CN1204067C - Method for on-line producing low radiation film glass by floating process - Google Patents
Method for on-line producing low radiation film glass by floating process Download PDFInfo
- Publication number
- CN1204067C CN1204067C CN 01142650 CN01142650A CN1204067C CN 1204067 C CN1204067 C CN 1204067C CN 01142650 CN01142650 CN 01142650 CN 01142650 A CN01142650 A CN 01142650A CN 1204067 C CN1204067 C CN 1204067C
- Authority
- CN
- China
- Prior art keywords
- glass
- low
- tin
- source
- proplastid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011521 glass Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000005855 radiation Effects 0.000 title claims abstract description 10
- 238000007667 floating Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 239000005329 float glass Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910000085 borane Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 9
- -1 stablizer Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical group Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- VMZCHSVMQLKOOM-UHFFFAOYSA-N [Sn].C(CCC)C(=C(C(=O)O)CCCC)C(=O)O Chemical compound [Sn].C(CCC)C(=C(C(=O)O)CCCC)C(=O)O VMZCHSVMQLKOOM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229940033355 lauric acid Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- AAZXYDTXKRXEHM-UHFFFAOYSA-M butyltin(1+);chloride Chemical compound CCCC[Sn]Cl AAZXYDTXKRXEHM-UHFFFAOYSA-M 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 4
- 229910052810 boron oxide Inorganic materials 0.000 abstract description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 229910000410 antimony oxide Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- 238000004062 sedimentation Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- DLBIVAXRKUJUQO-UHFFFAOYSA-N [C].[B]=O Chemical compound [C].[B]=O DLBIVAXRKUJUQO-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000005344 low-emissivity glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to method for the on-line production of low-radiation film float glass. The present invention utilizes a chemical vapor deposition method to deposit a complex film layer composed of a silicon oxide and boron oxide shielding layer mixed with carbon and a tin oxide and antimony oxide low-radiation layer mixed with fluorine and phosphorus on the surface of hot glass. Compared with the prior art, at the same temperature, a film layer manufactured in the method has the advantages of high deposition rate, homogeneous film layers, small surface resistance, high electric conductivity, low radiation rate, favorable abrasive resistance and strong alkali resistance; moreover, the present invention has the advantages of stable production and high production efficiency, and is suitable for manufacturing large-sized low-radiation glass.
Description
Technical field
The present invention relates to the method for on-line producing low radiation film glass by floating process.Be to utilize chemical vapor deposition method specifically, at the glass surface cvd silicon oxide of heat, the screen layer of boron oxide carbon dope and the composite film that stannic oxide, weisspiessglanz are mixed the low radiating layer of fluorine, phosphorus.
Background technology
People habitually practise at coating low-radiation film on glass, change the radiation and the reflection characteristic of glass centering far infrared rays as tin oxide film, but directly at glass surface plating low-radiation film, because the alkalimetal ion of glass inside is moved to glass surface easily, the electric heating property of its meeting deterioration rete, surface resistivity is increased and the physical and chemical stability reduction, and make low radiating layer produce the white opacity body, transparency reduces.
Known that in the art many kinds of methods can be used to apply glass, these methods comprise vacuum magnetic-control sputtering method, hot spray process, sol-gel method, chemical vapor deposition method etc., it as application number 96110665 Chinese patent, set forth a kind of by chemical vapor deposited mode on 630～640 ℃ sheet glass that moves or float glass matrix, utilize tin tetrachloride and water pre-mixing to form single steam flow, the method for deposition stannic oxide rete.Mixing is to carry out in the presence of low-level chain triacontanols such as hydrogen fluoride, methyl alcohol, ethanol, can realize that the tin tetrachloride of single steam flow and water only react to each other in the zone of matrix surface in formation coating on glass.The reactive material that this method relates to requires moment decomposition reaction at high temperature, and is wayward, complex process.
Application number is 94118301 Chinese patent, has proposed to utilize on floatation glass production line chemical vapor deposition method online production sunlight controlling coated glass, and the coated glass that this method is produced does not possess low radiance substantially.
Summary of the invention
The method that the purpose of this invention is to provide a kind of on-line producing low radiation film glass by floating process.
The method of production low-radiation film coated glass provided by the invention, be to utilize chemical vapor deposition method, adopt suitable proplastid gas mixture stage by stage at the glass surface cvd silicon oxide of heat, the screen layer of boron oxide carbon dope and the composite film that stannic oxide, weisspiessglanz are mixed the low radiating layer of fluorine, phosphorus.This method may further comprise the steps:
1) in the floatation glass production line molten tin bath, uses chemical vapor deposition method, will be by silane, borine, ethene, containing proplastid gas mixture that oxygen source, rare gas element form, to be deposited on temperature with the speed that is higher than 400 /S be 620～700 ℃ float glass matrix surface, forming coat-thickness at glass surface is that 40～90nm, specific refractory power are 1.6～1.8 screen layer coatings;
2) glass that will scribble screen layer is transferred to annealing furnace, at the annealing kiln temperature is the reactor that 550～610 ℃ of zones are provided with single passage admission structure, stanniferous source, antimony source and doping agent, stablizer, the catalyst premixing that utilizes this reactor to be vaporized closes the proplastid gas mixture of making, do carrier with air, be passed into the mobile float glass belt surface that scribbles screen layer, carry out thermolysis with the speed that is higher than 400 /S, formation thickness is 200～400nm, radiant ratio less than 0.15 low-radiation film coating.
In the proplastid gas mixture that above-mentioned plating screen layer is used, usually, silane concentration is 5～15%, and borane concentration is 1～15%, and ethylene concentration is 80～100%, and containing oxygen source concentration is 1～20%, with inert nitrogen gas or argon-dilution.
The said oxygen source that contains is carbonic acid gas, nitrous oxide or triethyl-phosphite.
Generally, the volume ratio of the proplastid gas mixture of plating screen layer is: borine: silane: ethene: contain oxygen source=0.00050～0.006: 0.5～1.5: 2～12: 2～8.
The Xi Yuan of the proplastid gas mixture of the low radiating layer of plating can select trifluoroacetic acid-butyl tindichloride ester, dibutyl butene dioic acid tin, dibutyl two (laurostearic acid) tin, dibutyltin diacetate, tin tetrachloride, trichlorine-butyl tin for use.Preferred trifluoroacetic acid-butyl tindichloride ester.
The antimony source of the proplastid gas mixture of the low radiating layer of plating can be selected butter of antimony, antimony tribro-for use.Preferred butter of antimony.
Adopt doping agent can make the sedimentation velocity of gas mixture be higher than 400 /S among the present invention, produce easier control.The doping agent phosphorus source is phosphorus trifluoride, triethyl-phosphite, preferred phosphorus trifluoride.The fluorine source is phosphorus trifluoride, trifluoroacetic acid, phenylfluoroform, preferred phosphorus trifluoride.
Stablizer can be selected ethyl acetate, methyl methacrylate, butyl methacrylate, diacetyl oxide, methyl iso-butyl ketone (MIBK), α-methacrylic acid for use.Ethyl acetate.Because the decomposition temperature of ethyl acetate is higher, its existence can prevent that mixed gas from undesirable pre-reaction taking place.
Catalyzer is selected water vapour, ethanol, methyl alcohol for use.
The molecular fraction of each composition is respectively in the proplastid gas mixture of the low radiating layer of plating: tin source 1～10mol%, antimony source 1～5mol%, doping agent 0.1～3mol%, stablizer 0.5～3mol%, catalyzer 0.1～2.5mol%, all the other are air.
In the present invention, owing to added ethene and contained oxygen source etc., formed carbonaceous silica coating structure, screen layer can not only stop the diffusion of alkalimetal ion, simultaneously also because its 1.6～1.8 suitable specific refractory power, a decay color layers is provided,, has played and weakened the iridescent effect in order to reduce low radiating layer on glass because of the radiation reflected colour that the infrared external reflection height presents.
Ethene and contain the adding of oxygen source has improved the visible transmission ratio of low-radiation film coated glass, has reduced specific refractory power, has strengthened its alkali-resistivity greatly simultaneously, and concrete outcome sees Table 1.
Table 1
| Numbering | Borine: silane: ethene: carbonic acid gas (volume ratio) | Transmittance (%) | Specific refractory power | Alkali-resistivity (h) |
| 1 | 0.002∶1∶0∶0 | 20.5 | 3.50 | 1.2 |
| 2 | 0.002∶1∶0.5∶0 | 37.7 | 2.52 | 6.9 |
| 3 | 0.002∶1∶4∶4 | 80.8 | 2.35 | 18.5 |
| 4 | 0.002∶1∶8∶4 | 82.5 | 1.70 | 29.2 |
| 5 | 0.002∶1∶10∶4 | 82.8 | 1.69 | 29.3 |
| 6 | 0.002∶1∶0∶0.5 | 25.0 | 3.05 | 2.4 |
| 7 | 0.002∶1∶8∶2 | 35.6 | 1.72 | 18.8 |
| 8 | 0.002∶1∶8∶6 | 82.6 | 1.71 | 29.5 |
The process that the present invention utilizes the chemical vapor deposition method plating to contain the silicon oxide film of boron oxide, carbon and phosphorus is: absorption, decomposes, oxidation.The thermal decomposition process of silane is a deposition pyrolysis switching process, when the glass basis temperature is certain, decomposes productive rate one regularly, and sedimentation rate is with directly relevant with the molecule of absorption reaction agent.Silane (SiH
4) molecule has Si
+-H
-Ionic species, can be had the surface adsorption of positive potential.So can help SiH at the molecule that glass surface produces current potential corrigendum
4The absorption of molecule, thus sedimentation rate improved.Being mixed with of boron helps the corrigendum of glass surface current potential, improves the sedimentation rate of silane under uniform temp, forms silica coating with fast speed, avoids the depositing treatment district long.The mixed membranous layer that contains boron oxide that makes in this way has in uniform temp deposit speed height, characteristics that specific refractory power is moderate, and this is a screen layer for low radiating layer provides suitable bottom.
In the ideal case, SnO
2Being not have the electronics that can move freely in the film, is nonconducting isolator.But the tin dioxide film that makes with high-temperature hydrolysis forms a kind of N-type semiconductor because of having departed from stoichiometric ratio on its structure, and Hall coefficient is for negative, and electronic mobility is 10～50cm
2/ (V.s).Show the SnO that high-temperature hydrolysis makes by structural analysis
2Promptly there are oxonium ion O in the SnO and the Sn that have some amount in the crystal in the lattice
-2Omission, near the tin the oxonium ion omission will be unnecessary go out valence electron, and the not tight valence electron of these constraints is easy to be excited, and becomes current carrier, shows certain electron conduction; Owing to mobility of charge carrier, the reflection of centering far infrared wavelength is very high simultaneously, and the electric conductivity of film depends on the vacant situation of oxonium ion, the just concentration of current carrier.If make its nonstoichiometry ratio, and take the doping way to make it have high carrier concentration, will improve the electroconductibility of rete, reduce radiant ratio.In line with this principle, the present invention adds impurity Sb to tin dioxide thin film
5+, P
5+, F
-, provide electronics to make current carrier, electroconductibility is strengthened.
The adding of phosphorus trifluoride and butter of antimony has obviously reduced the surface resistivity and the radiant ratio of low-radiation film coated glass, has improved the reflection tone, specifically sees Table 2.
Table 2
| Numbering | Phosphorus trifluoride mol% | Butter of antimony mol% | Surface resistivity Ω/ | Radiant ratio E | Metric system colourity | |
| a * | b * | |||||
| 1 | 0 | 0 | 100 | 0.41 | 2.22 | -9.30 |
| 2 | 0 | 2.5 | 80 | 0.37 | -1.5 | -9.20 |
| 3 | 0.5 | 2.5 | 40 | 0.25 | -1.01 | -7.20 |
| 4 | 1.0 | 2.5 | 18 | 0.15 | -0.80 | -3.86 |
| 5 | 1.0 | 0 | 79 | 0.36 | 1.21 | -8.55 |
| 6 | 1.0 | 0.5 | 60 | 0.30 | 1.02 | -6.01 |
The method of on-line producing low radiation film glass by floating process provided by the invention is owing to reasonably adopted antimony source, doping agent, stablizer and catalyzer, and they combine with the effective of Xi Yuan, make proplastid gas mixture decomposition rate fast, and produces control easily.The rete that makes in this way than prior art at identical temperature deposit speed height, even film layer, surface resistivity is little, the electric conductivity height, radiant ratio is low, wear resistance is good, alkali-resistivity is strong.Owing to also contain weisspiessglanz in the low-radiation film layer, it and SnO
2At visible light absorption is arranged in conjunction with the colour center that forms, acting in conjunction produces complementary, and the transmission of control light has regulating effect to solar radiation.The inventive method also have produce stable, production efficiency is high, product performance are excellent, is fit to make the advantage of big specification low emissivity glass.
Embodiment
Use example below, further set forth method of the present invention.
Embodiment:
In the floatation glass production line molten tin bath, the glass ribbon top is provided with reactor; Be used for the proplastid gas mixture with silane, borine, ethene, carbonic acid gas, guiding is also mobile along glass surface to be coated; 645 ℃ of glass ribbon surface temperatures; 430 meters/hour of the pull speed of glass ribbon; Silane concentration 10%, borane concentration 10%; Ethylene concentration 99%; Gas concentration lwevel 20%; The volume ratio of wherein mixing gas is a borine: silane: ethene: carbonic acid gas=0.002: 1: 8: 4, with nitrogen as diluent gas; Deposition makes screen layer.Measure the specific refractory power 1.7 of rete, visible transmission is than 82.5%, thicknesses of layers 60nm.
The glass ribbon that scribbles screen layer is advanced to the annealing furnace front end; The reactor of single passage admission structure is set above it; The proplastid gas mixture of trifluoroacetic acid-butyl tindichloride ester, butter of antimony, phosphorus trifluoride, ethyl acetate, water composition is fed the glass ribbon surface of 600 ℃ of heat, in 6 seconds treatment times, do carrier with air.The molecular fraction of proplastid gas mixture is: trifluoroacetic acid-butyl tindichloride ester 2.8mol%; Butter of antimony 2.52mol%; Phosphorus trifluoride, ethyl acetate, water three amount to 3.2mol%; All the other are air.
Recording the thicknesses of layers of two membranes after compound is 290nm, surface resistivity 18 Ω/, radiant ratio E=0.15; The reflection colour of rete is sky-blue (a
*=-0.80, b
*=-3.86).
Claims (2)
1. the method for on-line producing low radiation film glass by floating process is characterized in that it may further comprise the steps:
1) in the floatation glass production line molten tin bath, uses chemical vapor deposition method, will be by silane, borine, ethene, contain oxygen source, it is 620～700 ℃ float glass matrix surface that the proplastid gas mixture that rare gas element is formed is deposited on temperature with the speed that is higher than 400 /S, forming coat-thickness at glass surface is 40～90nm, specific refractory power is 1.6～1.8 the coating with shielding effect, silane in the proplastid gas mixture, borine, ethene and contain the concentration of oxygen source after and be respectively 5～15% with inert gas dilution, 1～15%, 80～100% and 1～20%, their volume ratio is: borine: silane: ethene: contain oxygen source=0.00050～0.006: 0.5～1.5: 2～12: 2～8;
2) glass that will scribble screen layer is transferred to annealing furnace, at the annealing kiln temperature is the reactor that 550～610 ℃ of zones are provided with single passage admission structure, the stanniferous source that utilizes this reactor to be vaporized, antimony source and doping agent, stablizer, catalyst premixing closes the proplastid gas mixture of making, do carrier with air, be passed into the mobile float glass belt surface that scribbles screen layer, carry out thermolysis with the speed that is higher than 400 /S, formation thickness is 200～400nm, radiant ratio is less than 0.15 the coating with low radiance, the molecular fraction of each composition is respectively in the proplastid gas mixture of the low radiating layer of plating: tin source 1～10mol%, antimony source 1～5mol%, doping agent 0.1～3mol%, stablizer 0.5～3mol%, catalyzer 0.1～2.5mol%, all the other are air;
The above-mentioned oxygen source that contains is carbonic acid gas, nitrous oxide or triethyl-phosphite, and rare gas element is nitrogen or argon gas; Xi Yuan is trifluoroacetic acid-butyl tindichloride ester, dibutyl butene dioic acid tin, dibutyl two (laurostearic acid) tin, dibutyltin diacetate, tin tetrachloride or three chloro-butyl tin; The antimony source is butter of antimony or antimony tribro-; Doping agent is a triethyl-phosphite, trifluoroacetic acid, phosphorus trifluoride or phenylfluoroform.
2. press the method for the described production low-radiation film coated glass of claim 1, the stablizer that it is characterized in that plating the proplastid gas mixture of low radiating layer is ethyl acetate, methyl methacrylate, butyl methacrylate, diacetyl oxide, methyl iso-butyl ketone (MIBK) or α-Jia Jibingxisuan, and catalyzer is water vapour, ethanol or methyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01142650 CN1204067C (en) | 2001-12-12 | 2001-12-12 | Method for on-line producing low radiation film glass by floating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01142650 CN1204067C (en) | 2001-12-12 | 2001-12-12 | Method for on-line producing low radiation film glass by floating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1425620A CN1425620A (en) | 2003-06-25 |
| CN1204067C true CN1204067C (en) | 2005-06-01 |
Family
ID=4676882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01142650 Expired - Lifetime CN1204067C (en) | 2001-12-12 | 2001-12-12 | Method for on-line producing low radiation film glass by floating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204067C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951283A (en) * | 2014-05-10 | 2014-07-30 | 蚌埠玻璃工业设计研究院 | Method for producing transparent conducting film glass |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077824B (en) * | 2007-02-14 | 2011-11-30 | 中国建材国际工程有限公司 | Method for depositing tin oxide base thin film on mobile hot glass surface |
| CN106007397A (en) * | 2016-05-12 | 2016-10-12 | 东莞泰升玻璃有限公司 | Low-radiation coated glass manufacturing technology |
| CN108358467B (en) * | 2018-04-02 | 2020-06-23 | 威海中玻新材料技术研发有限公司 | Multi-color low-radiation sunlight control coated glass and preparation method thereof |
| JP7020458B2 (en) * | 2019-07-12 | 2022-02-16 | Ａｇｃ株式会社 | Glass substrate with film and its manufacturing method |
-
2001
- 2001-12-12 CN CN 01142650 patent/CN1204067C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951283A (en) * | 2014-05-10 | 2014-07-30 | 蚌埠玻璃工业设计研究院 | Method for producing transparent conducting film glass |
| CN103951283B (en) * | 2014-05-10 | 2016-04-13 | 蚌埠玻璃工业设计研究院 | A kind of method of producing transparent conducting film glass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1425620A (en) | 2003-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4847157A (en) | Glass coating method and resulting article | |
| US10837108B2 (en) | Chemical vapor deposition process for depositing a silica coating on a glass substrate | |
| US8734903B2 (en) | Process for forming a silica coating on a glass substrate | |
| CN101618952B (en) | Method for on-line producing transparent conducting film glass by floating way | |
| CA1333461C (en) | Method of depositing textured tin oxide | |
| CN101475320A (en) | Float online production method for low radiation film glass | |
| EP2737105A1 (en) | Apcvd of doped titanium oxide and the coated article made thereby | |
| CN1204067C (en) | Method for on-line producing low radiation film glass by floating process | |
| CN1291938C (en) | Production process of transparent conductive low-radiation glass coating | |
| CN116669448B (en) | TCO conductive film glass for perovskite solar cell and preparation process thereof | |
| CN101475319B (en) | Method for online production of TCO film glass by float process | |
| EP2391743B1 (en) | Method of depositing an electrically conductive titanium oxide coating on a substrate | |
| JP2001036117A (en) | Photoelectric conversion device board | |
| US11542194B2 (en) | Coated glass article, method of making the same, and photovoltaic cell made therewith | |
| WO2022114027A1 (en) | Film-attached glass substrate, and method for manufacturing same | |
| CN101077824B (en) | Method for depositing tin oxide base thin film on mobile hot glass surface | |
| CN118373605A (en) | Preparation method of conductive film glass with controllable color neutrality and multi-interface structure | |
| WO2016132131A1 (en) | A chemical vapour deposition process for depositing an iron doped tin oxide coating and a coated glass article formed thereby |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Zhejiang city of Hangzhou province Xihu District GUCUI Road No. 8 new science and technology building seven floor Patentee after: Hangzhou Bluestar New Material Technical Co., Ltd. Address before: Building 6, building 119, Wensanlu Road, Xihu District, Zhejiang, Hangzhou Patentee before: Lanxing New Material Technology Co., Ltd., Zhejiang Univ. |
|
| C56 | Change in the name or address of the patentee |
Owner name: HANGZHOU LANXING NEW MATERIALS TECHNOLOGY CO., LTD Free format text: FORMER NAME: LANXING NEW MATERIAL TECHNOLOGY CO., LTD., ZHEJIANG UNIV. |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shaanxi LAN-STAR Glass Co., Ltd. Assignor: Hangzhou Bluestar New Material Technical Co., Ltd. Contract fulfillment period: 2006.3.19 to 2014.3.17 Contract record no.: 2009610000182 Denomination of invention: Method for on-line producing low radiation film glass by floating process Granted publication date: 20050601 License type: Exclusive license Record date: 20091221 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2006.3.19 TO 2014.3.17; CHANGE OF CONTRACT Name of requester: SHAANXI BLUE STAR GLASS CO., LTD. Effective date: 20091221 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180621 Address after: 264200 -516-39, chess Hill Road, Cao Miao zi Town, Weihai port economic and Technological Development Zone, Shandong Patentee after: Weihai central Bose material technology R & D Co., Ltd. Address before: 310012 seven, New Asia science and technology building, 8 Gu Cui Road, Xihu District, Hangzhou, Zhejiang. Patentee before: Hangzhou Bluestar New Material Technical Co., Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20050601 |
|
| CX01 | Expiry of patent term |