CN114702850B - Vanadium dioxide composite powder temperature control coating and preparation method thereof - Google Patents
Vanadium dioxide composite powder temperature control coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a vanadium dioxide composite powder temperature-control coating, which belongs to the field of thermally-induced phase-change coating materials, and is formed by uniformly mixing vanadium dioxide composite powder in a polymer matrix, wherein the polymer matrix is one or more of polytetrafluoroethylene, polycarbonate, self-cleaning coating and organic silicon resin, and the vanadium dioxide composite powder is nano-grade M X WO 3 The powder is obtained by compounding nano-grade vanadium dioxide powder, M X WO 3 The element M in the powder is at least one of Li, na, K, rb, cs, be, mg, ca, sr and Ba, and the value range of x is 0-1. The invention also provides a method for preparing the vanadium dioxide composite powder temperature-control coating. The comprehensive sunlight regulating capacity of the temperature-control paint can reach 10%, the sunlight transmittance can reach 70%, and the preparation method is simple.
Description
Technical Field
The invention belongs to the field of thermally-induced phase-change coating materials, and particularly relates to a vanadium dioxide composite powder temperature-control coating and a preparation method thereof.
Background
The building energy consumption accounts for 40% of the global energy consumption, wherein more than 50% of the building energy consumption is air conditioning energy consumption, and the heat insulation and preservation of the building have important significance for building energy conservation. On the premise of not reducing the area of the building glass, the energy-saving aim can be achieved by improving the temperature control performance of the glass. If the glass has good temperature control performance, the heat outside the building can be introduced indoors at low temperature, and the heat outside the building is isolated outdoors at high temperature, so that the effect of regulating and controlling the room temperature is achieved. In addition, along with the large-scale application of glass curtain walls, glass roofs and glass structures in high-rise buildings, the problem of cleaning glass is more and more remarkable, the adoption of a high-rise cleaning mode is not economical and inconvenient and has a certain potential safety hazard, and the search for glass with a self-cleaning function has become a hot spot and a difficult point of research in various countries of the world. Therefore, there is a need to develop a coating having temperature control properties and self-cleaning properties.
The vanadium dioxide nano powder has a low phase transition temperature and obvious optical and electrical properties before and after phase transition, so that the vanadium dioxide nano powder has great research potential in the field of building curtain walls. Vanadium dioxide is used as a thermochromic material, can be subjected to reversible phase transformation at 68 ℃, has a monoclinic rutile structure at normal temperature, has higher transmissivity to infrared wave bands and visible wave bands, and shows the property of a semiconductor. When the temperature is higher than the phase transition temperature of 68 ℃, vanadium dioxide is of a tetragonal rutile structure, has lower transmittance to the infrared band and the visible light band, mainly shows higher absorption and reflection characteristics, and shows the property of metal. The transmittance of the vanadium dioxide is particularly obviously changed in the infrared band, and based on the property, the purpose of automatically adjusting the room temperature can be realized by utilizing the cyclic phase change of the vanadium dioxide, and the energy consumption and the greenhouse gas emission can be reduced by applying the vanadium dioxide to the intelligent temperature control nano composite coating.
Conventional methods for preparing vanadium dioxide nano-powder are such as microwave assisted heating, sol-gel method, thermal decomposition method, oxidation-reduction method, one-step hydrothermal method, two-part hydrothermal method and the like. The patent application with publication number of CN110203972A discloses a preparation method of M-phase vanadium dioxide nanometer split, which adopts a one-step hydrothermal method to prepare vanadium dioxide, and the obtained nanometer vanadium dioxide powder has the characteristics of higher purity, controllable size and mass production.
But at present VO 2 One of the main problems of the powder in the practical application of the intelligent window is as follows: VO (VO) 2 The phase transition temperature of the nano particles is 68 ℃, and the doping of elements can effectively reduce VO 2 To around room temperature but would result in a reduction in visible light transmittance and solar light conditioning.
The publication No. CN109233362A discloses a self-cleaning nano heat-insulating paint based on cesium tungsten bronze and a preparation method thereof, and provides a self-cleaning nano heat-insulating paint based on cesium tungsten bronze and a preparation method thereof, and WCl is used 6 And CsOH.5H 2 O is used as a raw material, PVP is used as a surfactant, acetic acid is used as an acid catalyst, a hydrothermal method is used for preparing nano cesium tungsten bronze particles, and nano TiO is prepared 2 Particles, then, nano cesium tungsten bronze particles and nano TiO 2 Ball milling and dispersing the particles, the silane coupling agent and water together to prepare cesium tungsten bronze/TiO 2 Composite particle water-based slurry, finally, cesium tungsten bronze/TiO is adjusted 2 The concentration of the composite particle aqueous slurry is used for obtaining the self-cleaning nano heat-insulating coating. However, the coating does not have room temperature control function, and the coating uses cesium tungsten bronze as a main content and mainly utilizes the heat insulation capability of the cesium tungsten bronze. When the room temperature is low, the coating cannot introduce external sunlight heat into the room, and cannot realize the function of room temperature regulation.
Therefore, a novel intelligent temperature control coating needs to be developed to realize the function of automatically regulating and controlling the indoor temperature according to the outdoor temperature, so that the indoor energy consumption of a building is truly reduced, and the effect of being warm in winter and cool in summer is achieved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the vanadium dioxide composite powder temperature control coating and the preparation method thereof, which utilize tungsten bronze to absorb light in a near infrared band so as to convert the light into heat, thereby promoting the phase change of the vanadium dioxide, further realizing the transmission or shielding of the light in different bands and finally realizing the room temperature regulation function, and further solving the problem that the heat insulation coating in the prior art cannot really realize the function of regulating the high temperature and the low temperature.
In order to achieve the aim, the invention provides a vanadium dioxide composite powder temperature-control coating, which is formed by uniformly mixing vanadium dioxide composite powder in a polymer matrix, wherein the polymer matrix is one or more of polytetrafluoroethylene, polycarbonate, self-cleaning coating and organic silicon resin, and the vanadium dioxide composite powder is nano-grade M X WO 3 The powder is obtained by compounding nano-scale vanadium dioxide powder, wherein M X WO 3 The element M in the powder is at least one of Li, na, K, rb, cs, be, mg, ca, sr and Ba, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1: (40-100), nano-scale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-scale vanadium dioxide powder is (0.2-2.0): 1.
further, nanoscale M X WO 3 The particle size of the powder is 20 nm-50 nm.
Further, the particle size of the nano-grade vanadium dioxide powder is 20 nm-150 nm.
Further, nanometer level M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-scale vanadium dioxide powder is (0.2-1.0): 1.
further, after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the coating can be prepared into a film by a spray coating method, a spin coating method or a knife coating method.
According to a second aspect of the present invention, there is also provided a method for preparing the vanadium dioxide composite powder temperature-controlled paint as described above, comprising mixing nano-scale vanadium dioxide powder and nano-scale M X WO 3 Mixing the mixture in a mixed solution of ethanol and deionized water, and then performing ball milling to obtain a suspension of the vanadium dioxide composite powder, wherein the concentration of the vanadium dioxide composite powder in the suspension is 0.004 g/ml-0.01 g/ml, and the concentration of the vanadium dioxide composite powder in the suspension is sphericalAnd after the grinding is finished, taking out the vanadium oxide composite powder, and centrifugally cleaning to obtain pure and dry nano-scale vanadium dioxide composite powder.
Further, the surface modification is carried out on the nano-grade vanadium dioxide composite powder, so that the nano-grade vanadium dioxide composite powder can be uniformly dissolved in a polymer matrix, and uniform slurry is obtained.
Further, the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1: (1-4).
Further, the ball milling time is 0.5-2 h.
Further, the nano-scale vanadium dioxide powder is prepared by adopting a one-step hydrothermal method, specifically, ammonium metavanadate and hydrazine monohydrochloride are weighed and dissolved in deionized water, and the molar ratio of the hydrazine monohydrochloride to the ammonium metavanadate is 3: (8-12), magnetically stirring and dissolving to obtain brown solution, slowly dripping a set amount of hydrochloric acid until the solution is blue transparent, slowly dripping ammonia water into the blue transparent solution until the pH value of the solution is 7-8, obtaining a earthy yellow precipitate, dispersing the precipitate in deionized water again, carrying out ultrasonic treatment to obtain brown precursor suspension, transferring the brown precursor suspension into a reaction kettle, sealing, placing the reaction kettle in a hydrothermal oven, carrying out hydrothermal reaction at 210-280 ℃ for 18-48 h, taking out the product, centrifuging, washing with water, alcohol for multiple times, placing the centrifugal precipitate in a vacuum drying oven, and drying to obtain the nano-scale vanadium dioxide powder.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
in the invention, the nanometer level M X WO 3 Compounding the powder with nano-level vanadium dioxide powder to obtain vanadium dioxide composite powder, dispersing the vanadium dioxide composite powder in a polymer matrix to obtain the temperature-controlled coating, wherein a small amount of M is added into the temperature-controlled coating X WO 3 And (3) powder. In operation, VO 2 The phase change is caused by temperature, the low-temperature monoclinic phase is changed into the high-temperature rutile phase, and VO 2 The phase transition of (2) is accompanied by significant infrared transmissionThe transmittance is changed to change the infrared light transmittance from high to low, M X WO 3 The powder is an inorganic infrared absorber which has high visible light transmittance and strong absorption effect on near infrared with the wavelength of more than 1100nm, and has excellent near infrared shielding performance. VO is to be provided with 2 Powder and M X WO 3 Compounding, using M X WO 3 The near infrared absorptivity of (2) ensures that the surface of the coating is heated up more quickly to reach VO 2 And M X WO 3 The transmittance of the composite powder can enable the coating of the composite powder to have higher visible light transmittance. After the nano vanadium dioxide composite powder prepared by the method is prepared into a coating, the phase transition temperature of the coating is reduced by 27 ℃ compared with that of undoped nano vanadium dioxide powder, and the self-regulating capability of the nano vanadium dioxide powder is not weakened because VO 2 Powder and M X WO 3 Compounding is carried out without changing VO 2 The powder has a crystal structure, the comprehensive solar light regulating capability of the temperature control coating can reach 10 percent, and the solar light transmittance can reach 70 percent.
According to the preparation method, the nano vanadium dioxide powder with smaller particles is prepared by using a one-step hydrothermal method, other powder is introduced for compounding, the phase transition temperature is reduced, the crystal lattice of the vanadium dioxide powder is not damaged, the synergistic advantages of the two strategies are combined, and the prepared nano vanadium dioxide powder has good optical performance. The invention continuously adopts the surface modifier to carry out surface grafting modification on the vanadium dioxide nano powder, so that the vanadium dioxide nano powder can be well dispersed in a polymer matrix, thereby preparing the coating with 70 percent of visible light transmittance and 104 degrees of hydrophobic angle. The method has the advantages of simple process flow, low energy consumption, easy operation and suitability for large-scale production.
Drawings
FIG. 1 is an XRD pattern for the M-phase vanadium dioxide powder prepared and used in example 1;
FIG. 2 is an XRD pattern of cesium tungsten bronze powder used in example 1;
FIG. 3 is a DSC of the vanadium dioxide composite powder of example 3;
FIG. 4 is a graph showing the transmittance versus wavelength of the waterproof coating prepared from the vanadium dioxide composite powder temperature-controlled coating obtained in example 3 at different temperatures;
FIG. 5 is a graph showing the particle size distribution of the vanadium dioxide composite powder obtained in example 3;
FIG. 6 is an SEM image of the vanadium dioxide composite powder obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Most of the energy in the sunlight is concentrated in the visible light region and the infrared light region, and the energy in the visible light region and the infrared light region account for about 95 percent of the energy, especially the near infrared light region in the infrared light region accounts for about 50 percent of the highest solar energy. Considering that light transmittance needs to be maintained in daily application, especially in automotive glass, higher requirements are put on the light transmittance of the glass, and national standards prescribe that the visible light transmittance of the front-end and front-side window glass of the automobile must be higher than 70%. Therefore, a transparent heat-insulating coating which has high selective permeability to sunlight, ensures that the visible light transmittance meets the regulations (more than or equal to 70 percent) and can effectively isolate ultraviolet rays and near infrared rays in the sunlight is researched as a research hot spot in the field of the current glass surface functional coating.
VO 2 The reversible phase change of the metal-insulator occurs at about 68 ℃, the single-inclined crystal M phase is adopted at low temperature, and the transmittance of near infrared light (800 nm-2500 nm) is high; the R phase with a rutile structure at high temperature has low near infrared transmittance, and the paint prepared by utilizing the property allows a large amount of near infrared light to pass through at low temperature, so that the indoor temperature is increased, the near infrared transmittance is reduced at high temperature, and the energy consumption of an air conditioner required for maintaining the indoor constant temperature is reduced by about 40%. M is M x WO 3 The light-heat-sensitive fluorescent material has strong near infrared absorption at the near infrared of 800-1200 nm, good shielding property for near infrared light with the wavelength of more than 1200nm, and higher photo-heat conversion efficiency, and can be used as a photo-heat reagent. In the invention, a small amount of M is added x WO 3 Is favorable toBy their photothermal conversion properties, in particular VO 2 /M x WO 3 Cs is utilized by the composite powder x WO 3 Is used for absorbing near infrared light of 800 nm-1200 nm, converting the near infrared light into heat and providing the heat for VO 2 The phase change is carried out, and the high transmittance property can improve the overall transmittance of the film.
In actual engineering practice, in VO 2 /Cs x WO 3 The surface of the composite powder is grafted with organic groups for modification, so that the composite powder has good dispersibility in various organic solvents, is beneficial to being dispersed in most oily paint on the market, and is convenient to use, and after the paint is prepared into a coating, the coating has a hydrophobic angle of 104 degrees, visible light transmittance of more than 70 percent and solar light adjustment capability of more than 10 percent.
VO 2 The phase transition theory of (a) is mainly the MIT (metal-insulator transition) theory: transition between low Wen Shanxie phase (M) and high temperature gold ambary phase (R). The corresponding macroscopic property change is manifested in two ways, one is a change in electrical properties: jump in resistivity and conductivity of the film before and after phase change, sudden increase in carrier concentration: second, change in optical properties: VO before low-temperature phase transition 2 The film has high infrared light transmittance, and the infrared light transmittance of the film is rapidly reduced after high-temperature phase change: the change of optical properties is also represented by the reflectivity and absorptivity of the film. VO (VO) 2 In the process of changing the M phase of the metal R phase semiconductor of the hair semiconductor M phase-metal R phase with a crystal structure, hysteresis phenomenon exists between the severe optical property and the change of the electrical property. Thus, the phase transition process can be seen as a change of the M-phase monoclinic structure to the R-phase rutile structure due to temperature.
Inorganic infrared absorbing agent MxWO 3 Indium is not contained, so that high visible light transmittance can be realized, the near infrared light with the wavelength of more than 1100nm can be absorbed and isolated, and the near infrared shielding performance is excellent. Inorganic infrared absorbing agent MxWO 3 The transparent heat shielding material is a novel environment-friendly energy-saving material, and has very wide application prospect in the fields of building window glass and automobile glass.
The invention will be described in detail below with reference to the drawings and the detailed description.
Example 1
(1) Preparation of nano vanadium dioxide powder by hydrothermal method
4.5g of ammonium metavanadate was weighed into a beaker, 60ml of deionized water was added for magnetic stirring, and then 1.0. 1.0 g hydrazine hydrochloride was weighed and 10ml of deionized water was added to form a hydrazine hydrochloride solution. And adding hydrazine hydrochloride solution into the ammonium metavanadate dispersion liquid, dropwise adding a certain amount of hydrochloric acid solution until the solution is blue transparent, and stopping dropwise adding hydrochloric acid until the solution is brown, wherein the amount of the dropwise adding hydrochloric acid is approximately 15-20ml. And (3) dropwise adding ammonia water into the blue solution under stirring to precipitate the blue solution, wherein the precipitate is earthy yellow, and regulating the pH value to 7-8 by using a pH meter. And centrifuging the suspension in a centrifuge to obtain a precipitate, dispersing the precipitate in deionized water again, performing ultrasonic treatment to obtain a brown precursor suspension, transferring the precursor into a polytetrafluoroethylene reaction kettle, sealing and tightly placing the precursor in a hydrothermal oven, setting the temperature and the time, taking out the product after the reaction is finished, centrifuging, washing with water and alcohol for 3 times, and drying the centrifuged precipitate in a vacuum drying oven at 100 ℃ for 6 hours to obtain M-phase vanadium dioxide powder.
(2) Preparation of nano vanadium dioxide composite powder
0.1g of VO prepared in the step (1) is weighed 2 Weighing 0.06gM of the powder X WO 3 Powder (tungsten bronze), M in this example is Cs, will be 0.06gCs X WO 3 Dispersing the powder into an alcohol-water solution consisting of 15ml of ethanol and 15ml of deionized water, continuously stirring at 1500r/min for 30min after ultrasonic treatment, adding the suspension into a ball milling tank, and setting the ball milling time to be 1h. And after ball milling, taking out the product, performing centrifugal water washing and alcohol washing for 3 times, and drying the centrifugal precipitate in a vacuum drying oven at 70 ℃ for 4 hours to obtain the nano vanadium dioxide composite powder.
(3) Preparation of vanadium dioxide composite powder coating
And (3) adding 0.2g of composite powder into 7mL of Polytetrafluoroethylene (PTFE) emulsion respectively, fully stirring for 12h to fully crosslink the two to prepare plastic slurry, and coating by using a spin coating method to obtain the vanadium dioxide composite intelligent temperature control coating.
X-ray diffraction (XRD) testing of the M-phase vanadium dioxide powder prepared and used in steps (1) and (2) as shown in FIG. 1, and comparing with standard card, the powder is identical to M-phase VO 2 Powder, cs 0.33 WO 3 As shown in FIG. 2, the XRD of the powder shows that Cs is as shown in FIG. 2 0.33 WO 3 And the crystallization diagram of the powder has characteristic peak-to-average corresponding to crystal faces.
Example 2
(1) Preparation of nano vanadium dioxide powder by hydrothermal method
4.5g of ammonium metavanadate was weighed into a beaker, 60ml of deionized water was added for magnetic stirring, and then 1.0. 1.0 g hydrazine hydrochloride was weighed and 10ml of deionized water was added to form a hydrazine hydrochloride solution. And adding hydrazine hydrochloride solution into the ammonium metavanadate dispersion, wherein the solution is brown, dropwise adding a certain amount of hydrochloric acid solution which changes the color from yellow to green and generates a large number of bubbles, continuously dropwise adding hydrochloric acid until the solution is blue transparent, stopping dropwise adding hydrochloric acid, and dropwise adding hydrochloric acid with the volume of approximately 15-20ml. And (3) dropwise adding ammonia water into the blue solution under stirring to precipitate the blue solution, wherein the precipitate is earthy yellow, and regulating the pH value to 7-8 by using a pH meter. And centrifuging the suspension in a centrifuge to obtain a precipitate, dispersing the precipitate in deionized water again, performing ultrasonic treatment to obtain a brown precursor suspension, transferring the precursor into a polytetrafluoroethylene reaction kettle, sealing and tightly placing the precursor in a hydrothermal oven, setting the temperature and the time, taking out the product after the reaction is finished, centrifuging, washing with water and alcohol for 3 times, and drying the centrifuged precipitate in a vacuum drying oven at 100 ℃ for 6 hours to obtain M-phase vanadium dioxide powder.
(2) Preparation of nano vanadium dioxide composite powder
Weighing 0.1g of the nano-scale VO prepared in the step (1) 2 Powder, 0.08gM X WO 3 Dispersing the powder into an alcohol-water solution consisting of 15ml of ethanol and 30ml of deionized water, stirring for 30min at 1500r/min after ultrasonic treatment, adding the suspension into a ball milling tank, and setting the ball milling time to be 1.5h. After ball milling, taking out the product, performing centrifugal water washing and alcohol washing for 3 times, and drying the centrifugal precipitate in a vacuum drying oven at 70 ℃ for 4 hours to obtain nano dioxygenVanadium compound powder.
(3) Preparation of vanadium dioxide composite powder coating
And (3) adding 0.2g of composite powder into 7mL of Polytetrafluoroethylene (PTFE) emulsion respectively, fully stirring for 18h to fully crosslink the two to prepare plastic slurry, and coating by using a spin coating method to obtain the vanadium dioxide composite intelligent temperature control coating.
Example 3
(1) Preparation of nano vanadium dioxide powder by hydrothermal method
4.5g of ammonium metavanadate was weighed into a beaker, 60ml of deionized water was added for magnetic stirring, and then 1.0. 1.0 g hydrazine hydrochloride was weighed and 10ml of deionized water was added to form a hydrazine hydrochloride solution. And adding hydrazine hydrochloride solution into the ammonium metavanadate dispersion, wherein the solution is brown, dropwise adding a certain amount of hydrochloric acid solution which changes the color from yellow to green and generates a large number of bubbles, continuously dropwise adding hydrochloric acid until the solution is blue transparent, stopping dropwise adding hydrochloric acid, and dropwise adding hydrochloric acid with the volume of approximately 15-20ml. And (3) dropwise adding ammonia water into the blue solution under stirring to precipitate the blue solution, wherein the precipitate is earthy yellow, and regulating the pH value to 7-8 by using a pH meter. And centrifuging the suspension in a centrifuge to obtain a precipitate, dispersing the precipitate in deionized water again, performing ultrasonic treatment to obtain a brown precursor suspension, transferring the precursor into a polytetrafluoroethylene reaction kettle, sealing and tightly placing the precursor in a hydrothermal oven, setting the temperature and the time, taking out the product after the reaction is finished, centrifuging, washing with water and alcohol for 3 times, and drying the centrifuged precipitate in a vacuum drying oven at 100 ℃ for 6 hours to obtain M-phase vanadium dioxide powder.
(2) Preparation of nano vanadium dioxide composite powder
0.1g of the VO2 powder prepared in the step (1) and 0.08g of the MXWO3 powder are weighed and dispersed into an alcohol-water solution consisting of 15ml of ethanol and 45ml of deionized water, after ultrasonic treatment, stirring is carried out for 30min at 1500r/min, and then the suspension is added into a ball milling tank, and the ball milling time is set for 2h. And after ball milling, taking out the product, performing centrifugal water washing and alcohol washing for 3 times, and drying the centrifugal precipitate in a vacuum drying oven at 70 ℃ for 4 hours to obtain the nano vanadium dioxide composite powder.
(3) Preparation of vanadium dioxide composite powder coating
And (3) adding 0.2g of composite powder into 7mL of Polytetrafluoroethylene (PTFE) emulsion respectively, fully stirring for 24h to fully crosslink the two to prepare plastic slurry, and coating by using a spin coating method to obtain the vanadium dioxide composite intelligent temperature control coating.
FIG. 3 is a DSC graph of the vanadium dioxide composite powder of example 3, showing that the temperature required for phase transition of vanadium dioxide is reduced to 43.5 ℃ after cesium tungsten bronze powder is added. Fig. 4 is a graph showing the transmittance-wavelength curves of the waterproof coating prepared from the vanadium dioxide composite powder temperature-control coating obtained in example 3 at different temperatures, wherein the visible light transmittance of the film of the composite powder reaches over 70% and the solar light adjustment capability reaches 10% at 20 ℃ and 90 ℃. FIG. 5 is a graph showing the particle size distribution of the vanadium dioxide composite powder obtained in example 3, wherein the particle size of the composite powder is mainly 20 to 50nm. Fig. 6 is an SEM image of the vanadium dioxide composite powder obtained in example 3, which shows that the particle size and the particle size distribution map are identical.
Example 4
Firstly, preparing nano-grade vanadium dioxide powder by adopting a one-step hydrothermal method, specifically, weighing ammonium metavanadate and hydrazine monohydrochloride, dissolving the ammonium metavanadate and the hydrazine monohydrochloride in deionized water, wherein the molar ratio of the hydrazine monohydrochloride to the ammonium metavanadate is 3:8, magnetically stirring and dissolving to obtain brown solution, slowly dropwise adding a set amount of hydrochloric acid until the solution is blue transparent, slowly dropwise adding ammonia water into the blue transparent solution, dropwise adding ammonia water until the pH value of the solution is 7-8 to obtain a earthy yellow precipitate, dispersing the precipitate in deionized water again, carrying out ultrasonic treatment to obtain brown precursor suspension, transferring the brown precursor suspension into a reaction kettle, sealing, placing the reaction kettle in a hydrothermal oven, carrying out hydrothermal reaction at 210 ℃ for 18h, taking out a product, centrifuging, washing with alcohol for multiple times, placing the centrifugal precipitate in a vacuum drying oven, and drying to obtain the nano-grade vanadium dioxide powder.
Then, the nano-scale vanadium dioxide powder and the nano-scale M X WO 3 Mixing in a mixed solution of ethanol and deionized water, and then ball milling for 0.5h. Obtaining a suspension of vanadium dioxide composite powder, wherein two of the suspension areAnd after ball milling is finished, taking out the vanadium oxide composite powder, and centrifugally cleaning to obtain pure and dry nano-scale vanadium dioxide composite powder. Wherein, the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1:1.
finally, uniformly mixing the vanadium dioxide composite powder in a polymer matrix to obtain the temperature-control coating, wherein the polymer matrix is polycarbonate, and the vanadium dioxide composite powder is nano-scale M X WO 3 The powder is obtained by compounding nano-scale vanadium dioxide powder, wherein M X WO 3 The element M in the powder is Li, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1:40, nanometer M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.2:1. nanoscale M X WO 3 The particle size of the powder was 20nm. The particle size of the nano-grade vanadium dioxide powder is 20nm. Nanoscale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.2:1.
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the method for preparing the coating into the film can be a knife coating method.
Example 5
Firstly, preparing nano-scale vanadium dioxide powder by adopting a one-step hydrothermal method, wherein the specific method is the same as in example 4, and the molar ratio of hydrazine monohydrochloride to ammonium metavanadate is 3:12, the hydrothermal reaction temperature is 280 ℃, and the hydrothermal reaction time is 48h.
Next, a vanadium dioxide composite powder was prepared in the same specific procedure as in example 4, except that the ball milling time was 2 hours. The concentration of the vanadium dioxide composite powder in the suspension is 0.01g/ml, and the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1:4.
finally, the vanadium dioxide composite powder is uniformly mixed in a polymer matrix to obtain the temperature-control coating, and the specific steps are the same as those of the embodiment 5, except that the polymer matrix is Cheng WeiNanometer self-cleaning paint, wherein M X WO 3 The element M in the powder is Rb, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1:100, nano-scale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 2.0:1. nanoscale M X WO 3 The particle size of the powder was 50nm. The particle size of the nano-grade vanadium dioxide powder is 150nm. Nanoscale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 1.0:1.
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the method for preparing the coating into the film can be a knife coating method.
Example 6
Firstly, preparing nano-scale vanadium dioxide powder by adopting a one-step hydrothermal method, wherein the specific method is the same as in example 4, and the molar ratio of hydrazine monohydrochloride to ammonium metavanadate is 3:10, the hydrothermal reaction temperature is 240 ℃, and the hydrothermal reaction time is 33 hours.
Next, a vanadium dioxide composite powder was prepared in the same specific procedure as in example 4, except that the ball milling time was 1 hour. The concentration of the vanadium dioxide composite powder in the suspension is 0.007g/ml, and the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1:3.
finally, the vanadium dioxide composite powder is uniformly mixed in a polymer matrix to obtain the temperature-controlled coating, and the specific steps are the same as those of the embodiment 5, except that the polymer matrix is self-cleaning coating (self-cleaning coating is commercially available, such as model ZS-511 of the self-cleaning coating with the aim of Cheng Wei), wherein M X WO 3 The element M in the powder is Be, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1:60, nanometer grade M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 1:1. nanoscale M X WO 3 The particle size of the powder was 30nm. The particle size of the nano-grade vanadium dioxide powder is 90nm. Vanadium dioxide composite powderNanoscale M in vivo X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.6:1.
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the method for preparing the coating into the film can be spin coating.
Example 7
Firstly, preparing nano-scale vanadium dioxide powder by adopting a one-step hydrothermal method, wherein the specific method is the same as in example 4, and the molar ratio of hydrazine monohydrochloride to ammonium metavanadate is 3:10, the hydrothermal reaction temperature is 270 ℃, and the hydrothermal reaction time is 40h.
Next, a vanadium dioxide composite powder was prepared in the same specific procedure as in example 4, except that the ball milling time was 0.9h. The concentration of the vanadium dioxide composite powder in the suspension is 0.009g/ml, and the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1:2.
finally, uniformly mixing the vanadium dioxide composite powder in a polymer matrix to obtain the temperature-control coating, wherein the specific steps are the same as those of the embodiment 5, except that the polymer matrix is organic silicon resin, wherein M X WO 3 The element M in the powder is Mg, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1:90, nano-scale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 1.5:1. nanoscale M X WO 3 The particle size of the powder was 29nm. The particle size of the nano-grade vanadium dioxide powder is 120nm. Nanoscale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.8:1.
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the coating can be prepared into a film by spraying.
Example 8
Firstly, preparing nano-scale vanadium dioxide powder by adopting a one-step hydrothermal method, wherein the specific method is the same as in example 4, and the molar ratio of hydrazine monohydrochloride to ammonium metavanadate is 3:9, the hydrothermal reaction temperature is 230 ℃, and the hydrothermal reaction time is 20h.
Next, a vanadium dioxide composite powder was prepared in the same specific procedure as in example 4, except that the ball milling time was 0.5 to 2 hours. The concentration of the vanadium dioxide composite powder in the suspension is 0.005g/ml, and the volume ratio of the ethanol to the deionized water in the mixed solution of the ethanol and the deionized water is 1:1.9.
finally, uniformly mixing the vanadium dioxide composite powder in a polymer matrix to obtain the temperature-control coating, wherein the specific steps are the same as those of the embodiment 5, except that the polymer matrix is a mixture of polytetrafluoroethylene and polycarbonate, wherein M X WO 3 The element M in the powder is Sr, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1:60, nanometer grade M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.8:1. nanoscale M X WO 3 The particle size of the powder was 45nm. The particle size of the nano-grade vanadium dioxide powder is 30nm. Nanoscale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-grade vanadium dioxide powder is 0.6:1.
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%. Specifically, the coating can be prepared into a film by a spray coating method, a spin coating method or a knife coating method.
In practical engineering practice, the surface modification is carried out on the nano-scale vanadium dioxide composite powder, so that the nano-scale vanadium dioxide composite powder can be uniformly dissolved in a polymer matrix to obtain uniform slurry. Specific modifications are as follows: 0.2g of vanadium dioxide composite powder is dispersed in an alcohol-water solution composed of 20mL of ethanol and 20mL of ultrapure water, and the solution is continuously subjected to ultrasonic treatment and stirred for 4 hours at a rotating speed of 1000rmp/min to obtain a suspension with good dispersibility. Adding 15mL of butyl oleate into the suspension, stirring at a rotating speed of 1000rmp/min for 0.5h to obtain an oil-water mixture, adding the oil-water mixture into a 100mL hydrothermal reaction kettle, and completing the organic grafting reaction at a reaction temperature of 80 ℃ for 6 h; and centrifuging the powder obtained after the hydrothermal reaction is finished for 5min at a rotating speed of 1000rmp/min, separating to obtain a product, washing the product with deionized water and ethanol for 3 times respectively, and drying the product in vacuum at 80 ℃ for 5h to obtain the modified vanadium dioxide composite powder with the surface grafted with the organic groups.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A vanadium dioxide composite powder temperature-control coating is characterized in that the coating is formed by uniformly mixing vanadium dioxide composite powder in a polymer matrix, wherein the polymer matrix is one or more of polytetrafluoroethylene, polycarbonate and self-cleaning coating, and the vanadium dioxide composite powder is nano-scale M X WO 3 The powder is obtained by compounding nano-scale vanadium dioxide powder, wherein M X WO 3 The element M in the powder is at least one of Rb, be, mg, ca, sr and Ba, the value range of x is 0-1, and the mass ratio of the vanadium dioxide composite powder to the polymer matrix is 1: (40-100),
nanoscale M X WO 3 The particle size of the powder is 20 nm-50 nm,
the grain diameter of the nano-grade vanadium dioxide powder is 20 nm-150 nm,
nanoscale M in vanadium dioxide composite powder X WO 3 The mass ratio of the powder to the nano-scale vanadium dioxide powder is (0.2-1.0): 1,
in operation, M is used X WO 3 The near infrared absorptivity of (2) ensures that the surface of the coating is heated up more quickly to reach VO 2 By M X WO 3 The transmittance of the composite powder enables the coating of the composite powder to have higher visible light transmittance and VO 2 Powder and M X WO 3 Compounding without changing VO 2 The crystal structure of the powder can retain nanometer VO 2 The adjusting capability of the powder body per se,
after the coating is prepared into a film, the visible light transmittance is not lower than 70%, and the solar light adjustment capability is not lower than 10.1%.
2. A method for preparing the vanadium dioxide composite powder temperature-control coating according to claim 1, which is characterized in that nano-scale vanadium dioxide powder and nano-scale M X WO 3 Mixing the materials in a mixed solution of ethanol and deionized water, and then performing ball milling to obtain a suspension of vanadium dioxide composite powder, wherein the concentration of the vanadium dioxide composite powder in the suspension is 0.004 g/ml-0.01 g/ml, and after ball milling, taking out the vanadium oxide composite powder, and performing centrifugal cleaning to obtain pure and dry nano-grade vanadium dioxide composite powder.
3. The method for preparing the vanadium dioxide composite powder temperature-control coating according to claim 2, wherein the nano-scale vanadium dioxide composite powder is subjected to surface modification so that the nano-scale vanadium dioxide composite powder can be uniformly dispersed in a polymer matrix to obtain uniform slurry.
4. The method for preparing the vanadium dioxide composite powder temperature-control coating according to claim 3, wherein the volume ratio of ethanol to deionized water in the mixed solution of ethanol and deionized water is 1: (1-4).
5. The method for preparing the vanadium dioxide composite powder temperature-control coating according to claim 4, wherein the ball milling time is 0.5-2 h.
6. The method for preparing the vanadium dioxide composite powder temperature-control coating according to claim 5, wherein the nano-scale vanadium dioxide powder is prepared by a one-step hydrothermal method, specifically, ammonium metavanadate and hydrazine monohydrochloride are weighed and dissolved in deionized water, and the molar ratio of the hydrazine monohydrochloride to the ammonium metavanadate is 3: (8-12), magnetically stirring and dissolving to obtain brown solution, slowly dripping a set amount of hydrochloric acid until the solution is blue transparent, slowly dripping ammonia water into the blue transparent solution until the pH value of the solution is 7-8, obtaining a earthy yellow precipitate, dispersing the precipitate in deionized water again, carrying out ultrasonic treatment to obtain brown precursor suspension, transferring the brown precursor suspension into a reaction kettle, sealing, placing the reaction kettle in a hydrothermal oven, carrying out hydrothermal reaction at 210-280 ℃, taking out the product, centrifuging, washing with alcohol for multiple times, placing the centrifugal precipitate in a vacuum drying box, and drying to obtain the nano-scale vanadium dioxide powder.
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