CN1478746A - Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film - Google Patents
Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film Download PDFInfo
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- CN1478746A CN1478746A CNA031303781A CN03130378A CN1478746A CN 1478746 A CN1478746 A CN 1478746A CN A031303781 A CNA031303781 A CN A031303781A CN 03130378 A CN03130378 A CN 03130378A CN 1478746 A CN1478746 A CN 1478746A
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Abstract
A self-cleaning antifog nano TiO2-SiO2 glass member is prepared from metal salt, titanate and silicate through preparing Ti sol doped by metal salt, preparing Si sol, mixing, pretreating glass, coating the sol mixture on glass by immersing it in the sol mixture, and post-treating in muffle furnace by staged heat treating. Its advantages are high photocatalytic activity and hydrophilicity, high chemical stability, no-poison and low cost.
Description
Technical field
The present invention relates to a kind of employing sol-gel technique and on glass surface, prepare nanometer non-stoichiometric TiO
2-SiO
2The method of self-cleaning antifog glass film.The technology of preparing that belongs to glass surface nano functional film.
Background technology
Along with the raising of expanding economy, living standards of the people and the increase of fundamental construction investment scale, quantity such as the public building in automobile, city, high-rise building, star hotel and villa are poly-to be increased, and all will use a large amount of glass in these facilities.And these glass can run into problems such as dirt and atomizing in use usually, and the cleaning of buildings brings great inconvenience to live particularly for people's traffic safety and work normally.Along with the direction of glass towards ecology develops, adopting novel surface treatment technology modified glass surface and giving its function such as self-cleaning, antifog becomes one of developing direction of current glass technology for making.
Since TiO in 1972
2Photocatalysis characteristic found by Japanese scientist since, with TiO
2For the photocatalyst material of representing obtains extensive studies and exploitation, TiO
2Photocatalyst material has caused the extensive concern in the world to the obvious removal effect of all contaminations in the environment.TiO
2Photocatalyst can resolve into water and carbonic acid gas fully with the pollutent that biological process, chemical method can't be degraded, and does not cause secondary pollution; It also has functions such as sterilization, deodorizing simultaneously, and environment is had good decontamination effect improving.Hubei Sanxia New Building Materials Co., Ltd. relies on TiO
2Characteristic successfully produce TiO with independent intellecture property
2Self-cleaning antifog glass, the technical performance index of this glass is: the immersion back is acidproof in 1M HCl and 1M NaOH, alkali resistance is all better; Transmittance is greater than 68%; Wear resistance is greater than 75r; Degradation rate is greater than 94% (degraded acetone); Wetting angle is little 3 °; Sterilizing rate is greater than 98%.
Because TiO
2The photocatalyst greater band gap can only be by ultraviolet ray excited, and the compound solar energy utilization rate and the photo-quantum efficiency of making in the electronics that produces of optical excitation and hole is very low.In order to overcome these shortcomings, adopt means such as noble metal decorated, metal ion mixing, semi-conductor be compound to carry out modification usually, obtained effect preferably.1997, Fujishima research group found, TiO
2After uviolizing, can produce stronger Superhydrophilic, have higher lipophilicity simultaneously, i.e. parents' characteristic.Recently people find again, to TiO
2The middle SiO that adds
2Can increase its in the dark super hydrophilic stability.Therefore, TiO
2Stronger photocatalytic-oxidation voltinism and Superhydrophilic provide the reliable technique foundation for the improvement from clean and anti-fog function of glass.
Summary of the invention
The object of the present invention is to provide a kind of nanometer non-stoichiometric TiO
2-SiO
2The preparation method of self-cleaning antifog glass film.It is simple that this method has preparation technology, and the glassy membrane by the preparation of this method has photocatalytic activity height, strong hydrophilicity, visible light-responded strong, characteristics such as chemical stability is high, nontoxic, cost is low, anti-pollution and easy cleaning.
For achieving the above object, the present invention is realized by following technical proposals.To comprise that metal-salt, titanic acid ester and silicon ester are raw material, prepare nanometer non-stoichiometric TiO through the preparation that comprises the adulterated titanium colloidal sol of metal-salt, the preparation of silicon sol, the mixing of system film sol, the pre-treatment of glass, the dip-coating of system film sol and the aftertreatment of film
2-SiO
2The processing method of self-cleaning antifog glass film, the preparation of described silicon sol are that silicon ester, ethanol, water and acid are mixed, and in 35～75 ℃ of 1～4h that reflux, its mass ratio is silicon ester/ethanol/water/acid=1: 1～5: 1～4: 0.01～0.05 then; The preparation of described preparation liquid is that titanium colloidal sol and silicon sol are mixed, and is 0.5～25 to carry out by titanium/silicon mass ratio; The pre-treatment of described glass is that the acid solution of glass with 0.2～3mol/L soaked 2～5 hours, uses ethanol and the clean also drying of washed with de-ionized water after 20～30 minutes again with the vibration of ultrasonic cleaning machine then; The dip-coating of described system film sol is glass to be immersed stop in the colloidal sol that the speed with 5～10 cm per minute proposes after 5～10 minutes.It is characterized in that: the preparation of the adulterated titanium colloidal sol of metal-salt is that titanic acid ester is dissolved in the alcoholic solvent, add methyl ethyl diketone, the mixing solutions that under violent stirring, adds acid and deionized water then, add metal salt solution at last, its mass ratio is: titanic acid ester/alcohol/water/acid/methyl ethyl diketone/metal-salt=1: 15～20: 1～5: 0.1～0.4: 0.3～0.8: 0.002～0.01; The aftertreatment of film is that the glass that will be coated with film places muffle furnace in 350～450 ℃ of sintering 1 hour, 450～500 ℃ of sintering 1～1.5 hour, obtains the non-stoichiometric TiO that crystal grain is 10～380nm in 1～1.5 hour thermal treatment of 500～600 ℃ of sintering at last then
2-SiO
2The self-cleaning antifog glass film.
Above-mentioned metal-salt is ferric sulfate, iron nitrate and lead nitrate, preferred iron nitrate and lead nitrate.
The invention has the advantages that by being entrained in of metal ion and prepare nanometer non-stoichiometric TiO on the glass surface
2-SiO
2The self-cleaning antifog film.This film has that preparation technology is simple, photocatalytic activity is high, strong hydrophilicity, visible light-responded strong, chemical stability is high, nontoxic, cost is low, anti-pollution and easy cleaning etc.
Embodiment
Embodiment one: take by weighing the methyl ethyl diketone that adds 40g after metatitanic acid tetramethyl ester 100g is dissolved in the 1500g methyl alcohol again, add entry 200g and hydrochloric acid 30g under violent stirring, add ferric sulfate 0.8g at last again; Take by weighing methyl silicate 50g, ethanol 100g, water 150g and hydrochloric acid 1g mix and are incorporated in 35 ℃ of backflow 2h; Adulterated titanium colloidal sol of ferric sulfate and silicon sol are mixed; The sulphuric acid soln of slide glass glass with 1mol/L soaked 2 hours, use ethanol and washed with de-ionized water totally also dry after 20 minutes again with the vibration of ultrasonic cleaning machine then; Glass immersed in the colloidal sol stop that the speed with 6 cm per minute proposes after 5 minutes; The glass that has been coated with film is placed 380 ℃ of muffle furnace sintering 1 hour, 460 ℃ of sintering 1 hour, obtain the non-stoichiometric TiO that crystal grain is 56～90nm after 1.5 hours at 550 ℃ of sintering at last then
2-SiO
2The self-cleaning antifog glass film.The glass acid resistance alkali resistance of filming after tested better (was soaked 24 hours in the hydrochloric acid of 1mol/L and is soaked after 24 hours in the sodium hydroxide of 1mol/L and do not have dissolution phenomena), transmittance is 68%, wear resistance is 78r, the acetone of degraded 97% in photo catalysis reactor, and wetting angle is 1 °.
Embodiment two: take by weighing the methyl ethyl diketone that adds 20g after tetraethyl titanate 50g is dissolved in the 750g ethanol again, add entry 50g and nitric acid 5g under violent stirring, add iron nitrate 0.25g at last again; Take by weighing tetraethoxy 50g, ethanol 100g, water 150g and nitric acid 1g mix and are incorporated in 40 ℃ of backflow 2h; Adulterated titanium colloidal sol of iron nitrate and silicon sol are mixed; The hydrochloric acid soln of slide glass glass with 2mol/L soaked 3 hours, use ethanol and washed with de-ionized water totally also dry after 25 minutes again with the vibration of ultrasonic cleaning machine then; Glass immersed in the colloidal sol stop that the speed with 5 cm per minute proposes after 10 minutes; The glass that has been coated with film is placed 420 ℃ of muffle furnace sintering 1 hour, 490 ℃ of sintering 1 hour, obtain the non-stoichiometric TiO that crystal grain is 130～190nm after 1.5 hours at 560 ℃ of sintering at last then
2-SiO
2The self-cleaning antifog glass film.。The glass acid resistance alkali resistance of filming after tested better (was soaked 24 hours in the hydrochloric acid of 1mol/L and is soaked after 24 hours in the sodium hydroxide of 1mol/L and do not have dissolution phenomena), transmittance is 69%, wear resistance is 79r, the acetone of degraded 98% in photo catalysis reactor, and wetting angle is 1 °.
Embodiment three: take by weighing the methyl ethyl diketone that adds 60g after metatitanic acid orthocarbonate 150g is dissolved in the 3000g butanols again, add entry 150g and phosphoric acid 30g under violent stirring, add lead nitrate 0.6g at last again; Take by weighing tetraethoxy 450g, ethanol 450g, water 450g and phosphoric acid 22g mix and are incorporated in 50 ℃ of backflow 2h; Adulterated titanium colloidal sol of lead nitrate and silicon sol are mixed; The salpeter solution of slide glass glass with 3mol/L soaked 4 hours, use ethanol and washed with de-ionized water totally also dry after 30 minutes again with the vibration of ultrasonic cleaning machine then; Glass immersed in the colloidal sol stop that the speed with 6 cm per minute proposes after 8 minutes; The glass that has been coated with film is placed 400 ℃ of muffle furnace sintering 1 hour, 470 ℃ of sintering 1 hour, obtain the non-stoichiometric TiO that crystal grain is 201～290nm after 1.5 hours at 580 ℃ of sintering at last then
2-SiO
2The self-cleaning antifog glass film.The acid resistance alkali resistance of film good (in the hydrochloric acid of 1mol/L, soaked 24 hours and in the sodium hydroxide of 1mol/L, soaked after 24 hours and do not have dissolution phenomena) after tested, transmittance is 68%, wear resistance is 78r, the acetone of degraded 98% in photo catalysis reactor, and wetting angle is 2 °.
Claims (2)
1, a kind of nanometer non-stoichiometric TiO
2-SiO
2The preparation method of self-cleaning antifog glass film, this method is prepared nanometer non-stoichiometric TiO to comprise that metal-salt, titanic acid ester and silicon ester are raw material through the preparation that comprises the adulterated titanium colloidal sol of metal-salt, the preparation of silicon sol, the mixing of system film sol, the pre-treatment of glass, the dip-coating of system film sol and the aftertreatment of film
2-SiO
2The processing method of self-cleaning antifog glass film, the preparation of described silicon sol are that silicon ester, ethanol, water and acid are mixed, and in 35～75 ℃ of 1～4h that reflux, its mass ratio is silicon ester/ethanol/water/acid=1: 1～5: 1～4: 0.01～0.05 then; The preparation of described preparation liquid is that titanium colloidal sol and silicon sol are mixed, and is 0.5～25 to carry out by titanium/silicon mass ratio; The pre-treatment of described glass is that the acid solution of glass with 0.2～3mol/L soaked 2～5 hours, uses ethanol and the clean also drying of washed with de-ionized water after 20～30 minutes again with the vibration of ultrasonic cleaning machine then; The dip-coating of described system film sol is glass to be immersed stop in the colloidal sol that the speed with 5～10 cm per minute proposes after 5～10 minutes, it is characterized in that: the preparation of the adulterated titanium colloidal sol of metal-salt is that titanic acid ester is dissolved in the alcoholic solvent, add methyl ethyl diketone, the mixing solutions that under violent stirring, adds acid and deionized water then, add metal salt solution at last, its mass ratio is: titanic acid ester/alcohol/water/acid/methyl ethyl diketone/metal-salt=1: 15～20: 1～5: 0.1～0.4: 0.3～0.8: 0.002～0.01; The aftertreatment of film is that the glass that will be coated with film places muffle furnace in 350～450 ℃ of sintering 1 hour, 450～500 ℃ of sintering 1～1.5 hour, obtains the non-stoichiometric TiO that crystal grain is 10～380nm in 1～1.5 hour thermal treatment of 500～600 ℃ of sintering at last then
2-SiO
2The self-cleaning antifog glass film.
2, by the described nanometer non-stoichiometric of claim 1 TiO
2-SiO
2The preparation method of self-cleaning antifog glass film is characterized in that: metal-salt is ferric sulfate, iron nitrate and lead nitrate, preferred iron nitrate and lead nitrate.
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| CNA031303781A CN1478746A (en) | 2003-07-09 | 2003-07-09 | Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film |
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| CNA031303781A CN1478746A (en) | 2003-07-09 | 2003-07-09 | Preparation methd of nanometer non-complete ratio Tio2Sio2 self-cleaning fog preventing glass film |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100545114C (en) * | 2005-01-31 | 2009-09-30 | 同济大学 | Glass-base nanometer self-cleaning titania film and preparation method thereof |
| CN102862341A (en) * | 2012-09-03 | 2013-01-09 | 常熟华冶薄板有限公司 | Self-cleaning high-corrosion-resistance plating layer steel plate and preparation method thereof |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN102950843A (en) * | 2012-11-29 | 2013-03-06 | 大连创达技术交易市场有限公司 | Automotive glass with anti-fog and self-cleaning functions |
| CN102997126A (en) * | 2012-08-22 | 2013-03-27 | 苏州金科信汇光电科技有限公司 | Wall washer lamp with self-cleaning function |
| CN103288358A (en) * | 2012-02-22 | 2013-09-11 | 中国科学院理化技术研究所 | Super-hydrophilic, self-cleaning and mist-proof anti-reflection coating and preparation method thereof |
| CN103553358A (en) * | 2013-11-08 | 2014-02-05 | 蚌埠玻璃工业设计研究院 | Method for preparing Fe3+/SiO2/TiO2 nano composite film |
| CN104231683A (en) * | 2014-08-25 | 2014-12-24 | 北京市建筑工程研究院有限责任公司 | Titanium dioxide-silicon dioxide composite photocatalytic coating and preparation method thereof |
| CN105293948A (en) * | 2015-10-08 | 2016-02-03 | 中山大学 | Preparation method for hydrophobic organic-modified silicate thin film with adjustable refractive index and silicate thin film |
-
2003
- 2003-07-09 CN CNA031303781A patent/CN1478746A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100545114C (en) * | 2005-01-31 | 2009-09-30 | 同济大学 | Glass-base nanometer self-cleaning titania film and preparation method thereof |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN102875032B (en) * | 2011-07-15 | 2015-09-02 | 比亚迪股份有限公司 | Sol composition and preparation method thereof, form the method for self-cleaning anti-reflection film and self-cleaning anti-reflective glass at glass surface |
| CN103288358A (en) * | 2012-02-22 | 2013-09-11 | 中国科学院理化技术研究所 | Super-hydrophilic, self-cleaning and mist-proof anti-reflection coating and preparation method thereof |
| CN102997126A (en) * | 2012-08-22 | 2013-03-27 | 苏州金科信汇光电科技有限公司 | Wall washer lamp with self-cleaning function |
| CN102862341A (en) * | 2012-09-03 | 2013-01-09 | 常熟华冶薄板有限公司 | Self-cleaning high-corrosion-resistance plating layer steel plate and preparation method thereof |
| CN102950843A (en) * | 2012-11-29 | 2013-03-06 | 大连创达技术交易市场有限公司 | Automotive glass with anti-fog and self-cleaning functions |
| CN103553358A (en) * | 2013-11-08 | 2014-02-05 | 蚌埠玻璃工业设计研究院 | Method for preparing Fe3+/SiO2/TiO2 nano composite film |
| CN103553358B (en) * | 2013-11-08 | 2016-01-27 | 蚌埠玻璃工业设计研究院 | A kind of Fe 3+/ SiO 2/ TiO 2the preparation method of nano compound film |
| CN104231683A (en) * | 2014-08-25 | 2014-12-24 | 北京市建筑工程研究院有限责任公司 | Titanium dioxide-silicon dioxide composite photocatalytic coating and preparation method thereof |
| CN105293948A (en) * | 2015-10-08 | 2016-02-03 | 中山大学 | Preparation method for hydrophobic organic-modified silicate thin film with adjustable refractive index and silicate thin film |
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