WO2022183738A1

WO2022183738A1 - Reactor for chemical vapor deposition method-based coated glass

Info

Publication number: WO2022183738A1
Application number: PCT/CN2021/123791
Authority: WO
Inventors: 韩高荣; 刘军波; 刘涌; 莫建良
Original assignee: 浙江大学
Priority date: 2021-03-02
Filing date: 2021-10-14
Publication date: 2022-09-09
Also published as: CN112777943A; CN112777943B

Abstract

A reactor for chemical vapor deposition method-based coated glass, comprising: a gas inlet chamber of which the temperature may be independently preset and capable of implementing independent and uniform gas distribution on an ingoing reactant gas in the length direction of the reactor, and a steel beam carrying body. The gas inlet chamber comprises a pressure equalization cavity, and a hot medium cavity that surrounds the pressure equalization cavity and is controlled by an external control system and used for controlling the temperature of the reactant gas in the pressure equalization cavity; the steel beam carrying body comprises the gas inlet chamber, a gas inlet passage, a reaction chamber, a gas exhaust passage, and a gas exhaust chamber that constitute a reactant gas passage. The steel structure of the air inlet chamber is independent of the steel structures of the reaction chamber and the gas exhaust chamber and is connected to the steel structures of the reaction chamber and the gas exhaust chamber by means of sliding block bolts, and a thermal insulation material is provided at the connections. Different temperature control of the gas inlet chamber and the reaction chamber, and the gas exhaust chamber that can be uniformly arranged in the transverse direction of a glass ribbon are achieved, so that the process controllability and product quality of chemical vapor deposition method-based coated glass are effectively improved, and thus the present invention is suitable for plate glass production line applications.

Description

A reactor for chemical vapor deposition coated glass

technical field

The invention relates to the field of on-line production of coated glass by a flat glass production line, in particular to a reactor for coating glass by chemical vapor deposition.

Background technique

Coated glass is one of the important building materials in the field of building energy saving. It not only retains the light transmission properties of windows, but also develops into a glass that can effectively block heat transfer. The coated glass is heated and tempered into insulating glass or vacuum glass. It is endowed with many new functions such as special energy saving, environmental protection, safety and decoration of ordinary flat glass; at the same time, because coated glass has good electrical conductivity and thermal processing properties, it becomes the substrate glass for solar cells and electronic products.

Coated glass can be divided into two processes: online coated glass and offline coated glass according to the manufacturing process. The so-called online coated glass is the process in which raw materials such as quartz sand are melted and clarified in a furnace to manufacture flat glass, and the coating is grafted in a suitable temperature range. Equipment, the coating precursor is evenly sprayed on the glass surface with a higher temperature through the coating equipment, the coating precursor is pyrolyzed at high temperature, and the reactant is deposited on the glass plate to form a process with a certain functional film layer; The main process of offline coating technology is vacuum cathode magnetron sputtering coating process, which means that the original flat glass sheet is washed and dried and then transported to a vacuum chamber. The process of hitting the target, exciting the target ions, and finally depositing on the glass surface to form a film with a certain function is a very mature process. The biggest difference between online coated glass and offline coated glass is that online coated glass can be thermally processed at will and does not require additional energy during the manufacturing process, while offline coated glass requires strict and harsh conditions to meet the requirements and consumes a lot of electricity. Therefore, online coating is a good direction for the development of coated glass.

The core equipment of online coating is a reactor that can uniformly coat the entire glass production line in the width direction. The mainstream process of online coating implementation is grafting on the float glass production line. The float glass production line is composed of raw material system, melting furnace, tin bath, transition roller table, annealing kiln, online monitoring system, cold end cutting and packing. , the online coating position is mainly in the area where the temperature of the tin bath and the annealing kiln is 500~700℃, and the width of this area is generally between 4000~5600mm, so this requires the main equipment of the online coating here - coating reaction It has good thermal stability, good rigidity, and at the same time, it has an inlet chamber that meets the temperature required for the reaction precursor, a reaction chamber that is different from the temperature requirement of the inlet chamber, and an exhaust chamber that can be evenly arranged in the lateral direction of the glass ribbon. Air chamber.

The main companies with float glass coating technology are: Pilkington Company of the United Kingdom, PPG Company of the United States, Saint-Gobain Company of France, Graveble Company of Belgium, and Weihai my country Glass New Material Technology Research and Development Co., Ltd., etc. American PPG and French Saint-Gobain originally purchased the patented technology of Pilkington, UK. The common feature of these three companies is to arrange coating equipment in the reducing atmosphere in the tin bath, while the Belgian Graveber and Weihai The characteristic of Glass New Material Technology R&D Co., Ltd. is that the coating equipment is arranged in the oxidizing atmosphere of the transition table and the A0 area of the annealing kiln.

US Patent US4088471A introduces a U-shaped single-channel reactor used in the low temperature section of the tin bath of a float glass production line. The inlet chamber of the reactor is immersed in the cooling medium water of the steel beam, and consists of an upstream block, a central block and a downstream block. It is directly or indirectly connected with the steel beam to form a U-shaped channel entering the gas reaction zone, that is, the gas enters the upstream channel of the U-shaped channel uniformly from the gas inlet chamber through the gas distribution member and preheats to the temperature before the pyrolysis reaction, and then It enters the reaction zone of the U-shaped channel formed by the central block and the hot glass ribbon, and the reacted exhaust gas enters the exhaust chamber through the other side of the U-shaped channel to remove the reaction zone. Therefore, the equipment uses the water temperature to keep the temperature of the intake chamber constant below 100 °C. Water is the cooling medium of the steel beam as a whole. The temperature of the reaction zone is controlled by an insulating gasket to adjust the interface temperature of the reaction zone. For silane as the main gas decomposition reaction deposition Elemental silicon is very effective. Its advantage is that it is suitable for deposition and coating process of small flow, low temperature and pure gas. The disadvantage is that the temperature of the reaction zone is greatly affected by the cooling medium water, and the temperature of the reaction chamber can only be within the cooling medium cooling range. , the control cannot be adjusted arbitrarily.

In view of the above deficiencies, US Patent US4857097A proposes structural improvements in related processes, such as changing the toe structure of the downstream block of the U-shaped channel to a circular arc, so as to introduce the outside gas medium, improve the coating cycle, and play a very important role. Connecting the exhaust chamber to the main steel beam is beneficial to the stability of the exhaust chamber and the intake chamber. However, the temperature control of the reaction zone and the temperature control of the inlet chamber remain as they were.

U.S. Patent US5065696A introduces a reactor capable of implementing double U-shaped channels and a single U-shaped channel reactor. The patent specification describes the use of steel parts to form a bearing steel beam with cooling medium cooling across the float process. On both sides of the glass tin bath, two relatively independent air inlet chambers without direct cooling medium are provided with air distributors at the outlet nozzles, and the lower end is composed of a central block with good thermal conductivity and a mixing chamber with a fingerboard that promotes mixing , so that the gas enters the mixing chamber from the independent inlet chamber through the respective nozzles and is mixed and guided to the upper surface of the hot glass ribbon. The temperature of the central block is controlled by the electric heating element, and the unreacted or reaction product waste gas enters the exhaust channel, and the exhaust gas is discharged. There is an even exhaust fingerboard in the air channel.

US Patent US5286295A introduces a reactor with a single-entry double-row double U-shaped structure composed of four graphites of different shapes. The patent specification analyzes in detail the optimal length of the upstream and downstream reaction zones within the same reaction time. It adapts to the problem that the reaction gas flow is large and the reaction is uniform, which lays a theoretical foundation for the practical application of the reactor.

US patent US9540277B2 introduces a single-inlet, double-row, double-U-shaped structure reactor capable of separating various reactants from each other and composed of four main parts to form an inlet channel, a gas distribution channel, a reaction channel and an exhaust channel. It is described in detail that the air intake channel is a uniform air distribution chamber for air intake composed of main body parts, cover plate parts, baffle parts and gas adjustment parts. The temperature control of this part mainly relies on the cooling pipe in the middle of the main body part. To meet the temperature of the reaction chamber and the temperature of the intake air, the control is difficult, the use effect is single, and the requirements for the precursor material of the reaction are relatively strong. The glass plate is less than 10mm, which is not conducive to the implementation of gas uniformity, especially the implementation of large-flow reactive gas coating reaction.

Chinese patent ZL201510014233.1 proposes an online float glass atmospheric pressure chemical vapor deposition coating reactor that utilizes waste heat of exhaust gas and has the effect of enhancing convective heat transfer, adjusting the airflow on the surface of the glass ribbon, and preventing the backflow of dust exhaust process. The mixing chamber and the exhaust gas chamber are arranged in the thermal insulation shell, the pre-mixing chamber is connected to the gas inlet pipe of the coating precursor, and the pre-mixing chamber is embedded in the exhaust gas chamber. Decrease the coating reaction temperature. However, independent control of the temperature of the premix chamber and the exhaust chamber is not achieved.

SUMMARY OF THE INVENTION

In view of the above-mentioned technical problems and the deficiencies in the art, the present invention provides a reactor for coating glass by chemical vapor deposition, including an air inlet chamber, a steel beam carrier, a gas U-shaped channel and an exhaust chamber, etc. , a chemical vapor deposition process can be used to deposit a film with certain functions on a glass substrate that moves heat.

A reactor for chemical vapor deposition coated glass, comprising an air inlet chamber and a steel beam carrier capable of independently and uniformly distributing gas independently and uniformly to the incoming reaction gas in the length direction of the reactor;

The intake chamber:

comprising a pressure equalization cavity and a heat medium cavity surrounding the pressure equalization cavity and controlled by an external control system for controlling the temperature of the reaction gas in the pressure equalization cavity;

The pressure equalization cavity is provided with an air inlet pipe for the reaction gas to enter, and a plurality of small holes are regularly distributed along the length direction of the reactor on the pipe wall of the air inlet pipe;

At the outlet of the bottom of the pressure equalizing cavity, a damping belt with a plurality of micropores for uniform air distribution is arranged, and the damping belt is selected from a sintered plate or a stacked orifice plate, and the stacked orifice plate is composed of longitudinally arranged and alternately distributed Composed of flat belt and toothed belt.

The steel beam bearing body includes:

an air intake passage communicating with the outlet of the air intake chamber and having an adjustable temperature gradient from top to bottom;

a reaction chamber communicated with the outlet of the air inlet channel and the outside, and formed with the hot glass ribbon, the reaction gas in the reaction gas can be coated with the hot glass ribbon, and the concentration and flow rate are uniform;

an exhaust channel that communicates with the outlet of the reaction chamber and can uniformly discharge the reaction waste gas in the length direction of the reactor;

an exhaust chamber communicating with the outlet of the exhaust passage and capable of discharging the reaction exhaust gas, and a cooling medium cavity for controlling the temperature of the reaction exhaust gas in the exhaust chamber is arranged around the exhaust chamber;

The intake chamber, the intake channel, the reaction chamber, the exhaust channel, and the exhaust chamber constitute a reaction gas channel, wherein the intake channel, the reaction chamber, and the exhaust channel constitute a single U-shaped or double U-shaped channel, and the reaction The gas undergoes preheating, reaction and discharge processes in this channel;

The air inlet chamber is connected to the steel beam carrier by a non-welded form (for example, through a pressing device), and the steel structure of the air inlet chamber is independent of the steel structures of the reaction chamber and the exhaust chamber.

The invention realizes the different temperature control of the air inlet chamber and the reaction chamber, and the exhaust chamber which can be evenly arranged in the lateral direction of the glass ribbon. , suitable for flat glass production line applications.

The existing technology and the chemical vapor deposition device used are only suitable for pure gas or a single vaporized gas mixture operating at a certain temperature. The temperature of the reaction mixture cannot be adjusted according to the requirements of different raw material characteristics. The temperature of the reaction chamber and the temperature of the inlet chamber are related, that is, when the temperature of the reaction chamber increases, the temperature of the inlet chamber also increases accordingly, and it is easy to produce an early reaction in the inlet chamber, which affects the coating efficiency and quality. The reactor of the present invention is different from the known chemical vapor reaction deposition device. The inlet chamber is relatively independent from the inlet passage, reaction chamber, exhaust passage, exhaust chamber, etc. The inlet chamber can be independently heated, which can be more suitable for coating The requirements of the precursor raw materials for coating production, and the reactor of the present invention also has the function of uniform gas distribution in the vertical glass advancing direction, that is, the length direction of the reactor (in Figure 1, the direction perpendicular to the paper).

Preferably, the air inlet chamber includes a pressure equalization cavity and a heat medium cavity surrounding the pressure equalization cavity, controlled by an external control system, and used to control the temperature of the reaction gas in the pressure equalization cavity. The pressure equalization cavity can ensure stable and balanced pressure in the length direction of the reactor under the premise of a certain reaction gas flow rate, and its outlet is connected with the air inlet channel. Preferably, the pressure equalizing cavity and the heat medium cavity are welded by high-quality carbon steel with a thickness of not less than 5 mm, and the pressure resistance and air tightness are greater than 0.5 MPa/24h. The heat medium in the heat medium cavity may be water or heat-conducting oil, preferably heat-conducting oil. Further preferably, the heat transfer oil with a temperature resistance of 320°C or higher.

Preferably, the pressure equalizing cavity is provided with an air inlet pipe for the reaction gas to enter. The diameter of the air intake pipe is preferably 10 to 35 mm, more preferably 15 to 25 mm.

A plurality of small holes are regularly distributed on the wall of the air inlet pipe along the length direction of the reactor, so as to ensure stable and balanced pressure and uniform gas distribution in the length direction of the reactor. The diameter of the small holes is preferably 1-5 mm, more preferably 1-3 mm, most preferably 1.5-2 mm, and the spacing is preferably 5-25 mm, more preferably 5-15 mm, and most preferably 10 mm.

Preferably, a damping belt with a plurality of micro-holes for uniform air distribution is provided at the outlet of the bottom of the pressure equalizing cavity. The diameter of the micropores is preferably 0.2 to 1.5 mm, more preferably 0.5 to 0.8 mm. The damping band can be fixed on the lower end of the pressure equalizing cavity by clamping with two fixing blocks. The height of the damping belt is preferably not less than 15 mm, more preferably 20 mm, and the thickness is preferably 5-25 mm, and further preferably 7-15 mm. The damping band is preferably made from a sintered plate or a perforated plate. The perforated plate preferably consists of longitudinally arranged and alternately distributed flat belts and toothed belts. The flat belt and toothed belt are preferably made of stainless steel. The thickness of the flat belt is preferably 0.05-0.5mm, more preferably 0.08-0.15mm, and the peak-to-valley range of the toothed belt (referring to the height difference between the peak and the trough when the toothed belt is laid flat) is preferably 0.3 ~1.5 mm, more preferably 0.5 to 0.75 mm, and the distance between the crests is preferably not more than 1.5 mm, more preferably 1.0 mm.

Preferably, the intake passage is surrounded by a first steel structure and an upstream block, a center block, or a first steel structure and two center blocks, and the first steel structure is used to form the refrigerant medium cavity, and the row The air chamber, the cooling medium cavity and the center block are all located on the inner side of the U-shaped channel. The center block is located under the first steel structure and the gap between the center block and the first steel structure is adjustable, so that the center can be adjusted. The temperature of the block is to meet the conditions for the reaction gas to deposit the functional film on the upper surface of the glass. The gap between the first steel structure and the center block can be adjusted by adding spacers. The temperature of the center block is preferably 150 to 500°C, more preferably 180 to 380°C.

The temperature of the inlet passage gradually increases from top to bottom, forming a preheating passage for the reaction gas. The temperature of the preheating channel is preferably 50-420°C, more preferably 100-350°C. The width of the air intake passage is preferably 5 to 25 mm, more preferably 7 to 15 mm.

The reaction chamber is a reaction channel for coating formed by the central block and the hot glass ribbon, and the reaction chamber is directly placed on the hot glass ribbon. Under the guidance of the channel, the reactant gas is rapidly preheated, contacts with the hot glass ribbon in the reaction chamber, a chemical reaction occurs, and the reaction product is deposited on the hot glass ribbon to form a film with certain functions.

Below the central block is the hot glass ribbon, the temperature is the highest, and the temperature of the cold medium above the central block is lower. By adjusting the distance between the cold medium cavity and the central block below it, the temperature range of the central block in the middle can be controlled, such as An intake passage with a gradually increasing temperature from top to bottom can be formed.

The material of the center block is preferably silicon carbide or graphite, and the graphite includes isostatic graphite, high-purity graphite, anode graphite, and the like.

In a preferred example, the exhaust passage is surrounded by the center block and the exhaust block, and the width is preferably 10-40 mm, more preferably 20-35 mm.

The exhaust chamber is controlled to a constant temperature through the cooling medium cavity, so as to ensure the stable air pressure in the exhaust chamber, which is conducive to the stable and uniform extraction of exhaust gas.

Preferably, the exhaust chamber is welded by high-strength carbon steel plates and pipes.

Preferably, the exhaust chamber communicates with the exhaust passage through a slit. A plurality of the slits may be provided along the length 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 set independently.

The cooling medium in the cooling medium cavity may be water or heat-conducting oil, preferably heat-conducting oil.

The length of the single U-shaped channel horizontal section used for coating is preferably not more than 300 mm, more preferably 120-280 mm, and still more preferably 160-265 mm.

The total length of the double U-shaped channel horizontal section used for coating is preferably not more than 550 mm, more preferably 400-465 mm.

Preferably, the steel structure of the intake chamber is connected with the steel structures of the reaction chamber and the exhaust chamber through slider bolts, and the connection is preferably provided with a thermal insulation material for thermal insulation. The thermal insulation material includes aluminum silicate fiber felt and the like.

As a general inventive concept, the present invention also provides a method for depositing a coating film by using the reactor, comprising: the reaction gas is preheated in the air inlet chamber and then flows into the air inlet channel after being preheated and distributed at a constant pressure, and after further preheating Arriving in the reaction chamber, the reaction gas reacts chemically on the glass surface, the product is deposited on the glass surface to form a film, and the reaction waste gas containing the reaction gas flows into the exhaust chamber through the exhaust passage and is discharged to the outdoor or recovery device.

The invention mainly relates to a special equipment and method for making coated glass on a flat glass production line, especially a float glass production line by chemical vapor deposition, which can be widely used in flat glass, especially a float glass production line.

Compared with the prior art, the main advantages of the present invention include: the inlet chamber of the reactor of the present invention is relatively independent from the inlet passage, the reaction chamber, the exhaust passage, the exhaust chamber, etc., the inlet chamber can be independently heated, and is not affected by the The influence of the steel beam carrier can better meet the requirements of the coating precursor raw materials for coating production, better realize the inlet temperature gradient and preheating effect, and avoid problems such as the reaction of the reaction gas in the inlet chamber. The reactor of the present invention also has the function of uniform gas distribution in the vertical glass advancing direction, that is, the length direction of the reactor. In addition, the setting of the damping belt also makes the flow of the reaction gas in the air inlet channel more stable and uniform, which is beneficial to the subsequent coating of the reaction chamber.

Description of drawings

Fig. 1 is the cross-sectional structure schematic diagram of the single U-shaped channel coating reactor of the present invention;

Fig. 2 is the cross-sectional structural schematic diagram of the steel beam carrier and the reaction chamber of the single U-channel coating reactor of the present invention;

3 is a schematic diagram of the cross-sectional structure of the air inlet chamber of the single U-channel coating reactor of the present invention;

Fig. 4 is the cross-sectional structure schematic diagram of the double U-shaped channel coating reactor of the present invention;

Fig. 5 is the cross-sectional structural schematic diagram of the steel beam carrier and the reaction chamber of the double U-shaped channel coating reactor of the present invention;

FIG. 6 is a schematic diagram of the cross-sectional structure of the air inlet chamber of the double U-channel coating reactor of the present invention.

Detailed ways

The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The operation method without specifying the specific conditions in the following examples is usually in accordance with the conventional conditions, or in accordance with the conditions suggested by the manufacturer.

The float glass production line is that the glass raw materials mixed according to a certain proportion are continuously put into the float glass melting furnace through the conveying device, and the molten glass solution with certain fluidity is formed through the chemical reaction of high temperature melting. The runner gate controls a certain flow rate, so that the molten glass flows into the tin bath, and the space in the tin bath and the temperature of the tin bath are jointly controlled by the electric heating controller and the tin bath cooler, so that the glass liquid is gradually cooled to form a certain width. The glass sheet with the thickness and thickness is drawn into the annealing furnace for annealing, and finally the glass product is formed. The tin bath is composed of a space protected by a mixed gas of nitrogen and hydrogen and the molten metal tin is carried. It can be seen that the tin bath space is a reducing atmosphere, which prevents the oxidation of the molten tin liquid and makes the glass liquid or glass plate float on it at the same time. Float glass with high flatness is formed. Referring to the accompanying drawings 1 and 4 of the description, it can be seen that the reactors 1 and 4 for chemical vapor deposition coated glass according to the present invention are all devices implemented in the float glass production line, and are suitable for single or multiple gases to carry out chemical vapor deposition reaction. The device is suitable for the reaction of different total amount of gas, and it is also suitable for various kinds of chemical vapor deposition reactions that can be produced on a hot substrate by vaporizing the coating precursor to form a gaseous substance to form a film layer with different design requirements, as described here. A hot substrate, such as a hot float glass substrate 68, uniformly produces glass with a solar thermal reflection, low emissivity or transparent conductive film coating by chemical vapor deposition film formation on the hot substrate.

1) Description of the coating film reactor 1 of the present invention:

As shown in FIGS. 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 (ie, a pressure equalizing cavity) to accommodate the coating reaction gas, and a chamber is provided in the chamber. The inlet pipe 22 is made of 304 or 316L stainless steel. The pipe traverses the gas chamber in the length direction of the coating reactor. The diameter of the pipe 22 is not greater than 32mm. 15mm, the spacing is most preferably 10mm; the diameter of the small hole is between 1mm and 5mm, and the size of the small hole is preferably between 1mm and 3mm; the diameter of the small hole is most preferably 1.5mm to 2mm; The diameter of the trachea is preferably 15-25mm, the diameter of the holes is preferably 2mm, and the spacing between the holes is preferably 10mm;

The air damping belt installed at the lower end of the cavity 50 is connected with the long slit 26 with a width W9, wherein the width W9 of the long slit 26 corresponding to the reactor 1 is not greater than 10mm, and the device of the present invention is preferably 7mm; the long slit is installed With a damping belt with uniform air distribution, the damping belt is preferably but not limited to sintered plates and perforated plates of a certain thickness. The device of the present invention preferentially selects a perforated plate, and the perforated plate is made of 304 or 316L stainless steel flat plate. The belt is composed of a stainless steel toothed belt. The thickness of the flat belt is between 0.05mm and 0.5mm. The device of the present invention is preferably 0.08 to 0.15mm. It is preferably 0.5-0.75mm, the distance between the crests is not more than 1.5mm, and the preferred distance between the crests is 1.0mm; the damping belt is fixed on the lower end of the cavity 50 by clamping two fixing blocks 23; the height H1 of the damping belt is not less than 15mm , the height H1 of the damping belt of the coating film reactor 1 of the present invention is preferably 20 mm.

Outside the cavity 50 are the heat medium cavities 24 and 84, which are respectively composed of high-strength welded steel plates or

profiles

25, 27, 28, and 29 to form the heat medium cavities 24 and 84. The inflow of the heat medium cavity is not limited to water. , hot oil and other media, the device of the present invention preferably uses heat transfer oil with a maximum temperature of not lower than 320 ° C. The heat transfer oil is accurately controlled to the temperature required by the project precursor through electric heating on the outside, so as to keep the chamber 50 in the process. controlled temperature.

The connection between the air inlet chamber 2 of the main body of the coating film reactor device 1 of the present invention and the upper end of the steel beam carrier 3 of the other main body is performed by co-fastening the special pressure block and high temperature resistant bolts, and the lower end is fastened together. The seal is fixed by the limit groove and the seal.

The steel beam carrier 3 of the other main body of the coating reactor device 1 of the present invention contains an inlet preheating channel 7 (ie, an inlet channel) of the reaction precursor, a reaction chamber 66 formed with hot flat glass, and a reaction pair. The exhaust channel 8 of the product exhaust gas and the unreacted precursor, the exhaust chamber 9 and the bearing beam 69 carrying the first four functions, the steel beam bearing body 3 is processed and manufactured from profiles of various materials.

The air inlet channel 7 of the steel beam carrier 3 of the coating reactor 1 of the present invention is composed of

metal profiles

19, 20, and upstream blocks 12 and center blocks 13 processed from non-metallic materials. The metal profiles 19, 20 are in this In the present invention, channel-shaped steel materials are preferred, while the upstream block 12 and the center block 13 are silicon carbide and graphite with fast heat transfer, uniform thermal conductivity, and machinability. In the present invention, isostatic graphite and high-purity graphite are preferred. , more preferably isostatic graphite, the inlet channel 7 is connected to the outlet of the damping zone of the inlet chamber, the coating reaction precursor gas is gradually heated isothermally under the control of a certain flow rate, and the gas leaves the damping zone to the inlet channel 7 After good homogenization, it is guided to the hot and clean glass ribbon 68 , and the cavity space 66 formed by the hot glass ribbon 68 and the central block 13 becomes the key area for chemical reaction, and the reactive substances are deposited on the hot glass ribbon 68 . surface, forming the desired or designed film; reaction by-products and unreacted precursor gases flow naturally with the gas into the exhaust channel 8 formed by the central block 13,

downstream blocks

14, 17 and

metal profiles

18, 19, 21 , and then enter the exhaust chamber 9 through a specially designed exhaust slit, and then discharge. The

chambers

58, 59, 60, 61, 62, 63, 64, and 65 composed of metal material profiles are the passages for the cooling medium of the entire bearing beam. The cooling medium is mainly water and high-temperature hot oil. The cooling medium used in the device of the present invention is mainly water, and the temperature of the water is controlled not to exceed 35°C, and the device of the present invention preferably does not exceed 25°C.

The coating reactor 1 of the present invention is suitable for the mixed gas flow in a completely laminar state. It is well known that the Reynolds number Re is a dimensionless parameter that can accurately describe the gas flow state, that is,

Among them, ρ and μ are the density and dynamic viscosity coefficient of the gas, and υ is the gas flow rate. Therefore, under a given gas condition, the Reynolds number is proportional to the gas flow rate. In pipe flow, the experimental results show that the Reynolds number is less than 2300 flow is laminar, and the Reynolds number for fluid in two parallel plates

b is the distance between two flat plates, the Reynolds number of the film coating reactor 1 of the present invention is required to be no greater than 350, and the Reynolds number of the coating film reactor 1 of the present invention is preferably no greater than 200. Therefore, for this reaction The size of the slit width W1 of the inlet channel 7 of the reactor is not greater than 10mm, and the slit width W1 of the present invention is preferably 7mm; it also illustrates that the total flow rate of the maximum mixed gas of the coating reactor 1 of the present invention is not greater than 10Nm ³ / h, the coating reactor 1 of the present invention preferably has a total mixed gas volume of 8.5 Nm ³ /h.

The height H2 of the air inlet channel 7 of the film coating reactor 1 of the present invention is not less than 100 mm, and the height H2 of the air inlet channel 7 of the film coating reactor 1 of the present invention is preferably 125 mm; The total height H4 of the key reaction chamber 66 is not greater than 12mm, and H4 is preferably 8mm in the present invention, and the flow length W2 of the reaction mixture is not greater than 300mm, the coating reactor of the present invention is preferably 120mm～300mm, and the best consideration is preferably 160～265mm ;

The deposition rate and deposition time of the coating film reactor 1 of the present invention are determined by the pulling speed υ _f of the float glass, the mixed gas conveying speed υ _g , and the flow length W2 of the reactor chamber, wherein: the deposition time

The deposition rate is one of the indicators to measure the deposition capacity of the chemical vapor deposition coating reactor. Limited by the temperature range of the float glass production line and the glass pulling speed, the deposition time cannot be infinitely long, which determines the length of the reaction chamber. It is strictly limited, and the film thickness of the final film-forming product is required to reach 80 to 600 nm, and a relatively high deposition rate is required. The film deposition rate of the coating reactor of the present invention is not less than 20 nm/s. The deposition rate of the film coating reactor is preferably not less than 30 nm/s.

2) description of coating film reactor 2 of the present invention:

As shown in FIGS. 4 to 6 , one of the main bodies of the film coating reactor device 2 of the present invention is the air inlet chamber 5 , which is provided with a chamber 75 (ie, a pressure equalizing cavity) to accommodate the coating film reaction gas. The air inlet pipe 51 is made of 304 or 316L stainless steel. The pipe traverses the gas chamber in the length direction of the coating reactor. The diameter of the pipe 51 is not greater than 32mm, and the pipes are distributed with holes with a diameter not greater than 5mm and a mutual spacing of not greater than 30mm. The diameter of the inlet pipe of the reactor 2 of the present invention is preferably 25 mm, the diameter of the holes is preferably 2 mm, and the spacing between the holes is preferably 10 mm.

The air damping belt installed at the lower end of the cavity 75 is connected with the long slit 57 with a width W10, wherein the width W10 of the long slit 57 corresponding to the reactor 2 is not greater than 20mm, and the device of the present invention is preferably 15mm; the long slit is installed With a damping belt with uniform air distribution, the damping belt is preferentially considered but not limited to a certain thickness of sintered plate and perforated plate. The device of the present invention preferentially selects a perforated plate, and the perforated plate is made of 304 or 316L stainless steel. It is composed of a flat belt and a stainless steel toothed belt. The thickness of the flat belt is between 0.05mm and 0.5mm. The device of the present invention is preferably 0.1mm. 0.6mm, the distance between the crests is not more than 1.5mm, and the preferred distance between the crests is 1.0mm; the damping belt is fixed on the lower end of the cavity 75 by clamping two fixing blocks 23; the height H5 of the damping belt is not less than 15mm, the The height H5 of the damping belt of the film coating reactor 1 is preferably 25 mm.

Outside the cavity 75 are the

heat medium cavities

49 and 83, which are made of high-strength welded steel plates or

profiles

48, 52, 53, 54, 74 and 90 to form the

heat medium cavities

49 and 83. 83 The flowing medium is but not limited to water, hot oil, etc. The device of the present invention preferably has a heat transfer oil whose maximum operating temperature is not lower than 320°C, and the heat transfer oil is accurately controlled to the temperature required by the project precursor gas through electric heating on the outside. , in order to maintain the chamber 75 at a process controlled temperature.

The connection between the inlet chamber 5 of the main body of the coating film reactor device 4 of the present invention and the upper end of the steel beam carrier 6 of the other main body is realized by the joint fastening of special pressing blocks and high temperature resistant bolts, and makes the The lower end is fixed and sealed through a limit groove and a seal.

The steel beam carrier 6 of the other main body of the coating reactor device 4 of the present invention contains an inlet preheating channel 71 (ie, an inlet channel) of the reaction precursor, a reaction chamber 67 formed with a hot flat glass 68, and a reaction pair. The

exhaust gas channels

72, 87, the

exhaust chambers

73, 88 of the product exhaust gas and the unreacted precursor, and the bearing beam 70 carrying the first four functions, the steel beam bearing body 6 is processed and manufactured from profiles of various materials.

The air inlet channel 71 of the steel beam carrier 6 of the film coating reactor device 4 of the present invention is composed of metal profiles 34, 35, and an upstream center block 30 and a downstream center block 76 processed from non-metallic materials. The metal profiles 34, 35, 35 In the present invention, channel-shaped steel materials are preferred, while the upstream center block 30 and the downstream center block 76 are silicon carbide and graphite with fast heat transfer, uniform thermal conductivity, and machinability, and isostatic pressing is preferred in the present invention. Graphite and high-purity graphite, more preferably isostatic graphite, the inlet passage 71 is connected to the outlet of the inlet chamber through the damping belt, the coating reaction precursor gas is gradually heated isothermally under the control of a certain flow rate, and the gas leaves the damping The ribbon is well homogenized in the air inlet channel 71 and directed to the hot clean glass ribbon 68, and the

spaces

67 and 77 formed by the hot glass ribbon 68 and the upstream center block 30 and the downstream center block 76 become the key to the chemical reaction. zone, the reactive species are deposited on the upper surface of the hot glass ribbon 68 to form the desired or designed thin film; the reaction by-products and unreacted precursor gases flow naturally with the gas into the rows of the upstream and downstream

central blocks

30, 76 The air blocks 31, 32, 33, 78, 79, 80, 93 and the

exhaust passages

72, 87 formed by the metal profiles 34, 35 enter the exhaust chamber 73 through the specially designed exhaust slits, and then are discharged. The

chambers

40, 41, 42, 43, 44, 45, 46, 47, 81, and 82 composed of metal profiles are the channels for the flow of the cooling medium of the entire bearing beam. The cooling medium is mainly composed of water and high-temperature hot oil. Mainly, the cooling medium used in the device of the present invention is mainly high-temperature heat-conducting oil, and the temperature of the heat-conducting oil is controlled not to exceed 325°C, and the device of the present invention preferably does not exceed 225°C.

The film coating reactor device 4 of the present invention is suitable for the state where the mixed gas flow is in a completely laminar flow state. It is known from the foregoing that the Reynolds number for the fluid in two parallel flat plates

b is the distance between two flat plates, the Reynolds number of the film coating reactor 4 of the present invention is required to be no greater than 750, and the Reynolds number of the coating film reactor 4 of the present invention is preferably no greater than 500. Therefore, for this reaction The size of the slit width W6 of the inlet channel 71 of the reactor is not more than 20mm, and the slit width W6 of the present invention is preferably 15mm; it also shows that the total flow rate of the maximum mixed gas of the coating reactor 4 of the present invention is not greater than 35Nm ³ / h, the minimum total mixed gas flow is not less than 12Nm ³ /h, and the film coating reactor 4 of the present invention preferably has a total mixed gas volume of 25Nm ³ /h.

The height H6 of the air inlet channel 71 of the film coating reactor device 4 of the present invention is not less than 100 mm, and the height H6 of the air inlet channel 71 of the film coating reactor 4 of the present invention is preferably 125 mm; The total height H8 of the

key reaction chambers

67 and 77 is not more than 12mm, and H4 is preferably 8mm in the present invention.

The deposition rate and deposition time of the coating film reactor device 4 of the present invention are determined by the pulling speed υ _f of the float glass, the mixed gas conveying speed υ _g , and the lengths W5 and W7 of the reactor chamber, wherein: the deposition time

Total deposition time t = t _upstream + t _downstream ,

Therefore, the flow length of the reaction mixture gas in the coating reactor 2 of the present invention is designed to be W5≤W7, and W5 and W7 are not greater than 300mm. The coating reactor of the present invention preferably has W5=180～200mm, W7=220～265mm, and film deposition The rate is not less than 20 nm/s, and the deposition rate of the film coating reactor of the present invention is preferably not less than 30 nm/s.

Example 1

Using the above-mentioned film coating reactor 1, the film coating reactor 1 is placed at a position where the temperature of the tin liquid under the glass plate on both sides of the tin bath of the float glass production line is 625 ° C, and the height of the lower surface of the reactor from the glass plate is 5mm, Adjust the hot oil circulation system to control the oil temperature of the heat transfer oil to enter the intake chamber at 200°C, and keep it at this temperature; at the same time, adjust the hot oil circulation system to control the oil temperature of the main bearing beam at 130°C, so that the bearing beam is at this temperature Good rigidity can be maintained under this condition, so that the reactor can be kept level on the float glass plate; by adjusting the thermal insulation material between the bottom plate 19 of the main bearing beam and the center block 13, the temperature of the center block 13 can be adjusted under this working condition. Keep at 200～220℃.

The tetrabutyl titanate raw material was placed in a standard bubbler, the temperature of the bubbler was controlled at 170 ° C, and the flow rate of 6.21 standard cubic meters per hour, which had been heated to a temperature of 170 ° C by a heater, was passed through nitrogen gas. Into the bubbler, at the same time, it is mixed with dilute nitrogen with a flow rate of 2.25 standard cubic meters per hour, and then the temperature is kept at 180 ° C and is transported to the reactor, and is transported to the upper surface of the hot glass ribbon through the reactor;

Under this condition, the glass ribbon was moved under the reactor at a pulling speed of 415 m/h, and a titanium dioxide film with a thickness of 85 nm was deposited at a deposition rate of 36.8 nm/sec. The color value of the titanium dioxide film was detected L*=65.5 , a*=5.22, b*=1.01.

Example 2

Using the above-mentioned film coating reactor 2, the film coating reactor 2 was placed at a position where the temperature of the tin liquid under the glass plate on both sides of the float glass production line was 615 ° C, and the height of the lower surface of the reactor from the glass plate was 5mm, Adjust the hot oil circulation system to control the oil temperature of the heat transfer oil to enter the intake chamber at 160°C, and keep it at this temperature; at the same time, adjust the hot oil circulation system to control the oil temperature of the main bearing beam at 130°C, so that the bearing beam is at this temperature Good rigidity can be maintained under this condition, so that the reactor can be kept level on the float glass plate; by adjusting the thermal insulation material between the main bearing beam bottom plates 34, 35 and the center blocks 30, 76, under this working condition, the center The temperature of the block 13 is maintained at 190-200°C.

The tetrabutyl titanate raw material is placed in a standard bubbler, the temperature of the bubbler is controlled at 160 ° C, and the flow rate is 9.85 standard cubic meters per hour, which has been heated to a temperature of 160 ° C by a heater. Into the bubbler, supplemented with a flow rate of 15.05 standard cubic meters per hour and well-heated diluent gas to mix well, keep the temperature at 160 ° C pipeline to the reactor, and through the reactor to the hot glass ribbon the upper surface of the;

Under this condition, the glass ribbon was moved under the reactor at a pulling speed of 498 m/h, and a TiO2 film with a thickness of 176 nm was deposited at a deposition rate of 55.3 nm/sec. The color value of the TiO2 film was detected L*=63.8 , a*=9.64, b*=-0.50.

In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims

A reactor for coating glass by chemical vapor deposition is characterized in that it comprises an air inlet chamber and a steel inlet chamber capable of independently and uniformly distributing the incoming reaction gas in the length direction of the reactor, the temperature of which can be independently preset. beam carrier;

The intake chamber:

comprising a pressure equalization cavity and a heat medium cavity surrounding the pressure equalization cavity and controlled by an external control system for controlling the temperature of the reaction gas in the pressure equalization cavity;

The pressure equalization cavity is provided with an air inlet pipe for the reaction gas to enter, and a plurality of small holes are regularly distributed along the length direction of the reactor on the pipe wall of the air inlet pipe;

At the outlet of the bottom of the pressure equalizing cavity, a damping belt with a plurality of micropores for uniform air distribution is arranged, and the damping belt is selected from a sintered plate or a perforated plate, and the laminated orifice plate is composed of longitudinally arranged and alternately distributed Composed of flat belt and toothed belt;

The steel beam bearing body includes:

an air intake passage communicating with the outlet of the air intake chamber and having an adjustable temperature gradient from top to bottom;

a reaction chamber communicated with the outlet of the air inlet channel and the outside, and formed with the heated glass ribbon, the reaction gas in the reaction chamber can contact the heated glass ribbon for reaction coating, and the concentration and flow rate are uniform;

an exhaust channel that communicates with the outlet of the reaction chamber and can uniformly discharge the reaction waste gas in the length direction of the reactor;

an exhaust chamber communicating with the outlet of the exhaust passage and capable of discharging the reaction exhaust gas, and a cooling medium cavity for controlling the temperature of the reaction exhaust gas in the exhaust chamber is arranged around the exhaust chamber;

The inlet chamber, the inlet channel, the reaction chamber, the exhaust channel, and the exhaust chamber constitute a reaction gas channel, wherein the inlet channel, the reaction chamber, and the exhaust channel constitute a single U-shaped or double U-shaped channel, and the reaction The gas undergoes preheating, reaction and discharge processes in this channel;

The intake chamber is connected to the steel beam carrier in a non-welded form, and the steel structure of the intake chamber is independent of the steel structure of the reaction chamber and the exhaust chamber.
The reactor for chemical vapor deposition coated glass according to claim 1, wherein the pressure equalizing cavity and the heat medium cavity are welded by high-quality carbon steel with a thickness of not less than 5 mm, and are pressure-resistant The air tightness is greater than 0.5MPa/24h; the heat medium in the heat medium cavity is water or heat transfer oil, and the heat transfer oil has a temperature resistance of more than 320°C;

The diameter of the air inlet pipe is 10-35 mm; the regularly distributed small holes of the air inlet pipe are spaced between 5 mm and 25 mm, and the diameter of the small holes is between 1 mm and 5 mm.
The reactor for coating glass by chemical vapor deposition method according to claim 1, wherein the diameter of the pores of the damping belt composed of the flat belt and the toothed belt is 0.2-1.5 mm, and the thickness of the flat belt is 0.2-1.5 mm. 0.05-0.5mm, the peak-to-valley range of the toothed belt is 0.3-1.5mm, and the distance between the peaks is not more than 1.5mm;

The damping band is fixed on the lower end of the pressure equalizing cavity by means of clamping two fixing blocks, the height of the damping band is not less than 15mm, and the thickness is 5-25mm.
The reactor for chemical vapor deposition coated glass according to claim 1, wherein the air inlet channel is surrounded by a first steel structure and an upstream block, a center block, or a first steel structure and two center blocks The temperature gradually increases from top to bottom to form a preheating channel for the reaction gas;

The first steel structure is used to form the cooling medium cavity; the exhaust chamber, the cooling medium cavity and the center block are all located inside the U-shaped channel; the center block is located under the first steel structure and The gap with the first steel structure is adjustable, so that the temperature of the center block can be adjusted;

The reaction chamber is a reaction channel for coating formed by the central block and the hot glass ribbon, and the reaction chamber is directly placed on the hot glass ribbon.
The reactor for chemical vapor deposition coated glass according to claim 4, wherein the material of the center block is silicon carbide or graphite, and the graphite includes isostatic graphite; the temperature of the center block is The temperature of the preheating channel is 50-420 °C, and the width of the intake channel is 5-25 mm.
The reactor for chemical vapor deposition coated glass according to claim 4 or 5, characterized in that, the exhaust passage is surrounded by the center block and the exhaust block, and is used for discharging the reacted products. Mixed gas composed of gas and unreacted gas, the width of the exhaust channel is 10mm to 40mm.
The reactor for chemical vapor deposition coated glass according to claim 1, characterized in that, the exhaust chamber is formed by welding high-strength carbon steel plates and pipes, and the exhaust chamber is connected to the exhaust chamber through a slit. The exhaust channel is connected, and 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 cooling medium in the cooling medium cavity is water or heat-conducting oil.
The reactor for coating glass by chemical vapor deposition method according to claim 1, wherein the length of the single U-shaped channel horizontal section used for coating is not more than 300mm, and the double U-shaped channel horizontal section is used for coating The total length is not more than 550mm.
The reactor for chemical vapor deposition coated glass according to claim 1, wherein the steel structure of the intake chamber is connected with the steel structures of the reaction chamber and the exhaust chamber through slider bolts, and the connection is A thermal insulation material is provided at the place, and the thermal insulation material includes an aluminum silicate fiber felt.
A method for depositing a coating film using the reactor according to any one of claims 1 to 9, wherein the method comprises: the reaction gas is preheated in an air inlet chamber and then flows into an air inlet channel after being preheated and distributed at a constant pressure, and further preheated After reaching the reaction chamber, the reaction gas reacts chemically on the glass surface, the product is deposited on the glass surface to form a film, and the reaction waste gas containing the reaction gas flows into the exhaust chamber through the exhaust channel and is discharged to the outdoor or recovery device.