WO2011118375A1 - Filler for glass production container, filler layer for glass production container, glass production apparatus, and method for producing glass production apparatus - Google Patents

Abstract

Disclosed is a filler for a glass production container, which is capable of providing a fired coating film that has high hydrogen blocking performance. Specifically disclosed is a filler for a glass production container, which is filled between a supporting body and a glass production container that is formed of a noble metal. The surface of the glass production container is coated with a coating material that contains a glass component and forms a fired coating film on the surface of the glass production container. The filler for a glass production container contains a glass component.

Description

Glass production container filler, glass production container filler layer, glass production apparatus, and glass production apparatus production method

The present invention relates to a filler for a glass production container, a filler layer for a glass production container formed by firing the glass, a glass production apparatus including the same, and a method for producing the glass production apparatus. In particular, the present invention relates to a coating material for forming a fired film on the surface of a noble metal glass production container, comprising a glass production container having a glass component coated on the surface and a support material. The present invention relates to a filler for a glass production container filled in between, a filler layer for a glass production container formed by firing it, a glass production apparatus including the same, and a method for producing the glass production apparatus.

Conventionally, as a glass production container for producing high-quality glass such as optical glass and display glass, a glass production container made of a noble metal such as Pt or an alloy containing a noble metal (hereinafter referred to as “Pt container”). Is widely used. The reason is that the Pt container has high rigidity even in a high temperature atmosphere of 1000 ° C. or higher and hardly contaminates the internal glass. In addition, the container for glass manufacture is normally fixed by the outer side being covered with a support material, and the filler being filled and solidified in the gap between the container for glass manufacture and the support material.

However, when a Pt container is used for the production of glass, bubbles due to moisture in the glass may be generated on the surface of the container on the molten glass side. The cause of this bubble is that oxygen generated by the decomposition of water contained in the glass passes through the Pt container and is released to the outside, so that the oxygen concentration of the molten glass located near the surface of the Pt container Is considered to increase (specifically, refer to Patent Document 1). That is, according to Patent Document 1, hydrogen generated by the reaction shown in the following formula (1) passes through the Pt container and is released to the outside, while oxygen that cannot pass through the Pt container is located near the surface of the Pt container. It is believed that by dissolving in the molten glass, the oxygen concentration of the molten glass located near the surface of the Pt container becomes higher than the solubility limit and bubbles are generated.

OH ⁻ → 1 / 2O ₂ + 1 / 2H ₂ + e ⁻ (1)

In particular, so-called non-alkali glass that is substantially free of alkali metal components and used as display glass has a high viscosity even at high temperatures and is difficult to defoam. Cheap.

In view of such problems, for example, the following Patent Documents 1 to 4 propose a method for suppressing the generation of bubbles due to moisture in glass when a container made of Pt or an alloy containing Pt is used. ing.

For example, in Patent Document 1 below, by controlling the partial pressure of hydrogen outside the Pt container with respect to the partial pressure of hydrogen inside the Pt container at the time of glass production, bubbles caused by moisture in the glass are controlled. A method for suppressing the occurrence has been proposed.

In the following Patent Documents 2 and 3, a method for suppressing the generation of bubbles due to moisture in the glass by reducing the hydrogen permeability of the Pt container by applying a glass barrier coating to the outer surface of the Pt container is proposed. Has been.

Moreover, in the following patent document 4, generation | occurrence | production of the bubble resulting from the water | moisture content in glass is suppressed by coat | covering the outer surface of a Pt container with the coating material containing a refractory component containing an alumina and silica, and a glass component. A method has been proposed.

Special table 2001-503008 gazette JP-T-2004-523449 Special table 2006-522001 gazette WO2006 / 030737 A1 Publication

If an attempt is made to suppress the generation of bubbles due to moisture in the glass by the method described in Patent Document 1, it is necessary to continue supplying hydrogen during glass production. For this reason, there exists a problem that the manufacturing cost of glass rises. Also, if the hydrogen partial pressure outside the Pt container is too high, hydrogen will pass through the Pt container from the outside of the Pt container and enter the Pt container and melt into the glass melt, which may cause hydrogen bubbles. There is. Therefore, there is a problem that it is difficult to sufficiently suppress the generation of bubbles in the glass melt. In addition, hydrogen promotes the reaction between platinum and glass components, and as a result, platinum damage may occur and molten glass may flow out.

As described in Patent Documents 2 to 4, when a barrier coating layer containing a glass component is formed on the outer surface of a Pt container to suppress generation of bubbles due to moisture in the glass, It is not always necessary to continue supplying hydrogen. In particular, as described in Patent Document 4, when the outer surface of a Pt container is coated with a coating material containing a refractory component such as alumina particles and silica particles together with a glass component, described in Patent Documents 2 and 3. Thus, it is easy to obtain a higher hydrogen barrier property than when a barrier coating layer made of a glass component is formed. Therefore, generation | occurrence | production of the bubble resulting from the water in a glass melt can be suppressed effectively.

However, as a result of intensive studies by the present inventors, even if the outer surface of the Pt container is covered with a barrier coating layer containing a glass component and a refractory component as described in Patent Document 4, the generation of bubbles is sufficient. It was found that there are cases where it cannot be suppressed. As a result of further intensive studies, the inventors have found that the reason why the generation of bubbles cannot be sufficiently suppressed is that the coating material and the mortar that is the filler react with each other in the step of forming the barrier coating layer by firing. It has been found that the hydrogen gas shielding property of the coating layer is lower than the desired hydrogen gas shielding property.

The present invention has been made in view of the above points, and its purpose is to provide a container body and a support material, the surface of which is coated with a coating material for forming a fired film on the surface of a glass manufacturing container made of precious metal. It is an object of the present invention to provide a filler for glass production containers that can be formed between the two, and can form a fired coating film that does not easily react with the coating material and has a high hydrogen shielding property in the coating material firing step.

The filler for a glass production container according to the present invention is used to form a fired film on the surface of a glass production container made of a noble metal, and the glass production container and the support material having a coating material containing a glass component coated on the surface. It is a filler filled in between.

In the present invention, the “glass production container” refers to a member having an inner surface in contact with the glass melt and an outer surface not in contact with the glass melt and capable of holding or transporting the glass melt. . The “glass production container” includes a container capable of holding a glass melt such as a melting tank, a clarification tank, and a stirring tank, a glass transport pipe capable of transporting the glass melt, and a molding member. Here, the “forming member” refers to a member used for forming a glass melt into a member having a predetermined shape. Accordingly, the “molding member” includes a molding sleeve, a nozzle, and the like.

In the present invention, “a glass production container made of noble metal” refers to a glass production container made of a noble metal or an alloy containing a noble metal. Specific examples of the noble metal include Pt, Rh, Ir, Pd, Au and the like. Examples of the alloy containing a noble metal include an alloy containing one or more selected from the group consisting of Pt, Rh, Ir, Pd and Au. Specific examples of the alloy containing a noble metal include a Pt / Rh alloy, a Pt / Ir alloy, and a Pt / Pd alloy.

In the present invention, the “support material” is a member for supporting the glass manufacturing container. The support material is made of, for example, a refractory provided around the glass manufacturing container.

The filler for glass production containers according to the present invention contains a glass component. For this reason, it is hard to react with the coating material containing a glass component compared with the filler like the mortar which does not contain the conventional glass component, for example. Therefore, by using the filler for glass production containers according to the present invention, it is possible to suppress a deviation in the composition of the fired film due to the reaction between the coating material and the filler. That is, by using the filler for glass production containers according to the present invention, a fired film having a desired composition and high hydrogen gas shielding properties can be formed. Therefore, it is possible to manufacture a glass manufacturing apparatus in which hydrogen gas bubbles are less likely to be generated in the glass melt.

From the viewpoint of suppressing the reaction between the coating material and the filler during firing of the coating material, the glass component content in the glass production container filler is preferably close to the glass component content in the coating material. Here, in order to form a fired film having a high hydrogen gas shielding property, the content of the glass component in the coating material is preferably 20% by mass or more, and more preferably 45% by mass or more. For this reason, it is preferable that content of the glass component in the filler for glass manufacturing containers is also 20 mass% or more, and it is more preferable that it is 45 mass% or more.

More preferably, the glass component content in the glass production container filler is in the range of 0.9 to 1.5 times the glass component content in the coating material.

Note that the type and form of the glass component are not particularly limited. As a form of the glass component, for example, glass powder can be used. As a kind of glass component, it is preferable that it is glass with a high glass softening temperature. Specifically, the glass component is preferably borosilicate glass or silicate glass, for example, borosilicate glass or silicate glass with a low content of alkali metal or alkaline earth metal. More preferably. It is preferable that the kind of glass component contained in the filler for glass manufacturing containers is substantially equal to the kind of glass component contained in the coating material.

In the present invention, the glass component includes crystallized glass.

Incidentally, as described above, from the viewpoint of reducing the reactivity with the coating material, the filler for glass production containers needs to contain a glass component. However, the glass component has a low melting point and is easily melted as compared with, for example, a refractory component. For this reason, at the time of baking of a coating material, it exists in the tendency for a glass component to melt | dissolve and to fall out from a filler layer easily. As a result, the filler layer contracts, and a gap may be generated between the glass production container and the support material. If it does so, it may become impossible to fix a glass manufacturing container firmly to a support material.

When the glass component falls off and a gap is generated between the glass production container and the support material, it is usually difficult to fill the gap because the gap is not so large.

For this reason, the filler for glass production containers is composed of alumina fibers and alumina fine particles having an average particle diameter in the range of 5 nm to 50 nm (hereinafter referred to as “alumina fine particles having an average particle diameter in the range of 5 nm to 50 nm” together with the glass component. "Is simply referred to as" alumina fine particles "). In this case, it becomes difficult for the glass component to fall off from the filler layer when the coating material is fired. Therefore, the shrinkage of the filler layer during firing of the coating material is effectively suppressed. Therefore, it can suppress that a clearance gap produces between a glass manufacturing container and a support material. As a result, the glass production container can be firmly fixed to the support material.

In the present invention, the “average particle diameter” means D ₅₀ (volume-based average particle diameter), which is a value measured by a laser diffraction / scattering particle size distribution analyzer.

In the present invention, “alumina fiber” is a material having an elongated shape and containing alumina as a main component. For example, the alumina fiber is preferably substantially cylindrical. The diameter of the alumina fiber in the cross section is preferably about 1 μm to 30 μm. The average particle diameter (fiber length) in the longitudinal direction of the alumina fiber is preferably about 20 μm to 300 μm. The ratio of the average particle diameter in the longitudinal direction of the alumina fiber to the diameter in the cross section of the alumina fiber ((average particle diameter in the longitudinal direction of the alumina fiber) / (diameter in the cross section of the alumina fiber)) ranges from 2 to 200 It is preferable to be within.

Further, the alumina fiber may be composed only of alumina, or may contain alumina as a main component and further contain other than alumina as a subcomponent. The content of alumina in the alumina fiber is preferably 60% by mass or more, and more preferably 90% by mass or more.

It is thought that the reason why the glass component can be prevented from falling off from the filler layer when the coating material is baked by including the alumina fiber in the filler for the glass production container is as follows. That is, it is considered that the alumina fiber having an elongated shape and having a high melting point plays a role as a structure maintaining member for the filler layer, so that the structure of the filler layer is not easily broken.

On the other hand, it is thought that the reason why the glass component can be prevented from falling off from the filler layer during firing of the coating material by including the alumina fine particles in the filler for glass production container is as follows. That is, the alumina fine particles having a small average particle diameter are easily dissolved in the glass component at the time of firing the coating material even at a low temperature. For this reason, when alumina fine particles are contained in the filler for glass production containers, it dissolves in the glass component from a relatively low temperature when the coating material is fired. As a result, the viscosity of the glass component increases from the low temperature. Therefore, it becomes difficult for the glass component to fall off the filler layer. In addition, the alumina fine particles having a small average particle diameter are highly reactive, and easily generate crystals with a high melting point together with other materials contained in the glass component. For this reason, when alumina fine particles are contained in the filler for glass production containers, a high melting point crystal is generated from a relatively low temperature during the firing of the coating material, and the high melting point crystal is the structure of the filler layer. It functions as a maintenance member. Therefore, it becomes difficult for the glass component to fall off the filler layer.

A specific example of the high melting point crystal produced by the reaction with the alumina fine particles is a mullite crystal. Here, “mullite” is an aluminum silicate compound represented by Al ₂ O ₃ .nSiO ₂ (where n is in the range of 1/2 to 2/3) and stable at high temperatures. Since the mullite crystals have a particularly high rigidity at high temperatures, it is particularly effective to generate mullite when the coating material is fired.

As described above, the main effect obtained by adding alumina fibers is different from the main effect obtained by adding alumina fine particles. For this reason, it is preferable that the filler for glass manufacturing containers contains both an alumina fiber and an alumina fine particle. In particular, when the glass manufacturing container is used at a high temperature such as 1300 ° C. or higher, it is preferable that the glass manufacturing container filler contains both alumina fibers and alumina fine particles.

In that case, the structure maintaining effect by alumina fibers, the viscosity increasing effect of the glass component by dissolving the alumina fine particles in the glass component, and the high melting point crystal forming effect by the reaction of the alumina fine particles can be obtained. Dropping of the glass component from the filler layer can be more effectively suppressed.

In the present invention, the total amount of alumina fiber and alumina fine particles in the filler for glass production container is preferably 5% by mass or more. This is because if the total amount of the alumina fibers and the alumina fine particles is too small, the glass component may not be sufficiently removed from the filler layer during firing of the coating material. The total amount of alumina fibers and fine alumina particles in the filler for glass production container is preferably substantially equal to the total amount of alumina fibers and fine alumina particles in the coating material. Here, from the viewpoint of obtaining a fired film having a high hydrogen gas shielding property, the total amount of alumina fibers and alumina fine particles in the coating material is preferably 5% by mass to 25% by mass, and 5% by mass to 20% by mass. It is more preferable that Therefore, the total amount of alumina fibers and alumina fine particles in the filler for glass production containers is also preferably 5% by mass to 25% by mass, and more preferably 5% by mass to 20% by mass.

When the filler for glass production container contains only alumina fiber of alumina fiber and alumina fine particles, the content of alumina fiber in the filler for glass production container is 5% by mass to 25% by mass. It is preferably 5% by mass to 15% by mass.

When the filler for glass production containers contains only alumina fine particles of alumina fibers and alumina fine particles, the content of the alumina fine particles in the filler for glass production containers is 5% by mass to 20% by mass. It is preferably 5% by mass to 15% by mass.

When the filler for glass production containers contains both alumina fibers and alumina fine particles, the content of alumina fibers in the filler for glass production containers is preferably 5% by mass to 20% by mass. The content of alumina fine particles in the filler for glass production containers is preferably 5% by mass to 20% by mass, and preferably 5% by mass to 15% by mass. .

The glass production container filler according to the present invention preferably contains a Si component in the glass component. If the Si component is contained in the glass component, mullite is likely to precipitate due to the reaction with the alumina fine particles. Moreover, it is preferable that the filler for glass manufacturing containers contains a silica particle. In this case, the content of silica particles is preferably 15% by mass to 35% by mass, and more preferably 20% by mass to 30% by mass. If the content of silica particles is too small, mullite crystals may be difficult to form, or the shrinkage of the filler during firing of the coating material may become too large. On the other hand, when the content of the silica particles is too large, the content of the glass component is reduced accordingly, so that the reaction between the coating material and the filler during firing of the coating material may not be sufficiently suppressed. The average particle size of the silica particles is preferably 0.5 μm to 100 μm, and more preferably 1 μm to 50 μm. If the average particle diameter of the silica particles is too small, the gap between the silica particles inside the filler becomes large, and excessive shrinkage may occur during firing. On the other hand, if the average particle diameter of the silica particles is too large, it may be difficult to dissolve in the glass, the formation of mullite will be slow, and the flow of vitreous during firing may be difficult to suppress.

By the way, the filler for glass production containers according to the present invention is generally used as a paste by adding water. Specifically, a paste produced by adding water to a filler for glass production containers and kneading is filled between a glass production container having a coating material coated on the surface and a support material. Then, the filler for glass manufacturing containers is also baked with the baking of the coating material, and a filler layer for glass manufacturing containers is formed between the glass manufacturing container and the support material.

For this reason, when there is too much water content in the paste containing the filler for glass manufacturing containers and water, the filler for glass manufacturing containers will shrink | contract greatly at the time of baking, and a crack etc. will generate | occur | produce in a filler layer. There is a case. For this reason, from the viewpoint of suppressing shrinkage of the filler for glass production containers during firing, it is preferable that the water content in the filler for glass production containers is small.

However, if the water content in the glass production container filler is too small, the fluidity of the paste glass production container filler will decrease, and if the clearance between the glass production container and the support material is small, It becomes difficult to reliably fill the filler for the paste-like glass production container between the production container and the support material. That is, it becomes easy to produce the part which is not filled with the filler for paste-form glass manufacturing containers between a glass manufacturing container and a support material.

Thus, when water is simply added to the filler for glass production containers to produce a filler for paste-like glass production containers, high filling properties and suppression of shrinkage of the filler for glass production containers during firing are achieved. It is difficult to achieve both.

Here, when the filler for glass production containers contains a peptizer together with water, good fluidity can be obtained and high filling can be achieved even when the water content is reduced. Can do. For example, it becomes possible to reliably fill the paste-like glass production container filler even in a very narrow gap of about 5 mm. Therefore, it is preferable that the filler for glass manufacturing containers contains a peptizer with water.

Here, the “peptizer” refers to a drug that peptidizes the solid content of the filler for glass manufacturing containers. Peptidation refers to the dispersion of solidified solids. Many peptizers are generally in a solution state and may be used in a state dissolved in a solvent such as water.

Specific examples of the peptizer include ammonium carboxylate polymer compounds such as polycarboxylic acid ammonium salt, sodium salt of carboxylic acid, sodium salt of phosphoric acid, and the like. Among these, an ammonium carboxylate polymer compound is preferable because it has a large effect of improving the fluidity of the filler. In the present invention, one type of these peptizers may be used, or a plurality of types of peptizers may be used in combination.

The content of the peptizer is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the glass production container filler, and is in the range of 1 to 10 parts by mass. It is preferably within the range of 1 to 9 parts by mass. If the content of the peptizer with respect to the solid content of the filler for glass production containers is too small, the effect of improving the dispersibility of the solid content by adding the peptizer may not be sufficiently obtained. On the other hand, if the content of the peptizer relative to the solid content of the filler for glass manufacturing containers is too large, the organic component contained in the peptizer itself, particularly the carbon component, reduces the glass component in the filler. The characteristic may be changed.

When water and a peptizer are added to the glass production container filler, the water content is in the range of 10 to 65 parts by mass with respect to 100 parts by mass of the glass production container filler. It is preferably within a range of 15 to 60 parts by mass, and more preferably within a range of 20 to 50 parts by mass. When there is too little content of water with respect to solid content of the filler for glass manufacturing containers, the dispersibility of solid content will worsen and the fluidity | liquidity of the filler for paste-form glass manufacturing containers may become low too much. On the other hand, when there is too much water content with respect to solid content of the filler for glass manufacturing containers, the shrinkage amount of the filler for glass manufacturing containers at the time of baking may become large too much.

The filler layer for glass production containers according to the present invention is obtained by firing the filler for glass production containers according to the present invention. As above-mentioned, the filler for glass manufacturing containers which concerns on this invention does not react easily with a coating material at the time of baking. Therefore, by using the filler layer for a glass production container according to the present invention, it is possible to produce a glass production container in which bubbles are not easily generated in the glass.

In addition, the firing temperature of the filler for glass production containers can be appropriately set according to the composition of the filler for glass production containers. The firing temperature of the filler for glass production containers can be, for example, about 900 ° C. to 1600 ° C.

A glass manufacturing apparatus according to the present invention includes a glass manufacturing container made of a noble metal having a fired coating formed on a surface thereof, a support material, and a filler for a glass manufacturing container positioned between the glass manufacturing container and the support material. The glass manufacturing container filler layer according to the present invention is used as the glass manufacturing container filler layer. For this reason, glass with few bubbles can be manufactured by manufacturing glass using the glass manufacturing apparatus of this invention.

The glass manufacturing apparatus according to the present invention is filled with the filler for a glass manufacturing container according to the present invention, for example, between a glass manufacturing container on which a coating material for forming a fired coating is applied and a support material. And it can manufacture by baking. Here, for example, when the support material is low in moisture permeability, the moisture is vaporized in the firing step, and the pressure in the region between the glass production container and the support material increases rapidly. As a result, the coating material layer and the glass manufacturing container may be damaged. Therefore, it is preferable that the support material has high moisture permeability. Specifically, the support material preferably has a porosity of 1% or more, more preferably 7% or more. However, if the porosity of the support material is too high, the rigidity of the support material may be too low. Therefore, the porosity of the support material is preferably 20% or less, and more preferably 15% or less.

When the porosity of the support material is in the range of 1% to 20%, the thickness of the support material is preferably in the range of 5 mm to 200 mm, and more preferably in the range of 25 mm to 100 mm. By adopting the support material having such a thickness, it is possible to ensure a sufficiently excellent moisture permeability while ensuring a sufficiently high rigidity of the support material. Moreover, it can suppress that a glass manufacturing apparatus enlarges too much by making the thickness of a support material into the said range. When it is necessary to install a refractory with a low porosity in relation to the operating temperature of the glass manufacturing container, use the refractory with the above porosity only on the surface layer part that contacts the filler. You may comprise a part with a refractory material with a small porosity.

The clearance between the glass production container and the support material is preferably in the range of 1 mm to 200 mm, and more preferably in the range of 1 mm to 20 mm. If the clearance between the glass production container and the support material is too small, it may be difficult to reliably fill the glass production container filler between the glass production container and the support material. On the other hand, if the clearance between the glass production container and the support material is too large, moisture may be insufficiently removed during the firing.

In the present invention, the fired film formed on the surface of the glass production container is formed by firing a coating material containing a glass component, and is for suppressing the permeation of hydrogen gas. That is, the fired coating has a lower hydrogen gas permeability than the glass production container. The coating material preferably contains a glass component and a refractory component for holding the glass component.

Although the glass component contained in the coating material is not particularly limited, for example, borosilicate glass or silicate glass is preferable, and borosilicate glass having a low content of alkali metal or alkaline earth metal is preferable. A silicate glass is more preferable.

The content of the glass component in the coating material is not particularly limited, but is preferably 20% by mass or more, preferably 40% by mass to 70% by mass, and further preferably 50% by mass to 60% by mass. preferable. When the content of the glass component in the coating material is too small, the hydrogen gas shielding property of the fired film may not be sufficiently obtained. On the other hand, when the content of the glass component in the coating material is too large, the glass component tends to fall off during firing, and the shielding property of hydrogen gas may deteriorate.

Refractory components contained in the coating material include silica and alumina. The coating material preferably contains all of the glass component, silica, and alumina. In this case, the content of silica in the coating material is preferably 15% by mass to 40% by mass, and more preferably 20% by mass to 30% by mass. If the coating material contains too little silica, less silica will dissolve in the glass component and the glassy viscosity will not increase, so the coating will flow and fall off during firing, or the firing coating will have low rigidity. There is. When the content of silica in the coating material is too large, alumina is relatively decreased and the amount of mullite crystals generated is decreased, so that the rigidity of the fired film may be decreased.

The average particle diameter of silica contained in the coating material is preferably 50 μm or less, and more preferably 10 μm or less. In particular, it is preferable to use colloidal silica containing finer silica particles. This is because if the average particle size of silica contained in the coating material is too large, silica will not easily dissolve in the glass component, so that the formation of mullite will be slow and it may be difficult to suppress the flow of the glass component during firing. .

“Colloidal silica” refers to silica particles having an average particle diameter of 1 nm to 30 nm dispersed in a dispersion medium.

The content of alumina in the coating material is preferably 10% by mass to 40% by mass, and more preferably 16% by mass to 27% by mass. If the content of alumina in the coating material is too large, the vitreous may be insufficient and cracks may occur in the fired film. If the content of alumina in the coating material is too small, the amount of alumina that dissolves in the glass component decreases, and the viscosity of the vitreous is not sufficiently high, and the glass component may fall off during firing. The alumina contained in the coating material is preferably alumina particles having an average particle diameter of 1 μm to 100 μm. By adding alumina particles having such an average particle diameter, deformation and sagging of the fired film can be effectively suppressed, and a uniform fired film can be easily formed. It is preferable to further add alumina fine particles or alumina fibers having an average particle diameter of nano-order (for example, 5 nm to 50 nm). Alumina fine particles are rapidly dissolved in glass components. For this reason, since the viscosity of the glass component can be increased by adding alumina fine particles, it is possible to suppress the glass component from falling off during firing. Moreover, the strength of the fired film can be improved by adding alumina fiber.

It should be noted that the composition of the coating material needs to be appropriately adjusted depending on the operating temperature of the glass production container. For example, when the operating temperature of the glass production container is as high as 1300 ° C. or higher, it is preferable to increase the content of the refractory component or to use glass having a higher softening temperature as the glass component.

The manufacturing method of the glass manufacturing apparatus according to the present invention includes a step of applying a coating material for forming a fired film on the surface of a glass manufacturing container made of noble metal, and a step of providing a support material around the glass manufacturing container. And a step of filling a filler between the glass production container and the support material, and a step of firing the coating material and the filler to form a fired coating and a filler layer. In the manufacturing method of the glass manufacturing apparatus according to the present invention, the filler contains a glass component.

According to the present invention, it is possible to suitably manufacture the glass manufacturing apparatus according to the present invention, which can manufacture glass with less bubbles.

In the present invention, the coating material can be applied onto the surface of the glass manufacturing container made of precious metal by, for example, spraying with a spray, or using a brush or a spatula. Especially, it is preferable to apply | coat the coating material on the surface of the glass manufacturing container made from a noble metal by spraying with a spray. This is because the coating material can be applied uniformly.

Filling of the filler can be performed, for example, by pouring a filler having fluidity into the clearance between the glass production container and the support material.

In the present invention, a fired film is formed by firing the coating material, and a filler layer is formed by firing the filler. The firing temperature of the coating material and the filler can be appropriately set according to the composition of the coating material and the filler. The coating material and the fired coating can be fired at, for example, about 900 ° C. to 1600 ° C.

Note that prior to firing the coating material and the filler, the filler and the like may be dried.

According to the present invention, it is possible to provide a filler for a glass production container that is difficult to react with a coating material in the firing step of the coating material and can form a fired film having a high hydrogen shielding property.

Fig.1 (a) is a typical perspective view of the member for evaluation used for evaluation of a filling property and shrinkage | contraction property. FIG. 1B is a schematic plan view of an evaluation member used for evaluation of fillability and shrinkability. FIG.1 (c) is a typical side view of the member for evaluation used for evaluation of filling property and shrinkability. FIG. 2 is a cross-sectional photograph of Sample 1 in the fillability evaluation. FIG. 3 is a cross-sectional photograph of Sample 2 in the fillability evaluation. FIG. 4 is a cross-sectional photograph of Sample 3 in the fillability evaluation. FIG. 5 is a cross-sectional photograph of Sample 5 in the fillability evaluation. FIG. 6 is a cross-sectional photograph of Sample 6 in the fillability evaluation. FIG. 7 is a cross-sectional photograph of Sample 1 in the shrinkage evaluation. FIG. 8 is a cross-sectional photograph of Sample 2 in shrinkage evaluation. FIG. 9 is a cross-sectional photograph of Sample 3 in shrinkage evaluation. FIG. 10 is a cross-sectional photograph of Sample 5 in the shrinkage evaluation. FIG. 11 is a cross-sectional photograph of Sample 6 in the shrinkage evaluation. FIG. 12 is a plan photograph after firing of the filler button produced from Sample 10. FIG. 13 is a side photograph after firing the filler button produced from Sample 10. FIG. 14 is a plan photograph after firing of the filler button produced from Sample 11. FIG. 15 is a side photograph after firing of the filler button produced from Sample 11. FIG. 16 is a plane photograph after firing of the filler button produced from Sample 12. FIG. 17 is a plane photograph after firing of the filler button produced from Sample 13. FIG. 18 is a plane photograph after firing of the filler button produced from Sample 15. FIG. 19 is a plane photograph after firing of the filler button prepared from Sample 15. FIG. 20 is a plane photograph after firing of the filler button produced from Sample 16. FIG. 21 is a plane photograph after firing of the filler button prepared from Sample 16.

Hereinafter, the present invention will be described in more detail based on experimental examples. However, the following experimental examples are merely illustrative. The present invention is not limited to the following experimental examples.

<< Experiment 1 >>
In Experimental Example 1, the content of moisture and peptizer in the filler for glass production containers (hereinafter, “filler for glass production containers” is simply referred to as “filler”) and the flow of the filler The relationship between the properties and shrinkage during firing was evaluated.

Specifically, a plurality of types of fillers were prepared by variously changing the amount of water to be added and the amount of peptizer. With respect to the plural kinds of fillers, the filling property and shrinkage were evaluated.

(Filling material production)
Fillers (samples 1 to 6) were prepared by kneading the solids shown in Table 1 below with the amounts of water and peptizer shown in Table 2 below.

As the glass powder, non-alkali glass OA-10G manufactured by Nippon Electric Glass Co., Ltd. was used. The average particle diameter of the glass powder was 10 μm.

The average particle diameter of the alumina fine particles used was 20 nm.

As the alumina fiber, Denka Alsene B97N3 (average fiber diameter: 3 μm, Al ₂ O ₃ : 97 mass%, SiO ₂ : 3 mass%) manufactured by Denki Kagaku Kogyo Co., Ltd. was pulverized with a mixer (average particle diameter: 25 μm). ~ 32 μm) was used.

As the alumina particles, AL-42A (average particle diameter: 45 μm to 55 μm) manufactured by Sumitomo Chemical Co., Ltd. was used.

As the silica particles, MK Fine N (average particle size: 45 μm to 55 μm) manufactured by TAM was used.

As the peptizer, polyacrylic acid ammonium salt (Seruna D305 manufactured by Chukyo Yushi Co., Ltd.) was used.

(Evaluation of fillability)
The evaluation of the filling property was performed using the evaluation member 1 shown in FIG. As shown in FIG. 1, the evaluation member 1 includes first and second alumina tubes 11 and 12 bonded to a substrate 10 made of alumina using an Aron ceramic (Aron Ceramic D manufactured by Toagosei Co., Ltd.). I have. As the first and second alumina tubes 11 and 12, those manufactured by Nikkato Co., Ltd. made of SSA-S were used. The first alumina tube 11 has an inner diameter of 18 mm and an outer diameter of 25 mm. The second alumina tube 12 is arranged coaxially with the first alumina tube 11. The inner diameter of the second alumina tube 12 is 35 mm, and the outer diameter is 42 mm. For this reason, the width of the clearance 13 between the first and second alumina tubes 11 and 12 is 5 mm. The heights of the first and second alumina tubes 11 and 12 are 50 mm.

Each sample of the filler prepared above was poured into the clearance 13 of the evaluation member 1 and then dried at 60 ° C. for half a day. Thereafter, the evaluation member 1 was cut using a diamond cutter, and the state of the filler was visually evaluated.

Here, the case where the entire clearance 13 is filled with a filler is indicated as “◯”. The clearance 13 was filled with the filler to some extent, but the case where the filler stopped flowing in the middle and a large gap was generated in the clearance 13 was indicated as “Δ”. The case where the viscosity of the filler was too high and the filler did not enter the clearance 13 at all was indicated as “x”. The results are shown in Table 2 above. Moreover, cross-sectional photographs of Samples 1 to 3, 5 and 6 are shown in FIGS.

(Evaluation of shrinkage)
Each sample of the prepared filler was poured into the clearance 13 of the evaluation member 1 separate from the evaluation of the filling property, and then dried at 60 ° C. for half a day. After that, it was heated to 1300 ° C. at a heating rate of 10 ° C./min in an electric furnace, held at 1300 ° C. for one day, annealed at 710 ° C. for 1 hour, and cooled to room temperature at a cooling rate of 2 ° C./min. . Thereafter, the evaluation member 1 was cut using a diamond cutter, and the state of the filler was visually observed.

Here, the case where cracks or the like did not occur in the filler layer was indicated as “◯”, and the case where cracks or the like occurred in the filler layer was indicated as “x”. The results are shown in Table 2 above. Further, cross-sectional photographs of Samples 1 to 3, 5, and 6 are shown in FIGS.

(Evaluation of sample 1)
Sample 1 having a water content of 33 parts by mass and a peptizer content of 3 parts by mass with respect to 100 parts by mass of the solid content had good filling properties and a low shrinkage rate.

(Evaluation of sample 2)
Sample 2 with a water content of 48 parts by mass and a peptizer content of 1 part by mass with respect to 100 parts by mass of the solid content had good filling properties and a low shrinkage.

(Evaluation of sample 3)
Sample 3 containing no peptizer had a lower fillability than Sample 2 despite the water content being similar to Sample 2.

(Evaluation of sample 4)
Unlike Sample 3, Sample 4 which does not contain a peptizer and has a small water content of 33 parts by mass with respect to 100 parts by mass of solids was difficult to fill the clearance 13 with slurry. Sample 4 was not evaluated for shrinkage.

(Evaluation of sample 5)
Although it did not contain a deflocculant, Sample 5 had a high water content of 69 parts by mass with respect to 100 parts by mass of solids, and it was possible to produce a slurry and good filling properties. However, the shrinkage ratio during firing was high, and large cracks occurred in the filler layer.

(Evaluation of sample 6)
Sample 6 having a water content of 26 parts by mass and a peptizer content of 9 parts by mass with respect to 100 parts by mass of the solid content has good filling properties despite the low water content. The shrinkage rate was low.

From the above results, it can be seen that even when the water content is low, the fluidity of the filler slurry can be increased by adding the peptizer, and as a result, the filling property can be improved. Moreover, it turns out that the shrinkage rate at the time of baking can be made low by content of water with respect to 100 mass parts of solid content being 65 mass parts or less, Preferably, it is 60 mass parts or less, More preferably, it is 50 mass parts or less. It can also be seen that the more preferred amount of peptizer added is 1 to 10 parts by mass with respect to 100 parts by mass of the solid content.

<< Experiment 2 >>
Filler slurries having the compositions shown in Tables 3 to 5 below were prepared. The prepared slurry was poured into a mold to prepare a filler button having a diameter of 35 mm and a thickness of 10 mm. Thereafter, the button diameter after firing for 24 hours at the temperatures shown in Tables 3 to 5 was measured. As a result, when the diameter of the button was increased by firing, the filler was flowing during firing, and the result was “x”. In addition, the case where the diameter of the button was 10% or more smaller than that before firing due to firing was marked as “x” because it was greatly contracted. On the other hand, when the diameter of the button by firing becomes smaller within 10% or less than before firing, or when the diameter of the button does not change by firing, no large flow occurs during firing and the button does not shrink significantly. As a thing, it was set as "(circle)". The results are shown in Tables 3 to 5 below. FIGS. 12 and 13 show planar photographs after firing of the filler button produced from Sample 10. FIG. FIG. 14 and FIG. 15 show a plane photograph after firing of the filler button produced from Sample 11. FIG. FIG. 16 shows a planar photograph after firing of the filler button produced from Sample 12. FIG. FIG. 17 shows a planar photograph after firing of the filler button produced from Sample 13. FIG. FIGS. 18 and 19 show a plane photograph after firing of the filler button produced from Sample 15. FIG. 20 and FIG. 21 show a plane photograph after firing of the filler button produced from Sample 16. FIG.

In addition, as a filler slurry, what added 33 mass parts of water and 3 mass parts of peptizers (polyacrylic acid ammonium salt (Cerna D305 by Chukyo Yushi Co., Ltd.)) with respect to 100 mass parts of the following solid content. It was used. The same alumina fine particles, alumina fibers, alumina particles, and silica particles as those used in Experimental Example 1 were used.

The button diameter change rate (%) shown in Tables 3 to 5 below is ((diameter of the button after firing) − (diameter of the button before firing)) / (diameter of the button before firing).

As shown in Tables 3 to 5, Samples 7 to 12, 14, 15, 17, and 18 containing alumina fibers or alumina fine particles had a small flow of glass components during firing. From this result, it can be seen that the flow of the glass component during firing can be effectively suppressed by including at least one of alumina fiber and alumina fine particles. Further, among samples 7 to 16 where the firing temperature was 1300 ° C., samples 7 to 9, 12, 14, and 15 had a smaller flow of glass components during firing. From this result, it can be seen that when the alumina fiber is contained in an amount of 5% by mass or more, or the alumina fiber is not contained, it is more preferable that the alumina fine particle is contained in an amount of 10% by mass or more.

<< Experimental Example 3 >>
First, 50% by mass of glass powder (average particle size: 10 μm), 10% by mass of alumina fine particles (average particle size: 20 nm), 10% by mass of alumina fibers (average particle size: 30 μm), and alumina particles (average particle size) : 56 μm) containing 7% by mass and silica fine particles (colloidal silica, average particle size: 10 nm) of 23% by mass, and a coating material prepared by adding 200 g of methylcellulose 1.5% by mass aqueous solution to 100 g of these raw material powders did. The coating material is applied to the outer surface of a crucible made of platinum rhodium alloy having an inner diameter of 46 mm and a height of 40 mm and containing 10% by mass of rhodium in several times using an air spray, whereby a coating layer having a thickness of 1 mm Formed.

Next, the crucible formed with the coating layer was placed in a refractory crucible having an inner diameter of 56 mm so that a clearance of 5 mm was formed, and a filler slurry having the composition shown in Table 6 below was poured into the clearance, Dry at room temperature. Then, it baked at 1300 degreeC for 3 days, and cooled to room temperature. Thereby, the coating layer becomes a fired film. The glass powder, alumina fine particles, alumina fibers, alumina particles, and silica particles shown in Table 6 were the same as those in Experimental Example 2.

Next, non-alkali glass (OA-10G manufactured by Nippon Electric Glass Co., Ltd.) was put into the crucible, and the temperature was raised to 1300 ° C. and held at 1300 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, and the glass in the crucible was observed using a digital scope (VHX-500F, manufactured by Keyence Corporation), and the area ratio of bubbles per unit area was calculated. The results are shown in Table 6 below.

Also, as a comparative example (sample 27), an experiment was performed under the same conditions except that alumina castable (NC-UFR-MF manufactured by Mino Ceramics Co., Ltd.) was used as the filler slurry. The results are shown in Table 6 below.

From the result shown in Table 6, it can suppress effectively that a bubble generate | occur | produces in glass melt by using the filler containing a glass component. Further, the ratio of the content ratio of the glass component in the filler to the content ratio of the glass component in the fired film ((the content ratio of the glass component in the filler) / (the content ratio of the glass component in the fired film)), It can be seen that by setting the “glass component content ratio” in Table 6 to 0.9 to 1.5, the generation of bubbles can be more effectively suppressed.

Claims (17)

1. A filler used to form a fired film on the surface of a glass manufacturing container made of precious metal, and filled between a glass manufacturing container coated with a coating material containing a glass component and a support material. ,
   Filler for glass production container containing glass component.
2. The filler for glass production containers according to claim 1, wherein the content of the glass component is 20% by mass or more.
3. 3. The filler for a glass manufacturing container according to claim 1, wherein the content of the glass component is in the range of 0.9 to 1.5 times the content of the glass component in the coating material.
4. The filler for glass production containers according to any one of claims 1 to 3, further comprising at least one of alumina fibers and alumina fine particles having an average particle diameter in the range of 5 nm to 50 nm.
5. The filler for glass production containers according to claim 4, wherein the total amount of the alumina fibers and the alumina fine particles having an average particle diameter in the range of 5 nm to 50 nm is 5% by mass or more.
6. 6. The glass production container filler according to any one of claims 1 to 5, wherein the glass component contains a Si component.
7. The filler for glass manufacturing containers according to any one of claims 1 to 6, further comprising silica particles.
8. The filler for glass production containers according to any one of claims 1 to 7, further comprising water and a peptizer.
9. The filler for glass production containers according to claim 8, wherein the content of the peptizer is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the glass production container filler. .
10. 10. The filler for glass production containers according to claim 8 or 9, wherein the water content is in the range of 10 parts by mass to 65 parts by mass with respect to 100 parts by mass of the solid content of the filler for glass production containers.
11. The peptizer is at least one selected from the group consisting of an ammonium carboxylate polymer compound, a sodium salt of carboxylic acid, and a sodium salt of phosphoric acid. Filler for glass manufacturing containers.
12. A filler layer for glass production containers formed by firing the filler for glass production containers according to any one of claims 1 to 11.
13. The glass manufacturing container filling according to claim 12, which is located between a glass manufacturing container made of noble metal having the fired coating formed on the surface, the support material, and the glass manufacturing container and the support material. A glass manufacturing apparatus comprising a material layer.
14. The glass manufacturing apparatus according to claim 13, which is a refractory having a porosity of the support material in the range of 1% to 20%.
15. The glass manufacturing apparatus according to claim 14, wherein the thickness of the support material is in the range of 5 mm to 200 mm.
16. The glass manufacturing apparatus according to any one of claims 13 to 15, wherein a clearance between the glass manufacturing container and the support material is in a range of 1 mm to 200 mm.
17. A step of applying a coating material for forming a fired film on the surface of a glass production container made of precious metal, a step of providing a support material around the glass production container, and the glass production container and the support material. A step of filling a filler in between, and a step of firing the coating material and the filler to form the fired coating and the filler layer,
    The manufacturing method of the glass manufacturing apparatus in which the said filler contains a glass component.

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