CN100500603C - Method for preparing nano multiple films on surface of glass - Google Patents
Method for preparing nano multiple films on surface of glass Download PDFInfo
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- CN100500603C CN100500603C CNB2005100426202A CN200510042620A CN100500603C CN 100500603 C CN100500603 C CN 100500603C CN B2005100426202 A CNB2005100426202 A CN B2005100426202A CN 200510042620 A CN200510042620 A CN 200510042620A CN 100500603 C CN100500603 C CN 100500603C
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Abstract
The present invention relates to a method for preparing nano multilayer film on glass surface. Said invention utilizes the combination of sol-gel method and spray pyrolysis method to prepare first layer silicon dioxide film, second layer antimony-fluorine combination doped tin dioxide film and third layer composite film using silicon dioxide and titanium dioxide as main component. Said invention also provides the concrete function of the above-mentioned energy layer film, and said glass has the hydrophobic and bacteriostatic characteristics.
Description
Technical field
The present invention relates to a kind of preparation method of glass surface film, particularly a kind of preparation method of nano multiple films on surface of glass.
Background of invention
The transparent conductive substrate that adopts in flat-panel display devices such as the liquid crystal of photoelectron industry, plasma is to prepare the oxide-based transparent conductive film of one deck at glass surface, the kind of this type oxide transparent conductive film is a lot, as: the Indium sesquioxide (ITO) of adulterated stannic oxide, adulterated zinc oxide and tin dope etc.In the industrial application, take into account electroconductibility and light transmission, this class film mainly adopts the Indium sesquioxide (ITO) of tin dope at present, owing to contain the rare elements indium, cost is higher.Its preparation method mainly adopts magnetron sputtering, chemical vapour deposition, sol-gel method, spray pyrolysis etc., wherein: magnetron sputtering, chemical vapour deposition need to carry out in vacuum or the chemical reaction chamber, have very big difficulty aspect the preparation large area film, and cost is higher; Though sol-gel method and spray pyrolysis can prepare large area film, the electroconductibility of film, light transmission and homogeneity are relatively poor, and production efficiency is lower.
In the preparation of low radiation (Low-E) glass such as cladding glass of construction industry, also be to prepare the layer of transparent conductive film at glass surface, it mainly is metal (Ag etc.) coating that its core constitutes, have the ir radiation ability that good reflection comes from the outside, compare with oxide-based coating, the metallic coating hardness of this class glass surface is very low, scrubbing resistance not, not corrosion-resistant, adopt the form of double glazing to use usually, cost is higher.
In addition, in the preparation of the windshield glass of automobile industry, also be printing or glue and wire belt on glass substrate, finish demist, snow removing by electrically heated.Because this method affect sight line is mainly used in can't using on front windshield on the rear seat windscreen of automobile.The demist of front windshield mainly relies on air blast, and effect and efficient are relatively poor.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of suitable large-area glass off-line coated deep processing, the also online large-area coating film production of suitable existing floatation glass production line, coated glass is being possessed outside the characteristic of electrically conducting transparent, have the preparation method of the nano multiple films on surface of glass of detesting water, composite environmental-friendly functional performance such as antibacterial simultaneously.
For achieving the above object, the preparation method that the present invention adopts is:
1) preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel, the mixed in molar ratio that said tetraethoxy, carbon chain lengths are pressed 1:10～25:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:40～80 with stannous chloride dihydrate or four water tin chlorides and deionized water dissolving carbon chain lengths less than 4 short carbon chain alcohol in, in isothermal reactor, stirred 20～24 hours in 60～80 ℃, be that benchmark 1 adds the fluorine-containing organic acid or derivatives thereof that mol ratio is 0.1～0.4:0.02～0.06:40～80 respectively with stannous chloride dihydrate or four water tin chlorides again, the muriatic carbon chain lengths of antimony is less than 4 short carbon chain alcohol solution, under 80～90 ℃ of constant temperature, continue to stir 3～6 hours, be cooled to 30～40 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio of pressing 1:20～40:0.01 is at metatitanic acid fourth fat Ti (OBu)
4Or titanium tetrachloride TiCl
4And carbon chain lengths is less than adding organic acid or mineral acid in 4 the short carbon chain alcohol, at room temperature in sealed vessel, stirred 4～6 hours, 40～50 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 2～4 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:0.2～4, obtain the silica-titania complex sol; Step 1)-3) carbon chain lengths in less than 4 short carbon chain alcohol employed be with a kind of alcohol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 300～600 ℃ in the process furnace;
Adopt liquid pressure pump to be pressurized to 0.1～0.5MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, the control silica membrane is 40～80nm at the thickness of glass baseplate surface;
The tindioxide colloidal sol that antimony-fluorine is composite mixed adopts pressure pump to be pressurized to 0.1～0.5MPa and to be transported to the atomizing lance head, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, the composite mixed tin dioxide thin film of control antimony-fluorine is 100～300nm at the thickness of glass baseplate surface;
Adopt pressure pump to be pressurized to 0.1～0.5MPa and to be transported to the atomizing lance head silica-titania complex sol, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, control silica-titania laminated film is 20～60nm at the thickness of glass baseplate surface.
Another characteristics of the present invention are: carbon chain lengths is ethanol, b propanol, propyl carbinol or methyl alcohol less than 4 short carbon chain alcohol; Organic acid or mineral acid are that fluorine-containing organic acid of hydrochloric acid, nitric acid, acetate or oxalic acid and derivative thereof are trifluoroacetic acid, hydrofluosillicic acid, Neutral ammonium fluoride or fluorobenzene; The muriate of antimony is butter of antimony or antimony pentachloride; High pressure draft is air, nitrogen or oxygen.
The present invention combines sol-gel method with spray pyrolysis: adopt multiple doping to improve optics, the electric property and functional of thin film coating in the colloidal sol preparation; In the spray pyrolysis process, adopt fine atomizing to improve thin film deposition homogeneity and compactness; On film layer structure, adopt nano-multilayer film to deaden that foreign ion is possessing outside the characteristic of electrically conducting transparent coated glass to the diffusion of conductive membrane layer in the glass substrate, can have the water of detesting, composite environmental-friendly functional performance such as antibacterial simultaneously.Can be used for the windshield, function composite environmental protection glass curtain wall of transparent conductive substrate that the photoelectron industry uses, demist snow removing etc.
Embodiment
Embodiment 1: the surface of ordinary glass plated film
1) preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel; Tetraethoxy, carbon chain lengths are done the mixed in molar ratio of catalyzer by 1:15:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:40 with stannous chloride dihydrate and deionized water dissolving in ethanol, in isothermal reactor, stirred 20 hours in 80 ℃, adding mol ratio more respectively is the trifluoroacetic acid of 0.1:0.03:40, the ethanol solution of butter of antimony, under 90 ℃ of constant temperature, continue to stir 3 hours, be cooled to 40 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio of pressing 1:40:0.01 is at metatitanic acid fourth fat (Ti (OBu)
4Ethanol in add hydrochloric acid, at room temperature in sealed vessel, stirred 6 hours, 50 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 4 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:2, obtain the silica-titania complex sol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 300 ℃ in the air furnace;
A, adopt hydro-pump to be pressurized to 0.1MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high-pressure air thorough mixing of 3Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 40cm, the control silica membrane is 40nm at the thickness of glass baseplate surface;
B, tindioxide colloidal sol that antimony-fluorine is composite mixed are with the condition of above-mentioned A process, and the composite mixed tin dioxide thin film of control antimony-fluorine is 200nm at the thickness of glass baseplate surface;
C, with the condition of silica-titania complex sol with above-mentioned A process, control silica-titania laminated film is 40nm at the thickness of glass baseplate surface.
Finish coating process, just obtain having transparent, conduction, antibacterial, the multi-layer nano function laminated film glass of detesting water.
Embodiment 2: the toughened glass surface coating
The preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel; Tetraethoxy, carbon chain lengths are done the mixed in molar ratio of catalyzer by 1:20:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:40 with four water tin chlorides and deionized water dissolving in b propanol, in isothermal reactor, stirred 23 hours in 70 ℃, add the hydrofluosillicic acid that mol ratio is 0.3:0.02:80, the b propanol solution of antimony pentachloride more respectively, under 82 ℃ of constant temperature, continue to stir 5 hours, be cooled to 35 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio by 1:30:0.01 adds nitric acid, at room temperature stirred 4 hours in sealed vessel in the b propanol of titanium tetrachloride, 40 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 2 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:0.2, obtain the silica-titania complex sol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 420 ℃ in the radiant-type furnace;
A, adopt magnetic drive pump to be pressurized to 0.2MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high pressure nitrogen thorough mixing of 5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 30cm, the control silica membrane is 80nm at the thickness of glass baseplate surface;
B, tindioxide colloidal sol that antimony-fluorine is composite mixed are with the condition of above-mentioned A process, and the composite mixed tin dioxide thin film of control antimony-fluorine is 100nm at the thickness of glass baseplate surface;
C, with the condition of silica-titania complex sol with above-mentioned A process, control silica-titania laminated film is 50nm at the thickness of glass baseplate surface.
Finish the toughened glass that coating process just obtains having transparent, conduction, antibacterial, the multi-layer nano function laminated film of detesting water.
Embodiment 3: the coated toughened glass of tempering behind the pre-plated film
The preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel; Tetraethoxy, carbon chain lengths are done the mixed in molar ratio of catalyzer by 1:25:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:80 with stannous chloride dihydrate and deionized water dissolving in propyl carbinol, in isothermal reactor, stirred 22 hours in 60 ℃, adding mol ratio more respectively is the Neutral ammonium fluoride of 0.2:0.04:40, the butanol solution of butter of antimony, under 88 ℃ of constant temperature, continue to stir 4 hours, be cooled to 32 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio of pressing 1:40:0.01 is at metatitanic acid fourth fat (Ti (OBu)
4Propyl carbinol in add acetate, at room temperature in sealed vessel, stirred 5 hours, 48 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 3 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:4, obtain the silica-titania complex sol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 500 ℃ in the air furnace;
A, adopt surge pump to be pressurized to 0.3MPa silicon dioxide gel and be transported to the atomizing lance head, behind 4Mpa high pressure oxygen thorough mixing, carry out atomizing spraying, deposit to the glass surface at a distance of 50cm, the control silica membrane is 50nm at the thickness of glass baseplate surface;
B, tindioxide colloidal sol that antimony-fluorine is composite mixed are with the condition of above-mentioned A process, and the composite mixed tin dioxide thin film of control antimony-fluorine is 150nm at the thickness of glass baseplate surface;
C, with the condition of silica-titania complex sol with above-mentioned A process, control silica-titania laminated film is 20nm at the thickness of glass baseplate surface.
Insert follow-up glass tempering and handle line, carry out tempering and handle.Just obtain having transparent, conduction, bacteriostatic multi-layer nano function laminated film toughened glass.
Embodiment 4: the conducting glass substrate surface coating
The preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel; Tetraethoxy, carbon chain lengths are done the mixed in molar ratio of catalyzer by 1:10:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:40 with four water tin chlorides and deionized water dissolving in methyl alcohol, in isothermal reactor, stirred 24 hours in 75 ℃, adding mol ratio more respectively is the fluorobenzene of 0.2:0.06:40, the methanol solution of antimony pentachloride, under 80 ℃ of constant temperature, continue to stir 6 hours, be cooled to 30 ℃ still aging more than 8 hours;
3) film preparation
With the glass substrate of cleaning, insert and be heated to 380 ℃ in the radiant-type furnace;
A, adopt hydro-pump to be pressurized to 0.5MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high-pressure air thorough mixing of 3.5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 60cm, the control silica membrane is 60nm at the thickness of glass baseplate surface;
B, tindioxide colloidal sol that antimony-fluorine is composite mixed are with the condition of above-mentioned A process, and the composite mixed tin dioxide thin film of control antimony-fluorine is 180nm at the thickness of glass baseplate surface;
Finish coating process and just obtain having multi-layer nano function film glass transparent, conduction.
Embodiment 5: the windshield transparent conducting glass
The preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel; Tetraethoxy, carbon chain lengths are done the mixed in molar ratio of catalyzer by 1:15:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:60 with four water tin chlorides and deionized water dissolving in ethanol, in isothermal reactor, stirred 20 hours in 65 ℃, adding mol ratio more respectively is the trifluoroacetic acid of 0.4:0.04:60, the ethanolic soln of butter of antimony, under 85 ℃ of constant temperature, continue to stir 4.5 hours, be cooled to 37 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio of pressing 1:20:0.01 is at metatitanic acid fourth fat (Ti (OBu)
4Ethanol in add hydrochloric acid, at room temperature in sealed vessel, stirred 4.5 hours, 45 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 2.5 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:3, obtain the silica-titania complex sol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 600 ℃ in the radiant-type furnace;
A, adopt magnetic drive pump to be pressurized to 0.4MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high-pressure air thorough mixing of 4.5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20cm, the control silica membrane is 70nm at the thickness of glass baseplate surface;
B, tindioxide colloidal sol that antimony-fluorine is composite mixed are with the condition of above-mentioned A process, and the composite mixed tin dioxide thin film of control antimony-fluorine is 300nm at the thickness of glass baseplate surface;
C, with the condition of silica-titania complex sol with above-mentioned A process, control silica-titania laminated film is 60nm at the thickness of glass baseplate surface.
Insert follow-up glass tempering and handle line, carry out tempering and handle.Just obtain having transparent, conduction, bacteriostatic multi-layer nano function laminated film tempering windshield.
The thickness of each layer film of the present invention can be controlled with the concentration of adjusting colloidal sol, the flow or the spray deposition time of colloidal sol according to glass substrate.
The present invention combines sol-gel method and prepare silicon-dioxide, composite mixed tindioxide, the silica-titania multi-layer nano film of antimony-fluorine on glass substrate with spray pyrolysis.
The thick about 40～80nm of the first layer silica membrane wherein, main effect is to deaden elements such as sodium in the glass substrate, potassium, iron to spread in the film to being coated with subsequently, improves between rete the bonding interface characteristic simultaneously and improves transmittance.The second layer is the composite mixed tin dioxide thin film of preparation thickness about 100～300nm left and right sides antimony-fluorine, realize the electrically conducting transparent characteristic and the electrically heated characteristic of glass substrate, the 3rd layer is that the silica-titania of preparation thickness about 20～60nm is main laminated film, makes glass have the water of detesting, antagonistic property.
The present invention's off-line coated deep processing of large-area glass that suits, for the coated glass that the tempering requirement is arranged, technology provided by the invention all can be carried out plated film, the also online large-area coating film production of suitable existing floatation glass production line in that the tempering of glass is forward and backward.
Claims (6)
1, the preparation method of nano multiple films on surface of glass is characterized in that:
1) preparation of silicon dioxide gel: at first tetraethoxy, carbon chain lengths are mixed with deionized water less than 4 short carbon chain alcohol and add organic acid again or mineral acid is made catalyzer, in encloses container, mix under the room temperature, make it add water decomposition and polyreaction, make silicon dioxide gel, the mixed in molar ratio that said tetraethoxy, carbon chain lengths are pressed 1:10～25:4:0.05 less than 4 short carbon chain alcohol, deionized water and organic acid or mineral acid;
2) preparation of the composite mixed tindioxide colloidal sol of antimony-fluorine: the mol ratio of pressing 1:2:40～80 with stannous chloride dihydrate or four water tin chlorides and deionized water dissolving carbon chain lengths less than 4 short carbon chain alcohol in, in isothermal reactor, stirred 20～24 hours in 60～80 ℃, be that benchmark 1 adds the fluorine-containing organic acid or derivatives thereof that mol ratio is 0.1～0.4:0.02～0.06:40～80 respectively with stannous chloride dihydrate or four water tin chlorides again, the muriatic carbon chain lengths of antimony is less than 4 short carbon chain alcohol solution, under 80～90 ℃ of constant temperature, continue to stir 3～6 hours, be cooled to 30～40 ℃ still aging more than 8 hours;
3) silica-titania complex sol preparation: the mol ratio of pressing 1:20～40:0.01 is at metatitanic acid fourth fat Ti (OBu)
4Or titanium tetrachloride TiCl
4And carbon chain lengths is less than adding organic acid or mineral acid in 4 the short carbon chain alcohol, at room temperature in sealed vessel, stirred 4～6 hours, 40～50 ℃ of ageings more than 8 hours, obtain TiO 2 sol, again TiO 2 sol was mixed, stirs 2～4 hours with the molar ratio of silicon dioxide gel according to Si:Ti=1:0.2～4, obtain the silica-titania complex sol; Step 1)-3) carbon chain lengths in less than 4 short carbon chain alcohol employed be with a kind of alcohol;
4) film preparation
With the glass substrate of cleaning, insert and be heated to 300～600 ℃ in the process furnace;
Adopt liquid pressure pump to be pressurized to 0.1～0.5MPa silicon dioxide gel and be transported to the atomizing lance head, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, the control silica membrane is 40～80nm at the thickness of glass baseplate surface;
The tindioxide colloidal sol that antimony-fluorine is composite mixed adopts pressure pump to be pressurized to 0.1～0.5MPa and to be transported to the atomizing lance head, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, the composite mixed tin dioxide thin film of control antimony-fluorine is 100～300nm at the thickness of glass baseplate surface;
Adopt pressure pump to be pressurized to 0.1～0.5MPa and to be transported to the atomizing lance head silica-titania complex sol, behind the high pressure draft thorough mixing of 3～5Mpa, carry out atomizing spraying, deposit to the glass surface at a distance of 20～60cm, control silica-titania laminated film is 20～60nm at the thickness of glass baseplate surface.
2, the preparation method of nano multiple films on surface of glass according to claim 1 is characterized in that: said carbon chain lengths is ethanol, b propanol, propyl carbinol or methyl alcohol less than 4 short carbon chain alcohol.
3, the preparation method of nano multiple films on surface of glass according to claim 1 is characterized in that: said organic acid or mineral acid are hydrochloric acid, nitric acid, acetate or oxalic acid.
4, the preparation method of nano multiple films on surface of glass according to claim 1 is characterized in that: said fluorine-containing organic acid and derivative thereof are trifluoroacetic acid, hydrofluosillicic acid, Neutral ammonium fluoride or fluorobenzene.
5, the preparation method of nano multiple films on surface of glass according to claim 1 is characterized in that: the muriate of said antimony is butter of antimony or antimony pentachloride.
6, the preparation method of nano multiple films on surface of glass according to claim 1 is characterized in that: said high pressure draft is air, nitrogen or oxygen.
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| 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 |
| FI20061014A0 (en) * | 2006-11-17 | 2006-11-17 | Beneq Oy | Process for diffusion coating |
| CN101003420B (en) * | 2007-01-04 | 2010-12-15 | 上海工程技术大学 | Technique for preparing Nano Sn02/Ti02 composite film in use for photovoltaic conversion |
| FI123798B (en) * | 2007-04-23 | 2013-10-31 | Beneq Oy | Energy saving glass and a method of making it |
| CN101070226B (en) * | 2007-06-22 | 2012-01-25 | 中国洛阳浮法玻璃集团有限责任公司 | Producing method of low-radiation self-cleaning composite function glass |
| KR101455890B1 (en) * | 2007-07-23 | 2014-11-03 | 아사히 가라스 가부시키가이샤 | Float glass making process and float glass making equipment |
| CN101894601B (en) * | 2010-06-10 | 2011-11-02 | 泰阳电子(东莞)有限公司 | Transparent conductive film and preparation method thereof |
| CN103183480A (en) * | 2011-12-28 | 2013-07-03 | 上海北玻玻璃技术工业有限公司 | Preparation method for AZO coated glass |
| CN103936059B (en) * | 2014-03-20 | 2015-08-26 | 扬州明晟新能源科技有限公司 | A kind of preparation method of SnO 2 thin film |
| CN108249779B (en) * | 2018-03-21 | 2023-12-08 | 上海耀皮玻璃集团股份有限公司 | Coating layer capable of realizing electric heating, coated glass comprising coating layer, electric heating glass and application |
| CN109534687A (en) * | 2019-01-11 | 2019-03-29 | 中建材（宜兴）新能源有限公司 | A kind of high dust-proof film liquid and preparation method thereof thoroughly of photovoltaic glass |
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