CN100545114C - Glass-base nanometer self-cleaning titania film and preparation method thereof - Google Patents
Glass-base nanometer self-cleaning titania film and preparation method thereof Download PDFInfo
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- CN100545114C CN100545114C CNB2005100237126A CN200510023712A CN100545114C CN 100545114 C CN100545114 C CN 100545114C CN B2005100237126 A CNB2005100237126 A CN B2005100237126A CN 200510023712 A CN200510023712 A CN 200510023712A CN 100545114 C CN100545114 C CN 100545114C
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Abstract
The invention provides a kind of glass-base nanometer self-cleaning titania film and preparation method thereof, it is characterized in that preparing in the process of film at sol-gel processing, in coating raw material titanium colloidal sol, add a certain amount of soluble additive, make it under thermal treatment temp, form the sodium salt crystalline phase with the sodium ion that diffuses into thin film of titanium oxide from matrix, thereby eliminate the influence of sodium ion diffusion couple titanium oxide structure, promotes oxidn titanium film forms the nano-anatase phase, improves the catalytic self-cleaning net effect of film with this.
Description
Technical field
The present invention relates to a kind of glass-base nanometer self-cleaning titania film, particularly relate to a kind of novel photocatalysis on all kinds of glass such as building glass, vehicle glass, opticglass and various architectural pottery, snitaryware surface that is used for from clean film.
Background technology
The titanium oxide powder of nanocrystal yardstick or thin film of titanium oxide have photocatalytic effect under UV-irradiation, the multiple organic pollutant of can degrading.Therefore when thin film of titanium oxide coated during in high temperature resistant inorganic substrate material surfaces such as glass, these materials will manifest the self-cleaning net effect of degradation of organic substances under the irradiation of light sources such as sunlight.
The preparation thin film of titanium oxide can be used technologies such as magnetron sputtering, vapour deposition and collosol and gel.Sol-gel method can obtain to have the nanoscale anatase crystal structure of more remarkable self-cleaning net effect than other technology, and the then easier usually formation amorphous structure of other technological process does not have significant self-cleaning net effect.And in the sol-gel technology process, on glass that contains alkalimetal oxide such as sodium ion or ceramic matrix surface coated behind the titanium colloidal sol, when thermal treatment formed thin film of titanium oxide, sodium ion must diffuse to thin film of titanium oxide inside from matrix.According to existing result of study, this phenomenon can influence titanium oxide and form the nanostructured anatase crystalline phase, the degree of crystallinity of anatase octahedrite is descended, even make titanium oxide amorphous structure occur.No matter be any structure, the catalytic self-cleaning net effect of thin film of titanium oxide will be declined to a great extent, so that completely lose.
The diffusion phenomena of matrix sodium ion almost are inevitably in the film preparation process, because the film of inorganic materials all need just may form the mortise of matrix and film under comparatively high temps.And sodium ion also receives publicity for many years for the harm of thin film of titanium oxide photocatalysis performance.In order to reduce or to eliminate alkalimetal ion diffusion couple thin film of titanium oxide such as sodium ion in various glass or the ceramic matrix from clean Effect on Performance, existing a kind of technology is elder generation's coated one deck silicon oxide film on glass basis, utilizes the silicon oxide film that increases between matrix and the oxidation titanium film to reduce effectively or hinder a shelves sodium ion to diffuse to oxidation titanium film.But increase one deck silicon oxide film production cost is risen, and all will be affected from clean adhesion of thin film and uniformity coefficient.Existing another kind of technology is with mineral acid glass to be carried out pre-treatment before the preparation thin film of titanium oxide, or after forming, thin film of titanium oxide carries out acid treatment, or (CN1400185A prepares the method for high-activity titanium dioxide film self-cleaning glass material all to carry out acid treatment before and after the thin film of titanium oxide coated; CN1400186A, the method for raising titanium dioxide film self-cleaning glass photocatalytic activity).Suitable acid treatment can make the sodium ions content in the titanium oxide layer almost reduce to zero, thereby improves the photocatalytic activity from clean film.But the waste liquid that produces in view of mineral acid treatment technology can have a negative impact to environment, and the acid waste liquid that carries out in order to reduce environmental pollution is handled, and the coated glass after the acid treatment needs water cleaning once more etc., will strengthen whole thin film of titanium oxide preparation procedure and cost.Therefore the technology that the present reduction matrix sodium ion that adopts extends influence all needs to increase processing sequence and production cost.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can prepare self-cleaning titania film and preparation method with sol-gel method containing on sodium oxide glass or the ceramic matrix.Other oxide film that this preparation method need not beyond the additional thin film of titanium oxide spreads to stop sodium ion, also need not before and after plated film, to carry out acid treatment, only need in the preparation process of titanium oxide colloid, to add a certain amount of SSS specific soluble substance, just can reach the disadvantageous effect that reduces or eliminate sodium ion diffusion couple self-cleaning titania film photocatalytic activity in the heat treatment process.The present invention can be simply, economical, improve the activity of the photocatalytic degradation pollutent of self-cleaning titania film effectively.
A kind of glass-base nanometer self-cleaning titania film, the matrix of film is a glass material, mix various ingredients and form titanium colloidal sol, described polycomponent comprises titanium alkoxide, stabilizing agentof sol and alcoholic solvent, and add special additive therein, wherein, described titanium alkoxide is butyl (tetra) titanate, titanium ethanolate; Described alcoholic solvent is ethanol, propyl alcohol, Virahol, butanols; Described stabilizing agentof sol control hydrolysis polymerization process is one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid, and these mixing solutionss of forming form stable titanium colloidal sol through hydrolysis and polyreaction more; Described special additive is one or more the combination in ammonium tungstate, silicotungstic acid, phosphoric acid, trimethyl phosphite 99, etherophosphoric acid and the boric acid, through Overheating Treatment, form one or more crystalline phases in water glass, sodium wolframate, sodium phosphate and the Sodium Tetraborate in thin film of titanium oxide respectively, matrix surface forms the TiOx nano film of 0.1 micron of thickness.
A kind of glass-base nanometer self-cleaning titania film preparation method uses the Prepared by Sol Gel Method film, and its preparation process is as follows:
1) mixed with titanium alkoxide, stabilizing agentof sol, additive and alcoholic solvent form mixing solutions, and wherein, described titanium alkoxide is butyl (tetra) titanate, titanium ethanolate; Described alcoholic solvent is ethanol, propyl alcohol, Virahol, butanols; Described stabilizing agentof sol control hydrolysis polymerization process is one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid, and these mixing solutionss of forming form stable titanium colloidal sol through hydrolysis and polyreaction more; Described additive is one or more the combination in ammonium tungstate, silicotungstic acid, phosphoric acid, trimethyl phosphite 99, etherophosphoric acid and the boric acid;
2) mix solution at normal temperatures, make each component thorough mixing and react formation titanium colloidal sol;
3) the coated titanium colloidal sol on the glass basis material with rotational method or crystal pulling method;
4) at 100 ℃ of oven dry titanium sol pellicles;
5) the titanium sol pellicle was 500～600 ℃ of thermal treatments 15 minutes to 1 hour, and forming with the nanostructured anatase is the thin film of titanium oxide of principal crystalline phase.
The present invention is achieved in that with glass or pottery be matrix, with the liquid mixture that adds SSS specific soluble substance, form specific titanium colloidal sol through sol-gel process, this titanium colloidal sol coated on glass or ceramic matrix surface, is obtained thin film of titanium oxide through Overheating Treatment.Whole process comprises the preparation of definite composition colloidal sol, and colloid forms film at matrix surfaces such as glass, and the oven dry of film heating.The material that forms self-cleaning titania film in the invention comprises titanium alkoxide raw materials such as butyl (tetra) titanate, titanium ethanolate; The vehicle substance of dissolving such as ethanol, Virahol, propyl alcohol, butanols titanium alkoxide; The stabilizing agentof sol of control titanium sol-hydrolysis polymerization process is as one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid etc.; And be used to eliminate the soluble additive of sodium ion among the present invention to the photocatalytic self-cleaning negative impact, as one or more combination of ammonium tungstate, silicotungstic acid, phosphoric acid, trimethyl phosphite 99, etherophosphoric acid, boric acid etc., the concrete content and the combination of additive are decided on glass basis composition, thermal treatment temp and heat treatment time.Above-mentioned titanium alkoxide, solvent and various additive be hybrid reaction at room temperature, can be used for film preparation after a few hours to a couple of days.The glass or the pottery of cleaning surfaces are immersed above-mentioned colloidal sol, can obtain sol layer with the mode of lifting, or a certain amount of colloidal sol is layered on the glass basis surface, obtain the uniform sol layer with rotational method.After sol layer drying and the heat treated, promptly forming with nanostructured anatase is the film of main crystalline phase.The thin film of titanium oxide of this invention process preparation has higher catalytic self-cleaning net effect, and the ability of organic dye such as its photocatalytic degradation tropeolin-D is higher than the effect of adding silicon oxide film blocking layer and pickling glass ceramic matrix.
Characteristics of the present invention are that a certain amount of additive that is added can be dissolved in alcoholic solvent, simultaneously in heat treatment process, these additives preferentially form the sodium salt crystalline phase with the sodium ion that diffuses into thin film layer, for example water glass, Sodium Tetraborate, sodium wolframate, sodium phosphate etc.And the formation of sodium salt crystalline phase can not influence the anatase phase that titanium oxide forms nanoscale, therefore can guarantee the photocatalytic self-cleaning activity of thin film of titanium oxide.Simultaneously some contain the sodium salt crystalline phase and self have the active characteristics of the titanium oxide photochemical catalyst of raising.
Another characteristics of the present invention are not need significantly to change sol-gel process or increase other operation, have kept the basic craft course of preparation TiOx nano film, and can significantly improve the photocatalytic activity of self-cleaning titania film simultaneously.This invention is equally applicable to the preparation of glass or ceramic surface titanium oxide porous membrane.
Embodiment
Under the room temperature, the additive that adds any one or a few combinations such as soluble silicotungstic acid, phosphoric acid, boric acid in the ethanolic soln that is dissolved with the titanium alkoxide closes, add the wherein stabilizing agentof sol of one or more combination such as methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, sulfuric acid simultaneously, mix more than 20 minutes.Slowly add certain water gaging then and make titanium alkoxide generation hydrolytic-polymeric reaction.It is about more than one hour constantly to mix solution in this process.The mixed sols that forms can be used to prepare film in a few hours or a couple of days.Slowly take out after the free of contamination glass of surface clean or ceramic member immersed colloid, then in succession 100 ℃ of dryings 10 minutes, 400～600 ℃ of thermal treatments 15～60 minutes.The cooling back has good photocatalytic self-cleaning performance at the thin film of titanium oxide of glass or ceramic surface formation.
Embodiment 1, and a certain amount of butyl (tetra) titanate (20ml), methyl ethyl diketone (1ml) are dissolved in ethanol (60ml), mixes after 30-40 minute, adds the ammonium tungstate, methyl ethyl diketone (0.3ml), the H that are equivalent to butyl (tetra) titanate quality 2mol%
2O
2(1ml) and hydrochloric acid (0.3ml), form mixing solutions, after fully stirring, form brown colloid.Select for use the building glass of cleaning to impregnated in the above-mentioned colloidal solution or the colloidal solution of some amount is dropped in glass surface (optionally the glass surface size of coated and decide), form uniform colloid film at glass surface with crystal pulling method or rotational method.Film 500 ℃ of thermal treatments 1 hour, obtains water white thin film of titanium oxide then 100 ℃ of dryings 20 minutes.Zhi Bei the tungsten thin film of titanium oxide thickness of mixing is about 0.1 micron like this.Degradation rate to tropeolin-D is 5 * 10
-4Mg.cm
-2.min
-1, be titanium deoxid film degradation speed about more than 3 times of general method preparation.
Embodiment 2, with a certain amount of butyl (tetra) titanate (20ml), methyl ethyl diketone (1ml) with respect to the phosphoric acid of butyl (tetra) titanate quality 2mol%, are dissolved in ethanol (60ml) solvent, stir at normal temperatures 1～2 hour, form lurid colloidal sol.The glass sample of cleaning is immersed in the above-mentioned colloidal solution or with some amount colloidal solution and drops in glass surface, with lifting or rotational method forms the film of the above-mentioned colloidal sol of one deck at glass.With this film 100 ℃ of dryings 30 minutes, then 550～600 ℃ of thermal treatments 15 to 30 minutes, can obtain thickness be about 0.1 micron mix phosphorus oxidation titanium film.This film is about 3 times of thin film of titanium oxide degradation rate of general method preparation to the degradation rate of tropeolin-D.
Photocatalytic activity test in above-mentioned two examples selects for use the degradation rate of colored compound methyl orange solution to express.Concrete test process is: the methyl orange aqueous solution of preparation 10mg/L concentration, 2.5 * 2.5cm the glass specimen that is coated with thin film of titanium oxide is placed the 50ml methyl orange solution, the ultraviolet high-pressure mercury lamps of two 125W is placed 25cm place, test soln top, fill the logical recirculated cooling water cooling of container outer wall of methyl orange solution, and place water-bath, monitor bath temperature with temperature measurer, make the methyl orange solution temperature remain on 23 ℃ ± 2 ℃, guarantee can not influence the degradation rate test of tropeolin-D because ultraviolet lighting causes the solution intensification with this.Feed little air in the methyl orange solution, be beneficial to the carrying out of titanium oxide photochemical catalyst reaction in the solution.After the methyl orange solution of certain hour light-catalyzed reaction takes out, with the absorbancy of spectrophotometer test methyl orange solution at the 470nm place.Because dissolved tropeolin-D concentration is proportional to absorbancy in the solution, can calculate the degradation rate of tropeolin-D according to the variation of absorbancy.
Claims (2)
1, a kind of glass-base nanometer self-cleaning titania film is characterized in that:
The matrix of film is a glass material, mixes various ingredients and forms titanium colloidal sol, and described polycomponent comprises titanium alkoxide, stabilizing agentof sol and alcoholic solvent, and adds special additive therein, and wherein, described titanium alkoxide is butyl (tetra) titanate, titanium ethanolate; Described alcoholic solvent is ethanol, propyl alcohol, Virahol, butanols; Described stabilizing agentof sol control hydrolysis polymerization process is one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid, and these mixing solutionss of forming form stable titanium colloidal sol through hydrolysis and polyreaction more; Described special additive is one or more the combination in ammonium tungstate, silicotungstic acid, phosphoric acid, trimethyl phosphite 99, etherophosphoric acid and the boric acid, through Overheating Treatment, form one or more crystalline phases in water glass, sodium wolframate, sodium phosphate and the Sodium Tetraborate in thin film of titanium oxide respectively, matrix surface forms the TiOx nano film of 0.1 micron of thickness.
2, a kind of glass-base nanometer self-cleaning titania film preparation method is characterized in that:
Use the Prepared by Sol Gel Method film, its preparation process is as follows:
1) mixed with titanium alkoxide, stabilizing agentof sol, additive and alcoholic solvent form mixing solutions, and wherein, described titanium alkoxide is butyl (tetra) titanate, titanium ethanolate; Described alcoholic solvent is ethanol, propyl alcohol, Virahol, butanols; Described stabilizing agentof sol control hydrolysis polymerization process is one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid, and these mixing solutionss of forming form stable titanium colloidal sol through hydrolysis and polyreaction more; Described additive is one or more the combination in ammonium tungstate, silicotungstic acid, phosphoric acid, trimethyl phosphite 99, etherophosphoric acid and the boric acid;
2) mix solution at normal temperatures, make each component thorough mixing and react formation titanium colloidal sol;
3) the coated titanium colloidal sol on the glass basis material with rotational method or crystal pulling method;
4) at 100 ℃ of oven dry titanium sol pellicles;
5) the titanium sol pellicle was 500～600 ℃ of thermal treatments 15 minutes to 1 hour, and forming with the nanostructured anatase is the thin film of titanium oxide of principal crystalline phase.
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| CN100545114C true CN100545114C (en) | 2009-09-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844001B (en) * | 2006-04-26 | 2010-12-01 | 同济大学 | TiO2/PI hybridized film with optic catalytic self-cleaning function and preparation method thereof |
| CN101143763B (en) * | 2007-08-28 | 2010-08-18 | 杭州蓝星新材料技术有限公司 | Method for on-line producing sunlight controlling coated glass by float method |
| CN103657586B (en) * | 2013-11-19 | 2015-07-15 | 浙江大学 | Preparation method of novel SiO2-coated TiO2 material |
Citations (5)
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|---|---|---|---|---|
| CN1260767A (en) * | 1997-03-14 | 2000-07-19 | Ppg工业俄亥俄公司 | Photocatalytic-activated self-cleaning article and method of making same |
| CN1400186A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for raising titanium dioxide film self-cleaning glass photocatalytic activity |
| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
| CN1478746A (en) * | 2003-07-09 | 2004-03-03 | 天津大学 | Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film |
| WO2004085701A1 (en) * | 2003-03-25 | 2004-10-07 | Pilkington Plc | Titania coatings |
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- 2005-01-31 CN CNB2005100237126A patent/CN100545114C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260767A (en) * | 1997-03-14 | 2000-07-19 | Ppg工业俄亥俄公司 | Photocatalytic-activated self-cleaning article and method of making same |
| CN1400186A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for raising titanium dioxide film self-cleaning glass photocatalytic activity |
| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
| WO2004085701A1 (en) * | 2003-03-25 | 2004-10-07 | Pilkington Plc | Titania coatings |
| CN1478746A (en) * | 2003-07-09 | 2004-03-03 | 天津大学 | Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film |
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Application publication date: 20050928 Assignee: Zhangzhou Kibing Glass Co.,Ltd. Assignor: Tongji University Contract record no.: 2010310000037 Denomination of invention: Glass-base nanometer self-cleaning titania film and its prepn process Granted publication date: 20090930 License type: Exclusive License Record date: 20100413 |
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