WO2011136109A1 - Molten glass treatment apparatus, process for production thereof, and use thereof - Google Patents
Molten glass treatment apparatus, process for production thereof, and use thereof Download PDFInfo
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- WO2011136109A1 WO2011136109A1 PCT/JP2011/059753 JP2011059753W WO2011136109A1 WO 2011136109 A1 WO2011136109 A1 WO 2011136109A1 JP 2011059753 W JP2011059753 W JP 2011059753W WO 2011136109 A1 WO2011136109 A1 WO 2011136109A1
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- glass
- molten glass
- processing apparatus
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- molten
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
- C03B5/1672—Use of materials therefor
- C03B5/1675—Platinum group metals
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/225—Refining
- C03B5/2252—Refining under reduced pressure, e.g. with vacuum refiners
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
Definitions
- the present invention relates to a molten glass processing apparatus, a manufacturing method thereof, and an application thereof.
- platinum or a platinum alloy is generally used as a material of a member that comes into contact with molten glass.
- the platinum alloy is an alloy containing rhodium (Rh), iridium (Ir), ruthenium (Ru), gold (Au) and the like in addition to platinum (Pt).
- Platinum and platinum alloys have high melting points, are not easily oxidized in the air, and have low reactivity with molten glass, and are therefore suitable as materials for members that are in contact with molten glass.
- the glass when glass or the like is used as the material for the hydrogen low-permeability layer, the glass may thermally flow downward due to its own weight and be separated from the outer surface of the member.
- alkali-free glass has been used for flat panel displays (FPD) such as liquid crystal displays (LCD).
- FPD flat panel displays
- the alkali-free glass is a glass that does not substantially contain an alkali metal, and has a melting temperature higher by 100 ° C. or more than a general soda lime glass. For this reason, the use temperature of the member is high, and the above problem is easily realized.
- Oxyfuel combustion burners have better heating efficiency than air combustion burners.
- the water concentration in the upper space in the melting tank increases, so the water concentration dissolved in the molten glass increases. For this reason, the above problem is easily realized.
- This invention is made
- the present invention provides a member made of platinum or a platinum alloy whose inner surface is in contact with molten glass, a glass layer covering at least a part of the outer surface of the member, and at least the outer side of the glass layer.
- a molten glass processing apparatus comprising a heat-resistant fiber body infiltrated with The heat-resistant fiber body includes glass fiber or ceramic fiber, and is expressed by mass% based on oxide, and the SiO 2 content is 50% or more, The glass forming the glass layer has a viscosity of 10 2.5 dPa ⁇ s or more at the use temperature,
- a molten glass processing apparatus is provided in which the glass layer includes voids that are not in communication with the outside air.
- the molten glass processing apparatus is an apparatus for processing molten glass, for example, an apparatus for melting, clarifying, adjusting temperature, conveying, stirring and the like of molten glass.
- the molten glass processing apparatus of this invention is not limited to this.
- FIG. 1 is a sectional view of a molten glass processing apparatus in use according to an embodiment of the present invention.
- the molten glass processing apparatus 1 covers at least a part of a platinum or platinum alloy member 3 whose inner surface 31 is in contact with the molten glass 2 and an outer surface 32 of the member 3.
- a glass layer 4 and a heat-resistant fiber body 5 in which at least the outer side (the side opposite to the member 3) of the glass layer 4 penetrates are provided.
- the glass layer 4 covers at least a part of the outer surface 32 of the member 3, thereby suppressing hydrogen contained in the molten glass 2 from passing through the member 3 and dissipating to the outside.
- the heat-resistant fiber body 5 suppresses the glass layer 4 from heat flowing.
- the member 3 is made of platinum or a platinum alloy.
- the platinum alloy is an alloy containing rhodium (Rh), iridium (Ir), ruthenium (Ru), gold (Au) and the like in addition to platinum (Pt). Since platinum and platinum alloys have the characteristics that they have a high melting point, are not easily oxidized in the atmosphere, and have low reactivity with the molten glass 2, they are suitable as materials for the member 3 with which the molten glass 2 comes into contact.
- the shape of the member 3 is set according to the type and application of the molten glass processing apparatus 1.
- the shape of the member 3 is set to a box shape or a tube shape.
- the molten glass 2 is in contact with the inner surface 31 of the member 3, and the glass layer 4 is in contact with the outer surface 32 of the member 3.
- the glass layer 4 covers at least part of the outer surface 32 of the member 3, thereby suppressing hydrogen contained in the molten glass 2 from passing through the member 3 and dissipating to the outside.
- the decomposition of dissolved water is suppressed. Therefore, it is possible to suppress the generation of bubbles due to the decomposition of moisture. Moreover, volatilization of platinum or the like can be suppressed.
- the glass forming the glass layer 4 is not particularly limited, but, for example, expressed in terms of mass% based on oxide, SiO 2 : 50 to 72%, Al 2 O 3 : 0.5 to 24%, preferably 0.5 to 23%, B 2 O 3 : 0-12%, MgO: 0-8%, CaO: 0-14.5%, SrO: 0-24%, BaO: 0-13.5%, Na 2 O + Li 2 O + K 2 O: 0 to 15%, MgO + CaO + SrO + BaO is 9 to 29.5%. At this time, it may further contain ZrO 2 : 0 to 5%.
- the glass forming the glass layer 4 is preferably non-alkali glass. This is to prevent alkali metal in the glass layer 4 from being mixed into the molten glass 2 when the member 3 is damaged.
- the alkali-free glass for forming the glass layer 4 is not particularly limited.
- SiO 2 50 to 66%
- Al 2 O 3 10.5 to 24%, preferably 10. 5-22%
- B 2 O 3 0-12%
- SrO: 0-24% SrO: 0-24%
- MgO + CaO + SrO + BaO is 9 to 29.5%.
- it may further contain ZrO 2 : 0 to 5%.
- SiO 2 58 to 66%
- Al 2 O 3 15 to 22%
- B 2 O 3 5 to 12%
- MgO 0 to 8%
- CaO 0 in terms of mass% based on oxide. -9%
- SrO 3 to 12.5%
- BaO 0 to 2%
- MgO + CaO + SrO + BaO is 9 to 18%.
- the glass forming the glass layer 4 has a viscosity ⁇ of 10 2.5 dPa ⁇ s or more (preferably 10 2.8 dPa ⁇ s or more, more preferably 10 3.5 dPa ⁇ s or more) at the use temperature. .
- the viscosity ⁇ is preferably 10 4.8 dPa ⁇ s or less, more preferably 10 4.5 dPa ⁇ s or less, at the use temperature.
- the operating temperature refers to the temperature when the member 3 is in contact with the molten glass 2.
- the operating temperatures of the molten glass 2, the member 3, and the glass layer 4 are usually substantially the same.
- the penetration depth D2 of the glass layer 4 into the heat resistant fiber body 5 is desirably 0.1 mm or more.
- the penetration depth D2 means an average value. If the penetration depth D2 is too small, it is difficult to suppress the heat flow of the glass layer 4 by the heat resistant fiber body 5.
- the glass forming the glass layer 4 is desirably glass having higher wettability to the member 3 than the heat-resistant fiber body 5 at the use temperature. Thereby, the adhesiveness of the glass layer 4 and the member 3 can be improved.
- the contact angle ⁇ a between the glass forming the glass layer 4 and the material constituting the member 3 depends on the type of glass, but is 30 to 60 °, preferably 30 ° C., preferably 45-55 °.
- the contact angle is based on the contact angle defined in JIS R 3257-1999.
- the contact angle ⁇ a is set such that a test plate formed of a material constituting the member 3 (for example, platinum or a platinum alloy) is installed horizontally, and a glass droplet forming the glass layer 4 is left on the test plate. Measured. This contact angle can be measured by a commercially available apparatus.
- the contact angle ⁇ b between the glass forming the glass layer 4 and the material constituting the heat resistant fiber body 5 is, for example, 60 to 110 °, preferably 70 to 110 ° at the operating temperature. It is.
- contact angle (theta) b is too small, the adhesiveness of the glass layer 4 and the member 3 will worsen.
- the contact angle ⁇ b is too large, the adhesion between the glass layer 4 and the heat-resistant fiber body 5 is deteriorated.
- the contact angle ⁇ b is set such that a test plate (for example, a glass plate or a ceramic plate) formed with the same composition as the material (for example, glass or ceramics) constituting the heat-resistant fiber body 5 is installed horizontally.
- the glass droplets forming 4 are placed on a test plate and measured.
- the thickness D1 (including the penetration depth D2) of the glass layer 4 is desirably 0.2 mm or more.
- the thickness D1 means an average value. If the thickness D1 is too small, the effect of providing the glass layer 4 is not sufficiently exhibited. On the other hand, if the thickness D1 is excessive, the glass forming the glass layer 4 is thermally flowed downward by its own weight, and the glass layer 4 is separated from the member 3. Therefore, the thickness D1 is preferably 3 mm or less, more preferably less than 1 mm, further preferably 0.9 mm or less, and particularly preferably 0.8 mm or less.
- the glass layer 4 of the present embodiment includes voids 7 and 9 that are not in communication with outside air, as shown in FIG.
- the voids 7 and 9 are distributed in the glass layer 4.
- the gap 7 is open to the outer surface 32 of the member 3, and the gas in the gap 7 is in contact with the outer surface 32 of the member 3.
- the void 7 suppresses hydrogen from permeating the member 3 from the inside to the outside, and thus suppresses the generation of bubbles in the molten glass 2. The reason is not fully understood, but the following reasons (1) to (3) are possible.
- Hydrogen is contained as atoms in the solid and liquid such as the member 3 and the glass layer 4 and is contained as molecules in the gas in the gap 7. Therefore, in order for hydrogen to move from the member 3 to the glass layer 4 through the gap 7, the molecules need to be decomposed into atoms after the atoms are combined into molecules. Since these bonds and decomposition require a predetermined energy, the movement of hydrogen is suppressed.
- the void 7 forms a contact interface between the glass forming the glass layer 4 and the member 3, thereby expressing the surface tension of the glass with respect to the member 3, and the glass thermally flows with respect to the member 3. Is suppressed.
- the air gap 9 is configured so that the gas in the air gap 9 does not contact the outer surface 32 of the member 3.
- the gap 9 suppresses hydrogen from permeating the member 3 from the inside to the outside for the same reason as the above (2), and consequently suppresses the generation of bubbles in the molten glass 2.
- the gaps 7 and 9 not communicating with the outside air occupy 2 to 70% of the cross section of the glass layer 4 in total. If the ratio of the voids 7 and 9 is too low, the effects (1) to (3) described above cannot be obtained sufficiently. On the other hand, if the proportion of the gaps 7 and 9 is too high, the gaps 7 and 9 communicate with the outside air, and the mechanical strength of the glass layer 4 is lowered.
- a more preferred range is 5 to 65%, a further preferred range is 10 to 60%, and a particularly preferred range is 20 to 50%.
- the glass layer 4 of the present embodiment is assumed to include both the gaps 7 and 9, the present invention is not limited to this.
- the glass layer 4 may include only the voids 7.
- gap 7 and 9 of this embodiment is formed in the part which is not osmose
- the heat-resistant fiber body 5 may be formed in a portion penetrating. Incidentally, in this case, the gas in the gaps 7 and 9 comes into contact with the heat resistant fiber body 5.
- the heat resistant fiber body 5 suppresses the heat flow of the glass layer 4. Further, the heat resistant fiber body 5 extends outward from the glass layer 4, thereby blocking the flow of outside air in contact with the glass layer 4. This is because when fresh outside air comes into contact with the glass layer 4, the hydrogen concentration and moisture concentration of the gas in the gaps 7 and 9 are lowered.
- the heat resistant fiber body 5 includes glass fiber or ceramic fiber.
- heat resistance means that in the case of glass fiber, the glass fiber has a softening point higher than the use temperature, and in the case of ceramic fiber, it means that the ceramic fiber has a melting point higher than the use temperature. . Since these fibers are hardly thermally deformed at the use temperature, the heat flow of the glass layer 4 can be suppressed.
- the heat resistant fiber body 5 is an aggregate of these fibers.
- a plurality of fibers may be knitted in a cloth shape, or a plurality of fibers may be entangled in a lump shape.
- a fabric in which a plurality of fibers are knitted is excellent in flexibility and workability.
- the average length of the fibers is preferably 10 mm or more.
- the heat-resistant fibrous body 5 is expressed by mass% based on oxide, and has a SiO 2 content of 50% or more. When the SiO 2 content is less than 50%, the glass that forms the glass layer 4 with respect to the heat-resistant fiber body 5 has too high wettability, so that the glass flows out through the heat-resistant fiber body 5 and the glass layer 4 Is separated from the member 3.
- the thickness D3 (including the penetration depth D2) of the heat resistant fiber body 5 is preferably 0.5 mm or more.
- the thickness D3 means an average value.
- the heat-resistant fiber body 5 has insufficient rigidity, and the effect of suppressing the heat flow of the glass layer 4 cannot be sufficiently obtained.
- the heat insulating member 6 may be provided outside the heat resistant fiber body 5.
- the heat insulating member 6 is made of a refractory or the like. The heat insulating member 6 relaxes cooling by the outside air and suppresses deformation of the member 3, the heat resistant fiber body 5, and the like due to the liquid pressure of the molten glass 2.
- This manufacturing method includes a step of forming a glass layer 4 by forming a coating layer containing glass powder between the member 3 and the heat-resistant fiber body 5 and firing the coating layer.
- a coating layer 8 is formed by applying a slurry containing glass powder to at least a part of the outer surface 32 of the member 3 and drying it.
- the slurry preferably contains an inorganic binder or an organic binder.
- an inorganic binder colloidal silica or the like is used.
- an organic binder a water-soluble polymer (for example, trade name: Metrows, manufactured by Shin-Etsu Chemical Co., Ltd.) is used.
- the method of applying the slurry may be a general method, and for example, a spray coating method, a spin coating method, a screen printing method, a brush coating, or the like is used. Instead of applying the slurry, a film obtained by drying the slurry may be attached.
- the temperature for drying the applied slurry is preferably 40 to 130 ° C.
- the heat-resistant fiber body 5 is attached to the outside of the coat layer 8. In that case, you may hold
- the assembly shown in FIG. 3 is fired. Thereby, the glass powder contained in the coat layer 8 is heat-fluidized to become the glass layer 4 shown in FIG. 1, and the gap between the glass powders becomes the gaps 7 and 9 shown in FIG.
- Calcination conditions are appropriately set according to the type of glass powder and the ratio of voids 7 and 9.
- the firing is performed in the atmosphere at substantially the same temperature as the use temperature.
- the molten glass processing apparatus 1 shown in FIG. 1 is obtained. Since this manufacturing method does not require a thermal spraying device or the like, it is possible to provide the glass layer 4 and the heat-resistant fiber body 5 on the member 3 which is an existing facility.
- the heat resistant fiber body 5 was stuck on the outer side of the coating layer 8, but this invention is not limited to this.
- the inside of the heat resistant fiber body 5 is attached to the outer surface 32 of the member 3 and dried to form the coat layer 8. Also good.
- FIG. 4 is a block diagram of a glass manufacturing apparatus provided with the molten glass processing apparatus 1.
- the glass manufacturing apparatus 10 includes a dissolution tank 11, a clarification tank 12, a stirring tank 13, and a forming apparatus 14.
- the dissolution tank 11, the clarification tank 12, the stirring tank 13, and the molding apparatus 14 are connected by transfer pipes 15 to 17.
- the melting tank 11 melts the glass raw material to produce molten glass.
- the inner wall of the dissolution tank 11 is provided with a raw material inlet, a plurality of burners, and the like.
- the burner include an air combustion burner and an oxyfuel combustion burner. From the viewpoint of environmental protection, an oxyfuel combustion burner is preferable.
- the glass raw material charged from the raw material inlet is heated by the radiant heat of the flame spouted by the burner to become molten glass.
- the molten glass is sent to the clarification tank 12 through the transport pipe 15.
- the clarification tank 12 floats and removes bubbles contained in the molten glass. These bubbles are mainly generated when the powdery glass raw material is melted. In order to promote the rising of bubbles, for example, the upper space in the clarification tank 12 may be decompressed. The molten glass in the clarification tank 12 is sent to the stirring tank 13 through the transport pipe 16.
- the agitation tank 13 agitates and homogenizes the molten glass.
- a rotating member such as a stirrer is used.
- the molten glass in the stirring tank 13 is sent to the molding apparatus 14 via the transport pipe 17.
- the forming device 14 forms molten glass into a predetermined shape.
- the forming device 14 may be a general device used for forming molten glass. For example, when the molten glass is formed into a strip shape, a float forming device or a fusion forming device is used as the forming device 14.
- molding apparatus 14 uses a casting molding apparatus, when shape
- the molten glass processing apparatus 1 is used for at least some inner walls (particularly, side walls and bottom walls) of the dissolution tank 11, the clarification tank 12, the stirring tank 13, and the transfer pipes 15 to 17.
- the glass manufacturing apparatus 10 by this embodiment is equipped with the molten glass processing apparatus 1 and the shaping
- a plurality of types of raw materials are mixed to prepare a glass raw material.
- SiO 2 50 to 72%
- Al 2 O 3 0.5 to 24%, preferably 0.5 to 23%
- B 2 O 3 0 to 12%
- MgO 0-8%
- CaO 0-14.5%
- SrO 0-24%
- BaO 0-13.5%
- MgO + CaO + SrO + BaO is 9
- a plurality of types of raw materials are prepared so that the glass is ⁇ 29.5% (in this case, ZrO 2 may further contain 0 to 5%).
- an alkali-free glass raw material for example, SiO 2 : 50 to 66%, Al 2 O 3 : 10.5 to 24%, preferably 10.5 to 22%, expressed in terms of mass% based on oxide.
- 2 O 3 0-12%, MgO: 0-8%, CaO: 0-14.5%, SrO: 0-24%, BaO: 0-13.5%, MgO + CaO + SrO + BaO is 9-29.
- Plural kinds of raw materials are prepared so as to be an alkali-free glass of 5% (which may further contain ZrO 2 : 0 to 5% at this time).
- SiO 2 58 to 66%
- Al 2 O 3 15 to 22%
- B 2 O 3 5 to 12%
- MgO 0 to 8%
- CaO 0 in terms of mass% based on oxide.
- a plurality of kinds of raw materials are prepared so as to be an alkali-free glass containing ⁇ 9%, SrO: 3 to 12.5%, BaO: 0 to 2% and MgO + CaO + SrO + BaO being 9 to 18%.
- the prepared glass raw material is put into the melting tank 11 to produce molten glass.
- the manufactured molten glass is sent to the clarification tank 12 through the transport pipe 15, and bubbles contained therein are floated and removed. These bubbles are mainly generated when the powdery glass raw material is melted.
- the upper space in the clarification tank 12 may be decompressed.
- the molten glass in the clarification tank 12 is sent to the agitation tank 13 via the transport pipe 16, and the molten glass is agitated and homogenized.
- the molten glass in the agitation tank 13 is sent to the molding device 14 via the transport pipe 17 and molded into a predetermined shape.
- the molding method include a float method, a fusion method, and a casting method. The molded molten glass is gradually cooled and then cut into predetermined dimensions as necessary to obtain a product.
- the molten glass processing apparatus 1 is used for at least some inner walls (particularly, side walls and bottom walls) of the dissolution tank 11, the clarification tank 12, the stirring tank 13, and the transfer pipes 15 to 17.
- the glass manufacturing method by this embodiment shape
- Example 1 to Example 12 (Molten glass processing equipment) First, a crucible made of platinum alloy (platinum 90% by mass, rhodium 10% by mass) was prepared as a member in contact with the molten glass. This crucible conforms to JIS H 6201-1986 and has a predetermined shape (height: 27 mm, upper outer diameter: 25 mm, bottom outer diameter: 15 mm, capacity: 10 cc, mass: 8.0 g).
- the slurry was applied to the outer surface of the prepared crucible and dried in the atmosphere at 90 ° C. for 2 hours to form a coat layer.
- the slurry used was prepared by mixing 67 parts by mass of glass powder (particle size: # 320 under) and 33 parts by mass of an aqueous Metrose solution (concentration: 0.3% by mass).
- As the glass powder any one of glasses A to D shown in Table 1 was used. Glasses A to C are alkali-free glass.
- the composition of each glass AD is shown in Table 1.
- the heat-resistant fiber body impregnated with the above-mentioned Metrose aqueous solution was attached to the outside of the coat layer.
- One of the following commercially available products was used as the heat resistant fiber body. That is, a quartz glass cloth (made by Nichias, Siltex cloth, SiO 2 : 99% by mass or more), a ribbon-like ceramic cloth (made by Nichias, SiO 2 : 53 mass) as a plurality of fibers knitted into a cloth shape.
- alumina cloth manufactured by Nichias, Al 2 O 3 : 99% by mass or more
- zirconia cloth manufactured by Zirker, ZrO 2 : about 90% by mass, Y 2 O 3 : About 10% by mass
- silica alumina cloth manufactured by Denka, SiO 2 : 20% by mass, Al 2 O 3 : 80% by mass.
- quartz glass wool manufactured by Tosoh Corporation, SiO 2 : 99% by mass or more
- a heat insulating member As the heat insulating member, a refractory having a bottomed cylindrical shape (external dimensions: 48 mm ⁇ 48 mm ⁇ 48 mm, recess depth: 26 mm, recess inner diameter: 32 mm) containing alumina and silica was used.
- molten glass is put into a platinum alloy crucible, heat-treated for 1 hour at an operating temperature T in an air atmosphere having a low moisture concentration (absolute humidity: 3 g / m 3 ), and then cooled to room temperature to melt.
- a glass processing apparatus was manufactured.
- the molten glass charged into the crucible includes non-alkali glass (in terms of mass% based on oxide, SiO 2 : 59.4%, Al 2 O 3 : 17.6%, B 2 O 3 : 7.9% MgO: 3.3%, CaO: 3.8%, SrO: 8.0%).
- This alkali-free glass had a ⁇ -OH value B indicating the water content of 0.5 mm ⁇ 1 before being put into the crucible.
- the ⁇ -OH value B was calculated by measuring the glass thickness C and transmittance T of a glass using a Fourier transform infrared spectrophotometer (FT-IR) and substituting the measurement results into the following equation.
- B (1 / C) log 10 (T1 / T2) (where T1: transmittance of glass at a reference wavenumber of 4000 / cm (unit:%), T2: minimum transmittance of glass near a hydroxyl absorption wavenumber of 3570 / cm) (unit:%))
- the ratio of bubbles contained in the molten glass is obtained by imaging the inside of the crucible of the molten glass processing apparatus manufactured from above with a camera, and the ratio of the area S2 of bubbles to the area S1 of the upper surface of the molten glass in the captured image (S2 / S1). ⁇ 100).
- the ratio of the bubbles is preferably 15% or less, more preferably 3% or less in consideration of the high-quality display quality recently required for flat panel displays for plasma displays and liquid crystal displays. More preferably, it is 1% or less.
- the thickness of the glass layer, the proportion of voids in the cross section of the glass layer, the adhesion between the glass layer and the crucible, the thickness of the heat-resistant fiber body, the penetration depth of the glass layer into the heat-resistant fiber body is the melt produced
- the glass processing apparatus was halved vertically, and the cut surface was examined by observation with a microscope.
- the thickness of the glass layer, the thickness of the heat-resistant fiber body, and the penetration depth of the glass layer into the heat-resistant fiber body are average values measured at 15 points on the cut surface.
- Viscosity ⁇ (unit: dPa ⁇ s) at the use temperature T of the glass forming the glass layer is obtained by putting a glass having the same composition as the glass into a platinum crucible and melting it, and rotating a viscometer (manufactured by Motoyama). And measured.
- the contact angle ⁇ b at the use temperature T was measured using a high-temperature contact angle meter (manufactured by Cruz).
- Examples 1 to 5 a glass layer was formed on the outer surface of the platinum alloy crucible, and the heat flow of the glass layer was suppressed by the heat resistant fiber body. Further, the glass layer contained voids that were not in communication with the outside air and were open to the member. Therefore, it can be seen that in Examples 1 to 5, the proportion of bubbles contained in the molten glass is smaller than in Examples 6 to 12.
- Example 7 since the heat-resistant fiber body was not used, the glass layer thermally flowed downward due to its own weight, and a part of the glass layer was separated from the crucible.
- Example 9 since the viscosity ⁇ at the use temperature T of the glass forming the glass layer was less than 10 2.5 dPa ⁇ s, the glass layer thermally flowed downward due to its own weight, and a part thereof was separated from the crucible. .
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Abstract
Description
前記耐熱性繊維体は、ガラス繊維またはセラミックス繊維を含み、酸化物基準の質量%表示で、SiO2含有量が50%以上であり、
前記ガラス層を形成するガラスは、使用温度において、102.5dPa・s以上の粘度を有し、
前記ガラス層には、外気と連通していない空隙が含まれている、溶融ガラス処理装置を提供する。 In order to solve the above object, the present invention provides a member made of platinum or a platinum alloy whose inner surface is in contact with molten glass, a glass layer covering at least a part of the outer surface of the member, and at least the outer side of the glass layer. A molten glass processing apparatus comprising a heat-resistant fiber body infiltrated with
The heat-resistant fiber body includes glass fiber or ceramic fiber, and is expressed by mass% based on oxide, and the SiO 2 content is 50% or more,
The glass forming the glass layer has a viscosity of 10 2.5 dPa · s or more at the use temperature,
A molten glass processing apparatus is provided in which the glass layer includes voids that are not in communication with the outside air.
溶融ガラス処理装置は、溶融ガラスを処理する装置であって、例えば、溶融ガラスの溶解、清澄、調温、搬送、撹拌などのための装置である。なお、本発明の溶融ガラス処理装置はこれに限定されない。 (Molten glass processing equipment)
The molten glass processing apparatus is an apparatus for processing molten glass, for example, an apparatus for melting, clarifying, adjusting temperature, conveying, stirring and the like of molten glass. In addition, the molten glass processing apparatus of this invention is not limited to this.
次に、上記溶融ガラス処理装置1を製造する方法について説明する。 (Method for manufacturing molten glass processing apparatus)
Next, a method for manufacturing the molten glass processing apparatus 1 will be described.
次に、上記溶融ガラス処理装置1を備えるガラス製造装置について説明する。 (Glass manufacturing equipment)
Next, the glass manufacturing apparatus provided with the said molten glass processing apparatus 1 is demonstrated.
次に、上記ガラス製造装置10を用いたガラス製造方法について説明する。 (Glass manufacturing method)
Next, the glass manufacturing method using the said glass manufacturing apparatus 10 is demonstrated.
(溶融ガラス処理装置)
最初に、溶融ガラスが接触する部材として、白金合金製(白金90質量%、ロジウム10質量%)のルツボを用意した。このルツボは、JIS H 6201-1986に準拠したものであって、所定形状(高さ:27mm、上部外径:25mm、底部外径:15mm、容量:10cc、質量:8.0g)を有する。 [Example 1 to Example 12]
(Molten glass processing equipment)
First, a crucible made of platinum alloy (platinum 90% by mass, rhodium 10% by mass) was prepared as a member in contact with the molten glass. This crucible conforms to JIS H 6201-1986 and has a predetermined shape (height: 27 mm, upper outer diameter: 25 mm, bottom outer diameter: 15 mm, capacity: 10 cc, mass: 8.0 g).
次に、溶融ガラス処理装置を評価した。 (Evaluation of molten glass processing equipment)
Next, the molten glass processing apparatus was evaluated.
溶融ガラス処理装置の評価結果を表2~表3に示す。ここで、例1~例5は実施例であり、例6~例12は比較例である。なお、ガラス層が熱流動しその一部がルツボから剥離した例7、9~12については、ガラス層の特性(粘度ηを除く)を測定できなかった。 (Evaluation results)
The evaluation results of the molten glass processing apparatus are shown in Tables 2 to 3. Here, Examples 1 to 5 are Examples, and Examples 6 to 12 are Comparative Examples. In Examples 7 and 9 to 12, in which the glass layer was heat-fluidized and part of the glass layer was peeled off from the crucible, the characteristics of the glass layer (excluding viscosity η) could not be measured.
本出願は、2010年4月28日出願の日本特許出願2010-104350に基づくものであり、その内容はここに参照として取り込まれる。 Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application 2010-104350 filed on April 28, 2010, the contents of which are incorporated herein by reference.
2 溶融ガラス
3 部材
31 内表面
32 外表面
4 ガラス層
5 耐熱性繊維体
6 断熱部材
7 空隙
8 コート層
9 空隙
10 ガラス製造装置
11 溶解槽
12 清澄槽
13 撹拌槽
14 成形装置
15~17 搬送管 DESCRIPTION OF SYMBOLS 1 Molten
Claims (14)
- 内表面が溶融ガラスに接触する白金製または白金合金製の部材と、該部材の外表面の少なくとも一部を覆うガラス層と、該ガラス層の少なくとも外側が浸透している耐熱性繊維体とを備える溶融ガラス処理装置であって、
前記耐熱性繊維体は、ガラス繊維またはセラミックス繊維を含み、酸化物基準の質量%表示で、SiO2含有量が50%以上であり、
前記ガラス層を形成するガラスは、使用温度において、102.5dPa・s以上の粘度を有し、
前記ガラス層には、外気と連通していない空隙が含まれている溶融ガラス処理装置。 A member made of platinum or platinum alloy whose inner surface is in contact with molten glass, a glass layer covering at least a part of the outer surface of the member, and a heat-resistant fiber body in which at least the outer side of the glass layer penetrates A molten glass processing apparatus comprising:
The heat-resistant fiber body includes glass fiber or ceramic fiber, and is expressed by mass% based on oxide, and the SiO 2 content is 50% or more,
The glass forming the glass layer has a viscosity of 10 2.5 dPa · s or more at the use temperature,
The molten glass processing apparatus in which the said glass layer contains the space | gap which is not connected with external air. - 前記ガラス層の厚さが1mm未満である請求項1に記載の溶融ガラス処理装置。 The molten glass processing apparatus according to claim 1, wherein the glass layer has a thickness of less than 1 mm.
- 前記空隙は前記部材に対して開放されており、前記空隙内の気体が前記部材に接触している請求項1または2に記載の溶融ガラス処理装置。 The molten glass processing apparatus according to claim 1 or 2, wherein the gap is open to the member, and gas in the gap is in contact with the member.
- 前記空隙は、前記ガラス層の断面の2~70%を占めている請求項1~3のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 3, wherein the voids occupy 2 to 70% of a cross section of the glass layer.
- 前記ガラス層を形成するガラスは、使用温度において、前記耐熱性繊維体よりも前記部材に対する濡れ性の高いガラスである請求項1~4のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 4, wherein the glass forming the glass layer is glass having higher wettability to the member than the heat-resistant fiber body at a use temperature.
- 前記ガラス層を形成するガラスは、無アルカリガラスである請求項1~5のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 5, wherein the glass forming the glass layer is alkali-free glass.
- 前記ガラス層の厚さが0.2mm以上である請求項1~6のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 6, wherein the glass layer has a thickness of 0.2 mm or more.
- 前記ガラス層の前記耐熱性繊維体への浸透深さが0.1mm以上である請求項1~7のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 7, wherein a penetration depth of the glass layer into the heat resistant fiber body is 0.1 mm or more.
- 前記耐熱性繊維体の厚さが0.5mm以上である請求項1~8のいずれか1つに記載の溶融ガラス処理装置。 The molten glass processing apparatus according to any one of claims 1 to 8, wherein the heat-resistant fiber body has a thickness of 0.5 mm or more.
- 請求項1~9のいずれか1つに記載の溶融ガラス処理装置を製造する方法であって、
前記部材と前記耐熱性繊維体との間に、ガラス粉末を含むコート層を形成し、焼成することで、前記ガラス層を形成する工程を含む溶融ガラス処理装置の製造方法。 A method for producing a molten glass processing apparatus according to any one of claims 1 to 9,
The manufacturing method of the molten glass processing apparatus including the process of forming the said glass layer by forming the coating layer containing glass powder between the said member and the said heat resistant fiber body, and baking. - 請求項1~9のいずれか1つに記載の溶融ガラス処理装置と、前記溶融ガラス処理装置から供給される溶融ガラスを所定形状に成形する成形装置とを備えるガラス製造装置。 A glass manufacturing apparatus comprising: the molten glass processing apparatus according to any one of claims 1 to 9; and a molding apparatus that forms the molten glass supplied from the molten glass processing apparatus into a predetermined shape.
- 請求項1~9のいずれか1つに記載の溶融ガラス処理装置から供給される溶融ガラスを所定形状に成形するガラス製造方法。 A glass manufacturing method for forming molten glass supplied from the molten glass processing apparatus according to any one of claims 1 to 9 into a predetermined shape.
- 前記溶融ガラスは、無アルカリガラスである請求項12に記載のガラス製造方法。 The glass manufacturing method according to claim 12, wherein the molten glass is alkali-free glass.
- 前記溶融ガラスは、酸化物基準の質量%表示で、SiO2:58~66%、Al2O3:15~22%、B2O3:5~12%、MgO:0~8%、CaO:0~9%、SrO:3~12.5%、BaO:0~2%を含有し、MgO+CaO+SrO+BaOが9~18%の無アルカリガラスである請求項12に記載のガラス製造方法。 The molten glass is expressed by mass% on the basis of oxide, SiO 2 : 58 to 66%, Al 2 O 3 : 15 to 22%, B 2 O 3 : 5 to 12%, MgO: 0 to 8%, CaO The glass manufacturing method according to claim 12, wherein the glass is a non-alkali glass containing 0 to 9%, SrO: 3 to 12.5%, BaO: 0 to 2%, and MgO + CaO + SrO + BaO being 9 to 18%.
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KR1020127028007A KR20130080781A (en) | 2010-04-28 | 2011-04-20 | Molten glass treatment apparatus, process for production thereof, and use thereof |
JP2012512803A JP5692223B2 (en) | 2010-04-28 | 2011-04-20 | Molten glass processing apparatus, manufacturing method thereof, and use thereof |
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KR (1) | KR20130080781A (en) |
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WO2012048811A1 (en) * | 2010-10-11 | 2012-04-19 | Heraeus Materials Technology Gmbh & Co. Kg | REDUCTION OF THE EVAPORATION RATE OUT OF PLATINUM AND Pt ALLOYS |
WO2012048812A1 (en) * | 2010-10-11 | 2012-04-19 | Heraeus Materials Technology Gmbh & Co. Kg | REDUCTION OF Pt AND Rh EVAPORATION LOSSES AT HIGH TEMPERATURES BY USING A BARRIER LAYER |
JP2012101970A (en) * | 2010-11-09 | 2012-05-31 | Nippon Electric Glass Co Ltd | Molten glass transfer tube |
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WO2015002148A1 (en) * | 2013-07-03 | 2015-01-08 | 株式会社フルヤ金属 | Container and method for recovering metallic element |
JP2020524216A (en) * | 2017-06-19 | 2020-08-13 | コーニング インコーポレイテッド | Refractory article, coating composition for preventing redox reaction, and method for producing refractory article |
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Also Published As
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TWI477465B (en) | 2015-03-21 |
TW201200482A (en) | 2012-01-01 |
CN102869621B (en) | 2014-12-24 |
CN102869621A (en) | 2013-01-09 |
KR20130080781A (en) | 2013-07-15 |
JPWO2011136109A1 (en) | 2013-07-18 |
JP5692223B2 (en) | 2015-04-01 |
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