WO2010041305A1 - ガラス製造装置および製造方法 - Google Patents
ガラス製造装置および製造方法 Download PDFInfo
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- WO2010041305A1 WO2010041305A1 PCT/JP2008/068195 JP2008068195W WO2010041305A1 WO 2010041305 A1 WO2010041305 A1 WO 2010041305A1 JP 2008068195 W JP2008068195 W JP 2008068195W WO 2010041305 A1 WO2010041305 A1 WO 2010041305A1
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- glass
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- molten glass
- alumina
- manufacturing apparatus
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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
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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
Definitions
- the present invention relates to a glass manufacturing apparatus and a glass manufacturing method using the manufacturing apparatus.
- platinum or platinum and other noble metal elements such as rhodium (Rh), gold (Au), iridium (Ir ) Or an alloy with ruthenium (Ru) is used (hereinafter, platinum and platinum alloys are collectively referred to as a platinum material in the present specification).
- Platinum materials are used as these constituent materials because they have a high melting point and do not deteriorate because they do not form an oxide layer in the atmosphere. It is also excellent in stability and has a low risk of contaminating molten glass.
- the apparatus temperature in a glass manufacturing process changes with the processing contents, it exists in the high temperature environment of about 900 degreeC or more.
- the platinum material can maintain sufficient durability for a long period of time without contaminating the molten glass inside the apparatus even under such a high temperature environment due to the above characteristics.
- alkali-free glass in the case of an alkali-free glass substrate that does not substantially contain an alkali metal oxide used in liquid crystal displays (LCDs), organic electroluminescence displays (OLEDs), inorganic electroluminescence displays, etc., alkali-free glass has a high melting point. Since the viscosity is higher than that of the alkali-containing glass, the bubbles in the molten glass are difficult to float and it is difficult to suppress the bubbles.
- Patent Documents 1 to 4 In order to solve this problem, it has been proposed to provide a dense hydrogen-impermeable film on the outer surface of the platinum material (see Patent Documents 1 to 4).
- the material for the dense hydrogen-impermeable film include glass, ceramic, and metal.
- the hydrogen impervious dense film proposed by the prior art is focused on the molecular diameter and ion diameter of hydrogen, and by providing a dense film with a hydrogen impervious material, etc., hydrogen is exposed to the outside through the film. Although it was intended to prevent the release, it was not possible to sufficiently reduce the generation of bubbles during glass production. Due to the fact that the coating on the outer surface of the platinum material does not necessarily become a dense film intended, deterioration of the coating due to use in a high temperature environment, peeling of the coating due to the difference in the thermal expansion coefficient between the platinum material and the coating, etc. Thus, it is considered that hydrogen has been released to the outside through the coating.
- the present invention provides a glass production apparatus capable of effectively and stably preventing the generation of bubbles during glass production and preventing the remaining of bubbles in the produced glass product and It aims at providing the glass manufacturing method.
- the present invention is a glass manufacturing apparatus having a member made of platinum or a platinum alloy in contact with molten glass, Fe is contained in an amount of 0.2 to 5% by mass in terms of Fe 2 O 3 with respect to the total amount of the alumina-based ceramic particles on the back surface side of the surface in contact with the molten glass of the member, and Fe redox (Fe 2+ A glass production apparatus is provided in which a layer containing alumina-based ceramic particles having a changing point at which / Fe 2+ + Fe 3+ ) rises is formed.
- the platinum or platinum alloy member is preferably a container for containing molten glass.
- the molten glass temperature range is preferably 1250 to 1650 ° C.
- the alumina ceramic particles preferably contain 10% by mass or more of mullite.
- the present invention also provides a glass manufacturing method using the glass manufacturing apparatus of the present invention.
- the glass to be manufactured has a mass percentage display based on oxides (the total of SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO and BaO is 100%). so, SiO 2 50-70%, Al 2 O 3 5-25%, B 2 O 3 1-20%, MgO 0-10%, CaO 0-17%, SrO 0-17%, BaO 0-20%, MgO + CaO + SrO + BaO 8-30% It is preferable that it is an alkali free glass containing.
- the glass manufacturing apparatus and the glass manufacturing method of the present invention it is possible to effectively and stably prevent the generation of bubbles at the platinum interface or the platinum alloy interface in contact with the molten glass during glass manufacturing. As a result, it is possible to produce a glass having a good quality in which residual bubbles are suppressed.
- the alkali-free glass produced by the glass production apparatus and the glass production method of the present invention is a substrate glass for a flat panel display, particularly a liquid crystal display (LCD), an organic electroluminescence display (OLED), an inorganic electroluminescence It is suitable for the use of substrate glass for flat panel displays such as displays.
- FIG. 1 is a schematic view showing a configuration example of a glass manufacturing apparatus.
- FIG. 2A is a view showing the platinum alloy crucible used in the example
- FIG. 2B is a view showing the zirconia brick base used in the example.
- 2 (c) is a view showing a state where the crucible of FIG. 2 (a) is installed in the recess of the base of FIG. 2 (b).
- FIG. 3 is a graph plotting the relationship between Fe redox and temperature for the alumina-based ceramic particles of Examples 1, 3 and 5.
- FIG. 1 is a schematic view showing a configuration example of a glass manufacturing apparatus.
- a glass manufacturing apparatus 1 shown in FIG. 1 includes a dissolution tank 2, a clarification tank 3 provided on the downstream side of the dissolution tank 2, an agitation tank 4 provided on the downstream side of the clarification tank 3, and an agitation tank 4.
- a melting tank 2, a clarification tank 3, a stirring tank 4 and a molding apparatus 5 are conduits (communication flow paths) 6 and 7 for circulating molten glass, respectively. , 8 are connected.
- the dissolution tank 2 is provided with a burner, an electrode, and the like, and can dissolve the glass raw material.
- a molten glass outlet is formed on the downstream side of the melting tank 2, and the melting tank 2 and the clarification tank 3 communicate with each other via a conduit 6 having the outlet as an upstream end.
- the clarification tank 3 is a part where clarification of the glass is mainly performed, and fine bubbles contained in the molten glass are levitated by the clarification gas released from the clarifier and removed from the molten glass.
- a molten glass outlet is formed on the downstream side of the clarification tank 3, and the clarification tank 3 and the agitation tank 4 communicate with each other via a conduit 7 having the outlet as an upstream end.
- the agitation tank 4 is a part where the molten glass is agitated and homogenized mainly by a stirrer or the like.
- An outflow port is formed on the downstream side of the stirring tank 4, and the stirring tank 4 and the molding device 5 communicate with each other via a conduit 8 having the outflow port as an upstream end.
- the forming device 5 is a part that mainly forms glass into a desired shape, and is appropriately selected according to the shape of the glass product to be manufactured. For example, when the glass product is a glass substrate for a flat panel display, a float molding device, a downdraw molding device, or the like is used.
- the portions of the melting tank 2 to the conduit 8 that are in contact with the molten glass are required to have heat resistance that can withstand high-temperature environments and corrosion resistance to the molten glass.
- Platinum alloys are preferably used.
- the glass manufacturing apparatus of the present invention has a platinum or platinum alloy member in contact with the molten glass, and Fe is added to Fe 2 O with respect to the total amount of the alumina-based ceramic particles on the back side of the surface of the member in contact with the molten glass.
- a layer containing alumina ceramic particles having a changing point where Fe redox (Fe 2+ / Fe 2+ + Fe 3+ ) rises in the molten glass temperature range is formed, containing 0.2 to 5% by mass in terms of 3 It is characterized by being.
- a platinum or platinum alloy container that accommodates the molten glass may be mentioned.
- the present invention is not limited to this, and widely includes platinum or platinum alloy members that are in contact with the molten glass when the glass manufacturing apparatus is used.
- a platinum or platinum alloy container containing molten glass will be described as a specific example of a member made of platinum or a platinum alloy in contact with the molten glass.
- the portion described as a container for containing molten glass is interpreted as a platinum or platinum alloy member.
- the container for storing molten glass widely includes a container for temporarily holding or storing molten glass.
- Agitation tank 4, and conduits 6, 7, 8 are applicable.
- At least one of the above-described containers for containing the molten glass is made of a platinum material, and the rear surface side of the surface in contact with the molten glass of the container made of the platinum material, that is, FIG.
- the above-mentioned alumina-based ceramic particle layer is formed outside the container wall surface made of platinum material.
- the change in the valence of Fe occurs as the temperature of the platinum material rises due to the rise in the molten glass temperature (assuming that the temperature outside the platinum material container is approximately the same as the molten glass temperature), but Fe is the valence. After the change, it is considered that the bubble residual suppression effect is maintained substantially constant while the temperature of the platinum material is kept constant thereafter.
- the alumina-based ceramic particles need to contain a sufficient amount of Fe.
- the alumina-based ceramic particles must contain 0.2 to 5% by mass of Fe in terms of Fe 2 O 3 with respect to the total amount of the alumina-based ceramic particles, and may contain 0.5% by mass or more. preferable.
- the Fe content is preferably 5% by mass or less in terms of Fe 2 O 3 .
- Fe contained in the alumina-based ceramic particles needs to be in a state in which a valence change from Fe 3+ to Fe 2+ easily occurs during use of the glass manufacturing apparatus. For this reason, Fe contained in the alumina-based ceramic particles needs to have a changing point where Fe redox (Fe 2+ / Fe 2+ + Fe 3+ ) rises in the molten glass temperature range.
- Fe redox Fe 2+ / Fe 2+ + Fe 3+
- this temperature is referred to as a change point at which Fe redox (Fe 2+ / Fe 2+ + Fe 3+ ) increases. More specifically, the point at which the first derivative value of the approximate curve of the above-described plot starts to increase as the temperature rises is referred to as a change point.
- the Fe redox (Fe 2+ / Fe 2+ + Fe 3+ ) of the alumina-based ceramic particles can be determined by a redox titration method. Specifically, a sample of alumina ceramic particles is heated to a predetermined temperature at a rate of 300 ° C. per hour, held at the predetermined temperature for 1 hour, cooled to room temperature, and dissolved by dissolving the measurement sample with hydrofluoric acid.
- Fe 2+ indicator is added to the liquid, and the amount of Fe 2+ is measured by spectroscopic measurement. Further, after a measurement sample was dissolved hydrofluoric acid, the Fe 3+ in the lysate reduction treatment to Fe 2+, obtaining the Fe 3+ + Fe 2+ content was measured in the same manner Fe 2+ content in the manner described .
- the molten glass temperature range refers to the temperature range experienced by the molten glass in the glass manufacturing process from melting to pre-molding. In the glass manufacturing apparatus 1 shown in FIG. 1, the temperature range which a molten glass experiences from the melting tank 2 to the conduit
- the molten glass temperature range varies depending on the type of glass and the components of the glass production apparatus, but is usually 1250 to 1650 ° C. in the case of alkali-free glass. Preferably, it is the molten glass temperature range for every container which comprises the glass manufacturing apparatus mentioned later.
- the alumina-based ceramic particles used in the present invention have a transition point where Fe redox rises in the molten glass temperature range, when the molten glass temperature range is 1250 to 1650 ° C., it may contain 10% by mass or more of mullite. preferable.
- the mullite content is more preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.
- the alumina-based ceramic particles may contain only mullite as a crystal phase, but as long as the mullite content satisfies the above range, other crystal phases, specifically, badeleyite and corundum are contained. Also good.
- the content of the glass phase in the alumina-based ceramic particles is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and 10% by mass or less. It is particularly preferred.
- the content of the glass phase is more than 50% by mass, the surface of the mullite phase is covered with the glass phase, and there is a tendency that the residual effect of suppressing bubbles due to the change in the valence of Fe cannot be sufficiently exhibited.
- an alumina ceramic particle layer is formed on the back side of the surface of the container made of platinum material that contacts the molten glass, that is, on the outside of the container wall surface (for example, in the case of a crucible container, the side surface and bottom surface).
- alumina ceramic particles are filled to a desired thickness outside the wall surface of the container.
- the thickness is preferably 1 mm or more, more preferably 2 mm or more in consideration of exerting the effect of suppressing residual bubbles. Further, if it is too thick, ceramic particles are required more than necessary, so that it is preferably 40 mm or less.
- a refractory block is provided outside the wall surface of the container with a predetermined distance from the container, and alumina ceramic particles are filled in a gap between the container and the refractory block.
- the refractory block is not particularly limited as long as it is refractory and can hold alumina-based ceramic particles.
- it is a fired refractory, specifically, alumina zircon, zircon, sillimanite, chamotte Examples thereof include alumina and magnesia bricks.
- alumina bricks are preferred.
- the alumina ceramic of particles is used in the present invention.
- it may be anything that is pulverized to a particle size of about 2 mm or less, and is not intended to be adjusted to have a specific particle size distribution.
- the particle size refers to the size of particles passing through the sieve having the size.
- the shape of the ceramic particles may be spherical, square, irregular, or the like.
- the particle size is preferably 2 mm or less.
- the particle size is preferably 10 ⁇ m or more.
- the alumina-based ceramic particles filled on the outside of the wall surface of the platinum material container can be appropriately selected according to the temperature of the molten glass contained in the container.
- the temperature of the molten glass in the glass production apparatus is different for each platinum material container, that is, for each component of the platinum material glass production apparatus (container for containing molten glass).
- the temperature of the molten glass in the melting tank 2 is about 1400 to 1650 ° C.
- the temperature of the molten glass in the clarification tank 3 is about 1300 to 1550 ° C.
- the temperature of the molten glass in the stirring tank 4 is about 1250 to 1400 ° C.
- the temperature of the molten glass in the conduit 6 is about 1400 to 1600 ° C.
- the temperature of the molten glass in the conduit 7 is about 1300 to 1500 ° C.
- the temperature of the molten glass in the conduit 8 is about 1250 to 1350 ° C. Accordingly, in the present invention, Fe redox (Fe 2+ / Fe 2+ + Fe 3+ ) rises outside the wall surface of the platinum material container constituting the glass manufacturing apparatus in the temperature range of the molten glass accommodated in the container. Alumina-based ceramic particles having a transition point are filled.
- the glass manufacturing method of the present invention is the same as the conventional method except that the glass manufacturing apparatus of the present invention described above is used. Therefore, the raw material prepared so that it may become a desired glass composition is thrown into the melting tank 2 of the glass manufacturing apparatus shown in FIG. 1, and the molten glass obtained by heating and melting the conduit 6, the clarification tank 3, the conduit 7, and the stirring tank 4. Pass through the conduit 8 and the molding apparatus 5 in this order to obtain a glass product of a desired shape.
- an alkali-free glass is shown below as a glass suitable for production in the present invention.
- the alkali-free glass shown below is suitable as a substrate glass for a liquid crystal display (LCD).
- This alkali-free glass is expressed in terms of mass percentage based on oxide, SiO 2 50-70%, Al 2 O 3 5-25%, B 2 O 3 1-20%, MgO 0-10%, CaO 0-17%, SrO 0-17%, BaO 0-20%, MgO + CaO + SrO + BaO 8-30% Containing.
- the above mass percentage is obtained SiO 2, Al 2 O 3, B 2 O 3, MgO, CaO, the total of SrO and BaO is 100%.
- SiO 2 is an essential component, and if it exceeds 70%, the solubility of the glass decreases, and it tends to devitrify. Preferably it is 64% or less. If it is less than 50%, the specific gravity increases, the strain point decreases, the thermal expansion coefficient increases, and the chemical resistance decreases. Preferably it is 55% or more.
- Al 2 O 3 is a component that suppresses the phase separation of the glass and increases the strain point, and is essential. If it exceeds 25%, devitrification tends to occur, and chemical resistance decreases. Preferably it is 22% or less. If it is less than 5%, the glass tends to undergo phase separation, or the strain point decreases. Preferably it is 10% or more.
- B 2 O 3 is a component that reduces the specific gravity, increases the solubility of the glass, and makes it difficult to devitrify, and is essential. If it exceeds 20%, the strain point is lowered, the chemical resistance is lowered, or the volatilization at the time of melting the glass becomes remarkable and the inhomogeneity of the glass is increased. Preferably it is 12% or less. If it is less than 1%, the specific gravity increases, the solubility of the glass decreases, and devitrification easily occurs. Preferably it is 6% or more.
- MgO is a component that reduces the specific gravity and improves the solubility of the glass. If it exceeds 10%, the glass tends to undergo phase separation, devitrification tends to occur, or chemical resistance decreases. Preferably it is 7% or less. It is preferable to contain 1% or more of MgO.
- CaO can be contained up to 17% in order to increase the solubility of the glass and make it difficult to devitrify. If it exceeds 17%, the specific gravity increases, the thermal expansion coefficient increases, and devitrification tends to occur. Preferably it is 14% or less. It is preferable to contain 2% or more of CaO.
- SrO can be contained up to 17% in order to suppress the phase separation of the glass and make it difficult to devitrify. If it exceeds 17%, the specific gravity increases, the coefficient of thermal expansion increases, and devitrification tends to occur. Preferably it is 14% or less. It is preferable to contain 3% or more of SrO.
- BaO can be contained up to 20% in order to suppress the phase separation of the glass and make it difficult to devitrify. If it exceeds 20%, the specific gravity increases and the thermal expansion coefficient becomes large. Preferably it is 1% or less, and it is more preferable not to contain substantially.
- the total content of the alkaline earth metal oxide (RO), that is, (MgO + CaO + SrO + BaO) is too small, it is difficult to melt the glass, so it is 8% or more.
- the amount is too large, the density of the glass increases, so it is 30% or less. Preferably, it is 10 to 30%.
- alkali-free glass is expressed in terms of mass percentage based on oxide, SiO 2 55-64%, Al 2 O 3 10-22%, B 2 O 3 6-12%, MgO 1-7%, CaO 2-14%, SrO 3-14%, BaO 0-1%, MgO + CaO + SrO + BaO 10-30% It is more preferable to contain.
- the above mass percentage is obtained SiO 2, Al 2 O 3, B 2 O 3, MgO, CaO, the total of SrO and BaO is 100%.
- F, Cl, SO 3 , SnO 2 , Fe 2 O 3 or the like can be added as a clarifier in a total amount of 5% by mass or less based on 100% by mass of the glass raw material. .
- Table 1 shows the alumina-based ceramic particles used in the examples. The particle diameter was 10 ⁇ m to 2 mm. In Table 1, the ratio (mass% basis) between the crystal phase and the glass phase in the alumina-based ceramic particles was determined by measuring the ratio of each crystal phase by a powder X-ray diffraction (XRD) method.
- XRD powder X-ray diffraction
- the ratio of the crystal phase is determined from the XRD intensity ratio between the pure substance (badeleite, zircon, mullite, corundum, etc.) of each crystal phase and the sample, and the glass is calculated from the difference between the sample and the total ratio of each crystal phase.
- the proportion of phases was determined.
- standard) in an alumina type ceramic particle was calculated
- ⁇ RO x in the composition ratio is the total of oxidation impurities other than Al 2 O 3 , SiO 2 , ZrO 2 , and Fe 2 O 3 , R is a metal element, O is oxygen, and x is a stoichiometric ratio.
- FIG. 3 shows a graph plotting the relationship between Fe redox and temperature for the alumina-based ceramic particles of Examples 1, 3 and 5.
- the crucible of FIG. 2 (a) is installed in the recess of the base of FIG. 2 (b), and the gap (the gap between the recess of the base and the bottom of the crucible is 3 to 5 mm) as shown in FIG. 2 (c).
- What filled the alumina type ceramic particle shown in Table 1 was installed in the heating furnace, and was heated to 1400 degreeC.
- alkali-free glass was poured into the crucible of FIG. 2 while being kept at 1400 ° C. and dissolved.
- the composition of the alkali-free glass is expressed in terms of mass percentage on the basis of oxide, 59.4% of SiO 2 , 17.6% of Al 2 O 3 , 7.9% of B 2 O 3 , 3.3% of MgO, and CaO 3.
- the alumina-based ceramic particles of Examples 5 and 6 have a redox change point of 950 ° C., at the molten glass temperature (1400 ° C.) of the example, due to Fe valence change (Fe 3+ ⁇ Fe 2+ ). It is considered that the bubble residual suppression effect could not be exhibited.
- the alumina-based ceramic particles of Example 7 have a redox change point of 1350 ° C., but the Fe 2 O 3 content is less than 0.2% by mass, so that the Fe valence change (Fe 3+ ⁇ Fe 2 It is probable that the residual effect of bubbles due to + ) was not fully exhibited.
- the alkali-free glass produced by the glass production apparatus and the glass production method of the present invention is a substrate glass for a flat panel display, particularly a liquid crystal display (LCD), an organic electroluminescence display (OLED), an inorganic electroluminescence display, etc. It is suitable for the use of the substrate glass for flat panel displays.
- LCD liquid crystal display
- OLED organic electroluminescence display
- inorganic electroluminescence display etc. It is suitable for the use of the substrate glass for flat panel displays.
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Abstract
Description
ガラス製造工程における装置温度は、その処理内容により異なるが、約900℃以上の高温環境下にある。白金材料は、上記特性からこのような高温環境下でも装置内部の溶融ガラスを汚染することなく、長期間十分な耐久性を維持することができる。
特に、液晶ディスプレイ(LCD)、有機エレクトロルミネッセンス・ディスプレイ(OLED)、無機エレクトロルミネッセンス・ディスプレイ等に使用されるアルカリ金属酸化物を実質的に含有しない無アルカリガラス基板の場合、無アルカリガラスが高融点であり、アルカリ含有ガラスと比較して高粘性であるため、溶融ガラス中の気泡が浮上しにくく、気泡の抑制が難しい。
該部材の溶融ガラスが接する面の裏面側に、アルミナ系セラミック粒子の全量に対しFeをFe2O3換算で0.2~5質量%含有し、溶融ガラス温度域にFeレドックス(Fe2+/Fe2++Fe3+)が上昇する変化点を有するアルミナ系セラミック粒子を含む層が形成されていることを特徴とするガラス製造装置を提供する。
SiO2 50~70%、
Al2O3 5~25%、
B2O3 1~20%、
MgO 0~10%、
CaO 0~17%、
SrO 0~17%、
BaO 0~20%、
MgO+CaO+SrO+BaO 8~30%
を含有する無アルカリガラスであることが好ましい。
特に、本発明のガラス製造装置およびガラス製造方法で製造される無アルカリガラスは、フラットパネルディスプレイ用の基板ガラス、特に、液晶ディスプレイ(LCD)、有機エレクトロルミネッセンス・ディスプレイ(OLED)、無機エレクトロルミネッセンス・ディスプレイ等のフラットパネルディスプレイ用の基板ガラスの用途に好適である。
2:溶解槽
3:清澄槽
4:攪拌槽
5:成形装置
6,7,8:導管
図1は、ガラス製造装置の一構成例を示した模式図である。図1に示すガラス製造装置1は、溶解槽2と、該溶解槽2の下流側に設けられた清澄槽3と、清澄槽3の下流側に設けられた攪拌槽4と、攪拌槽4の下流側に設けられた成形装置5と、を有し、溶解槽2、清澄槽3、攪拌槽4および成形装置5は、それぞれ、溶融ガラスを流通させるための導管(連絡流路)6,7,8によって接続されている。
溶解槽2は、バーナー、電極等が設けられ、ガラス原料を溶解することができる。溶解槽2の下流側には溶融ガラスの流出口が形成されており、該流出口を上流端とする導管6を介して溶解槽2と清澄槽3とが連通している。
清澄槽3は、主としてガラスの清澄が行われる部位であり、溶融ガラス中に含まれる微細な泡が清澄剤から放出される清澄ガスにより浮上され、溶融ガラスから除去される。清澄槽3の下流側には溶融ガラスの流出口が形成されており、該流出口を上流端とする導管7を介して清澄槽3と攪拌槽4とが連通している。
攪拌槽4は、主としてスターラー等により溶融ガラスを攪拌し、均質化する部位である。攪拌槽4の下流側には流出口が形成されており、流出口を上流端とする導管8を介して攪拌槽4と成形装置5とが連通している。
成形装置5は、主としてガラスを所望の形状に成形する部位であり、製造するガラス製品の形状に応じて適宜選択される。例えば、ガラス製品がフラットパネルディスプレイ用のガラス基板である場合、フロート成形装置、ダウンドロー成形装置等が使用される。
ここで、溶融ガラスと接する白金製もしくは白金合金製の部材の具体例としては、溶融ガラスを収容する白金製もしくは白金合金製の容器が挙げられる。但し、これに限定されず、ガラス製造装置の使用時において、溶融ガラスと接する白金製もしくは白金合金製の部材を広く含む。以下、本明細書において、溶融ガラスと接する白金製もしくは白金合金製の部材の具体例として、溶融ガラスを収容する白金製もしくは白金合金製の容器を挙げて説明するが、溶融ガラスを収容する容器以外の白金製もしくは白金合金製の部材については、溶融ガラスを収容する容器と記載されている部分を白金製もしくは白金合金製の部材として解釈する。
溶融ガラスを収容する容器とは、ガラス製造工程において、溶融ガラスを一時的に保持または収容する容器を広く含み、図1に示すガラス製造装置1の一構成例では、溶解槽2、清澄槽3、攪拌槽4、および導管6,7,8が該当する。
したがって、本発明のガラス製造装置は、上記した溶融ガラスを収容する容器のうち、少なくとも1つは白金材料製であり、該白金材料製の容器の溶融ガラスと接する面の裏面側、すなわち、図1に示すガラス製造装置の一構成例では、白金材料製の容器壁面の外側に、上記のアルミナ系セラミック粒子層が形成される。
なお、アルミナ系セラミック粒子のFeレドックス(Fe2+/Fe2++Fe3+)は、酸化還元滴定法により求めることができる。具体的には、アルミナ系セラミック粒子の試料を毎時300℃の速度で所定の温度まで昇温し、所定の温度で1時間保持した後、室温まで冷却し、測定試料をフッ酸で溶解した溶解液にFe2+指示薬を加えて、分光測定によりFe2+量を測定する。また、測定試料をフッ酸溶解した後、溶解液中のFe3+をFe2+に還元処理し、前記の方法で同様にFe2+量を測定してFe3++Fe2+量を求める。
Feレドックス(Fe2+/Fe2++Fe3+)が上昇する変化点が溶融ガラス温度域にあれば、ガラス製造装置の使用時、より具体的には、溶融ガラスを収容する容器の白金材料製の壁面が溶融ガラスと接している状態において、アルミナ系セラミック粒子に含まれるFeの価数変化(Fe3+→Fe2+)が起こりやすい状態になる。
溶融ガラス温度域とは、溶解から成形前までのガラス製造工程において、溶融ガラスが経験する温度域を指す。図1に示すガラス製造装置1において、溶解槽2から導管8までで溶融ガラスが経験する温度域を指す。溶融ガラス温度域は、ガラスの種類やガラス製造装置の構成要素によっても異なるが、無アルカリガラスの場合、通常1250~1650℃である。好ましくは、後述するガラス製造装置を構成する容器ごとの溶融ガラス温度域である。
アルミナ系セラミック粒子は、結晶相としてムライトのみを含有するものであってもよいが、ムライト含有量が上記範囲を満足する限り、他の結晶相、具体的には、バデレアイト、コランダムを含有してもよい。また、他の成分として、ジルコン、シリマナイト等を含有してもよい。
アルミナ系セラミック粒子中のガラス相の含有量は、50質量%以下であることが好ましく、30質量%以下であることがより好ましく、20質量%以下であることがさらに好ましく、10質量%以下であることが特に好ましい。ガラス相の含有量が50質量%超であると、ムライト相表面がガラス相で覆われてしまい、Feの価数変化による気泡の残留抑制効果が十分発揮できない傾向にある。
なお、本発明で粒子のアルミナ系セラミックを用いるのは、白金材料製の容器の壁面外側に充填するのに好都合だからである。したがって、粒径2mm以下程度に粉砕されたものであればよく、特定の粒度分布となるように調整したものを意図したものではない。
本発明において粒径とは、その大きさの目開きのふるいを通る粒子の大きさをいう。例えば、粒径2mm以下の粒子の場合には、2mmの目開きのふるいを通る粒子のことをいう。したがって、セラミック粒子の形状は、球形、角型、不定形等を問わない。容器周囲に充分な接触点をもってセラミック粒子を充填させることを考慮すると、粒径は2mm以下が好ましい。また、充填する際の飛散防止を考慮すると粒径は10μm以上が好ましい。
したがって、本発明では、ガラス製造装置を構成する白金材料製の容器の壁面外側に、該容器に収容される溶融ガラス温度域にFeレドックス(Fe2+/Fe2++Fe3+)が上昇する変化点を有するアルミナ系セラミック粒子を充填する。
この無アルカリガラスは、酸化物基準の質量百分率表示で、
SiO2 50~70%、
Al2O3 5~25%、
B2O3 1~20%、
MgO 0~10%、
CaO 0~17%、
SrO 0~17%、
BaO 0~20%、
MgO+CaO+SrO+BaO 8~30%
を含有する。
なお、上記の質量百分率表示は、SiO2、Al2O3、B2O3、MgO、CaO、SrOおよびBaOの合計を100%としたものである。
SiO2 55~64%、
Al2O3 10~22%、
B2O3 6~12%、
MgO 1~7%、
CaO 2~14%、
SrO 3~14%、
BaO 0~1%、
MgO+CaO+SrO+BaO 10~30%
を含有することがより好ましい。
なお、上記の質量百分率表示は、SiO2、Al2O3、B2O3、MgO、CaO、SrOおよびBaOの合計を100%としたものである。
本実施例では、図2(a)に示す白金合金製(白金ロジウム合金、ロジウム10質量%)のルツボ(JIS H6201(1986.11.1)準拠)と、図2(b)に示すジルコニアレンガ製の基台(耐火性ブロック)を用いて白金合金界面での気泡の発生状況を評価した。図2(a)に示すルツボ、および図2(b)に示す基台の寸法はそれぞれ以下の通りである。
ルツボ
高さ:27mm
上部径:25mm
底部径:15mm
容量:10cc
質量:8.0g
基台
外部寸法:48mm×48mm×48mm
凹部深さ:26mm
凹部径:35mm
また、実施例で使用したアルミナ系セラミック粒子を表1に示す。粒子径は10μm~2mmであった。表1中、アルミナ系セラミック粒子中の結晶相とガラス相との割合(質量%基準)は、粉末X線回折(XRD)法により各結晶相の割合を測定して求めた。具体的には、各結晶相の純物質(バデレアイト、ジルコン、ムライト、コランダム等)と試料とのXRD強度比から結晶相の割合を求め、試料と各結晶相の割合の合計との差からガラス相の割合を求めた。また、アルミナ系セラミック粒子における組成比(質量%基準)は蛍光X線分析により求めた。なお、組成比におけるΣROxはAl2O3、SiO2、ZrO2、Fe2O3以外の酸化不純物の合計で、Rは金属元素、Oは酸素、xは化学量論比を示す。
無アルカリガラスが溶解した後、さらに1400℃で1時間保持し、白金合金界面、すなわち、ルツボ壁面での気泡の発生を観察した。結果を表1に示す。表1において、例1~例4は実施例、例5~例7は比較例を示す。表1中、気泡占有率は図2(a)のルツボ底面において、気泡が占める面積の割合であり、0%は測定限界以下であったことを示している。
表1の結果から明らかなように、例1~例4のアルミナ系セラミック粒子は、効果的にかつ安定して気泡の残留を抑制することができた。一方、例5、例6のアルミナ系セラミック粒子は、レドックス変化点が950℃であるため、実施例の溶融ガラス温度(1400℃)ではFeの価数変化(Fe3+→Fe2+)による気泡の残留抑制効果を発揮できなかったものと考えられる。また、例7のアルミナ系セラミック粒子は、レドックス変化点が1350℃であるが、Fe2O3含有量が0.2質量%未満であるため、Feの価数変化(Fe3+→Fe2+)による気泡の残留抑制効果を十分発揮できなかったものと考えられる。
Claims (6)
- ガラスの製造装置であって、溶融ガラスと接する白金製もしくは白金合金製の部材を有し、
該部材の溶融ガラスが接する面の裏面側に、アルミナ系セラミック粒子の全量に対しFeをFe2O3換算で0.2~5質量%含有し、溶融ガラス温度域にFeレドックス(Fe2+/Fe2++Fe3+)が上昇する変化点を有するアルミナ系セラミック粒子を含む層が形成されていることを特徴とするガラス製造装置。 - 前記白金製もしくは白金合金製の部材が、溶融ガラスを収容する容器であることを特徴とする請求項1に記載のガラス製造装置。
- 前記溶融ガラス温度域が、1250~1650℃であることを特徴とする請求項1または2に記載のガラス製造装置。
- 前記アルミナ系セラミック粒子が、ムライトを10質量%以上含有することを特徴とする請求項1ないし3のいずれかに記載のガラス製造装置。
- 請求項1ないし4のいずれかに記載のガラス製造装置を用いたガラス製造方法。
- 製造されるガラスが、酸化物基準の質量百分率表示(SiO2、Al2O3、B2O3、MgO、CaO、SrOおよびBaOの合計を100%とする)で、
SiO2 50~70%、
Al2O3 5~25%、
B2O3 1~20%、
MgO 0~10%、
CaO 0~17%、
SrO 0~17%、
BaO 0~20%、
MgO+CaO+SrO+BaO 8~30%
を含有する無アルカリガラスであることを特徴とする請求項5に記載のガラス製造方法。
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JP2012180243A (ja) * | 2011-03-02 | 2012-09-20 | Nippon Electric Glass Co Ltd | ガラス物品製造装置及びガラス物品製造方法 |
CN108529853A (zh) * | 2018-04-10 | 2018-09-14 | 湖北新华光信息材料有限公司 | 一种玻璃连熔炉及熔制方法 |
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JPWO2013024649A1 (ja) * | 2011-08-16 | 2015-03-05 | 旭硝子株式会社 | 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 |
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