CN101186448A - Method for increasing gas-chromism thin film gas-chromism speed - Google Patents
Method for increasing gas-chromism thin film gas-chromism speed Download PDFInfo
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- CN101186448A CN101186448A CNA200710171818XA CN200710171818A CN101186448A CN 101186448 A CN101186448 A CN 101186448A CN A200710171818X A CNA200710171818X A CN A200710171818XA CN 200710171818 A CN200710171818 A CN 200710171818A CN 101186448 A CN101186448 A CN 101186448A
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Abstract
The invention pertains to the technical field of gasochromic film, in particular to a method for improving gasochromism speed of the gasochromic film. The invention adopts sol-gel method for preparing the stable solution containing various metal oxides and the compound solution thereof; and various methods are employed for coating transparent and even gasochromic film on common glass or polished silicon wafer, and ultraviolet or high energy ray and high energy-particle mixing with catalyst are employed in the gasochromic film method so as to change the structure of film and enhance the coloring response speed of the gasochromism of the sol-gel technique, shorten coloring saturation time. Compared with the non treatment film, the gasochromism efficiency are greatly improved; and the performance is the same as the gasochromism produced by magnetron sputtering method, while, cost is greatly reduced; and the produced film by the invention also has the same advantages as the electrochromic film. The invention makes up the shortages of gasochromism smart window made by sol-gel preparation method, thus the smart window technique can be more mature.
Description
Technical field
The invention belongs to the gas chromism film technical field, be specifically related to a kind of method that improves gas-chromism thin film gas-chromism speed.
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 has been compeled as pressing as a fire singeing one's eyebrows.Buildings is one of high energy consumption unit, and its energy consumption has reached 27.6% of social total energy consumption, 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 referred discussion agenda of 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 modern architecture, 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 smart windows, can solve this difficult problem.
Causing the look smart windows can be dynamic, reversible, at random the sunlight by 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, causing the look smart windows, to be divided into thermochromism, photochromic and electrochromism etc. several.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, its optical characteristics is (as transmissivity, color) can be according to the variation of surrounding environment, pass through electric field action, the common injection that ion and electronics take place is extracted out together, the optical characteristics of material is taken place continuously, reversible, at random change, thereby realize that optical density(OD) is adjustable continuously, therefore, has most actual application prospect, the U.S., developed country such as Japan and Europe and domestic how tame unit are carrying out commercial applications research, but this look smart windows that causes is made of the device architecture complexity usually five layer film materials, influence factor is many, the preparation cost height, and be 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 the look material in the world shows that a kind of off-color material that has similar variable color mechanism to electrochromism---gas chromism film is just causing people's very big interest.This look smart windows that causes only causes look film and one deck catalyst layer or one deck look film that causes of containing catalyzer as thin as a wafer by one deck and constitutes, gas molecule (as hydrogen) is an atom by catalyst decomposes, cause change of optical property by diffusing into to cause in the look material, thereby cause continuous, reversible, the variation at random of thin-film material transmissivity.This solid-state structure cause that the look 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 a 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 the look film, and electrochromism and discoloration effect take place.And for gas-discoloration smart windows device, hydrogen molecule resolves into hydrogen atom behind catalyst action, diffuse to cause in the look film and cause colouring effect, and fade when Sauerstoffatom or air diffuser produce to the film, 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 hydrogen atom velocity of diffusion of the gas-discoloration window device that thin-film material is made, diffusion uniformity, colour consistency, variable color speed, wearing quality are just furtherd investigate.
Ultraviolet lamp is a kind of light source that is used for radiating ultraviolet band specially, and the light that it sends is divided into A band (400-315nm), B wave band (315-280nm) and C-band (280-10nm).General low pressure mercury lamp commonly used has a strong line spectrum at the 253.7nm place of C-band.Because UV-light is a kind of high band radiation of high energy, coating material solidified so it has sterilization, sterilization, material is carried out the function of modification etc. and use.
Energetic ray (as: X ray, gamma-rays etc.) is shorter, the more high-octane electromagnetic radiation of a class wavelength ratio ultraviolet ray.As X ray is a kind of photon radiation, is hertzian wave in essence, and very strong penetration power is arranged.Its wavelength region is 0.01～100 (1 =1 * 10
-8Cm).Energy exchange effect with material when mainly being slowed down by orbital electron transition of atom internal layer or high-energy electron produces, and the X-ray tube that normal utilization has condition of high vacuum degree in the laboratory produces.Because energetic ray has the energy higher than ultraviolet ray, they are more effective to the modifying function of material, therefore also are used for carrying out the research of material modification.
High energy particle is the shell in the modern particle scattering experiment, is the most useful instrument of research material primitive structure.It utilizes electromagnetic field to quicken charged particle and obtain by accelerator or collider.Advanced high energy accelerator and collider are mainly used in front line science, and that low energy accelerator has extensively transferred to is civilian, at subjects such as Materials science, solid-state physics, molecular biology, address, archaeologies important application are arranged.The particle that is accelerated can change the character of material or the sudden change cultivation new variety of inducing plant gene by irradiation, can diagnose and treat tumour, can also produce a large amount of isotropic substances, is used for industrial and agricultural production.
But also do not find at present to adopt ultraviolet lamp, energetic ray or high energy particle radiotechnology to improve amorphous WO
3The relevant patent 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 method that improves gas-chromism thin film gas-chromism speed.
The method of the raising gas-chromism thin film gas-chromism speed that the present invention proposes, described gas chromism film is WO
3Film, MoO
3Film or with WO
3Be the laminated film that basement membrane is formed, concrete steps are as follows:
(1) adopt the various colloidal sols of Prepared by Sol Gel Method:
Adopt the sol-gel method to prepare WO respectively
3Colloidal sol, MoO
3Colloidal sol, SiO
2Colloidal sol, V
2O
5Colloidal sol, TiO
2Colloidal sol, NiO colloidal sol;
(2) mix the WO of catalyzer
3Colloidal sol, MoO
3Colloidal sol and the preparation of mixing the laminated film complex sol of catalyzer:
1. to the WO of step (1) gained
3Colloidal sol, MoO
3Mix catalyzer in the colloidal sol respectively, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, preserved standby under normal pressure zero degree condition; The mol ratio of catalyzer and tungsten, molybdenum is 1: 40～1: 100, and catalyzer is the platiniferous inorganic salt or contains the palladium inorganic salt; As K
2[PtCl
6], PdCl
2Deng;
2. mix the preparation of the complex sol of catalyzer:
With WO
3Colloidal sol is basement membrane, mixes MoO respectively
3Colloidal sol, SiO
2Colloidal sol, V
2O
5Colloidal sol, TiO
2Colloidal sol, NiO colloidal sol or tensio-active agent, and then to various mixing WO
3Mix catalyzer in the based sols, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel colloidal sol, preserved standbyly under normal pressure zero degree condition, finally obtained the stable complex sol of mixing catalyzer respectively; The mol ratio of catalyzer and tungsten is 1: 40～1: 100, and catalyzer is the platiniferous inorganic salt or contains the palladium inorganic salt,, as K
2[PtCl
6], PdCl
2Deng; The mol ratio of tungsten and molybdenum, silicon, vanadium, titanium, nickel is 10: 1～6: 1, and the mol ratio of tungsten and tensio-active agent is 15: 1～10: 3;
(3) mix the WO of catalyzer
3Film, MoO
3Film and WO
3The preparation of based coextruded film:
Employing lifts dip process, rotary plating method, meniscus method, casting method, coating method or spraying method and prepares the WO that mixes catalyzer
3Film, MoO
3Film and WO
3Based coextruded film; The gained film is toasted in air atmosphere, and roasting glue temperature is 50 ℃-150 ℃, and the time is 50-70 minute;
(4) mix the aftertreatment of the various gas chromism films of catalyzer:
The film that step (3) is obtained carries out ultraviolet ray, energetic ray or high energy particle radiation, and wherein common 200nm-400nm gas chromism film of uv irradiation time is 20 minutes-30 minutes, is extended for 30-60 minute more than the 500nm, promptly gets desired product.
Among the present invention, adopt in the step (2) and lift dip process, pull rate is 4-6.5cm/min; Adopt the rotary plating method, precoating speed is 900-1100r/min, and spin coating speed is 2500-3500r/min.
Among the present invention, described tensio-active agent adopts in cetyl trimethylammonium bromide (CTAB) or the polyoxyethylene (PEO) etc. any.
For uv-radiation, utilize the existing formula rough calculation that situation is carried out in the integrated box again.Utilize W
Film=w/d
2W
FilmBy film is received radiation quantity; W is the power of source of radiation; D is the distance of film and source of radiation.Consider the spatial radiating condition, complicated factors such as conditioned reflex are recommended as the 10cm radiation length at present.Common 200nm-400nm gas chromism film of uv irradiation time is 20 minutes-30 minutes, is extended for 30-60 minute more than the 500nm, promptly gets desired product.
And for energetic ray and high energy particle source of radiation, in specific professional energetic ray and high energy particle source of radiation laboratory, carry out, and radiated time also will differently according to the model of different source of radiation be determined with irradiation distance.
Select radiation environment and carry out irradiation.Radiation environment is different and change according to the film of source of radiation and irradiation.For pure WO
3Deng the gas-discoloration response of film its Working environment within 1 minute own is that air gets final product, if be doping WO
3, MoO
3The gas-discoloration time of response of waiting self is greater than 1 minute film, and it is argon-mixed to fill an amount of pressure hydrogen as required for uv-radiation.Then can only under vacuum, carry out for high energy particle and energetic ray.
The concrete parameter of irradiation can be done appropriate change with concrete environment, but can reach necessary requirement in the time of the invention provides substantially.Film at the big material preparation of indivedual bound energy can consider to adopt the argon-mixed atmosphere of pressure hydrogen.The present invention has the following advantages: the radiation treatment technology shortens the gas-discoloration time of response that colloidal sol-gel method prepares gas chromism film greatly, improved corresponding speed greatly, make the reaction times reduce to 5-10 within second, more help the practical application of gas chromism film.And cost is low, and technology is simple, and environmental protection is energy-conservation.
(5) the various gas-chromism thin film gas-chromism performances of gained are tested: adopt of the test of ultraviolet/visible/infrared spectrophotometer the gas-chromism thin film gas-chromism performance of mixing catalyzer of special processing.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 the transmissivity that causes look front and back film is tested.
Experimental result shows, after the gas chromism film of mixing catalyzer carried out ultraviolet ray, energetic ray or high energy particle radiation, find that film forms vesicular structure, the gas-discoloration speed of film is accelerated greatly, time of response shortened in 5～10 seconds, and the variable color degree of film is just near saturated in 60～100 seconds, and particularly the treatment time surpassed after 15 minutes, and effect is more obvious.
The present invention adopts the amorphous of Prepared by Sol Gel Method to mix the gas chromism film material of catalyzer, adopt high voltage mercury lamp, energetic ray source or high energy particle producer film to be carried out the radiation of different time, thereby to the gas chromism film material modification that amorphous is mixed catalyzer, improved the technological method of gas-discoloration speed that amorphous is mixed the gas chromism film material of catalyzer.
The present invention adopts the test of the gas-chromism thin film gas-chromism performance of mixing catalyzer that ultraviolet/visible/infrared spectrophotometer handled ultraviolet.The gas chromism film that the present invention handled is compared with untreated film, has significantly improved the variable color efficient 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.
Description of drawings
Fig. 1 handles front and back for embodiment 1 medium ultraviolet and mixes palladium WO
3Film variable color curve comparison diagram.
Fig. 2 mixes palladium WO for different time ultraviolet among the embodiment 1 after handling
3Film variable color graphic representation.
Fig. 3 mixes palladium WO for embodiment 1 medium ultraviolet after handling
3The film surface structure iron.
Fig. 4 is the comparison diagram of film refractive index before and after embodiment 1 medium ultraviolet is handled.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: preparation WO
3Film, concrete steps are as follows:
(1) WO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 35 gram tungsten powder and 200ml 30% superoxol (N
W: N
H2O2=1: 4) stir, fully react and be placed in the whizzer in 50 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 500ml, toward mix the dehydrated alcohol of 300ml to the solution, 80 ℃ of following oil baths backflows 1.5 hours, be converted into safran to colloidal sol and promptly obtain WO
3Ethanol colloidal sol.Can be according to the experiment needs, with the WO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the WO of desired concn
3Colloidal sol.The colloidal sol of preparation can at room temperature be stablized and deposits more than 3 months.
(2) mix the WO of catalyzer
3The preparation of colloidal sol:
Mixing catalyzer in the colloidal sol of step (1) gained, is to mix PdCl at 50: 1 according to W and Pd molar ratio
2As catalyzer.Normal temperature fully stirred 2 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix palladium WO
3The preparation of film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes palladium WO to use miniature pulling machine
3Film, this experiment all are coated with the WO that mixes palladium with the V=4.5cm/min pull rate
3Transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (Chemat Technology, Inc., USA).Precoating speed is 1000r/min, and spin coating speed is 3000r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 50 ℃ of thermal treatment 3min of film.
Perhaps (C) adopts the meniscus method to mix palladium WO at slide glass or polished silicon slice surface preparation
3Film;
Perhaps (D) adopts casting method to mix palladium WO at slide glass or polished silicon slice surface preparation
3Film;
Perhaps (E) adopts coating method to mix palladium WO in the plastics film surface preparation
3Film;
Perhaps (F) adopts spraying method to mix palladium WO at slide glass or polished silicon slice surface preparation
3Film;
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treat 1h with 50 ℃.
(4) mix palladium WO
3The ultraviolet of film is handled
Make the uv irradiation case: outer wall is made by stainless steel, sealing all around, and one-sided have a removable stroke of door.Around moving door enclosed slot is arranged, preventing has ultraviolet radiation to go out under the situation of closing the door.The back side at chest is provided with ventilation opening, and exhaust fan is installed at the ventilation opening place, for dispelling the heat in the case.Serial ultraviolet lamp is installed in the box top, forms the homogeneous radiation field, in the middle of case is interior an adjustable for height specimen holder is set, and is used to place the gas-discoloration sample.
Mix palladium WO with what prepare
3Film is put into the uv irradiation case, and for the general thin that prevents the pollution of the environment adopts 1000 watts of high voltage mercury lamps, film and ultraviolet source distance are 10cm.The common 200nm-400nmWO of irradiation time
3Film is 20 minutes.
(5) mix palladium WO
3The test of film gas-discoloration performance
The WO that mixes palladium 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.) transmissivity 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.
The result shows that after the uv irradiation, the colour response time that causes of gas-discoloration shortened in 5 seconds, caused look fully within 60 seconds.
Embodiment 2: mix platinum MoO
3The preparation of film
(1) MoO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 3 gram tungsten powder and 20ml 30% superoxol (N
W: N
H2O2=1: 4) stir, fully react and be placed in the whizzer in 30 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 300ml, mix the dehydrated alcohol of 50ml in the made solution,, be converted into safran to colloidal sol and promptly obtain MoO 80 ℃ of following oil baths backflows 1.5 hours
3Ethanol colloidal sol.Can be according to the experiment needs, with the MoO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the MoO of desired concn
3Colloidal sol.The colloidal sol of preparation can at room temperature be stablized and deposits more than 3 months.
(2) mix the MoO of platinum
3The preparation of colloidal sol:
Mixing catalyzer in the colloidal sol of step (1) gained, is to mix K at 60: 1 according to Mo and Pt molar ratio
2[PtCl
6] as catalyzer.Normal temperature fully stirred 2.5 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix platinum MoO
3The preparation of film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes palladium MoO to use miniature pulling machine
3Film, this experiment all are coated with the MoO that mixes palladium with the V=5cm/min pull rate
3Transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (ChematTechnology, Inc., USA).Precoating speed is 900r/min, and spin coating speed is 2500r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 40 ℃ of thermal treatment 2min of film.
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treated 50 minutes with 100 ℃.
Perhaps (C) adopts the meniscus method to mix platinum MoO at slide glass or polished silicon slice surface preparation
3Film;
Perhaps (D) adopts casting method to mix platinum MoO at slide glass or polished silicon slice surface preparation
3Film;
Perhaps (E) adopts coating method to mix platinum MoO in the plastics film surface preparation
3Film;
Perhaps (F) adopts spraying method to mix platinum MoO at slide glass or polished silicon slice surface preparation
3Film;
(4) mix platinum MoO
3The X ray of film is handled
In the X ray emission test chamber of specialty, the employing tube voltage is 200KV, penetration power be the X-ray tube of 24mm as source of radiation, mix platinum MoO with what prepare
3Film is put into irradiation box, and film and X-ray tube source of radiation distance are 10cm.MoO about irradiation 500nm
3The film time is 40 minutes.
(5) mix platinum MoO
3The test of film gas-discoloration performance
Adopt the ultraviolet/visible/MoO that mix platinum of infrared spectrophotometer (V-570 type, Jasco Inc.) to handling
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.) transmissivity 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.
The result shows, mixes platinum MoO
3The film gas-discoloration time of response shortened within 60 seconds; It is 3-5 minute that Primordial Qi causes the variable color time of response.Reach and cause this saturation time of color base in 120 seconds.
Embodiment 3: mix palladium WO
3-MoO
3The preparation of laminated film
(1) WO
3-MoO
3The preparation of complex sol
1. WO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 35 gram tungsten powder and 175ml 30% superoxol (N
W: N
H2O2=1: 3.5) stir, fully react and be placed in the whizzer in 70 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 1000ml, toward mix the dehydrated alcohol of 500ml to the solution,, 85 ℃ of following oil baths backflows 2 hours, be converted into safran to colloidal sol and promptly obtain WO
3Ethanol colloidal sol.Can be according to the experiment needs, with the WO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the WO of desired concn
3Colloidal sol.
2. MoO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 3 gram tungsten powder and 20ml 30% superoxol (N
W: N
H2O2=1: 4) stir, fully react and be placed in the whizzer in 30 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 300ml, mix the dehydrated alcohol of 50ml in the made solution,, be converted into safran to colloidal sol and promptly obtain MoO 80 ℃ of following oil baths backflows 1.5 hours
3Ethanol colloidal sol.Can be according to the experiment needs, with the MoO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the MoO of desired concn
3Colloidal sol.
3. mix palladium WO
3-MoO
3The preparation of complex sol
Experiment is with the WO of preparation
3And MoO
3Colloidal sol is raw material, and the colloidal sol that following table is measured different volumes respectively mixes, and fully stirs then to be made into different mol ratio example WO
3-MoO
3Mixed sols.The colloidal sol of preparation can at room temperature be stablized and deposits more than 3 months.
Table 1 different mol ratio example WO
3-MoO
3The preparation of complex sol
| N W∶N Mo | V 0.3M-WO3(ml) | V 0.3M-MoO3(ml) |
| 10∶1 | 50 | 5 |
| 8∶1 | 40 | 5 |
| 7∶1 | 49 | 7 |
(2) mix the WO of palladium
3-MoO
3The preparation of complex sol:
WO to step (1) gained
3-MoO
3Mixing catalyzer in the complex sol, is to mix Pd (NO at 50: 1 according to W and Pd molar ratio
3)
2As catalyzer.Normal temperature fully stirred 3 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix palladium WO
3-MoO
3The preparation of laminated film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes palladium WO to use miniature pulling machine
3-MoO
3Laminated film, this experiment all are coated with the WO that mixes palladium with the V=6.5cm/min pull rate
3-MoO
3The composite transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (Chemat Technology, Inc., USA).Precoating speed is 1100r/min, and spin coating speed is 3500r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 45 ℃ of thermal treatment 5min of film.
Perhaps (C) adopts the meniscus method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-MoO
3Laminated film;
Perhaps (D) adopts casting method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-MoO
3Laminated film;
Perhaps (E) adopts coating method to mix palladium WO in the plastics film surface preparation
3-MoO
3Laminated film;
Perhaps (F) adopts spraying method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-MoO
3Laminated film;
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treated 70 minutes with 150 ℃.
(4) mix palladium WO
3-MoO
3The X ray of laminated film is handled
In the X ray emission test chamber of specialty, the employing tube voltage is 200KV, penetration power be the X-ray tube of 30mm as source of radiation, mix palladium WO with what prepare
3-MoO
3Laminated film is put into irradiation box, and film and X-ray tube source of radiation distance are 10cm.WO about irradiation 600nm
3-MoO
3The film time is 40 minutes.
(5) mix palladium WO
3-MoO
3The test of laminated film gas-discoloration performance
Adopt the ultraviolet/visible/WO that mix palladium of infrared spectrophotometer (V-570 type, Jasco Inc.) to handling
3-MoO
3The test of laminated 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.) transmissivity 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.
The result shows, mixes palladium WO
3-MoO
3The laminated film gas-discoloration time of response shortened within 10 seconds; It is 3-5 minute that Primordial Qi causes the variable color time of response.Reach and cause this saturation time of color base in 100 seconds.
Embodiment 4: mix platinum WO
3-SiO
2The preparation of laminated film
(1) WO
3-SiO
2The preparation of complex sol
1. WO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 35 gram tungsten powder and 175ml 30% superoxol (N
W: N
H2O2=1: 3.5) stir, fully react and be placed in the whizzer in 70 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 1000ml, toward mix the dehydrated alcohol of 500ml to the solution,, 85 ℃ of following oil baths backflows 2 hours, be converted into safran to colloidal sol and promptly obtain WO
3Ethanol colloidal sol.Can be according to the experiment needs, with the WO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the WO of desired concn
3Colloidal sol.
2. SiO
2The preparation of colloidal sol
According to a certain amount of ethanol, ammoniacal liquor and three kinds of raw materials of tetraethoxy of taking by weighing, ammoniacal liquor and tetraethoxy are mixed the abundant stirring in back 20 minutes respectively with half ethanol.After stirring end, more a kind of mixing solutions is added drop-wise in the another kind of mixing solutions lentamente, fully stirs simultaneously.With the mixing solutions of gained at room temperature seal aging 3-7 days, when mixed solution presents light blue opalescence, again with it with 80 ℃ of reflux 10 hours.The pH value of colloidal sol is about 6.0.
3. WO
3-SiO
2The preparation of complex sol
Earlier measure 40mlWO with test tube
3Colloidal sol places three beakers stand-by for 3 parts, again with the another test tube measure 2,6 respectively, 12mlSiO
2Colloidal sol adds in above-mentioned 3 beakers, is configured to SiO
2Doping is the WO of 5%, 15%, 30% (volume ratio)
3-SiO
2Complex sol.The mixed sols stable performance is placed and was not seen muddiness and gel phenomenon in one month.
(2) mix the WO of platinum
3-SiO
2The preparation of complex sol:
WO to step (1) gained
3-SiO
2Mixing catalyzer in the complex sol, is to mix Na at 50: 1 according to W and Pt molar ratio
2[PtCl
6] as catalyzer.Normal temperature fully stirred 3 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix platinum WO
3-SiO
2The preparation of laminated film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes platinum WO to use miniature pulling machine
3-SiO
2Laminated film, this experiment all are coated with the WO that mixes platinum with the V=6.5cm/min pull rate
3-SiO
2The composite transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (Chemat Technology, Inc., USA).Precoating speed is 1100r/min, and spin coating speed is 3500r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 45 ℃ of thermal treatment 5min of film.
Perhaps (C) adopts the meniscus method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-SiO
2Laminated film;
Perhaps (D) adopts casting method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-SiO
2Laminated film;
Perhaps (E) adopts coating method to mix platinum WO in the plastics film surface preparation
3-SiO
2Laminated film;
Perhaps (F) adopts spraying method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-SiO
2Laminated film;
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treated 70 minutes with 150 ℃.
(4) mix platinum WO
3-SiO
2The gamma-rays of film is handled
In the gamma-rays emission test chamber of specialty, mix platinum WO with what prepare
3-SiO
2Film is put into irradiation box, adopts the γShe Xiantanshang instrument as source of radiation, and film and γShe Xiantanshang instrument source of radiation distance are 10cm.Mix platinum WO about irradiation 800nm
3-SiO
2The film time is 40 minutes.
(5) mix platinum WO
3-SiO
2The test of laminated film gas-discoloration performance
Adopt the ultraviolet/visible/WO that mix platinum of infrared spectrophotometer (V-570 type, Jasco Inc.) to handling
3-SiO
2The test of laminated 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.) transmissivity 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.
The result shows, mixes platinum WO
3-SiO
2The laminated film gas-discoloration time of response shortened within 10 seconds; Reach and cause this saturation time of color base in 100 seconds.
Embodiment 5: mix palladium WO
3The preparation of-CTAB laminated film
(1) WO
3The preparation of-CTAB complex sol
1. WO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 35 gram tungsten powder and 175ml 30% superoxol (N
W: N
H2O2=1: 3.5) stir, fully react and be placed in the whizzer in 70 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 1000ml, toward mix the dehydrated alcohol of 500ml to the solution,, 85 ℃ of following oil baths backflows 2 hours, be converted into safran to colloidal sol and promptly obtain WO
3Ethanol colloidal sol.Can be according to the experiment needs, with the WO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the WO of desired concn
3Colloidal sol.
2. WO
3The preparation of-CTAB complex sol
Earlier measure 50mlWO with test tube
3Colloidal sol places three beakers stand-by for 3 parts, with electronic balance respectively smellyization of the cetyl trimethyl ammonium of weighing 1mmol, 2mmol, 4mmol, 6mmol, 8mmol add in above-mentioned 3 beakers, stirred 2-3 hour, be configured to WO
3-SiO
2Complex sol.The mixed sols stable performance is placed and was not seen muddiness and gel phenomenon in one month.
(2) mix the WO of palladium
3The preparation of-CTAB complex sol:
WO to step (1) gained
3Mixing catalyzer in the-CTAB complex sol, is to mix PdSO at 50: 1 according to W and Pd molar ratio
4As catalyzer.Normal temperature fully stirred 3 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix palladium WO
3The preparation of-CTAB laminated film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes palladium WO to use miniature pulling machine
3-CTAB laminated film, this experiment all are coated with the WO that mixes palladium with the V=6.5cm/min pull rate
3-CTAB composite transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (Chemat Technology, Inc., USA).Precoating speed is 1100r/min, and spin coating speed is 3500r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 45 ℃ of thermal treatment 5min of film.
Perhaps (C) adopts the meniscus method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-CTAB laminated film;
Perhaps (D) adopts casting method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-CTAB laminated film;
Perhaps (E) adopts coating method to mix palladium WO in the plastics film surface preparation
3-CTAB laminated film;
Perhaps (F) adopts spraying method to mix palladium WO at slide glass or polished silicon slice surface preparation
3-CTAB laminated film;
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treated 70 minutes with 150 ℃.
(4) mix palladium WO
3The ultraviolet of-CTAB laminated film is handled
Make the uv irradiation case: outer wall is made by stainless steel, sealing all around, and one-sided have a removable stroke of door.Around moving door enclosed slot is arranged, preventing has ultraviolet radiation to go out under the situation of closing the door.The back side at chest is provided with ventilation opening, and exhaust fan is installed at the ventilation opening place, for dispelling the heat in the case.Serial ultraviolet lamp is installed in the box top, forms the homogeneous radiation field, in the middle of case is interior an adjustable for height specimen holder is set, and is used to place the gas-discoloration sample.
Mix platinum WO with what prepare
3-CTAB film is put into irradiation box, and the ultraviolet lamp that adopts 300 watts is as source of radiation, and film and ultraviolet lamp tube source of radiation distance are 10cm.Mix platinum WO about irradiation 500nm
3-CTAB film the time is 40 minutes.
(5) mix palladium WO
3The test of-CTAB laminated film gas-discoloration performance
Adopt the ultraviolet/visible/WO that mix palladium of infrared spectrophotometer (V-570 type, Jasco Inc.) to handling
3The test of-CTAB laminated 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.) transmissivity 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.
The result shows, WO
3-CTAB laminated film gas-discoloration the time of response shortened within 10 seconds; Reach and cause this saturation time of color base in 100 seconds.
Embodiment 6: mix platinum WO
3-V
2O
5The preparation of laminated film
(1) WO
3-V
2O
5The preparation of complex sol
1. WO
3The preparation of colloidal sol
Under normal temperature and pressure conditions, with 35 gram tungsten powder and 175ml 30% superoxol (N
W: N
H2O2=1: 3.5) stir, fully react and be placed in the whizzer in 70 minutes, with the centrifugal 10min of 2000rap/min speed, filter light yellow transparent solution.Adopt the round-bottomed flask of 1000ml, toward mix the dehydrated alcohol of 500ml to the solution,, 85 ℃ of following oil baths backflows 2 hours, be converted into safran to colloidal sol and promptly obtain WO
3Ethanol colloidal sol.Can be according to the experiment needs, with the WO that makes
3Colloidal sol adds the dehydrated alcohol dilution, is mixed with the WO of desired concn
3Colloidal sol.
2. V
2O
5The preparation of colloidal sol
With VO (OC
3H
7)
3, the second alcohol and water mixes with certain mol proportion example, leaves standstill and adopts centrifugation 2500 rev/mins of rotations 20 minutes after two hours, to remove unreacted residual substance, obtains vitreosol russet.This colloidal sol has stability preferably, and room temperature can be deposited the long period.
3. WO
3-V
2O
5The preparation of complex sol
Earlier measure 40mlWO with test tube
3Colloidal sol places three beakers stand-by for 3 parts, again with the another test tube measure 2,6 respectively, 12ml V
2O
5Colloidal sol adds in above-mentioned 3 beakers, is configured to SiO
2Doping is the WO of 5%, 15%, 30% (volume ratio)
3-V
2O
5Complex sol.The mixed sols stable performance is placed and was not seen muddiness and gel phenomenon in one month.
(2) mix the WO of platinum
3-V
2O
5The preparation of complex sol:
WO to step (1) gained
3-V
2O
5Mixing catalyzer in the complex sol, is to mix PtCl at 50: 1 according to W and Pt molar ratio
2As catalyzer.Normal temperature fully stirred 3 hours down, treated that colloidal sol is little sorrel stable sol, preserves under normal pressure zero degree condition after all dissolvings.
(3) mix platinum WO
3-V
2O
5The preparation of laminated film
(A) lift the immersion plating plated film
(DPM-UMRno5586 CNRS-UCBLI) respectively in ultrasonic cleaning in peracid, alkali and acetone, dries up on the slide glass handled and the polished silicon slice preparation and mixes platinum WO to use miniature pulling machine
3-V
2O
5Laminated film, this experiment all are coated with the WO that mixes platinum with the V=6.5cm/min pull rate
3-V
2O
5The composite transparent film.
Perhaps (B) rotary plating method
Filming equipment be KW-4A type sol evenning machine (Chemat Technology, Inc., USA).Precoating speed is 1100r/min, and spin coating speed is 3500r/min.Select for use silicon chip or K9 glass as substrate according to different test requests.In gas-discoloration test, in order to obtain thicker film, adopt multiple spin coating, between per twice spin coating all with 45 ℃ of thermal treatment 5min of film.
Perhaps (C) adopts the meniscus method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-V
2O
5Laminated film;
Perhaps (D) adopts casting method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-V
2O
5Laminated film;
Perhaps (E) adopts coating method to mix platinum WO in the plastics film surface preparation
3-V
2O
5Laminated film;
Perhaps (F) adopts spraying method to mix platinum WO at slide glass or polished silicon slice surface preparation
3-V
2O
5Laminated film;
At last, with the sample of all preparations, in air atmosphere, with roasting glue machine (the KW-4AH-600 type, CHEMATTECHNOLOGY, INC., USA, operation temperature area are 0-600 ℃, temperature rise rate be 1 ℃/sec) heat-treated 70 minutes with 150 ℃.
(4) mix platinum WO
3-V
2O
5The high energy particle of film is handled
In the high energy particle emission test chamber of specialty, mix platinum WO with what prepare
3-V
2O
5Film is put into the radiation case, adopts ordinary cyclotron as source of radiation, and film and magnetic resonance acceleator distance are 10cm.WO about radiation 500nm
3-V
2O
5The film time is 10 minutes.
(5) mix platinum WO
3-V
2O
5The test of laminated film gas-discoloration performance
Adopt the ultraviolet/visible/WO that mix platinum of infrared spectrophotometer (V-570 type, Jasco Inc.) to handling
3-V
2O
5The test of laminated 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.) transmissivity 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.
The result shows, mixes platinum WO
3-V
2O
5The laminated film gas-discoloration time of response shortened within 10 seconds; Reach and cause this saturation time of color base in 100 seconds.
Above-described embodiment is only in order to illustrate technological thought of the present invention and characteristics; its purpose is to make those of ordinary skill in the art can understand content of the present invention and implements according to this; the scope of this patent also not only is confined to above-mentioned specific embodiment; be all equal variation or modifications of doing according to the spirit that the utility model disclosed, still be encompassed in the protection domain of the present utility model.
Claims (3)
1. a method that improves gas-chromism thin film gas-chromism speed is characterized in that described gas chromism film is WO
3Film, MoO
3Film or with WO
3Laminated film for basement membrane is formed is characterized in that concrete steps are as follows:
(1) adopt the various colloidal sols of Prepared by Sol Gel Method:
Adopt the sol-gel method to prepare WO respectively
3Colloidal sol, MoO
3Colloidal sol, SiO
2Colloidal sol, V
2O
5Colloidal sol, TiO
2Colloidal sol, NiO colloidal sol;
(2) mix the WO of catalyzer
3Colloidal sol, MoO
3Colloidal sol and the preparation of mixing the laminated film complex sol of catalyzer:
1. to the WO of step (1) gained
3Colloidal sol, MoO
3Mix catalyzer in the colloidal sol respectively, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel stable sol, preserved standby under normal pressure zero degree condition; The mol ratio of catalyzer and tungsten, molybdenum is 1: 40～1: 100, and catalyzer is the platiniferous inorganic salt or contains the palladium inorganic salt;
2. mix the preparation of the complex sol of catalyzer:
With WO
3Colloidal sol is basement membrane, mixes MoO respectively
3Colloidal sol, SiO
2Colloidal sol, V
2O
5Colloidal sol, TiO
2Colloidal sol, NiO colloidal sol or tensio-active agent, and then to various mixing WO
3Mix catalyzer in the based sols, normal temperature stirred 2～3 hours down, when treating that colloidal sol is little sorrel colloidal sol, preserved standbyly under normal pressure zero degree condition, finally obtained the stable complex sol of mixing catalyzer respectively; The mol ratio of catalyzer and tungsten is 1: 40～1: 100, and catalyzer is the platiniferous inorganic salt or contains the palladium inorganic salt, and the mol ratio of tungsten and molybdenum, silicon, vanadium, titanium, nickel is 10: 1～6: 1, and the mol ratio of tungsten and tensio-active agent is 15: 1～10: 3;
(3) mix the WO of catalyzer
3Film, MoO
3Film and WO
3The preparation of based coextruded film:
Employing lifts dip process, rotary plating method, meniscus method, casting method, coating method or spraying method and prepares the WO that mixes catalyzer
3Film, MoO
3Film and WO
3Based coextruded film; The gained film is toasted in air atmosphere, and roasting glue temperature is 50 ℃-150 ℃, and the time is 50-70 minute;
(4) mix the aftertreatment of the various gas chromism films of catalyzer:
The film that step (3) is obtained carries out ultraviolet ray, energetic ray or high energy particle radiation, and wherein common 200nm-400nm gas chromism film of uv irradiation time is 20 minutes-30 minutes, is extended for 30-60 minute more than the 500nm, promptly gets desired product;
(5) the various gas-chromism thin film gas-chromism performances of gained are tested:
Adopt ultraviolet, visible or infrared spectrophotometer that the gas-discoloration performance of the product of step (4) gained is tested.
2. the method for raising gas-chromism thin film gas-chromism speed according to claim 1 is characterized in that adopting in the step (2) lifting dip process, and pull rate is 4-6.5cm/min; Adopt the rotary plating method, precoating speed is 900-1100r/min, and spin coating speed is 2500-3500r/min.
3. the method for raising gas-chromism thin film gas-chromism speed according to claim 1 is characterized in that described tensio-active agent adopts in cetyl trimethylammonium bromide or the polyoxyethylene any.
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