CN102603204A - Photochromic glass - Google Patents

Photochromic glass Download PDF

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Publication number
CN102603204A
CN102603204A CN201210060413XA CN201210060413A CN102603204A CN 102603204 A CN102603204 A CN 102603204A CN 201210060413X A CN201210060413X A CN 201210060413XA CN 201210060413 A CN201210060413 A CN 201210060413A CN 102603204 A CN102603204 A CN 102603204A
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Prior art keywords
photochromic
glass
parts
film
oxide
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CN201210060413XA
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CN102603204B (en
Inventor
董清世
张麒
李文情
周禾
叶茵
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Xinyi environmental protection special glass (Jiangmen) Co., Ltd.
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Xinyi Ultra-thin Glass (Dongguan) Co Ltd
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Abstract

The invention relates to photochromic glass, which comprises a glass base. A photochromic film is arranged on the surface of the glass base, and comprises components including, by weight, from 70 to 100 parts of tungsten oxide, from 5 to 30 parts of titanium dioxide and from 3 to 10 parts of zinc oxide. The photochromic is provided with the photochromic film, the components of the film include the tungsten oxide (WO3), the titanium dioxide (TiO2), the zinc oxide (ZnO) and the like, the photochromic glass has functions of automatically changing transmittance and shading coefficient, is simple in preparation process, low in cost and fine in photochromic effect, and is nontoxic and pollution-free, toxic and flammable organic films made of helical pyran compound, azo compound, condensed-ring aromatic compound and the like are omitted, and the oxide such as the WO3 and the like is uninflammable and is high in safety performance.

Description

Photochromic glass
Technical field
The present invention is specifically related to a kind of photochromic glass about the glass technology field.
Background technology
Photochromic glass is a kind of novel energy-saving glass, and glass tarnished the transmitance that has reduced light and carried heat gradually when illumination strengthened; Glass recovered bright again when illumination weakened, the transmitance that has improved light and carried heat.This can be with sooner or later and the environmental change in the four seasons, and change the intelligent glass of transmittance and shading coefficient automatically, have the not available advantages of star's energy-saving glass such as low radiation Low-E, caused people's special concern.
Photochromic glass had been invented by Corning Incorporated in 1964, was in glass body, to have mixed silver halide and photosensitizers, and shortcoming is high, the function singleness of cost, and current is used to make industry such as high quality color changeable glasses, and can't large-scale application at building field.
At present, there is the photochromic plate holder of multilayer is held between two blocks of sheet glass a kind of photochromic sandwich glass that makes; Also there is argent and halogen simple substance are joined respectively in other frit a kind of lens blank that makes with photochromic effect; Perhaps adopt heat treating process or reduction facture to produce a kind of bulk glass of colour-changed due to gradual light-changing; Even some has directly installed traditional photo chromic glass such as silver halide respectively on the vehicle body of car, automobile, commercial vehicle and passenger vehicle, does not belong to photochromic glass technical field patent.In addition, the external also patent of some photochromic glass, but be mostly improvement technology to silver halide and photosensitizers system, and electrochromic substance the patent documentation of the photochromic glass of plated film type do not occur all in glass body so far.
Summary of the invention
In view of this, provide that a kind of cost is low, effective, the photochromic glass of nontoxic pollution-free.
A kind of photochromic glass, it comprises glass basis, and said glass basis surface has one deck photochromic film, and said photochromic film comprises the component of following weight part:
Tungsten oxide 99.999 70-100 part,
Titanium oxide 5-30 part,
Zinc oxide 3-10 part.
Above-mentioned photochromic glass adopts photochromic film, and film comprises Tungsten oxide 99.999 (WO 3), titanium oxide (TiO 2), zinc oxide components such as (ZnO), have automatic change transmittance and shading coefficient function, preparation technology is simple; Cost is low, and photochromic effect is good, nontoxic pollution-free; Need not use poisonous, inflammable organic films such as spiral pyrylium compound, azo cpd and condensed ring aromatic compound, WO 3Nonflammable Deng oxide compound, safe.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is described further, in the accompanying drawing,
Fig. 1 is the photochromic glass structural representation of the embodiment of the invention one.
Fig. 2 is WO 3-H 2C 2O 4-TiO 2The variation of the transmittance of-ZnO photochromic glass sample, solar light irradiation after 3 minutes the sunshine transmittance reduce by 15% shading coefficient and descend approximately 0.14, unglazed photograph can fade 50% after 60 minutes, can fade fully behind the several hrs.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, the photochromic glass 10 of the embodiment of the invention one is shown, it comprises glass basis 12, and glass basis 12 surfaces have one deck photochromic film 14, and photochromic film 14 comprises the component of following weight part:
Tungsten oxide 99.999 70-100 part,
Titanium oxide 5-30 part,
Zinc oxide 3-10 part.
In an embodiment of the present invention, this photochromic film 14 is filmed for what sol-gel method was processed, also comprises the oxalic acid of 10-40 weight part in filming, and the parts by weight of titanium oxide are preferably 5-15.The material of filming in a preferred embodiment, is formed and parts by weight are:
80 parts of Tungsten oxide 99.999s,
20 parts of oxalic acid,
10 parts of titanium oxide,
5 parts in zinc oxide.
Particularly, the thickness 10nm~500nm of photochromic film 14, preferably, the thickness of photochromic film 14 is 200nm.Glass basis 12 can be the glass material of using always.
The detailed process of Prepared by Sol Gel Method photochromic glass is following:
Take by weighing commercial Tungsten oxide 99.999, titanium oxide, Zinc oxide particles and oxalic acid crystal, parts by weight are WO 3: H 2C 2O 4: TiO 2: ZnO=(70~100): (10~40): (5~15): (3~10), be dispersed in and form coating fluid in the deionized water, with spraying equipment with this coating fluid uniform deposition at clean glass substrate (matrix), 50~80 ℃ down the oven dry back form WO 3-H 2C 2O 4-TiO 2-ZnO optically variable films.
Please consult Fig. 1 again; The structure composition of embodiments of the invention two photochromic glasses 10 and thickness etc. are basic identical with embodiment one; The main difference part is the plated film that photochromic film 14 is processed for magnetron sputtering method, and the material of said plated film is formed and parts by weight are:
Tungsten oxide 99.999 70-100 part,
Titanium oxide 5-30 part,
Zinc oxide 3-10 part.
Preferably, the material of said plated film composition and parts by weight thereof are:
80 parts of Tungsten oxide 99.999s,
20 parts of titanium oxide,
5 parts in zinc oxide.
The detailed process that magnetron sputtering method prepares photochromic glass is following:
The mixed powder of titanium oxide, zinc oxide and Tungsten oxide 99.999 is customized to ceramic target, and ratio of weight and number is WO 3: TiO 2: ZnO=(70~100): (5~30): (3~10) prepare the process using technology commonly used of this ceramic target.Then, at mixed atmosphere deposit one deck WO of argon gas and oxygen 3-TiO 2-ZnO photochromic film is on glass substrate (matrix).
In concrete the application, photochromic glass 10 can be used as all kinds glass, for example can be various building glasses, also can be automobile skylight glass, side window glass etc.Photochromic glass 10 receives illumination effect and produce corresponding look to become, and is as shown in Figure 1, when energy greater than WO 3, TiO 2Shine 10 last times of photochromic glass with the light 16 of ZnO energy gap, promptly be radiated on the photochromic film 14, electron-hole pair produces immediately, and light induced electron gets into WO 3Conduction band, with the W that closes on 6+In conjunction with generating blue W 5+, be metachromasia; When no rayed, the pentavalent W that the oxygen molecule oxidation is blue 5+Become sexivalent W 6+, be color fading reaction.Doped Ti O 2Can quicken WO with ZnO 3Variable color and the speed of fading, and TiO 2As the binary oxide system collaborative enhancement is arranged also with ZnO; Doping oxalic acid can consume photohole, makes more light induced electron participate in W 6+Generate W 5+Photochemical reaction, increase the blue degree of depth and variable color energy-saving effect.
Hence one can see that, and photochromic glass 10 of the present invention adopts photochromic film 14, can regulate the shade of film 14 automatically along with the power of external light 16, for example adopts WO 3-H 2C 2O 4-TiO 2During-ZnO film layer, become light blue, mazarine by colourless, carry out variable color fast, variable color efficient is high and stable, when being used for building glass, can regulate light and heat in the inlet chamber automatically, reduces utilization ratios such as fan, air-conditioning, cuts down the consumption of energy.And, owing to adopt oxide compound, nonflammable; Need not use poisonous, inflammable organic films such as spiral pyrylium compound, azo cpd and condensed ring aromatic compound yet; Make the photochromic glass asepsis environment-protecting, security is higher, can be widely used in various energy-saving glass field.
Below be concrete instance, with concrete structure, material composition, preparation technology and the detection effect that photochromic glass 10 of the present invention is described.
Instance 1 sol-gel method
Take by weighing commercial Tungsten oxide 99.999, titanium oxide, Zinc oxide particles and oxalic acid crystal, ratio of weight and number is WO 3: H 2C 2O 4: TiO 2: ZnO=80:20:10:5, be dispersed in and form coating fluid in the deionized water, with spraying equipment with this coating fluid uniform deposition at clean glass substrate (matrix), 60 ℃ down the oven dry back form WO 3-H 2C 2O 4-TiO 2-ZnO optically variable films, thickness are 100 nanometers.
Detect WO 3-H 2C 2O 4-TiO 2The variable color of-ZnO sample and energy-saving effect: directly sample is placed under the outdoor sunlight, fetches sample after 3 minutes and utilize the printing opacity appearance to detect.The result shows, solar light irradiation after 3 minutes glass colour become mazarine by light color, unglazed photograph takes off again after 60 minutes and is light color, this variable color-fade and can circulate repeatedly.
Specifically as shown in Figure 2, solar light irradiation is after 3 minutes, and the sunshine transmittance reduces by 15%, and shading coefficient descends about 0.14; Unglazed photograph can fade 50% after 60 minutes, can fade this variable color-fade and can circulate repeatedly behind the several hrs fully.
Instance 2 magnetron sputtering methods
The mixed powder of titanium oxide, zinc oxide and Tungsten oxide 99.999 is customized to ceramic target, and ratio of weight and number is WO 3: TiO 2: ZnO=80:20:5.The work for preparing this ceramic target is accomplished by target producer.Under the mixed atmosphere of argon gas and oxygen, deposition one deck WO 3-TiO 2-ZnO optically variable films is on glass substrate (matrix), and thickness is 200 nanometers.
Detect WO 3-TiO 2The variable color of-ZnO sample and energy-saving effect: directly sample is placed under the outdoor sunlight, fetches sample after 20 minutes and utilize the printing opacity appearance to detect.Glass colour becomes mazarine by light color as a result, and the sunshine transmittance reduces by 11%, and shading coefficient descends about 0.10; Unglazed photograph can fade 40% after 60 minutes, can fade this variable color-fade and can circulate repeatedly behind the several hrs fully.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. photochromic glass, it comprises glass basis, it is characterized in that, and said glass basis surface has one deck photochromic film, and said photochromic film is that Tungsten oxide 99.999-titanium oxide-zinc oxide combined films comprises the component of following weight part:
Tungsten oxide 99.999 70-100 part,
Titanium oxide 5-30 part,
Zinc oxide 3-10 part.
2. photochromic glass as claimed in claim 1; It is characterized in that; Said combined films photochromic film is the coating structure that sol-gel method is processed, and also comprises the oxalic acid of 10-40 weight part during said combined films is filmed, and the parts by weight of said titanium oxide are 5-15.
3. photochromic glass as claimed in claim 2 is characterized in that, said material of filming forms and parts by weight are:
80 parts of Tungsten oxide 99.999s,
20 parts of oxalic acid,
10 parts of titanium oxide,
5 parts in zinc oxide.
4. photochromic glass as claimed in claim 1 is characterized in that, said combined films photochromic film is the plated film that magnetron sputtering method is processed, and the material of said plated film is formed and parts by weight are:
80 parts of Tungsten oxide 99.999s,
20 parts of titanium oxide,
5 parts in zinc oxide.
5. photochromic glass as claimed in claim 1 is characterized in that, the thickness 10 nm~500nm of said photochromic film.
6. photochromic glass as claimed in claim 1 is characterized in that, the thickness of said photochromic film is 200nm.
7. photochromic glass as claimed in claim 1 is characterized in that, said photochromic glass is building glass, automobile skylight glass or side window glass.
CN201210060413.XA 2012-03-09 2012-03-09 Photochromic glass Active CN102603204B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627333A (en) * 2012-08-24 2014-03-12 信义超薄玻璃(东莞)有限公司 Photochromic powder, photochromic film, photochromic glass and preparation method thereof
CN103643871A (en) * 2013-11-15 2014-03-19 成都市翻鑫家科技有限公司 Novel window capable of adjusting light rays automatically
CN105620232A (en) * 2014-10-31 2016-06-01 中国航空工业集团公司西安飞机设计研究所 Sunshading device for aircraft cockpit
CN106218271A (en) * 2016-07-29 2016-12-14 温州鑫泰新材料股份有限公司 A kind of novel intelligent pen cap
CN107216047A (en) * 2017-06-16 2017-09-29 成都新柯力化工科技有限公司 A kind of preparation method of photochromic glass bilayer film
CN107523034A (en) * 2017-09-29 2017-12-29 浙江工贸职业技术学院 A kind of photochromic resin ophthalmic len and preparation method thereof
CN108645847A (en) * 2018-05-18 2018-10-12 山东大学 A method of oxygen is detected based on unformed tungsten oxide/polymer hybridisation nano fibrous membrane
CN109592909A (en) * 2019-01-31 2019-04-09 山西普思盈创科技有限公司 A kind of preparation method of antiultraviolet energy-saving glass
CN110623092A (en) * 2019-10-30 2019-12-31 湖南太青山茶业有限公司 Green tea tedding room
CN116730627A (en) * 2023-05-30 2023-09-12 咸宁南玻节能玻璃有限公司 Photochromic glass and preparation method thereof
WO2024007275A1 (en) * 2022-07-05 2024-01-11 北京仿生界面科学未来技术研究院 Smart window foil self-adaptive to illumination intensity, and preparation method therefor and use thereof

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CN1807321A (en) * 2005-12-31 2006-07-26 中国科学院广州能源研究所 Highly energy-saving coating glass automatically adjusting light according to environment temperature and multi-layed assembled glass body

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627333A (en) * 2012-08-24 2014-03-12 信义超薄玻璃(东莞)有限公司 Photochromic powder, photochromic film, photochromic glass and preparation method thereof
CN103643871A (en) * 2013-11-15 2014-03-19 成都市翻鑫家科技有限公司 Novel window capable of adjusting light rays automatically
CN105620232A (en) * 2014-10-31 2016-06-01 中国航空工业集团公司西安飞机设计研究所 Sunshading device for aircraft cockpit
CN106218271A (en) * 2016-07-29 2016-12-14 温州鑫泰新材料股份有限公司 A kind of novel intelligent pen cap
CN107216047B (en) * 2017-06-16 2019-11-08 新沂天源节能材料有限公司 A kind of preparation method of photochromic glass bilayer film
CN107216047A (en) * 2017-06-16 2017-09-29 成都新柯力化工科技有限公司 A kind of preparation method of photochromic glass bilayer film
CN107523034A (en) * 2017-09-29 2017-12-29 浙江工贸职业技术学院 A kind of photochromic resin ophthalmic len and preparation method thereof
CN107523034B (en) * 2017-09-29 2019-05-17 浙江工贸职业技术学院 A kind of photochromic resin spectacle lens and preparation method thereof
CN108645847A (en) * 2018-05-18 2018-10-12 山东大学 A method of oxygen is detected based on unformed tungsten oxide/polymer hybridisation nano fibrous membrane
CN109592909A (en) * 2019-01-31 2019-04-09 山西普思盈创科技有限公司 A kind of preparation method of antiultraviolet energy-saving glass
CN110623092A (en) * 2019-10-30 2019-12-31 湖南太青山茶业有限公司 Green tea tedding room
WO2024007275A1 (en) * 2022-07-05 2024-01-11 北京仿生界面科学未来技术研究院 Smart window foil self-adaptive to illumination intensity, and preparation method therefor and use thereof
CN116730627A (en) * 2023-05-30 2023-09-12 咸宁南玻节能玻璃有限公司 Photochromic glass and preparation method thereof

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Patentee before: Xinyi Ultra-thin Glass (DongGuan) Co., Ltd.