CN112777943B - Reactor for chemical vapor deposition method coated glass - Google Patents
Reactor for chemical vapor deposition method coated glass Download PDFInfo
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- CN112777943B CN112777943B CN202110231874.8A CN202110231874A CN112777943B CN 112777943 B CN112777943 B CN 112777943B CN 202110231874 A CN202110231874 A CN 202110231874A CN 112777943 B CN112777943 B CN 112777943B
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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
- C03C17/001—General methods for coating; Devices therefor
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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
- C03C17/2456—Coating containing TiO2
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
Abstract
The invention discloses a reactor for coating glass by a chemical vapor deposition method, which comprises an air inlet chamber and a steel beam supporting body, wherein the air inlet chamber can independently preset the temperature and can independently and uniformly distribute gas to the entering reaction gas in the length direction of the reactor; the air inlet chamber comprises a pressure equalizing cavity and a heat medium cavity which surrounds the pressure equalizing cavity and is controlled by an external control system and used for controlling the temperature of reaction gas in the pressure equalizing cavity; the steel beam bearing body comprises an air inlet chamber, an air inlet channel, a reaction chamber, an exhaust channel and an exhaust chamber, and a reaction gas channel is formed. The air inlet chamber steel constructs the steel structure independent from reaction chamber, exhaust chamber, and it is connected with the steel structure of reaction chamber, exhaust chamber through the slider bolt, and insulation material is established to the junction. The invention realizes different temperature control of the air inlet chamber and the reaction chamber and the exhaust chambers which can be uniformly arranged in the transverse direction of the glass ribbon, effectively improves the process controllability and the product quality of the coated glass for the chemical vapor deposition method, and is suitable for the application of a flat glass production line.
Description
Technical Field
The invention relates to the field of on-line production of coated glass on a plate glass production line, in particular to a reactor for coated glass by a chemical vapor deposition method.
Background
The coated glass is one of important building materials in the field of building energy conservation, the light-transmitting performance of a window is reserved, the coated glass is developed into glass with a function of efficiently blocking heat transfer, and the coated glass is heated and tempered to be made into hollow glass or vacuum glass, so that the coated glass is endowed with multiple special new functions of energy conservation, environmental protection, safety, decoration and the like of common plate glass; meanwhile, the coated glass has good conductive and thermal processing performances, so that the coated glass becomes substrate glass of solar cells and electronic products.
The coated glass can be divided into two processes of on-line coated glass and off-line coated glass according to the manufacturing process, wherein the on-line coated glass is a process of melting and clarifying raw materials such as quartz sand by a melting furnace to manufacture flat glass, coating equipment is grafted in a proper temperature area, a coated precursor is uniformly sprayed on the surface of the glass with higher temperature by the coating equipment, the coated precursor is subjected to pyrolysis reaction at high temperature, and a reactant is deposited on the glass plate to form a film layer with a certain function; the main process currently prevailing in the off-line coating technology is a vacuum cathode magnetron sputtering coating process, which refers to a process in which a flat glass sheet is washed, dried and then conveyed to a vacuum chamber, ions formed by ionizing gas impact a target material at a certain speed under the action of an electric field and a magnetic field, the target material ions are excited, and finally, the ions are deposited on the surface of glass to form a film layer with certain functions. The greatest difference between the online production of coated glass and the offline production of coated glass is that the online coated glass can be processed at will without additional energy in the production process, while the offline coated glass can be prepared under strict and harsh conditions and only needs to consume a large amount of electric energy, so the online coating is a good direction for developing coated glass.
The core equipment of the on-line coating is a reactor which can uniformly perform coating in the width direction of the whole glass production line. The main process for on-line coating implementation is grafting on a float glass production line, the float glass production line is composed of a raw material system, a melting furnace, a tin bath, a transition roller table, an annealing furnace, an on-line monitoring system and a cold end cutting and packing box, the on-line coating position is mainly in a region of the tin bath and the annealing furnace with the temperature of 500-700 ℃, and the width of the region is generally 4000-5600 mm, so that the main device of on-line coating, namely a coating reactor, at the position is required to have good thermal stability and good rigidity, and simultaneously, the coating reactor has an air inlet chamber which can keep the temperature required by a reaction precursor, a reaction chamber which is different from the temperature requirement of the air inlet chamber, and an exhaust chamber which can be uniformly arranged in the transverse direction of a glass strip.
Companies with float on-line coated glass technology mainly include: british Pilkington, American PPG, France Saigban, Belgiura Weber, and Wehai glass New Material technology research and development Limited in China. The original technologies of both the united states PPG and the french saint gobain were developed by purchasing the patent technology of pilkinton, england, which have in common the feature of arranging the coating equipment in the reducing atmosphere in the tin bath, while the new material technology development limited company of glaweber and wehai glass, belgium, has the feature of arranging the coating equipment in the oxidizing atmosphere in the transition roller table and annealing kiln a 0.
The US patent 4088471A describes a U-shaped single-channel reactor used in the low temperature section of the tin bath of the float glass production line, the air inlet chamber of the reactor is immersed in the cooling medium water of the steel beam, the upstream block, the center block and the downstream block are directly or indirectly connected with the steel beam to form a U-shaped channel entering the gas reaction area, namely, the gas uniformly enters the upstream channel of the U-shaped channel from the air inlet chamber through the gas distribution piece to be preheated to the temperature before the pyrolysis reaction, then enters the reaction area of the U-shaped channel formed by the center block and the hot glass belt, and the waste gas of the reaction enters the exhaust chamber through the other side of the U-shaped channel to be discharged from the reaction area. Therefore, the equipment utilizes the water temperature to keep the temperature of the air inlet chamber constant below 100 ℃, the water is the cooling medium of the whole steel beam, the temperature of the reaction zone is controlled by the heat insulation gasket to adjust the interface temperature of the reaction zone, the equipment is very effective for decomposing, reacting and depositing simple substance silicon by taking silane as a main gas, and the equipment is suitable for the deposition and coating process of small-flow, low-temperature and pure gas.
In the united states patent US4857097A, structural improvement related to the above disadvantages is proposed, for example, the toe structure of the downstream block of the U-shaped channel is changed into a circular arc shape to introduce the external gas medium into the channel, so as to improve the coating period, which plays a very large role, and at the same time, the exhaust chamber is connected with the main steel beam, which is beneficial to the stability of the exhaust chamber and the intake chamber. The aspects of reaction zone temperature control and gas inlet chamber temperature control remain the same.
The U.S. Pat. No. 3, 5065696A describes a reactor with double U-shaped channels and a single U-shaped channel, which is enclosed by steel members and can be made into a load-bearing steel beam with cooling medium to cross over two sides of a float glass tin bath, two relatively independent air inlet chambers without direct cooling medium are provided with air distribution members at the nozzle of the outlet, the lower end is a mixing chamber which is composed of a central block member with good heat conduction performance and is provided with finger plates for promoting mixing, air enters the mixing chamber from the independent air inlet chambers through respective nozzles and is mixed and then guided to the upper surface of the hot glass strip, the temperature of the central block is controlled by an electric heating element, unreacted or reaction product waste gas enters an exhaust channel, and the exhaust channel is internally provided with an exhaust uniform finger plate.
The U.S. Pat. No. 4, 5286295A describes a reactor with a single-inlet double-outlet double U-shaped structure composed of four graphite blocks with different shapes, and the patent specification analyzes the optimal length of the upstream and downstream reaction zones in the same reaction time in detail, and also adapts to the problem of large reaction gas flow and uniform reaction, thereby laying a theoretical foundation for the reactor in practical application, and the temperature of the gas inlet chamber and the reaction zone is the same as that of the U.S. Pat. No. 3, 4088471A.
The US patent 9540277B2 introduces a single-in double-row double-U-shaped reactor which can separate various reactants from each other and is composed of four main body parts to form an air inlet channel, an air distribution channel, a reaction channel and an exhaust channel, and the patent details that the air inlet channel is an air inlet uniform air distribution chamber composed of the main body parts, a cover plate part, a baffle part and an air adjusting part, the temperature control of the part mainly depends on a cooling pipe in the middle of the main body parts, the cooling pipe not only needs to meet the temperature of the reaction chamber but also needs the air inlet temperature, the control difficulty is high, the use effect is single, the requirement on a precursor material of the reaction is strong, meanwhile, the air adjusting part is positioned at the bottom of an air outlet of the air inlet chamber and is less than 10mm away from a hot glass plate, the implementation of the air uniformity is not facilitated, and the implementation of the large-flow reaction gas coating reaction is particularly not facilitated.
Chinese patent ZL201510014233.1 proposes an on-line float glass atmospheric pressure chemical vapor deposition coating reactor which utilizes waste gas heat and has the effects of strengthening convection heat transfer, adjusting the surface air flow of the glass belt, and preventing the backflow of dust exhaust process, wherein a reaction precursor premixing chamber and an exhaust gas chamber are arranged in a heat-insulating housing, the premixing chamber is connected with a coating precursor gas inlet pipe, and the premixing chamber is embedded in the exhaust gas chamber, and the reaction precursor gas is preheated by strengthening convection by utilizing the waste gas heat and fully mixing in the inlet chamber to reduce the coating reaction temperature. But independent control of the temperature of the premix chamber and the exhaust chamber is not achieved.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a reactor for coating glass by a chemical vapor deposition method, which comprises an air inlet chamber, a steel beam bearing body, a gas U-shaped channel, an exhaust chamber and the like, and can deposit a film with certain functions on a moving hot glass substrate by adopting a chemical vapor deposition process.
A reactor for coating glass by a chemical vapor deposition method comprises an air inlet chamber and a steel beam supporting body, wherein the air inlet chamber can independently preset the temperature and can independently and uniformly distribute the entering reaction gas in the length direction of the reactor;
the air inlet chamber:
the device comprises a pressure equalizing cavity and a heat medium cavity which surrounds the pressure equalizing cavity and is controlled by an external control system and used for controlling the temperature of reaction gas in the pressure equalizing cavity;
an air inlet pipe for reaction gas to enter is arranged in the pressure equalizing cavity, and a plurality of small holes are regularly distributed on the pipe wall of the air inlet pipe along the length direction of the reactor;
the damping belt is provided with a plurality of micropores and used for uniformly distributing air at an outlet at the bottom of the pressure-equalizing cavity, the damping belt is selected from a sintered plate or a laminated plate, and the laminated plate consists of a flat belt and a toothed belt which are longitudinally arranged and alternately distributed.
The steel beam carrier includes:
the air inlet channel is communicated with the outlet of the air inlet chamber and is provided with an adjustable temperature gradient from top to bottom;
the reaction chamber is communicated with the outlet of the gas inlet channel and the outside and is formed by the hot glass strip, and the reaction gas in the reaction chamber can contact with the hot glass strip for coating and has uniform concentration and flow rate;
the exhaust channel is communicated with the outlet of the reaction chamber and can uniformly discharge reaction waste gas in the length direction of the reactor;
the exhaust chamber is communicated with the outlet of the exhaust channel and can exhaust reaction waste gas, and a cold medium cavity for controlling the temperature of the reaction waste gas in the exhaust chamber is arranged around the exhaust chamber;
the gas inlet chamber, the gas inlet channel, the reaction chamber, the gas outlet channel and the gas outlet chamber form a reaction gas channel, wherein the gas inlet channel, the reaction chamber and the gas outlet channel form a single U-shaped or double U-shaped channel, and the reaction gas undergoes the processes of preheating, reaction and discharge in the channel;
the air inlet chamber is connected with the steel beam carrier body in a non-welding mode (for example, through a pressing device), and the steel structure of the air inlet chamber is independent of the steel structure of the reaction chamber and the exhaust chamber.
The invention realizes different temperature control of the air inlet chamber and the reaction chamber and the exhaust chambers which can be uniformly arranged in the transverse direction of the glass ribbon, has novel technical thought, effectively improves the process controllability and the product quality of the coated glass by the chemical vapor deposition method, and is suitable for the application of a plate glass production line.
The chemical vapor deposition device in the prior art and the used chemical vapor deposition device are only suitable for devices in which pure gas or single vaporized gas mixture operates at a certain temperature, the temperature of reaction mixed gas cannot be adjusted along with the requirements of different raw material characteristics, the temperature of the reaction chamber and the temperature of the gas inlet chamber are related, namely when the temperature of the reaction chamber is increased, the temperature of the gas inlet chamber is correspondingly increased, advanced reaction is easily generated in the gas inlet chamber, and the film coating efficiency and quality are influenced. The reactor of the invention is different from the known chemical vapor reaction deposition device, the air inlet chamber is relatively independently arranged with the air inlet channel, the reaction chamber, the exhaust channel, the exhaust chamber and the like, the air inlet chamber can be independently heated, the requirement of the coating precursor raw material on coating production can be better adapted, and simultaneously, the reactor of the invention also has the function of uniformly distributing air in the direction vertical to the advancing direction of glass, namely the length direction of the reactor (in figure 1, the direction vertical to the paper).
Preferably, the air inlet chamber comprises a pressure equalizing cavity and a heat medium cavity which surrounds the pressure equalizing cavity, is controlled by an external control system and is used for controlling the temperature of reaction gas in the pressure equalizing cavity. The pressure-equalizing cavity can ensure stable and balanced pressure in the length direction of the reactor on the premise of certain reaction gas flow, and an outlet of the pressure-equalizing cavity is connected with the gas inlet channel. Preferably, the pressure equalizing cavity and the heat medium cavity are both formed by welding high-quality carbon steel with the thickness not less than 5mm, and the pressure-resistant airtightness is greater than 0.5MPa/24 h. The heat medium in the heat medium cavity can be water or heat conduction oil, and is preferably heat conduction oil. Further preferably, the heat conducting oil can resist the temperature of above 320 ℃.
Preferably, an air inlet pipe for reaction gas to enter is arranged in the pressure equalizing cavity. The diameter of the air inlet pipe is preferably 10-35 mm, and more preferably 15-25 mm.
The pipe wall of the air inlet pipe is regularly distributed with a plurality of small holes along the length direction of the reactor, thereby ensuring stable and balanced pressure in the length direction of the reactor and uniform air distribution. The diameter of the small hole is preferably 1-5 mm, more preferably 1-3 mm, most preferably 1.5-2 mm, and the distance is preferably 5-25 mm, more preferably 5-15 mm, and most preferably 10 mm.
Preferably, a damping belt which is provided with a plurality of micropores and is used for uniformly distributing air is arranged at the bottom outlet of the pressure equalizing cavity. The diameter of the micropores is preferably 0.2-1.5 mm, and more preferably 0.5-0.8 mm. The damping belt can be fixed at the lower end of the pressure equalizing cavity in a mode of clamping by two fixing blocks. The height of the damping belt is preferably not less than 15mm, more preferably 20mm, and the thickness is preferably 5-25 mm, more preferably 7-15 mm. The damping strip is preferably selected from a sintered plate or a stacked orifice plate. The hole-stacking plate is preferably composed of flat belts and toothed belts which are arranged longitudinally and distributed alternately. The flat belt and the toothed belt are preferably made of stainless steel. The thickness of the flat belt is preferably 0.05-0.5 mm, more preferably 0.08-0.15 mm, the peak-trough range (height difference between peaks and troughs when the toothed belt is flatly placed) of the toothed belt is preferably 0.3-1.5 mm, more preferably 0.5-0.75 mm, and the distance between peaks is preferably not more than 1.5mm, more preferably 1.0 mm.
Preferably, the air inlet channel is surrounded by a first steel structure and an upstream block, a central block or a first steel structure and two central blocks, the first steel structure is used for forming the refrigerant medium cavity, the exhaust chamber, the refrigerant medium cavity and the central block are all positioned on the inner side of the U-shaped channel, the central block is positioned below the first steel structure, the gap between the central block and the first steel structure is adjustable, and therefore the temperature of the central block can be adjusted to meet the condition that the reaction gas deposits the functional film on the surface of the glass. The gap between the first steel structure and the center block can be adjusted by adding a shim. The temperature of the central block is preferably 150-500 ℃, and further preferably 180-380 ℃.
The temperature of the gas inlet channel is gradually increased from top to bottom to form a preheating channel of the reaction gas. The temperature of the preheating channel is preferably 50-420 ℃, and further preferably 100-350 ℃. The width of the air inlet channel is preferably 5-25 mm, and more preferably 7-15 mm.
The reaction chamber is a reaction channel for coating composed of the central block and a hot glass ribbon, and the reaction chamber is directly arranged on the hot glass ribbon. Under the guide of the channel, the reaction gas is quickly preheated, and contacts with the hot glass strip in the reaction chamber to generate chemical reaction, and the reaction product is deposited on the hot glass strip to form a film with a certain function.
The lower part of the central block is the hot glass belt, the temperature is highest, the temperature of the refrigerant medium above the central block is lower, and the temperature range of the central block in the middle can be controlled by adjusting the distance between the refrigerant medium cavity and the central block below the refrigerant medium cavity, so that an air inlet channel with the temperature gradually rising from top to bottom can be formed.
The material of the central block is preferably silicon carbide or graphite, and the graphite comprises isostatic pressure graphite, high-purity graphite, anode graphite and the like.
In a preferred embodiment, the exhaust channel is enclosed by the central block and the exhaust block, and the width of the exhaust channel is preferably 10-40 mm, and more preferably 20-35 mm.
The exhaust chamber is controlled to be at a constant temperature through a coolant medium cavity, so that the internal air pressure is stable, and the stable and uniform extraction of waste gas is facilitated.
Preferably, the exhaust chamber is formed by welding a high-strength carbon steel plate and a pipe.
Preferably, the exhaust chamber communicates with the exhaust passage through a slit. The slits may be provided in plurality along the length direction of the reactor. The length of the slit opening along the length direction of the reactor is preferably 200-450 mm, more preferably 250-350 mm, and the height along the vertical direction of the reactor is preferably 1.5-12.5 mm, more preferably 2-12 mm. The length and width of each slit can be independently set.
The refrigerant medium in the refrigerant medium cavity can be water or heat transfer oil, and is preferably heat transfer oil.
The length of the horizontal section of the single U-shaped channel for coating is preferably not more than 300mm, more preferably 120-280 mm, and even more preferably 160-265 mm.
The total length of the horizontal sections of the double U-shaped channels for coating is preferably not more than 550mm, and further preferably 400-465 mm.
Preferably, the steel structure of the air inlet chamber is connected with the steel structures of the reaction chamber and the exhaust chamber through slide block bolts, and the joints are preferably provided with heat insulation materials for heat insulation. The heat insulating material comprises an aluminum silicate fiber felt and the like.
As a general inventive concept, the present invention also provides a method of depositing a coating film using the reactor, including: the reaction gas flows into the gas inlet channel after being preheated by the gas inlet chamber and distributed at a constant pressure, reaches the reaction chamber after being further preheated, the reaction gas generates chemical reaction on the surface of the glass, the product is deposited on the surface of the glass to form a film, and the reaction waste gas containing reaction residual gas flows into the gas outlet chamber through the gas outlet channel and is discharged to the outside or a recovery device.
The invention mainly relates to a special device and a method for manufacturing coated glass on a flat glass production line, in particular on a float glass production line by using a chemical vapor deposition method, and can be widely applied to the flat glass production line, in particular to the float glass production line.
Compared with the prior art, the invention has the main advantages that: the air inlet chamber of the reactor is relatively independently arranged with the air inlet channel, the reaction chamber, the exhaust channel, the exhaust chamber and the like, the air inlet chamber can be independently heated and is not influenced by a steel beam bearing body, the requirements of coating precursor raw materials on coating production can be better met, the realization of air inlet temperature gradient and preheating effect can be better realized, the problems that reaction gas reacts in the air inlet chamber and the like are avoided, and meanwhile, the reactor also has the function of uniformly distributing the gas in the direction vertical to the advancing direction of glass, namely the length direction of the reactor. In addition, the arrangement of the damping belt enables the reaction gas in the gas inlet channel to flow more stably and uniformly, and is beneficial to the coating of a subsequent reaction chamber.
Drawings
FIG. 1 is a schematic cross-sectional structure of a single U-channel membrane coating reactor of the present invention;
FIG. 2 is a schematic cross-sectional view of a steel beam carrier and a reaction chamber of the single U-shaped channel coating reactor of the present invention;
FIG. 3 is a schematic cross-sectional view of an inlet plenum of a single U-channel coated reactor of the present invention;
FIG. 4 is a schematic cross-sectional structure of a dual U-channel membrane reactor of the present invention;
FIG. 5 is a schematic cross-sectional view of a steel beam carrier and a reaction chamber of the dual U-shaped channel coating reactor of the present invention;
FIG. 6 is a schematic diagram of the cross-sectional structure of an inlet chamber of a dual U-shaped channel film coating reactor of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The float glass production line is characterized in that glass raw materials mixed according to a certain proportion are continuously fed into a float glass melting furnace through a conveying device, molten glass solution with certain flow performance is formed through high-temperature melting chemical reaction, after bubbles are discharged from a clarification area, certain flow is controlled through a flow gate plate, the molten glass flows into a tin bath, the space and the temperature of the molten tin in the tin bath are controlled through an electric heating controller and a tin bath cooler together, the molten glass is cooled gradually, the formed glass plate with certain width and thickness is pulled into an annealing furnace for annealing, and finally a glass product is formed. The tin bath is composed of a space protected by mixed gas of nitrogen and hydrogen and molten metal tin, and the space of the tin bath is a reducing atmosphere, so that molten tin is prevented from being oxidized, and meanwhile, glass liquid or a glass plate floats on the molten tin to form float glass with high flatness. Referring to the attached fig. 1 and 4 of the specification, the reactors 1 and 4 for chemical vapor deposition coated glass according to the present invention are both devices implemented in a float glass production line, suitable for performing chemical vapor deposition reaction by single or multiple gases, respectively suitable for reaction of different total gas amounts, and suitable for forming different design requirement films by performing chemical vapor deposition reaction on a hot substrate after vaporizing a coating precursor to form gaseous substances, wherein the hot substrate such as a hot float glass substrate 68 is subjected to chemical vapor deposition film forming on the hot substrate to uniformly prepare glass with solar heat reflection, low radiation or transparent conductive film coating.
1) Description of the membrane reactor 1 according to the invention:
as shown in fig. 1 to 3, one of the main bodies of the film coating reactor device 1 of the present invention is an air inlet chamber 2, which is provided with a chamber 50 (i.e. a pressure equalizing cavity) for accommodating a film coating reaction gas, wherein an air inlet pipe 22 made of 304 or 316L stainless steel is arranged in the chamber, the pipe traverses the air chamber in the length direction of the film coating reactor, the diameter of the pipe 22 is not more than 32mm, the distance between the small holes distributed on the pipe is 5mm to 25mm, the preferred distance between the small holes is 5mm to 15mm, and the most preferred distance is 10 mm; the diameter of the small hole is between 1mm and 5mm, and the size of the small hole is preferably between 1mm and 3 mm; the diameter of the small hole is most preferably 1.5 mm-2 mm; the diameter of an air inlet pipe of the reactor 1 is preferably 15-25 mm, the diameter of holes is preferably 2mm, and the distance between the holes is preferably 10 mm;
the gas distribution damping belt arranged at the lower end of the cavity 50 is connected with the long slit 26 with the width W9, wherein the width W9 of the long slit 26 corresponding to the reactor 1 is not more than 10mm, and the device of the invention is preferably 7 mm; the damping belt with uniform air distribution function is installed on the long slit, the damping belt preferably considers but is not limited to a sintering plate and a hole folding plate with a certain thickness, the hole folding plate is preferably selected by the device, the hole folding plate is composed of a stainless steel flat belt and a stainless steel toothed belt, the materials of the stainless steel flat belt and the stainless steel toothed belt are 304L or 316L, the thickness of the flat belt is 0.05 mm-0.5 mm, the device is preferably 0.08-0.15 mm, the wave crest and wave trough range difference of the toothed belt is 0.3 mm-1.5 mm, the device is preferably 0.5-0.75 mm, the distance between wave crests is not more than 1.5mm, and the distance between wave crests is preferably 1.0 mm; the damping belt is fixed at the lower end of the cavity 50 in a manner of clamping by two fixing blocks 23; the height H1 of the damping strips is not less than 15mm and the height H1 of the damping strips of the membrane reactor 1 according to the invention is preferably 20 mm.
The outside of the cavity 50 is provided with heat medium cavities 24, 84, the heat medium cavities 24 and 84 are respectively composed of high-strength welded steel plates or profiles 25, 27, 28 and 29, the inflow of the heat medium cavities is not limited to water, hot oil and other mediums, the device of the invention preferably uses heat conduction oil with the maximum temperature of not lower than 320 ℃, and the heat conduction oil is accurately controlled to the temperature required by the project precursor by an electric heating mode on the outside so as to keep the cavity 50 at the process control temperature.
The connection between the inlet chamber 2 of one main body of the membrane coating reactor device 1 and the upper end of the steel beam bearing body 3 of the other main body is implemented by fastening a special pressing block and a high-temperature-resistant bolt together, and the lower end is fixedly sealed by a limiting groove and a sealing element.
The steel beam carrier 3 of the other main body of the coating film reactor device 1 of the invention contains a reaction precursor inlet preheating channel 7 (namely an inlet channel), a reaction chamber 66 formed by hot plate glass, a reaction by-product waste gas and unreacted precursor exhaust channel 8, an exhaust chamber 9 and a carrier beam 69 for carrying the former four functions, and the steel beam carrier 3 is manufactured by processing section bars made of various materials.
The air inlet channel 7 of the steel beam supporting body 3 of the coating film reactor 1 of the invention is composed of metal profiles 19 and 20, an upstream block 12 and a central block 13 which are processed by non-metal materials, the metal profiles 19 and 20 are preferably made of channel steel materials in the invention, the upstream block 12 and the central block 13 are silicon carbide and graphite which have the advantages of rapid heat transfer, uniform heat conduction and processability, in the invention, isostatic pressure graphite and high-purity graphite are preferred, isostatic pressure graphite is more preferred, the upper surface of the air inlet channel 7 is connected with the outlet of an air inlet chamber damping zone, coating film reaction precursor gas is gradually heated isothermally under the control of a certain flow rate, the gas leaves the damping zone and is guided to a hot and clean glass strip 68 after being well homogenized, and a cavity space 66 formed by the hot glass strip 68 and the central block 13 is a key area for chemical reaction, the reactive species are deposited on the upper surface of the hot ribbon 68 to form a desired or designed film; the reaction by-products and unreacted precursor gas naturally flow with the gas into the exhaust channel 8 formed by the central block 13, the downstream blocks 14, 17 and the metal profiles 18, 19, 21, pass through specially designed exhaust slots into the exhaust chamber 9, and are then exhausted. The chambers 58, 59, 60, 61, 62, 63, 64 and 65 formed by the metal material profiles are passages for the flowing of the refrigerant medium of the whole bearing beam, the refrigerant medium mainly comprises water and high-temperature hot oil, the refrigerant medium used by the device mainly comprises water, the temperature of the water is controlled to be not more than 35 ℃, and the temperature of the device is preferably not more than 25 ℃.
The membrane reactor 1 according to the invention is suitable for use in a state in which the flow of a gas mixture is in a completely laminar flow, and as is known, the Reynolds number Re is a dimensionless parameter which makes it possible to accurately describe the state of the gas flow, i.e.
Wherein rho and mu are density and dynamic viscosity coefficient of the gas, and upsilon is gas flow velocity, so that the Reynolds number is in direct proportion to the gas flow velocity under the condition of given gas working condition; in pipe flow, experimental results demonstrate that flows with Reynolds numbers less than 2300 are laminar, while Reynolds numbers for fluids in two parallel plates
b is the spacing between the two plates, the Reynolds number of the membrane reactor 1 according to the invention is not more than 350, the Reynolds number of the membrane reactor 1 according to the invention is preferably not more than 200, and thus the size of the slit width W1 for the inlet channel 7 of the reactor is not more than 10mm, the slit width W1 according to the invention is preferably 7 mm; it is also stated that the maximum total flow of the gas mixture of the membrane reactor 1 according to the invention is not more than 10Nm3Per, the preferred total mixed gas quantity of the coating reactor 1 according to the invention is 8.5Nm3/h。
The height H2 of the inlet channel 7 of the inventive membrane reactor 1 is not less than 100mm, the height H2 of the inlet channel 7 of the inventive membrane reactor 1 is preferably 125 mm; the total height H4 of the reaction chamber 66 which is the key of the coating film reactor 1 is not more than 12mm, the H4 is preferably 8mm, the flowing length W2 of the reaction mixed gas is not more than 300mm, the coating film reactor is preferably 120 mm-300 mm, and the best consideration is preferably 160-265 mm;
the deposition rate and deposition time of the coating reactor 1 according to the invention are determined by the drawing speed upsilon of the float glassfMixed gas transport velocity upsilongThe reactor chamber flow length W2, wherein: deposition time
The deposition rate is one of indexes for measuring the deposition capacity of the chemical vapor deposition coating film reactor, is limited by a temperature interval of a float glass production line and a glass drawing speed, the deposition time cannot be infinitely long, so that the length of a reaction chamber is strictly limited, and a relatively high deposition rate is required when the film thickness of a finally formed film reaches 80-600 nm, the film deposition rate of the coating film reactor is not less than 20nm/s, and the deposition rate of the coating film reactor is preferably not less than 30 nm/s.
2) Description of the membrane reactor 2 according to the invention:
as shown in fig. 4 to 6, one of the main bodies of the membrane-coating reactor device 2 of the present invention is an inlet chamber 5, which is provided with a chamber 75 (i.e., a pressure equalizing cavity) for accommodating a membrane-coating reaction gas, and an inlet pipe 51 made of 304 or 316L stainless steel is provided in the chamber, and the pipe 51 is arranged across the gas chamber in the longitudinal direction of the membrane-coating reactor, and has a diameter of not more than 32mm, and holes having a diameter of not more than 5mm and a distance of not more than 30mm are distributed on the pipe, and the diameter of the inlet pipe of the reactor 2 of the present invention is preferably 25mm, the diameter of the holes is preferably 2mm, and the distance between the holes is preferably 10 mm.
An air distribution damping belt arranged at the lower end of the cavity 75 and connected with a long slit 57 with a width W10, wherein the width W10 of the long slit 57 corresponding to the reactor 2 is not more than 20mm, and the device of the invention is preferably 15 mm; the damping belt with uniform gas distribution function is installed on the long slit, the damping belt preferably considers but is not limited to a sintering plate and a hole folding plate with certain thickness, the hole folding plate is preferably selected by the device, the hole folding plate is composed of a stainless steel flat belt and a stainless steel toothed belt, the materials of the stainless steel flat belt and the stainless steel toothed belt are 304L or 316L, the thickness of the flat belt is 0.05 mm-0.5 mm, the device is preferably 0.1mm, the distance between wave crests and wave troughs of the toothed belt is 0.3 mm-1.5 mm, the device is preferably 0.6mm, the distance between wave crests is not more than 1.5mm, and the distance between wave crests is preferably 1.0 mm; the damping belt is fixed at the lower end of the cavity 75 in a manner of clamping by two fixing blocks 23; the height H5 of the damping strips is not less than 15mm and the height H5 of the damping strips of the membrane reactor 1 according to the invention is preferably 25 mm.
The outside of the cavity 75 is provided with heat medium cavities 49 and 83, the heat medium cavities 49 and 83 are composed of high-strength welded steel plates or profiles 48, 52, 53, 54, 74 and 90, the flowing medium of the heat medium cavities 49 and 83 is not limited to water, hot oil and the like, the device of the invention preferably uses heat conduction oil with the maximum temperature of not lower than 320 ℃, and the heat conduction oil is accurately controlled to the temperature required by the project precursor gas through an electric heating mode on the outer side so as to keep the cavity 75 at the temperature controlled by the process.
The connection of an inlet chamber 5 of one main body of the membrane coating reactor device 4 of the invention and the upper end of a steel beam bearing body 6 of the other main body is implemented by fastening a special pressing block and a high temperature resistant bolt together, and the lower end is fixed and sealed by a limit groove and a sealing element.
The steel beam carrier 6 of the other main body of the membrane reactor device 4 of the present invention contains a reaction precursor inlet preheating channel 71 (i.e. inlet channel), a reaction chamber 67 formed by hot plate glass 68, reaction by-product waste gas and unreacted precursor waste gas channels 72, 87, exhaust chambers 73, 88 and a carrier beam 70 for carrying the former four functions, and the steel beam carrier 6 is manufactured by processing various material profiles.
The inlet channel 71 of the steel beam carrier 6 of the membrane reactor device 4 of the present invention is composed of metal profiles 34, 35 and upstream and downstream central blocks 30, 76 made of non-metallic material, the metal profiles 34, 35 are preferably made of channel steel in the present invention, the upstream and downstream central blocks 30, 76 are silicon carbide and graphite with fast heat transfer, uniform heat conduction and workability, in the present invention, isostatic graphite and high purity graphite are preferred, isostatic graphite is more preferred, the inlet channel 71 receives the inlet chamber through the outlet of the damping belt, the coating reaction precursor gas is gradually isothermally heated under the control of a certain flow rate, the gas leaves the damping belt to be well homogenized in the inlet channel 71 and is guided to the hot clean glass belt 68, the spaces 67 and 77 formed by the hot glass belt 68 and the upstream and downstream central blocks 30, 76 become the critical region for chemical reaction, the reactive species are deposited on the upper surface of the hot ribbon 68 to form a desired or designed film; the reaction by-products and unreacted precursor gas naturally flow with the gas into the exhaust passages 72, 87 formed by the exhaust blocks 31, 32, 33, 78, 79, 80, 93 of the upstream and downstream central blocks 30, 76 and the metal profiles 34, 35, and then enter the exhaust chamber 73 through the specially designed exhaust slit, and then are exhausted. The chambers 40, 41, 42, 43, 44, 45, 46, 47, 81, 82 formed by the metal section bars are the channels for the flow of the refrigerant medium of the whole bearing beam, the refrigerant medium mainly comprises water and high-temperature hot oil, the refrigerant medium used by the device of the invention mainly comprises high-temperature heat-conducting oil, the temperature of the heat-conducting oil is controlled not to exceed 325 ℃, and the device of the invention preferably does not exceed 225 ℃.
The membrane-coated reactor device 4 of the invention is suitable for the mixed gas flowing in a completely laminar state,from the foregoing, the Reynolds number for a fluid in two parallel plates
b is the spacing between the two plates, the Reynolds number of the inventive coating reactor 4 is required to be not more than 750, the Reynolds number of the inventive coating reactor 4 is preferably not more than 500, whereby the size of the slit width W6 for the inlet channel 71 of the reactor is not more than 20mm, the slit width W6 of the invention is preferably 15 mm; it is also stated that the maximum total flow of the gas mixture of the coating reactor 4 according to the invention is not more than 35Nm3H, minimum total mixed gas flow rate not less than 12Nm3Per, the preferred total mixed gas quantity of the coating reactor 4 according to the invention is 25Nm3/h。
The height H6 of the inlet channel 71 of the membrane-coated reactor device 4 according to the invention is not less than 100mm, the height H6 of the inlet channel 71 of the membrane-coated reactor device 4 according to the invention is preferably 125 mm; whereas the total height H8 of the reaction chambers 67 and 77, which is critical for the membrane-coated reactor 4 according to the invention, is not more than 12mm, the invention H4 is preferably 8 mm.
The deposition rate and deposition time of the inventive membrane reactor device 4 is determined by the drawing speed upsilon of the float glassfMixed gas transport velocity upsilongThe reactor chamber flow length is determined by W5 and W7, wherein: deposition time
Total deposition time t ═ tUpstream of+tDownstream，
Therefore, the flowing length of the reaction mixed gas of the film coating reactor 2 is designed to be W5 ≤ W7, W5 and W7 are not more than 300mm, the film coating reactor is preferably selected from W5 mm 180-200 mm, W7 mm 220-265 mm, the film layer deposition rate is not less than 20nm/s, and the film coating reactor is preferably selected from the film coating reactor of the invention, the deposition rate is not less than 30 nm/s.
Example 1
The coating film reactor 1 is used, the coating film reactor 1 is placed at a position where the temperature of molten tin under glass plates at two sides of a tin bath of a float glass production line is 625 ℃, the height of the lower surface of the reactor from the glass plates is 5mm, and a hot oil circulating system is adjusted to control the temperature of heat conducting oil to be 200 ℃ and enter an air inlet chamber and keep the temperature below the temperature; meanwhile, the oil temperature of the main carrier beam is controlled to be 130 ℃ by adjusting a hot oil circulating system, so that the carrier beam can keep good rigidity at the temperature, and the reactor can be kept horizontal on the surface of a float glass plate; the temperature of the central block 13 is kept between 200 and 220 ℃ under the working condition by adjusting the heat insulation material between the main bearing beam bottom plate 19 and the central block 13.
Placing tetrabutyl titanate raw material into a standard bubbler, controlling the temperature of the bubbler at 170 ℃, introducing nitrogen which has the flow rate of 6.21 standard cubic meters per hour and is heated to the temperature of 170 ℃ by a heater into the bubbler, simultaneously adding diluted nitrogen with the flow rate of 2.25 standard cubic meters per hour, mixing, keeping the temperature of the mixture at 180 ℃, conveying the mixture to a reactor through a pipeline, and conveying the mixture to the upper surface of a hot glass ribbon through the reactor;
under these conditions, the glass ribbon was moved under the reactor at a drawing speed of 415 m/h, and a titanium dioxide film having a thickness of 85 nm, which was measured to have a color value L of 65.5, a of 5.22, and b of 1.01, was deposited at a deposition rate of 36.8 nm/s.
Example 2
The coating film reactor 2 is used, the coating film reactor 2 is placed at the position where the temperature of molten tin under glass plates at two sides of a tin bath of a float glass production line is 615 ℃, the height of the lower surface of the reactor from the glass plates is 5mm, and a hot oil circulating system is adjusted to control the temperature of the heat conducting oil to be 160 ℃ and enter an air inlet chamber and keep the temperature of the heat conducting oil at the temperature; meanwhile, the oil temperature of the main carrier beam is controlled to be 130 ℃ by adjusting a hot oil circulating system, so that the carrier beam can keep good rigidity at the temperature, and the reactor can be kept horizontal on the surface of a float glass plate; the temperature of the central block 13 is kept between 190 ℃ and 200 ℃ under the working condition by adjusting the heat insulation materials between the main bearing beam bottom plates 34 and 35 and the central blocks 30 and 76.
Placing a tetrabutyl titanate raw material into a standard bubbler, controlling the temperature of the bubbler to be 160 ℃, introducing nitrogen gas with the flow rate of 9.85 standard cubic meters per hour, heating the nitrogen gas to the temperature of 160 ℃ by a heater into the bubbler, fully mixing the nitrogen gas with the flow rate of 15.05 standard cubic meters per hour and well-heated diluent gas, maintaining the temperature at 160 ℃, conveying the mixture to a reactor by a pipeline, and conveying the mixture to the upper surface of a hot glass ribbon by the reactor;
under these conditions, the glass ribbon was moved under the reactor at a drawing speed of 498 m/h, and a titanium dioxide film having a thickness of 176 nm was deposited at a deposition rate of 55.3 nm/s, and the titanium dioxide film was measured to have a color value L of 63.8, a of 9.64, and b of-0.50.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A reactor for coating glass by a chemical vapor deposition method is characterized by comprising an air inlet chamber and a steel beam supporting body, wherein the air inlet chamber can independently and uniformly distribute the entering reaction gas at a preset temperature in the length direction of the reactor;
the air inlet chamber:
the device comprises a pressure equalizing cavity and a heat medium cavity which surrounds the pressure equalizing cavity and is controlled by an external control system and used for controlling the temperature of reaction gas in the pressure equalizing cavity;
an air inlet pipe for reaction gas to enter is arranged in the pressure equalizing cavity, and a plurality of small holes are regularly distributed on the pipe wall of the air inlet pipe along the length direction of the reactor;
a damping belt which is provided with a plurality of micropores and is used for uniformly distributing air is arranged at an outlet at the bottom of the pressure equalizing cavity, the damping belt is selected from a sintered plate or a hole stacking plate, and the hole stacking plate consists of a flat belt and a tooth-shaped belt which are longitudinally arranged and alternately distributed;
the steel beam carrier includes:
the air inlet channel is communicated with the outlet of the air inlet chamber and is provided with an adjustable temperature gradient from top to bottom;
the reaction chamber is communicated with the outlet of the gas inlet channel and the outside and is formed by the hot glass strip, and the reaction gas in the reaction chamber can contact with the hot glass strip for reaction and film coating and has uniform concentration and flow rate;
the exhaust channel is communicated with the outlet of the reaction chamber and can uniformly discharge reaction waste gas in the length direction of the reactor;
the exhaust chamber is communicated with the outlet of the exhaust channel and can exhaust reaction waste gas, and a cold medium cavity for controlling the temperature of the reaction waste gas in the exhaust chamber is arranged around the exhaust chamber;
the gas inlet chamber, the gas inlet channel, the reaction chamber, the gas outlet channel and the gas outlet chamber form a reaction gas channel, wherein the gas inlet channel, the reaction chamber and the gas outlet channel form a single U-shaped or double U-shaped channel, and the reaction gas undergoes the processes of preheating, reaction and discharge in the channel;
the air inlet chamber is connected with the steel beam bearing body in a non-welding mode, and the steel structure of the air inlet chamber is independent of the steel structures of the reaction chamber and the exhaust chamber.
2. The reactor for the chemical vapor deposition coated glass according to claim 1, wherein the pressure equalizing cavity and the heat medium cavity are both welded by high-quality carbon steel with the thickness not less than 5mm, and the pressure-resistant airtightness is more than 0.5MPa/24 h; the heat medium in the heat medium cavity is water or heat conducting oil, and the heat conducting oil can resist the temperature of more than 320 ℃;
the diameter of the air inlet pipe is 10-35 mm; the distance between the small holes of the air inlet pipe which are regularly distributed is 5 mm-25 mm, and the size diameter of the small holes is 1 mm-5 mm.
3. The reactor for chemical vapor deposition coated glass according to claim 1, wherein the damping belt composed of a flat belt and a toothed belt has a micropore diameter of 0.2 to 1.5mm, a thickness of the flat belt is 0.05 to 0.5mm, a peak-to-trough range of the toothed belt is 0.3 to 1.5mm, and a pitch between peaks is not more than 1.5 mm;
the damping belt is fixed at the lower end of the pressure-equalizing cavity in a mode that two fixing blocks are clamped, the height of the damping belt is not less than 15mm, and the thickness of the damping belt is 5-25 mm.
4. The reactor for coating glass by a chemical vapor deposition method according to claim 1, wherein the gas inlet channel is surrounded by a first steel structure and an upstream block, a central block or a first steel structure and two central blocks, the temperature of the gas inlet channel is gradually increased from top to bottom to form a preheating channel of reaction gas;
the first steel structure is used for forming the refrigerant medium cavity; the exhaust chamber, the cold medium cavity and the central block are all positioned on the inner side of the U-shaped channel; the central block is positioned below the first steel structure, and the gap between the central block and the first steel structure is adjustable, so that the temperature of the central block can be adjusted;
the reaction chamber is a reaction channel for coating composed of the central block and a hot glass ribbon, and the reaction chamber is directly arranged on the hot glass ribbon.
5. The reactor for chemical vapor deposition coated glass according to claim 4, wherein the material of the central block is silicon carbide or graphite, and the graphite comprises isostatic graphite; the temperature of the central block is 150-500 ℃, the temperature of the preheating channel is 50-420 ℃, and the width of the air inlet channel is 5-25 mm.
6. The reactor for chemical vapor deposition coated glass according to claim 4 or 5, wherein the exhaust passage is defined by the central block and the exhaust block, and is used for exhausting a mixed gas of a generated gas after reaction and an unreacted gas, and the width of the exhaust passage is 10mm to 40 mm.
7. The reactor for chemical vapor deposition coated glass according to claim 1, wherein the exhaust chamber is formed by welding a high-strength carbon steel plate and a pipe, the exhaust chamber is communicated with the exhaust channel through a slit, the length of the slit opening along the length direction of the reactor is 200-450 mm, and the length along the vertical direction of the reactor is 1.5-12.5 mm;
the refrigerant medium in the refrigerant medium cavity is water or heat conducting oil.
8. The reactor of claim 1, wherein the horizontal section of the single U-shaped channel has a length of no more than 300mm for coating, and the horizontal section of the double U-shaped channel has a total length of no more than 550mm for coating.
9. The reactor for chemical vapor deposition coated glass according to claim 1, wherein the steel structure of the gas inlet chamber is connected with the steel structure of the reaction chamber and the steel structure of the exhaust chamber through slide block bolts, and the joints are provided with heat insulation materials, wherein the heat insulation materials comprise aluminum silicate fiber felts.
10. A method of depositing a coating using the reactor of any one of claims 1 to 9, comprising: the reaction gas flows into the gas inlet channel after being preheated by the gas inlet chamber and distributed at a constant pressure, reaches the reaction chamber after being further preheated, the reaction gas generates chemical reaction on the surface of the glass, the product is deposited on the surface of the glass to form a film, and the reaction waste gas containing reaction residual gas flows into the gas outlet chamber through the gas outlet channel and is discharged to the outside or a recovery device.
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| CN202110231874.8A CN112777943B (en) | 2021-03-02 | 2021-03-02 | Reactor for chemical vapor deposition method coated glass |
| PCT/CN2021/123791 WO2022183738A1 (en) | 2021-03-02 | 2021-10-14 | Reactor for chemical vapor deposition method-based coated glass |
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| CN115806393A (en) * | 2022-12-09 | 2023-03-17 | 耀华(秦皇岛)玻璃技术开发有限公司 | Online siliceous sunlight coating system of super large sheet width float glass |
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| GB1507996A (en) * | 1975-06-11 | 1978-04-19 | Pilkington Brothers Ltd | Coating glass |
| US5065696A (en) * | 1987-05-18 | 1991-11-19 | Libbey-Owens-Ford Co. | Temperature controlled distributor beam for chemical vapor deposition |
| US4793282A (en) * | 1987-05-18 | 1988-12-27 | Libbey-Owens-Ford Co. | Distributor beam for chemical vapor deposition on glass |
| GB2209176A (en) * | 1987-08-28 | 1989-05-04 | Pilkington Plc | Coating glass |
| FR2672518B1 (en) * | 1991-02-13 | 1995-05-05 | Saint Gobain Vitrage Int | NOZZLE WITH DISSYMMETRIC SUPPLY FOR THE FORMATION OF A COATING LAYER ON A TAPE OF GLASS, BY PYROLYSIS OF A GAS MIXTURE. |
| CN2230760Y (en) * | 1994-09-26 | 1996-07-10 | 秦皇岛开发区蓝光玻璃新技术公司 | Online glass coating apparatus for float process |
| CN100340512C (en) * | 2005-11-08 | 2007-10-03 | 浙江大学蓝星新材料技术有限公司 | Apparatus for on-line coating film of float glass |
| CN101844873B (en) * | 2009-03-24 | 2012-12-19 | 深圳市拓日新能源科技股份有限公司 | On-line film coating method of conductive glass and on-line film coating device |
| CN201770773U (en) * | 2010-06-25 | 2011-03-23 | 蚌埠玻璃工业设计研究院 | Gas distributing device for film coating of large-size substrate |
| CN202337730U (en) * | 2011-11-19 | 2012-07-18 | 蚌埠玻璃工业设计研究院 | Reactor for glass coating |
| CN202626033U (en) * | 2012-06-29 | 2012-12-26 | 海阳中浮新型建材有限公司 | Online coating machine for hanging type float glass |
| CN103058530B (en) * | 2013-01-23 | 2015-05-06 | 秦皇岛玻璃工业研究设计院 | Film plating device and method for preparing TCO (Transparent Conducting Oxide) glass online by floating method |
| CN104561938B (en) * | 2015-01-09 | 2017-04-19 | 浙江大学 | Online normal-pressure chemical vapor deposition film-plating reactor through floatation process |
| CN112777943B (en) * | 2021-03-02 | 2021-11-19 | 浙江大学 | Reactor for chemical vapor deposition method coated glass |
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