among them, n(C 6 H 8 O 7 •H 2 O):n(W)=0.95:1.

[0085] 2) Hafnium tetrachloride HfCl 4Dissolve in anhydrous ethanol, add to mixed solution A after complete dissolution, and stir evenly to obtain mixed solution B; wherein n(Hf):n(W)=0.08:1.

[0086] 3) Cesium carbonate Cs 2 CO 3 Dissolve in deionized water, add to mixed solution B after complete dissolution, stir thoroughly in a glass reactor to obtain a mixed solution, which is a light yellow slurry; wherein n(Hf+W):n(A)=1:0.35.

[0087] 4) Nano titanium dioxide TiO with a particle size of 10-50nm 2 Dispersed in deionized water, stirred at 80°C to obtain a suspension with a mass fraction of 5%; under stirring, the nano titanium dioxide suspension was added dropwise to the mixed solution at a rate of 0.5-2 mL / min to obtain a modified tungsten bronze precursor solution; wherein, TiO 2 The mass of the modified tungsten bronze accounts for 0.35% of the product.

[0088] In the modified tungsten bronze precursor solution, tungsten hexachloride WCl 6 、Hafnium tetrachloride HfCl 4 , citric acid monohydrate C 6 H 8 O 7 •H 2 O, Cesium carbonate Cs 2 CO 3 and TiO 2 The total concentration is 50%, and % refers to the mass percentage of the total mass of the material in the modified tungsten bronze precursor solution.

[0089] 5) The modified tungsten bronze precursor solution was heated at 230°C for 24 hours. After the reaction was completed, it was cooled to room temperature to obtain a light blue solution. The light blue solution was spray dried to obtain a light blue powder. The inlet air temperature of the spray drying was 200°C, the outlet air temperature was 90°C, and the feed rate was 15mL / min. The light blue powder was placed in a tubular furnace and calcined at 500°C for 6 hours in an argon atmosphere.

[0090] The prepared modified tungsten bronze is a powder with a primary particle size of 20-30nm.

[0091] Step (2) and step (3) are the same as those in Example 1.

[0092] Example 3

[0093] (1) Preparation of modified tungsten bronze (Cs 0.37 M 0.08 W 0.92 O 3)·0.04(TiO 2 )

[0094] 1) Dissolve tungsten hexachloride WCl 6 in deionized water. After complete dissolution, add citric acid monohydrate C 6 H 8 O 7 •H 2 O and stir to dissolve to obtain a mixed solution A; wherein, n(C 6 H 8 O 7 •H 2 O):n(W)=1.05:1.

[0095] 2) Dissolve hafnium tetrachloride HfCl 4 in absolute ethanol. After complete dissolution, add it to the mixed solution A and stir evenly to obtain a mixed solution B; wherein, n(Hf):n(W)=0.09:1.

[0096] 3) Dissolve cesium carbonate Cs 2 CO 3 in deionized water. After complete dissolution, add it to the mixed solution B and stir thoroughly in a glass reaction kettle to obtain a mixed liquid, which is a light yellow slurry; wherein, n(Hf + W):n(A)=1:0.37.

[0097] 4) Disperse nano-titanium dioxide TiO 2 with a particle size of 10 - 50 nm in deionized water and stir at 80 °C to obtain a suspension with a mass fraction of 5%; under stirring, add the nano-titanium dioxide suspension dropwise to the mixed liquid at a rate of 0.5 - 2 mL / min to prepare a modified tungsten bronze precursor solution; wherein, the mass of TiO 2 accounts for 0.4% of the product modified tungsten bronze.

[0098] In the modified tungsten bronze precursor solution, the total concentration of tungsten hexachloride WCl 6 , hafnium tetrachloride HfCl 4 , citric acid monohydrate C 6 H 8 O 7 •H 2 O, cesium carbonate Cs 2 CO 3 and TiO 2 is 50%, and % refers to the mass percentage of the total material in the modified tungsten bronze precursor solution.

[0099] 5) The modified tungsten bronze precursor solution was heated at 230°C for 24 hours. After the reaction was completed, it was cooled to room temperature to obtain a light blue solution. The light blue solution was spray dried to obtain a light blue powder. The inlet air temperature of the spray drying was 200°C, the outlet air temperature was 90°C, and the feed rate was 15mL / min. The light blue powder was placed in a tubular furnace and calcined at 500°C for 6 hours in an argon atmosphere.

[0100] The prepared modified tungsten bronze is a powder with a primary particle size of 20-30nm.

[0101] Step (2) and step (3) are the same as those in Example 1.

[0102] Comparative Example 1

[0103] (1) Preparation of modified tungsten bronze (Cs 0.33 M 0.11 W 0.89 O 3 )·0.02(TiO 2 )

[0104] 1) Tungsten hexachloride WCl 6 Dissolve in deionized water and add citric acid monohydrate C after it is completely dissolved 6 H 8 O 7 •H 2 O, stirring and dissolving to obtain a mixed solution A; wherein n(C 6 H 8 O 7 •H 2 O):n(W)=0.7:1.

[0105] 2) Hafnium tetrachloride HfCl 4 Dissolve in anhydrous ethanol, add to mixed solution A after complete dissolution, and stir evenly to obtain mixed solution B; wherein n(Hf):n(W)=0.12:1.

[0106] 3) Cesium carbonate Cs 2 CO 3 Dissolve in deionized water, add to mixed solution B after complete dissolution, stir thoroughly in a glass reactor to obtain a mixed solution, which is a light yellow slurry; wherein n(Hf+W):n(A)=1:0.33.

[0107] 4) Nano titanium dioxide TiO with a particle size of 10-50nm 2 Dispersed in deionized water, stirred at 80°C to obtain a suspension with a mass fraction of 5%; under stirring, the nano titanium dioxide suspension was added dropwise to the mixed solution at a rate of 0.5-2 mL / min to obtain a modified tungsten bronze precursor solution; wherein, TiO2 The mass of [substance] accounts for 0.2% of the product modified tungsten bronze.

[0108] In the modified tungsten bronze precursor solution, tungsten hexachloride WCl 6 , hafnium tetrachloride HfCl 4 , citric acid monohydrate C 6 H 8 O 7 •H 2 O, cesium carbonate Cs 2 CO 3 and TiO 2 The total concentration is 50%, where % refers to the mass percentage of the total material in the modified tungsten bronze precursor solution.

[0109] 5) Heat the above-mentioned modified tungsten bronze precursor solution at 230 °C for 24 h. After the reaction is completed, cool it to room temperature to obtain a light blue solution; spray-dry the light blue solution to obtain a light blue powder; among them, the inlet air temperature of the spray drying is 200 °C, the outlet air temperature is 90 °C, and the feeding speed is 15 mL / min. Place the light blue powder in a tube furnace and calcine it at 500 °C for 6 h under an argon atmosphere.

[0110] The prepared modified tungsten bronze is a powder with a primary particle size of 20 - 30 nm.

[0111] Steps (2) and (3) are the same as those in Example 1.

[0112] Comparative Example 2

[0113] (1) Prepare modified tungsten bronze (Cs 0.25 M 0.04 W 0.96 O 3 )·0.05(TiO 2 )

[0114] 1) Dissolve tungsten hexachloride WCl 6 in deionized water. After complete dissolution, add citric acid monohydrate C 6 H 8 O 7 •H 2 O and stir to dissolve to obtain a mixed solution A; among them, n(C 6 H 8 O 7 •H 2 O):n(W)=1.3:1.

[0115] 2) Dissolve hafnium tetrachloride HfCl 4 in absolute ethanol. After complete dissolution, add it to the mixed solution A and stir evenly to obtain a mixed solution B; among them, n(Hf):n(W)=0.04:1.

[0116] 3) Dissolve cesium carbonate Cs 2 CO 3 in deionized water. After complete dissolution, add it to the mixed solution B and stir thoroughly in a glass reaction kettle to obtain a mixed solution, which is a pale yellow slurry; wherein, n(Hf + W):n(A) = 1:0.25.

[0117] 4) Disperse nano-titanium dioxide TiO with a particle size of 10 - 50 nm 2 in deionized water and stir at 80 °C to obtain a suspension with a mass fraction of 5%; under stirring, add the nano-titanium dioxide suspension dropwise to the mixed solution at a rate of 0.5 - 2 mL / min to prepare a modified tungsten bronze precursor solution; wherein, the mass of TiO 2 accounts for 0.5% of the product modified tungsten bronze.

[0118] In the modified tungsten bronze precursor solution, the total concentration of tungsten hexachloride WCl 6 , hafnium tetrachloride HfCl 4 , citric acid monohydrate C 6 H 8 O 7 •H 2 O, cesium carbonate Cs 2 CO 3 and TiO 2 is 50%, and % refers to the mass percentage of the total material in the modified tungsten bronze precursor solution.

[0119] 5) Heat the above-mentioned modified tungsten bronze precursor solution at 230 °C for 24 h. After the reaction is completed, cool it to room temperature to obtain a light blue solution; spray-dry the light blue solution to obtain a light blue powder; wherein, the inlet air temperature of the spray drying is 200 °C, the outlet air temperature is 90 °C, and the feeding speed is 15 mL / min. Place the light blue powder in a tube furnace and calcine it at 500 °C for 6 h in an argon atmosphere.

[0120] The prepared modified tungsten bronze is a powder with a primary particle size of 20 - 30 nm.

[0121] Steps (2) and (3) are the same as those in Example 1.

[0122] Comparative Example 3

[0123] Based on Example 1, do not add HfCl 4 and TiO 2 , and the rest is the same as in Example 1.

[0124] Effect Example 1 Physical and Chemical Properties

[0125] The XRD pattern of the modified tungsten bronze prepared in Example 1 is as shown in Figure 1 . It can be seen from Figure 1 that diffraction peaks are present at approximately 2θ = 25.3°, 37.8°, and 48.0°, which match the main diffraction peaks of TiO 2 . Thus, it can be known that in the product modified tungsten bronze, Ti is dispersed in the lattice structure of tungsten bronze in the form of TiO 2 nanoparticles or forms a composite structure with tungsten bronze.

[0126] The SEM image of the modified tungsten bronze prepared in Example 1 is as shown in Figure 2 . It can be seen from Figure 1 that the primary particle size of the modified tungsten bronze is 20 - 30 nm.

[0127] The particle size distribution of the heat - insulating slurry was measured by dynamic light scattering (DLS), and each group was tested in parallel 3 times. The particle size distribution diagram of the heat - insulating slurry prepared in Example 1 is as shown in Figure 3 , and it can be seen that the primary particle size of this heat - insulating slurry is 20 - 30 nm.

[0128] Effect Example 2 Aging Performance

[0129] For the coated glass plates prepared in the above - mentioned examples and comparative examples, an infrared barrier rate (IR), visible light transmittance (VL), and color (L, a, and b) were measured using a solar film tester, and the color and haze of the coating were measured using a bench - top color difference instrument.

[0130] The coated glasses were subjected to constant - temperature and - humidity aging tests and ultraviolet aging tests, respectively.

[0131] Constant - temperature and - humidity aging test: The above - mentioned coated glass was placed in an aging chamber at constant temperature and humidity (85% humidity, 85 °C). After 72 h, the infrared barrier rate (IR), visible light transmittance (VL), color (L, a, and b), and haze were measured again using the above - mentioned method. The test results are shown in Table 1.

[0132] Ultraviolet aging test: According to GA / T 744 - 2013 Radiation Resistance Test, the above - mentioned coated glass was placed in an aging chamber, and irradiated with light having a spectral wavelength of 300 - 800 nm. The radiation intensity was 1000 W / m 2 ±100 W / m 2 . Within the entire sample area, the deviation of the radiation intensity should not be greater than ±10%. The blackboard temperature in the aging chamber was 63 °C ± 3 °C, and continuous light irradiation was used. The total test time was 600 h.

[0133] The infrared barrier rate (IR), visible light transmittance (VL), color (L, a, and b), and haze were measured again using the above - mentioned method. The test results are shown in Table 2.

[0134] Table 1

[0135]

[0136] Table 2

[0137]

[0138] As can be seen from Table 1 and Table 2, at 0 h, the IR values of Examples 1-3 were significantly higher than those of the comparative examples, indicating that the product of the present invention has excellent infrared barrier performance and low haze.

[0139] After aging for 72 h under constant temperature and humidity conditions (Table 1) and after aging for 600 h under ultraviolet conditions (Table 2), the aging differences in IR and haze of Examples 1-3 were significantly smaller than those of the comparative examples. Thus, it can be shown that the infrared barrier performance and haze of the coating of the present invention have good stability during the aging process.

[0140] Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that this is only for illustration purposes. The protection scope of the present invention is defined by the appended claims. Without departing from the principles and essence of the present invention, those skilled in the art can make various changes or modifications to these embodiments, but these changes and modifications all fall within the protection scope of the present invention.

Claims

1. A modified tungsten bronze, characterized in that: The chemical formula of the modified tungsten bronze is (A x M y W 1-y O3)·z(TiO2), wherein A is selected from one or more of Na, K, Rb and Cs, M is selected from one or more of Hf, Mo, Ta and Nb; and 0.25≤x≤0.4, 0<y<0.1, 0<z≤0.

04.

2. The modified tungsten bronze according to claim 1, characterized in that: A is Na and / or Cs; And / or, M is Hf; And / or, x is 0.30-0.38, such as 0.33, 0.35 or 0.37; and / or, said y is 0.04-0.09, for example 0.05, 0.07 or 0.08; and / or, said z is 0.01-0.04, such as 0.01, 0.03 or 0.04; And / or, in the modified tungsten bronze, the TiO2 nanoparticles are uniformly dispersed in the lattice structure of the tungsten bronze or form a composite structure with the tungsten bronze; And / or, the primary particle size of the modified tungsten bronze is 20-30 nm.

3. A method for preparing modified tungsten bronze, characterized in that: It includes the following steps: The tungsten salt, the M metal salt and the complex are mixed, and then mixed with the A metal salt to obtain a mixed solution; TiO2 is added to the mixed solution to obtain a modified tungsten bronze precursor; the modified tungsten bronze precursor is subjected to hydrothermal reaction and calcined to obtain a modified tungsten bronze; Wherein, M in the M metal salt is selected from one or more of Hf, Mo, Ta and Nb; A in the A metal salt is selected from one or more of Na, K, Rb and Cs; The molar ratio of M in the M metal salt and the metal W in the tungsten salt is (0-0.10):1; the molar ratio of the total molar amount of the metal W in the tungsten salt and the M in the M metal salt to the molar ratio of A in the A metal salt is 1:(0.25-0.4); the mass concentration of TiO2 in the modified tungsten bronze is 0-0.4% and not 0%.

4. The method for preparing the modified tungsten bronze according to claim 3, characterized in that: The tungsten salt is selected from WCl6 and / or Na2WO3; And / or, the M metal salt is selected from one or more of HfCl4, MoCl6, TaCl5 and NbCl5, such as HfCl4; and / or, the molar ratio of M in the M metal salt to the metal W in the tungsten salt is (0.04-0.09):1, such as 0.05:1, 0.08:1 or 0.09:1; And / or, the complex is a weak acid and / or a sugar substance; the weak acid is preferably citric acid monohydrate and / or oxalic acid; the sugar substance is preferably glucose and / or sucrose; and / or, the molar ratio of the complex to the metal W in the tungsten salt is (0.7-1.3):1, preferably (0.8-1.1):1, for example 0.95:1, 1:1 or 1.05:1; And / or, the metal salt A is selected from one or more of Cs2CO3, CsOH, Na2CO3 and NaOH, preferably Cs2CO3 and / or CsOH; and / or, the molar ratio of the sum of the moles of the metal W in the tungsten salt and the M in the M metal salt to the molar ratio of A in the A metal salt is 1:(0.30-0.38), for example, 1:0.33, 1:0.35 or 0.37; And / or, the mixed liquid further comprises a solvent; the solvent is preferably deionized water and / or anhydrous ethanol; And / or, the particle size of the TiO2 is 10-100 nm, preferably 10-50 nm; And / or, the TiO2 is added dropwise to the mixed solution in the form of a suspension; the dropping speed is preferably 0.5-2 mL / min; Preferably, the mass fraction of the suspension is 3-8%, for example 5%; Preferably, the suspension is prepared by dispersing TiO2 in water; the dispersion temperature is preferably 70-90°C, such as 80°C; And / or, the mass concentration of TiO2 in the modified tungsten bronze is 0.1-0.4%, such as 0.1%, 0.35% or 0.4%; And / or, in the modified tungsten bronze precursor, the mass concentration of the material is 40-60%, for example 50%, where % refers to the mass percentage of the total mass of tungsten salt, M metal salt, complex, A metal salt and TiO2 in the modified tungsten bronze precursor.

5. The method for preparing the modified tungsten bronze according to claim 3, characterized in that: The temperature of the hydrothermal reaction is 230-260° C., for example 230° C.; And / or, the hydrothermal reaction time is 12-48h, for example 24h; And / or, a drying operation is further included after the hydrothermal reaction and before the calcination; the drying is preferably spray drying; the inlet temperature of the spray drying is preferably 180-220° C., for example, 200° C., the outlet temperature of the spray drying is preferably 80-100° C., for example, 90° C., and the feed rate of the spray drying is preferably 10-20 mL / min, for example, 15 mL / min; and / or, the calcination temperature is 500-600° C., for example 500° C.; And / or, the calcination time is 4-8h, for example 6h; And / or, the calcination is performed under an inert atmosphere; the inert atmosphere is preferably argon or nitrogen.

6. A modified tungsten bronze, characterized in that: It is prepared by the preparation method as described in any one of claims 3 to 5; Preferably, the primary particle size of the modified tungsten bronze is 20-30 nm.

7. A slurry composition, characterized in that: The invention comprises the modified tungsten bronze as claimed in any one of claims 1, 2 and 6 and an additive.

8. The slurry composition according to claim 7, characterized in that The content of the modified tungsten bronze is 10-40%, for example 30%; and / or, the pH value of the slurry composition is 5-6; and / or, the primary particle size of the slurry composition is 20-30 nm; and / or, the auxiliary agent is selected from one or more of a dispersant, a UV absorber, a photooxidation stabilizer and a pH adjuster; Preferably, the dispersant is selected from one or more of BYK2070, BYK7410 and TEGO245; Preferably, the content of the dispersant is 1-10%, for example 10%; Preferably, the ultraviolet absorber is selected from UV-531; Preferably, the content of the ultraviolet absorber is 0.1-0.5%, for example 0.1%; Preferably, the photo-oxidation stabilizer is selected from siloxane photo-oxidation stabilizers, more preferably benzotriazole siloxane photo-oxidation stabilizers; Preferably, the content of the photo-oxidation stabilizer is 0.1-0.5%, for example 0.1%; Preferably, the pH adjuster is selected from triethanolamine; Preferably, the content of the pH adjuster is 1-5%, for example 2%; And / or, the slurry composition further comprises an organic solvent; Preferably, the organic solvent is one or more of methanol, ethanol, isopropanol, tert-butanol, pentane, hexane, octane, benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, acetone, methyl butyl ketone, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, acetonitrile, pyridine, dichloromethane, chlorobenzene, dichlorobenzene, ethyl ether and petroleum ether, such as xylene; Preferably, the content of the organic solvent is 54-83.8%, for example 57.8%; The above percentages are the mass percentages of each material in the slurry.

9. A coating, characterized in that: It comprises the modified tungsten bronze according to any one of claims 1, 2 and 6, or the slurry composition according to claim 7 or 8.

10. Use of the modified tungsten bronze according to any one of claims 1, 2 and 6, the slurry composition according to claim 7 or 8, or the coating according to claim 9 in the field of thermal insulation materials.

Images