CN112174210B - Preparation method of aqueous dispersion-free nano cesium tungsten oxide coating - Google Patents
Preparation method of aqueous dispersion-free nano cesium tungsten oxide coating Download PDFInfo
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Abstract
The invention relates to the technical field of nano materials, in particular to a preparation method of a water-based dispersion-free nano cesium tungsten oxide coating. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating comprises the steps of weighing cesium salt and tungsten salt, adding a chelating agent and water, heating to 150-160 ℃, and reacting for 5-6 hours; heating to 230-260 ℃ under the ultrasonic condition, and reacting for 3-4h to obtain a dispersion liquid of cesium tungsten oxide; then cooling to 50-80 ℃, adding a water-based dispersant and a defoaming agent, heating to 160-180 ℃, and carrying out an activation reaction for 5-6h to obtain activated nano cesium tungsten oxide sol; and finally, concentrating until the solid content is 45-50%, and performing spray drying to obtain the water-based dispersion-free nano cesium tungsten oxide coating. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating has the advantages of simple process, short preparation period, cost saving, no need of secondary grinding and processing, and safe and convenient storage and transportation.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a water-based dispersion-free nano cesium tungsten oxide coating.
Background
WO 3 The composite oxide (tungsten bronze) has excellent performances in the aspects of electrochromism, catalysis, gas sensitivity and the like, generally refers to metal oxide with darker metal luster, and is usually a metal conductor or a metal semiconductor, and the tungsten bronze is shown as A x WO 3 However, depending on the type and molar number of the cation (A, x value), the structure and color shade of the compound may vary (J Analytical and Pyrolysis,2000, 56. At present, potassium cesium tungsten bronze and cesium tungsten bronze are more produced, and the cesium tungsten bronze is widely used for preparing a conductive film and used as a heat insulating agent in a glass transparent heat insulating coating due to low resistance, excellent visible light transmittance and excellent near infrared shielding performance.
CN201310749555.1 discloses a preparation method of cesium tungsten oxide superfine powder, the particle size of the cesium tungsten oxide superfine powder prepared by the method is about 120nm, secondary grinding is needed to be applied to downstream industries, time and labor are wasted, and secondary pollution is easy to occur.
CN201680007541.4 discloses a near infrared absorbing particle dispersion and a method for producing the same, but the dispersion, particularly the petroleum solvent dispersion of the present invention, is flammable and explosive, and has high transportation cost, high storage requirement, and relatively high potential safety hazard.
CN201680036863.1 discloses a heat ray shielding film, a heat ray shielding interlayer transparent substrate, an automobile, a building, a dispersion, a mixed composition, a method for producing a dispersion, a dispersion liquid, and a method for producing a dispersion liquid. According to the preparation method of the composite tungsten oxide dispersoid and the dispersion liquid disclosed by the invention, the preparation of the dispersoid and the dispersion liquid is equivalent to the secondary processing of cesium tungsten oxide, a grinding procedure is required, the equipment is expensive, and the process is complex.
Disclosure of Invention
The invention aims to provide a preparation method of a water-based dispersion-free nano cesium tungsten oxide coating, which has the advantages of simple process, short preparation period, cost saving, no need of secondary grinding and processing, and safe and convenient storage and transportation.
The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating comprises the following steps:
(1) Weighing cesium salt and tungsten salt according to a Cs/W molar ratio of 1.5-3.4, adding a chelating agent and water, heating to 150-160 ℃, and reacting for 5-6 hours to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to 230-260 ℃ under the ultrasonic condition, and reacting for 3-4h to obtain a dispersion liquid of cesium tungsten oxide;
(3) Cooling the dispersion liquid obtained in the step (2) to 50-80 ℃, adding a water-based dispersing agent and a defoaming agent, heating to 160-180 ℃ under the ultrasonic condition, and carrying out an activation reaction for 5-6 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) concentrating the activated nano cesium tungsten oxide sol obtained in the step (3) until the solid content is 45-50%, and then performing spray drying to obtain the aqueous dispersion-free nano cesium tungsten oxide coating.
In the step (1), the cesium salt is cesium nitrate, cesium hydroxide or cesium chloride;
the tungsten salt is ammonium metatungstate or ammonium paratungstate;
the chelating agent is amino trimethylene phosphonic acid or ethylene diamine tetramethylene phosphonic acid sodium; the molar ratio of the chelating agent to the total amount of cesium tungsten is 3-5:1;
the adding amount of the water is 60-80% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of the cesium salt, the tungsten salt, the chelating agent, the water, the aqueous dispersing agent and the defoaming agent.
In the steps (1), (2) and (3), the heating rate is 2-5 ℃/min.
The solid content of the dispersion liquid obtained in the step (2) is 20-40%, wherein the crystal form of the cesium tungsten oxide is Cs 0.3 WO 3 Or Cs 0.32 WO 3 The average particle size is 30-80nm.
In the step (3), the aqueous dispersant is one of polyurethane, polyamide, polyether and organosilicon dispersants; the adding amount is 1.5-2% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of the cesium salt, the tungsten salt, the chelating agent, the water-based dispersing agent and the defoaming agent.
In the step (3), the defoaming agent is one of high-carbon alcohol, silicon and polyether defoaming agents; the adding amount is 0.5-1.0% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of cesium salt, tungsten salt, chelating agent, water, aqueous dispersant and defoaming agent.
In the step (2) and the step (3), the reaction is carried out in a reaction kettle with an ultrasonic device, and the ultrasonic conditions are as follows: the ratio of the volume of the reaction kettle to the power of the ultrasonic device is (5-10) L:1kW.
In the step (4), the stirring speed is 20-25r/min in the concentration process; the concentration temperature is 50-70 deg.C.
And (4) sieving the spray-dried nano cesium tungsten oxide coating by using a 400-mesh sieve, and sealing and storing.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared by the method is directly dissolved in water, and the particle size of the cesium tungsten oxide in the obtained dispersion liquid is 30-80nm.
The invention applies the electric double layer principle to the preparation of the water-based dispersion-free nano cesium tungsten oxide coating. The anionic dispersing agent selected by the invention must be dissolved in water, and the anionic dispersing agent is ionized in the water to form anions which have certain surface activity and are adsorbed by the surface of cesium tungsten oxide. The anion is closely adsorbed by the surface of cesium tungsten oxide, which is called surface ion, the ion with opposite charge in water is called counter ion, the counter ion and the surface ion are adsorbed by static electricity, one part of the counter ion is combined with the cesium tungsten oxide and the surface ion tightly, and becomes a whole body in water, which has negative charge, and the other part of the counter ion surrounds the periphery to form a diffusion layer. An electric double layer is thus formed between the surface ions and the counter ions. According to the double-electric-layer structure, the polar end of the outer-layer dispersant has strong affinity with water, so that the wetting degree of cesium tungsten oxide particles by water is increased, and the surface charge is increased by the double-electric-layer structure, so that the particles are far away due to electrostatic repulsion, and the stability of the whole system is maintained. Even if water is evaporated in the spray drying process, the structure of the cesium tungsten oxide particles is not damaged because the dispersant is still present on the surfaces of the particles, and when the cesium tungsten oxide particles are redispersed in water, an electric double layer structure is formed again and suspended in water, so that the effect of dispersion avoidance is achieved.
The addition amount of the aqueous dispersant is controlled within a limited range, and too small addition amount can prolong the time of the dispersion-free cesium tungsten oxide in the dispersion-free dissolving process, reduce the production efficiency, increase the particle size and influence the use effect; the excessive addition amount increases the raw material cost, prolongs the spray drying time and increases the production cost, and reduces the compatibility of the dispersant in the use process of downstream customers.
When the aqueous dispersing agent is added into the dispersion liquid of cesium tungsten oxide, the temperature of the dispersion liquid of cesium tungsten oxide needs to be controlled to be more than 50 ℃, and when the aqueous dispersing agent is added, the nano dispersion liquid obtained in the step (2) is re-agglomerated due to too low temperature, so that irreversible influence is generated, and the dispersing effect cannot be achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation process is taken as a breakthrough point, the dispersion-free coating is directly synthesized in the preparation process, and the secondary grinding dispersion of the cesium tungsten oxide is avoided, so that the secondary pollution is avoided, and the cost is reduced;
(2) The cesium tungsten oxide coating prepared by the method is solid powder, so that compared with the dispersion liquid in the prior art, the transportation cost is reduced, and the potential safety hazard in the transportation and storage processes is reduced;
(3) The prepared dispersion-free nano cesium tungsten oxide coating can be directly dissolved in water without secondary sanding, and is applied to the fields of heat insulation glass, heat insulation films, adhesive sheets, laser welding, infrared sensing, intelligent control and the like.
Drawings
FIG. 1 is an XRD pattern of cesium tungsten oxide as obtained in example 1 of the present invention;
FIG. 2 is a graph of the particle size of cesium tungsten oxide obtained in example 1 of the present invention;
fig. 3 is a spectrum of the particle size of the aqueous dispersion-free nano cesium tungsten oxide coating re-dissolved in water prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of cesium tungsten oxide as obtained in example 2 of the present invention;
FIG. 5 is a particle size spectrum of cesium tungsten oxide obtained in example 2 of the present invention;
fig. 6 is a particle size distribution diagram of the aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 2 of the present invention redissolved in water.
FIG. 7 is an XRD pattern of cesium tungsten oxide as obtained in example 3 of the present invention;
FIG. 8 is a particle size spectrum of cesium tungsten oxide obtained in example 3 of the present invention;
fig. 9 is a particle size spectrum of the re-dissolution of the aqueous dispersion-free nano cesium tungsten oxide coating into water, which is prepared in example 3 of the present invention;
FIG. 10 is a particle size distribution diagram of the re-dissolution of the aqueous dispersion-free nano cesium tungsten oxide coating into water, prepared in comparative example 1 of the present invention;
FIG. 11 is a particle size spectrum of the re-dissolution of the aqueous dispersion-free nano cesium tungsten oxide coating into water prepared in comparative example 2 of the present invention;
fig. 12 is a transmission electron microscope image of a downstream customer using the waterborne dispersion-free nano cesium tungsten oxide coating prepared in embodiment 1 of the present invention;
FIG. 13 is a transmission electron microscope image of a downstream customer using the waterborne dispersion-free nano-cesium tungsten oxide coating prepared in comparative example 2 of the present invention;
FIG. 14 is a particle size distribution diagram of the re-dissolution of the aqueous dispersion-free nano cesium tungsten oxide coating into water, prepared in comparative example 3 of the present invention;
FIG. 15 is a particle size spectrum of commercially available uncoated nano-cesium tungsten oxide powder redissolved in water;
fig. 16 shows the effect of re-dissolving the commercially available uncoated nano cesium tungsten oxide powder (left) in water and re-dissolving the aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 3 (right) in water and standing for 24 hours.
Detailed Description
In the following examples, the crystalline form of cesium tungsten oxide was examined using a german bruke D8X-ray diffractometer; and detecting the particle size of the cesium tungsten oxide by adopting a Zhuhai Oumeik NS90 laser particle size distribution instrument.
Example 1
The aqueous dispersion-free nano cesium tungsten oxide coating is prepared by the following method:
(1) Weighing 6.82g (0.0349 mol) of cesium nitrate, 24.77g of ammonium metatungstate, 182.64g of amino trimethylene phosphonic acid and 1111.95g of pure water, uniformly mixing, heating to 150 ℃ at the heating rate of 2 ℃/min, and preserving heat for 6 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 230 ℃ at a heating rate of 2 ℃/min, and preserving heat for 4 hours to obtain a cesium tungsten oxide dispersion liquid with a solid content of 21%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 1, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in fig. 2, and the average particle size is 45.9nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 50 ℃, adding 19.84g of polyester dispersant (Tibet Some corporation, wetting dispersant 910) and 6.22g of polyether defoamer (Foamaster 155) into the dispersion liquid, heating the mixture to 160 ℃ at a heating rate of 2 ℃/min, and carrying out heat preservation and activation for 6 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 20r/min, adjusting the temperature to 50 ℃, concentrating until the solid content is 45%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 1 was dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 3, and the average particle size is 46.6nm.
In the course of using by downstream customers, the aqueous dispersion of the dispersion-free nano cesium tungsten oxide coating prepared in example 1 was subjected to transmission electron microscope scanning, and the result is shown in fig. 12.
Example 2
The aqueous dispersion-free nano cesium tungsten oxide coating is prepared by the following method:
(1) Weighing 10.76g (0.064 mol) of cesium chloride, 61.78g of ammonium paratungstate, 517.13g of ethylenediamine tetramethylene phosphonate and 1593.70g of pure water, uniformly mixing, heating to 160 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 260 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain a dispersion liquid of cesium tungsten oxide, wherein the solid content is 39%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 4, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in fig. 5, and the average particle size is 65.4nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 60 ℃, adding 43.67g of a water-based organic silicon dispersant (Taiwan modest enterprise, ltd., wetting dispersant 904S) and 21.83g of a polyether defoamer (Bocheng chemical Co., ltd., dongguan), heating to 180 ℃ at a heating rate of 5 ℃/min, and carrying out heat preservation and activation for 5 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 25r/min, adjusting the temperature to 70 ℃, concentrating until the solid content is 50%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 2 was dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 6, and the average particle size is 67.2nm.
Example 3
The aqueous dispersion-free nano cesium tungsten oxide coating is prepared by the following method:
(1) Weighing 5.23g (0.0349 mol) of cesium hydroxide, 24.77g of ammonium metatungstate, 182.64g of amino trimethylene phosphonic acid and 1111.95g of pure water, uniformly mixing, heating to 155 ℃ at the heating rate of 4 ℃/min, and preserving heat for 5.5 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 240 ℃ at a heating rate of 4 ℃/min, and preserving heat for 3.5 hours to obtain a dispersion liquid of cesium tungsten oxide, wherein the solid content is 20%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 7, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in fig. 8, and the average particle size is 55.1nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 80 ℃, adding 19.84g of polyester dispersant (Hydropalat 875, basf China Co., ltd.) and 6.22g of organic silicon defoamer (SP-825, bocheng chemical Co., ltd., dongguan), heating to 170 ℃ at the heating rate of 4 ℃/min, and carrying out heat preservation and activation for 5.5h to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 20r/min, adjusting the temperature to 60 ℃, concentrating until the solid content is 45%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 3 was dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 9, and the average particle size is 56.8nm.
Comparative example 1
To illustrate the influence of the amount of the aqueous dispersant on the dispersion-free effect, compared with example 1, the comparative example adds the aqueous dispersant accounting for 1% of the total mass of the reaction system to prepare the aqueous dispersion-free nano cesium tungsten oxide coating, and the method comprises the following steps:
(1) Weighing 6.82g (0.0349 mol) of cesium nitrate, 24.77g of ammonium metatungstate, 182.64g of amino trimethylene phosphonic acid and 1111.95g of pure water, uniformly mixing, heating to 150 ℃ at the heating rate of 2 ℃/min, and preserving heat for 6 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 230 ℃ at a heating rate of 2 ℃/min, and preserving heat for 4 hours to obtain a cesium tungsten oxide dispersion liquid with a solid content of 21%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 1, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in fig. 2, and the average particle size is 45.9nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 50 ℃, adding 13.5g of polyester dispersant (Tibet Some corporation, wetting dispersant 910) and 6.22g of polyether defoamer (Foamaster 155) into the dispersion liquid, heating the mixture to 160 ℃ at a heating rate of 2 ℃/min, and carrying out heat preservation and activation for 6 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 20r/min, adjusting the temperature to 50 ℃, concentrating until the solid content is 45%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in comparative example 1 is dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 10, and the average particle size is 116nm.
As can be seen from fig. 10, the addition amount of the aqueous dispersant of comparative example 1 is too small compared to example 1, and the average particle size of the finally obtained cesium tungsten oxide without dispersion is 116nm, and the particle size is large, which affects the use effect.
Comparative example 2
To illustrate the influence of the amount of the aqueous dispersant on the dispersion-free effect, compared with example 1, the comparative example adds the aqueous dispersant accounting for 3% of the total mass of the reaction system to prepare the aqueous dispersion-free nano cesium tungsten oxide coating, and the method comprises the following steps:
(1) Weighing 6.82g (0.0349 mol) of cesium nitrate, 24.77g of ammonium metatungstate, 182.64g of amino trimethylene phosphonic acid and 1111.95g of pure water, uniformly mixing, heating to 150 ℃ at the heating rate of 2 ℃/min, and preserving heat for 6 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 230 ℃ at a heating rate of 2 ℃/min, and preserving heat for 4 hours to obtain a dispersion liquid of cesium tungsten oxide, wherein the solid content is 21%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 1, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in fig. 2, and the average particle size is 45.9nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 50 ℃, adding 41.2g of polyester dispersant (Tibet Some corporation, wetting dispersant 910) and 6.22g of polyether defoamer (Foamaster 155) into the dispersion liquid, heating the mixture to 160 ℃ at a heating rate of 2 ℃/min, and carrying out heat preservation and activation for 6 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 20r/min, adjusting the temperature to 50 ℃, concentrating until the solid content is 45%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
Dissolving the aqueous dispersion-free nano cesium tungsten oxide coating prepared in the comparative example 2 in water, wherein the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 11, and the average particle size is 68.8nm; in the course of using by downstream customers, the aqueous dispersion of the dispersion-free nano cesium tungsten oxide coating prepared in comparative example 2 was subjected to transmission electron microscope scanning, and the result is shown in fig. 13.
As can be seen from FIG. 11, the excessive addition of the aqueous dispersant of comparative example 2 causes the particle size of the dispersion-free powder to increase to some extent as compared with example 1, but the average particle size is still less than 80nm, which is within the use requirement range. However, as can be seen from fig. 13 and 12, in the process of using by a downstream customer, the sample prepared in comparative example 2 has an agglomeration phenomenon, the compatibility is reduced, and the using effect is affected; the sample prepared in the example 1 has no agglomeration phenomenon and has good use effect.
Comparative example 3
To illustrate the effect of the temperature at which the aqueous dispersant is added on the dispersion-free effect, the aqueous dispersant is added at a lower temperature of the cesium tungsten oxide dispersion to prepare an aqueous dispersion-free nano cesium tungsten oxide capsule, compared to example 2, by the following method:
(1) Weighing 10.76g (0.064 mol) of cesium chloride, 61.78g of ammonium paratungstate, 517.13g of ethylenediamine tetramethylene phosphonate and 1593.70g of pure water, uniformly mixing, heating to 160 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 hours to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a reaction kettle with an ultrasonic device, opening an ultrasonic device, heating to 260 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain a dispersion liquid of cesium tungsten oxide, wherein the solid content is 39%; wherein the XRD pattern of cesium tungsten oxide is shown in figure 4, and the crystal form is Cs 0.3 WO 3 Or Cs 0.32 WO 3 (ii) a The particle size spectrum of the cesium tungsten oxide in the dispersion is shown in FIG. 5, which showsThe average grain diameter is 65.4nm;
(3) Cooling the dispersion liquid obtained in the step (2) to 30 ℃, adding 43.67g of a water-based organic silicon dispersant (Taiwan modest enterprise, ltd., wetting dispersant 904S) and 21.83g of a polyether defoamer (Bocheng chemical Co., ltd., dongguan), heating to 180 ℃ at a heating rate of 5 ℃/min, and carrying out heat preservation and activation for 5 hours to obtain activated nano cesium tungsten oxide sol;
(4) And (4) transferring the activated nano cesium tungsten oxide sol obtained in the step (3) into a concentration kettle, adjusting the stirring speed to 25r/min, adjusting the temperature to 70 ℃, concentrating until the solid content is 50%, cooling, spray drying, sieving with a 400-mesh sieve, and sealing and packaging to obtain the water-based dispersion-free nano cesium tungsten oxide coating.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in comparative example 3 is dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 14, and the average particle size is 123nm.
In comparison with example 2, comparative example 3, cooling the dispersion of cesium tungsten oxide to 30 ℃, the low temperature causes re-agglomeration of the dispersed nano cesium tungsten oxide, and the addition of water cannot re-disperse the agglomerated nanoparticles, resulting in an increase in the particle size of the dispersion-free particles.
Comparative example 4
This comparative example uses commercially available uncoated nano-cesium tungsten oxide powder to compare with the aqueous dispersion-free nano-cesium tungsten oxide coating prepared in example 3 by the following method:
separately weighing 10g of commercially available uncoated nano cesium tungsten oxide powder and 10g of the waterborne dispersion-free nano cesium tungsten oxide coating prepared in example 3, dissolving the commercially available uncoated nano cesium tungsten oxide powder and the waterborne dispersion-free nano cesium tungsten oxide coating in 40g of distilled water, dissolving and dispersing the commercially available uncoated nano cesium tungsten oxide powder and the waterborne dispersion-free nano cesium tungsten oxide coating for 30min under the magnetic stirring of 150r/min, and then detecting the particle size.
The particle size spectrum of the commercially available cesium tungsten oxide powder without coating in the dispersion liquid is shown in fig. 15, the average particle size of the commercially available cesium tungsten oxide powder is 2310nm, the cesium tungsten oxide powder reaches the micron level, the cesium tungsten oxide powder does not belong to a nano material, and the cesium tungsten oxide powder can meet the use requirement only by secondary grinding.
The aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 3 is dissolved in water, and the particle size spectrum of the cesium tungsten oxide in the obtained dispersion is shown in fig. 9, wherein the average particle size of the cesium tungsten oxide is 56.8nm, and the cesium tungsten oxide can be used without secondary grinding.
Fig. 16 is a diagram showing the effect of commercially available uncoated nano cesium tungsten oxide powder and the aqueous dispersion-free nano cesium tungsten oxide coating prepared in example 3 after being dissolved in water again and left standing for 24 hours. As can be seen from fig. 16, after 24h of standing, the commercially available dispersion of uncoated nano cesium tungsten oxide powder was layered, the upper layer was clear solution, and the lower layer was cesium tungsten oxide precipitate; in contrast, example 3 formed a uniform, stable dispersion of aqueous dispersion-free coated cesium tungsten oxide.
Claims (6)
1. A preparation method of a water-based dispersion-free nano cesium tungsten oxide coating is characterized by comprising the following steps: the method comprises the following steps:
(1) Weighing cesium salt and tungsten salt according to a Cs/W molar ratio of 1.5-3.4, adding a chelating agent and water, heating to 150-160 ℃, and reacting for 5-6h to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to 230-260 ℃ under the ultrasonic condition, and reacting for 3-4h to obtain a dispersion liquid of cesium tungsten oxide;
(3) Cooling the dispersion liquid obtained in the step (2) to 50-80 ℃, adding a water-based dispersing agent and a defoaming agent, heating to 160-180 ℃ under the ultrasonic condition, and carrying out an activation reaction for 5-6 hours to obtain activated nano cesium tungsten oxide sol;
(4) Concentrating the activated nano cesium tungsten oxide sol obtained in the step (3) until the solid content is 45-50%, and then performing spray drying to obtain an aqueous dispersion-free nano cesium tungsten oxide coating;
in the step (1), the cesium salt is cesium nitrate, cesium hydroxide or cesium chloride; the tungsten salt is ammonium metatungstate or ammonium paratungstate;
the chelating agent is amino trimethylene phosphonic acid or ethylene diamine tetramethylene phosphonic acid sodium, and the molar ratio of the chelating agent to the total amount of cesium tungsten is 3-5:1;
the adding amount of water is 60-80% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of cesium salt, tungsten salt, chelating agent, water, aqueous dispersant and defoamer;
the solid content of the dispersion liquid obtained in the step (2) is 20-40%, wherein the crystal form of the cesium tungsten oxide is Cs 0.3 WO 3 Or Cs 0.32 WO 3 The average grain diameter is 30-80nm;
in the step (3), the aqueous dispersant is an organic silicon dispersant; the adding amount is 1.5-2% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of cesium salt, tungsten salt, chelating agent, water, aqueous dispersant and defoaming agent;
the prepared aqueous dispersion-free nano cesium tungsten oxide coating is directly dissolved in water, and the particle size of the cesium tungsten oxide in the obtained dispersion liquid is 30-80nm.
2. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating according to claim 1, characterized in that: in the steps (1), (2) and (3), the heating rate is 2-5 ℃/min.
3. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating body according to claim 1, characterized in that: in the step (3), the defoaming agent is one of high-carbon alcohol, silicon and polyether defoaming agents; the adding amount is 0.5-1.0% of the total mass of the reaction system, and the total mass of the reaction system is the sum of the mass of cesium salt, tungsten salt, chelating agent, water, aqueous dispersant and defoaming agent.
4. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating body according to claim 1, characterized in that: in the step (2) and the step (3), the reaction is carried out in a reaction kettle with an ultrasonic device, and the ultrasonic conditions are as follows: the ratio of the volume of the reaction kettle to the power of the ultrasonic device is (5-10) L:1kW.
5. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating body according to claim 1, characterized in that: in the step (4), the stirring speed is 20-25r/min in the concentration process; the concentration temperature is 50-70 deg.C.
6. The preparation method of the aqueous dispersion-free nano cesium tungsten oxide coating body according to claim 1, characterized in that: and (4) sieving the spray-dried nano cesium tungsten oxide coating by using a 400-mesh sieve, and sealing and storing.
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