CN111977693A - Device for preparing cesium tungsten bronze spherical nanocrystals and application method thereof - Google Patents
Device for preparing cesium tungsten bronze spherical nanocrystals and application method thereof Download PDFInfo
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- CN111977693A CN111977693A CN202010901362.3A CN202010901362A CN111977693A CN 111977693 A CN111977693 A CN 111977693A CN 202010901362 A CN202010901362 A CN 202010901362A CN 111977693 A CN111977693 A CN 111977693A
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Abstract
The invention provides a device for preparing cesium tungsten bronze spherical nanocrystals, which comprises a reaction device (1), a cooling device (2), a tubular furnace (3), a vacuum pump (4), a waste gas collecting device (5) and a gas guide tube, wherein the reaction device is arranged in the shell; wherein, reaction unit (1) holds device (14) including reaction chamber (11), cylindrical cooling tube (12), ultrasonic nebulizer (13) and solution, and cooling device (2) include inlet tube (21), outlet pipe (22) and cooler bin (23). The cesium tungsten bronze nanocrystalline prepared by the device consists of monodisperse solid microspheres, each microsphere is formed by stacking nanocrystalline grains, and the nanocrystalline grains are combined with each other under a weak acting force, so that the solid microspheres cannot have the agglomeration problem, are very easy to grind into nanocrystalline with good dispersibility, and can be used for configuring high-quality cesium tungsten bronze nano ink; meanwhile, the device for preparing the cesium tungsten bronze nanocrystalline is simple to operate, strong in practicability and short in period, and can be used for large-scale production.
Description
Technical Field
The invention relates to the technical field of transparent heat insulation materials and coatings, in particular to a device for preparing cesium tungsten bronze spherical nanocrystals and a using method thereof.
Background
Cesium tungsten bronze (Cs)xWO3) The compound is a functional compound with a non-stoichiometric ratio and a special oxygen octahedron structure, and has low resistivity and low-temperature superconducting performance. The cesium tungsten bronze film has good near-infrared shielding performance and small visible light absorption, and can be used as a good near-infrared heat insulation material. Meanwhile, the cesium tungsten bronze is processed into a nano material and then prepared into ink which can be compounded with a polymer, and a heat insulation product with higher optical quality can be prepared by spraying, blade coating, roller coating and other methods, and the manufacturing cost is very low, so that the cesium tungsten bronze has very attractive application prospects in the fields of automobiles and buildings.
At present, the cesium tungsten bronze nano powder mainly adopts a citric acid induced hydrothermal synthesis method, and the general process is as follows: adding a cesium source, citric acid and a tungsten source into a reaction kettle, carrying out hydrothermal reaction for 3 days at 190 ℃ to obtain a liquid product, and extracting, washing, separating and drying the liquid product to obtain cesium-tungsten bronze nano powder; or mixing a tungsten source, thiourea, a pH value regulator, oleylamine, a cesium source and water, and reacting for 10-30 hours at 180-220 ℃, but the hydrothermal synthesis method has the advantages of low yield, high pressure, long reaction period, potential safety hazard and unsuitability for large-scale production.
In addition, the cesium tungsten bronze nano material also has the technical problems of easy agglomeration, difficult dispersion and the like, and the prepared ink has poor stability and brings difficulties to practical application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a device for preparing cesium tungsten bronze spherical nanocrystals, which can prepare the cesium tungsten bronze spherical nanocrystals with good dispersibility and difficult agglomeration, wherein the prepared cesium tungsten bronze spherical nanocrystals can form a stable dispersion liquid in common solvents such as deionized water, ethanol, ethylene glycol monomethyl ether, dichloromethane and the like; meanwhile, the device is simple to operate, the reaction period for preparing the cesium tungsten bronze spherical nanocrystalline is short, and the device can be used for mass and large-scale production.
The invention also aims to provide a using method of the device for preparing the cesium tungsten bronze spherical nanocrystalline.
The purpose of the invention is realized by the following technical scheme:
a device for preparing cesium tungsten bronze spherical nanocrystals is characterized in that: comprises a reaction device, a cooling device, a tube furnace, a vacuum pump, a waste gas collecting device and an air duct; the reaction device comprises a reaction cavity, a cylindrical cooling pipe, an ultrasonic atomizer and a solution containing device, wherein the cylindrical cooling pipe is an annular pipe, the cross section of the cylindrical cooling pipe is U-shaped, the reaction cavity is a cylindrical cavity and is arranged in a U-shaped groove of the cylindrical cooling pipe, the inner wall of the cylindrical cooling pipe is coplanar with the outer wall of the reaction cavity, the ultrasonic atomizer is arranged at the bottom of the reaction cavity, the solution containing device is arranged on the upper side of the ultrasonic atomizer, and the outer wall of the solution containing device is fixedly connected with the side wall of the reaction cavity; the cooling device comprises a water inlet pipe, a water outlet pipe and a cooling box, wherein one end of the water inlet pipe is communicated with a water inlet at the top end of one side of the cylindrical cooling pipe, the other end of the water inlet pipe is communicated with the corresponding side of the cooling box, one end of the water outlet pipe is communicated with a water outlet at the top end of the cylindrical cooling pipe, which is far away from the water inlet, the other end of the water outlet pipe is communicated with the corresponding side of the cooling box, and the; the top of the reaction cavity is respectively communicated with a T-shaped air duct and an L-shaped air duct, the T-shaped air duct and the L-shaped air duct penetrate through the top of the reaction cavity and extend into the cavity, the bottom of the T-shaped air duct is lower than the bottom of the L-shaped air duct, the T-shaped air duct and the bottom of the L-shaped air duct are not in contact with the solution containing device, the other end of the L-shaped air duct is communicated with the tube furnace, and one end of the tube furnace, far away from the L-shaped air duct, is respectively communicated with a waste gas collecting device and a vacuum pump through an air outlet pipe and a vacuum pipe; the L-shaped air guide pipe positioned between the reaction cavity and the tube furnace is communicated with a first air inlet pipe, and the first air inlet pipe is communicated with one end of the T-shaped air guide pipe and is simultaneously communicated with a second air inlet pipe; the three sections at the turning point of the T-shaped air guide pipe are respectively provided with a first air guide valve, a second air guide valve and a third air guide valve, the second air inlet pipe is provided with a fourth air guide valve, one end of the first air inlet pipe, which is far away from the L-shaped air guide pipe, is provided with a fifth air guide valve, the connection point of the second air inlet pipe and the first air inlet pipe and the connection point of the T-shaped air guide pipe and the first air inlet pipe are both positioned between the fifth air guide valve and the L-shaped air guide pipe, the air outlet pipe is provided with a sixth air guide valve, and the vacuum pipe is provided with a seventh air guide valve.
In a further optimization, the solution containing device is of an arc-shaped structure.
For further optimization, the cooling box is provided with a cooling switch for controlling the circulating flow of cooling water.
The use method of the device for preparing the cesium tungsten bronze spherical nanocrystalline is characterized by comprising the following steps:
a. solution preparation and preparation work: dissolving a tungsten source and a cesium source in deionized water to form a solution, putting the solution into a solution containing device, closing all gas guide valves (namely a first gas guide valve, a second gas guide valve, a third gas guide valve, a fourth gas guide valve, a fifth gas guide valve, a sixth gas guide valve and a seventh gas guide valve), opening a cooling switch, and enabling cooling water to circularly flow in a cooling box and a U-shaped cooling pipe;
b. preparing a precursor: heating the tube furnace to a target temperature, keeping the temperature, then starting an ultrasonic atomizer power supply to atomize aqueous solution of a cesium source and a tungsten source into aerosol, opening a first air guide valve, a third air guide valve and a sixth air guide valve, introducing carrier gas from the first air guide valve, moving the aerosol into the tube furnace along with the carrier gas, thermally cracking the aerosol in the tube furnace, and depositing a white visible cesium tungsten bronze precursor on the inner wall of the tube furnace;
c. drying the precursor: closing the heating power supply of the tube furnace, the first gas guide valve, the third gas guide valve and the sixth gas guide valve, opening the seventh gas guide valve and the vacuum pump, vacuumizing and drying the tube furnace, and fully drying precursor powder in the tube furnace;
d. annealing treatment: closing the seventh air guide valve, opening the first air guide valve, the second air guide valve and the fourth air guide valve, and introducing H from the fourth air guide valve2Introducing N from the first air guide valve and the second air guide valve2Controlling air pressure, closing the first air guide valve, the second air guide valve and the fourth air guide valve, and heating and insulating the tube furnace;
e. completing the preparation: and (3) closing the power supply of the tube furnace, naturally cooling, opening the fifth gas guide valve, introducing air, opening the tube furnace when the air pressure is consistent with the external air pressure, and taking out the cesium tungsten bronze nanocrystals.
Preferably, the tungsten source is any one of ammonium tungstate or ammonium metatungstate or a mixture thereof.
Further preferably, the cesium source is any one of cesium hydroxide or cesium carbonate or a mixture thereof.
Further optimizing, the molar ratio of the tungsten element to the cesium element in the solution in the step a is 0.2-0.33: 1.
For further optimization, the tungsten (namely W) in the solution of the step a6+) The concentration of (b) is 0.2 to 1 mol/L.
And c, further optimizing, wherein the target temperature in the step b is 120-230 ℃, and the time for heat preservation and thermal cracking is 30-300 min.
And c, further optimizing, wherein in the step b, the cesium source and tungsten source aqueous solution is fully atomized into 20-30 mu m of aerial fog by the ultrasonic atomizer, and the atomization rate is 2-8 ml/min.
And c, further optimizing, wherein the carrier gas introduced in the step b is any one of argon and nitrogen or a mixture thereof, and the gas flow rate is 5-12 ml/min.
And (c) further optimizing, wherein the vacuum degree of the vacuumizing and drying in the step c is-0.05 to-0.06 MPa.
For further optimization, H is introduced in the step c2And N2The volume ratio of (A) is 1/20-1/5, and the pressure in the tube furnace is 0.02-0.07 MPa.
And d, further optimizing, wherein the heating temperature of the tubular furnace in the step d is 400-550 ℃, and the heat preservation time is 1-5 h.
The cesium tungsten bronze nanocrystals in the step e are regular solid microspheres with the diameter of 2-5 microns, and the solid microspheres are independent from each other; each microsphere is formed by stacking 20-50 nm crystal grains.
In the conventional preparation process, the cesium tungsten bronze nano material has the technical problems of easy agglomeration, difficult dispersion and the like, so that the prepared ink has poor stability and is easy to generate precipitates, impurities and the like. According to the invention, a high-energy dispersion mechanism generated by a specific ultrasonic atomization process is matched with a raw material with a specific concentration, so that cesium ions enter a tungsten source and are uniformly dispersed, and meanwhile, a mixed solution of the cesium ions is dispersed into a plurality of small fog drops; then, the small fog drops subjected to ultrasonic atomization are cracked into an aggregation form with incompletely developed crystal grains by utilizing a thermal cracking process at a specific temperature, so that the acting force between the quasicrystal grains and the quasicrystal grains is reduced, and the thermal cracking process at the specific temperature further ensures that cesium ions are uniformly dispersed in the fog drops; finally, vacuum-pumping, drying and introducing H2And N2The mixed gas and annealing treatment reduce partial hexavalent tungsten ions into pentavalent tungsten ions to form tungsten oxide lattices, and cesium ions are uniformly dispersed in the tungsten source all the time, so that when the tungsten source forms the lattices, the cesium ions are filled in the tungsten oxide lattices in situ, stable grains with small mutual acting force and easy dispersion are formed, and further regular solid nanospheres formed by stacking grains with small mutual acting force are formed, thereby avoiding the agglomeration of the cesium tungsten bronze nano-materials, ensuring the good dispersibility of the cesium tungsten bronze nano-materials and improving the heat insulation performance of the tungsten bronze nano-materials.
The invention has the following technical effects:
the invention provides a device for preparing cesium tungsten bronze spherical nanocrystals, wherein the cesium tungsten bronze nanocrystals prepared by the device consist of monodisperse solid microspheres, each microsphere is formed by stacking nanocrystals, and the nanocrystals are combined with a weak acting force, so that the solid microspheres cannot have the agglomeration problem, are very easy to grind into nanocrystals with good dispersibility, and are used for configuring high-quality cesium tungsten bronze nano ink. Meanwhile, after the solid micro-spheres prepared by the device are ground, stable dispersion liquid is easily formed in common solvents such as deionized water, ethanol, ethylene glycol monomethyl ether, dichloromethane and the like through modification, so that the device can be compatible with low-cost spraying, blade coating, roller coating, ink-jet printing, spin coating and other technologies, and is applied to the field of heat insulation, wide in application range and large in application field.
The device is simple to operate, strong in practicability and short in period for preparing the cesium tungsten bronze, can be used for mass and large-scale production, raw materials for preparing the cesium tungsten bronze by the device do not need other auxiliaries, solvents and stabilizers except a tungsten source, a cesium source and deionized water, the product is single-phase and high-purity, the raw materials are all environment-friendly substances, toxic and harmful substances which have large influences on the nature and human beings are not generated in the production and use processes, and the requirements of environmental protection and economic conservation at present are met.
Drawings
Fig. 1 is a schematic structural diagram of a device for preparing cesium tungsten bronze spherical nanocrystals in an embodiment of the present invention.
Fig. 2 is a scanning electron microscope image of the cesium tungsten bronze spherical nanocrystal prepared in the example of the present invention.
Fig. 3 is an X-ray diffraction pattern of the cesium tungsten bronze spherical nanocrystal prepared in the example of the present invention.
FIG. 4 is a scanning electron microscope image of wet-milled monodisperse cesium tungsten bronze spherical nanocrystals prepared in the examples of the present invention.
Fig. 5 shows nano ink prepared from the cesium tungsten bronze spherical nanocrystals prepared in the example of the present invention.
Fig. 6 is a transmittance curve of a nano composite film prepared from the cesium tungsten bronze spherical nanocrystals prepared in the example of the present invention.
Wherein, 1, a reaction device; 11. a reaction chamber; 12. a cylindrical cooling tube; 13. an ultrasonic atomizer; 14. a solution containing device; 2. a cooling device; 21. a water inlet pipe; 22. a water outlet pipe; 23. a cooling tank; 3. a tube furnace; 4. a vacuum pump; 5. an exhaust gas collection device; 61. a T-shaped air duct; 62. an L-shaped air duct; 63. a first intake pipe; 64. a second intake pipe; 65. a vacuum tube; 66. an air outlet pipe; 611. a first air guide valve; 612. a second air guide valve; 613. a third air guide valve; 614. a fourth air guide valve; 615. a fifth gas guide valve; 616. a sixth air guide valve; 617. and a seventh air guide valve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
as shown in fig. 1, an apparatus for preparing cesium tungsten bronze spherical nanocrystals is characterized in that: comprises a reaction device 1, a cooling device 2, a tube furnace 3, a vacuum pump 4, an exhaust gas collecting device 5 and an air duct; the reaction device 1 comprises a reaction chamber 11, a cylindrical cooling pipe 12, an ultrasonic atomizer 13 and a solution containing device 14, wherein the cylindrical cooling pipe 12 is an annular pipe, the cross section of the cylindrical cooling pipe is U-shaped, the reaction chamber 11 is a cylindrical cavity and is arranged inside a U-shaped groove of the cylindrical cooling pipe 12, the inner wall of the cylindrical cooling pipe 12 is coplanar with the outer wall of the reaction chamber 11, the ultrasonic atomizer 13 is arranged at the bottom of the reaction chamber 11, the solution containing device 14 is arranged on the upper side of the ultrasonic atomizer 13, the outer wall of the solution containing device 14 is fixedly connected with the side wall of the reaction chamber 11, and the solution containing device 14 is of an arc-shaped structure and is similar to a bowl-shaped structure; the cooling device 2 comprises a water inlet pipe 21, a water outlet pipe 22 and a cooling box 23, one end of the water inlet pipe 21 is communicated with a water inlet at the top end of one side of the cylindrical cooling pipe 12, the other end of the water inlet pipe is communicated with the corresponding side of the cooling box 23, one end of the water outlet pipe 22 is communicated with a water outlet at the top end of the cylindrical cooling pipe 12 far away from the water inlet, the other end of the water outlet pipe is communicated with the corresponding side of the cooling; the cooling tank 23 is provided with a cooling switch for controlling the circulation flow of the cooling water. The top of the reaction cavity 11 is respectively communicated with a T-shaped air duct 61 and an L-shaped air duct 62, the T-shaped air duct 61 and the L-shaped air duct 62 both penetrate through the top of the reaction cavity 11 and extend into the cavity, the bottom of the T-shaped air duct 61 is lower than the bottom 62 of the L-shaped air duct, the T-shaped air duct 61 and the bottom of the L-shaped air duct 62 are not in contact with the solution containing device 14, the other end of the L-shaped air duct 62 is communicated with the tube furnace 3, and one end of the tube furnace 3, far away from the L-shaped air duct 62, is respectively communicated with the waste gas collecting device 5 and the vacuum pump 4 through an air outlet pipe 66 and a vacuum pipe; the L-shaped air duct 62 positioned between the reaction cavity 11 and the tube furnace 3 is communicated with a first air inlet pipe 63, and the first air inlet pipe 63 is communicated with one end of the T-shaped air duct 61 and a second air inlet pipe 64; three sections at the inflection point of the T-shaped air duct 61 are respectively provided with a first air guide valve 611, a second air guide valve 612 and a third air guide valve 613, the second air inlet pipe 64 is provided with a fourth air guide valve 614, one end of the first air inlet pipe 63, which is far away from the L-shaped air duct 62, is provided with a fifth air guide valve 615, the connection point of the second air inlet pipe 64 and the first air inlet pipe 63, the connection point of the T-shaped air guide pipe 61 and the first air inlet pipe 63 is positioned between the fifth air guide valve 615 and the L-shaped air duct 62, the air outlet pipe 66 is provided with a sixth air guide valve 616, and the vacuum pipe 65 is provided with a seventh air guide valve 617.
Example 2:
the use method of the device for preparing the cesium tungsten bronze spherical nanocrystal is characterized by comprising the following steps of:
a. solution preparation and preparation work: dissolving ammonium tungstate and cesium hydroxide in deionized water to form a solution, placing the solution into the solution containing device 14, closing all gas valves (i.e., the first gas valve 611, the second gas valve 612, the third gas valve 613, the fourth gas valve 614, the fifth gas valve 615, the sixth gas valve 616 and the seventh gas valve 617), and opening a cooling switch to enable cooling water to circularly flow in the cooling tank 23 and the U-shaped cooling pipe 12; wherein the molar ratio of tungsten to cesium in the solution is 0.33:1, tungsten (i.e., W)6+) The concentration of (2) was 0.2 mol/L.
b. Preparing a precursor: heating the tube furnace to 3-120 ℃ and preserving heat, then starting a power supply of an ultrasonic atomizer 13 to fully atomize the cesium source and tungsten source aqueous solution into 20-micron aerosol with the atomization rate of 2ml/min, opening a first air guide valve 611, a third air guide valve 613 and a sixth air guide valve 616, introducing argon gas from the first air guide valve 611 as carrier gas with the gas flow rate of 5ml/min, moving the aerosol into the tube furnace 3 along with the carrier gas to carry out thermal cracking in the tube furnace 3 for 260min, and finally depositing a white visible cesium tungsten bronze precursor on the inner wall of the tube furnace 3;
c. drying the precursor: closing the heating power supply of the tube furnace 3, the first air guide valve 611, the third air guide valve 613 and the sixth air guide valve 616, opening the seventh air guide valve 617 and the vacuum pump 4, vacuumizing and drying the tube furnace to ensure that the vacuum degree is-0.05 MPa, and fully drying the precursor powder in the tube furnace 3;
d. annealing treatment: closing the seventh air guiding valve 617, opening the first air guiding valve 611, the second air guiding valve 612 and the fourth air guiding valve 614, and introducing H from the fourth air guiding valve 6142N is introduced from the first air guiding valve 611 and the second air guiding valve 6122And controlling the air pressure, wherein H2And N2The volume ratio of the gas pressure in the tube furnace 3 is 1/20, the air pressure in the tube furnace 3 is 0.02MPa, then the first gas guide valve 611, the second gas guide valve 612 and the fourth gas guide valve 614 are closed, the tube furnace 3 is heated to 400 ℃, and the heat preservation time is 1 h;
e. completing the preparation: turning off the power supply of the tube furnace 3, naturally cooling, opening the fifth gas guide valve 615, introducing air, opening the tube furnace 3 when the air pressure is consistent with the external air pressure, and taking out the cesium tungsten bronze nanocrystals; wherein, the cesium tungsten bronze nanocrystals are regular solid microspheres with the diameter of about 2 μm, and the solid microspheres are independent from each other; each microsphere is formed by stacking crystal grains with the grain size of about 20 nm.
FIG. 3 is an X-ray diffraction pattern of the monodisperse cesium tungsten bronze spherical nanocrystal prepared in example 1, showing that the precursor is an underdeveloped quasicrystal before annealing, i.e., after thermal cracking, and that the Cs is highly pure after annealing0.33WO3The crystal form is complete and the performance is stable.
Example 3:
the use method of the device for preparing the cesium tungsten bronze spherical nanocrystal is characterized by comprising the following steps of:
a. solution preparation and preparation work: ammonium tungstate and ammonium metatungstateThe mixture of (3), cesium hydroxide and cesium carbonate is dissolved in deionized water to form a solution, the solution is placed in the solution containing device 14, all the gas valves (i.e., the first gas valve 611, the second gas valve 612, the third gas valve 613, the fourth gas valve 614, the fifth gas valve 615, the sixth gas valve 616 and the seventh gas valve 617) are closed, and the cooling switch is turned on to circulate cooling water in the cooling tank 23 and the U-shaped cooling pipe 12; wherein the molar ratio of tungsten to cesium in the solution is 0.27: 1, tungsten (i.e., W)6+) The concentration of (2) is 0.6 mol/L.
b. Preparing a precursor: heating the tube furnace to 3-160 ℃ and preserving heat, then starting a power supply of an ultrasonic atomizer 13 to fully atomize the cesium source and tungsten source aqueous solution into 25-micron aerosol with the atomization rate of 6ml/min, opening a first air guide valve 611, a third air guide valve 613 and a sixth air guide valve 616, introducing argon gas from the first air guide valve 611 as carrier gas with the gas flow rate of 9ml/min, moving the aerosol into the tube furnace 3 along with the carrier gas, carrying out thermal cracking in the tube furnace 3 for 180min, and finally depositing a white visible cesium tungsten bronze precursor on the inner wall of the tube furnace 3;
c. drying the precursor: closing the heating power supply of the tube furnace 3, the first air guide valve 611, the third air guide valve 613 and the sixth air guide valve 616, opening the seventh air guide valve 617 and the vacuum pump 4, vacuumizing and drying the tube furnace to ensure that the vacuum degree is-0.055 MPa, and fully drying the precursor powder in the tube furnace 3;
d. annealing treatment: closing the seventh air guiding valve 617, opening the first air guiding valve 611, the second air guiding valve 612 and the fourth air guiding valve 614, and introducing H from the fourth air guiding valve 6142N is introduced from the first air guiding valve 611 and the second air guiding valve 6122And controlling the air pressure, wherein H2And N2The volume ratio of the gas pressure in the tube furnace 3 is 1/10, the air pressure in the tube furnace 3 is 0.04MPa, then the first gas guide valve 611, the second gas guide valve 612 and the fourth gas guide valve 614 are closed, the tube furnace 3 is heated to 480 ℃, and the heat preservation time is 3 hours;
e. completing the preparation: turning off the power supply of the tube furnace 3, naturally cooling, opening the fifth gas guide valve 615, introducing air, opening the tube furnace 3 when the air pressure is consistent with the external air pressure, and taking out the cesium tungsten bronze nanocrystals; wherein, the cesium tungsten bronze nanocrystals are regular solid microspheres with the diameter of about 3 mu m, and the solid microspheres are mutually independent; each microsphere is formed by stacking crystal grains with the grain size of about 30 nm.
10g of monodisperse cesium tungsten bronze spherical nanocrystals prepared as in example 3 were added with 40ml of ethanol and 1ml of a silane coupling agent, and after grinding, they became monodisperse nanocrystals having a particle size of about 30nm, as shown in FIG. 4; meanwhile, after the monodisperse spherical cesium tungsten bronze nanocrystals in the step 32 are wet-milled, ethanol is added to prepare the nano ink with the concentration of 5wt%, as shown in fig. 5, the ink does not settle obviously after standing for more than 3 months, and the cesium tungsten bronze spherical nanocrystals are proved to have good dispersibility and are not easy to agglomerate.
Example 4:
the use method of the device for preparing the cesium tungsten bronze spherical nanocrystal is characterized by comprising the following steps of:
a. solution preparation and preparation work: dissolving ammonium metatungstate and cesium carbonate in deionized water to form a solution, putting the solution into the solution containing device 14, closing all gas valves (i.e. the first gas valve 611, the second gas valve 612, the third gas valve 613, the fourth gas valve 614, the fifth gas valve 615, the sixth gas valve 616 and the seventh gas valve 617), and opening a cooling switch to enable cooling water to circularly flow in the cooling box 23 and the U-shaped cooling pipe 12; wherein the molar ratio of tungsten to cesium in the solution is 0.2: 1, tungsten (i.e., W)6+) The concentration of (2) is 1 mol/L.
b. Preparing a precursor: heating the tube furnace 3 to 220 ℃ and preserving heat, then starting a power supply of an ultrasonic atomizer 13 to fully atomize the cesium source and tungsten source aqueous solution into 30-micron aerosol with the atomization rate of 8ml/min, opening a first air guide valve 611, a third air guide valve 613 and a sixth air guide valve 616, introducing argon gas from the first air guide valve 611 as carrier gas with the gas flow rate of 12ml/min, moving the aerosol into the tube furnace 3 along with the carrier gas, carrying out thermal cracking in the tube furnace 3 for 100min, and finally depositing a white visible cesium tungsten bronze precursor on the inner wall of the tube furnace 3;
c. drying the precursor: closing the heating power supply of the tube furnace 3, the first air guide valve 611, the third air guide valve 613 and the sixth air guide valve 616, opening the seventh air guide valve 617 and the vacuum pump 4, vacuumizing and drying the tube furnace to ensure that the vacuum degree is-0.06 MPa, and fully drying the precursor powder in the tube furnace 3;
d. annealing treatment: closing the seventh air guiding valve 617, opening the first air guiding valve 611, the second air guiding valve 612 and the fourth air guiding valve 614, and introducing H from the fourth air guiding valve 6142N is introduced from the first air guiding valve 611 and the second air guiding valve 6122And controlling the air pressure, wherein H2And N2The volume ratio of the gas pressure in the tube furnace 3 is 1/5, the air pressure in the tube furnace 3 is 0.07MPa, then the first gas guide valve 611, the second gas guide valve 612 and the fourth gas guide valve 614 are closed, the tube furnace 3 is heated to 550 ℃, and the heat preservation time is 5 hours;
e. completing the preparation: turning off the power supply of the tube furnace 3, naturally cooling, opening the fifth gas guide valve 615, introducing air, opening the tube furnace 3 when the air pressure is consistent with the external air pressure, and taking out the cesium tungsten bronze nanocrystals; wherein, the cesium tungsten bronze nanocrystals are regular solid microspheres with the diameter of about 5 μm, and the solid microspheres are mutually independent; each microsphere is formed by stacking crystal grains of about 50 nm.
10g of the monodisperse cesium tungsten bronze spherical nanocrystal prepared in example 4 was added with 40ml of ethylene glycol methyl ether and 1ml of a silane coupling agent, and after grinding, the ethylene glycol methyl ether was added to prepare a nano ink having a concentration of 5 wt%.
Adding 20% polyurethane acrylate prepolymer by volume into the nano ink, spraying the nano ink on the surface of glass, and performing ultraviolet curing to obtain a cesium tungsten bronze nano composite film on the surface of the glass; the transmittance curve of the cesium tungsten bronze nanocomposite film is shown in FIG. 6, and it can be seen that the transmittance is 1.5mg/m2The cesium tungsten bronze material can block more than 80% of infrared rays, and the transmittance of the film in the visible light region is kept at about 70%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A device for preparing cesium tungsten bronze spherical nanocrystals is characterized in that: comprises a reaction device (1), a cooling device (2), a tubular furnace (3), a vacuum pump (4), an exhaust gas collecting device (5) and an air guide pipe; the reaction device (1) comprises a reaction cavity (11), a cylindrical cooling pipe (12), an ultrasonic atomizer (13) and a solution containing device (14), wherein the cylindrical cooling pipe (12) is an annular pipe, the cross section of the cylindrical cooling pipe is U-shaped, the reaction cavity (11) is a cylindrical cavity and is installed inside a U-shaped groove of the cylindrical cooling pipe (12), the inner wall of the cylindrical cooling pipe (12) is coplanar with the outer wall of the reaction cavity (11), the ultrasonic atomizer (13) is installed at the bottom of the reaction cavity (11), the solution containing device (14) is installed on the upper side of the ultrasonic atomizer (13), and the outer wall of the solution containing device (14) is fixedly connected with the side wall of the reaction cavity (11); the cooling device (2) comprises a water inlet pipe (21), a water outlet pipe (22) and a cooling box (23), one end of the water inlet pipe (21) is communicated with a water inlet at the top end of one side of the cylindrical cooling pipe (12), the other end of the water inlet pipe is communicated with the corresponding side of the cooling box (23), one end of the water outlet pipe (22) is communicated with a water outlet at the top end of the cylindrical cooling pipe (12), which is far away from the water inlet, the other end of the water outlet pipe is communicated with the corresponding side of the cooling box (23), and the water inlet is higher than; the top of the reaction cavity (11) is provided with a T-shaped air duct (61) and an L-shaped air duct (62) which are respectively communicated, the T-shaped air duct (61) and the L-shaped air duct (62) penetrate through the top of the reaction cavity (11) and extend into the cavity, the bottom of the T-shaped air duct (61) is lower than the bottom of the L-shaped air duct (62), the other end of the L-shaped air duct (62) is communicated with the tubular furnace (3), and one end of the tubular furnace (3) far away from the L-shaped air duct (62) is respectively communicated with a waste gas collecting device (5) and a vacuum pump (4) through an air outlet pipe (66) and a vacuum pipe (65); the L-shaped air duct (62) positioned between the reaction cavity (11) and the tubular furnace (3) is communicated with a first air inlet pipe (63), and the first air inlet pipe (63) is communicated with one end of the T-shaped air duct (61) and is simultaneously communicated with a second air inlet pipe (64); three sections of the turning point of the T-shaped air duct (61) are respectively provided with a first air guide valve (611), a second air guide valve (612) and a third air guide valve (613), the second air inlet duct (64) is provided with a fourth air guide valve (614), one end of the first air inlet duct (63) far away from the L-shaped air duct (62) is provided with a fifth air guide valve (615), the connection point of the second air inlet duct (64) and the first air inlet duct (63) and the connection point of the T-shaped air duct (61) and the first air inlet duct (63) are both positioned between the fifth air guide valve (615) and the L-shaped air duct (62), the air outlet duct (66) is provided with a sixth air guide valve (616), and the vacuum tube (65) is provided with a seventh air guide valve (617).
2. The apparatus for preparing cesium tungsten bronze spherical nanocrystals according to claim 1, wherein: the cooling box (23) is provided with a cooling switch.
3. The use method of the apparatus for producing cesium tungsten bronze spherical nanocrystals according to claim 1 or 2, characterized by:
a. solution preparation and preparation work: dissolving a tungsten source and a cesium source in deionized water to form a solution, putting the solution into a solution containing device (14), closing all gas guide valves, opening a cooling switch, and enabling cooling water to circularly flow in a cooling box (23) and a U-shaped cooling pipe (12);
b. preparing a precursor: heating the tube furnace (3) to a target temperature and keeping the temperature, then starting a power supply of an ultrasonic atomizer (13) to atomize aqueous solution of a cesium source and a tungsten source into aerosol, opening a first air guide valve (611), a third air guide valve (613) and a sixth air guide valve (616), introducing carrier gas from the first air guide valve (611), moving the aerosol into the tube furnace (3) along with the carrier gas, carrying out thermal cracking in the tube furnace (3), and depositing a white visible cesium tungsten bronze precursor on the inner wall of the tube furnace (3);
c. drying the precursor: closing the heating power supply of the tube furnace (3), the first air guide valve (611), the third air guide valve (613) and the sixth air guide valve (616), opening the seventh air guide valve (617) and the vacuum pump (4), vacuumizing and drying the tube furnace (3), and fully drying the precursor powder in the tube furnace (3);
d. annealing treatment: closing the seventh air guide valve (617), opening the first air guide valve (611), the second air guide valve (612) and the fourth air guide valve (614), and introducing H from the fourth air guide valve (614)2Introducing N from the first air guide valve (611) and the second air guide valve (612)2Controlling air pressure, closing the first air guide valve (611), the second air guide valve (612) and the fourth air guide valve (614), and heating and preserving heat of the tube furnace (3);
e. completing the preparation: and (3) closing the power supply of the tube furnace (3), after natural cooling, opening the fifth gas guide valve (615), introducing air, and opening the tube furnace (3) when the air pressure is consistent with the external air pressure, and taking out the cesium tungsten bronze nanocrystals.
4. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the tungsten source is any one of ammonium tungstate or ammonium metatungstate or a mixture thereof.
5. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the cesium source is any one of cesium hydroxide or cesium carbonate or a mixture thereof.
6. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the molar ratio of the tungsten element to the cesium element in the solution in the step a can be 0.2-0.33: 1.
7. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the carrier gas introduced in the step b is any one of argon and nitrogen or a mixture thereof, and the gas flow rate can be 5-12 ml/min.
8. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the vacuum degree of the vacuum pumping drying in the step c can be-0.05 to-0.06 MPa.
9. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: and d, heating the tubular furnace in the step d at the temperature of 400-550 ℃, and keeping the temperature for 1-5 hours.
10. The use method of the device for preparing cesium tungsten bronze spherical nanocrystals, according to claim 3, wherein: the cesium tungsten bronze nanocrystals in the step e are regular solid microspheres with the diameter of 2-5 microns, and the solid microspheres are independent from one another; each microsphere is formed by stacking 20-50 nm crystal grains.
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