CN102277023A - Transparent heat-insulation coating for glass and preparation method thereof - Google Patents
Transparent heat-insulation coating for glass and preparation method thereof Download PDFInfo
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- CN102277023A CN102277023A CN2011101854797A CN201110185479A CN102277023A CN 102277023 A CN102277023 A CN 102277023A CN 2011101854797 A CN2011101854797 A CN 2011101854797A CN 201110185479 A CN201110185479 A CN 201110185479A CN 102277023 A CN102277023 A CN 102277023A
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Abstract
The invention discloses a transparent heat-insulation coating for glass and a preparation method thereof. The coating contains cesium tungsten copper powder of which the general formula is Cs0.1-3.5WO3, wherein the crystalline phase composition is Cs0.2WO3 or Cs0.32WO3, the powder granularity is 100-1300nm, and the specific surface area is 7-50m<2>/g. The transparent heat-insulation coating for glass has functions of causing visible light to pass and shading near infrared and also has a self regulation function for light, i.e., the effect on causing visible light to pass and shading near infrared is further enhanced along with the strengthening of the illumination intensity and the prolonging of the illumination time. Thus, the transparent heat-insulation coating is especially suitable for preparing a transparent heat-insulation film on the surface of the glass, is an intelligent transparent heat-insulation coating for glass and has a wide application prospect in the heat insulation field of building window glass and automobile glass. The coating has simple components and is suitable for large-scale industrial production and practical application.
Description
Technical field
The present invention relates to a kind of novel glass heat-insulating coating, relate in particular to glass transparent insulating coating that contains caesium tungsten bronze(s) powder and preparation method thereof with near infrared shielding function.
Background technology
Traditional glass can play translucent effect, but thermal and insulating performance is relatively poor.The solar radiation Wavelength distribution is 300～2500nm, and wherein ultraviolet part accounts for 14%, and visible light partly accounts for 40%, and infrared rays partly accounts for 44%.Glass transparent insulating coating is a kind of glass surface that is coated on, and under the precondition of the certain visible light transmissivity of maintenance, is the functional coating of main heat insulation mode to reduce glass near infrared sheltering coefficient.The current oxide particle that is usually used in preparing glass transparent insulating coating has tin indium oxide (ITO) (Electroceram, 2009,23:361-366), tin-antiomony oxide (ATO) (Thin solid film, 1997,295:95-100), zinc oxide aluminum (AZO) (Electroceram, 2009,23:341-345) powder such as grade.In recent years, tungsten bronze(s) mixed monovalent cation Cs because of its interesting photoelectric properties, photochromic and superconductivity have caused people's extensive concern in the Tungsten oxide 99.999
+Caesium tungsten bronze(s) (the Cs that the back forms
xWO
3) have near low-resistivity characteristics excellent low-temperature superconducting performance and the room temperature.Recently, discover, by the caesium tungsten bronze(s) (Cs of hexagonal structure
xWO
3) the glass surface transparent film of preparation have than ito thin film more excellent visible light see through and near infrared light screening performance (J.Am.Ceram.Soc., 2007,90 (12): 4059-4061; Journal of Solid State Chemistry, 2010,183 (10): 2456-2460).Caesium tungsten bronze(s) powder will be widely used in preparing glass surface transparent heat insulating dope or thermal insulation film as a kind of novel near infrared masking material, be with a wide range of applications aspect the energy-conservation and vehicle glass heat-insulation and heat-preservation in architectural glazings.
Therefore, the invention provides a kind of interpolation Cs
xWO
3Glass surface transparent heat insulating dope of powder and preparation method thereof.
Summary of the invention
One of purpose of the present invention is to provide a kind of novel glass surface transparent heat insulating dope (hereinafter being called coating) and preparation method thereof.Containing general formula in the described coating is Cs
0.1-3.5WO
3Caesium tungsten bronze(s) powder, described powder crystalline phase consists of Cs
0.2WO
3Or Cs
0.32WO
3, powder size is that 100～1300nm, specific surface area are 7～50m
2/ g.
The content of caesium tungsten bronze(s) powder is 0.0135～0.05g/ml in the coating of the present invention.
Also contain polyvinyl butyral acetal (PVB), polyvinyl alcohol (PVA) or pyroxylin (e) cement (collodion) in the coating of the present invention as membrane-forming agent.
The present invention further provides the preparation method of above-mentioned coating, comprised the caesium tungsten bronze(s) powder and the membrane-forming agent blended step that reach mentioned above, described caesium tungsten bronze(s) powder crystalline phase consists of Cs
0.2WO
3Or Cs
0.32WO
3, powder size is that 100～1300nm, specific surface area are 7～50m
2/ g; Described membrane-forming agent is polyvinyl butyral acetal (PVB), polyvinyl alcohol (PVA) or pyroxylin (e) cement (collodion).Preferably polyethylene alcohol (PVA) wherein.
Comparatively particularly, above-mentioned coating preparation method of the present invention comprises the steps:
1. be that the aqueous citric acid solution of 1～4mol/L is that solvent prepares the slurry I that PVA content is 0.05～0.15g/ml with water or concentration;
2. caesium tungsten bronze(s) powder is grinding, a ultra-sonic dispersion in the 2mol/L aqueous citric acid solution at water or concentration, gets slurry II;
3. according to volume ratio 1: 3～1: 1 slurry II is joined among the slurry I, makes wherein that caesium tungsten bronze(s) powder content is 0.0135～0.05g/ml, then with mixture at 80 ℃ of stirred in water bath heating 30min, placed again 2 days, glass transparent insulating coating.
Also contain defoamer among the slurry I described in the above-mentioned coating preparation method of the present invention.Those skilled in the art can determine the concrete kind and the consumption of defoamer routinely according to prior art, and the present invention uses the SN-DEFOAMER1340 defoamer.
Among the above-mentioned coating preparation method of the present invention, the preparation method of slurry I is: polyvinyl alcohol (PVA) is soaked in 1～3h in the aqueous citric acid solution that water or concentration are 1～4mol/L, add defoamer, then with mixture heated and stirred 1～3h in 95 ℃ of water-baths, obtain slurry I after filtering, wherein PVA content is 0.05g/ml～0.15g/ml.
Among the above-mentioned coating preparation method of the present invention, described step 1. with step 2. in employed solvent preferably water.
The most preferably, the preparation method of glass surface transparent heat insulating dope of the present invention comprises the steps:
1. polyvinyl alcohol (PVA) is soaked in 1～3h in the water, adds SN-DEFOAMER 1340 defoamers, with mixture heated and stirred 1～3h in 95 ℃ of water-baths, obtain slurry I after filtering then, wherein PVA content is 0.05g/ml～0.15g/ml;
2. caesium tungsten bronze(s) powder grinds ultra-sonic dispersion 20min behind the 5min in water, repeats to grind the operation with ultra-sonic dispersion, until obtaining even, stable caesium tungsten bronze(s) slurry II;
3. according to volume ratio 1: 3～1: 1 slurry II is joined among the slurry I, makes wherein that caesium tungsten bronze(s) powder content is 0.0135～0.05g/ml, then with mixture at 80 ℃ of stirred in water bath heating 30min, placed again 2 days, glass transparent insulating coating.
Glass transparent insulating coating of the present invention contains a kind of novel near infrared and covers particle---caesium tungsten bronze(s) (Cs
xWO
3) nano-powder, this coating has visible light transmissive and near infrared shielding function, and has the light self-regulating function, promptly along with intensity of illumination and light application time prolong, visible light transmissive and near infrared screening effect can further strengthen thereupon, therefore being particularly suitable for preparing transparent heat-insulated insulation film made at glass surface, is a kind of glass transparent insulating coating of intelligence, is with a wide range of applications in architectural glazings and vehicle glass heat preservation and insulation field.This coating is made of polyvinyl alcohol membrane-forming agents such as (PVA), and the coating component is simple, is suitable for large-scale industrial production and practical application.
Description of drawings
Accompanying drawing 8 width of cloth of the present invention:
Fig. 1～6 be respectively applied the prepared glass surface transparent heat insulating dope of embodiment 1～6 glass before and after ultraviolet lighting the ultraviolet-visible transmitted spectrum.
Fig. 7 has applied the glass of embodiment 1～4 prepared coating and the heat insulation test result of blank glass.
Fig. 8 has applied the glass of embodiment 5～6 prepared coating and the heat insulation test result of blank glass.
Embodiment
The invention provides a kind of novel glass surface transparent heat insulating dope and preparation method thereof.Containing general formula in the described coating is Cs
0.1-3.5WO
3Caesium tungsten bronze(s) powder, described powder crystalline phase consists of Cs
0.2WO
3Or Cs
0.32WO
3, powder size is that 100～1300nm, specific surface area are 7～50m
2/ g.The preparation method of described coating comprises above-mentioned caesium tungsten bronze(s) powder and membrane-forming agent, polyvinyl butyral acetal (PVB), polyvinyl alcohol (PVA) or pyroxylin (e) cement (collodion), blended step.The caesium tungsten bronze(s) powder that reaches described in the invention described above prepares by the following method:
1. be the precursor solution that 0.01～0.35: 1 preparation contains wolframic acid, cesium carbonate and reducing substances according to the Cs/W mol ratio, solvent is the mixture of water or ethanol and 1: 4 by volume～4: 1 compositions of water;
2. precursor solution places autoclave, reacts 1～3d under 180～200 ℃ of conditions, and the gained precipitation obtains caesium tungsten bronze(s) powder through aftertreatment.
Described in the above-mentioned method for preparing caesium tungsten bronze(s) powder in the precursor solution concentration of wolframic acid be 0.1～1.0mol/L.
Reducing substances described in the above-mentioned method for preparing caesium tungsten bronze(s) powder is a citric acid.The concentration of citric acid is 0.1～1.5mol/L in the precursor solution.
Can use following method preparation precursor solution: under the agitation condition, the cesium carbonate aqueous solution of 0.1～1.0mol/L is added to the wolframic acid aqueous solution of 0.1～1.0mol/L, adds citric acid then, continue to stir 1～2h after supplying solvent.In the technique scheme, preferably making water is precursor solution, prepared Cs
xWO
3The granularity of powder is slightly smaller.
The compound method of the wolframic acid aqueous solution is sodium wolframate to be dissolved in be mixed with the sodium wolframate aqueous solution in the deionized water in the above-mentioned method for preparing caesium tungsten bronze(s) powder, obtain wolframic acid solution after then the sodium wolframate aqueous solution being exchanged by the vinylbenzene Zeo-karb, the concentration that makes wolframic acid solution is 0.1～1.0mol/L.
The step of preparation precursor solution in the above-mentioned method for preparing caesium tungsten bronze(s) powder can be to add citric acid simple substance or concentration is the aqueous citric acid solution of 1～5mol/L.The preferred latter.
In the above-mentioned method for preparing caesium tungsten bronze(s) powder, described step 2. to gained sedimentary aftertreatment comprise that washing, alcohol are washed, centrifugal, vacuum or inferior vacuum drying step.Wherein said inferior vacuum is vacuum tightness 0.09MPa, can obtain by following method: the centrifugal product deposit sample that obtains is put into Erlenmeyer flask, with soft rubber ball sealing Erlenmeyer flask with holes, vacuum pump is inserted soft rubber ball, Erlenmeyer flask is vacuumized, vacuum tightness remains on 0.09MPa, then Erlenmeyer flask is put into 50～80 ℃ of water-baths, can carry out inferior vacuum drying treatment to sample.
More specifically, the above-mentioned method for preparing caesium tungsten bronze(s) powder comprises the steps:
1. prepare the wolframic acid aqueous solution, cesium carbonate aqueous solution and citric acid solution respectively;
Wolframic acid aqueous solution preparation: according to the concentration of the wolframic acid solution that will prepare, accurate a certain amount of sodium wolframate of weighing, be dissolved in the deionized water, obtain the sodium wolframate aqueous solution, then the sodium wolframate aqueous solution is obtained the wolframic acid aqueous solution by vinylbenzene Zeo-karb exchange back, the concentration of the gained wolframic acid aqueous solution is 0.1～1.0mol/L;
The citric acid solution preparation: the weighing citric acid is dissolved in the deionized water, obtains citric acid solution, and concentration is 1～5mol/L;
The cesium carbonate aqueous solution preparation: according to the concentration of the cesium carbonate aqueous solution that will prepare, accurately a certain amount of cesium carbonate of weighing is dissolved in it in deionized water, obtains cesium carbonate aqueous solution, and the concentration of cesium carbonate aqueous solution is 0.1～1.0mol/L;
2. prepare precursor solution: stir on one side, on one side cesium carbonate aqueous solution is joined in the wolframic acid aqueous solution, add citric acid solution then, add a certain amount of dehydrated alcohol (or not adding ethanol) again and continue to stir 1～2h, obtain the reaction precursor liquid solution of preparation caesium tungsten bronze(s);
3. precursor solution is transferred in the autoclave, reaction 1～3d under 180～200 ℃, process washing, alcohol are washed, centrifugal treating, obtain Cs
xWO
3Deposit sample after 50～80 ℃ of vacuum or inferior vacuum drying treatment, obtains caesium tungsten bronze(s) (Cs
xWO
3) powder.
If no special instructions, the caesium tungsten bronze(s) (Cs to adopting aforesaid method to make
xWO
3) measured performance parameter of powder and coating products adopts following method:
(1) (X-ray diffraction XRD) analyzes the synthetic Cs of institute to utilize the D/max-3B X-ray diffractometer
xWO
3The crystalline phase of powder is formed, and adopts Cu K alpha-ray, and pipe is pressed 40.0kV, electric current 20mA, 5 °～70 ° of sweep limits.
(2) SSA-4200 aperture and the specific surface area analysis instrument that utilizes Bi Aode Electron Technology Co., Ltd to produce characterizes Cs
xWO
3The specific surface area of powder, adsorbed gas are N
2
(3) the Zetasize 3000HSA laser particle size analyzer that utilizes Britain MALVERN instrument company to produce characterizes Cs
xWO
3The size distribution of powder and average size.Concrete testing method: prepared powder is scattered in the water, directly tests its particle size distribution and median size in ultrasonic wave behind the ultrasonic 5min; Perhaps earlier with Cs
xWO
3Powder 0.272g is scattered in the PVA solution of 1g/10ml, is mixed with uniform sizing material, then with Cs
xWO
3/ PVA slurry is scattered in the water, tests Cs in its slurry in ultrasonic wave behind the ultrasonic 5min
xWO
3The particulate median size.
(4) utilize Lambda35 type ultraviolet-visible spectrophotometer produced in USA in 300～1100nm scope, to characterize Cs
xWO
3The ultraviolet-visible of powder-near infrared absorption performance.Concrete testing method: with BaCl
2Be background, with pressed by powder at BaCl
2On the sheet, characterize the near infrared absorption performance by testing its absorbancy.
(5) preparation of glass surface transparent film:
A certain amount of thermal insulating coating is poured on the slide glass, make coating smooth drawout equably on slide glass with glass stick, vertically lift an end of slide glass then fast, make unnecessary coating under action of gravity, flow out, keep plumbness 1h at room temperature, can obtain having the transparent heat-insulated film of glass surface of certain transparency, uniformity coefficient, planeness.
In the coating on the common large-size sheet glass: simple glass is placed on the fixed pan, stick on two long edges of rectangle simple glass sheet with scotch tape then and on the fixed pan, simple glass is fixed, at this moment formed both sides by the groove of scotch tape as projection in surface of ordinary glass.Pipette a certain amount of serum material in groove one end with glue head dropper, the serum material roller is applied to glass sheet surface, form certain thickness film at glass surface thus with clean glass stick.
(6) utilize Lambda35 type ultraviolet-visible spectrophotometer produced in USA in 300～1100nm scope, to characterize ultraviolet-visible-near-infrared transmission spectrum that glass surface is filmed, to estimate the visible light transmissive and the near infrared screening performance of glass surface film.
(7) test of photochromic or near infrared shield light inherent regulation intelligent function: will scribble Cs
xWO
3The sheet glass of film, behind different times such as ultraviolet lamp (275nm) irradiation 10min, 30min, the transmitted spectrum of specimen is once more estimated the photochromic properties of glass surface film and the near infrared screening performance variation relation with light application time with this.
(8) test of glass film sample heat-proof quality: prepare insulated space with cystose, the design insulated space is of a size of 5 * 10 * 10.5 (cm
3), simple glass sheet area is 7 * 12 (cm
2), area 6.4 * 11 (cm film
2); The case inner bottom part is covered with black iron plate, the surface that red water temp meter (100 ℃) is close to black iron plate.
Test process: the glass that will scribble thermal insulating coating, be placed on the heat insulating and sealing spatial window, allow the part that scribbles film cover the spatial window fully, use the 250W infrared lamp, apart from window vertical range 25cm irradiation, the recording thermometer reading is with the variation relation of irradiation time.With with quadrat method blank testing sheet glass the temperature during as window over time, the two contrast can obtain the effect of heat insulation of thermal insulating coating.
Mode with specific embodiment is further described technical scheme of the present invention below, the content that does not limit the present invention in any way.
Embodiment 1
1. the Cs for preparing Cs/W (mol ratio)=0.3: 1
0.3WO
3Powder.
A certain amount of sodium wolframate of weighing is dissolved in the deionized water, is made into the sodium tungstate solution of 0.5mol/L, utilizes the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtains the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 20ml of 0.5mol/L, put into beaker, the citric acid solution of 1 adding 30ml 2mol/L in the stirring, slowly the cesium carbonate solution of Dropwise 5 ml 0.3mol/L continues to stir 1h, obtains to prepare Cs
0.3WO
3The reaction precursor liquid solution of powder; The reaction precursor liquid solution of above-mentioned preparation is transferred in the autoclave 200 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain blue Cs in inferior vacuum
0.3WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation: the 10g PVAC polyvinylalcohol is soaked in 2mol/L, 2h in the citric acid of 100ml, be added dropwise to 4 defoamers, heated and stirred 1h in 95 ℃ of water-baths then obtains transparent after filtering and polyvinyl alcohol (PVA) slurry of suitable viscosity is arranged.
3. glass transparent insulating coating preparation: take by weighing 0.272g caesium tungsten bronze(s) powder, at 2mol/L, fully grind 5min in the 10ml citric acid, ultra-sonic dispersion 20min grinds so repeatedly then, ultrasonic 3 times, obtains uniform slurry; Join then in the PVA slurry that 10ml prepared, stirring heating 30min in 80 ℃ of water-baths places 2d then, can obtain glass transparent insulating coating to be coated with.
After measured, this Cs
0.3WO
3The crystalline phase of powder is six side Cs
0.32WO
3, it is dispersed in the deionized water, the mean particle size that records is 188.5nm, specific surface area is 41.67m
2/ g; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.3WO
3The glass sample of transparent heat insulating dope has the highest light transmission rate at visible light 799nm wavelength place, is 62%; 1100nm wavelength place has minimum light transmission rate in the near-infrared region, is 49%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 607nm wavelength place has the highest light transmission rate, is 56%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 29%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 80 ℃, and coated glass sample insulated space displays temperature is 54.8 ℃, 25.2 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 86.8 ℃, and coated glass sample insulated space displays temperature is 66.2 ℃, 24.6 ℃ of the temperature difference, and behind the 54min, the temperature difference remains on 24.8 ℃.
Embodiment 2
1. the Cs for preparing Cs/W (mol ratio)=0.3: 1
0.3WO
3Powder.
A certain amount of sodium wolframate of weighing is dissolved in the deionized water, is made into the sodium tungstate solution of 0.5mol/L, utilizes the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtains the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 20ml of 0.5mol/L, put into beaker, the citric acid of 1 adding 12.6g in the stirring, after stirring, slowly the cesium carbonate solution of Dropwise 5 ml 0.3mol/L adds 10ml dehydrated alcohol and 20ml deionized water then, continue to stir 1h, obtain preparation Cs
0.3WO
3The reaction precursor liquid solution of powder; The reaction precursor liquid solution of above-mentioned preparation is transferred in the autoclave 190 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain nattier blue Cs in inferior vacuum
0.3WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation:
The 10g PVAC polyvinylalcohol at room temperature is immersed in 2h in the 100ml deionized water, is added dropwise to 4 defoamers, heated and stirred 2.5h in 95 ℃ of water-baths then obtains white PVA slurry transparent slightly, that suitable viscosity is arranged after filtering through 200 mesh sieves.
3. glass transparent insulating coating preparation: the caesium tungsten bronze(s) powder of 0.272g is fully ground 5min in the 5ml deionized water, ultra-sonic dispersion 20min grinds so repeatedly then, ultrasonic 3 times, obtains even, stable caesium tungsten bronze(s) (Cs
xWO
3) slurry; Then with resulting caesium tungsten bronze(s) (Cs
xWO
3) slurry joins in the PVA slurry of the 15ml that step obtains in 2., at 80 ℃ of stirred in water bath heating 30min, places 2d, obtains glass transparent insulating coating to be coated with.
After measured, this Cs
0.3WO
3The crystalline phase of powder is six side Cs
0.32WO
3, it is dispersed in the polyvinyl alcohol water solution (polyvinyl alcohol concentration 1g/10ml), the mean particle size that records is 1270nm, specific surface area is 28.47m
2/ g; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.3WO
3The glass sample of transparent heat insulating dope has the highest light transmission rate at visible light 785nm wavelength place, is 50%; 1100nm wavelength place has minimum light transmission rate in the near-infrared region, is 45%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 712nm wavelength place has the highest light transmission rate, is 50%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 37%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 80 ℃, and coated glass sample insulated space displays temperature is 65 ℃, 15 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 86.8 ℃, and coated glass sample insulated space displays temperature is 72.8 ℃, 14 ℃ of the temperature difference, and behind the 42min, the temperature difference remains on 14 ℃.
Embodiment 3
1. the Cs for preparing Cs/W (mol ratio)=0.3: 1
0.3WO
3Powder.
Take by weighing a certain amount of sodium wolframate, be dissolved in the deionized water, be made into the sodium tungstate solution of 0.5mol/L, utilize the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtain the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 20ml of 0.5mol/L, put into beaker, the citric acid of 1 adding 12.6g in the stirring, after stirring, slowly the cesium carbonate solution of Dropwise 5 ml 0.3mol/L adds the 30ml dehydrated alcohol then, continues to stir 1h, obtains to prepare Cs
0.3WO
3The reaction precursor liquid solution of powder; The reaction precursor liquid solution of above-mentioned preparation is transferred in the autoclave 190 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain nattier blue Cs in inferior vacuum
0.3WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation: 2. with embodiment 2 steps;
3. glass transparent insulating coating preparation: 3. with embodiment 2 steps;
After measured, this Cs
0.3WO
3The crystalline phase of powder is six side Cs
0.32WO
3, it is dispersed in the polyvinyl alcohol water solution (polyvinyl alcohol concentration 1g/10ml), the mean particle size that records is 1032nm, specific surface area is 27.44nm; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.3WO
3The glass sample of transparent heat insulating dope is behind external radiation exposure 10min, and it has the highest light transmission rate at visible light 877nm wavelength place, is 39%; The place has minimum light transmission rate at 780～1100nm near-infrared region 1100nm wavelength, is 36%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 737nm wavelength place has the highest light transmission rate, is 37%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 25%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 80 ℃, and coated glass sample insulated space displays temperature is 59.8 ℃, 21.2 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 86.8 ℃, and coated glass sample insulated space displays temperature is 66.5 ℃, 20.3 ℃ of the temperature difference, and behind the 50min, the temperature difference remains on 20.6 ℃.
Embodiment 4
1. the Cs for preparing Cs/W (mol ratio)=0.3: 1
0.3WO
3Powder.
Take by weighing a certain amount of sodium wolframate, be dissolved in the deionized water, be made into the sodium tungstate solution of 0.5mol/L, utilize the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtain the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 10ml of 0.5mol/L, put into beaker, the citric acid of 1 adding 12.6g in the stirring, after stirring, slowly the cesium carbonate solution of Dropwise 5 ml 0.15mol/L adds the 40ml dehydrated alcohol then, continues to stir 1h, obtains to prepare Cs
0.3WO
3The reaction precursor liquid solution of powder; The reaction precursor liquid solution of above-mentioned preparation is transferred in the autoclave 190 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain nattier blue Cs in inferior vacuum
0.3WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation: 2. with embodiment 2 steps;
3. glass transparent insulating coating preparation: 3. with embodiment 2 steps;
After measured, this Cs
0.3WO
3The crystalline phase of powder is six side Cs
0.32WO
3, it is dispersed in the polyvinyl alcohol water solution (polyvinyl alcohol concentration 1g/10ml), the mean particle size that records is 561nm, specific surface area is 25.65m
2/ g; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.3WO
3The glass sample of transparent heat insulating dope has the highest light transmission rate at visible light 716nm wavelength place, is 56%; The place has minimum light transmission rate at 780～1100nm near-infrared region 1100nm wavelength, is 50%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 676nm wavelength place has the highest light transmission rate, is 54%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 40.5%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 80 ℃, and coated glass sample insulated space displays temperature is 66.5 ℃, 13.5 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 86.8 ℃, and coated glass sample insulated space displays temperature is 73.5 ℃, 14 ℃ of the temperature difference, behind the 30min, the temperature difference remains on 13.3 ℃, and the temperature difference remains on 12.8 ℃ behind the 50min.
Embodiment 5
1. the Cs for preparing Cs/W (mol ratio)=0.35: 1
0.35WO
3Powder.
Take by weighing a certain amount of sodium wolframate, be dissolved in the deionized water, be made into the sodium tungstate solution of 0.5mol/L, utilize the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtain the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 60ml of 0.5mol/L, put into beaker, the citric acid of 1 adding 37.8g after stirring, slowly drips the cesium carbonate solution of 15ml 0.35mol/L in the stirring, adds the 90ml dehydrated alcohol then, continues to stir 1h, obtains preparation Cs
0.35WO
3The reaction precursor liquid solution of powder; Divide three groups to be transferred in three 100ml autoclaves the reaction precursor liquid solution of above-mentioned preparation, 190 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain nattier blue Cs in inferior vacuum
0.35WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation: the PVA that takes by weighing 10g is soaked in 2h in the 100ml deionized water at room temperature, be added dropwise to 4 defoamers then, at 80 ℃ of stirred in water bath 2h, filter the 1g/10ml PVA aqueous solution that obtains having certain viscosity through 200 mesh sieves again;
3. glass transparent insulating coating preparation: 3. with embodiment 2 steps;
After measured, this Cs
0.35WO
3The crystalline phase of powder is six side Cs
0.32WO
3, it is dispersed in the polyvinyl alcohol water solution (polyvinyl alcohol concentration 1g/10ml), the mean particle size that records is 520nm, specific surface area is 7.41m
2/ g; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.3WO
3The glass sample of transparent heat insulating dope has the highest light transmission rate at visible light 681nm wavelength place, is 50.4%; The place has minimum light transmission rate at 780～1100nm near-infrared region 1100nm wavelength, is 34.2%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 659nm wavelength place has the highest light transmission rate, is 48.7%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 30.4%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 78 ℃, and coated glass sample insulated space displays temperature is 61 ℃, 17 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 84.8 ℃, and coated glass sample insulated space displays temperature is 68.5 ℃, 16.3 ℃ of the temperature difference, and behind the 64min, the temperature difference remains on 15 ℃.
Embodiment 6
1. the Cs for preparing Cs/W (mol ratio)=0.1: 1
0.1WO
3Powder.
Take by weighing a certain amount of sodium wolframate, be dissolved in the deionized water, be made into the sodium tungstate solution of 0.5mol/L, utilize the vinylbenzene Zeo-karb that sodium tungstate solution is carried out ion-exchange, obtain the wolframic acid solution of 0.5mol/L; Measure the wolframic acid solution 60ml of 0.5mol/L, put into beaker, the citric acid of 1 adding 37.8g after stirring, slowly drips the cesium carbonate solution of 15ml 0.1mol/L in the stirring, adds the 90ml dehydrated alcohol then, continues to stir 1h, obtains preparation Cs
0.1WO
3The reaction precursor liquid solution of powder; Divide three groups to be transferred in three 100ml autoclaves the reaction precursor liquid solution of above-mentioned preparation, 190 ℃ of following continuous hydro-thermal reaction 3d; With reacted throw out wash successively, alcohol washes 3 times, through after the centrifugation, 50 ℃ of oven dry 10h down obtain nattier blue Cs in inferior vacuum
0.1WO
3Powder.
2. polyvinyl alcohol (PVA) solution preparation: 2. with embodiment 5 steps;
3. glass transparent insulating coating preparation: 3. with embodiment 2 steps;
After measured, this Cs
0.1WO
3The crystalline phase of powder is six side Cs
0.2WO
3, it is dispersed in the polyvinyl alcohol water solution (polyvinyl alcohol concentration 1g/10ml), the mean particle size that records is 566nm, specific surface area 43.2m
2/ g; Ultraviolet-visible pectrophotometer test result: scribble Cs
0.1WO
3The glass sample of transparent heat insulating dope has the highest light transmission rate at visible light 674nm wavelength place, is 62.6%; The place has minimum light transmission rate at 780～1100nm near-infrared region 1100nm wavelength, is 49%, compares with the high permeability of visible region, has descended in the transmitance of near-infrared region 1100nm
The test result of photochromic or near infrared shield light inherent regulation intelligent function: behind ultraviolet lighting 30min, visible light 666nm wavelength place has the highest light transmission rate, is 61.8%; Having minimum light transmission rate at 780nm～1100nm near-infrared region 1100nm wavelength place, is 46.5%, compares with the high permeability of visible region, has descended near infrared 1100nm transmitance
Heat insulation test result: behind infrared lamp irradiation 20min, blank glass (not being coated with membrane sample) insulated space displays temperature is 78 ℃, and coated glass sample insulated space displays temperature is 70 ℃, 8 ℃ of the temperature difference; Behind infrared lamp irradiation 30min, blank glass (not being coated with membrane sample) insulated space displays temperature is 84.8 ℃, and coated glass sample insulated space displays temperature is 78 ℃, 6.8 ℃ of the temperature difference.
Claims (10)
1. glass transparent insulating coating, it is characterized in that containing in this coating general formula is Cs
0.1-3.5WO
3Caesium tungsten bronze(s) powder, described powder crystalline phase consists of Cs
0.2WO
3Or Cs
0.32WO
3, powder size is that 100～1300nm, specific surface area are 7～50m
2/ g.
2. the described glass transparent insulating coating of claim 1, the content that it is characterized in that caesium tungsten bronze(s) powder in the described coating is 0.0135～0.05g/ml.
3. the described glass transparent insulating coating of claim 2 is characterized in that also containing in the described coating polyvinyl butyral acetal, polyvinyl alcohol or pyroxylin (e) cement as membrane-forming agent.
4. the preparation method of the described glass transparent insulating coating of claim 1 is characterized in that comprising with caesium tungsten bronze(s) powder and membrane-forming agent blended step, wherein:
Described caesium tungsten bronze(s) powder crystalline phase consists of Cs
0.2WO
3Or Cs
0.32WO
3, powder size is that 100～1300nm, specific surface area are 7～50m
2/ g;
Described membrane-forming agent is polyvinyl butyral acetal, polyvinyl alcohol or pyroxylin (e) cement.
5. the described method of claim 4 is characterized in that described membrane-forming agent is a polyvinyl alcohol.
6. the described method of claim 5 comprises the steps:
1. be that the aqueous citric acid solution of 1～4mol/L is that solvent prepares the slurry I that PVA content is 0.05～0.15g/ml with water or concentration;
2. caesium tungsten bronze(s) powder is grinding, a ultra-sonic dispersion in the 2mol/L aqueous citric acid solution at water or concentration, gets slurry II;
3. according to volume ratio 1: 3～1: 1 slurry II is joined among the slurry I, makes wherein that caesium tungsten bronze(s) powder content is 0.0135～0.05g/ml, then with mixture at 80 ℃ of stirred in water bath heating 30min, placed again 2 days, glass transparent insulating coating.
7. the described method of claim 6 is characterized in that also containing defoamer among the described slurry I.
8. the described method of claim 7, the preparation method who it is characterized in that described slurry I is: polyvinyl alcohol is soaked in 1～3h in the aqueous citric acid solution that water or concentration are 1～4mol/L, add defoamer, then with mixture heated and stirred 1～3h in 95 ℃ of water-baths, obtain slurry I after filtering, wherein PVA content is 0.05g/ml～0.15g/ml.
9. arbitrary described method in the claim 6～8, it is characterized in that described step 1. with step 2. in employed solvent be water.
10. the described method of claim 9 is characterized in that comprising the steps:
1. polyvinyl alcohol is soaked in 1～3h in the water, adds SN-DEFOAMER 1340 defoamers, with mixture heated and stirred 1～3h in 95 ℃ of water-baths, obtain slurry I after filtering then, wherein PVA content is 0.05g/ml～0.15g/ml;
2. caesium tungsten bronze(s) powder grinds ultra-sonic dispersion 20min behind the 5min in water, repeats to grind the operation with ultra-sonic dispersion, until obtaining even, stable caesium tungsten bronze(s) slurry II;
3. according to volume ratio 1: 3～1: 1 slurry II is joined among the slurry I, makes wherein that caesium tungsten bronze(s) powder content is 0.0135～0.05g/ml, then with mixture at 80 ℃ of stirred in water bath heating 30min, placed again 2 days, glass transparent insulating coating.
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