CN101613187B - Method for improving WO3 film gaschromic cycle performance - Google Patents
Method for improving WO3 film gaschromic cycle performance Download PDFInfo
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- CN101613187B CN101613187B CN2009100553013A CN200910055301A CN101613187B CN 101613187 B CN101613187 B CN 101613187B CN 2009100553013 A CN2009100553013 A CN 2009100553013A CN 200910055301 A CN200910055301 A CN 200910055301A CN 101613187 B CN101613187 B CN 101613187B
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Abstract
The invention belongs to the technical field of the environmental and energy-saving material and relates to a method for improving WO3 films gaschromic cycle performance by doping WO3 sol with inorganic substances which can increase the porosity of WO3 gaschromic films; wherein, the inorganic substances contain SiO2, Al2O3, P2O5, Fe2 O3 and CuO2. Sol-gel method is adopted to prepare stable WO3 composite sol; the pulling method or spin-coating technique is used to plate transparent and uniform composite catalyst-doped WO3 porous films on common glass. Compared with the untreated films, the gaschromic films which are prepared from the doped and combined sol has dramatically increased gaschromic cycle performance; compared with the gaschromic films which are prepared by magnetron sputtering and other methods, the performance of the films prepared by the invention is the same and the cost is largely reduced; compared with the electrochomeric films, the films have the same advantages. The method makes up for detects of the gaschromic smart window which is prepared by sol-gel method so that the smart window technology tends to be more mature.
Description
Technical field
The invention belongs to environmental protection, energy-saving material technical field, relate to WO
3Film gas-discoloration technology especially improves WO
3The method of film gaschromic cycle performance.
Background technology
At present, energy shortage has become the problem that governments at all levels are concerned about day by day, and the use of cleaning, regeneration, the safe and reliable energy is extremely urgent.Buildings is one of high energy consumption unit, and its energy consumption has reached 27.6% of social total energy consumption in China, and will be above 33%, and wherein 40% power loss is caused by window, for the 2-3 of developed country doubly.According to statistics, under heating or air-conditioning condition, the heat that winter, single glass port was lost accounts for the 30-50% of thermal load, and inject indoor consume 20-30% that cold account for air conditioner load because of solar radiant heat sees through glass port summer.Therefore, the discussion agenda has been mentioned in the comprehensive utilization of new energy-saving material and power-saving technology and sun power.If plating layer of transparent heat-insulation and heat-preservation thin-film material, conserve energy effectively on the window glass of this high energy consumption.Estimate the annual about 7 dollars/m of thermosteresis of layer glass window when plated film (not) according to U.S. MIT
2,, can make the window thermosteresis reduce to annual about 3.2 dollars/m if behind plating layer of transparent heat-insulation and heat-preservation thin-film material on glass
2Estimate that according to Sweden Uppsala university under the weather condition of central europe, plating layer of transparent heat-insulation and heat-preservation film can make household energy conservation 20%, office space energy-conservation 12% on window-glass.
As far back as the eighties in last century, countries such as Europe, the U.S., Japan, China have just carried out transparent heat-insulated heat preservation energy-saving thin-film material research, and have obtained good application (being glass curtain wall) in the building in modern times, have reached energy-saving effect preferably.But this material function is single, spectral response curve is fixed.No matter be fine day or daytime, indoorly still adopt lighting, people can't enjoy the sunlight of the Nature, and summer is energy-conservation, then the power consumption in winter; Otherwise winter is energy-conservation, and then consume energy summer.For our area, residing temperate zone, its optical characteristics and energy conservation characteristic can't be regulated with season, circadian variation.Therefore, for comfortable human settlements, Working environment is provided, for a long time, people seeking a kind of can intelligent control, optical characteristics can change with external environment and take place reversible changely, integrates energy-conservation, decoration, heat insulation, the coated glass material that is incubated.Cause the birth of look property smart windows, can solve this difficult problem.
Causing look property smart windows can be dynamic, reversible, at random the sunlight through window is carried out intellectuality control; Can be widely used in building, automobile, spaceship etc. as high energy efficiency sunlight control energy-saving window; Be adapted to the development of modern architecture mansion especially, for the manufacturing of modern energy-saving window system provides brand-new method of design.
Usually, cause look property smart windows and be divided into several kinds of thermochromism, photochromic and electrochromism etc.Say that from action mode photochromic and thermochromism are a kind of passive type off-color materials, only in ambient conditions such as light intensity, metachromatism just takes place when temperature changes, people can not regulate and control flexibly.Electrochromic material then is active functional materials, and its optical characteristics (like transsmissivity, color) can be according to the variation of surrounding environment, through electric field action; The common injection that ion and electronics take place is extracted out together, makes the optical characteristics of material that continuous, reversible, variation at random take place, thereby realizes that optical density(OD) is adjustable continuously; Therefore; Have most actual application prospect, developed country such as the U.S., Japan and Europe and domestic how tame unit are carrying out commercial applications research, but this look property smart windows that causes is made up of five layer film materials usually; Device architecture is complicated, influence factor is many, preparation cost is high, and is difficult to big area production.Though the existing automobile of this electrochromic material falls small size commerical prods such as visor, sunglasses, as large-sized building energy conservation window commercial applications that still is unrealized so far.
In recent years, the current research that causes look property material in the world shows that a kind of off-color material that has similar variable color mechanism with electrochromism---gas chromism film is just causing people's very big interest.This look property smart windows that causes only causes the look film that causes that look film and one deck catalyst layer or one deck as thin as a wafer contain catalyzer by one deck and constitutes; Gas molecule (like hydrogen) is an atom by catalyst decomposes; Cause change of optical property through diffusing into to cause in the look material, thereby cause continuous, reversible, the variation at random of thin-film material transsmissivity.This solid-state structure cause that look property material structure is simple, influence factor is few, and optical adjustment wider, be convenient to big area production, the no energy consumption of device operation.This novel gas-discoloration smart windows rate is at first taken proposition of thinkling sound's Hough solar energy system institute and development by Germany, and the university of few countries such as the U.S., Slovenia, institute have carried out this respect work in succession afterwards.Domestic only have units such as Tongji University, Guangzhou solar energy research institute of the Chinese Academy of Sciences to carry out this respect research at present.
On principle, electrochromism smart windows device is that little positively charged ion and electronics dual injection and extraction under electric field action cause look property film, and electrochromism and discoloration effect take place.And for gas-discoloration smart windows device; Hydrogen molecule resolves into Wasserstoffatoms behind catalyst action; Diffuse to cause in the look property film and cause colouring effect, fade and in Sauerstoffatom or air diffuser to film, produce, therefore; Both hydrogen inject/withdraw from the driving mechanism difference, thereby require the microstructure characteristic of thin-film material different.
In the world current, the amorphous WO of the tool application prospect of concentrated research
3The gas-discoloration performance of thin-film material is main, just how to improve with amorphous WO
3Problems such as the Wasserstoffatoms velocity of diffusion of the gas-discoloration window device that thin-film material is processed, diffusion uniformity, colour consistency, variable color speed, wearing quality are just furtherd investigate.
SiO
2Perhaps P
2O
5, Al
2O
3, Fe
2O
3The colloidal sol of the material stable etc. relative hydrogen is a kind of common cheap material, with the film of this material prepn have that raw material is cheap, preparation technology simple, the characteristics of physics and stable chemical performance etc.
Also do not adopt WO3/SiO2 two to disperse adulterated technology to improve amorphous WO mutually at present
3The related patent U.S. Patent No. report of the gas-discoloration performance of thin-film material.
Summary of the invention
The object of the present invention is to provide a kind of raising WO
3The method of film gaschromic cycle performance.
A kind of raising WO
3The method of film gaschromic cycle performance, employing can improve WO
3The inorganics of gas chromism film porosity is to WO
3Colloidal sol mixes, and said inorganics comprises SiO
2, Al
2O
3/ AAO template, P
2O
5, Fe
2O
3, CuO
2
Further: may further comprise the steps:
Preparation WO
3Colloidal sol;
Choose and prepare SiO
2, Al
2O
3Colloidal sol;
The WO of catalyzer is mixed in preparation
3/ SiO
2, WO
3/ Al
2O
3Colloidal sol:
The WO of catalyzer is mixed in preparation
3/ SiO
2, WO
3/ Al
2O
3Film.
WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol;
SiO
2The preparation of colloidal sol:
SiO
2The preparation process of colloidal sol relates generally to the hydrolysis in silicon source, and hydrolysis rate is very relevant with ratio, solution pH value and the room temperature condition of silicon source, water, below we recommend with positive tetraethyl orthosilicate hydrolysis
(1) chooses and prepare SiO
2Colloidal sol
1. acidic catalyst SiO
2The preparation of colloidal sol:
Accurately measure deionized water, absolute ethyl alcohol, silicon source (as: tetraethoxy) respectively with volumetric flask and transfer pipet; Ratio can suitably be adjusted according to the demand of experimental temperature, silicon source category, test period; We recommend with the tetraethoxy is the silicon source; The employing ratio is under the room temperature condition: (wherein the proportional action of absolute ethyl alcohol is strength of solution to 23.5/100/77.8; Causing corresponding adjustings such as color depth with the required film of reality, is the better ratio of film forming with the ratio of this kind water and TEOS, also can be according to other raw material response regulation); The ratio of deionized water and tetraethoxy need be taken multiple factors such as water in the WO3 colloidal sol, silicon source, room temperature into consideration, the ratio when crucial ratio is not less than collosol and gel, is not more than the film forming ratio of colloidal sol that influences.
Wherein the accurate weighing concentrated hydrochloric acid of amount according to removing ionized water (can adopt multiple acid catalysis; For example: wolframic acid, nitric acid, phosphoric acid, oxalic acid etc.) be mixed with the hydrochloric acid soln of pH＜7; Recommend PH=2, pour among the beaker A, will clean magnetic agitation and put into a beaker A for; The absolute ethyl alcohol that to accurately measure required positive tetraethyl orthosilicate and aequum is again poured among the beaker A successively; Be placed on the magnetic stirrer after with cleaning film and bungee and stir, according to the acid SiO of top recommendation ratio preparation the sealing of beaker A bottleneck
2The colloidal sol churning time is just can make acid SiO in 2-4 hour
2Colloidal sol can adopt relatively shorter churning time if pH value is smaller.
Perhaps 2. base catalysis SiO
2The preparation of colloidal sol:
The base catalysis legal system is equipped with SiO
2Required starting material of colloidal sol and proportioning ratio can suitably be adjusted according to the demand of experimental temperature, silicon source category, test period; The recommendation molar ratio is following: tetraethoxy (TEOS): ethanol: (ammoniacal liquor of this ratio is hydrolysis ratio faster in ammoniacal liquor=1/38/2.45; Other ratios also can); The process for preparation of colloidal sol should carry out under less than 60% environment in clean cleaning, relative humidity, and concrete steps are following: the absolute ethyl alcohol of accurately measuring aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker A; The strong aqua of accurately measuring the pH=12 of aequum with transfer pipet pours that (ammoniacal liquor of this ratio is hydrolysis ratio faster among the beaker A into; Other ratios also can; Relate to the amount that need as far as possible reduce ammoniacal liquor of mixing with WO3, but need pH＞7, need the environment of an alkalescence.); To clean magnetic agitation and put into a beaker A for, and be placed on after with cleaning film and bungee beaker A bottleneck being sealed and stir on the magnetic stirrer about 20min, reach aim of even dispersion;
The absolute ethyl alcohol of accurately measuring required tetraethoxy and aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker B successively; To clean magnetic agitation and put into a beaker B for, and be placed on after with cleaning film and bungee beaker B bottleneck being sealed and stir on the magnetic stirrer about 20min, reach aim of even dispersion; With magnet along outer wall with taking out in magnetic agitation among the beaker A, and mixing solutions among the beaker A is poured in the pear shape separatory funnel; Mixing solutions in the pear shape separatory funnel is dropwise splashed among the beaker B that is placed on the magnetic stirring apparatus lentamente, keep simultaneously stirring; Drip and finish about continued stirring 2h it to be mixed, take out the stirrer among the beaker B with magnet along outer wall subsequently;
Beaker B is rested under the stable environment (16-24 ℃ with film and the bungee good seal of cleaning; Relative humidity＜50%) wears out; Colloidal sol after aging is light blue emulsion state; This moment, colloidal sol endocorpuscular median size was less than 10nm, colloidal sol taken out pour in the round-bottomed flask, and colloidal sol must not the submergence flask more than 2/3; In round-bottomed flask, add a small amount of clean molecular sieve and prevent bumping, fixedly be immersed in flask in the heating in water bath pot that fills silicone oil with iron stand then; Regulate oil bath temperature between 80 ℃～85 ℃, keep the slight boiling condition of colloidal sol liquid level; Utilize snakelike return line to reflux, test at the return line mouth of pipe, to pH test paper no change, stop to heat, treat behind the naturally cooling flask to be taken out with the quantitative pH test paper after wetting; Pour colloidal sol in beaker sealing preservation;
Perhaps 3. other SiO
2The preparation of colloidal sol
Utilize silicon source such as positive tetraethyl orthosilicate, Union carbide A-162 and alcohol to mix the colloidal sol that is made into respective concentration in required ratio (this ratio is adjusted according to the situation in the actually operating, and value is any).
Perhaps 4. Al
2O
3The preparation of colloidal sol
Volumetric flask and transfer pipet are accurately measured Aluminum chloride anhydrous+deionized water+ethanol+propylene oxide (6mmol: 0.65ml: 6-40ml: 0.32ml) respectively; Perhaps aluminum isopropylate+water+Virahol+catalyzer (acid or alkali, be example) with hydrochloric acid, ratio is 1mmol: 3mmol: 1-10ml: 0.1mmol (this ratio); (top two kinds of ratios need be taken multiple factors such as the interior water of WO3 colloidal sol, aluminium source, room temperature into consideration; Ratio when crucial ratio is not less than collosol and gel, be not more than the film forming ratio of colloidal sol that influences; Can only provide recommendation at this; The amount of these two kinds of catalyzer is the recommendation ratio, and catalyzer suggestion is used the mode that drips not form gel to be) will accurately measure required colloidal sol and pour in the beaker; Be placed on the magnetic stirrer after with the sealing of beaker bottleneck with cleaning film and bungee and stir, churning time is 4 hours; Aging 1 hour of 50 degree.
(3) WO
3And SiO
2The complex sol preparation:
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, dispersion ratio (SiO
2/ WO
3Mol ratio)＞0/1 the raising of cycle performance is all arranged, and circulative decay is different, but is easier to utilize dry means to reach circulative recovery when＞1/1.Here advise that mol ratio is: 1/1.
(4) mix the WO of catalyzer
3/ SiO
2The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and said catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute.
Perhaps 3. AAO template is 70nm Al
2O
3Template soak power prepared mix palladium WO
3In the colloidal sol, concussion is 30 minutes in ultrasonic; Take out this Al
2O
3Template is mixed gained the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute.
In order to obtain thicker film, adopt and improve WO
3The method of collosol concentration or pull rate; Concentration is high more, and the faster film of pull rate thick more (concrete numerical value needs according to ambient conditions adjustment between colloidal sol, plated film) perhaps adopts the method for multiple spin coating; Between per twice spin coating, with film thermal treatment 2-5min between 40-55 ℃ of temperature.
WO
3With SiO
2Dispersion uniformly is compound, above-mentioned SiO
2Colloidal sol preparation method and proportioning are two kinds of SiO that instance relates to
2Colloidal sol can adopt any type of SiO
2Colloidal sol is to carry out WO
3Dispersion, such as utilizing HNO
3All kinds of acid such as acid, wolframic acid perhaps adopt other silicon source to prepare SiO as catalyzer
2
WO to gained
3Film gas-discoloration performance is tested:
The WO that mixes catalyzer that employing ultraviolet/visible/infrared spectrophotometer (V-570 type, Jasco Inc.) was handled ultraviolet
3The test of film gas-discoloration performance.The glass of plated film is sealed into the device of hollow (inboard plated film) structure with uncoated glass edge with glass cement, and stay an aperture (being stayed), formation gas-discoloration device by feeding hydrogen.During test gas-discoloration characteristic, feeding volume content is the argon gas of 5% hydrogen, adopts 4 ρ/min airshed and 0.15MPa air pressure.With ultraviolet/visible/infrared spectrophotometer (V-570 type, Jasco Inc.) transsmissivity that causes look front and back film is tested wavelength region 190-2500cm
-1, wavelength accuracy is 1.5nm, and light source is a halogen tungsten lamp at visible region, and ultraviolet region is a deuterium lamp, and light source automaticallyes switch.
Experimental result shows, through dispersive WO
3/ SiO
2Complex sol, film WO
3/ SiO
2Be uniformly dispersed, the stability of film is improved; Film is become by the fine and close attitude of single WO3 film has the large space aperture structure, H in the film
2The discrepancy of O becomes and is more prone to, and circulates still not seen after 500 times significantly to weaken sign.With WO
3/ SiO
21.25: 1 left and right adjusting of mol ratio can prepare the gas-discoloration window of good through performance and cycle performance.
The present invention adopts two, and to disperse adulterated method mutually be to improve the WO that amorphous is mixed catalyzer
3The circulative technological method of the gas-discoloration of thin-film material.
The present invention adopts the WO of Prepared by Sol Gel Method
3Colloidal sol and SiO
2Colloidal sol disperses mutually to mix through two according to a certain percentage, obtains the WO that amorphous stable and that have a large space aperture structure is mixed catalyzer
3Film, thus reach the WO that lets amorphous mix catalyzer
3The modification of thin-film material.
The present invention adopts ultraviolet/visible/infrared spectrophotometer (V-570 type, Jasco Inc.) to the composite mixed WO that mixes catalyzer
3The test of film gas-discoloration performance.The gas chromism film and single WO mutually that prepare with mode of the present invention
3Film compare, significantly improved the cycle performance of gas-discoloration; To cause form and aspect more identical than performance with the gas chromism film of method such as magnetron sputtering preparation, and cost is significantly with low; Comparing with electrochomeric films also has same advantage.The shortcoming of the gas-discoloration smart windows of Prepared by Sol Gel Method before the present invention has well remedied makes this type of smart windows technology more be tending towards ripe.
Description of drawings
Fig. 1 is the common palladium WO that mixes among the embodiment 1
3Film gas-discoloration design sketch
Fig. 2 mixes palladium WO among the embodiment 1
3/ SiO
2Film gas-discoloration design sketch
Fig. 3 is the common palladium WO that mixes among the embodiment 1
3Film circulation variable color curve
Fig. 4 mixes palladium WO among the embodiment 1
3/ SiO
2450 times-500 times circulation variable color curves of film
Fig. 5 mixes palladium WO among the embodiment 1
3The film surface structure iron.
Fig. 6 mixes palladium WO among the embodiment 1
3/ SiO
2The film surface structure iron
Fig. 7 mixes palladium WO among the embodiment 1
3The shape appearance figure of film microcosmic.
Fig. 8 mixes palladium WO among the embodiment 1
3/ SiO
2The shape appearance figure of film microcosmic
Fig. 9 is different content SiO among the embodiment 1
2The cyclicity synoptic diagram of laminated film.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1: prepare two phase mixing and doping WO3/SiO
2Film, concrete steps are following:
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) preparation of acidic catalyst SiO2 colloidal sol
Accurately measure deionized water respectively with volumetric flask and transfer pipet, absolute ethyl alcohol (Eth), tetraethoxy (TEOS), ratio is: 23.5/100/77.8; Be mixed with the hydrochloric acid soln of PH=2 according to the accurate weighing concentrated hydrochloric acid of amount of removing ionized water, pour among the beaker A, will clean magnetic agitation and put into a beaker A for; The absolute ethyl alcohol (Eth) that to accurately measure required positive tetraethyl orthosilicate and aequum is again poured among the beaker A successively; Be placed on the magnetic stirrer after with the sealing of beaker A bottleneck with cleaning film and bungee and stir, churning time is 4 hours;
(3) WO
3And SiO
2The complex sol preparation
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, the ratio of this kind colloidal sol according to the thickness of required film with cause color depth and regulate, WO3/SiO is adopted in this dispersion ratio suggestion
2Mol ratio is 1.25/1
(4) mix the WO3/SiO of catalyzer
2The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
Embodiment 2: prepare two phase mixing and doping WO3/SiO
2The preparation of film
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) preparation of acidic catalyst SiO2 colloidal sol
Accurately measure deionized water respectively with volumetric flask and transfer pipet, absolute ethyl alcohol (Eth), tetraethoxy (TEOS), ratio is: 23.5/100/77.8; Be mixed with the acid solution of PH=2 according to the accurate weighing concentrated hydrochloric acid of amount of removing ionized water (or nitric acid, oxalic acid, phosphoric acid), pour among the beaker A, will clean magnetic agitation and put into a beaker A for; The absolute ethyl alcohol (Eth) that to accurately measure required positive tetraethyl orthosilicate and aequum is again poured among the beaker A successively; Be placed on the magnetic stirrer after with the sealing of beaker A bottleneck with cleaning film and bungee and stir, churning time is 4 hours;
(3) WO
3And SiO
2The complex sol preparation
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, the ratio of this kind colloidal sol according to the thickness of required film with cause color depth and regulate, WO3/SiO is adopted in this dispersion ratio suggestion
2Mol ratio is 1.25/1
(4) mix the WO3/SiO of catalyzer
2The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
Embodiment 3: prepare two phase mixing and doping WO3/SiO
2The preparation of film
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) preparation of base catalysis SiO2 colloidal sol
The base catalysis legal system is equipped with under required starting material of SiO2 colloidal sol and the proportioning (mol ratio): tetraethoxy (TEOS): ethanol (EtOH): ammoniacal liquor (NH3H2O)=1/38/2.45; The process for preparation of colloidal sol should carry out under less than 60% environment in clean cleaning, relative humidity, and concrete steps are following: the absolute ethyl alcohol (Eth) of accurately measuring aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker A; The strong aqua of accurately measuring the PH=12 of aequum with transfer pipet is poured among the beaker A; To clean magnetic agitation and put into a beaker A for, and be placed on the magnetic stirrer after with cleaning film and bungee beaker A bottleneck being sealed and stir, churning time is 20min; The absolute ethyl alcohol (Eth) of accurately measuring required tetraethoxy (TEOS) and aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker B successively; To clean magnetic agitation and put into a beaker B for, and be placed on the magnetic stirrer after with cleaning film and bungee beaker A bottleneck being sealed and stir, churning time is 20min; With magnet along outer wall with taking out in magnetic agitation among the beaker A, and mixing solutions among the beaker A is poured in the pear shape separatory funnel; Mixing solutions in the pear shape separatory funnel is dropwise splashed among the beaker B that is placed on the magnetic stirring apparatus lentamente, keep simultaneously stirring; Drip and finish continued stirring 2h, take out the stirrer among the beaker B with magnet along outer wall subsequently.Beaker B rested on film and the bungee good seal of cleaning (20 ℃, relative humidity 20%) wear out digestion time under the stable environment: 72h; Colloidal sol after aging is light blue emulsion state (the endocorpuscular median size of colloidal sol this moment is less than 10nm), colloidal sol is taken out pour in the round-bottomed flask, and colloidal sol must not the submergence flask more than 2/3; In round-bottomed flask, add a small amount of clean molecular sieve and prevent bumping, then flask fixedly is immersed in the heating in water bath pot that fills silicone oil with iron stand.Regulate oil bath temperature between 80 ℃～85 ℃, keep the slight boiling condition of colloidal sol liquid level; Utilize snakelike return line to reflux, return time is looked colloidal sol, and what are different; Quantitative PH test paper with after wetting is tested at the return line mouth of pipe, to PH test paper no change, stops to heat, and treats behind the naturally cooling flask to be taken out; Pour colloidal sol in beaker sealing preservation.
(3) WO
3And SiO
2The complex sol preparation
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, the ratio of this kind colloidal sol according to the thickness of required film with cause color depth and regulate, WO3/SiO is adopted in this dispersion ratio suggestion
2Mol ratio is 1.25/1
(4) mix the WO3/SiO of catalyzer
2The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
Embodiment 4: prepare two phase mixing and doping WO3/SiO
2The preparation of film
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) preparation of Si colloidal sol
Accurately measure tetraethoxy (TEOS) or Union carbide A-162 and alcohol respectively with volumetric flask and transfer pipet, ratio is: 77.8/100; Be placed on the magnetic stirrer after with the sealing of beaker A bottleneck with cleaning film and bungee and stir, churning time is half a hour;
(3) WO
3And SiO
2The complex sol preparation
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, the ratio of this kind colloidal sol according to the thickness of required film with cause color depth and regulate, WO3/SiO is adopted in this dispersion ratio suggestion
2Mol ratio is 1/1
(4) mix the WO3/SiO of catalyzer
2The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
Embodiment 5: prepare two phase mixing and doping WO3/Al
2O
3The preparation of film
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) Al
2O
3The preparation of colloidal sol
Volumetric flask and transfer pipet are accurately measured Aluminum chloride anhydrous+deionized water+ethanol+propylene oxide (6mmol: 0.65ml: 6-40ml: 0.32ml) respectively; Perhaps aluminum isopropylate+water+Virahol+catalyzer (acid or alkali, be example) with hydrochloric acid, ratio is 1mmol: 3mmol: 1-10ml: 0.1mmol; Pour in the beaker accurately measuring required colloidal sol; Be placed on the magnetic stirrer after with the sealing of beaker bottleneck with cleaning film and bungee and stir, churning time is 4 hours; Aging 1 hour of 50 degree.
(3) WO
3And Al
2O
3The complex sol preparation
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, the ratio of this kind colloidal sol according to the thickness of required film with cause color depth and regulate, WO3/SiO is adopted in this dispersion ratio suggestion
2Mol ratio is 1.25/1
(4) mix the WO3/Al of catalyzer
2O
3The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(5) mix the WO of catalyzer
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
Embodiment 6: prepare two phase mixing and doping WO3/Al
2O
3The preparation of film
(1) WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol.
(2) mix the WO3/SiO of catalyzer
2The preparation of colloidal sol:
In the colloidal sol of step (1) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and catalyzer is K
2[PtCl
4] or PdCl
2
(3) WO
3Colloidal sol and Al
2O
3The laminated film preparation of template
70nm Al
2O
3Template is immersed in (2) prepared colloidal sol, and concussion is 30 minutes in ultrasonic; Take out this Al
2O
3Template is mixed gained the WO of catalyzer
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute;
The film cycle performance of this method preparation is good, still has no obvious decay later on 500 times.
The present invention should utilize the interpolation material to reduce WO to solidify dispersion technology
3Reunion improve, WO
3The porosity of gas chromism film and then realization gas chromism film recycle the life-span.Adopt the Sol-gel method to prepare stable WO
3Complex sol; Adopt crystal pulling method or spin-coating method on simple glass, to be coated with transparent and uniform composite catalyst-doped WO
3Porous membrane.This solidifies the pore texture that dispersion technology improves and strengthened film, has reduced WO
3Between interaction, improved the sol-gel technique preparation gas chromism film recycle life-span and thermostability.The gas chromism film that the colloidal sol of crossing through doped and compounded of the present invention prepares is compared with untreated film, has significantly improved the cyclicity of gas-discoloration; To cause form and aspect more identical than performance with the gas chromism film of method such as magnetron sputtering preparation, and cost is significantly with low; Comparing with electrochomeric films also has same advantage.The present invention has well remedied the shortcoming of the gas-discoloration smart windows of Prepared by Sol Gel Method, makes this type of smart windows technology more be tending towards ripe.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (5)
1. one kind is improved WO
3The method of film gaschromic cycle performance is characterized in that: employing can improve WO
3The inorganics of gas chromism film porosity is to WO
3Colloidal sol mixes, and said inorganics comprises SiO
2, Al
2O
3
Said method comprising the steps of:
(1) preparation WO
3Colloidal sol;
(2) choose and prepare SiO
2, Al
2O
3Colloidal sol;
(3) WO
3And SiO
2, Al
2O
3The complex sol preparation:
(4) WO of catalyzer is mixed in preparation
3/ SiO
2, WO
3/ Al
2O
3Colloidal sol:
(5) WO of catalyzer is mixed in preparation
3/ SiO
2, WO
3/ Al
2O
3Film;
Said WO
3The preparation of colloidal sol:
Adopt the sol-gel method, at normal temperatures and pressures, with tungsten powder and superoxol stirring reaction 50-70 minute, the mol ratio of tungsten powder and hydrogen peroxide was 1: 3～1: 4, spinning, and filtration obtains light yellow transparent solution; In gained solution, add absolute ethyl alcohol then, the add-on of absolute ethyl alcohol is 1/2 to 4/5 of a container volume, 75-85 ℃ of oil bath backflow 1.5-2 hour, is converted into safran to colloidal sol, promptly obtains WO
3Ethanol colloidal sol;
Said SiO
2, Al
2O
3The preparation of colloidal sol: comprising:
1. acid SiO
2The preparation of colloidal sol:
Accurately measure deionized water, absolute ethyl alcohol, silicon source employing tetraethoxy respectively with volumetric flask and transfer pipet; Ratio can suitably be adjusted according to the demand of experimental temperature, silicon source category, test period, and deionized water and tetraethoxy employing ratio are under the room temperature condition: 23.5/77.8; Wherein be mixed with the acid solution of pH＜7, pour among the beaker A, will clean magnetic agitation and put into a beaker A for according to the accurate weighing acid of amount of removing ionized water; The absolute ethyl alcohol that to accurately measure required tetraethoxy and aequum is again poured among the beaker A successively; Be placed on the magnetic stirrer after with cleaning film and bungee and stir, according to the acid SiO of aforementioned proportion preparation the sealing of beaker A bottleneck
2The colloidal sol churning time is just can make acid SiO in 2-4 hour
2Colloidal sol;
Perhaps 2. alkaline SiO
2The preparation of colloidal sol:
The base catalysis legal system is equipped with SiO
2Required starting material of colloidal sol and proportioning ratio; Molar ratio is following: tetraethoxy (TEOS): ethanol: ammoniacal liquor=1/38/2.45; The process for preparation of colloidal sol should carry out under less than 60% environment in clean cleaning, relative humidity, and step is following: the absolute ethyl alcohol of accurately measuring aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker A; The strong aqua of accurately measuring the pH=12 of aequum with transfer pipet is poured among the beaker A; To clean magnetic agitation and put into a beaker A for, and be placed on after with cleaning film and bungee beaker A bottleneck being sealed and stir on the magnetic stirrer about 20min, reach aim of even dispersion;
The absolute ethyl alcohol of accurately measuring required tetraethoxy and aequum 1/2 with volumetric flask and transfer pipet is poured among the beaker B successively; To clean magnetic agitation and put into a beaker B for, and be placed on after with cleaning film and bungee beaker B bottleneck being sealed and stir on the magnetic stirrer about 20min, reach aim of even dispersion; With magnet along outer wall with taking out in magnetic agitation among the beaker A, and mixing solutions among the beaker A is poured in the pear shape separatory funnel; Mixing solutions in the pear shape separatory funnel is dropwise splashed among the beaker B that is placed on the magnetic stirring apparatus lentamente, keep simultaneously stirring; Drip and finish about continued stirring 2h it to be mixed, take out the stirrer among the beaker B with magnet along outer wall subsequently;
Beaker B is rested under the stable environment with the film and the bungee good seal of cleaning: 16-24 ℃; Relative humidity＜50% wears out; Colloidal sol after aging is light blue emulsion state; This moment, colloidal sol endocorpuscular median size was less than 10nm, colloidal sol taken out pour in the round-bottomed flask, and colloidal sol must not the submergence flask more than 2/3; In round-bottomed flask, add a small amount of clean molecular sieve and prevent bumping, fixedly be immersed in flask in the heating in water bath pot that fills silicone oil with iron stand then; Regulate oil bath temperature between 80 ℃～85 ℃, keep the slight boiling condition of colloidal sol liquid level; Utilize snakelike return line to reflux, test at the return line mouth of pipe, to pH test paper no change, stop to heat, treat behind the naturally cooling flask to be taken out with the quantitative pH test paper after wetting; Pour colloidal sol in beaker sealing preservation;
Perhaps 3. other SiO
2The preparation of colloidal sol:
Utilize Union carbide A-162 silicon source and alcohol to be made into the colloidal sol of respective concentration by required mixed;
Perhaps 4. Al
2O
3The preparation of colloidal sol:
Volumetric flask and transfer pipet are accurately measured Aluminum chloride anhydrous+deionized water+ethanol+propylene oxide, perhaps aluminum isopropylate+water+Virahol+catalyzer respectively; Pour in the beaker accurately measuring required colloidal sol; Be placed on the magnetic stirrer after with the sealing of beaker bottleneck with cleaning film and bungee and stir, churning time is 4 hours; Aging 1 hour of 50 degree;
Said WO
3And SiO
2, Al
2O
3The complex sol preparation:
In the colloidal sol of step (1) gained, add step (2) gained colloidal sol, dispersion ratio: SiO
2: WO
3Mol ratio is>=1/1 or Al
2O
3: WO
3Mol ratio is: 1/1;
The said WO that mixes catalyzer
3/ SiO
2, WO
3/ Al
2O
3The preparation of colloidal sol:
In the colloidal sol of step (3) gained, mix catalyzer, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, under normal pressure zero degree condition, preserved subsequent use; The mol ratio of catalyzer and tungsten powder is 1: 40～1: 100, and said catalyzer is K
2[PtCl
4] or PdCl
2
2. method according to claim 1 is characterized in that: the said WO that mixes catalyzer
3/ SiO
2, WO
3/ Al
2O
3Film preparation: adopt to lift dip process or adopt the preparation of rotary plating method:
1. adopt and lift dip process is mixed catalyzer in slide glass or polished silicon slice surface preparation WO
3/ SiO
2, WO
3/ Al
2O
3Film, pull rate are 4-6.5cm/min;
Perhaps: 2. adopt the rotary plating method, prepare the WO that mixes catalyzer at silicon chip or K9 glass surface
3/ SiO
2, WO
3/ Al
2O
3Film, precoating speed are 900-1100r/min, and spin coating speed is 2500-3500r/min;
Gained is mixed the WO of catalyzer
3/ SiO
2, WO
3/ Al
2O
3Film is in air atmosphere, and roasting glue temperature is 50 ℃-250 ℃, and the time is 50-70 minute.
3. method according to claim 1 is characterized in that: in order to obtain thicker film, adopt and improve WO
3The method of collosol concentration or pull rate, concentration are high more, and the faster film of pull rate is thick more; Perhaps adopt the method for multiple spin coating, between per twice spin coating, with film thermal treatment 2-5min between 40-55 ℃ of temperature.
4. method according to claim 1 is characterized in that: said acid SiO
2Catalyzer is a kind of in hydrochloric acid, wolframic acid, nitric acid, phosphoric acid, the oxalic acid in the preparation of colloidal sol, regulates pH=2.
5. method according to claim 1 is characterized in that: said Al
2O
3In the preparation of colloidal sol, the ratio of Aluminum chloride anhydrous+deionized water+ethanol+propylene oxide is 6mmol: 0.65ml: 6-40ml: 0.32ml; Perhaps the ratio of aluminum isopropylate+water+Virahol+hydrochloric acid is 1mmol: 3mmol: 1-10ml: 0.1mmol.
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| CN102248737B (en) * | 2011-04-14 | 2013-08-14 | 天津大学 | Cr2O3 or NiO porous film material using WO3 as base material and method for manufacturing air-sensitive sensor |
| CN102899645A (en) * | 2011-07-28 | 2013-01-30 | 北京汇福康医疗技术有限公司 | Medical metal surface corrosion-resistant coating with excellent bioactivity, and preparation method thereof |
| CN107460562B (en) * | 2017-08-02 | 2019-02-01 | 肇庆市华师大光电产业研究院 | One-step method prepares Copper-cladding Aluminum Bar tungstic acid composite nano-fiber material |
| CN107512853B (en) * | 2017-08-17 | 2020-07-24 | 浙江大学 | Al with mosaic structure 2O3/WO3Nano composite electrochromic film and preparation method thereof |
| CN108706955A (en) * | 2018-08-09 | 2018-10-26 | 李群华 | Aerogel composite, extensible structure, the application in climate regulation field |
| CN110282629A (en) * | 2019-06-29 | 2019-09-27 | 贵州省分析测试研究院 | A kind of method that molybdenum disilicide based material diffusion coefficient verifies the preparation method of diaphragm and calculates diffusion coefficient in film |
| CN110511059A (en) * | 2019-07-11 | 2019-11-29 | 江苏大学 | Tungstic acid air-sensitive membrane material, tungstic acid base composite air-sensitive membrane material, preparation method and application |
| CN111634949A (en) * | 2020-05-15 | 2020-09-08 | 桂林电子科技大学 | WO (WO)xSolution preparation method, ultraviolet device using the same and preparation method thereof |
| CN111777100A (en) * | 2020-06-28 | 2020-10-16 | 四川硅迪新材料有限公司 | Modified molybdenum trioxide sol and preparation method thereof |
| CN113200683A (en) * | 2021-04-02 | 2021-08-03 | 同济大学 | Preparation method of gasochromic film |
| CN113277742A (en) * | 2021-05-13 | 2021-08-20 | 东南大学 | WO prepared based on sol-gel method3/SiO2Composite film, preparation method and application thereof |
| CN115463652A (en) * | 2022-09-16 | 2022-12-13 | 福州大学 | Preparation method of tungsten trioxide liquid photocatalyst with antibacterial function |
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