WO2021008564A1 - Matériau de protection thermique transparent, dispersion de microparticules de protection thermique transparente, leur procédé de préparation et d'utilisation - Google Patents

Matériau de protection thermique transparent, dispersion de microparticules de protection thermique transparente, leur procédé de préparation et d'utilisation Download PDF

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WO2021008564A1
WO2021008564A1 PCT/CN2020/102163 CN2020102163W WO2021008564A1 WO 2021008564 A1 WO2021008564 A1 WO 2021008564A1 CN 2020102163 W CN2020102163 W CN 2020102163W WO 2021008564 A1 WO2021008564 A1 WO 2021008564A1
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transparent heat
shielding
nitrogen
tungsten
heat
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PCT/CN2020/102163
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English (en)
Chinese (zh)
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金平实
曹逊
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中国科学院上海硅酸盐研究所
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Publication of WO2021008564A1 publication Critical patent/WO2021008564A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the invention belongs to the field of functional nano new materials, and specifically relates to a transparent heat-shielding material, a transparent heat-shielding nano powder and a transparent heat-shielding microparticle dispersion, which can be widely used in heat-shielding paints, heat-shielding films, heat-shielding glasses, and Various application fields of light-to-heat conversion materials.
  • the wavelength range of sunlight is about 300-2500nm, of which the wavelength range of visible light is 380-780nm, and the wavelength of near-infrared is 780-2500nm.
  • the near-infrared part of sunlight is largely shielded, which helps to save energy and reduce emissions and improve the comfort of living spaces.
  • the market has a huge potential demand for transparent heat shielding materials and products.
  • the new type of transparent infrared heat-shielding coatings, films, plates, and fiber products made by combining inorganic nano heat-shielding materials and resins have gradually expanded the market scale and application fields.
  • Traditional inorganic nano heat shielding materials include transparent conductive materials (such as ITO, ATO, etc.), or lanthanum hexaboride (LaB 6 ), and recently discovered series of transparent heat shielding materials with tungsten bronze structure (doped tungsten bronze) , Because of its high visible light transmittance and excellent heat-shielding, heat-storage and heat preservation performance, it is widely concerned.
  • Patent Document 1 discloses a method for preparing a tungsten oxide-based transparent heat shielding material with excellent performance.
  • This material can be represented by the general formula MxWyOz, where the M element is an alkali metal, alkaline earth metal, rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Choose one or more of Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re.
  • Patent Document 2 discloses a metal element doped tungsten bronze structure heat shielding nanopowder, the doping element is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se, One or several mixed elements of Te, Ti, Mn, Fe, Co, Ni, Cu or Zn.
  • Non-Patent Documents 1-4 that the performance degradation mechanism is due to the metal-doped tungsten bronze structure fine particles (such as cesium tungsten bronze CWO) in the composite material (such as PET heat shielding film) formed with resin , Due to the lack of cesium on the surface of CWO particles and the reaction with hydrogen to cause reversible photochromism (coloring), or the performance failure (fading) caused by the oxidation of the surface of CWO particles in a humid and hot environment.
  • the metal-doped tungsten bronze structure fine particles such as cesium tungsten bronze CWO
  • the composite material such as PET heat shielding film
  • Patent Document 1 Japanese Patent JP2005-187323A;
  • Patent Document 2 Chinese Patent CN107200357A;
  • Non-Patent Document 1 K. Adachi, Y. Ota, H. Tanaka, M. Okada, N. Oshimura, A. Tofuku, Chromatic instabilities in cesium-doped tungsten bronze nanoparticles, J. Appl. Phys. 114 (19) (2013) 11.
  • Non-Patent Document 2 Yunxiang Chena,b,1, Xianzhe Zeng, Yijie Zhou, Rong Li, Heliang Yao, Xun Cao, Ping Jin, Core-shell structured CsxWO3@ZnO with excellent stability and high performance on near-infrared shielding, Ceramics International 44 (2016) 2738-2744,
  • Non-Patent Document 3 Yijie Zhou, ab Ning Li, ab Yunchuan Xin, a Xun Cao, Shidong Ji and Ping Jin, CsxWO3 nanoparticle-based organic polymer transparent foils: low haze, high near infraredshielding ability and excellent photochromic stability, J. Mater. Chem. C, 2017, 5, 6251-6258.
  • Non-Patent Document 4 Xianzhe Zeng, Yijie Zhou, Shidong Ji, Hongjie Luo, Heliang Yao, Xiao Huang and Ping Jin, The preparation of a high performance nearinfrared shielding Cs xWO3/SiO2 composite resin coating and research on its optical stability under ultraviolet Illumination, J. Mater. Chem. C, 2015, 3, 8050-8060.
  • the purpose of the present invention is to provide a new type of doped tungsten bronze heat shielding material with stable performance to solve the problem of unstable optical performance of materials and resin products.
  • the traditional doped tungsten bronze structure has a larger band gap, that is, its ability to shield ultraviolet rays is low. Excessive ultraviolet irradiation is not conducive to the shielding ability and life of the heat shielding resin product, and adding too much ultraviolet shielding additives may cause an increase in cost and a decrease in optical and mechanical properties.
  • the red shift of the absorption end can be realized, and the ultraviolet absorption rate of the structure can be increased. While increasing the ultraviolet shielding efficiency, it also effectively suppresses the photochromic caused by the heat shielding resin. The color changes.
  • the inventor designed a new doped tungsten bronze structure that can simultaneously reduce the lattice constant and the red shift of the absorption end.
  • the present invention provides a transparent heat-shielding material, which is obtained by doping nitrogen in a tungsten bronze structure with a chemical formula of M x WO 3- ⁇ , where M is an alkali metal or alkaline earth metal Any one or more of rare earth elements, 0.1 ⁇ x ⁇ 1, W is tungsten, O is oxygen, and 0 ⁇ 0.5.
  • nitrogen doping in the traditional tungsten bronze structure allows nitrogen to enter the tungsten-oxygen skeletal structure to replace part of the oxygen, thereby causing distortion of the crystal lattice, making the crystal lattice smaller and making the doped metal ions difficult to escape. Thereby increasing the stability of the structure.
  • nitrogen doping and the substitution of oxygen change the forbidden band width of the original crystal structure, reduce the forbidden band width, red shift the absorption end, and increase the ultraviolet shielding performance.
  • the composition of the transparent heat shielding material is represented by the general formula M x WO y N z , where N is nitrogen, 2.5 ⁇ y+z ⁇ 3.
  • the ratio of z to y is 1/4 or less, preferably 1/10 or less, more preferably 1/20 or less.
  • the present invention provides a method for preparing any of the above-mentioned transparent heat shielding materials, including the following steps:
  • the mixture of the tungsten source and the M metal source in the formula M x WO y N z is kept at 450 to 750° C. for 2 to 8 hours in a vacuum state with a nitrogen-containing atmosphere.
  • the present invention provides a method for preparing any of the above-mentioned transparent heat shielding materials, including the following steps:
  • the obtained precursor is kept at 400-700°C for 1-8 hours in a vacuum state with a nitrogen-containing atmosphere.
  • the tungsten source is selected from at least one of tungsten oxide, tungstic acid, and ammonium tungstate, preferably ammonium tungstate.
  • the M metal source is a carbonate of element M, preferably cesium carbonate.
  • the nitrogen-containing atmosphere is ammonia, nitrogen or a mixed gas thereof, or a mixed gas of the foregoing gas and hydrogen.
  • the present invention provides a transparent heat-shielding microparticle.
  • the material of the transparent heat-shielding microparticle is any of the above-mentioned transparent heat-shielding materials, and the diameter of the transparent heat-shielding microparticle is in the range of 1 nm to 1000 nm.
  • the present invention provides a transparent heat-shielding fine particle dispersion formed by dispersing the above-mentioned transparent heat-shielding fine particles in a medium.
  • the medium is selected from any one of resin-containing liquids, transparent resin films, transparent resin film plates, glass substrates, chemical fibers, and fabrics.
  • the medium can be selected from a variety of transparent bodies, such as resin, glass, aerogel and the like.
  • resin-based media have high transparency, various forms, and easy processing.
  • the media is preferably various resin-based media, preferably resin media with higher transparency, such as PET (polyethylene terephthalate), PE (polyethylene ), EVA (ethylene-vinyl acetate copolymer), PVB (polyvinyl butyral), PI (polyimide), PC (polycarbonate), etc.
  • the present invention it is possible to provide a transparent heat-shielding material, transparent heat-shielding microparticles, and a dispersion of transparent heat-shielding microparticles with stable performance.
  • FIG. 1 is an XRD (X-Ray Diffraction) diffraction spectrum of a nitrogen-doped cesium tungsten bronze powder according to an embodiment of the present invention.
  • FIG. 3 is a scanning electron micrograph of a nitrogen-doped cesium tungsten bronze powder according to an embodiment of the present invention.
  • Fig. 4 is a transmittance spectrum of a heat-shielding laminated glass according to an embodiment of the present invention.
  • the transparent heat shielding material of an embodiment of the present invention is obtained by doping nitrogen in a tungsten bronze structure.
  • the structure of the tungsten bronze can be represented by the chemical formula M x WO 3- ⁇ , where M is any one or more of alkali metals, alkaline earth metals and rare earth elements, 0.1 ⁇ x ⁇ 1, W is tungsten, O is oxygen, and 0 ⁇ 0.5.
  • the stability of the doped tungsten bronze structure is related to the ion radius of the doping element.
  • the alkali metal doped tungsten bronze structure the larger the alkali metal ion radius, the more stable the structure. Therefore, when M contains an alkali metal, the alkali metal is preferably cesium.
  • the composition of the transparent heat shielding material is represented by the general formula M x WO y N z , where N is nitrogen, 2.5 ⁇ y+z ⁇ 3.
  • the tungsten bronze structure before undoped N can be in an oxygen-deficient state. After N doping, N can replace the position of O and can also occupy oxygen vacancies. In some embodiments, y+z ⁇ 3- ⁇ .
  • the nitrogen-oxygen ratio (ie z/y) after doping should not exceed 1/4, preferably not more than 1/10, and more preferably not more than 1/20.
  • the nitrogen-oxygen ratio (ie z/y) after doping is preferably 1/100 or more, which can ensure that the performance of tungsten bronze is improved.
  • the transparent heat-shielding fine particles according to an embodiment of the present invention are formed of the above-mentioned transparent heat-shielding material.
  • the diameter of the transparent heat shielding fine particles may be 1 nm to 1000 nm, preferably 10 nm to 100 nm, and more preferably 20 nm to 50 nm. This is because although particles with a diameter ranging from 1nm to 1000nm can form transparent heat-shielding materials and products with the medium, too large a particle size is likely to cause diffuse reflection of visible light and reduce the transparency of the product; while a too small particle size is not easy to be crushed and more It is difficult to achieve uniform dispersion in the medium.
  • Dispersing the above-mentioned transparent heat-shielding fine particles in a medium can form a transparent heat-shielding fine particle dispersion.
  • the medium may be a transparent body.
  • the transparent heat-shielding fine particles are uniformly dispersed in the resin-containing liquid to obtain an aqueous or solvent-based transparent heat-shielding coating.
  • the transparent heat-shielding paint is coated on the substrate to obtain a transparent heat-shielding coating film.
  • transparent heat-shielding fine particles are uniformly dispersed or coated on a glass substrate to obtain transparent heat-shielding glass.
  • the transparent heat-shielding fine particles are uniformly dispersed in a transparent resin film (for example, PET, PE, PI, PVB, or EVA) or resin sheet (PC) to obtain a transparent heat-shielding film or sheet product.
  • a transparent resin film for example, PET, PE, PI, PVB, or EVA
  • PC resin sheet
  • the transparent heat-shielding particles are uniformly dispersed in chemical fibers (such as polyester, nylon, acrylic, chlorinated, vinylon, spandex, polyolefin stretch yarn, etc.) to obtain heat storage and thermal insulation fibers, which are combined with fabrics (clothes, quilts, quilts, etc.). Filling, etc.) products.
  • chemical fibers such as polyester, nylon, acrylic, chlorinated, vinylon, spandex, polyolefin stretch yarn, etc.
  • a mixture of a tungsten source and a M source (M is any one or more of alkali metals, alkaline earth metals, and rare earth elements) is heat-treated in a vacuum state with a nitrogen-containing atmosphere to obtain a transparent heat shielding material.
  • the tungsten source (raw material containing tungsten element) is preferably a substance containing both tungsten element and oxygen element.
  • it may be selected from at least one of tungsten oxide, tungstic acid, ammonium tungstate, etc., and is more preferably a substance that also contains nitrogen.
  • ammonium tungstate is preferably a substance that also contains nitrogen.
  • ammonium tungstate The tungsten element combines with oxygen to form a tungsten bronze structure crystalline bone during the synthesis process, and doped metal elements are introduced into the polyhedral vacancies of the bone to produce infrared absorption. Since ammonium tungstate contains ammonium root, which is nitrogen element, the nitrogen element existing in the starting material is beneficial to nitrogen doping. Moreover, ammonium tungstate has high solubility in water, which is conducive to the uniform mixing and chemical reaction of raw materials.
  • the M source (raw material containing the M element) can be selected from salts of carbonates, chlorides, sulfates, and organic acid salts of the M elements that do not contain other metals other than M.
  • the M element is an alkali metal
  • the M source is preferably an alkali metal carbonate, because the carbonate is cheap and good, has high solubility in water, can form a high-concentration ion dispersion, and promote the uniform mixing and chemical reaction of the raw materials.
  • the M source is cesium carbonate, because cesium tungstate has a large ion radius and high stability.
  • the tungsten source and the M source are mixed uniformly to obtain a mixture.
  • the method can be to directly mix the tungsten source and the M source uniformly; or to separately prepare the tungsten source and the M source into solutions and mix the solutions uniformly, and then dry the mixed solution.
  • the resulting mixture was placed in a reaction device.
  • the reaction device is preferably a dynamic reaction device such as a rotary kiln, so that the reaction is more sufficient and uniform.
  • a gas containing nitrogen such as ammonia, nitrogen or a mixed gas thereof, is passed; or hydrogen can be added to the above gas to form a reducing mixed gas as required.
  • the total gas flow can be 10-1000 standard milliliters per minute.
  • the volume ratio of the nitrogen-containing gas to the hydrogen gas can be (1 ⁇ 99): (99 ⁇ 1). Keep the reaction device in a vacuum state and heat it from room temperature to 450-750°C for 2-8 hours.
  • the rotary kiln is preferably turned on.
  • the transparent heat-shielding material obtained is crushed to a particle size range of 1 nm to 1000 nm to obtain transparent heat-shielding particles.
  • the tungsten source nano-powder is used as a raw material to directly obtain nano-sized transparent heat-shielding particles without pulverization.
  • the tungsten source nano powder is preferably a nano tungsten oxide powder, and its particle size is preferably less than 100 nanometers, more preferably less than 50 nanometers.
  • the source of M can be as described above and will not be repeated here.
  • the M source is dissolved in the solvent to prepare a solution.
  • the solvent used can be selected from at least one of water, alcohol, and ether, preferably methanol or ethanol, because it is easy to volatilize, which is beneficial to improve the drying efficiency; the volatilized alcohol can be reused through the recovery system to reduce environmental load.
  • Disperse the tungsten source nano powder in the M source solution mix uniformly, stir for a period of time, for example, 5 to 120 minutes, and then dry to obtain a nano precursor.
  • the obtained nano precursor is placed in a reaction device.
  • the reaction device is preferably a dynamic reaction device such as a rotary kiln, so that the reaction is more sufficient and uniform.
  • a gas containing nitrogen such as ammonia, nitrogen or a mixed gas thereof, is passed; or hydrogen can be added to the above gas to form a reducing mixed gas as required.
  • the total gas flow can be 10-1000 standard milliliters per minute.
  • the volume ratio of the nitrogen-containing gas to the hydrogen gas can be (1 ⁇ 99): (99 ⁇ 1). Keep the reaction device in a vacuum state and heat it from room temperature to 400-700°C for 1-8 hours.
  • the rotary kiln is preferably turned on.
  • the tungsten bronze crystals are heated in the vacuum state of the nitrogen-containing atmosphere before the formation of the tungsten bronze crystals, and the heating is started from room temperature to the highest temperature and kept for a certain period of time, and the nitrogen-containing atmosphere is always maintained during the cooling process. With the vacuum state, it is easy to achieve sufficient nitrogen doping.
  • the tungsten bronze crystal is formed, for example, the tungsten bronze crystal is subjected to a nitrogen-containing atmosphere heat treatment, it is difficult to achieve sufficient nitrogen doping. Even if there is a certain amount of doping, under the same heat treatment conditions, the doping amount is much smaller than the present invention.
  • the obtained powder has a single-phase cesium tungsten bronze crystal structure ( Figure 1).
  • Figure 1 Through a more detailed comparison and analysis of the XRD diffraction peaks, compared with the theoretical ratio of the hexagonal cesium tungsten bronze (Cs 0.33 WO 3 ) diffraction peak, the diffraction peak position is slightly shifted to a higher angle (for example, at 27.8 The diffraction position of the (200) lattice near ° is shifted to a high angle by about 0.2°), which can be considered to be caused by the distortion of the lattice constant caused by nitrogen doping.
  • the moisture and the like that are gradually generated during the reaction are gradually exhausted from the vacuum during the initial heating process.
  • the nitrogen-containing raw materials and the nitrogen element in the ammonia atmosphere are added to the cesium tungsten bronze crystal lattice formation reaction process from room temperature, and the nitrogen-doped cesium tungsten bronze crystal structure is finally formed after gradually heating and treating.
  • the important reasons for achieving nitrogen doping are: 1) using a nitrogen-containing tungsten source, 2) heating in an ammonia-containing vacuum state before forming cesium tungsten bronze crystals, 3) heating from room temperature to the highest temperature and maintaining Keep the powder in an ammonia atmosphere and vacuum state for a certain period of time and during the cooling process.
  • the cesium tungsten bronze crystal is formed, for example, it is difficult to achieve sufficient nitrogen doping when the cesium tungsten bronze crystal is heat-treated in a nitrogen-containing atmosphere.
  • Figure 2 is a transmission electron microscope photo of the obtained powder.
  • the powder is in the form of particles with a particle size of ⁇ hundreds of nanometers.
  • the furnace is kept at a certain degree of vacuum; the furnace rotary device is turned on, the temperature is raised from room temperature to 500°C within 2 hours, and the temperature is kept at this temperature for 8 hours; the heating is stopped and the furnace temperature is naturally cooled to near room temperature; the rotary furnace door is opened to discharge, Obtain the determined nitrogen-doped cesium tungsten bronze powder.
  • Figure 3 is a scanning electron micrograph of the obtained powder.
  • the powder is composed of nitrogen-doped cesium tungsten bronze nanocrystals with an average particle size of about 60nm. Its morphology and particle size distribution are similar to those of nano-tungsten oxide containing tungsten raw materials. Due to the use of nano-tungsten oxide as the raw material, the uniform dispersion of cesium ion alcohol solution, and the heat treatment at a lower temperature, the obtained nitrogen-doped cesium tungsten bronze nano-powder basically maintains the original nanometer size. In this preparation method, the pulverization process is not required, and the nano powder is directly used to obtain the nano heat shielding product.
  • PVB heat-shielding intermediate film obtained in Example 3 Cut an appropriate amount of the PVB heat-shielding intermediate film obtained in Example 3, place it between two pieces of glass (3mm ⁇ 30mm ⁇ 30mm), place it on a heating table, and keep it under pressure at 95°C for a certain period of time. After cooling down, PVB is obtained Cover the heat with laminated glass.
  • the optical transmittance of the heat-shielding laminated glass (N-CWO) obtained in Example 4 was measured with a spectrophotometer, and compared with the use of cesium tungsten bronze nanopowders without nitrogen doping (except during heating Except that only hydrogen is used to avoid nitrogen doping, the preparation method is the same as that in Example 2).
  • the cesium tungsten bronze heat-shielding laminated glass (CWO) obtained by the same method as in Examples 3 and 4 was compared. The results are shown in Figure 4. Shown.
  • the heat-shielding laminated glass made of nitrogen-doped cesium tungsten bronze has a higher infrared rejection rate and also achieves a partial red shift of the absorption end.
  • Example 2 Take 100 g of the nitrogen-doped cesium tungsten bronze nanopowder obtained in Example 2, 2 g of the dispersant and 200 g of toluene into the sand mill, keep it at a rotation speed of 2600 r/min for 5 hours, and obtain a nitrogen-doped cesium tungsten bronze dispersion after taking it out.
  • dispersion A Measure 25 g of the above dispersion, mix it with 75 g of silicone resin, 4 g of polymerization inhibitor, and 1 g of BYK-385N to obtain dispersion A.
  • the powder obtained above was heated in an NH 3 atmosphere with a flow rate of 500 ml/min at 450°C for 60 minutes to obtain a cesium tungsten bronze powder product, which was measured by XRD and it was located at (200) crystal near 27.8°
  • the lattice diffraction position is slightly shifted to the high angle, and the shift is about 0.05°, which indicates that the cesium tungsten bronze after the subsequent heat treatment has nitrogen doping.
  • the reaction formula can be expressed by the following formula:

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Abstract

L'invention concerne un matériau de protection thermique transparent, une dispersion de nanoparticules de protection thermique transparente, leur procédé de préparation et d'utilisation. Le matériau de protection thermique transparent est obtenu par dopage d'azote dans une structure de bronze de tungstène ayant une formule chimique de MxWO3- δ, M représentant un ou plusieurs métaux alcalins quelconques, un métal alcalino-terreux et un élément des terres rares, 0,1≤x≤1, W représente tungstène, O représente oxygène, et 0≤δ≤0,5. Par dopage de l'azote dans une structure de bronze de tungstène classique, l'azote pénètre dans la structure de squelette de tungstène-oxygène pour remplacer une partie de l'oxygène, ce qui entraîne la distorsion du réseau cristallin, de sorte que ce dernier devient petit, et que les ions métalliques dopés ne s'échappent pas facilement, ce qui permet d'augmenter la stabilité de la structure.
PCT/CN2020/102163 2019-07-17 2020-07-15 Matériau de protection thermique transparent, dispersion de microparticules de protection thermique transparente, leur procédé de préparation et d'utilisation WO2021008564A1 (fr)

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