CN1400185A - Method for preparing high-activity titanium dioxide film self-cleaning glass material - Google Patents
Method for preparing high-activity titanium dioxide film self-cleaning glass material Download PDFInfo
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- CN1400185A CN1400185A CN 01128305 CN01128305A CN1400185A CN 1400185 A CN1400185 A CN 1400185A CN 01128305 CN01128305 CN 01128305 CN 01128305 A CN01128305 A CN 01128305A CN 1400185 A CN1400185 A CN 1400185A
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Abstract
The method for preparing high-activity titanium dioxide film self-cleaning glass material, applicable to the fields of building glass, car glass and optical glass, uses general glass as base body for coating film and includes the following steps: cleaning glass surface, drying, sweeping with nitrogen gas, sol preparation, impregnating and coating, drying, crystallization heat treatment, pickling and surface after-treatment. The sodium ion content of titanium dioxide film can be controlled in 0.3%, carbon content of film surface is reduced, surface hydroxy content is increased and the optical catalytic activity of glass can be greatly raised. Said invention adopts line production process, and can effectively control product quality.
Description
Technical field
The present invention relates to a kind of in the sheet glass substrate deposition of titanium oxide and thus obtained glass, or rather, the present invention relates to the glass material of Prepared by Sol Gel Method titanium dioxide coating film and be applicable to the method for suitability for industrialized production.
Background technology
People often use various sanitising agents to clean window glass, cladding glass or vehicle glass, reason is because airborne organic pollutant adheres to glass surface, is difficult to use pure water that the organic pollutant of glass surface is washed and make the glass surface cleaning totally.If plate one deck high reactivity transparent titanium dioxide film on common soda-lime glass surface, this purifying air for the automatically cleaning of glass surface and indoor and outdoor is quite useful.The method for preparing transparent dioxy titanium film at glass surface has many kinds, as chemical vapour deposition, and magnetron sputtering, sol-gel process etc.But prepared dioxy titanium film does not have good photocatalytic activity usually, reason is as with the titanium deoxid film of chemical vapour deposition or magnetron sputtering preparation non-crystalline state normally, perhaps the content of anatase octahedrite phase is low in the film, and film is fine and close, specific surface area is low, so the photocatalytic activity of Zhi Bei titanium deoxid film is high or do not have a photocatalytic activity like this, thereby the TiO 2 coating film glass of preparation does not so possess self-cleaning net work energy.Opposite employing sol-gel process prepares titanium deoxid film at glass surface and has many outstanding advantages: (1) does not need special equipment or device; (2) help the doping of titanium deoxid film or various ingredients plated film simultaneously; (3) phase structure of film and composition can be controlled, as are controlled to be 100% anatase octahedrite phase; (4) film has vesicular structure, thereby specific surface area is big, the The adsorbed hydroxyl content height, and also pore structure can control effectively by adding superpolymer or tensio-active agent.Because the phase structure of titanium dioxide has decisive influence with mutually content, specific surface area and The adsorbed hydroxyl content etc. to photocatalytic activity, so sol-gel process is the effective ways of preparation Photoactive titania film.But the sodium ion in the glass diffuses into when thermal treatment in the freshly prepd titanium deoxid film, has reduced the photocatalytic activity of titanium deoxid film widely.Reason is the formation that the sodium ion of high density can stop photolytic activity anatase octahedrite phase, and the deathnium that the sodium ion of lower concentration can form light induced electron or space at the surface or the body of titanium deoxid film.For harmful effect that stops the sodium pollutent and the photocatalytic activity that strengthens titanium deoxid film, people have carried out many research work, but all there is such or such deficiency, for example, before the plating titanium deoxid film, in common soda-lime glass surface plating layer of silicon dioxide, silicon dioxide layer can stop sodium ion to diffuse in the titanium deoxid film fully like this, makes the photocatalytic activity of titanium dioxide obtain significant improvement earlier.But the homogeneity of film, transmittance and sticking power are affected, and technology is difficult to control and repeats plated film time and cost increase.Also have the people with glass basis earlier with nitric acid or vitriolization, the sodium ion in the glass is partly cemented out, form the diffusion trapping layer of sodium ion and then plated film at glass surface.But this method can not stop sodium ion to diffuse in the titanium deoxid film fully, and prepared TiO 2 coating film self-cleaning glass photocatalytic activity is not high, does not have from clean function.
GB patent specification 2026454B has described a kind of method, in the method, when glass ribbon comes out to push ahead, coating chamber is arranged in the top of hot float glass belt from float bath, and this method is difficult to control coating quality, and operation is complicated.
The Chinese invention patent communique on April 24th, 1996 disclosed manufacture method of a kind of heat treatable double-sided coating glass and products thereof, notification number CN1121054, its plated film step comprises glass substrate-cleaning-oven dry-and sol-gel processing plated film, and its photocatalytic activity is not high.
Summary of the invention
The method for preparing high-activity titanium dioxide film self-cleaning glass material that the purpose of this invention is to provide a kind of simple, effective modern production in enormous quantities that also suits.
The object of the present invention is achieved like this: a kind of method for preparing high-activity titanium dioxide film self-cleaning glass material is the plated film matrix with common glass, comprises step:
(a) clean: glass surface is cleaned;
(b) drying: glass surface is carried out drying treatment;
(c) nitrogen purging: glass surface is purged with high pure nitrogen;
(d) colloidal sol preparation:
(e) immersion plating: in constant temperature, cleaning, fp environment, glass surface is carried out immersion plating membrane; By certain speed glass is sunk in the colloidal sol, behind the stop certain hour, with certain speed glass is carried again and be drawn out to the immersion plating pond;
(f) drying: carry out drying treatment with steam or the clean warm air glass surface after to immersion plating;
(g) crystallization and thermal treatment: the glass behind the plated film is carried out crystallization and thermal treatment, be warming up to certain temperature spot earlier, the insulation certain hour is reduced to normal temperature again;
(h) acid soak: coated glass is carried out acid treatment; In certain density dilute acid soln, sodium ion, the calcium ion of displacement glass surface are proposed after glass soaked certain hour;
(i) washing: wash with the glass of pure water after, remove the residual acid solution of glass surface to acid soak;
(j) drying:, the glass after the washing is carried out drying treatment with steam or clean warm air.
The cleaning of glass surface comprises:
(a) washing composition cleans: the organism of removing glass surface with washing composition;
(b) acid is cleaned: with dilute acid soln glass surface is cleaned;
(c) water flushing: with softening water glass surface is washed, remove the washing composition and the acid-soluble material that remain on the glass surface;
(d) pure water cleans: with deionized water glass surface is washed, remove surface contaminants.
With steam or clean warm air glass surface is carried out drying treatment, the time was at 10-50 minute.
The speed of sinking to is 20-50cm/min, and the residence time is 30s-3min, and pull rate is 15-35cm/min.
Surface drying time is no less than 25min.
Heat treated heat-up rate is 20-40 ℃/min, and soaking time is 60-100min, cooling rate 15-20 ℃/min.
The used acid of acid soak is mineral acid or organic acid, and mineral acid comprises nitric acid, sulfuric acid, sulfurous acid, hydrochloric acid, and organic acid comprises acetate, formic acid, and acid is one or more the combination in above-mentioned mineral acid or the organic acid.
Dilute acid soln concentration when acid soak is handled is 0.005-5M soak time 3min-120min, temperature 0-70 ℃ of acid.
TiO 2 sol is by the preparation of titanium hydrolysis of alkoxide, and the titanium alkoxide is one or both combinations in positive metatitanic acid fourth fat, metatitanic acid isopropyl ester and the metatitanic acid second fat, and the volumetric molar concentration of titanium alkoxide is 0.01-1M; The combination of one or more in solvent for use ethanol, Virahol, propyl alcohol or the water.
Added the complexing stablizer in titanium oxide sol, the complexing stablizer is the combination of one or both in ketone, the Diethylene Glycol in trolamine, diethanolamine, the acetate, and its add-on is the 0.05-10% of titanium dioxide quality in the colloidal sol.
Because the present invention adopts cleaning, dry, nitrogen purging, the colloidal sol preparation, immersion plating, dry, crystallization and thermal treatment, acid soak, operations such as aftertreatment prepare titanium deoxid film glass, titanium deoxid film on common soda-lime glass surface by Prepared by Sol Gel Method, because thermal treatment makes a large amount of sodium ions diffuse into the film from glass basis, film contains the sodium ion about about 6-10% (atomic percentage conc) usually, thereby the photocatalytic activity of titanium deoxid film is very weak or do not have a photocatalytic activity, when the titanium deoxid film surface after peracid treatment, the sodium ion on titanium deoxid film surface can be removed fully or be controlled in 0.3%, and the photocatalytic activity of titanium dioxide film self-cleaning glass can be improved more than 1 times.If matrix is a silica glass, the titanium deoxid film surface of quartz glass substrate surface is after peracid treatment, photocatalytic activity also can improve more than 30%, and this is because after the surface acid processing, the carbon content decline of film surface and The adsorbed hydroxyl content increase cause.And the present invention selects the mode of streamline operration production technique, both met domestic and international production technique custom, is easy to effectively control quality product again, grasps the rule that industrialization is produced.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
T, D, H, E and P represent metatitanic acid fourth fat, diethanolamine, water, dehydrated alcohol and polyoxyethylene glycol (PEG) respectively.
It is as follows to be suitable for industrial method:
1, original sheet glass: choose former of fine float glass, frame is adorned stand-by.Require macroscopic irregularitys such as glass is fresh, nothing scuffing.
2, section: will carry out cutting to glass by manufacturing technique requirent and user.Scale error ≯ ± 1.5mm.
3, edging: use the abrasive band edge polisher, polished in glass cutting limit.Require glass periphery not have burr.
4, washing composition cleans: with washing composition glass surface is cleaned on cleaning machine, with organism such as the oils of removing glass surface, staff greases.
5, acid is cleaned: with dilute acid soln glass surface is cleaned on cleaning machine, with inorganics and displacement glass surface part Na such as the adsorptive of removing glass surface, atmospheric polluting materials
+, Ca
2+Ion.
6, water flushing: on rinsing machine, glass surface is washed, to remove washing composition and the acid-soluble material that remains in glass surface with softening water.
7, pure water cleans: with deionized water glass surface is cleaned on cleaning machine, with the dirt of thorough cleaning glass surface, guarantee that the glass surface cleaning is clean.
In order to allow glass basis and titanium deoxid film form firm Chemical bond, used glass basis surface must clean up.
8, drying: with steam or clean warm air glass surface is carried out drying treatment, the time is at 10-50 minute, do not have the globule of extension and free from dust to reach glass surface, stigmatosis is as the criterion.
9, nitrogen purging: with high pure nitrogen glass surface is purged, to remove the aqueous vapor of glass surface better; And, reduce or stop thing such as water, dust, greasy dirt in the glass surface absorbed air with the nitrogen protection glass surface.
10, colloidal sol preparation: carry out immersion plating liquid---the preparation of colloidal sol.The requirement proportioning is proper, weighing accurate, it is complete to mix, leave standstill, viscosity is suitable, as clear as crystal.
Wherein the preparation of colloidal sol is: with the titanium alkoxide is the titanium source, the titanium alkoxide is dissolved in organic solvent such as the dehydrated alcohol under constantly stirring, add trolamine or other negative contact agents simultaneously, hydrolysis rate with control titanium alkoxide, stir after 2 hours, the mixture that adds alcohol and water again allows alkoxide with suitable speed hydrolysis, promptly can help plated film after 2 hours.TiO
2The composition of colloidal sol sees Table 1.
Table 1 T
05D
1H
1The composition of EP colloidal sol
| Sample | ??Ti(OC 4H 9) 4?????/ml | ?NH(C 2H 5OH) 2????/ml | ????H 2O ????/ml | ???C 2H 5OH ?????/ml | ???PEG ????/g | |
| ??T 05D 1H 1E | ????17.02 | ????4.08 | ????0.9 | ????77.28 | ????0 | |
| ??T 05D 1H 1EP 025 | ????17.02 | ????4.08 | ????0.9 | ????77.28 | ????0.25 | ??2000PEG |
| ??T 05D 1H 1EP 05 | ????17.02 | ????4.08 | ????0.9 | ????77.28 | ????0.5 | ??2000PEG |
| ??T 05D 1H 1EP 10 | ????17.02 | ????4.08 | ????0.9 | ????77.28 | ????1.0 | ??2000PEG |
| ??T 05D 1H 1EP 20 | ????17.02 | ????4.08 | ????0.9 | ????77.28 | ????2.0 | ??2000PEG |
11, immersion plating: in constant temperature, cleaning, fp environment, glass surface is carried out immersion plating membrane with specific equipment.By the constant speed degree glass is sunk in the colloidal sol, behind the stop certain hour, with certain speed glass is lifted to going out the immersion plating pond again.Requirement is sunk to speed at 20-50cm/min, and the residence time, pull rate was at 15-35cm/min, to guarantee thicknesses of layers at 30s-3min.Steady non-jitter is sunk to, lifts in requirement.Plated film adopts the dip-coating method plated film, and pull rate is 1-6mm/s, and 100 ℃ of dryings 10 minutes, then 500-600 ℃ of thermal treatment 1 hour, film was cooled to low temperature (less than 200 ℃) or room temperature to film earlier,
12, drying: carrying out drying treatment with steam or the clean warm air glass surface after to immersion plating on the specific equipment.To reach except that moisture content and to increase film strength, prevent the rete distortion.Require time of drying ≮ 25min.
13, crystallization and thermal treatment: on the specific equipment glass behind the plated film is being carried out crystallization and thermal treatment.The energy of specific equipment heating usefulness is chosen one or more among electricity, coal, diesel oil, heavy oil, the Sweet natural gas.After being warming up to certain temperature spot with certain speed earlier, the insulation certain hour is cooled to normal temperature with certain speed again.Require 20-40 ℃/min of heat-up rate, soaking time 60-100min, cooling rate 15-20 ℃/min.Requirement heats up steadily, insulation is abundant, glass is indeformable, glass surface is bright.
14, acid soak: on specific equipment, coated glass is carried out acid treatment.In certain density dilute acid soln, propose after glass soaked 30min-120min.Na with the displacement glass surface
+, Ca
2+Ion, the self-cleaning property of raising glass.Promptly can carry out surface acid and handle, acid can be that mineral acid also can be an organic acid, the concentration of acid can height can be low, as H with 1M concentration
2SO
4The freshly prepd titanium deoxid film of solution-treated takes out titanium deoxid film from acid solution after 2 hours.
15, washing: with pure water the glass behind the acid bubble is being washed on the specific equipment.To remove the residual acid solution of glass surface.Require to clean.
16, drying: on specific equipment,, the glass after the washing is carried out drying treatment with steam or clean warm air.To guarantee the dry exclusion of glass surface.Film is washed with tap water earlier, and then use rinsed with deionized water, oven dry at last, the content of sodium ion can drop to 0 from 9% in the film.
17, cut edge: on special-purpose cutter's table, plated film and dried glass cut edge handle and change little cutting greatly.Mainly be the immersion plating pond is left at excision Glass hanging place at last when the part of immersion plating and immersion plating do not lift part, to guarantee quality product.
18, quality test:, glass quality is tested with specialized instrument and equipment in the production scene.Interventions Requested comprise glass size size, transmittance, scratch resistance ability, wettability, photocatalytic, rete stability.Check density is as the criterion with every batch.
19, finished product: the product through being up to the standards, pack the back warehouse-in by the packaging standard of coated glass.
Claims (10)
1. a method for preparing high-activity titanium dioxide film self-cleaning glass material is the plated film matrix with common glass, comprises step:
(a) clean: glass surface is cleaned;
(b) drying: glass surface is carried out drying treatment;
(c) nitrogen purging: glass surface is purged with high pure nitrogen;
(d) colloidal sol preparation:
(e) immersion plating: in constant temperature, cleaning, fp environment, glass surface is carried out immersion plating membrane; By certain speed glass is sunk in the colloidal sol, behind the stop certain hour, with certain speed glass is carried again and be drawn out to the immersion plating pond;
(f) drying: carry out drying treatment with steam or the clean warm air glass surface after to immersion plating;
(g) crystallization and thermal treatment: the glass behind the plated film is carried out crystallization and thermal treatment, be warming up to certain temperature spot earlier, the insulation certain hour is reduced to normal temperature again;
(h) acid soak: coated glass is carried out acid treatment; In certain density dilute acid soln, sodium ion, the calcium ion of displacement glass surface are proposed after glass soaked certain hour;
(i) washing: wash with the glass of pure water after, remove the residual acid solution of glass surface to acid soak;
(j) drying:, the glass after the washing is carried out drying treatment with steam or clean warm air.
2, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1 is characterized in that the cleaning of glass surface comprises:
(a) washing composition cleans: the organism of removing glass surface with washing composition;
(b) acid is cleaned: with dilute acid soln glass surface is cleaned;
(c) water flushing: with softening water glass surface is washed, remove the washing composition and the acid-soluble material that remain on the glass surface;
(d) pure water cleans: with deionized water glass surface is washed, remove surface contaminants.
3, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1 is characterized in that with steam or clean warm air glass surface being carried out drying treatment, and the time was at 10-50 minute.
4, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1, it is characterized in that sinking to speed is 20-50cm/min, and the residence time is 30s-3min, and pull rate is 15-35cm/min.
5, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1 is characterized in that surface drying time is no less than 25min.
6, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1 is characterized in that heat treated heat-up rate is 20-40 ℃/min, and soaking time is 60-100min, cooling rate 15-20 ℃/min.
7, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1, it is characterized in that the used acid of acid soak is mineral acid or organic acid, mineral acid comprises nitric acid, sulfuric acid, sulfurous acid, hydrochloric acid, organic acid comprises acetate, formic acid, and acid is one or more the combination in above-mentioned mineral acid or the organic acid.
8, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1 is characterized in that the dilute acid soln concentration when acid soak is handled is 0.005-5M soak time 3min-120min, temperature 0-70 ℃ of acid.
9, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 1, it is characterized in that TiO 2 sol is prepared by the titanium hydrolysis of alkoxide, the titanium alkoxide is one or both combinations in positive metatitanic acid fourth fat, metatitanic acid isopropyl ester and the metatitanic acid second fat, and the volumetric molar concentration of titanium alkoxide is 0.01-1M; The combination of one or more in solvent for use ethanol, Virahol, propyl alcohol or the water.
10, the method for preparing high-activity titanium dioxide film self-cleaning glass material according to claim 9, it is characterized in that in titanium oxide sol, having added the complexing stablizer, the complexing stablizer is one or both the combination in trolamine, diethanolamine, acetate acetone, the Diethylene Glycol, and its add-on is the 0.05-10% of titanium dioxide quality in the colloidal sol.
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|---|---|---|---|
| CN 01128305 CN1197803C (en) | 2001-07-31 | 2001-07-31 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
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|---|---|---|---|
| CN 01128305 CN1197803C (en) | 2001-07-31 | 2001-07-31 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004062795A1 (en) * | 2003-01-08 | 2004-07-29 | The Chinese University Of Hong Kong | Optically transparent tio2 thin films on glass having anti-bacterial and anti-virus activities and method for preparing the same |
| CN1296303C (en) * | 2005-04-07 | 2007-01-24 | 武汉理工大学 | One-step treatment process of sol filming for preparing toughening self-cleaning glass with film of titanium dioxide |
| CN1330413C (en) * | 2004-09-15 | 2007-08-08 | 上海师范大学 | Process for preparing TiO2 light catalytic transparent film |
| CN100348335C (en) * | 2004-04-16 | 2007-11-14 | 天津理工学院 | Device and process for producing nano TiO2 film by supersonic atomization |
| CN100406125C (en) * | 2006-01-19 | 2008-07-30 | 北京科技大学 | Method for preparing highly active Fe/Sn ion co-doped nano phtocatalyst of titanium dioxide |
| CN100545114C (en) * | 2005-01-31 | 2009-09-30 | 同济大学 | Glass-base nanometer self-cleaning titania film and preparation method thereof |
| CN101823842A (en) * | 2010-03-23 | 2010-09-08 | 杭州捷菱机械设备有限公司 | Method and equipment for producing coated glass |
| CN101058483B (en) * | 2007-04-06 | 2010-12-08 | 中国科学院上海硅酸盐研究所 | Method for preparing nanometer porous titanium oxide thick film |
| CN101575174B (en) * | 2009-06-19 | 2011-08-31 | 江苏蓝星玻璃有限公司 | Process for filming multi-specification glass |
| CN101333075B (en) * | 2007-06-29 | 2011-09-07 | 北京中科赛纳玻璃技术有限公司 | Method for preparing self-cleaning toughened glass |
| CN102515567A (en) * | 2011-12-14 | 2012-06-27 | 渤海大学 | Method for preparing nano CeO2 film having UV shielding property |
| CN102701601A (en) * | 2012-05-11 | 2012-10-03 | 佛山市高明贝特尔卫浴有限公司 | Preparation technique of self-cleaning and mildew-proof bathroom glass |
| CN106892574A (en) * | 2015-12-18 | 2017-06-27 | 北京有色金属研究总院 | A kind of superhydrophilic self-cleaning silica dioxide antireflection film and preparation method thereof |
| CN113109369A (en) * | 2021-05-22 | 2021-07-13 | 盐城市盐都区荣海实验器材厂 | Production and preparation process of glass slide |
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2001
- 2001-07-31 CN CN 01128305 patent/CN1197803C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004062795A1 (en) * | 2003-01-08 | 2004-07-29 | The Chinese University Of Hong Kong | Optically transparent tio2 thin films on glass having anti-bacterial and anti-virus activities and method for preparing the same |
| CN100348335C (en) * | 2004-04-16 | 2007-11-14 | 天津理工学院 | Device and process for producing nano TiO2 film by supersonic atomization |
| CN1330413C (en) * | 2004-09-15 | 2007-08-08 | 上海师范大学 | Process for preparing TiO2 light catalytic transparent film |
| CN100545114C (en) * | 2005-01-31 | 2009-09-30 | 同济大学 | Glass-base nanometer self-cleaning titania film and preparation method thereof |
| CN1296303C (en) * | 2005-04-07 | 2007-01-24 | 武汉理工大学 | One-step treatment process of sol filming for preparing toughening self-cleaning glass with film of titanium dioxide |
| CN100406125C (en) * | 2006-01-19 | 2008-07-30 | 北京科技大学 | Method for preparing highly active Fe/Sn ion co-doped nano phtocatalyst of titanium dioxide |
| CN101058483B (en) * | 2007-04-06 | 2010-12-08 | 中国科学院上海硅酸盐研究所 | Method for preparing nanometer porous titanium oxide thick film |
| CN101333075B (en) * | 2007-06-29 | 2011-09-07 | 北京中科赛纳玻璃技术有限公司 | Method for preparing self-cleaning toughened glass |
| CN101575174B (en) * | 2009-06-19 | 2011-08-31 | 江苏蓝星玻璃有限公司 | Process for filming multi-specification glass |
| CN101823842A (en) * | 2010-03-23 | 2010-09-08 | 杭州捷菱机械设备有限公司 | Method and equipment for producing coated glass |
| CN101823842B (en) * | 2010-03-23 | 2011-12-14 | 杭州捷菱机械设备有限公司 | Method and equipment for producing coated glass |
| CN102515567A (en) * | 2011-12-14 | 2012-06-27 | 渤海大学 | Method for preparing nano CeO2 film having UV shielding property |
| CN102701601A (en) * | 2012-05-11 | 2012-10-03 | 佛山市高明贝特尔卫浴有限公司 | Preparation technique of self-cleaning and mildew-proof bathroom glass |
| CN106892574A (en) * | 2015-12-18 | 2017-06-27 | 北京有色金属研究总院 | A kind of superhydrophilic self-cleaning silica dioxide antireflection film and preparation method thereof |
| CN113109369A (en) * | 2021-05-22 | 2021-07-13 | 盐城市盐都区荣海实验器材厂 | Production and preparation process of glass slide |
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| CN1197803C (en) | 2005-04-20 |
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