Preparation method and application of a kind of ball milling method-calcination process preparation cesium tungstate vanadium mixed heat insulation coating

Abstract

The application relates to a preparation method and application of a ball milling-calcination process-prepared cesium vanadium tungstate mixed heat insulation coating, and belongs to the technical field of heat insulation coatings. The application aims to solve the problems of high preparation cost, strict requirement on equipment, long preparation time and difficult morphology control of vanadium dioxide and cesium tungsten bronze used in the existing cooling coating. The prepared cesium vanadium tungstate mixed heat insulation coating is coated on the surface of glass, mainly aiming at blocking the infrared light thermal radiation in sunlight, the new type of high-efficiency heat insulation film utilizes the light absorption and phase change reflection characteristics of nanometer cesium tungsten bronze and vanadium dioxide to realize heat insulation. The application adjusts the proportion of cesium, vanadium and tungstate to adjust the heat insulation performance, the heat insulation coating is prepared through different proportions of acrylic resin / organic silicon resin, solvent, cesium vanadium tungstate mixed heat insulation coating and the like, and the heat insulation film with excellent infrared blocking property, good stability and excellent light transmittance is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of thermal insulation coatings, and particularly relates to a preparation method and application of a cesium vanadium tungstate mixed thermal insulation coating prepared by a ball milling-calcination process. Background Art

[0002] The background of cooling coatings stems from the concern about building energy efficiency and the urban heat island effect. As global temperatures rise and urbanization accelerates, urban areas are generally hotter than surrounding rural areas, which not only affects the comfort of residents but also increases the use of air conditioning and refrigeration equipment, leading to increased energy consumption and greenhouse gas emissions. To meet these challenges, scientists and engineers have developed cooling coatings that effectively reduce the temperature of buildings and other surfaces by reflecting sunlight, reducing heat absorption or enhancing insulation. As a new type of thermal management material, cooling coatings are widely used in buildings, electronic equipment and vehicles. They use a combination of special chemical components such as vanadium dioxide and cesium tungsten bronze to exhibit excellent heat reflection and dissipation properties. In addition, these materials are designed not only to consider the cooling effect, but also to pay attention to their stability and durability under different environmental conditions to ensure that they maintain excellent performance in various application scenarios.

[0003] Conventional methods for preparing vanadium dioxide (VO2) mainly include solid-phase reaction method, solution method, vapor deposition method and mechanical ball milling method. (1) The solid-phase reaction method is to mix a vanadium source (such as V2O5) with other reactants (such as carbon) and then calcine at high temperature. It has the advantages of simple equipment and low cost, but it is difficult to control the purity and crystal structure of the product. (2) The solution method uses hydrothermal or solvent thermal reaction to dissolve a vanadium source such as ammonium vanadate in a solvent, which can obtain uniform and size-controlled particles, but it requires high temperature and high pressure conditions and high equipment requirements. (3) The vapor deposition method (CVD) deposits the vanadium source in the gas phase to form a high-quality VO2 thin film, which is suitable for electronic devices, but it is expensive and the equipment is complex. (4) The mechanical ball milling method grinds the vanadium oxide powder by mechanical force to improve reactivity, reduce the reaction temperature and increase the yield, but it may lead to the introduction of impurities and the product morphology is difficult to control.

[0004] Traditional preparation methods for cesium tungsten bronze (CsxWO3) mainly include solid-phase synthesis, sol-gel method and hydrothermal synthesis method. (1) The solid-phase synthesis method is to mix a cesium source (such as cesium chloride) and a tungsten source (such as sodium tungstate) in proportion and then calcine at high temperature. The operation is simple, but it may lead to uneven particles and low yield. (2) The sol-gel method forms a sol through a chemical reaction, gelates under appropriate conditions, and finally calcines to obtain cesium tungsten bronze. This method helps to obtain uniform materials with controllable particle size, but the preparation process is relatively complicated and involves multiple steps. (3) The hydrothermal synthesis method synthesizes cesium tungsten bronze under hydrothermal conditions, which can improve the purity and crystallinity of the product under mild conditions. However, the reaction time may be long and the equipment cost is also high. Summary of the Invention

[0005] The purpose of the present invention is to solve the problems of high preparation cost, strict equipment requirements, long preparation time and difficult morphology control of vanadium dioxide and cesium tungsten bronze used in existing cooling coatings, and to provide a preparation method and application of cesium vanadium tungstate mixed insulation coating prepared by ball milling-calcination process.

[0006] This invention applies a cesium-vanadium tungstate hybrid thermal insulation coating to glass surfaces, primarily to block infrared solar thermal radiation. This new, highly efficient thermal insulation film utilizes the light absorption and phase-change reflective properties of nano-cesium tungsten bronze and vanadium dioxide to isolate heat. The thermal insulation performance is adjusted by regulating the ratio of cesium, vanadium, and tungstate. The thermal insulation coating is prepared using varying ratios of acrylic resin / silicone resin, solvent, and cesium-vanadium tungstate hybrid thermal insulation coating, resulting in a thermal insulation film with excellent infrared barrier properties, good stability, and excellent light transmittance.

[0007] A method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process is specifically completed in the following steps:

[0008] 1. Preparation of cesium vanadium tungstate catalyst:

[0009] ①, uniformly mix vanadium pentoxide, sodium tungstate and cesium carbonate to obtain a mixture;

[0010] ②. Add a reducing agent to the mixture to obtain a raw material; transfer the raw material to a ball mill;

[0011] ③. Add zirconium balls to the ball mill and continue ball milling for a period of time to obtain the ball-milled raw material;

[0012] ④. Place the ball-milled raw materials in a tube furnace, raise the temperature to the calcination temperature under a vacuum environment with nitrogen as the protective gas, and calcine at the calcination temperature to obtain a cesium vanadium tungstate catalyst;

[0013] 2. Preparation of thermal insulation coating:

[0014] ①. Mix the cesium vanadium tungstate catalyst, solvent and acrylic resin, and then stir magnetically for a period of time to obtain a viscous mixed solution;

[0015] ②. Add solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener and curing agent to the viscous mixed solution, continue magnetic stirring for a period of time to obtain cesium vanadium tungstate mixed thermal insulation coating.

[0016] Cesium vanadium tungstate mixed thermal insulation coating is used to prepare thermal insulation film containing cesium vanadium tungstate.

[0017] Principle of the present invention:

[0018] The present invention develops a ball milling-calcination mixing process; a cesium vanadium tungstate catalyst is prepared through the ball milling-high-temperature calcination mixing process, and the material is qualitatively and quantitatively analyzed through systematic physical and chemical tests and cooling performance tests, thereby screening out high-quality layers and optimal formulation conditions that can achieve efficient cooling. Furthermore, by designing a new cooling system, the practical application potential of the cesium vanadium tungstate-containing thermal insulation film is further enhanced; the material has both the ability of cesium tungstate to absorb thermal radiation in the infrared light region, and the characteristic of temperature phase transition due to the mixing of oxygen to form vanadium dioxide during the ball milling preparation process, thereby reflecting part of the infrared light. Therefore, the composite material has thermal insulation, durability and environmental adaptability, and can effectively reduce the surface temperature of buildings, reduce cooling requirements, thereby reducing energy consumption and alleviating the urban heat island effect.

[0019] Advantages of the present invention:

[0020] 1. The thermal insulation film containing cesium vanadium tungstate prepared by the present invention has a reasonable structure, and the flexibility of the thermal insulation performance of the thermal insulation film is improved by providing a thermal insulation layer;

[0021] 2. The cesium vanadium tungstate-containing thermal insulation film prepared by the present invention adopts a polycarboxylate comb-type dispersant to enhance the dispersibility of the mixture of vanadium dioxide and cesium tungsten bronze in the hydroxyl-containing acrylate solution; by adjusting the ratio of the polycarboxylate comb-type dispersant to vanadium dioxide and cesium tungsten bronze, the dispersion uniformity is optimized, thereby obtaining a thermal insulation film with excellent infrared barrier properties and stability, while ensuring that the thermal insulation film has good light transmittance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The UV-visible-infrared absorption spectra of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2, where Sample 1 is Example 1 and Sample 2 is Example 2;

[0023] Figure 2 The infrared spectra of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2 are shown in FIG. 1 , where Sample 1 is Example 1 and Sample 2 is Example 2.

[0024] Figure 3 The XRD patterns of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2 are shown in FIG. 1 , where Sample 1 is Example 1 and Sample 2 is Example 2.

[0025] Figure 4 High-resolution X-ray photoelectron spectroscopy of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Example 1 and Example 2. DETAILED DESCRIPTION

[0026] Specific embodiment 1: This embodiment is a preparation method of cesium vanadium tungstate mixed thermal insulation coating by ball milling-calcination process, which is completed in the following steps:

[0027] 1. Preparation of cesium vanadium tungstate catalyst:

[0028] ①, uniformly mix vanadium pentoxide, sodium tungstate and cesium carbonate to obtain a mixture;

[0029] ②. Add a reducing agent to the mixture to obtain a raw material; transfer the raw material to a ball mill;

[0030] ③. Add zirconium balls to the ball mill and continue ball milling for a period of time to obtain the ball-milled raw material;

[0031] ④. Place the ball-milled raw materials in a tube furnace, raise the temperature to the calcination temperature under a vacuum environment with nitrogen as the protective gas, and calcine at the calcination temperature to obtain a cesium vanadium tungstate catalyst;

[0032] 2. Preparation of thermal insulation coating:

[0033] ①. Mix the cesium vanadium tungstate catalyst, solvent and acrylic resin, and then stir magnetically for a period of time to obtain a viscous mixed solution;

[0034] ②. Add solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener and curing agent to the viscous mixed solution, continue magnetic stirring for a period of time to obtain cesium vanadium tungstate mixed thermal insulation coating.

[0035] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the mass ratio of vanadium pentoxide, sodium tungstate, and cesium carbonate described in step 1 (1) is (1g-25g):(0.5g-5g):(0.5g-5g). The other steps are the same as specific embodiment 1.

[0036] Specific embodiment 3: This embodiment differs from specific embodiments 1 or 2 in that the reducing agent in step 1 (2) is graphite, and the mass ratio of the reducing agent to vanadium pentoxide in step 1 (2) is (0.5g-5g):(1g-25g). The other steps are the same as those in specific embodiments 1 or 2.

[0037] Specific Embodiment 4: This embodiment differs from Specific Embodiments 1 to 3 in that the mass ratio of zirconium balls to raw materials in step 1 (3) is 10:1; the ball milling time in step 1 (3) is 3 to 10 hours; the forward rotation speed of the ball mill is 400 to 500 rpm, and the reverse rotation speed is 400 to 500 rpm, with forward and reverse rotation alternating every 30 to 180 minutes. The other steps are the same as Specific Embodiments 1 to 3.

[0038] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the heating rate in step 1 (4) is 5°C / min to 10°C / min; the calcination temperature in step 1 (4) is 750°C to 850°C, and the calcination time is 3 to 5 hours; and the particle size of the cesium vanadium tungstate catalyst in step 1 (4) is 20 nm to 50 nm. Other steps are the same as specific embodiments 1 to 4.

[0039] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that: the mass ratio of the cesium vanadium tungstate catalyst described in step 2 (1) to the volume ratio of the solvent is (0.1g to 5.0g):50mL; the volume ratio of the acrylic resin described in step 2 (1) to the solvent is (5mL to 20mL):50mL; the magnetic stirring reaction speed described in step 2 (1) is 300r / min to 800r / min, and the magnetic stirring reaction time is 3.5h to 4.5h; the acrylic resin described in step 2 (1) is a hydroxyl-containing acrylate with CAS number 94188-59-7, purchased from Sinopharm Chemical Reagent Co., Ltd.; the solvent described in step 2 (1) is one or more of ethyl acetate, toluene, and butanone. The other steps are the same as specific embodiments 1 to 5.

[0040] Specific embodiment 7: This embodiment differs from Specific embodiments 1 to 6 in that the solvent in step 2 (2) is one or more of ethyl acetate, toluene, and butanone; the silicone resin in step 2 (2) has a CAS number of 63148-58-3 and is purchased from Sinopharm Chemical Reagent Co., Ltd.; the thixotropic agent in step 2 (2) is bentonite; the hardening agent in step 2 (2) is a water-based polyurethane with a model number of A909856 and is purchased from MacLean Chemical Reagent Co., Ltd.; and the curing agent in step 2 (2) is hexamethylene diisocyanate. The other steps are the same as those in Specific embodiments 1 to 6.

[0041] Specific embodiment eight: This embodiment differs from specific embodiments one to seven in that: the volume ratio of the solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener, and curing agent described in step two (2) is 30 mL: (0.5 mL to 2 mL): (2 mL to 5 mL): 0.5 mL: 0.5 mL: 0.5 mL; the volume ratio of the solvent described in step two (2) to the solvent described in step two (2) is 30:50; the speed of continuing magnetic stirring in step two (2) is 300 r / min to 800 r / min, and the magnetic stirring reaction time is 1.5 h to 2.5 h. The other steps are the same as specific embodiments one to seven.

[0042] Specific embodiment nine: This embodiment is that the cesium vanadium tungstate mixed thermal insulation coating is used to prepare a cesium vanadium tungstate-containing thermal insulation film.

[0043] Specific embodiment 10: This embodiment differs from specific embodiments 1 to 9 in that a cesium vanadium tungstate-containing thermal insulation film is prepared by using a cesium vanadium tungstate mixed thermal insulation coating, which is specifically completed by the following steps:

[0044] The cesium vanadium tungstate mixed thermal insulation coating is applied to the surface of the substrate, and then dried and solidified to obtain a cesium vanadium tungstate-containing thermal insulation film;

[0045] The substrate is glass, polycarbonate or polymethyl methacrylate;

[0046] The drying and curing process is as follows: heating from room temperature to 40°C to 50°C, keeping warm at 40°C to 50°C for 5min to 15min, then heating to 55°C to 65°C, keeping warm at 55°C to 65°C for 5min to 15min, then heating to 75°C to 85°C, keeping warm at 75°C to 85°C for 5min to 15min, then heating to 95°C to 105°C, keeping warm at 95°C to 105°C for 5min to 15min, then heating to 110°C to 120°C, keeping warm at 110°C to 120°C for 5min to 15min, then cooling to 75°C to 85°C, keeping warm at 75°C to 85°C for 5min to 15min, and then cooling to room temperature to obtain a cesium vanadium tungstate-containing thermal insulation film;

[0047] The heating rate is 1°C / min to 5°C / min;

[0048] The cooling rate is 1°C / min to 5°C / min. The other steps are the same as those in the first to ninth embodiments.

[0049] The following examples are used to verify the beneficial effects of the present invention:

[0050] Example 1: A method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process is specifically completed according to the following steps:

[0051] 1. Preparation of cesium vanadium tungstate catalyst:

[0052] ①, uniformly mix vanadium pentoxide, sodium tungstate and cesium carbonate to obtain a mixture;

[0053] The mass ratio of vanadium pentoxide, sodium tungstate and cesium carbonate described in step 1① is 15g:5g:5g;

[0054] ②. Add a reducing agent to the mixture to obtain a raw material; transfer the raw material to a ball mill;

[0055] The reducing agent described in step 1② is graphite;

[0056] The mass ratio of the reducing agent to vanadium pentoxide in step 1② is 2g:15g;

[0057] ③. Add zirconium balls to the ball mill and continue ball milling for a period of time to obtain the ball-milled raw material;

[0058] The mass ratio of the zirconium balls to the raw materials described in step 1 (3) is 10:1;

[0059] The ball milling time in step 1 (3) is 5 hours; the forward rotation speed of the ball mill is 450 rpm, the reverse rotation speed of the ball mill is 450 rpm, and the forward and reverse rotations are alternated every 120 minutes;

[0060] ④. Place the ball-milled raw materials in a tube furnace, raise the temperature to the calcination temperature under a vacuum environment with nitrogen as the protective gas, and calcine at the calcination temperature to obtain a cesium vanadium tungstate catalyst;

[0061] The heating rate in step 1 (4) is 5°C / min;

[0062] The calcination temperature in step 1 (4) is 800°C and the calcination time is 3h;

[0063] The particle size of the cesium vanadium tungstate catalyst described in step 1 (4) is 30 nm;

[0064] 2. Preparation of thermal insulation coating:

[0065] ①. Mix the cesium vanadium tungstate catalyst, solvent and acrylic resin, and then stir magnetically for a period of time to obtain a viscous mixed solution;

[0066] The mass ratio of the cesium vanadium tungstate catalyst described in step 2① to the volume ratio of the solvent is 2.5g:50mL;

[0067] The volume ratio of the acrylic resin to the solvent described in step 2① is 10mL:50mL;

[0068] The speed of the magnetic stirring reaction in step 2① is 550 r / min, and the magnetic stirring reaction time is 4 h;

[0069] The acrylic resin described in step 2① is a hydroxyl-containing acrylate with a CAS number of 94188-59-7, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0070] The solvent described in step 2① is ethyl acetate;

[0071] ②, adding a solvent, a silicone resin, anhydrous ethanol, a thixotropic agent, a hardener and a curing agent to the viscous mixed solution, and continuing magnetic stirring for a period of time to obtain a cesium vanadium tungstate mixed thermal insulation coating (Sampe1);

[0072] The solvent described in step 2② is ethyl acetate;

[0073] The CAS number of the organosilicon resin described in step 2② is 63148-58-3, and it was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0074] The thixotropic agent described in step 2② is bentonite;

[0075] The hardening agent described in step 2② is polyurethane, model A909856, purchased from MacLean Chemical Reagent Co., Ltd.;

[0076] The curing agent described in step 2② is hexamethylene diisocyanate;

[0077] The volume ratio of the solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener and curing agent described in step 2② is 30mL:1mL:2.5mL:0.5mL:0.5mL:0.5mL;

[0078] The volume ratio of the solvent described in step 2② to the solvent described in step 2② is 30:50;

[0079] In step 2②, the magnetic stirring speed is continued at 550 r / min, and the magnetic stirring reaction time is 2 h.

[0080] Example 2: This example differs from Example 1 in that the mass ratio of vanadium pentoxide, sodium tungstate, and cesium carbonate in step 1 (1) is 15 g:2 g:2 g. The other steps and parameters are the same as those in Example 1.

[0081] Figure 1 The UV-visible-infrared absorption spectra of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2, where Sample 1 is Example 1 and Sample 2 is Example 2;

[0082] from Figure 1As can be seen, within the wavelength range of 0 to 500 nm, both Sample 1 and Sample 2 exhibit low absorption intensities. As the wavelength transitions to the 500 to 700 nm range, Sample 1's absorbance increases significantly. In stark contrast, Sample 2's absorption remains relatively stable, showing only a slight increase. In the 700 to 1200 nm wavelength range, Sample 1 maintains its high absorption level, while Sample 2's absorption does not change significantly. However, within the 1200 to 2500 nm wavelength range, Sample 1's absorbance decreases rapidly. Meanwhile, Sample 2 also exhibits a fluctuating decrease, but its absorbance remains higher than Sample 1. These differences in absorption properties indicate that the raw material ratio used to prepare the cesium vanadium tungstate hybrid thermal insulation coating significantly influences the material's light absorption intensity. Both samples exhibit excellent UV absorption and infrared reflectance, typical characteristics of thermal insulation materials. Overall, these materials are expected to exhibit excellent thermal insulation properties in applications such as outdoor thermal insulation coatings or architectural window films.

[0083] Figure 2 The infrared spectra of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2 are shown in FIG. 1 , where Sample 1 is Example 1 and Sample 2 is Example 2.

[0084] The molecular structure and chemical bonding are identified by measuring the absorption of infrared radiation by Sample 1 and Sample 2. Sample 1 absorbs infrared radiation at a wave number of 1000 cm -1 Up to 2000cm -1 There are several obvious absorption peaks between 1500cm and 2500cm. These peaks indicate that the sample may contain multiple functional groups or compounds. In particular, at about 1500cm -1 The strong absorption peak at 1700 cm- -1 Another significant peak nearby may be related to the C=O carbonyl group; while the spectral characteristics of Sample 2 are relatively simple. It has fewer and weaker absorption peaks in the same wavenumber range, which may mean that its chemical structure is relatively simple or lacks certain specific functional groups. In addition, the 3000cm -1 The broad and weak absorption bands above are usually attributed to OH stretching vibration, which suggests the possibility that the two samples contain hydroxyl groups or other oxygen-containing functional groups.

[0085] Figure 3 The XRD patterns of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Examples 1 and 2 are shown in FIG. 1 , where Sample 1 is Example 1 and Sample 2 is Example 2.

[0086] Figure 3The diffraction patterns of Samples 1 and 2 are quite similar, with distinct diffraction peaks appearing at multiple angles. These peaks represent specific arrangements of their crystal structures. Compared to Sample 1, the diffraction pattern of Sample 2 is smoother at some angles, suggesting that the crystal structure of Sample 2 may be more disordered or contain a larger amount of amorphous phase.

[0087] Figure 4 High-resolution X-ray photoelectron spectroscopy of the cesium vanadium tungstate mixed thermal insulation coatings prepared in Example 1 and Example 2;

[0088] Through X-ray spectral analysis, the absorption characteristics of different elements such as Cs3d, V2p and W4f in X-ray spectra are revealed. Survey spectrum ( Figure 4 a) provides a broader energy view, allowing us to identify the presence of other possible elements or impurities; V 2p, O 1s, Cs3d, C 1s spectra ( Figure 4 b, d, e, f) The peak shapes of the two samples are very similar, indicating that their main chemical environments are consistent. Figure 4 c) The main peak positions of the spectra are similar, but the height at 44 eV is slightly different, which may be caused by different raw material ratios of the thermal insulation coating.

[0089] Application Example 1: A cesium vanadium tungstate thermal insulation film is prepared using the cesium vanadium tungstate mixed thermal insulation coating prepared in Example 1, specifically by the following steps:

[0090] The cesium vanadium tungstate mixed thermal insulation coating is applied to the surface of the substrate, and then dried and solidified to obtain a cesium vanadium tungstate-containing thermal insulation film;

[0091] The substrate is glass;

[0092] The drying and curing process is as follows: heating from room temperature to 45°C, keeping warm at 45°C for 5 minutes, then heating to 60°C, keeping warm at 60°C for 5 minutes, then heating to 80°C, keeping warm at 80°C for 5 minutes, then heating to 100°C, keeping warm at 100°C for 5 minutes, then heating to 115°C, keeping warm at 115°C for 5 minutes, then cooling to 80°C, keeping warm at 80°C for 5 minutes, and then cooling to room temperature to obtain a cesium vanadium tungstate-containing thermal insulation film;

[0093] The heating rate is 5°C / min;

[0094] The cooling rate is 5°C / min.

[0095] Application Example 2: This application example differs from Application Example 1 in that a cesium vanadium tungstate thermal insulation film is prepared using the cesium vanadium tungstate mixed thermal insulation coating prepared in Example 2. Other steps and parameters are the same as those in Application Example 1.

[0096] First, using paper shells of the same size and material as raw materials and the same splicing method, a simple device with the same volume and five closed sides was made as a reactor. The notched surfaces were respectively configured with glass coated with a cesium vanadium tungstate thermal insulation film (coated glass) and ordinary glass. The same model of thermometer was installed at the same position on the inside of the device, and light energy was provided to the device at the same distance. The temperature inside the device was recorded at different times to compare and confirm the effect of the thermal insulation coating, as shown in Table 1. The experimental results show that when the temperature is between 20-50°C, the coated glass device is 5-7°C lower than the ordinary glass device. When the temperature is between 50-80°C, the coated glass device is 7-22°C lower than the ordinary glass device.

[0097] Coating performance test: light transmittance and infrared transmittance:

[0098] 1. Light transmittance: The test instrument is LS160 Transmission Meter;

[0099] 2. Infrared blocking rate: The testing instrument is LS160 Transmission Meter.

[0100] Table 1

[0101]

[0102]

[0103] Experiments show that at room temperature (20°C), the light transmittance of Example 1 is 75%, slightly lower than the 85% of ordinary glass. When the temperature rises to 55°C, the light transmittance of Example 1 drops to 60%, which is due to the light shielding properties of the cesium vanadium tungstate material. At room temperature (20°C), the light transmittance of Example 2 is 78%, slightly lower than the 85% of ordinary glass. When the temperature rises to 55°C, the light transmittance of Example 2 drops to 69%, which is due to the light shielding properties of the cesium vanadium tungstate material.

[0104] At room temperature (20°C), the infrared transmittance of Application Example 1 was 30%, far lower than the 80% of ordinary glass. When the temperature was raised to 55°C, the infrared transmittance of Application Example 1 was 18%, which was attributed to the excellent infrared absorption and reflection properties of the cesium vanadium tungstate material. At room temperature (20°C), the infrared transmittance of Application Example 2 was 16%, far lower than the 80% of ordinary glass. When the temperature was raised to 55°C, the infrared transmittance of Application Example 2 was 6.7%, which was attributed to the excellent infrared absorption and reflection properties of the cesium vanadium tungstate material.

[0105] The above results show that regulating the proportion of metals in the cesium vanadium tungstate thermal insulation coating can significantly regulate the response ability of the thermal insulation coating to light and achieve significant thermal insulation.

[0106] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing cesium vanadium tungstate mixed thermal insulation coating by ball milling-calcination process, characterized in that The preparation method is specifically completed according to the following steps:

1. Preparation of cesium vanadium tungstate catalyst: ①, uniformly mix vanadium pentoxide, sodium tungstate and cesium carbonate to obtain a mixture; The mass ratio of vanadium pentoxide, sodium tungstate and cesium carbonate described in step 1① is (1g~25g):(0.5g~5g):(0.5g~5g); ②. Add a reducing agent to the mixture to obtain a raw material; transfer the raw material to a ball mill; The reducing agent described in step 1② is graphite; The mass ratio of the reducing agent to vanadium pentoxide described in step 1② is (0.5g~5g):(1g~25g); ③. Add zirconium balls to the ball mill and then perform ball milling to obtain the ball-milled raw material; ④. Place the ball-milled raw materials in a tube furnace, raise the temperature to the calcination temperature under a vacuum environment with nitrogen as the protective gas, and calcine at the calcination temperature to obtain a cesium vanadium tungstate catalyst; 2. Preparation of thermal insulation coating: ①, mixing cesium vanadium tungstate catalyst, solvent and acrylic resin, and then stirring magnetically to react to obtain a viscous mixed solution; ②. Add solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener and curing agent to the viscous mixed solution, continue magnetic stirring to obtain cesium vanadium tungstate mixed thermal insulation coating.

2. The method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process according to claim 1, characterized in that The mass ratio of the zirconium balls to the raw materials described in step 1③ is 10:1; the ball milling time described in step 1③ is 3h~10h; the forward rotation speed of the ball mill is 400rpm~500rpm, the reverse rotation speed of the ball mill is 400rpm~500rpm, and the forward and reverse rotations are alternated every 30min~180min.

3. The method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process according to claim 1, characterized in that The heating rate in step 1 ④ is 5 ℃ / min ~ 10 ℃ / min; the calcination temperature in step 1 ④ is 750 ℃ ​​~ 850 ℃, and the calcination time is 3h ~ 5h; the particle size of the cesium vanadium tungstate catalyst in step 1 ④ is 20nm ~ 50nm.

4. The method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process according to claim 1, characterized in that The volume ratio of the mass of the cesium vanadium tungstate catalyst described in step 2 (1) to the solvent is (0.1g~5.0g):50mL; the volume ratio of the acrylic resin described in step 2 (1) to the solvent is (5mL~20mL):50mL; the speed of the magnetic stirring described in step 2 (1) is 300r / min~800r / min, and the magnetic stirring reaction time is 3.5h~4.5h; the acrylic resin described in step 2 (1) is a hydroxyl-containing acrylate; the solvent described in step 2 (1) is one or more of ethyl acetate, toluene and butanone.

5. The method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process according to claim 1, characterized in that The solvent described in step 2② is one or more of ethyl acetate, toluene and butanone; the thixotropic agent described in step 2② is bentonite; the hardening agent described in step 2② is water-based polyurethane, model A909856; the curing agent described in step 2② is hexamethylene diisocyanate.

6. The method for preparing a cesium vanadium tungstate mixed thermal insulation coating by a ball milling-calcination process according to claim 1, characterized in that The volume ratio of the solvent, silicone resin, anhydrous ethanol, thixotropic agent, hardener and curing agent described in step 2② is 30mL: (0.5mL~2mL): (2mL~5mL): 0.5mL: 0.5mL: 0.5mL; the speed of continuing magnetic stirring in step 2② is 300r / min~800r / min, and the magnetic stirring reaction time is 1.5h~2.5h.

7. Application of the cesium vanadium tungstate mixed thermal insulation coating prepared by the preparation method according to claim 1, characterized in that Cesium vanadium tungstate mixed thermal insulation coating is used to prepare thermal insulation film containing cesium vanadium tungstate.

8. The use of the cesium vanadium tungstate mixed thermal insulation coating according to claim 7, characterized in that The preparation of cesium vanadium tungstate thermal insulation film using cesium vanadium tungstate mixed thermal insulation coating is completed in the following steps: The cesium vanadium tungstate mixed thermal insulation coating is applied to the surface of the substrate, and then dried and solidified to obtain a cesium vanadium tungstate-containing thermal insulation film; The substrate is glass, polycarbonate or polymethyl methacrylate; The drying and curing process is as follows: heating from room temperature to 40°C to 50°C, keeping warm at 40°C to 50°C for 5min to 15min, then heating to 55°C to 65°C, keeping warm at 55°C to 65°C for 5min to 15min, then heating to 75°C to 85°C, keeping warm at 75°C to 85°C for 5min to 15min, then heating to 95°C to 105°C, keeping warm at 95°C to 105°C for 5min to 15min, then heating to 110°C to 120°C, keeping warm at 110°C to 120°C for 5min to 15min, then cooling to 75°C to 85°C, keeping warm at 75°C to 85°C for 5min to 15min, and then cooling to room temperature to obtain a cesium vanadium tungstate-containing thermal insulation film; The heating rate is 1°C / min to 5°C / min; The cooling rate is 1°C / min to 5°C / min.

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