CN115477478A - Solar control coated glass and online preparation method thereof - Google Patents
Solar control coated glass and online preparation method thereof Download PDFInfo
- Publication number
- CN115477478A CN115477478A CN202211166130.3A CN202211166130A CN115477478A CN 115477478 A CN115477478 A CN 115477478A CN 202211166130 A CN202211166130 A CN 202211166130A CN 115477478 A CN115477478 A CN 115477478A
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- China
- Prior art keywords
- glass
- gas
- coated glass
- solar control
- control coated
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000002834 transmittance Methods 0.000 abstract description 12
- 238000006298 dechlorination reaction Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 21
- 239000002131 composite material Substances 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
Abstract
The invention relates to a glass coating process, in particular to solar control coated glass and an online preparation method thereof. The online preparation method comprises the step of spraying mixed gas consisting of tetraisopropyl titanate, ammonia gas and nitrogen gas on the surface of glass to form a mixed film consisting of titanium dioxide and titanium nitride on the surface of the glass. The online preparation method provided by the invention does not need to carry out additional dephosphorization and dechlorination treatment on the coating tail gas, and can effectively reduce the production cost. Meanwhile, the visible light transmittance of the prepared solar control coated glass is controlled to be 50-80%, and the visible light reflectance is controlled to be below 20%.
Description
Technical Field
The invention relates to a glass coating process, in particular to solar control coated glass and an online preparation method thereof.
Background
In the existing coating process, titanium dioxide is deposited on the surface of glass to form a titanium dioxide coating, so that the optical properties of the glass, such as visible light transmittance, visible light reflectance and the like, are adjusted. For example, patent CN101173763B discloses a method for producing solar control coated glass on line by float process, which is based on Chemical Vapor Deposition (CVD) process, and takes nitrogen or argon as carrier gas, and thermally decomposes a vapor containing a titanium source, a dopant and a precursor on the surface of float glass to form a titanium dioxide film layer. However, in the production process, inevitable elements such as chlorine and phosphorus are mixed into the tail gas of the coating film, so that additional chlorine and phosphorus removal steps are required to be performed on the tail gas of the coating film, and the production cost is increased. Meanwhile, the reaction zone is narrow, so that the utilization rate of raw materials is low, and the problems of high light reflection, serious light pollution and the like of the prepared glass exist in the pure titanium dioxide coating.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: the sunlight control coated glass and the online preparation method thereof have the advantages that extra dephosphorization and dechlorination treatment is not needed to be carried out on the coating tail gas, and the visible light transmittance and reflectance of the coating are controllable.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: an on-line preparation method of solar control coated glass is characterized by that the mixed gas formed from tetraisopropyl titanate, ammonia gas and nitrogen gas is sprayed on the surface of the glass so as to form a mixed film formed from titanium dioxide and titanium nitride on the surface of the glass.
Further provides the solar control coated glass prepared by the online preparation method.
The invention has the beneficial effects that: the glass surface coating prepared by the invention is a mixed film of titanium dioxide and titanium nitride, and the visible light transmittance of the sunlight control coated glass can be effectively controlled to be 50-80% and the visible light reflectance can be controlled to be below 20% through the synergistic effect of the titanium dioxide and the titanium nitride. Meanwhile, the prepared mixed film has good chemical stability and long service life.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
An on-line preparation method of solar control coated glass is characterized by that the mixed gas formed from tetraisopropyl titanate, ammonia gas and nitrogen gas is sprayed on the surface of the glass so as to form a mixed film formed from titanium dioxide and titanium nitride on the surface of the glass.
Wherein tetraisopropyl titanate is mainly present in the form of vapor before being mixed with ammonia gas, and nitrogen as a carrier gas is mixed with tetraisopropyl titanate vapor after being preheated to promote rapid evaporation of tetraisopropyl titanate. When the mixed gas is sprayed onto the surface of the glass, tetraisopropyl titanate and ammonia gas are thermally decomposed. Part of titanium dioxide in the decomposition product of tetraisopropyl titanate reacts with nitrogen (carrier gas nitrogen and ammonia decomposition product) and hydrogen (ammonia decomposition product) to produce titanium nitride, and is deposited on the glass surface together with the rest of titanium dioxide to form the mixed film. That is, in the present embodiment, the temperature of the glass should be greater than or equal to the temperature at which tetraisopropyl titanate and ammonia gas thermally decompose. In a preferred embodiment, the tetraisopropyl titanate vapor is mixed with preheated nitrogen in a ratio and then ammonia is introduced into the mixture. Specifically, for the equipment, the flow of tetraisopropyl titanate liquid is controlled by a flowmeter and a valve, the liquid with the composite design flow enters an evaporator, is heated and evaporated into a gas state, nitrogen is added into the evaporator as carrier gas to promote the tetraisopropyl titanate to be evaporated in an accelerated manner, and ammonia is introduced into an outlet of the evaporator to be mixed with the tetraisopropyl titanate and the carrier gas nitrogen.
The main reasons why titanium nitride needs to be doped into the titanium dioxide film are as follows: although the titanium dioxide film can effectively block sunlight, the titanium dioxide film has high reflectivity and is easy to cause light pollution; the titanium nitride film has high visible light transmittance and low near infrared ray transmittance, and the energy contained in the near infrared ray is high. By properly mixing the two, proper lighting and heat preservation effects can be provided, and meanwhile, light pollution can be effectively reduced. And in the verification, the prepared sunlight control coated glass can control the visible light transmittance to be 50-80 percent and the visible light reflectance to be below 20 percent. Meanwhile, the reactor provided by the invention has a wider reaction area, and can effectively improve the utilization rate of raw materials and reduce the production cost.
Furthermore, because the prior doping agent is not used in the technical scheme provided by the invention, the film coating of the solar control film coating glass prepared by the online preparation method provided by the invention does not contain doping agent composition elements such as chlorine and phosphorus, and the like, and meanwhile, the tail gas in the preparation process is free from pollution of other elements, and the tail gas can reach the tail gas emission standard only after titanium dioxide is recovered. In one embodiment, the tail gas is treated by passing it through: tail gas generated by coating is pumped into the spray tower through the induced draft fan to be cooled and dissolved in water, and the tail gas can be directly discharged after solid (carbon dioxide) in the water is filtered out through the filter press.
Wherein the mixed gas consists of the following components:
0.1 to 0.3mol percent of tetraisopropyl titanate, 0.05 to 0.15mol percent of ammonia gas and 99.55 to 99.85mol percent of nitrogen gas.
In one embodiment, the mixed gas is composed of:
0.1mol% tetraisopropyl titanate, 0.05mol% ammonia and 99.85mol% nitrogen.
In another embodiment, the mixed gas is composed of:
0.2mol% tetraisopropyl titanate, 0.1mol% ammonia and 99.7mol% nitrogen.
In yet another embodiment, the mixed gas is composed of:
0.3mol% tetraisopropyl titanate, 0.15mol% ammonia and 99.55mol% nitrogen.
Preferably, since the coating is a previous step in the annealing lehr in the on-line production process, the surface temperature of the glass is preferably controlled in a temperature range of 580 to 600 ℃ before the float glass is advanced into and retreated from the annealing lehr. More preferably, the lateral temperature difference of the glass is controlled to be 600 ± 5 ℃. The temperature control can effectively meet the requirement of carrying out related reactions, and can improve the uniformity of the deposited composite film, thereby improving the quality of the prepared solar control coated glass. The on-line production process is particularly a production process which plays a role of a link between an upper process and a lower process.
Preferably, the moving speed of the glass in the coating process is preferably 200-600 m/h. More preferably, the moving speed is the same as the glass production rate.
The solar control coated glass prepared by the on-line preparation method. Wherein the thickness of the mixed film is 40 nm-90 nm. Illustratively, the thickness of the hybrid film is 41nm, 63nm, and 86nm.
Example 1
An on-line preparation method of solar control coated glass comprises the following steps:
s1, adjusting the transverse temperature difference of the glass surface to 600 +/-5 ℃;
s2, spraying mixed gas (0.1 mol% of tetraisopropyl titanate, 0.05mol% of ammonia gas and 99.85mol% of nitrogen gas) on the surface of the glass to form a composite film with the thickness of 41nm on the surface of the glass, wherein the visible light transmittance of the prepared sunlight control coated glass is 81%, and the visible light reflectance is 11%.
The present example was carried out under the following process conditions: the float line melting amount was 600t/d, the glass cutting width was 3.66m, the glass thickness was 5mm, the production speed was 510m/h, and the total amount of the mixed gas used was 73m 3 And h, the moving speed of the glass in the coating process is 510m/h.
The visible transmittance and reflectance were measured by BYK4775 in Germany through a haze Meter, AST-SE200BA ellipsometer in USA.
Example 2
An on-line preparation method of solar control coated glass is different from that of the embodiment 1 in that: 0.2mol% of tetraisopropyl titanate, 0.1mol% of ammonia gas and 98.7mol% of nitrogen gas, and the composite film is obtained, wherein the thickness of the composite film is 63nm, the visible light transmittance is 73%, and the visible light reflectance is 13%.
Example 3
An on-line preparation method of solar control coated glass is different from the embodiment 1 in that: 0.3mol% of tetraisopropyl titanate, 0.15mol% of ammonia gas and 99.55mol% of nitrogen, and the composite film with the thickness of 86nm, the visible light transmittance of 65% and the visible light reflectance of 16% is obtained. Through detection, the refractive index of the prepared sunlight control coated glass is 2.512, and meanwhile, the surface of the sunlight control coated glass presents light golden yellow color peculiar to titanium nitride.
Through calculation, the raw material utilization rate of the embodiment is 29%, and the general raw material utilization rate of the existing CVD method coating is 10-20%, namely the on-line preparation method provided by the application can effectively improve the raw material utilization rate, so that the production cost is reduced.
Comparative example 1
An on-line production method of solar control coated glass is different from the embodiment 3 in that: ammonia gas is not mixed, and nitrogen is used for complementing, so that the solar control coated glass with pure titanium dioxide coating is prepared. The visible light reflectance was 31%, and the refractive index was 2.316.
As can be seen from a comparison of the data of comparative example 1 and example 3, by using the mixed thin film of titanium nitride and titanium dioxide, the visible light reflectance is lower and the refractive index is higher, i.e., more excellent optical properties are exhibited.
In conclusion, the glass surface coating prepared by the invention is a mixed film of titanium dioxide and titanium nitride, and the visible light transmittance of the sunlight control coated glass can be effectively controlled to be 50-80% and the visible light reflectance is controlled to be below 20% through the synergistic effect of the titanium dioxide and the titanium nitride. Meanwhile, the prepared mixed film has good chemical stability and long service life.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (8)
1. An on-line preparation method of solar control coated glass is characterized in that mixed gas consisting of tetraisopropyl titanate, ammonia gas and nitrogen gas is sprayed on the surface of the glass to form a mixed film consisting of titanium dioxide and titanium nitride on the surface of the glass.
2. The on-line preparation method according to claim 1, wherein the mixed gas is composed of:
0.1 to 0.3mol percent of tetraisopropyl titanate, 0.05 to 0.15mol percent of ammonia gas and 99.55 to 99.85mol percent of nitrogen gas.
3. The on-line preparation method according to claim 2, wherein the mixed gas is composed of:
0.1mol% tetraisopropyl titanate, 0.05mol% ammonia and 99.85mol% nitrogen.
4. The on-line preparation method according to claim 2, wherein the mixed gas is composed of:
0.2mol% tetraisopropyl titanate, 0.1mol% ammonia and 99.7mol% nitrogen.
5. The on-line preparation method according to claim 1, wherein the mixed gas is composed of:
0.3mol% tetraisopropyl titanate, 0.15mol% ammonia and 99.55mol% nitrogen.
6. The on-line manufacturing method according to claim 1, wherein the glass has a lateral temperature difference of 600 ± 5 ℃.
7. A solar control coated glass produced by the on-line production method according to any one of claims 1 to 6.
8. The solar control coated glass of claim 7, wherein the thickness of the hybrid film is 40nm to 90nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211166130.3A CN115477478A (en) | 2022-09-23 | 2022-09-23 | Solar control coated glass and online preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211166130.3A CN115477478A (en) | 2022-09-23 | 2022-09-23 | Solar control coated glass and online preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115477478A true CN115477478A (en) | 2022-12-16 |
Family
ID=84393952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211166130.3A Pending CN115477478A (en) | 2022-09-23 | 2022-09-23 | Solar control coated glass and online preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115477478A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080014349A1 (en) * | 2004-11-19 | 2008-01-17 | Nippon Sheet Glass Company, Limited | Process For Producing Glass Plate With Thin Film |
| CN101143763A (en) * | 2007-08-28 | 2008-03-19 | 杭州蓝星新材料技术有限公司 | Method for on-line producing sunlight controlling coated glass by float method |
| CN103722816A (en) * | 2013-12-30 | 2014-04-16 | 深圳市东丽华科技有限公司 | High-intensity ultra-thin glass and preparation method thereof |
| CN105669044A (en) * | 2015-12-31 | 2016-06-15 | 株洲醴陵旗滨玻璃有限公司 | Online easy-cleaning coated glass and production method thereof |
-
2022
- 2022-09-23 CN CN202211166130.3A patent/CN115477478A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080014349A1 (en) * | 2004-11-19 | 2008-01-17 | Nippon Sheet Glass Company, Limited | Process For Producing Glass Plate With Thin Film |
| CN101143763A (en) * | 2007-08-28 | 2008-03-19 | 杭州蓝星新材料技术有限公司 | Method for on-line producing sunlight controlling coated glass by float method |
| CN103722816A (en) * | 2013-12-30 | 2014-04-16 | 深圳市东丽华科技有限公司 | High-intensity ultra-thin glass and preparation method thereof |
| CN105669044A (en) * | 2015-12-31 | 2016-06-15 | 株洲醴陵旗滨玻璃有限公司 | Online easy-cleaning coated glass and production method thereof |
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