CN102114419A - Preparation method of photocatalysis and transmission increasing sol and glass coating material - Google Patents
Preparation method of photocatalysis and transmission increasing sol and glass coating material Download PDFInfo
- Publication number
- CN102114419A CN102114419A CN 200910266057 CN200910266057A CN102114419A CN 102114419 A CN102114419 A CN 102114419A CN 200910266057 CN200910266057 CN 200910266057 CN 200910266057 A CN200910266057 A CN 200910266057A CN 102114419 A CN102114419 A CN 102114419A
- Authority
- CN
- China
- Prior art keywords
- ludox
- weight
- photocatalysis
- acid
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a photocatalysis and transmission increasing sol, wherein the method comprises the following steps: well mixing an acidic silicon oxide sol and an alkaline silicon oxide sol in a weight ratio of 1:0.5-10 to obtain a mixed silicon oxide sol, adjusting the pH of the mixed silicon oxide sol by an organic acid to 4-7.5; well mixing the mixed silicon oxide sol and a titanium oxide sol precursor in a weight ratio of 3-6:1 to obtain a transparent and clear mixed sol; well mixing the obtained transparent and clear mixed sol and a film-forming additive to obtain a photocatalysis and transmission increasing sol. The invention also provides a preparation method of a glass coating material. The glass coating material prepared by the method of the invention has a hydrophilic angle of 4.6-10.1 DEG, has a light transmittance higher than that of a glass substrate by 0.5-2%, and has a photocatalysis effect with a conversion rate of 20-30%.
Description
Technical field
The present invention relates to a kind of photocatalysis and anti-reflection preparation method and coating film on glass preparation methods of penetrating colloidal sol, specifically, relate to a kind of TiO
2/ SiO
2Composite photocatalyst and the anti-reflection preparation method who penetrates colloidal sol and a kind ofly have photocatalysis and an anti-reflection coating film on glass preparation methods of penetrating two kinds of functions.
Background technology
Present photocatalysis antireflecting coating adopts the method that applies film forming in silicon oxide particle and Titanium particles behind other film forming matter of doping more, and this method exists the uneven situation of mixing, the light transmission and the photocatalytic activity of the coating film on glass material that influence is made; The preparation method who also has a kind of more general photocatalysis coating, this method comprise preparation silica sol and titanium oxide sol earlier, then after the dilution with silica sol and titanium oxide sol blend.For example, a kind of preparation method of nanometer composite titania/silica photocatalyst sol is disclosed among the CN 10108860A, this method adopts controlled hydrolysis to prepare the ortho-titanic acid precipitation, adding particle diameter then is silicon dioxide gel, the hydrogen peroxide of 8-30nm, and the pH value of regulating mixed liquor with inorganic base or inorganic acid is 2-10; Wherein, the volume ratio of ortho-titanic acid and silica aqueous sol is 1: 0.25-5, Ti: H
2O
2The molecule mole ratio be 1-8,40-100 ℃ of down heating 0.5-12 hour obtains composite titania/silica photocatalyst sol.
Above-mentioned preparation method's complex process, though and the coating film on glass material that makes improved photocatalysis performance, light is anti-reflection, and to penetrate effect relatively poor, promptly is difficult to satisfy simultaneously photochemical catalyst performance and the anti-reflection performance demands of penetrating.
Summary of the invention
The technical problem to be solved in the present invention overcomes the coating film on glass material that existing method makes and is difficult to satisfy simultaneously photocatalysis performance and anti-reflection defective of penetrating performance demands, provide a kind of be different from prior art prepare photocatalysis and the anti-reflection method of penetrating colloidal sol and preparing the coating film on glass material, the coating film on glass material that adopts this method to make to make has photocatalysis simultaneously and anti-reflectionly penetrates two kinds of functions, and hydrophily is also fine.
The invention provides a kind of photocatalysis and the anti-reflection preparation method who penetrates colloidal sol, wherein, this method comprises: with acidic oxidation Ludox and alkaline oxygenated Ludox with 1: the weight ratio of 0.5-10 mixes, obtain the mixed oxidization Ludox, the pH that regulates this mixed oxidization Ludox with organic acid is 4-7.5; With the weight ratio is 3-6: 1 ratio mixes described mixed oxidization Ludox and titanium oxide sol presoma, obtains the mixed sols of transparent clarification; The mixed sols and the coalescents of the transparent clarification that obtains are mixed, obtain photocatalysis and the anti-reflection colloidal sol of penetrating.
The present invention also provides a kind of coating film on glass preparation methods, and wherein, this method comprises that photocatalysis and the anti-reflection colloidal sol of penetrating that will utilize method provided by the invention to make be coated on the glass substrate, toasts 1-8 hour film-forming down at 200-500 ℃.
The inventor is surprised to find that, by the pH value of using organic acid to regulate the mixed oxidization Ludox, can improve the photocatalysis effect and the light transmittance of the coating film on glass material that makes, and hydrophily is also fine.And, of the present invention preferred embodiment in, use solid organic acid can further improve photocatalysis effect, transmitance and the hydrophily of the coating film on glass material that makes.
The hydrophilic angle of the coating film on glass material that method of the present invention makes is 4.6-10.1 °, and light transmittance exceeds 0.5-2 percentage point than the light transmittance of glass substrate, and has the photocatalysis effect of 20-30% conversion ratio.
The specific embodiment
The invention provides a kind of photocatalysis and the anti-reflection preparation method who penetrates colloidal sol, wherein, this method comprises: with acidic oxidation Ludox and alkaline oxygenated Ludox with 1: the weight ratio of 0.5-10 mixes, obtain the mixed oxidization Ludox, the pH that regulates this mixed oxidization Ludox with organic acid is 4-7.5; With the weight ratio is 3-6: 1 ratio mixes described mixed oxidization Ludox and titanium oxide sol presoma, obtains the mixed sols of transparent clarification; The mixed sols and the coalescents of the transparent clarification that obtains are mixed, obtain photocatalysis and the anti-reflection colloidal sol of penetrating.
Wherein, the pH value of described acidic oxidation Ludox generally can be 1-5.The preparation method of described acidic oxidation Ludox has been conventionally known to one of skill in the art, for example can make by the following method: the total amount with the acidic oxidation Ludox that makes is a benchmark, and first catalyst mix of the water of the absolute ethyl alcohol of the saturated or unsaturated esters of silicon acis of 20-40 weight %, 50-70 weight %, 5-15 weight % and 0.1-1 weight % is even.Described first catalyst can be in hydrochloric acid, nitric acid and the sulfuric acid one or more.
The pH value of described alkaline oxygenated Ludox generally can be 7.5-10.The preparation method of described alkaline oxygenated Ludox has been conventionally known to one of skill in the art, for example by can following method making: the total amount with the alkaline oxygenated Ludox that makes is a benchmark, and second catalyst mix of the water of the absolute ethyl alcohol of the saturated or unsaturated esters of silicon acis of 5-20 weight %, 70-90 weight %, 0.1-5 weight % and 0.1-5 weight % is even.Described second catalyst can be in NaOH, potassium hydroxide and the ammoniacal liquor one or more, is preferably ammoniacal liquor.
Employed described saturated or unsaturated esters of silicon acis can be ethyl orthosilicate in above-mentioned preparation acidic oxidation Ludox or the alkaline oxygenated Ludox, the methyl methoxy base silane, dimethyldimethoxysil,ne, the trimethyl methoxy silane, tetraethoxysilane, MTES, dimethyldiethoxysilane, trimethylethoxysilane, ethyl trimethoxy silane, diethyl dimethoxy silane, in triethyl group methoxy silane and the triethyl-ethoxy-silicane alkane one or more.
Described organic acid can be liquid organic acid and/or solid organic acid, from photocatalysis effect and the aspect consideration of transmitance, the preferably solid organic acid that can further improve the coating film on glass material that makes.Described liquid organic acid is meant and is liquid organic acid under the normal temperature that described solid organic acid is meant and is solid-state organic acid at normal temperatures.Described liquid organic acid can be ethanedioic acid; Described solid organic acid can be in fumaric acid, malic acid, glutaric acid, itaconic acid, succinic acid and the tartaric acid one or more.
Described titanium oxide sol presoma can make by the following method: with weight ratio is 10-20: after 1 absolute alcohol and titanate esters mix, mix with the stabilizing agent of the 1-2 times of weight of titanate esters, described stabilizing agent is used to make the decomposition rate of butyl titanate more steady, and described stabilizing agent can be in diethanol amine, triethanolamine, diglycol and the Diethylene Glycol one or more.Described titanate esters can be butyl titanate.
Among the present invention, in confined conditions, under 50-90 ℃ temperature, carry out as the step 1 that described mixed oxidization Ludox and titanium oxide sol presoma are mixed.
After making the mixed sols of transparent clarification, preferably the mixed sols ageing with described transparent clarification mixed with coalescents after 3-24 hour, obtained photocatalysis and the anti-reflection colloidal sol of penetrating, and can make SiO by ageing
2Granulating is more even.
Among the present invention, described coalescents can contain Triton X-100 and viscosity modifier, the consumption of wherein said Triton X-100 and described viscosity modifier makes, with resulting photocatalysis and anti-reflection total amount of penetrating colloidal sol is benchmark, the content of described Triton X-100 is 0.1-10 weight %, and the content of described viscosity modifier is 0.1-10 weight %.Described viscosity modifier just can be in polyethylene glycol, softex kw and the polyvinylpyrrolidone one or more.
The chemical formula of described Triton X-100 is C
14H
22O (C
2H
4O)
n, n can be the value arbitrarily that exists, and is generally the integer of 3-20, is preferably the integer of 5-20.Described Triton X-100 can be commercially available, and employed Triton X-100 is the triton x-100 available from 1Guanghua Chemical Plant Co., Ltd., Guangdong in the embodiment of the invention, and for analyzing pure M646.86, calculating n is 10; Available from the Qu Latong X-114 of Shanghai day firstling Science and Technology Ltd., for analyzing pure M426.59, calculating n is 5.
The number-average molecular weight of described polyethylene glycol can be 400-800, and described polyethylene glycol can be commercially available, and employed polyethylene glycol is for to analyze pure model available from the import packing of 1Guanghua Chemical Plant Co., Ltd., Guangdong in the embodiment of the invention, and molecular weight is 600; The PEG400 of Qingdao Tian Liyuan biological production and polyethylene glycol 800 (being that number-average molecular weight is respectively 400 and 800 polyethylene glycol).
The weight average molecular weight of described polyvinylpyrrolidone can be 20,000-3,500,000, described polyvinylpyrrolidone can be commercially available, and for example can be the polyvinylpyrrolidone available from Guangzhou brilliance chemistry Co., Ltd., Factory, and its weight average molecular weight is 20,000-3,500,000.
The present invention also provides a kind of coating film on glass preparation methods, and wherein, this method comprises that photocatalysis and the anti-reflection colloidal sol of penetrating that will utilize method provided by the invention to make be coated on the glass substrate, toasts 1-8 hour film-forming down at 200-500 ℃.Photocatalysis in the coating film on glass material that makes and the thickness that increases transmission film generally can be 150nm to 1 μ m.
The present invention will be described in more detail below by embodiment.
Embodiment 1
Present embodiment is used to illustrate photocatalysis provided by the invention and anti-reflection preparation method and coating film on glass preparation methods of penetrating colloidal sol.
1, photocatalysis and anti-reflection preparation of penetrating colloidal sol
(1) preparation of acidic oxidation Ludox
Get the 160g absolute ethyl alcohol and add 18g water and 2g nitric acid, the back that stirs drips the 72g ethyl orthosilicate in solution.Make the acidic oxidation Ludox, the pH value is between 2-3.
(2) preparation of alkaline oxygenated Ludox
Get the 130g absolute ethyl alcohol, add 1.5g ammoniacal liquor, add 2g water, stir, drip the 13g ethyl orthosilicate then.Make alkaline oxygenated Ludox, the pH value is 8.5.
(3) preparation of mixed oxidization Ludox
Get 80g acidic oxidation Ludox, get the alkaline oxygenated Ludox of 100g, in whipping process, will dropwise in the alkaline oxygenated Ludox oxytropism silica sol, add the 10g ethanedioic acid again and regulate the pH value, make that the pH value is 6.Be mixed with the mixed oxidization Ludox.
(4) preparation of titanium oxide sol presoma
Measure the 31g absolute ethyl alcohol and pour in the beaker, add the 2g butyl titanate, magnetic agitation 10min adds the 3.19g diethanol amine.Be mixed with the titanium oxide sol presoma.
(5) preparation of mixed sols
55 ℃ of heating of water-bath mixed oxidization Ludox, and under agitation to wherein dripping the titanium oxide sol presoma, drip fully, continue to stir, until the colloidal sol clarification, obtain the mixed sols of transparent clarification.
(6) photocatalysis and anti-reflection preparation of penetrating colloidal sol
With the mixed sols ageing of the above-mentioned transparent clarification that obtains after 5 hours, the PEG600 that adds 5g (promptly analyzes pure model available from the import packing of 1Guanghua Chemical Plant Co., Ltd., Guangdong, number-average molecular weight is 600 polyethylene glycol), the Triton X-100 of 10g is (available from the triton x-100 of 1Guanghua Chemical Plant Co., Ltd., Guangdong, for analyzing pure M646.86, calculating n is 10), stir 10min, obtain photocatalysis and the anti-reflection colloidal sol of penetrating;
The consumption of wherein said Triton X-100 and polyethylene glycol makes, is benchmark with resulting photocatalysis and anti-reflection total amount of penetrating colloidal sol, and the content of described Triton X-100 is 4.1 weight %, and the content of described polyethylene glycol is 2.1 weight %.
2, the preparation of coating film on glass material
Utilization lifts mode and (purchases in the ultra-clear glasses model of south, Dongguan glass solar glass Co., Ltd at glass substrate, average transmittance is 91.5672%) last above-mentioned photocatalysis that obtains and the anti-reflection colloidal sol of penetrating of applying, coating amount makes that photocatalysis in the coating film on glass material make and the thickness that increases transmission film are 200nm, toasted 2 hours down at 350 ℃, obtain coating film on glass materials A 1.
Embodiment 2
Present embodiment is used to illustrate photocatalysis provided by the invention and anti-reflection preparation method and coating film on glass preparation methods of penetrating colloidal sol.
1, photocatalysis and anti-reflection preparation of penetrating colloidal sol
(1) preparation of acidic oxidation Ludox
With similarly prepare the acidic oxidation Ludox among the embodiment 1, different is, changes the consumption of nitric acid, makes that the pH value is 2.5.
(2) preparation of alkaline oxygenated Ludox
With similarly prepare alkaline oxygenated Ludox among the embodiment 1, different is, changes the consumption of ammoniacal liquor, makes that the pH value is 8.
(3) preparation of mixed oxidization Ludox
Get 20g acidic oxidation Ludox, get the alkaline oxygenated Ludox of 100g, in whipping process, will dropwise in the alkaline oxygenated Ludox oxytropism silica sol, add the 12g butene dioic acid again and regulate the pH value, make that the pH value is 6.5.Be mixed with the mixed oxidization Ludox.
(4) preparation of titanium oxide sol presoma
Measure the 31g absolute ethyl alcohol and pour in the beaker, add the 2g butyl titanate, magnetic agitation 10min adds the 3.19g diethanol amine.Be mixed with the titanium oxide sol presoma.
(5) preparation of mixed sols
70 ℃ of heating of water-bath mixed oxidization Ludox, and under agitation to wherein dripping the titanium oxide sol presoma, drip fully, continue to stir, until the colloidal sol clarification, obtain the mixed sols of transparent clarification.
(6) photocatalysis and anti-reflection preparation of penetrating colloidal sol
With the mixed sols ageing of the above-mentioned transparent clarification that obtains after 10 hours, PEG400 (the PEG400 of Qingdao Tian Liyuan biological production that adds 6g, be that number-average molecular weight is 400 polyethylene glycol), the Triton X-100 of 10g is (available from the Qu Latong X-114 of Shanghai day firstling Science and Technology Ltd., for analyzing pure M426.59, calculating n is 5), stir 10min, obtain photocatalysis and the anti-reflection colloidal sol of penetrating;
The consumption of wherein said Triton X-100 and polyethylene glycol makes, is benchmark with resulting photocatalysis and anti-reflection total amount of penetrating colloidal sol, and the content of described Triton X-100 is 1 weight %, and the content of described polyethylene glycol is 1 weight %.
2, the preparation of coating film on glass material
Utilization lifts mode and apply above-mentioned photocatalysis that obtains and the anti-reflection colloidal sol of penetrating on glass substrate similarly to Example 1, the TiO in the feasible coating film on glass material that makes of coating amount
2/ SiO
2The thickness of composite membrane is 280nm, toasts 8 hours down at 200 ℃, obtains coating film on glass materials A 2.
Embodiment 3
Present embodiment is used to illustrate photocatalysis provided by the invention and anti-reflection preparation method and coating film on glass preparation methods of penetrating colloidal sol.
1, photocatalysis and anti-reflection preparation of penetrating colloidal sol
(1) preparation of acidic oxidation Ludox
With similarly prepare the acidic oxidation Ludox among the embodiment 1, different is, changes the consumption of nitric acid, makes that the pH value is 3.5.
(2) preparation of alkaline oxygenated Ludox
With similarly prepare alkaline oxygenated Ludox among the embodiment 1, different is, changes the consumption of ammoniacal liquor, makes that the pH value is 9.
(3) preparation of mixed oxidization Ludox
Get 10g acidic oxidation Ludox, get the alkaline oxygenated Ludox of 100g, in whipping process,, add 10g apple acid for adjusting pH value again, make that the pH value is 7 dropwising in the alkaline oxygenated Ludox oxytropism silica sol.Be mixed with the mixed oxidization Ludox.
(4) preparation of titanium oxide sol presoma
Measure the 31g absolute ethyl alcohol and pour in the beaker, add the 2g butyl titanate, magnetic agitation 10min adds the 3.19g diethanol amine.Be mixed with the titanium oxide sol presoma.
(5) preparation of mixed sols
90 ℃ of heating of water-bath mixed oxidization Ludox, and under agitation to wherein dripping the titanium oxide sol presoma, drip fully, continue to stir, until the colloidal sol clarification, obtain the mixed sols of transparent clarification.
(6) photocatalysis and anti-reflection preparation of penetrating colloidal sol
With the mixed sols ageing of the above-mentioned transparent clarification that obtains after 20 hours, the PEG800 that adds 10g (purchases in the polyethylene glycol 800 of Qingdao Tian Liyuan biological production, be that number-average molecular weight is 800 polyethylene glycol), 10g with embodiment 1 in same Triton X-100, stir 10min, obtain photocatalysis and the anti-reflection colloidal sol of penetrating;
The consumption of wherein said Triton X-100 and polyethylene glycol makes, is benchmark with resulting photocatalysis and anti-reflection total amount of penetrating colloidal sol, and the content of described Triton X-100 is 8 weight %, and the content of described polyethylene glycol is 8 weight %.
2, the preparation of coating film on glass material
Utilization lifts mode and apply above-mentioned photocatalysis that obtains and the anti-reflection colloidal sol of penetrating on glass substrate similarly to Example 1, the TiO in the feasible coating film on glass material that makes of coating amount
2/ SiO
2The thickness of composite membrane is 300nm, toasts 1 hour down at 500 ℃, obtains coating film on glass materials A 3.
Embodiment 4
Present embodiment is used to illustrate photocatalysis provided by the invention and anti-reflectionly penetrates the preparation method of colloidal sol and have photocatalysis and anti-reflection coating film on glass preparation methods of penetrating two kinds of functions.
Prepare photocatalysis and the anti-reflection colloidal sol and have photocatalysis and the anti-reflection coating film on glass material of penetrating two kinds of functions penetrated similarly to Example 1, different is when the preparation of step (3) mixed oxidization Ludox, to replace liquid ethanedioic acid with solid-state tartaric acid.Finally make and have photocatalysis and anti-reflection coating film on glass materials A 4 of penetrating two kinds of functions.
Comparative Examples 1
Prepare photocatalysis similarly to Example 1 and anti-reflectionly penetrate colloidal sol and have photocatalysis and an anti-reflection coating film on glass material of penetrating two kinds of functions, different is, save step (2), in step (3), acidic oxidation Ludox with 180g replaces 80g acidic oxidation Ludox and the alkaline oxygenated Ludox of 100g, regulating the pH value with ethanedioic acid is 3, and the colloidal sol that makes uses as the mixed oxidization Ludox.Finally make and have photocatalysis and the anti-reflection coating film on glass materials A C1 that penetrates two kinds of functions.
Comparative Examples 2
Prepare photocatalysis and the anti-reflection colloidal sol and have photocatalysis and the anti-reflection coating film on glass material of penetrating two kinds of functions penetrated similarly to Example 1, different is that when the preparation of step (3) mixed oxidization Ludox, the hydrochloric acid that is used as inorganic acid replaces liquid ethanedioic acid.Finally make and have photocatalysis and the anti-reflection coating film on glass materials A C2 that penetrates two kinds of functions.
Comparative Examples 3
This Comparative Examples is used to illustrate existing photocatalysis and anti-reflection preparation method and photocatalysis obtained by this method and the anti-reflection coating film on glass material of penetrating colloidal sol and making of penetrating colloidal sol that provides.
Prepare composite titania/silica photocatalyst sol according to the described method of embodiment among the CN 10108860A, and make coating film on glass materials A 3 according to the method described in the embodiment of the invention 1.
Performance test
1, light transmittance test
Adopt LCD-5200 photoelectric characteristic tester, scanning 380-780nm wave band, according to each wave band distribution character of the disclosed sunshine of GBT2680-1994, the coating film on glass materials A 1-A4 of test implementation example 1-4 and Comparative Examples 1-3 and AC1-AC3 surface are to the light transmittance of visible light, and the result is as shown in table 1 below.
The difference of the light transmittance of coating film on glass material and the light transmittance of glass baseplate is big more, illustrates that the photocatalysis that makes and the anti-reflection anti-reflection effect of penetrating of penetrating colloidal sol are good more.
Table 1
| The coating film on glass material | Light transmittance (%) | Poor (%) of the light transmittance of coating film on glass material and the light transmittance of glass baseplate | |
| Embodiment 1 | A1 | 92.9832 | 1.4160 |
| Embodiment 2 | A2 | 93.0311 | 1.4639 |
| Embodiment 3 | A3 | 92.1020 | 0.5348 |
| Embodiment 4 | A4 | 93.5616 | 1.9944 |
| Comparative Examples 1 | AC1 | 88.3264 | -3.2408 |
| Comparative Examples 2 | AC2 | 89.7831 | -1.7841 |
| Comparative Examples 3 | AC3 | 87.7831 | -3.7841 |
2, photocatalytic activity test
1) measures the methylene blue solution that 20ml concentration is 20mg/L respectively, be contained in the culture dish of 100ml;
2) coating film on glass materials A 1-A4 and AC1-AC3 are put into culture dish respectively, decide the placement location of coating film on glass material, make that luminous range is 10cm, guarantee that the intensity of illumination is even according to light source;
3) culture dish is placed under 18W uviol lamp and the 40W mercury lamp and carry out illumination, allow the coating film on glass material be subjected to identical light intensity as far as possible.Observe methylene blue solution degraded situation behind the illumination 4h.
4) irradiation experiment end back is settled to 20ml to the methylene blue solution after degrading, and carries out the absorbance test, test result contrast methylene blue concentration-absorbance curve, and the degradation rate of calculating methylene blue solution, the result is as shown in table 2 below.
The degradation rate of methylene blue solution is high more, illustrates that the automatically cleaning effect of the coating film on glass material that makes is good more, i.e. photocatalysis effect is good more.
Table 2
| The coating film on glass material | The degradation rate of methylene blue solution (%) | |
| Embodiment 1 | A1 | 23 |
| Embodiment 2 | A2 | 20 |
| Embodiment 3 | A3 | 30 |
| Embodiment 4 | A4 | 28 |
| Comparative Examples 1 | AC1 | 15 |
| Comparative Examples 2 | AC2 | 18 |
| Comparative Examples 3 | AC3 | 24 |
3, hydrophilic angular measurement examination
With model is the full-automatic video microcosmic contact angle measurement difference tested glass Coating Materials A1-A4 of OCA40 and the hydrophilic angle of AC1-AC3.
Hydrophilic angle is more little, illustrates that the hydrophily of coating film on glass material is good more, has illustrated that the coating film on glass material is strong more to the automatically cleaning ability of water-soluble dirt.
Table 3
| The coating film on glass material | Hydrophilic angle (°) | |
| Embodiment 1 | A1 | 10.1 |
| Embodiment 2 | A2 | 7.2 |
| Embodiment 3 | A3 | 4.6 |
| Embodiment 4 | A4 | 5.3 |
| Comparative Examples 1 | AC1 | 13.6 |
| Comparative Examples 2 | AC2 | 14.3 |
| Comparative Examples 3 | AC3 | 9 |
From the table 1-3 data as can be seen, though the coating film on glass materials A C1 that makes with the Comparative Examples 1 of acidic oxidation Ludox and used the acidic oxidation Ludox and alkaline oxygenated Ludox only, light transmittance, photocatalytic activity and the hydrophily of regulating the coating film on glass materials A C2 that the Comparative Examples 2 of the pH value of mixed oxidization Ludox makes with inorganic acid are all good not as the coating film on glass materials A 1-A4 that embodiment of the invention 1-3 makes.
In addition, from the data of table 1-3 as can be seen, it is all good than the coating film on glass materials A 1 that the embodiment 1 that regulates the pH value of mixed oxidization Ludox with liquid organic acid makes to regulate light transmittance, photocatalytic activity and the hydrophily of the coating film on glass materials A 4 that the embodiment 4 of the pH value of mixed oxidization Ludox makes with solid organic acid.
In addition, from the table 1-3 data as can be seen, photocatalytic activity and the hydrophily of the coating film on glass materials A C3 that the composite titania/silica photocatalyst sol for preparing with existing method makes are suitable with embodiment, but the light transmittance of coating film on glass materials A C3 has reduced by 3.7841% than the light transmittance of glass substrate, and the coating film on glass materials A 1 that embodiment 1 makes has increased by 1.4160% than the light transmittance of glass substrate, improved photocatalysis performance though coating film on glass materials A C3 has been described, light is anti-reflection, and to penetrate effect relatively poor.
Claims (13)
1. a photocatalysis and the anti-reflection preparation method who penetrates colloidal sol is characterized in that this method comprises:
With acidic oxidation Ludox and alkaline oxygenated Ludox with 1: the weight ratio of 0.5-10 mixes, and obtains the mixed oxidization Ludox, and the pH that regulates this mixed oxidization Ludox with organic acid is 4-7.5;
With the weight ratio is 3-6: 1 ratio mixes described mixed oxidization Ludox and titanium oxide sol presoma, obtains the mixed sols of transparent clarification;
The mixed sols and the coalescents of the transparent clarification that obtains are mixed, obtain photocatalysis and the anti-reflection colloidal sol of penetrating.
2. method according to claim 1, wherein, the pH value of described acidic oxidation Ludox is 1-5, the pH value of described alkaline oxygenated Ludox is 7.5-10.
3. method according to claim 2, wherein, described acidic oxidation Ludox makes by the following method:
Total amount with the acidic oxidation Ludox that makes is a benchmark, first catalyst mix of the water of the absolute ethyl alcohol of the saturated or unsaturated esters of silicon acis of 20-40 weight %, 50-70 weight %, 5-15 weight % and 0.1-1 weight % is even, and described first catalyst is one or more in hydrochloric acid, nitric acid and the sulfuric acid.
4. method according to claim 2, wherein, described alkaline oxygenated Ludox makes by the following method:
Total amount with the alkaline oxygenated Ludox that makes is a benchmark, second catalyst mix of the water of the absolute ethyl alcohol of the saturated or unsaturated esters of silicon acis of 5-20 weight %, 70-90 weight %, 0.1-5 weight % and 0.1-5 weight % is even, and described second catalyst is one or more in NaOH, potassium hydroxide and the ammoniacal liquor.
5. according to claim 3 or 4 described methods, wherein, described saturated or unsaturated esters of silicon acis is one or more in ethyl orthosilicate, methyl methoxy base silane, dimethyldimethoxysil,ne, trimethyl methoxy silane, tetraethoxysilane, MTES, dimethyldiethoxysilane, trimethylethoxysilane, ethyl trimethoxy silane, diethyl dimethoxy silane, triethyl group methoxy silane and the triethyl-ethoxy-silicane alkane.
6. method according to claim 1, wherein, described organic acid is liquid organic acid and/or solid organic acid.
7. method according to claim 6, wherein, described liquid organic acid is an ethanedioic acid; Described solid organic acid is one or more in fumaric acid, malic acid, glutaric acid, itaconic acid, succinic acid and the tartaric acid.
8. method according to claim 1, wherein, described titanium oxide sol presoma makes by the following method:
With weight ratio is 10-20: after 1 absolute alcohol and titanate esters mix, mix with the stabilizing agent of the 1-2 times of weight of titanate esters, described stabilizing agent is one or more in diethanol amine, triethanolamine, diglycol and the Diethylene Glycol.
9. method according to claim 8, wherein, described titanate esters is a butyl titanate.
10. method according to claim 1, wherein, the step that described mixed oxidization Ludox and titanium oxide sol presoma are mixed is carried out under 50-90 ℃ temperature in confined conditions.
11. method according to claim 1, wherein, described coalescents contains Triton X-100 and viscosity modifier; The consumption of wherein said Triton X-100 and described viscosity modifier makes, with resulting photocatalysis and anti-reflection total amount of penetrating colloidal sol is benchmark, the content of described Triton X-100 is 0.1-10 weight %, and the content of described viscosity modifier is 0.1-10 weight %; The chemical formula of described Triton X-100 is C
14H
22O (C
2H
4O)
n, n is 3-20.
12. method according to claim 11, wherein, described viscosity modifier is one or more in polyethylene glycol, softex kw and the polyvinylpyrrolidone; The number-average molecular weight of described polyethylene glycol is 400-800; The weight average molecular weight of described polyvinylpyrrolidone is 20,000-3,500,000.
13. coating film on glass preparation methods, it is characterized in that, this method comprises and will utilize photocatalysis and the anti-reflection colloidal sol of penetrating that any described method makes among the claim 1-12 to be coated on the glass substrate, toasts 1-8 hour film-forming down at 200-500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910266057 CN102114419B (en) | 2009-12-30 | 2009-12-30 | Preparation method of photocatalysis and transmission increasing sol and glass coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910266057 CN102114419B (en) | 2009-12-30 | 2009-12-30 | Preparation method of photocatalysis and transmission increasing sol and glass coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102114419A true CN102114419A (en) | 2011-07-06 |
| CN102114419B CN102114419B (en) | 2013-01-30 |
Family
ID=44213406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910266057 Active CN102114419B (en) | 2009-12-30 | 2009-12-30 | Preparation method of photocatalysis and transmission increasing sol and glass coating material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102114419B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173043A (en) * | 2013-03-22 | 2013-06-26 | 扬州明晟新能源科技有限公司 | Production method with coating liquid for improving luminous flux of lamp glass |
| CN103468086A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | SiO2 based self-cleaning paint, self-cleaning glass and preparation method thereof |
| CN103468109A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | Preparation method of self-cleaning coating and self-cleaning glass |
| CN106381051A (en) * | 2016-08-23 | 2017-02-08 | 杭州国为光伏技术有限公司 | Photovoltaic coated glass protective solution, preparation method and application thereof |
| KR102233580B1 (en) * | 2020-12-11 | 2021-03-30 | 주식회사 태성콘텍 | (Photocatalyst Coating Agent, Manufacturing Method thereof and Concrete Block Coated thereby |
| CN117430976A (en) * | 2023-12-21 | 2024-01-23 | 浙江大华技术股份有限公司 | Composite material, inorganic composite film layer, optical window and preparation method |
| CN117430342A (en) * | 2023-12-21 | 2024-01-23 | 浙江大华技术股份有限公司 | Composite material, functional glass and preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284833C (en) * | 2005-04-07 | 2006-11-15 | 上海交通大学 | Method for preparing ultra hydrophilic coat of titanium dioxide by using tetrabutyl titanatc as precursor |
| CN100363437C (en) * | 2006-01-06 | 2008-01-23 | 浙江大学 | Method for preparing silicon-titanium micro-coarse structured hydrophilic film |
| CN100531898C (en) * | 2006-06-12 | 2009-08-26 | 中国科学院理化技术研究所 | Preparation process of nanometer composite titania/silica photocatalyst sol and transparent photocatalytic film |
-
2009
- 2009-12-30 CN CN 200910266057 patent/CN102114419B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173043A (en) * | 2013-03-22 | 2013-06-26 | 扬州明晟新能源科技有限公司 | Production method with coating liquid for improving luminous flux of lamp glass |
| CN103468086A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | SiO2 based self-cleaning paint, self-cleaning glass and preparation method thereof |
| CN103468109A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | Preparation method of self-cleaning coating and self-cleaning glass |
| CN103468086B (en) * | 2013-08-12 | 2015-07-29 | 广东南亮玻璃科技有限公司 | SiO 2base self-cleaning coating and self-cleaning glass and preparation method thereof |
| CN103468109B (en) * | 2013-08-12 | 2015-07-29 | 广东南亮玻璃科技有限公司 | The preparation method of self-cleaning coating and self-cleaning glass |
| CN106381051A (en) * | 2016-08-23 | 2017-02-08 | 杭州国为光伏技术有限公司 | Photovoltaic coated glass protective solution, preparation method and application thereof |
| CN106381051B (en) * | 2016-08-23 | 2018-12-11 | 杭州国为光伏技术有限公司 | A kind of photovoltaic coated glass protection liquid and its preparation method and application |
| KR102233580B1 (en) * | 2020-12-11 | 2021-03-30 | 주식회사 태성콘텍 | (Photocatalyst Coating Agent, Manufacturing Method thereof and Concrete Block Coated thereby |
| CN117430976A (en) * | 2023-12-21 | 2024-01-23 | 浙江大华技术股份有限公司 | Composite material, inorganic composite film layer, optical window and preparation method |
| CN117430342A (en) * | 2023-12-21 | 2024-01-23 | 浙江大华技术股份有限公司 | Composite material, functional glass and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102114419B (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102114419B (en) | Preparation method of photocatalysis and transmission increasing sol and glass coating material | |
| CN103031008B (en) | A kind of preparation method of antireflective plated film colloidal sol of self-cleaning high permeability bilayer | |
| US11442200B2 (en) | Low-reflection coated glass sheet, method for producing low-reflection coated substrate, and coating liquid for forming low-reflection coating of low-reflection coated substrate | |
| CN101549959B (en) | A method of nano self-cleaning glass production in the float glass production line | |
| US8999447B2 (en) | Method for manufacturing soil-resistant glass and soil-resistant glass | |
| CN110272645B (en) | Recoating anti-reflection super-hydrophobic coating and preparation method and application thereof | |
| CN106348616A (en) | Preparation method of SiO2/TiO2 antireflection film | |
| CN103496223A (en) | Antifog self-cleaning glass and preparation method thereof | |
| CN107285640A (en) | Enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power and preparation method thereof | |
| CN103508681B (en) | The preparation method of super hydrophilic antireflecting coating and super hydrophilic antireflecting coating | |
| CN104692671A (en) | Preparation method of super-hydrophobic self-cleaning glass based on ZnO nano array coating | |
| CN106291779A (en) | A kind of preparation method with high intensity wet-heat resisting cleaning anti-reflection coating | |
| CN100999624B (en) | Compounding of inorganic anti-pollution coating for high pressure insulator surface and preparation process thereof | |
| CA2735747A1 (en) | Titanium dioxide coatings and methods of forming titanium dioxide coatings having reduced crystallite size | |
| CN104071988B (en) | The preparation method of wear-resisting long-acting self-cleaning anti-reflection coating and wear-resisting long-acting self-cleaning anti-reflection coating | |
| CN109942205B (en) | Preparation method of anti-reflection self-cleaning coating on glass surface | |
| CN102219393A (en) | Mesoporous antireflective film and transparent conducting film composite coated glass and coating method thereof | |
| CN105070769B (en) | One has bionical bulge-structure SiO2the preparation method of antireflective coating | |
| CN114806238B (en) | Super-hydrophilic wear-resistant composite anti-reflection anti-fog coating and preparation method and application thereof | |
| WO2016002215A1 (en) | Low-reflection coating, substrate provided with low-reflection coating, and photoelectric conversion device | |
| CN106745227B (en) | Visible-light response nano TiO2And the preparation method of the self-cleaning ceramic film containing it | |
| CN103447017B (en) | Laser modification treatment process of titanium oxide photocatalytic film | |
| CN110040978B (en) | Preparation process of self-cleaning antifogging glass | |
| CN103555010B (en) | A kind of visible light-responded self-cleaning coating and manufacture method thereof | |
| CN110396309A (en) | TiOx nano porous coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |