CN1093067A - The preparation method of glass transparent insulating film and nozzle specially used - Google Patents

The preparation method of glass transparent insulating film and nozzle specially used Download PDF

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Publication number
CN1093067A
CN1093067A CN 93110358 CN93110358A CN1093067A CN 1093067 A CN1093067 A CN 1093067A CN 93110358 CN93110358 CN 93110358 CN 93110358 A CN93110358 A CN 93110358A CN 1093067 A CN1093067 A CN 1093067A
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China
Prior art keywords
shower nozzle
glass
gas
preparation
air chamber
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CN 93110358
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Chinese (zh)
Inventor
陈有鹏
马瑾
李淑英
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Shandong University
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Shandong University
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Priority to CN 93110358 priority Critical patent/CN1093067A/en
Publication of CN1093067A publication Critical patent/CN1093067A/en
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    • 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
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • 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
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The preparation method of a kind of glass transparent insulating film---SnO 2 thin film and nozzle specially used.This method adopts atmospheric pressure chemical vapor deposition technology, on flat glass production line, utilize the high temperature of newborn glass, with the tin tetrachloride source, fluorine Lyons is for oozing assorted agent, methyl alcohol is the auxiliary oxygen, and with purification nitrogen for carrying gas, with each composition gas-entrained after place two gas circuits in the shower nozzle of sheet glass top, by shower nozzle mouth outflow carrying out chemical reaction, generate stannic oxide, uniform deposition forms SnO 2 thin film on newborn sheet glass.This technology is simple, and materials are cheap, and production cost is low, is suitable for the production of big area continuous batch.The film physical strength height that this method makes, strong adhesion, chemical stability is good, and acid and alkali-resistance and corrosion.

Description

The preparation method of glass transparent insulating film and nozzle specially used
The present invention relates to a kind ofly, specifically be the waste heat that on flat glass production line, utilizes newborn glass, adopt the method for atmospheric pressure chemical vapor deposition prepared tin oxide transparent thermal isolation film and nozzle specially used at method and the nozzle arrangement for preparing transparent heat-insulating film on glass.
At present mainly contain metal alloy film, composite membrane (TiO in the thermal isolation film of countries use on building glass such as Germany, Switzerland, the U.S. 2/ Ag/TiO 2) and indium tin metal oxide compound (ITO), these several thermal isolation film have following shortcoming: visible light transmissivity is low, and daylighting is undesirable; Infrared reflectance is low, and effect of heat insulation is poor; A little less than sticking power and the corrosion stability,, need high vacuum because vacuum evaporation or magnetically controlled sputter method are adopted in the preparation of above-mentioned film more, high cleanliness, so the device structure complexity is difficult for the big area continuous production, raw material costliness in addition, the cost height is difficult to popularization and application.In recent years, the window material that is used for device such as silicon photocell abroad adopts SnO 2 thin film, this film visible light transmissivity height, the infrared reflectance height, good and the strong adhesion of chemical stability, its preparation method adopts advanced atmospheric pressure chemical vapor deposition method, as U.S. Pat .Pat 4146657, but the selected Xi Yuan of this patented method big organotin source-tin tetramethide [Sn(CH that is toxicity 3) 4], doping agent is organofluorine compound-organotin fluoroalkyl gas; In addition because the application of this glass film material only limits to the window material of photoelectric device, so its preparation also only limits to small area.
The present invention seeks to attempt to select for use a kind of nontoxic tin source material large-area preparation S on glass production line nO 2Transparent heat-insulating film has the method and the nozzle arrangement of this thermal isolation film glass to realize continuous batch production.
The inventive method realizes as follows: on ordinary plate glass production line (little horizontal drawing, float glass process production line), be positioned at the newborn sheet glass top of operation, its temperature before and after 500 ℃-600 ℃ glass transit place side by side laterally (vertical) with newborn glass run direction one group of shower nozzle is set, the mutual isolated gas circuit of two-way is arranged in the shower nozzle, with the anhydrous stannic chloride is the source, fluorine Lyons F 152Be doping agent, methyl alcohol is auxiliary, adding oxygen is oxygenant, nitrogen with purifying is to carry another gas circuit that gas is gone into tin tetrachloride and fluorine Lyons gas-entrained in shower nozzle, the purpose of doing like this is to avoid tin tetrachloride and oxygen to meet and give first reaction, two-way gas is come out by the shower nozzle place of chewing, uniform mixing carries out chemical reaction under 500 ℃ of-600 ℃ of temperature, generate stannic oxide, gas deposition is newborn on glass what move under normal pressure, tandem shower nozzle repeatedly with the steam state deposition of tin oxide after on glass, form uniform SnO 2 thin film, its basic chemical equation is:
Each gas component ratio by volume is: tin tetrachloride 4%, fluorine Lyons F 1520.05-0.3%, methyl alcohol 0.02%, nitrogen 35%, all the other are oxygen.The purpose in doped with fluorine Lyons is to improve the specific conductivity of film, thereby increases its infrared reflectance, adds the uniformity coefficient that auxiliary methyl alcohol can increase film with effect ground, and the reaction residual gas is drained by exhaust system by the space between before and after the shower nozzle.Gas is 10 liters/minute by the effusive total flux in the shower nozzle place of chewing; Newborn glass run speed control is at 1 meter/minute-8 meters/minute, and it is 3-15mm that shower nozzle is chewed apart from the distance of newborn sheet glass.
The nozzle specially used structure of the present invention is as follows: it is to be processed by two identical rectangle stainless steel plate symmetries, its length is slightly larger than the width of newborn glass, have three groove chambers from top to bottom successively along the steel plate length direction, be respectively first, the second and the 3rd air chamber, skewed slot-shower nozzle of receiving in below to lower rim has is chewed, lateral edges at first air chamber has air inlet port, air inlet port external welding intake ducting is connected with it, the macropore that is equated by spacing between first air chamber and second air chamber is connected, connecing the flat hole of open semicircle by mesopore arranged in a uniform between second air chamber and the 3rd air chamber is connected, between chewing, the 3rd air chamber and shower nozzle be communicated with by aperture, the fluting face of this two stainless steel plate gives and is processed into bright and clean smooth plane earlier, the stainless steel thin slice is placed in the middle of the two steel plate trough of belt faces, two steel plates is kept apart by the stainless steel thin slice.Form two isolated gas circuits, two stainless steel plates are carried secretly and are formed shower nozzle after the stainless steel thin slice is fixed by fastening assembly.
Utilize this inventive method to prepare SnO 2Heat-protecting glass technology is simple, and materials make suitable, need not clean heating specially, thus can reduce the cost cost, and be applicable to the production of big area continuous batch.The heat-protecting glass visible light average transmittances that utilizes this method to produce reaches 85%, and infrared reflectance (wavelength is at 10. μ places) is up to 90%.Fig. 1 is that to have thickness be 0.7 μ SnO 2The 3mm glass of film and same specification glass at the transmitance of visible light and near infrared light wave band and luminance factor, Fig. 2 is the reflectivity curve of 2.5 these heat-protecting glasses of μ to 25 μ infrared band.
The embodiment of the invention is as follows:
Example 1. shower nozzles are chewed apart from surperficial 5mm on glass, and gas ratio is: SnO 24%, fluorine Lyons 0.05%, methyl alcohol 0.02%, nitrogen 35%, all the other are oxygen, shower nozzle place glass temperature is 550 ℃, 1 meter/minute of glass run speed, shower nozzle is chewed 10 liters/minute of the total gas flow rates in place, and on glass to make thick be the film of 0.7 μ m at 3mm.
Example 2. fluorine Lyons doping ratios are 0.2%, and shower nozzle place glass temperature is 520 ℃, and all the other conditions are with example 1, and making thick is the film of 0.6 μ m.
Example 3. repeats example 1 preparation condition, and it is 10mm that shower nozzle is chewed apart from surface on glass, and glass run speed is 2 meters/minute, and making thick is the film of 0.5 μ m.
It is 4mm that example 4. shower nozzles are chewed apart from surface on glass, and this place's glass temperature is at 580 ℃, and glass run speed is 1.5 meters/minute, and all the other conditions are with example 1, and making thick is the film of 0.8 μ m.
Fig. 3 is the sectional view of shower nozzle of the present invention, wherein 1 is stainless steel plate, the 2nd, air inlet port, 3,4,5 be followed successively by first, second, third air chamber, the 6th, fastening assembly, the 7th, the stainless steel thin slice, the 8th, shower nozzle is chewed, and Fig. 4 is the front view of shower nozzle, wherein 9 is macropores, the 10th, mesopore connects flat hole, open half garden, and the 11st, aperture, Fig. 5 are the placement diagrammatic sketch of jet head sets on glass production line, wherein 12 is cylinders on the glass production line, the 13rd, the newborn glass of operation, the 14th, shower nozzle, the 15th, the exhaust system of residual gas.

Claims (6)

1, a kind of preparation method of glass transparent insulating film-SnO 2 thin film adopts atmospheric pressure chemical vapor deposition technology, it is characterized in that with tin tetrachloride being that Xi Yuan, oxygen are oxygenant, mix fluorine Lyons F 152, auxiliary methyl alcohol, and with purification nitrogen for carrying gas, respectively four stannic oxide, fluorine Lyons and oxygen and methanol gas are often gone into to have in one group of shower nozzle of isolated two gas circuits, laterally be placed on the newborn sheet glass top of moving in the glass production line before and after the shower nozzle side by side, this place's temperature is between 500 ℃-600 ℃, the gas of being chewed out by shower nozzle carries out chemical reaction generation stannic oxide behind this place's uniform mixing, uniform deposition is on glass in new life, form SnO 2 thin film thereon, the reaction residual gas is drained by exhaust system.
2, according to the preparation method of the described thermal isolation film of claim 1, it is characterized by described each gaseous constituent volume ratio and be: tin tetrachloride 4%, fluorine Lyons F 1520.05-0.3%, methyl alcohol 0.02%, nitrogen 35%, all the other are oxygen.
3,, it is characterized by described shower nozzle and chew anomaly sheet glass distance between 3-15mm according to the preparation method of the described thermal isolation film of claim 1.
4,, it is characterized by described newborn sheet glass travelling speed between 1 meter/minute-8 meters/minute according to the preparation method of the described thermal isolation film of claim 1.
5, according to the preparation method of the described thermal isolation film of claim 1, the total gas flow rate that it is characterized by the described shower nozzle place of chewing is 10 liters/minute.
6, a kind ofly be used for the nozzle specially used of the described method of claim 1, it is characterized by this shower nozzle is processed by two identical rectangle stainless steel plate symmetries, have three groove chambers from top to bottom successively along the steel plate length direction, be respectively first, second, the 3rd air chamber, skewed slot-shower nozzle of receiving in below to lower rim has is chewed, at the first air chamber lateral edges air inlet port is arranged, the macropore that is equated by spacing between first air chamber and second air chamber is connected, connecing flat hole, open half garden by mesopore arranged in a uniform between second air chamber and the 3rd air chamber is connected, between chewing, the 3rd air chamber and shower nozzle be communicated with by aperture, the fluting face of this two stainless steel plate gives and is processed into bright and clean smooth plane earlier, then the stainless steel thin slice is clipped between the steel plate, fixes the back to form shower nozzle with two isolation gas circuits by fastening assembly.
CN 93110358 1993-04-02 1993-04-02 The preparation method of glass transparent insulating film and nozzle specially used Pending CN1093067A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 93110358 CN1093067A (en) 1993-04-02 1993-04-02 The preparation method of glass transparent insulating film and nozzle specially used

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 93110358 CN1093067A (en) 1993-04-02 1993-04-02 The preparation method of glass transparent insulating film and nozzle specially used

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CN1093067A true CN1093067A (en) 1994-10-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006675A1 (en) * 1996-08-13 1998-02-19 Pilkington Plc Method of depositing tin oxide and titanium oxide coatings on flat glass and the resulting coated glass
CN102584019A (en) * 2012-01-31 2012-07-18 绥中滨海经济区红杉科技有限公司 Equipment and method for plating glass antireflective film through chemical vapor deposition process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006675A1 (en) * 1996-08-13 1998-02-19 Pilkington Plc Method of depositing tin oxide and titanium oxide coatings on flat glass and the resulting coated glass
EP1238948A1 (en) * 1996-08-13 2002-09-11 Pilkington Plc Method of depositing tin oxide and titanium oxide coatings on flat glass and the resulting coated glass
CN1094113C (en) * 1996-08-13 2002-11-13 皮尔金顿公共有限公司 Method of depositing tin oxide and titanium oxide coating on flat glass and resulting coated glass
CN102584019A (en) * 2012-01-31 2012-07-18 绥中滨海经济区红杉科技有限公司 Equipment and method for plating glass antireflective film through chemical vapor deposition process

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