CN114751456A - Preparation method and application of nanocrystalline tungsten bronze - Google Patents

Preparation method and application of nanocrystalline tungsten bronze Download PDF

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CN114751456A
CN114751456A CN202210438150.5A CN202210438150A CN114751456A CN 114751456 A CN114751456 A CN 114751456A CN 202210438150 A CN202210438150 A CN 202210438150A CN 114751456 A CN114751456 A CN 114751456A
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tungsten bronze
preparation
nanocrystalline
drying
nanocrystalline tungsten
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潮洛蒙
李佳新
马永红
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Inner Mongolia University of Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/445—Organic continuous phases
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • 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
    • C03C2218/00—Methods for coating glass
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    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

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Abstract

The invention belongs to the technical field of functional nano materials, and particularly relates to a preparation method and application of nanocrystalline tungsten bronze. The method comprises the steps of dissolving one or more of alkali metal compounds, alkaline earth metal compounds and rare earth compounds and tungstate in water by adopting a solid phase reaction method, uniformly stirring and drying in a drying oven, placing the obtained solid product in a high-temperature furnace filled with nitrogen-hydrogen mixed gas, reacting for 10-1200 min at 400-1200 ℃, and further placing in inert gas for continuously reacting for 10-1200 min to obtain the nanocrystalline tungsten bronze. The raw materials used in the preparation method are low in cost and environment-friendly, and the prepared nanocrystalline tungsten bronze particles are small, transparent and good in heat insulation stability, and the preparation method is simple and easy for large-scale production.

Description

Preparation method and application of nanocrystalline tungsten bronze
Technical Field
The invention belongs to the technical field of functional nano materials, and particularly relates to a preparation method and application of a tungsten bronze nano material.
Background
With the rapid development of the automobile industry and the increase of the area of the automobile glass, the demand of the high-transparency heat-insulating glass is increased in order to reduce the energy consumption of the air conditioner. The high-transparency heat-insulating material for the window can selectively transmit most visible light in sunlight and has strong absorption to ultraviolet and near infrared light, thereby playing a role in transparent heat insulation. At present, materials with transparent heat insulation performance are mainly concentrated on Antimony Tin Oxide (ATO), Indium Tin Oxide (ITO) or rare earth hexaboride and other materials, and the materials have some self limitations. For example, ATO and ITO materials both contain toxic elements of antimony or indium, which are deficient in reserves and high in cost, and cannot highly absorb light in a part of the wavelength range of the near infrared region. The rare earth hexaboride has harsh synthesis conditions, is difficult to prepare nano small particles with uniform size and good dispersibility, and also cannot highly absorb light in a part of wavelength range of a near infrared region.
Recent studies have found that tungsten bronze (M)xWO3) The material is a novel high-transparency heat-insulating material with excellent performance for windows, has the advantages of non-toxic raw materials, simple preparation process, low price and the like, and is an ideal material for manufacturing transparent heat-insulating coatings. However, tungsten bronze materials have serious drawbacks, although they have excellent transparent heat insulating properties. On one hand, the industrialized tungsten bronze powder needs to meet two conditions of small particle size and large-scale production, and the two conditions are difficult to meet simultaneously by the existing preparation method. The tungsten bronze particles prepared by the common solvothermal method have small size, but have low yield and poor environmental protection property; the solid phase reaction method has a large yield, but the obtained particle size is only in the micron order, resulting in poor transparent heat insulation performance. On the other hand, the tungsten bronze heat insulating film has a problem of optical property deterioration with the lapse of time, and such property deterioration due to instability causes local discoloration of the product due to the escape of M atoms from the particle surface in an actual environment or oxidation of the particle surface in a hot and humid environment. At present, the solution to this problem is to coat the tungsten bronze nanoparticles with other suitable materials to prevent the tungsten bronze particles from directly contacting the outside, thereby improving the stability thereof. The Chinese patent application with publication number CN113249091A discloses a preparation method of ATO-coated cesium tungsten bronze composite nano-powder, which adopts antimony-doped tin dioxide nano-particles to coat cesium tungsten bronze particles, thereby isolating cesium tungsten bronze kernel from contacting with external water or oxygen and improving the chemical stability of cesium tungsten bronze, but the preparation process is complex, and the coating is carried out because of the complex preparation processThe shell layer increases the size of particles, and the glass has poor transparent heat insulation effect.
In view of the above, the present invention provides a method for preparing nanocrystalline tungsten bronze, which can realize the large-scale preparation of nanocrystalline tungsten bronze with small particle size and stable transparent heat insulation performance.
Disclosure of Invention
(1) Technical problem to be solved
The invention aims to provide a preparation method of nanocrystalline tungsten bronze to solve the problems of large particle size and unstable transparent heat-insulating property of a tungsten bronze nano material.
(2) Technical scheme
In order to solve the above problems, an aspect of the present invention provides a method for preparing a nanocrystalline tungsten bronze, including the steps of:
s1, dissolving one or more of alkali metal compound, alkaline earth metal compound and rare earth compound and tungstate in water, and uniformly stirring;
s2, placing the mixture obtained in the step S1 in a drying oven for drying, and grinding to obtain a solid product;
s3, placing the solid product obtained in the step S2 in a high-temperature furnace, introducing a nitrogen-hydrogen mixed gas, and reacting for 10-1200 min at 400-1200 ℃;
s4, placing the solid product obtained after the reaction in the step S3 in an inert protective atmosphere for continuous reaction to obtain the nanocrystalline tungsten bronze.
Further, the chemical formula of the tungsten bronze is MxWO3Wherein 0 is<x<1, M is one or more of alkali metal, alkaline earth metal or rare earth element.
Further, in step S1, the tungstate is ammonium tungstate.
Further, in step S1, the alkali metal compound is a chloride of an alkali metal, the alkaline earth metal compound is a chloride of an alkaline earth metal, and the rare earth compound is a chloride of a rare earth element.
Further, in step S1, the stirring device is a magnetic stirrer, and the stirring time is 0.5 to 6 hours.
Further, in the step S2, the drying temperature is 60-200 ℃, and the drying time is 6-12 h.
Further, in step S3, the high temperature furnace is a tube furnace.
Further, in step S3, the reaction temperature is 400 to 1200 ℃, and the reaction time is 10 to 1200 min.
Further, in step S4, the inert protective atmosphere is nitrogen.
On the other hand, the invention provides the application of the nanocrystalline tungsten bronze prepared by the preparation method in energy-saving films, energy-saving glass and energy-saving electrical elements.
(3) Advantageous effects
In summary, the above technical solution of the present invention has the following advantages: the method comprises the steps of dissolving one or more of alkali metal compounds, alkaline earth metal compounds and rare earth compounds and tungstate in water by adopting a solid phase reaction method, uniformly stirring and drying in a drying oven, placing the obtained solid product in a high-temperature furnace filled with nitrogen-hydrogen mixed gas, reacting for 10-1200 min at 400-1200 ℃, and further placing in inert gas for continuously reacting for 10-1200 min to obtain the nanocrystalline tungsten bronze. The raw materials used by the preparation method are low in cost and environment-friendly, and the prepared nanocrystalline tungsten bronze particles are small, transparent and good in heat insulation stability, and the preparation method is simple and easy for large-scale production.
Drawings
FIG. 1 is an XRD pattern of lanthanum tungsten bronze nanocrystals prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the Lanthanated tungsten bronze nanocrystal prepared in example 1 of the present invention.
Fig. 3 is a scanning electron microscope image of the lanthanated tungsten bronze nanocrystal prepared in comparative example 1.
FIG. 4 is a graph showing the light absorption decay with time of the lanthanum tungsten bronze nanocrystals prepared in example 1 of the present invention.
FIG. 5 is a graph showing the light absorption attenuation with time of the tungsten bronze nanocrystals prepared in comparative example 2.
FIG. 6 is a graph comparing the thermal insulation performance of lanthanum tungsten bronze coated glass and blank glass prepared in example 2 of the present invention.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following detailed description of the embodiments and the accompanying drawings are provided to illustrate the principles of the invention and are not intended to limit the scope of the invention, i.e., the invention is not limited to the described embodiments.
The preparation method of the nanocrystalline tungsten bronze provided by the invention comprises the following steps:
s1, dissolving one or more of alkali metal compound, alkaline earth metal compound and rare earth compound and tungstate in water, and uniformly stirring;
s2, placing the mixture obtained in the step S1 in a drying oven for drying, and grinding to obtain a solid product;
s3, placing the solid product obtained in the step S2 in a high-temperature furnace, introducing a nitrogen-hydrogen mixed gas, and reacting for 10-1200 min at 400-1200 ℃;
s4, placing the solid product obtained after the reaction in the step S3 in an inert protective atmosphere for continuous reaction to obtain the nanocrystalline tungsten bronze.
Specifically, in step S1, the tungsten bronze has a chemical formula of MxWO3Wherein 0 is<x<1, M is at least one of alkali metal, alkaline earth metal or rare earth element.
Specifically, in step S1, the tungstate is ammonium tungstate. Preferably, the alkali metal compound is an alkali metal chloride, and can also be an alkali metal carbonate; the alkaline earth metal compound is chloride of alkaline earth metal, and can also be carbonate of alkaline earth metal; the rare earth compound is chloride of rare earth element, and can also be carbonate of rare earth element.
Specifically, in step S1, the stirring device is a magnetic stirrer, and the stirring time is 0.5 to 6 hours, preferably 1 hour.
Specifically, in step S2, the drying oven is a constant temperature drying oven; the drying temperature is 60-200 ℃, and preferably, the drying temperature is 180 ℃; the drying time is 6-12 h, and preferably 8 h.
Specifically, in step S2, the grinding time is preferably 30 min.
Specifically, in step S3, the high temperature furnace is a tube furnace.
Specifically, in step S3, the reaction temperature is 400 to 1200 ℃, preferably, the reaction temperature is 500 ℃; the reaction time is 10-1200 min, preferably 1 h.
Specifically, in step S4, the inert protective atmosphere is nitrogen, the reaction temperature is 400 to 1200 ℃, and preferably, the reaction temperature is 800 ℃; the reaction time is 10-1200 min, preferably 1 h.
On the other hand, the invention provides the application of the nanocrystalline tungsten bronze prepared by the preparation method in energy-saving films, energy-saving glass and energy-saving electric elements.
Specifically, the transparent heat-insulating coating glass is manufactured by loading nanocrystalline tungsten bronze on glass.
Specifically, the method for manufacturing the heat-insulating coating glass comprises the following steps: dissolving tungsten bronze nanocrystals in an ethanol solution, ultrasonically dispersing the tungsten bronze nanocrystals uniformly, adding PVB resin under the stirring condition, and stirring the mixture uniformly to obtain coating slurry. And then placing a glass sheet on a spin coater, rotating at the rotating speed of 2000r/min, dropping the prepared coating slurry on the glass sheet, rotating for 40s to obtain coated glass, and finally keeping the coated glass at 40 ℃ for 1h to remove residual liquid so as to obtain the heat-insulating coated glass.
Example 1
The preparation method of the nanocrystalline lanthanum tungsten bronze provided by the invention comprises the following steps:
s1, taking 0.0858g of lanthanum chloride and 0.6375g of ammonium tungstate, putting the two medicines into 100ml of deionized water, stirring for 1 hour in a magnetic stirrer, and uniformly stirring;
s2, putting the obtained mixture into a constant-temperature drying oven, drying at 180 ℃ for 8h, taking out the powder, and grinding for 30 min;
s3, putting the powder into a tube furnace, heating to 500 ℃, and simultaneously introducing mixed nitrogen and hydrogen gas (95/5) for reduction for 1 h; and then heating to 800 ℃, introducing nitrogen, and keeping the temperature for 1h to obtain the nanocrystalline lanthanum tungsten bronze.
Comparative example 1
The method for preparing the nanocrystalline tungsten bronze by using the lanthanum carbonate as the raw material comprises the following steps:
s1, putting 0.0801g of lanthanum carbonate and 0.6375g of ammonium tungstate into 100ml of deionized water, stirring for 1 hour in a ceramic crucible, and uniformly stirring;
step S2 and step S3 are the same as in embodiment 1.
Comparative example 2
The method for preparing the nanocrystalline tungsten bronze by adopting the solvothermal method comprises the following steps:
s1, 0.377g of cesium hydroxide was added to 150mL of benzyl alcohol solution, magnetically stirred for 20min, and then 0.9g of WCl6 was added to maintain the concentration of WCl6 in the precursor solution at 0.015 mol/L.
S2, transferring the solution into an autoclave with the temperature of 200 ℃ for reaction for 4 hours.
S3, washing the product with deionized water and alcohol for several times, collecting blue powder by centrifugation, and drying in vacuum at 60 ℃ for 2h to obtain tungsten bronze nanocrystals.
Fig. 1 is an XRD chart of the lanthanated tungsten bronze nanocrystal prepared in example 1 of the present invention, from which it can be seen that the lanthanated tungsten bronze prepared is a pure cubic structure. Fig. 2 is a scanning electron microscope image of the lanthana tungsten bronze nano material prepared in the embodiment 1, and it can be seen that the size of the prepared lanthana tungsten bronze nano particle is only 30-150 nm. Fig. 3 is a scanning electron microscope image of the lanthanated tungsten bronze nanomaterial prepared in comparative example 1, and comparing fig. 2 and fig. 3, it can be seen that lanthanated tungsten bronze particles obtained using lanthanum chloride as a raw material are significantly smaller in size, uniform in distribution, and good in dispersibility than those obtained using lanthanum carbonate as a raw material.
Fig. 4 is a schematic view showing the light absorption attenuation with time of the lanthanum tungsten bronze nanocrystal prepared in example 1 of the present invention, and fig. 5 is a schematic view showing the light absorption attenuation with time of the tungsten bronze nanocrystal prepared in comparative example 2 by the solvothermal method. Comparing fig. 4 and 5, it can be seen that the absorption of the tungsten bronze nanocrystal prepared by the solvothermal method in comparative example 2 for near infrared light after 100 days is greatly changed and the attenuation is extremely severe, while the absorption curve of the tungsten bronze nanocrystal prepared by example 1 of the present invention for infrared light after 100 days is still very stable.
Example 2
The nanocrystalline lanthanum tungsten bronze prepared in example 1 was prepared as heat-insulating coated glass, and the heat-insulating effect of the lanthanum tungsten bronze coated glass was tested.
The manufacturing method of the lanthanum tungsten bronze coating glass comprises the following steps:
s1, dissolving 0.2g of nanocrystalline lanthanum tungsten bronze prepared in example 1 in 20ml of ethanol solution, performing ultrasonic dispersion for 30min, adding 5g of PVB resin under strong magnetic stirring, and stirring for 20min to obtain coating slurry.
S2, placing the glass sheet on a spin coater, rotating at 2000r/min, dropping the prepared coating slurry on the glass sheet, rotating for 40S to obtain coated glass, and finally keeping the coated glass at 40 ℃ for 1h to remove residual liquid.
The method for testing the performance of the lanthanum-tungsten-bronze coating glass comprises the following steps: the prepared lanthanum tungsten bronze coating glass and blank glass are simultaneously placed on an experimental room, and the temperature change in the test room is measured after the glass and the blank glass are respectively irradiated by an infrared lamp for a period of time.
As can be seen from FIG. 6, the maximum indoor temperature of the blank glass on the laboratory room is as high as 36 ℃, while the best indoor temperature of the lanthanum tungsten bronze coated glass prepared in example 2 on the laboratory room is only 30.3 ℃, that is, the lanthanum tungsten bronze coated glass can reduce the temperature of the laboratory room by 5.7 ℃, which shows that the lanthanum tungsten bronze coated glass prepared by the method has good heat insulation effect.
In conclusion, in the preparation method of the nanocrystalline tungsten bronze, the rapid preparation of the nanocrystalline tungsten bronze is realized by adopting a solid-phase reaction method and a three-step method of dissolving, drying and high-temperature reduction of raw materials, the prepared nanocrystalline tungsten bronze has small particles and good transparency and stability, and the lanthanum tungsten bronze coating glass prepared by adopting the nanocrystalline tungsten bronze has good heat insulation property, and the preparation method has simple process and is easy for large-scale production.
It is to be understood that the invention is not limited to the specific steps and structures described above and shown in the attached drawings. Also, a detailed description of known process techniques is omitted herein for the sake of brevity.
The above description is only an example of the present application and is not limited to the present application. Various modifications and alterations to this application will become apparent to those skilled in the art without departing from the scope of this invention. Any modification, equivalent replacement, improvement or the like made within the spirit and principle of the present application shall be included in the scope of the claims of the present application.

Claims (10)

1. A preparation method of nanocrystalline tungsten bronze is characterized by comprising the following steps: the method comprises the following steps:
s1, dissolving one or more of alkali metal compound, alkaline earth metal compound and rare earth compound and tungstate in water, and uniformly stirring;
s2, placing the mixture obtained in the step S1 in a drying oven for drying, and grinding to obtain a solid product;
s3, placing the solid product obtained in the step S2 in a high-temperature furnace, introducing a nitrogen-hydrogen mixed gas, and reacting for 10-1200 min at 400-1200 ℃;
s4, placing the solid product obtained after the reaction in the step S3 in an inert protective atmosphere for continuous reaction to obtain the nanocrystalline tungsten bronze.
2. The production method according to claim 1, characterized in that: the chemical formula of the tungsten bronze is MxWO3Wherein 0 is<x<1, M is one or more of alkali metal, alkaline earth metal or rare earth element.
3. The method of claim 1, wherein: in step S1, the tungstate is ammonium tungstate.
4. The method of claim 1, wherein: in step S1, the alkali metal compound is a chloride of an alkali metal, the alkaline earth metal compound is a chloride of an alkaline earth metal, and the rare earth compound is a chloride of a rare earth element.
5. The method of claim 1, wherein: in the step S1, the stirring device is a magnetic stirrer, and the stirring time is 0.5-6 h.
6. The method of claim 1, wherein: in the step S2, the drying temperature is 60-200 ℃, and the drying time is 6-12 h.
7. The method of claim 1, wherein: in step S3, the high temperature furnace is a tube furnace.
8. The method of claim 1, wherein: in step S3, the reaction temperature is 400-1200 ℃, and the reaction time is 10-1200 min.
9. The method of claim 1, wherein: in step S4, the inert protective atmosphere is nitrogen.
10. The application of the nanocrystalline tungsten bronze is characterized in that: the application of the nanocrystalline tungsten bronze prepared by the preparation method of any one of claims 1 to 9 in energy-saving films, energy-saving glass and energy-saving electrical elements.
CN202210438150.5A 2022-04-25 2022-04-25 Preparation method and application of nanocrystalline tungsten bronze Pending CN114751456A (en)

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Cited By (1)

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CN116553836A (en) * 2023-07-08 2023-08-08 内蒙古科技大学 Tungsten bronze doped heat insulation glass and preparation method thereof

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