CN200985312Y - Low radiation self-cleaning glass - Google Patents
Low radiation self-cleaning glass Download PDFInfo
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- CN200985312Y CN200985312Y CN 200620077544 CN200620077544U CN200985312Y CN 200985312 Y CN200985312 Y CN 200985312Y CN 200620077544 CN200620077544 CN 200620077544 CN 200620077544 U CN200620077544 U CN 200620077544U CN 200985312 Y CN200985312 Y CN 200985312Y
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Abstract
The utility model discloses a low-radiation self-cleaning glass which comprises at least four layers wherein the first layer is a glass plate which is silicon-sodium-calcium glass; the secondary layer is a transmission layer made of silicon oxide or aluminium oxide which adulterates other oxide; the third layer is a low-radiation layer made of tin dioxide which adulterates fluorin and or antimony and the fourth layer is the self-cleaning layer which is also the outermost layer and made of titanium dioxide or doped titanium dioxide. The utility model has a dual-function of lower radiation and self-cleaning and adopts on-line high temperature pyrolytic spray coating. The utility model may be single-sheet service or bear a deep processing to play a toughened glass and of hot bend.
Description
[technical field]
The utility model relates to a kind of low radiation glass with clean, belongs to the glass coating technical field.
[background technology]
Low emissivity glass, English is Low Emissivity Glass, abbreviates Low-E glass as.Low-E glass is that to plate the film that multiple layer metal or other compounds form at glass surface be product.This product has high transmittance to visible light, and infrared rays (selecting infrared especially) is had very high reflectivity, has excellent heat insulation property.According to production technique, it is divided into off-line Low-E glass and online Low-E glass.
Off-line Low-E glass separates with floatation glass production line, generally adopts magnetically controlled sputter method production, is coated with stratified film on sheet glass successively, realizes the Low-E effect.Its advantage is to have best low radiation effect, and emissivity values can reach 0.05, even about 0.04.Can only about 0.15 and the radiant ratio of online Low-E is minimum.No. the 96104321.0th, pertinent literature such as Chinese patent application, Chinese patent No. 200410018113.0, No. 200420083199, No. 93105250.5.
Online Low-E glass is to realize in the production process of float glass, mainly adopts chemical vapor deposition (CVD) method or high temperature pyrolysis spraying method.Its advantage is that the tack between rete and the sheet glass is strong, can transport in the strange land, but the monolithic use also can be carried out various deep processings, as tempering, hot bending etc.
Chinese patent discloses a kind of method of float glass process online production low radiation coated glass for No. 01142650.0, this patent utilization CVD method, and the glass surface deposition low-radiation film layer in heat has 2 layers.The first layer is a screen layer, is made up of silicon oxide, the boron oxide of carbon dope; The second layer is made up of stannic oxide, the weisspiessglanz of doped with fluorine, phosphorus for low radiating layer.
Bibliographical information about glass with clean is many.Self-cleaning glass is glass with clean again, and multiple production technique is arranged at present both at home and abroad, as sol-gel technology, off-line magnetron sputtering or vacuum deposition process, online CVD (chemical vapour deposition) and various dip-coating, spraying coating process.
Online glass with clean is produced in the production process of float glass, compares with the off-line glass with clean, online glass with clean has mass or produces quantized advantage, realize serialization production, thereby production efficiency is provided, also reduced production cost on the other hand.The principal feature of online glass with clean is its processing characteristics, and this product can carry out strange land transportation as common float glass, also can carry out all kinds of deep processings operations, as cut, mill, hollow, tempering, hot bending, interlayer etc.The technology of making online glass with clean at present both at home and abroad mainly contains online CVD method.
The off-line glass with clean is compared with online glass with clean, does not realize serialization production, does not combine with floatation glass production line, so production efficiency is lower, production cost is higher.Shortcoming is that rete is relatively poor in the tack of glass surface, can not strange land transportation and operation, except blank operation in carrying out, can not carry out other deep processings operations, as hot bending, tempering etc.The production method that all belongs to the off-line glass with clean as sol-gel method, magnetron sputtering method, vacuum deposition method, spraying method, dip coating etc.
Online CVD method, be by chemical vapour deposition CVD method with titanium dioxide deposition to the sheet glass that moves of heat, and sheet glass is clean, this method generally in molten tin bath temperature be position between 650 ℃-720 ℃, this method has also made full use of the heat of glass pane surface in the float glass process, and do not need as sol-gel method, to reheat rete is solidified, saved the energy; And realized serialization production.This method generally is that liquid or solid-state organo-metallic titanium salt are gasified by thin-film evaporator, and under the drive of rare gas elementes such as nitrogen, raw material is deposited on the glass pane surface that moves of heat by decomposition under gas phase state like this, forms rete.The document that utilizes the CVD method to produce glass with clean has Chinese patent application No. 03130468.0, No. 02815882.2, No. 00818185.3, and Chinese patent No. 00808643.5, No. 200480007970.9, No. 01802678.8.
Magnetically controlled sputter method utilizes existing magnetron sputtering film device, by metal titanium is splashed to glass surface, generates titanium deoxid film in the glass surface oxidation, makes glass surface have certain wetting ability, and reaches self-cleaning effect.The document that utilizes this method to generate glass with clean has Chinese patent No. 99815987.5, No. 01802678.8, and No. the 02805314.1st, Chinese patent application.
Sol-gel process, titanium dioxide is mixed with colloidal sol, again glass is put into that this colloidal sol soaks into the mode that lifts and the even self-cleaning rete of two surface applied one decks that makes sheet glass, again with glass in High Temperature Furnaces Heating Apparatus, at the temperature sintering that surpasses 500 ℃, just can finish the conversion of rutile crystal type behind the several hrs to anatase crystal type.The document that utilizes this method to make glass with clean has Chinese patent No. 02147089.8, and Chinese patent application No. 02822422.1, No. 03817836.2.
Result for retrieval shows, relevant for the bibliographical information of low emissivity glass, also relevant for the bibliographical information of glass with clean, but only finds a report that utilizes the low radiation glass with clean of magnetron sputtering technique manufacturing, and this manufacture method is an off-line process.Chinese patent application discloses the low self-cleaning coated glass of radiation of a kind of titanium nitride base for No. 200410012951.7, this patent utilization magnetron sputtering technique, and its low radiating layer is mainly by TiN
xForm, the clean surfaces rete is by TiO
2Form.The manufacture method of this product belongs to off-line process, can not carry out deep processing operations such as hot bending, tempering; And the part titanium dioxide in the rete is metamict, causes glass surface wetting ability and the self-cleaning limited, and cost is also high.
[summary of the invention]
The utility model discloses a kind of low radiation glass with clean.This product comprises four layers at least: the first layer is a sheet glass; The second layer is a transition layer; The 3rd layer is low radiating layer; The 4th layer is self-cleaning layer, and self-cleaning layer is positioned at outermost layer.
The first layer is a Si-Na-Ca glass; Transition layer is made up of silicon oxide, perhaps is made up of the aluminum oxide of other oxide compounds that mix; Low radiating layer by doped with fluorine or/and the tindioxide of antimony form; Self-cleaning layer is made up of titanium dioxide or adulterated titanium dioxide.
Above-mentioned transition layer is an individual layer.Form by silicon oxide, perhaps form by the aluminum oxide of other oxide compounds that mix; And hotchpotch comprises at least a in vanadium oxide, chromic oxide, magnesium oxide, calcium oxide, the zinc oxide, and the shared weight percent of hotchpotch is no more than 10%.
Transition layer also can be made up of two-layer, and first transition layer is made up of silicon oxide or is made up of the aluminum oxide of other oxide compounds that mix, and the same with the composition of individual layer transition layer, first transition layer nestles up glass plies; Second transition layer is made up of tindioxide, between first transition layer and low radiating layer.
Or/and the tindioxide of antimony is formed, the mol ratio of the shared tin of hotchpotch is for being no more than 30% by doped with fluorine for low radiating layer, and thickness is 150-350nm.Low radiating layer is between transition layer and self-cleaning layer.
Self-cleaning layer is made up of titanium dioxide.Also can form, and hotchpotch comprises at least a in the following oxide compound: silicon oxide, cerium oxide, zinc oxide, aluminum oxide, zirconium white, cupric oxide, Praseodymium trioxide, Neodymium trioxide, lanthanum trioxide, platinum oxide, rhodium oxide, iridium oxide, palladous oxide, gold trioxide, ruthenium oxide by adulterated titanium dioxide.The shared weight percent of hotchpotch is no more than 10%.
Second layer thickness is 40-150nm; The threeply degree is 150-350nm; The 4th layer is 60-140nm.
All retes described in the utility model all adopt online high temperature pyrolysis spraying coating process to produce, used coating raw material is liquid, used device is the spray equipments of arranging more, and every row is provided with a plurality of spray guns, and the many rows of dependence spray equipments lateral separation is arranged, sprayed and the formation stratified film.
The characteristics of the low radiation glass with clean of the utility model are: 1) realized low radiation and self-cleaning dual-use function; 2) low-radiation film layer and self-cleaning rete all adopt on-line coating technology to produce; 3) can use by monolithic, also can carry out deep processing operations such as tempering, hot bending; 4) low-radiation film layer and self-cleaning rete all adopt the high temperature pyrolysis spraying coating process to realize.
After testing, the radiant ratio of this low radiation glass with clean is 0.17, and contact angle is minimum to be reached below 5 °.
Transition layer can be an individual layer, also can be double-deck.The individual layer transition layer is made up of silicon oxide, perhaps is made up of the aluminum oxide of other oxide compounds that mix.Transition layer also can be made up of two-layer, first transition layer is made up of silicon oxide or is made up of the aluminum oxide of other oxide compounds that mix, and hotchpotch comprises at least a in vanadium oxide, chromic oxide, magnesium oxide, calcium oxide, the zinc oxide, and first transition layer nestles up glass plies; Second transition layer is made up of tindioxide, between first transition layer and low radiating layer.
Acting as of transition layer: 1) sodium ion occupies significant proportion in glass, and ionic radius is little, moves easily; Increase transition layer and can prevent that the sodium ion in the sheet glass from moving to low radiating layer, low radiating layer is damaged; 2) improve tack and the sedimentation effect that hangs down radiating layer; 3) specific refractory power of transition layer is between sheet glass and low radiating layer, so transition layer also has certain inhibition iridescent effect.
Low radiating layer by doped with fluorine or/and the tindioxide of antimony form.That is to say that this layer can be made up of the tindioxide of doped with fluorine, also can form, also can form by the tindioxide of while doped with fluorine and antimony by the tindioxide of antimony dopant.Wherein the mol ratio of the shared tin of hotchpotch is for being no more than 30%.
Used material is mainly titanium dioxide in the self-cleaning layer, as everyone knows, titanium dioxide comprises brookite, anatase octahedrite and three kinds of crystal formations of rutile, wherein Detitanium-ore-type has very strong photocatalysis performance, and price is relatively cheap, so the titanium dioxide of Detitanium-ore-type is used in the utility model suggestion, use Detitanium-ore-type can produce the good glass with clean of photocatalysis performance; Certainly, rutile-type also has suitable photo-catalysis capability, so it is feasible adding a certain proportion of rutile-type in Detitanium-ore-type, but the shared ratio of suggestion rutile-type does not surpass 40%, and the titanium dioxide nano-particle of the utility model indication is Detitanium-ore-type, rutile-type or the mixing crystal formation of the two.
Self-cleaning layer also can be made up of adulterated titanium dioxide, and hotchpotch comprises at least a in the following oxide compound: silicon oxide, cerium oxide, zinc oxide, aluminum oxide, zirconium white, cupric oxide, Praseodymium trioxide, Neodymium trioxide, lanthanum trioxide, platinum oxide, rhodium oxide, iridium oxide, palladous oxide, gold trioxide, ruthenium oxide.
Silicon oxide can improve the wetting ability of glass with clean rete, reduces hydrophilic angle; Film strength be can also increase, stability and wearability improved.Cerium oxide disperses the water miscible liquid be composited through surface modification.Because CeO
24f
1Electronic structure has abundant transition of electron energy level, and is very responsive to photoabsorption, and has stronger oxidation activity, and therefore aspect photochemical catalytic oxidation, activity is stronger, particularly with nano-TiO
2The photocatalyst that is combined into, better effects if.And produce a large amount of negative oxygen ions, can improve indoor air environment.Platinum oxide, zinc oxide, cupric oxide etc. have similar effect.Add metal oxides such as zirconium white, Praseodymium trioxide, Neodymium trioxide, iridium oxide, also can improve the photochemical catalysis effect to a certain extent, also can improve water-repellancy, alkali-resistivity, wearability, wearing quality; Add-on does not have corresponding effect very little; Add-on is too many, the composition gelling easily takes place or condense deterioration of film outward appearance or photocatalysis reduction.
Should both have the advantage of low emissivity glass by low radiation glass with clean, have the advantage of glass with clean again.It is typical energy-saving environment-friendly glass.Except having low radiating characteristics, also have hydrophilic, degradable organic pollutant and obnoxious flavour, purify air, deodorizing, mildew-resistant, antifog, antibiotic, wear-resisting functions.
Used substrate glass comprises system mirror level glass, automotive grade glass, architectural grade glass in the utility model.It can be colourless transparent glass; Also can be various colored glass, as green glass, blue glass, smoked glass, cranberry glass etc.Be preferably colourless transparent glass.
Should be widely used by low radiation glass with clean, can be applied to fields such as glass port, vehicle glass, buildings glass, glass curtain wall, glass partition, glass door, urban public utilities, billboard.
[description of drawings]
The utility model will be further described in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the formation synoptic diagram of first embodiment of the low radiation glass with clean of the utility model.
Fig. 2 is the formation synoptic diagram of second embodiment of the low radiation glass with clean of the utility model.
[embodiment]
Embodiment one
Fig. 1 is the formation synoptic diagram of low radiation glass with clean, and as shown in Figure 1, low radiation glass with clean comprises 4 layers altogether, is followed successively by sheet glass 11, transition layer 12, low radiating layer 13, self-cleaning layer 14 from bottom to top, wherein:
Low radiating layer 13 is made up of the tindioxide of doped with fluorine and antimony, and the mol ratio of the shared tin of hotchpotch is for being no more than 30%, and thickness is 250nm.
Self-cleaning layer 14 is made up of titanium dioxide, and thickness is 80nm.
Product performance
Emissivity measurement: detect through the radiant ratio instrument, the radiant ratio of this low radiation glass with clean is 0.20.
Hydrophilic angular measurement: get 25mm * 25mm and hang down radiation glass with clean print, after cleaning up with distilled water, dehydrated alcohol, acetone, with 500W mercury lamp irradiation certain hour, distance is 500mm, and using contact angle measurement measurement print is 10 ° to the contact angle of water.
Photocatalysis performance detects: use oleic acid as degradation material, get 50mm * 50mm print, after cleaning up with distilled water, dehydrated alcohol, acetone, dry the weight of weighing glass with clean print; Evenly be coated with the oleic acid of last layer certainweight on glass with clean print surface, weigh; Be the ultra violet lamp certain hour of 254nm with predominant wavelength again, weighing scribbles the weight of oleic glass with clean once more.Utilize the difference between the weight three times, just can calculate glass with clean oleic degradation rate.After testing, the photocatalysis efficiency of this low radiation glass with clean is 82%.
Bactericidal property detects: according to standard GB 15979-2002 low radiation glass with clean being carried out antibacterial tests, is 93% to colibacillary sterilizing rate, is 93.5% to staphylococcic sterilizing rate.Illustrate that this low radiation glass with clean has enough bactericidal properties.
Other Performance Detection: carry out acid resistance, alkali resistance, wear resistance according to the index request of the standard GB/T14915.2-2002 of low radiation coated glass product and detect, the result is all qualified.
Embodiment two
Fig. 2 is the formation synoptic diagram of low radiation glass with clean, and as shown in Figure 2, low radiation glass with clean comprises 5 layers altogether, is followed successively by sheet glass 21, first transition layer 22, second transition layer 23, low radiating layer 24, self-cleaning layer 25 from bottom to top, wherein:
Self-cleaning layer 25 is made up of the titanium dioxide of doped cerium oxide and zinc oxide, and thickness is 100nm.
Product performance
Identical among used test method and test apparatus and the embodiment one.Test-results is as follows:
Emissivity measurement: detect through the radiant ratio instrument, the radiant ratio of this low radiation glass with clean is 0.17.
Hydrophilic angular measurement: after the UV-irradiation, using contact angle measurement measurement print is 4.5 ° to the contact angle of water.
Photocatalysis performance detects: use oleic acid as degradation material, utilize embodiment one described weight differential technique, the photocatalysis efficiency that records this low radiation glass with clean is 79%.
Bactericidal property detects: according to standard GB 15979-2002 low radiation glass with clean being carried out antibacterial tests, is 97% to colibacillary sterilizing rate, is 96% to staphylococcic sterilizing rate.Illustrate that this low radiation glass with clean has enough bactericidal properties.
Other Performance Detection: carry out acid resistance, alkali resistance, wear resistance according to the index request of the standard GB/T14915.2-2002 of low radiation coated glass product and detect, the result is all qualified.
Claims (5)
1 one kinds low radiation glass with clean is characterized in that:
At least comprise four layers, be followed successively by: the first layer is a sheet glass; The second layer is a transition layer; The 3rd layer is low radiating layer; The 4th layer is self-cleaning layer, and self-cleaning layer is positioned at outermost layer.
2 low radiation glass with clean as claimed in claim 1, it is characterized in that: glass coating is made up of Si-Na-Ca glass.
3 low radiation glass with clean as claimed in claim 1, it is characterized in that: transition layer is an individual layer, is formed or is made up of the aluminum oxide with hotchpotch by silicon oxide; Thickness is 40-150nm.
4 low radiation glass with clean as claimed in claim 1 is characterized in that: self-cleaning layer is made up of titanium dioxide or titanium dioxide with hotchpotch, and thickness is 60-140nm.
5 as claim 1 or 3 described low radiation glass with clean, and it is characterized in that: transition layer is made up of first transition layer and second transition layer; First transition layer is made up of silicon oxide or is made up of the aluminum oxide with hotchpotch, and nestles up glass plies; Second transition layer is made up of tindioxide, between first transition layer and low radiating layer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200620077544 CN200985312Y (en) | 2006-09-18 | 2006-09-18 | Low radiation self-cleaning glass |
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| CN 200620077544 CN200985312Y (en) | 2006-09-18 | 2006-09-18 | Low radiation self-cleaning glass |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323632A (en) * | 2011-09-16 | 2012-01-18 | 常州工业技术玻璃有限公司 | Reflection silver mirror used for solar energy thermal power generation and manufacturing method thereof |
| CN103003216A (en) * | 2010-07-28 | 2013-03-27 | 法国圣戈班玻璃厂 | Glazing panel |
| CN109879606A (en) * | 2019-03-28 | 2019-06-14 | 中国民航大学 | A kind of preparation method of Al and Ce co-doped TiO2 self-cleaning film |
| CN114105490A (en) * | 2021-12-16 | 2022-03-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
-
2006
- 2006-09-18 CN CN 200620077544 patent/CN200985312Y/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003216A (en) * | 2010-07-28 | 2013-03-27 | 法国圣戈班玻璃厂 | Glazing panel |
| CN103003216B (en) * | 2010-07-28 | 2015-08-12 | 法国圣戈班玻璃厂 | Window glass |
| CN102323632A (en) * | 2011-09-16 | 2012-01-18 | 常州工业技术玻璃有限公司 | Reflection silver mirror used for solar energy thermal power generation and manufacturing method thereof |
| CN109879606A (en) * | 2019-03-28 | 2019-06-14 | 中国民航大学 | A kind of preparation method of Al and Ce co-doped TiO2 self-cleaning film |
| CN114105490A (en) * | 2021-12-16 | 2022-03-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
| CN114105490B (en) * | 2021-12-16 | 2022-11-29 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
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| GR01 | Patent grant | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071205 Termination date: 20130918 |