WO2013024649A1 - フロートガラス製造装置、及び、これを用いたフロートガラス製造方法 - Google Patents

フロートガラス製造装置、及び、これを用いたフロートガラス製造方法 Download PDF

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Publication number
WO2013024649A1
WO2013024649A1 PCT/JP2012/067624 JP2012067624W WO2013024649A1 WO 2013024649 A1 WO2013024649 A1 WO 2013024649A1 JP 2012067624 W JP2012067624 W JP 2012067624W WO 2013024649 A1 WO2013024649 A1 WO 2013024649A1
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Prior art keywords
float glass
heat transfer
water
transfer material
bottom casing
Prior art date
Application number
PCT/JP2012/067624
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English (en)
French (fr)
Japanese (ja)
Inventor
康裕 楠木
信之 伴
丈宜 三浦
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to KR1020137031426A priority Critical patent/KR101944563B1/ko
Priority to CN201280031899.2A priority patent/CN103635437B/zh
Publication of WO2013024649A1 publication Critical patent/WO2013024649A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/16—Construction of the float tank; Use of material for the float tank; Coating or protection of the tank wall
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

  • the present invention relates to a float glass manufacturing apparatus and a float glass manufacturing method using the same.
  • the float process is widely known as a method for producing flat glass, and in recent years, it has been used for various purposes such as display glass in addition to conventional architectural window glass and automotive window glass. Yes.
  • the production of plate glass by the float process is carried out using a float bath with molten tin. Specifically, molten glass is poured onto the molten tin from the upstream side, and is formed into a desired thickness and width while being guided to a strip-shaped glass ribbon in a forming region disposed on the downstream side.
  • the float bath needs to hold molten tin at 500 ° C. or higher inside.
  • the float bath has a configuration in which the inner surface of the bottom casing constituting the lower portion thereof is lined with a fire-resistant bottom brick, and molten tin is filled therein.
  • molten tin can enter the seam of the refractory bottom brick and reach the bottom casing portion.
  • the lower part of the refractory block needs to be kept below the melting temperature of tin (231.9 ° C.).
  • Patent Document 1 a method of cooling by blowing air on the outer surface of the bottom casing has been employed.
  • Patent Documents 1 and 2 It is known that when temperature variation or fluctuation occurs in the bottom casing or the like in this way, gas is precipitated and released from the molten tin, and the gas comes into contact with the glass flowing on the molten tin. The problem of generating defects in the glass has occurred (Patent Documents 1 and 2).
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a float glass manufacturing apparatus capable of uniformly cooling the bottom casing below the float bath, and a float glass manufacturing method using the same.
  • the present invention provides a float glass manufacturing apparatus having a water cooling pipe for cooling a bottom casing covering a bottom brick bottom of a bathtub where molten tin is provided, wherein the water cooling pipe is at least of the bottom brick.
  • a heat transfer material is provided below the bottom casing along the joint position.
  • the heat transfer material has a hardness of 10 to 50 (Asker C) and a heat transfer coefficient ⁇ / d of 0.2.
  • the thickness d is 0.001 to 0.05 m, and ⁇ 10 3 to 1.6 ⁇ 10 3 W / (m 2 ⁇ K).
  • the present invention can make the temperature of the bottom casing more uniform by adding a water cooling mechanism to at least a portion of the bottom casing of the float glass manufacturing apparatus corresponding to the joints of the bottom brick disposed on the top casing. . Furthermore, it becomes possible to reduce or prevent the precipitation and generation of gas from molten tin.
  • FIGS. 1A and 1B demonstrate the outline of a common float glass manufacturing apparatus, and this invention is not limited to the apparatus which concerns.
  • FIG. 1A shows a cross-sectional view of a float glass manufacturing apparatus.
  • the float glass manufacturing apparatus has a structure in which a float bath roof 11 is arranged at the upper part and a float bathtub 12 is arranged at the lower part, and these are surrounded by these.
  • a float bath roof 11 is arranged at the upper part
  • a float bathtub 12 is arranged at the lower part, and these are surrounded by these.
  • molten tin 13 is provided, and the molten glass introduced from the upstream side of the apparatus on the molten tin 13 is formed into a glass ribbon 14 having a predetermined thickness as it goes downstream of the apparatus.
  • the molten tin 13 has an appropriate depth and temperature so that the float process can be performed, and the inside of the float glass manufacturing apparatus is maintained in a reducing atmosphere so that the molten tin is not oxidized.
  • a bottom brick 15 (hereinafter simply referred to as “brick”) is spread on the surface in contact with the molten tin.
  • the outer casing is covered with the bottom casing 16.
  • FIG. 1B shows a horizontal sectional view of the float glass manufacturing apparatus. This shows a cross-sectional view taken along line AA ′ in FIG. 1A.
  • the molten glass flow introduced from the left side in FIG. 1B is pushed from above by a top roll (rotating roll with grooves) 17 as shown in the figure, for example, to prevent the reduction of the glass ribbon width and adjust the thickness.
  • the molten glass from the melting kiln is formed on the molten tin into a glass ribbon 14 having a predetermined thickness, and is arranged on the right side in the figure, which is the next step. It is drawn out to a slow cooling kiln (not shown).
  • this invention is characterized by having a predetermined
  • FIGS. 4A to 4I described later are enlarged views of the periphery of the bottom casing portion of the float glass manufacturing apparatus. That is, for example, the part surrounded by the dotted line in FIG. 1A is enlarged, and in the float glass manufacturing apparatus of the present invention, the cross section of the part where the water-cooled tube is arranged via the heat transfer material at the joint position of the brick Is schematically shown.
  • FIG. 4C taking FIG. 4C as an example, the structure of the peripheral portion of the bottom casing will be described.
  • the brick 15 is at the top, and the bottom casing 16, the heat transfer material 18, and the water cooling pipe 19 are arranged in that order. It is.
  • molten tin 13 is disposed on the brick 15. Further, the heat transfer material 18 and the water cooling pipe 19 are arranged along the joint position of the brick 15. Even when there was a gap between the brick and the bottom casing (not shown), a simulation described later was performed assuming that the gap was filled with tin around the joint.
  • FIG. 4C the two bricks 15 and the joint positions that are the contact portions thereof are schematically shown. However, in the float glass manufacturing apparatus, many bricks 15 are arranged in the bottom casing 16 as described above. Yes. And in this invention, it has the above structures in the joint part of each brick at least.
  • the brick 15 is designed and arranged so that, when the float glass manufacturing apparatus is in steady operation, the brick 15 expands due to heat in the apparatus such as molten tin 13 so that no gap is generated between the bricks.
  • any material can be used for the bottom casing 16 as long as it has heat resistance and can maintain airtightness in the apparatus. However, in view of heat resistance, ease of processing, and cost, soft iron or stainless steel can be used. It is preferable that
  • the thermal conductivity ⁇ is in the range of 0.2 to 80 W / (m ⁇ K), more preferably in the range of 0.2 to 48 W / (m ⁇ K). In particular, the range is preferably 0.2 to 32 W / (m ⁇ K).
  • the heat transfer material 18 functions as a filler for increasing the adhesion between the two members in addition to the function of transferring the heat from the outer surface of the bottom casing 16 to the cooling water in the water cooling pipe 19. It functions as a cushioning material that prevents damage to the device due to thermal stress during startup and shutdown. Therefore, when it is necessary to select a material having a hardness that matches the above-mentioned purpose, if the hardness is higher than 50 (Asker C), the shape is difficult to deform, so that it is sufficient as a filler or cushioning material. Since it does not function and the adhesiveness of both members deteriorates, it is not preferable. Moreover, since it becomes difficult to construct when the hardness is lower than 10 (Asker C), it is not preferable. For this reason, the hardness having the above range was used.
  • FIG. 2A shows a simulation result of a temperature distribution state around the brick joint portion when the heat transfer coefficient (H) of the heat transfer material is changed.
  • calculation is performed using the structure shown in FIG. 4C as a model, and an enlarged view thereof is shown in FIG. 2B.
  • 2A indicates the horizontal distance from the brick joint as indicated by the arrow (X) in FIG. 2B.
  • the Y-axis has shown the temperature distribution of the outer surface of the bottom casing compared with the case of only air cooling, ie, the bottom casing surface by the side which has arrange
  • it shows as a temperature difference with the case of only air cooling.
  • FIG. 3 shows the temperature change of the joint portion when the heat transfer coefficient of the heat transfer material is changed as a temperature difference from the case of only air cooling.
  • the simulation was performed by the finite element method. As concrete conditions, molten tin 13 is in a steady state of 1200 ° C. and water in a water-cooled tube is in a steady state of 30 ° C., and brick 15 has a thermal conductivity of 1.4 W / (main component of SiO 2 and Al 2 O 3 as main components. m ⁇ K) bricks were used, and the bottom surface of the molten tin was separated from the bottom casing by 300 mm. The width of the water-cooled tube is 48 mm, and cooling is performed at the same temperature (30 ° C.) by 24 mm from the joint part to the left and right. In addition, cooling by air cooling is also performed.
  • the heat transfer coefficient is outside the range of 0.2 ⁇ 10 3 to 1.6 ⁇ 10 3 W / (m 2 ⁇ K)
  • cooling is not sufficient or excessively cooled. If the cooling is not sufficient, the object of the present invention for making the temperature of the bottom casing uniform cannot be sufficiently achieved. Moreover, when it cools too much, the temperature of a joint part will become temperature lower than another part, and since temperature distribution may reverse, it is unpreferable.
  • FIG. 3 shows the relationship between the heat transfer coefficient and the cooling effect of the joint part of the brick in the simulation.
  • the Y axis shows the temperature difference from the case of only air cooling.
  • the temperature is the temperature of the outer surface portion of the bottom casing corresponding to the joint portion of the brick, that is, the portion between the bottom casing and the heat transfer material. This shows that the higher the heat transfer coefficient, the higher the cooling effect.
  • the heat transfer coefficient is 0.1 ⁇ 10 3 W / (m 2 ⁇ K) has been shown, but in such a case, the cooling effect is lower than in the case of air cooling.
  • the temperature of the bottom casing which is the object of the present invention, can be uniformly cooled by selecting the heat transfer coefficient within the above range.
  • the thickness and heat conductivity of the heat transfer material 18 can be selected in order to set the heat transfer coefficient within the range.
  • the heat transfer material plays a role as a heat transfer medium for transferring heat and a role as a buffer material and a filler between the water-cooled tube and the bottom casing. For this reason, if the thickness is too thin, it cannot play a role as a sufficient cushioning material or filler, and if it is too thick, it lacks stability as a device and is easily affected by outside air or the like.
  • the thickness of the heat transfer material is preferably in the range of 0.001 m to 0.05 m, particularly preferably 0.001 to 0.03 m, 0.001 to More preferably, it is 0.02 m.
  • a heat transfer material having a heat conductivity ⁇ that takes the range of the heat transfer coefficient, but it is preferably 0.2 to 80 W / (m ⁇ K). 0.2 to 48 W / (m ⁇ K) is more preferable. In particular, it is preferably 0.2 to 32 W / (m ⁇ K).
  • the heat transfer material is not particularly limited as long as it satisfies the above conditions of hardness, heat transfer rate, heat conductivity, and thickness, and any material can be used. Specific examples include silicone resin, cement (including Portland cement, mixed cement, alumina cement), silicon cement, stainless wool, stainless felt, carbon wool, carbon felt, carbon cement, Dunseal (registered trademark), and the like. it can. As used herein, the term “silicone resin” has a broad meaning and includes silicone rubber and the like. In particular, the heat transfer material is preferably made of silicone resin or cement (including Portland cement, mixed cement, and alumina cement) from the viewpoint of easy availability and handling.
  • the heat transfer material 18 has the same width as the water-cooled tube 19 or a width larger than that.
  • the heat transfer material 18 has a function as a heat medium for assisting heat transfer between the bottom casing 16 and the water-cooled pipe 19, and functions as a filler and a buffer material for improving adhesion. It is because it is doing. For this reason, it is preferable to arrange so that at least the entire range of the water-cooled tube can be covered. Therefore, considering the cooling capacity and the like as will be described later, the width of the water cooling tube 19 is preferably 20 to 200 mm, more preferably 40 to 100 mm, and the width of the heat transfer material 18 is adjusted accordingly. The thickness is preferably 20 to 200 mm, more preferably 40 to 100 mm.
  • the shape of the heat transfer material is not particularly limited as long as it is configured so that the water-cooled tube is fixed to the surface of the bottom casing and heat conduction can be performed between the two.
  • the cross section can be provided in a substantially rectangular shape, or in FIGS. 4D, 4E, 4G, and 4I. As shown, the cross section can be provided in a substantially trapezoidal shape.
  • the shape and the configuration of the water-cooled pipe 19 are not limited as long as the water-cooled pipe 19 is arranged along the joint position of the bottom brick.
  • Examples of the shape of the water-cooled tube include a square tube as shown in FIGS. 4A, 4C, 4D, 4F, and 4H, and a circular tube as shown in FIGS. 4B, 4E, 4G, and 4I. It is done.
  • the square tube it is not specifically limited as the cross-sectional shape, Various shapes, such as a square and a rectangle, can be taken.
  • the cross-sectional shape of the circular tube is not limited, and various shapes such as a perfect circle and an ellipse can be taken.
  • 4A, 4B, and 4F to 4I can be provided with a plurality of water-cooled pipes centering on the joint portion, or as shown in FIGS. 4C to 4E. Large water-cooled tubes can also be provided.
  • a plurality of water cooling tubes can be provided on one heat transfer material as shown in FIGS. 4A and 4B.
  • each water cooling tube is provided.
  • a heat transfer material can also be provided for each tube.
  • an air-cooling nozzle 20 is provided between the water-cooled tubes and used together with air cooling to enhance the cooling effect. You can also.
  • the size of the water-cooled tube is not particularly limited. However, in order to arrange at a position corresponding to the joint portion of the brick, it is preferable to use one having a certain width in consideration of construction errors and the like.
  • the width is preferably 20 mm or more and 200 mm or less.
  • the thickness is more preferably 40 mm or more and 100 mm or less.
  • the width of the water-cooled tube here means the distance between both ends of the water-cooled tube when viewed in the horizontal direction regardless of the shape. This is because by having such a range, it can be surely installed so as to correspond to the joint portion of the brick, and furthermore, the joint portion of the brick and its periphery can be sufficiently cooled. .
  • the material of the water-cooled tube is not limited, and is appropriately selected in consideration of heat resistance, corrosion resistance, heat transfer, and the like.
  • a pipe made of metal such as stainless steel, soft iron, aluminum, or copper from the viewpoint of heat transfer performance, corrosion resistance, and the like.
  • soft iron or stainless steel it is more preferable to use soft iron or stainless steel in consideration of workability and cost.
  • the temperature and flow rate of water in the water-cooled pipe are not limited, and can be adjusted as appropriate while monitoring the temperature distribution of the bottom casing.
  • the water temperature is preferably controlled to be in the range of 20 to 40 ° C.
  • the temperature does not need to be uniform in the water-cooled tube, and means that the temperature falls within the temperature range as a whole. This is because, when the temperature of the cooling water is in the temperature range, it is possible to cool the bottom casing to an appropriate temperature range without excessively cooling the bottom casing.
  • the temperature of the bottom casing can be made uniform, so that generation of gas from the molten tin is suppressed, and glass with less defects due to gas can be manufactured. it can.
  • the entire bottom casing such as an air cooling mechanism similar to the ordinary float method is used. It is preferable to use a means for uniformly cooling the water. Further, the place where the water cooling mechanism of the present invention is provided is not limited to the joint part of the brick, and for example, if there is a part where the temperature is locally high in the bottom casing, the part is installed in the part. It is also possible.
  • a process similar to a normal float method can be employed. Specifically, after a raw material having a target glass composition is charged into a melting tank by a raw material charging machine to melt the raw material, a clarification and defoaming step is performed through a stirring device. Next, it is introduced into a float bath having the structure of the present invention, and after forming into a target plate thickness, for example, 0.1 to 0.7 mm, it is gradually cooled and processed to produce float glass.
  • any composition can be applied as long as the glass is manufactured by the float process, but an alkali-free glass containing the following components can be used. It can be used particularly advantageously when manufacturing.
  • each percentage has shown the mass percentage of the oxide basis.
  • SiO 2 50 to 73%, preferably 50 to 66% Al 2 O 3 : 10.5-24%
  • B 2 O 3 0 to 12%
  • BaO 0 to 13.5%
  • ZrO 2 alkali-free glass containing 0 to 5%.
  • the alkali-free glass has a melting point about 100 ° C. higher than that of the alkali glass, so that a temperature difference is likely to occur in the bottom casing. As a result, gas is likely to be released from the molten tin, which may cause defects on the glass surface.
  • alkali-free glass is often used for display applications, it is particularly undesirable to cause defects on the glass surface. Therefore, by adopting the float glass apparatus of the present invention and the glass manufacturing method using the same, it is possible to manufacture higher quality glass.
  • each percentage represents an oxide-based mass percentage.
  • SiO 2 58 to 66%
  • Al 2 O 3 15-22%
  • B 2 O 3 5-12%
  • MgO 0-8%
  • CaO 0-9%
  • SrO 3 to 12.5%
  • BaO 0-2%
  • MgO + CaO + SrO + BaO alkali-free glass containing 9 to 18%.
  • the present invention can be preferably applied to alkali-free glass containing the following components.
  • each percentage represents an oxide-based mass percentage.
  • SiO 2 50 to 61.5%
  • Al 2 O 3 10.5-18%
  • B 2 O 3 7 to 10%
  • MgO 2-5%
  • CaO 0 to 14.5%
  • SrO 0-24%
  • BaO 0 to 13.5%
  • MgO + CaO + SrO + BaO alkali-free glass containing 16 to 29.5%.
  • the oxide-based mass percentage display SiO 2 : 56 to 70% Al 2 O 3 : 14.5 to 22.5% B 2 O 3 : 0 to 2% MgO: 0 to 6.5% CaO: 0-9% SrO: 0 to 15.5% BaO: 0 to 2.5% MgO + CaO + SrO + BaO: alkali-free glass containing 10 to 26%.
  • SiO 2 54 to 73% Al 2 O 3 : 10.5 to 22.5%
  • B 2 O 3 1.5 to 5.5%
  • CaO 0-9%
  • SrO 0 to 16%
  • BaO 0 to 2.5%
  • MgO + CaO + SrO + BaO Alkali-free glass containing 8 to 25%.
  • the temperature difference and temperature distribution in the bottom casing can be reduced or eliminated, and the temperature of the entire bottom casing can be made uniform. And since the temperature of a bottom casing becomes uniform, the gas discharge

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PCT/JP2012/067624 2011-08-16 2012-07-10 フロートガラス製造装置、及び、これを用いたフロートガラス製造方法 WO2013024649A1 (ja)

Priority Applications (2)

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KR1020137031426A KR101944563B1 (ko) 2011-08-16 2012-07-10 플로트 유리 제조 장치 및 이것을 사용한 플로트 유리 제조 방법
CN201280031899.2A CN103635437B (zh) 2011-08-16 2012-07-10 浮法玻璃制造装置及使用该制造装置的浮法玻璃制造方法

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JP2011178103 2011-08-16
JP2011-178103 2011-08-16

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JP2015124123A (ja) * 2013-12-26 2015-07-06 旭硝子株式会社 フロート板ガラスの製造方法

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JP2016147786A (ja) * 2015-02-13 2016-08-18 旭硝子株式会社 フロート板ガラスの製造方法及びフロート板ガラスの製造装置

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JP2010202509A (ja) * 2009-03-03 2010-09-16 Lg Chem Ltd フロートガラス製造用フロート槽システム及びその冷却方法
JP2012036082A (ja) * 2010-08-11 2012-02-23 Lg Chem Ltd フロートガラス製造用フロート槽、及びフロート槽の冷却方法

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JP2015124123A (ja) * 2013-12-26 2015-07-06 旭硝子株式会社 フロート板ガラスの製造方法

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TW201309606A (zh) 2013-03-01
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