WO2012070508A1 - Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article - Google Patents

Abstract

Provided is a method for producing a ceramic member having a ceramic substrate such as an electrocast brick or the like, and a spray-deposited metal film covering the surface thereof, the method for producing a ceramic member exhibiting an excellent improvement effect on adhesion strength between the ceramic member and the spray-deposited metal film. A method for producing a ceramic member for use at temperatures below 1500°C, the method for producing a ceramic member having a step for performing a heat treatment at a temperature of 1500°C or higher after a spray-deposited metal film (2), which is selected from a group consisting of a platinum group metal and an alloy having as the principal component thereof one or more types of platinum group metals, has been formed on a ceramic substrate (1) comprising a sintered brick having as the principal component thereof an electrocast brick or zircon, and having 3-30 mass% thereof in a glassy state.

Description

Ceramic member and manufacturing method thereof, molten glass manufacturing apparatus and manufacturing method, glass article manufacturing apparatus and glass article manufacturing method

The present invention relates to a method for producing a ceramic member, a ceramic member obtained by the production method, a production apparatus for molten glass provided with the ceramic member, a production method for molten glass using the production apparatus, and a glass article comprising the ceramic member. The manufacturing apparatus of this invention, and the manufacturing method of the glass article using this manufacturing apparatus.

For example, a glass product such as a glass plate is obtained by producing molten glass from a glass raw material and molding the molten glass with a molding apparatus. In order to improve the quality of glass products after molding, a method using a vacuum degassing device was proposed to remove bubbles generated in the molten glass after melting the glass raw material in the melting tank and before molding with the molding device (For example, Patent Document 1).
Such a vacuum degassing apparatus includes a vacuum degassing tank whose inside is maintained at a predetermined degree of vacuum, and when the molten glass passes through the vacuum degassing tank, the bubbles contained in the molten glass are compared. Bubbles that have grown in a short period of time and have grown greatly float on the surface of the molten glass by the buoyancy and break the bubbles, thereby removing the bubbles from the molten glass.
The temperature of the molten glass flowing out of the melting tank is, for example, about 1200 to 1600 ° C. in the case of soda lime glass, but the temperature of the molten glass introduced into the vacuum degassing apparatus for effective vacuum degassing. Is about 1000 to 1500 ° C., and the temperature of the molten glass introduced into the vacuum degassing vessel is about 1000 to 1400 ° C.

In the vacuum degassing apparatus, since the member that contacts the molten glass such as the vacuum degassing tank needs to be excellent in heat resistance and corrosion resistance against the molten glass, a ceramic member such as an electroformed brick is used.
In order to further suppress erosion caused by molten glass, a method of coating an electroformed brick with a metal film has also been proposed. Further, in Patent Document 2 below, a concave portion for anchor is formed on the surface of the electroformed brick. In addition, a method is described in which a metal sprayed film is formed so as to fill the concave portion, thereby improving the adhesion strength between the electroformed brick and the metal film and suppressing the peeling of the metal film.

International Publication No. 2009/125750 Pamphlet Japanese Unexamined Patent Publication No. 2008-121073

However, in the method described in Patent Document 2, the adhesion strength between the electroformed brick and the metal film is not necessarily sufficient.
According to the knowledge of the present inventors, the anchor effect by the recesses has a small effect of improving the adhesion strength against the tensile force in the thickness direction of the metal film.

The present invention has been made in view of the above circumstances, and is a method of manufacturing a ceramic member having a ceramic base material such as an electroformed brick and a metal sprayed coating covering the surface thereof. It aims at providing the manufacturing method of the ceramic member excellent in the improvement effect of the adhesive strength with a film | membrane.
The present invention also provides a ceramic member obtained by such a manufacturing method, a manufacturing apparatus for molten glass provided with the ceramic member, a manufacturing method for molten glass using the manufacturing apparatus, a manufacturing apparatus for glass articles provided with the ceramic member, And it aims at providing the manufacturing method of the glass article using this manufacturing apparatus.

As a result of intensive studies, the inventors of the present invention formed a metal sprayed film on a ceramic substrate containing a glass phase of a predetermined amount or more, and then heat-treated under specific conditions, in particular, the thickness of the metal sprayed film. It has been found that the adhesion strength between the ceramic substrate and the metal sprayed film against the tensile force in the direction is remarkably improved. Moreover, when this heat processing was performed, it also discovered that it became the state with which the glass phase was filled in the micro space of the interface of a ceramic base material and a metal sprayed film, and came to complete this invention.

That is, the method for producing a ceramic member according to the present invention is a method for producing a ceramic member having a temperature of less than 1500 ° C. in use, and comprises electrocast brick or zircon as a main component containing 3 to 30% by mass of a glass phase. After forming a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys mainly composed of one or more platinum group metals on a ceramic base material composed of sintered bricks, It has the process of heat-processing at the temperature of 1500 degreeC or more. In the method for producing a ceramic member of the present invention, the temperature during use is preferably 1400 ° C. or lower.
It is preferable that a regular anchor recess is formed on the surface of the ceramic substrate, and the metal sprayed film is formed on the anchor recess.

The ceramic member of the present invention is a ceramic member obtained by the manufacturing method of the present invention, wherein a glass phase is filled in a space at an interface between the ceramic base material and the metal sprayed film. To do.
The ceramic member of the present invention is a ceramic member having a ceramic base material and a metal sprayed film provided on the surface of the ceramic member, and the temperature at the time of use is less than 1500 ° C., wherein the metal is a platinum group metal. , And at least one metal selected from the group consisting of alloys containing at least one platinum group metal as a main component, wherein the ceramic base material contains 3 to 30% by mass of a glass phase. A part of the glass phase is filled in a space at the interface between the ceramic base material and the sprayed metal film. The ceramic member of the present invention preferably has a temperature during use of 1400 ° C. or lower.
It is preferable that a regular anchor recess is formed on the surface of the ceramic substrate, and the metal sprayed film is formed so as to fill the anchor recess.

The present invention provides a molten glass manufacturing apparatus in which the ceramic member of the present invention is used as a member that contacts molten glass of less than 1500 ° C. In the present invention, it is preferable that the ceramic member of the present invention is used for a member that contacts molten glass of 1400 ° C. or lower.
The present invention includes 3 to 30% by mass of a glass phase in which a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is formed. Using a ceramic substrate made of electrocast brick or sintered brick mainly composed of zircon, constituting at least a part of a portion of the molten glass manufacturing apparatus in contact with the molten glass of less than 1500 ° C., manufacturing the molten glass Provided is an apparatus for producing molten glass obtained by heat-treating at least the ceramic substrate of the apparatus at a temperature of 1500 ° C. or higher.
The present invention uses a ceramic base material composed of electrocast bricks or sintered bricks mainly composed of zircon containing 3 to 30% by mass of a glass phase, and is in contact with molten glass of less than 1500 ° C. in a molten glass production apparatus. At least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is provided on at least a part of the ceramic base material. Next, there is provided a molten glass manufacturing apparatus obtained by heat-treating at least a ceramic substrate on which a metal sprayed film is formed in a molten glass manufacturing apparatus at a temperature of 1500 ° C. or higher.

This invention provides the manufacturing method of a molten glass which manufactures a molten glass using the manufacturing apparatus of the molten glass of this invention.
The present invention has a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after molding, and a member that contacts the molten glass at a temperature lower than 1500 ° C. Furthermore, a glass article manufacturing apparatus in which the ceramic member of the present invention is used is provided. The present invention has a means for manufacturing molten glass, a forming means for forming the obtained molten glass, and a slow cooling means for gradually cooling the glass after forming, and a member that contacts the molten glass at 1400 ° C. or lower. Further, it is preferable that the ceramic member of the present invention is used.
The present invention includes 3 to 30% by mass of a glass phase in which a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is formed. Using a ceramic substrate made of electrocast brick or sintered brick mainly composed of zircon, constituting at least a part of a portion of the molten glass manufacturing apparatus in contact with the molten glass of less than 1500 ° C., manufacturing the molten glass An apparatus for producing molten glass obtained by heat-treating at least the ceramic substrate of the apparatus at a temperature of 1500 ° C. or higher; a glass forming apparatus for forming molten glass; and a slow cooling apparatus for gradually cooling the glass after molding. An apparatus for manufacturing a glass article is provided.
The present invention uses a ceramic base material composed of electrocast bricks or sintered bricks mainly composed of zircon containing 3 to 30% by mass of a glass phase, and is in contact with molten glass of less than 1500 ° C. in a molten glass production apparatus. At least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is provided on at least a part of the ceramic base material. Next, a molten glass manufacturing apparatus is formed by heat-treating a ceramic substrate on which at least the metal sprayed film of the molten glass manufacturing apparatus is formed at a temperature of 1500 ° C. or higher. There is provided a glass article manufacturing apparatus having a glass forming apparatus for performing cooling and a slow cooling apparatus for gradually cooling the formed glass.
This invention provides the manufacturing method of a glass article which manufactures a glass article using the manufacturing apparatus of the glass article of this invention.

According to the present invention, a part of the glass phase is present in a space at the interface between the ceramic base material having a glass phase and a metal spray coating (hereinafter also referred to as a metal spray coating) covering the surface thereof. A ceramic member which is filled and has excellent adhesion strength between the ceramic substrate and the metal spray coating is obtained.

The apparatus for producing molten glass of the present invention is excellent in corrosion resistance against molten glass because the surface of the member in contact with the molten glass is coated with the metal sprayed film, and the metal sprayed film is difficult to peel off. Excellent.
By using the apparatus for producing molten glass of the present invention, it is possible to stably produce molten glass and glass articles.

It is sectional drawing which showed one Embodiment of the ceramic member of this invention. An example of the anchor recess is shown, in which (a) is a plan view and (b) is a cross-sectional view taken along line BB in (a). It is the longitudinal cross-sectional view which showed one Embodiment of the manufacturing apparatus of the molten glass of this invention. It is a block diagram which shows an example of the manufacturing method of the glass article of this invention. It is a figure explaining the measuring method of adhesion strength. It is a graph which shows the measurement result of adhesion strength. It is a cross-sectional photograph of the ceramic member obtained in Example 1, (a) is before heat treatment, (b) is after heat treatment, (a ′) is the mapping of the glass phase in (a), (b ') Shows the mapping of the glass phase in (b). It is a cross-sectional photograph of the ceramic member obtained in Example 2, (a) is before heat treatment, (b) is after heat treatment, and (b ') is an enlarged view of the main part of (b). It is a cross-sectional photograph of the ceramic member obtained in Comparative Example 1, (a) is before heat treatment, (b) is after heat treatment, and (b ') is an enlarged view of the main part of (b). In Example 3, it is a graph which shows the heat history used when melting and solidifying a glass raw material within the container which consists of a ceramic member. The results of Example 3 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of β-OH values. The results of Comparative Example 2 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of β-OH values. The results of Comparative Example 3 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of β-OH values. It is a cross-sectional photograph of the glass solidified in the container which consists of a ceramic member obtained in Reference Example 1. 6 is a graph showing the measurement result of β-OH value in Reference Example 1.

<Ceramic material>
FIG. 1 is a cross-sectional view showing an embodiment of the ceramic member of the present invention. Reference numeral 1 denotes a ceramic base material, reference numeral 2 denotes a metal sprayed film, and reference numeral 3 denotes an anchor recess.
The ceramic member of the present invention has a ceramic base material 1 and a metal sprayed film 2 provided on the surface thereof, and oozes out from the ceramic base material into a space at the interface between the ceramic base material 1 and the metal sprayed film 2. The filled glass phase (not shown) is filled.

<Ceramic substrate>
As the ceramic substrate 1, a brick containing 3 to 30% by mass of a glass phase is used. In order to obtain corrosion resistance to the molten glass, bricks having high density are preferable. From this viewpoint, electrocast bricks mainly composed of zirconia and the like described below or sintered bricks mainly composed of zircon are used.
When the content of the glass phase is less than 3% by mass, a phenomenon that the glass phase exudes from the ceramic substrate 1 hardly occurs when heat treatment described later is performed. If it exceeds 30% by mass, the amount of oozing out of the glass phase increases and the metal sprayed film tends to swell.

[Electroformed brick]
An electroformed brick is a brick that has at least one component selected from the group consisting of zirconia, alumina, silicate alumina, zircon-mullite, silica, and titania, and is cast by melting these raw materials completely in an electric furnace. , Consisting essentially of a crystal phase and a glass phase. In the present invention, one having a glass phase content of 3 to 30% by mass can be selected from known electroformed bricks.
The content of the glass phase in the ceramic substrate in the present invention is a value obtained by obtaining the area ratio of the glass phase relative to the total area of the crystal phase and the glass phase based on the cross-sectional photograph and converting this to the mass ratio. It is. Specifically, on the surface layer within 50 mm from the dense surface of the ceramic substrate that coats the metal sprayed film, using a reflected electron image (composition image) taken with an electron microscope at a magnification of 50 to 100 times, a glass phase and a crystal Obtained by binarizing the phase.
Specific examples of the electroformed brick used in the present invention include AZS (Al ₂ O ₃ —SiO ₂ —ZrO ₂ ) brick, high zirconia brick with increased zirconia content, and the like. Of these, AZS bricks are preferred because cracks that occur during heating or heat fluctuation are unlikely to occur.
The content of the glass phase of the AZS brick is preferably 10 to 25% by mass, and more preferably 15 to 20% by mass. The content of the glass phase of the AZS brick can be adjusted by the mixing ratio of the raw materials.
The composition of the AZS brick is preferably 40 to 55% by mass of Al ₂ O ₃ , 10 to 15% by mass of SiO ₂ , 30 to 45% by mass of ZrO ₂ , and 0.5 to 2.5% by mass of Na ₂ O. . Other components such as various metal oxides and inevitable impurities constituting the glass phase are preferably 2% or less, more preferably 1% or less.
The content of the glass phase of the high zirconia brick is preferably 2 to 20% by mass, and more preferably 4 to 15% by mass. The content of the glass phase of the high zirconia brick can be adjusted by blending.
As the composition of the high zirconia brick, Al ₂ O ₃ is preferably 0.5 to 20% by mass, SiO ₂ is 2 to 10% by mass, and ZrO ₂ is preferably 80 to 96% by mass. The other components include, for example, various metal oxides and inevitable impurities constituting the glass phase, including Na ₂ O, preferably 3% or less and more preferably 2% or less.

[Sintered bricks mainly composed of zircon]
The sintered brick mainly composed of zircon is a sintered brick containing 80 to 96% by mass of zircon, and substantially consists of a crystal phase and a glass phase. In the present invention, one having a glass phase content of 3 to 30% by mass can be selected from among known sintered bricks mainly composed of zircon.
The content of the glass phase in the sintered brick mainly composed of zircon is preferably 3 to 10% by mass, and more preferably 4 to 10% by mass. Content of the glass phase of the sintered brick which has a main component of zircon can be adjusted with the compounding ratio of raw material powder.
The composition of the sintered brick mainly composed of zircon is preferably 30 to 45% by mass of SiO ₂ , 50 to 70% by mass of ZrO _{2 and} 5% by mass or less of other metal oxides.

[Recess for anchor]
It is preferable that a regular anchor recess 3 is formed on the surface of the ceramic substrate 1. By providing the anchor recess 3, the adhesion strength between the ceramic substrate 1 and the metal sprayed film 2 is further improved. In particular, the adhesion strength against tensile stress in the direction parallel to the surface of the ceramic substrate 1 is improved.
2A and 2B show an example of the shape of the anchor recess 3. FIG. 2A is a plan view, and FIG. 2B is a cross-sectional view taken along line BB in FIG.
The anchor recess 3 of this example is provided with a plurality of linear grooves g having a rectangular cross-sectional shape in a lattice shape. The side surface of each groove g is perpendicular to the surface of the ceramic substrate 1, and the groove width w is constant.
In order to effectively obtain the anchor effect, the groove g constituting the anchor recess 3 needs to have a certain depth. However, if the depth is too deep, the strength of the surface layer portion of the ceramic substrate 1 is reduced and processed. It is also difficult. For example, the depth d of the groove g is preferably about 50 to 350 μm, more preferably about 150 to 250 μm.

The degree of dispersion of the stress generated between the metal sprayed film 2 and the ceramic substrate 1 varies depending on the groove pitch (inter-groove interval, which indicates the distance between the center lines of adjacent grooves) p. It is preferable to reduce the groove pitch p in order to reduce the stress applied to one place by dispersing the above. Considering the stress durability of the metal sprayed film 2 and the strength of the ceramic substrate 1, the groove pitch p is preferably about 2.5 mm or less, more preferably about 1.5 mm or less. For the same reason, it is preferable that the groove width w is narrow, and the groove width w is preferably narrow also from the viewpoint of maintaining the strength of the surface layer portion of the ceramic substrate 1. However, if the groove width w is narrower than the particle size of the metal particles to be sprayed, the grooves cannot be filled with the spray particles, so the groove width w is set to be equal to or larger than the particle size of the spray particles. For example, the groove width w is preferably 100 μm or more, and more preferably about 150 μm or more.

In order to maintain the strength at which the convex portion between adjacent grooves g does not break against the stress, the convex portion width x (= inter-groove interval, difference between groove pitch p and groove width w) according to the stress. It is necessary to ensure. The tensile stress applied from the metal spray film 2 in the direction parallel to the surface of the ceramic substrate 1 increases as the thickness m of the metal spray film 2 formed on the ceramic substrate 1 increases. In this respect, the width x of the convex portion is preferably about 4 times or more the thickness m of the metal sprayed film 2. Further, considering the point that the groove pitch p is reduced, the preferable width x of the convex portion is about 2.5 to 5 times the thickness m of the film.

As for the stress applied to the side surface of the groove g, the deeper the groove (that is, the larger the side surface), the more the stress is dispersed on the entire side surface, and the convex portion is less likely to break. Therefore, the smaller the ratio (p / d) of the groove pitch p to the groove depth d, the higher the stress dispersibility, and the easier it is to prevent the metal sprayed film 2 from peeling off. When the p / d value at which the stress is appropriately dispersed is obtained based on the above-mentioned preferable groove pitch p and groove depth d, it is preferably about 3 to 8.

The anchor recess is not limited to the shape shown in FIG. For example, substantially cylindrical holes may be regularly formed.
When intermittent holes are formed as an alternative to the grooves 3 as shown in FIG. 2, it is preferable to form holes at crossing positions of the orthogonal lattice (cross grid). Alternatively, it is preferably arranged at a staggered (staggered layout) position such that the hole pitch distance is uniform. For example, the hole pitch distance is preferably about 0.7 to 2.5 mm, more preferably about 1.0 to 1.6 mm. The pore diameter is preferably about 200 to 500 μm, more preferably 300 to 400 μm. The depth of the hole is preferably about 200 to 600 μm, more preferably about 300 to 500 μm.

When the anchor recess 3 is groove-shaped, the anchor recess 3 can be formed mechanically using a grinder equipped with a grinding blade composed of, for example, a grindstone or a diamond blade. Or you may carry out using high energy beams, such as a laser, and a high voltage | pressure water flow. In the case where the anchor recess 3 is hole-shaped, it can be formed using a grinding tool in the form of a pin drill or the like, or a high energy beam such as a laser or a high-pressure water stream. If the surface of the ceramic substrate 1 is adjusted to a highly accurate surface by cutting with a grinder or the like in advance before forming the anchor recess 3, the metal sprayed film 2 can be prevented from peeling off due to unexpected unevenness. This is preferable.

In the present invention, the anchor recess 3 may be either a groove shape or a hole shape. However, in the hole shape, the closed space (inside space of the hole) closed by the metal sprayed film is relatively small, and the hole has a uniform shape. Since the closed space can be formed one by one, the adhesion strength against the tensile force in the thickness direction of the metal sprayed film 2 is improved by filling the interface between the ceramic substrate 1 and the metal sprayed film 2 with a glass phase. It is preferable in that the effect is large. On the other hand, the groove-shaped direction has a relatively large closed space (inner space in the groove) closed by the metal sprayed film, and the closed space is constituted by a large groove, so the above effect is relatively low.

<Metal sprayed film>
The metal sprayed film 2 is a metal film formed by a spraying method. The thermal spraying method is a method in which metal particles heated to a high temperature are injected onto a substrate and a coating film is formed by deposition of the metal particles. Therefore, the metal sprayed film has a granular deposited structure in the cross section, unlike a solidified film formed by applying molten metal or the like.
As the metal, at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is used.
Examples of the platinum group metal include platinum (Pt), iridium (Ir), ruthenium (Ru), and rhodium (Rh). Examples of the alloy containing a platinum group metal as a main component include platinum alloys such as a Pt-5% Au alloy, a Pt-10% Ir alloy, and a Pt-10% Rh alloy.

<Manufacturing method of ceramic member>
First, the metal sprayed film 2 is formed on the ceramic substrate 1. When the anchor recess 3 is provided on the surface of the ceramic substrate 1, the metal sprayed film 2 is formed so as to cover the anchor recess 3. As a thermal spraying method, a known thermal spraying method such as a laser spraying method, a wire frame spraying method, a plasma spraying method, an arc spraying method, an oxyhydrogen flame spraying method, or the like can be appropriately used.
The particle diameter of the metal particles (flying spray particle diameter) injected in the thermal spraying method is preferably finer and can be reduced to about 40 μm depending on the type of thermal spraying method, but is generally about 50 to 150 μm.
The metal particles injected by the thermal spraying method are deposited on the surface of the ceramic substrate 1 to form the metal sprayed film 2. When the anchor recess 3 is formed on the surface of the ceramic substrate 1, the metal particles injected by the thermal spraying method fill the recess 3 and further deposit on the surface to form the metal sprayed film 2.
The thickness m of the metal sprayed film 2 can be appropriately adjusted depending on the amount of spraying. The greater the thickness, the greater the strain due to the tensile stress in the direction parallel to the surface of the ceramic substrate 1, so the thickness m of the sprayed film 2 (if there is a recess, the thickness at the portion without the recess) is 100 to 400 μm. The preferred range is 200 to 350 μm.

Since the temperature of the metal particles to be injected is generally about 700 to 1500 ° C., the temperature of the ceramic substrate during the thermal spraying is increased, for example, by preheating (that is, preheating). It is preferable to reduce the temperature difference from the base material because the adhesion between the metal sprayed film 2 and the ceramic base material 1 is improved. In this case, it is preferable that after the thermal spraying in a state where the ceramic substrate 1 is heated (preheated), it is gradually cooled to room temperature.
The temperature (preheating temperature) of the ceramic substrate 1 at the time of thermal spraying is preferably not higher than the solidification temperature of the injected metal particles, specifically about 200 to 500 ° C., more preferably 300 to 400 ° C. The cooling rate during slow cooling should be as slow as possible, preferably about 10 ° C./min or less.

Next, heat treatment is performed at a temperature of 1500 ° C. or higher with the metal sprayed film 2 formed on the ceramic substrate 1.
By performing such heat treatment, the glass phase oozes out from the ceramic base material 1 into a minute space at the interface between the ceramic base material 1 and the metal sprayed film 2, and a state in which the glass phase is filled in the space is obtained. . This is because when heated to a high temperature of 1500 ° C. or higher, the glass phase in the ceramic substrate easily flows, and due to the difference in thermal expansion between the glass phase and the ceramic phase, the glass phase is extruded into a minute space, It is thought that it spreads in the space.

In the present invention, the state in which the glass phase is filled in the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 means that the glass phase exists between the ceramic substrate 1 and the metal sprayed film 2 and the glass At least a part of the phase refers to a state in contact with both the ceramic substrate 1 and the metal sprayed film 2. Although some space may remain at the interface between the ceramic substrate 1 and the metal sprayed film 2, such space does not remain as much as possible in order to obtain good adhesion strength between the ceramic substrate 1 and the metal sprayed film 2. It is preferable. For example, in the cross-sectional photograph after the heat treatment, the remaining space without the glass phase is 20 area% or less with respect to the entire area of the space existing at the interface between the ceramic substrate 1 and the metal sprayed film 2. It is preferably 10 area% or less, and most preferably 0 area%.

When the heat treatment temperature is lower than 1500 ° C., it is difficult to obtain a state where the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase. This is because the flow state of the glass phase is insufficient, so that it cannot spread in the space in a short time, and the ceramic phase and the glass phase react with the passage of time. It is considered that a state where the space is filled with the glass phase cannot be obtained.
On the other hand, the upper limit of the heat treatment temperature needs to be lower than the melting point of the metal constituting the sprayed film 2.
Therefore, the heat treatment temperature is preferably set so that the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase in a preferable heat treatment time described later, which is lower than the melting point of the sprayed film 2. The preferred heat treatment temperature varies depending on the component composition of the ceramic substrate 1, but is preferably about 1500 to 1700 ° C, and more preferably about 1500 to 1600 ° C. Since the glass phase has high fluidity when the heat treatment temperature is within these ranges, the influence of the reaction between the ceramic phase and the glass phase on the effect of filling the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 with the glass phase is low. .
If the heat treatment time is too short, a large amount of space remains at the interface between the ceramic substrate 1 and the metal sprayed film 2. On the other hand, when the heat treatment time becomes long, the ceramic phase and the glass phase react with the passage of time, so that the phenomenon in which the glass phase is extruded into the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 does not easily proceed.
Therefore, it is preferable to set the heat treatment time so that these disadvantages do not occur. For example, it is preferably about 1 to 100 hours, and more preferably 10 to 50 hours.
According to the manufacturing method of the present invention, the ceramic member of the present invention in which the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase derived from the ceramic substrate is obtained.

<Uses of ceramic members>
The ceramic member of the present invention is a member having a temperature of less than 1500 ° C. during use. That is, it is used for a portion where the temperature during use is not assumed to be 1500 ° C. or higher.
In a member whose operating temperature is 1500 ° C. or higher, there is a possibility that the same effect as that of the present invention may be obtained as a result without performing heat treatment at 1500 ° C. or higher before use, and the present invention is applied to such a member. This is because the necessity is low.
For this reason, the ceramic member of the present invention is preferably a member having a temperature of 1450 ° C. or lower, more preferably a member having a temperature of 1400 ° C. or lower.

Since the metal sprayed film 1 is provided on the ceramic base material 1, the ceramic member of the present invention is excellent in corrosion resistance against molten glass. Therefore, the ceramic member of this invention is used suitably as a member which contacts the molten glass below 1500 degreeC in the apparatus used for manufacture of molten glass. The ceramic member of the present invention is more preferably used as a member that contacts molten glass at 1450 ° C. or lower, and more preferably as a member that contacts molten glass at 1400 ° C. or lower in an apparatus used for manufacturing molten glass. Used.
Specifically, the molten glass that has flowed out of the melting tank is preferably used as a member that comes into contact with the molten glass at a temperature of less than 1500 ° C., preferably through a vacuum degassing apparatus and sent to the molding apparatus. . In addition, the molten glass that has flowed out of the melting tank is more preferably used as a member that contacts the molten glass at 1450 ° C. or lower in the flow path until it is sent to the molding device through a vacuum degassing device, It is more suitably used as a member that contacts molten glass at 1400 ° C. or lower. For example, a member constituting the inner wall of the vacuum degassing tank, a member constituting the inner wall of the melting riser pipe provided upstream of the vacuum degassing tank, or a member constituting the inner wall of the downcomer pipe provided downstream of the vacuum degassing tank Is mentioned.

In the ceramic member of the present invention, since the metal sprayed film 2 is provided on the surface of the ceramic substrate 1, erosion of the ceramic substrate 1 can be suppressed even when it comes into contact with molten glass. Moreover, since the adhesion strength between the ceramic substrate 1 and the metal sprayed film 2 is excellent as shown in the examples described later, the metal sprayed film 2 is hardly peeled off and excellent in durability.

In addition, when the ceramic member of the present invention is used as a member that comes into contact with molten glass, bubbles are generated in the molten glass because the glass phase is filled in the space between the ceramic substrate and the metal sprayed film. The effect which suppresses is acquired.
That is, when moisture present in the molten glass is decomposed into oxygen and hydrogen on the surface of the metal spray film by the catalytic action of the platinum group metal, hydrogen passes through the metal spray film and oxygen passes through the metal spray film. It remains on its surface without. At this time, if hydrogen stays on the metal sprayed film, it combines with oxygen on the surface of the metal sprayed film to generate water, so that oxygen does not become bubbles.
However, in the conventional ceramic member, since there is a minute space at the interface between the metal sprayed film and the ceramic substrate that is the lower layer, the hydrogen that has permeated the metal sprayed film moves through the space, Hydrogen does not stay on the metal sprayed film. For this reason, oxygen on the surface of the metal sprayed film cannot be combined with hydrogen again, resulting in bubbles.
In the ceramic member of the present invention, since the glass phase is filled in the space between the metal spray film and the ceramic substrate, hydrogen stays in the metal spray film and recombines with oxygen to generate water. it can. Therefore, oxygen can be prevented from forming bubbles.

<Molded glass manufacturing equipment>
The apparatus for producing molten glass of the present invention uses the ceramic member of the present invention as a member that contacts molten glass of less than 1500 ° C. In the molten glass production apparatus of the present invention, the ceramic member of the present invention is preferably used for a member that contacts the molten glass at 1450 ° C. or lower, and the present invention is preferably applied to a member that contacts the molten glass at 1400 ° C. or lower. More preferably, the ceramic member is used.
Moreover, the apparatus for producing molten glass of the present invention comprises a glass phase in which a sprayed film of at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is formed. 3 to 30% by mass, using a ceramic base material made of electrocast brick or sintered brick mainly composed of zircon, less than 1500 ° C., preferably 1450 ° C. or less, more preferably 1400 ° C. of a molten glass production apparatus. It constitutes at least a part of a portion in contact with the molten glass having a temperature of not higher than ° C., and at least the ceramic substrate of the molten glass manufacturing apparatus is heat treated at a temperature of 1500 ° C. or higher.
Furthermore, the apparatus for producing molten glass of the present invention is an apparatus for producing molten glass using a ceramic base material comprising 3-30% by mass of a glass phase and comprising a sintered brick mainly composed of electroformed brick or zircon. It constitutes at least a part of a part in contact with the molten glass of less than 1500 ° C., preferably 1450 ° C. or less, more preferably 1400 ° C. or less, and a platinum group metal and a platinum group metal are formed on the ceramic substrate of the constituted part Forming a ceramic sprayed film of at least one metal selected from the group consisting of an alloy mainly composed of one or more of the following, and then forming a ceramic substrate on which at least the metal sprayed film of the molten glass manufacturing apparatus is formed Heat treatment is performed at a temperature of 1500 ° C. or higher.
FIG. 3 is a longitudinal sectional view showing an embodiment of the apparatus for producing molten glass according to the present invention. The apparatus of this embodiment is a melting tank 11 for melting glass raw materials and homogenizing and clarifying molten glass. The internal pressure is set to be lower than atmospheric pressure, and bubbles in the molten glass supplied from the melting tank 11 are floated. And the vacuum degassing device 12 for breaking the bubbles, the first conduit 13 connecting the melting tank 11 and the vacuum degassing device 12, and the molten glass flowing out from the vacuum degassing device 12 through the cooling tank 15 in the next step And a second conduit 14 for feeding to the forming means. The code | symbol G in a figure shows a molten glass.
The first conduit 13 is provided with a cooling means 13a and a stirring means 13b, and the molten glass flowing out of the melting tank 11 is cooled to 1000 ° C. or more and less than 1500 ° C. in the first conduit 13, It is introduced into the vacuum degassing device 12.
The vacuum degassing apparatus 12 includes a vacuum degassing tank 12a. The upstream side of the vacuum degassing tank 12a communicates with the first conduit 13 through the riser 12b, and is downstream of the vacuum degassing tank 12a. The side communicates with the second conduit 14 via the downcomer 12c. The insides of the vacuum degassing tank 12a, the rising pipe 12b, and the lowering pipe 12c are maintained in a vacuum environment, and the molten glass in the first conduit 13 is sucked up to the vacuum degassing tank 12a through the rising pipe 12b by the siphon effect. It is configured as follows. Further, the conduit 14 and subsequent parts are connected to the forming means via the cooling tank 15.

In the apparatus of the present embodiment, the members constituting the inner walls of the reduced pressure defoaming tank 12a, the rising pipe 12b, the lowering pipe 12c, and the cooling tank 15 of the reduced pressure defoaming apparatus 12 are ceramic members or metal according to the present invention. It consists of what heat-processes the ceramic base material in which the sprayed film was formed. That is, the inner walls of the vacuum degassing tank 12a, the riser pipe 12b, the downfall pipe 12c, and the cooling tank 15 are made of a ceramic base material whose inner surface is coated with a metal sprayed film. A glass phase is filled in a minute space at the interface.
The vacuum degassing apparatus 12 and the cooling tank 15 are first formed of a ceramic base material in which the inner walls of the vacuum degassing tank 12a, the ascending pipe 12b, the descending pipe 12c, and the cooling tank 15 are previously coated with a metal sprayed film. Then, after assembling into a series of shapes from the vacuum degassing apparatus 12 to the cooling tank 15, the inside of the series of structures including the vacuum degassing apparatus 12 and the cooling tank 15 is subjected to heat treatment at a predetermined temperature of 1500 ° C. or more, Subsequently, it is manufactured by a method of cooling below the use temperature. In addition, the ceramic member of the present invention forms the inner wall of the vacuum degassing tank 12a, the rising pipe 12b, the descending pipe 12c, and the cooling tank 15, and assembles into a series of shapes from the vacuum degassing apparatus 12 to the cooling tank 15. You can also. Further, the inner walls of the vacuum degassing tank 12a, the rising pipe 12b, the downfalling pipe 12c, and the cooling tank 15 are formed of a ceramic base material, and a metal sprayed film is formed on the surface of the base material on the side in contact with the molten glass. Then, the ceramic base material on which the metal sprayed film is formed can be heat-treated at a temperature of 1500 ° C. or higher.
After the device is manufactured in this way, it is used at a use temperature of less than 1500 ° C. Moreover, after manufacturing an apparatus in this way, it is preferably used at a use temperature of 1450 ° C. or less, and more preferably used at a use temperature of 1400 ° C. or less.
In addition, the assembly procedure of each part and the site | part using the ceramic member of this invention are not limited to said example. For example, since the molten glass temperature in the cooling bath 15 is lower than that in the upstream portion, the portion using the ceramic member of the present invention may be only the vacuum degassing device 12 and not used in the cooling bath 15. Alternatively, the portion of the vacuum degassing apparatus 12 that uses the ceramic member of the present invention may be only the vacuum degassing tank 12a, only the rising pipe 12b and the lowering pipe 12c, or only the lowering pipe 12c. Further, the ceramic member of the present invention may be used for the inner walls of the first conduit 13 and the second conduit 14.

<Method for producing molten glass>
The manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass using the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts the molten glass below 1500 degreeC. Moreover, the manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass which uses the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts 1450 degrees C or less molten glass. Furthermore, the manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass more preferable to use the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts 1400 degrees C or less molten glass. .
For example, in the method of manufacturing molten glass using the apparatus for manufacturing molten glass shown in FIG. 3, the molten glass that has flowed out of the melting tank 11 is 1000 ° C. or more and less than 1500 ° C. in the first conduit 13. After being cooled, it is introduced into the vacuum deaerator 12. Moreover, it is preferable that the molten glass flowing out from the melting tank 11 is introduced into the vacuum degassing apparatus 12 after being cooled to 1000 ° C. or higher and 1450 ° C. or lower in the first conduit 13. Furthermore, it is more preferable that the molten glass flowing out from the melting tank 11 is introduced into the vacuum degassing apparatus 12 after being cooled to 1000 ° C. or higher and 1400 ° C. or lower in the first conduit 13.
The inner walls of the reduced pressure defoaming tank 12a, the rising pipe 12b, the descending pipe 12c, and the cooling tank 15 of the vacuum degassing apparatus 12 are in contact with molten glass at 1000 ° C. or more and less than 1500 ° C., but the ceramic base constituting the inner wall Since the surface (that is, the inner surface) of the material is coated with the metal sprayed film, the corrosion resistance to the molten glass is excellent. Further, since the adhesion strength between the ceramic substrate and the metal sprayed film is excellent, the sprayed film is hardly peeled off and excellent in durability.
Furthermore, since the glass phase is filled in the interface between the metal sprayed film and the ceramic substrate which is the lower layer, even if moisture in the glass is decomposed into oxygen and hydrogen on the surface of the metal sprayed film, the hydrogen Can remain on the metal spray coating. Therefore, as described above, the hydrogen can be recombined with oxygen generated by the decomposition of moisture to generate water, so that generation of bubbles in the molten glass due to the oxygen is suppressed. be able to.

<Glass article manufacturing apparatus and method>
The apparatus for producing a glass article of the present invention comprises a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, and is less than 1500 ° C. The ceramic member of this invention is used for the member which contacts molten glass. Moreover, the apparatus for producing a glass article of the present invention has a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, and 1450 ° C. It is preferable that the ceramic member of this invention is used for the member which contacts the following molten glass. Furthermore, the apparatus for producing a glass article of the present invention comprises a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, at 1400 ° C. It is more preferable that the ceramic member of the present invention is used for the following member that contacts the molten glass.
The means for producing molten glass is preferably the molten glass production apparatus of the present invention. For example, as shown in FIG. 3, the apparatus has a forming means for forming molten glass downstream of the molten glass flow direction of the molten glass manufacturing apparatus, and a slow cooling means for gradually cooling the glass after forming downstream thereof. Can do. A processing means for further cutting and polishing may be provided downstream of the slow cooling means. Although not shown, various means such as a known float method, downdraw method, and fusion method can be used as the forming means. A well-known technique can also be used for the slow cooling means and the processing means.
FIG. 4 is a flowchart showing an example of a glass article manufacturing method using the glass article manufacturing apparatus according to the present invention.
In order to manufacture a glass article according to the method shown in FIG. 4, preferably, a molten glass G is obtained by a glass melting step S1 using the molten glass manufacturing apparatus of FIG. 3, and the molten glass G is sent to a forming means. After passing through the forming step S2 for forming into a shape, it is gradually cooled in the slow cooling step S3. Thereafter, the glass article G5 can be obtained by post-processing such as cutting and polishing in the post-processing step S4 as necessary.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
[Example 1]
In this example, AZS (Al ₂ O ₃ —SiO ₂ —ZrO ₂ ) brick is used as the ceramic substrate, and the surface of the brick is subjected to drilling with a regular arrangement as described below, and then metal spraying is performed. A substrate with a metal film was obtained, and the substrate with a metal film was subjected to heat treatment to produce a ceramic member. Hereinafter, the base material on which the metal sprayed film is formed on the surface of the ceramic base material is also referred to as a base material with a metal film.
Table 1 shows the results of measuring the component composition of the ceramic substrate used by fluorescent X-ray analysis. Further, the glass phase content obtained based on the cross-sectional photograph of the base material with the metal film before the heat treatment is shown in Table 1 (the same applies to Example 2 and Comparative Example 1 below). The glass phase content is calculated by the following method. Using an electron microscope, a 50-fold backscattered electron image (composition image) of the cross section of the base material with a metal film before heat treatment is taken from the base material surface to the position of 20 mm toward the inside of the base material. To do. For the obtained image, the total area of the crystal phase and the glass phase, and the area ratio of the glass phase relative to it, the value obtained by converting the area ratio into a mass ratio, the content of the glass phase (unit: Mass%).
First, AZS bricks were cut into 50 mm long × 50 mm wide × 10 mm high brick pieces, and anchor concave portions were formed on one side of the brick pieces using a fiber laser. The anchor recess was a substantially cylindrical hole, the hole diameter was 300 μm, the hole depth was 400 μm, and the hole pitch distance was 1 mm.
Subsequently, the brick piece was heated to 300 ° C. in an air atmosphere, and the thermal spraying of platinum was started on the surface on which the holes were formed by using a wire frame spraying method (flying spray particle diameter: about 100 μm, temperature about 100 ° C.). Thermal spraying was continued until the film thickness of the platinum coating reached 300 μm, and then the brick pieces were gradually cooled to room temperature to obtain a substrate with a metal film.
Two base materials with a metal film were produced under the same conditions, and one base material with a metal film was heat-treated at 1500 ° C. for 100 hours in an atmosphere in an electric furnace to obtain a ceramic member.
As a control, the other metal film-coated substrate was not subjected to heat treatment, and was used as it was as an untreated sample.

[Example 2]
In Example 1, except that the ceramic substrate was changed to high zirconia brick, a substrate with a metal film was obtained in the same manner, and the substrate with the metal film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. did. As a control, an untreated sample not subjected to heat treatment was prepared in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, except that the ceramic base material was changed to αβ alumina brick, a base material with a metal film was obtained in the same manner, and the base material with the metal film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. did. As a control, an untreated sample not subjected to heat treatment was prepared in the same manner as in Example 1.

[Evaluation methods]
(Adhesion strength)
From each of the ceramic member and untreated sample obtained in each example, three plate-like pieces each having a length of 14 mm, a width of 14 mm, and a height of 10 mm were cut out, and as shown in FIG. A test piece was prepared by bonding the tension jigs 24 and 25 using a thermosetting epoxy adhesive 23. In the figure, reference numeral 21 denotes a ceramic substrate, and 22 denotes a metal sprayed film.
Using a tensile strength measuring instrument (manufactured by TSE, product name: AUTOCOM / AC · 50KN-C), the tension jigs 24 and 25 are pulled away from each other under a speed condition of 0.5 mm / min. The load when the metal sprayed film 22 peeled off was measured. From the value (P) of the load at the time of peeling and the area (S) of the plate-like piece (ceramic member), the adhesion strength (P / S, unit is MPa) was determined. The result is shown in FIG.

As shown in the results of FIG. 6, in Comparative Example 1, the adhesion strength between the untreated sample and the ceramic member was almost equal. On the other hand, the adhesion strength of the ceramic members in Examples 1 and 2 is 3 times or more of the adhesion strength of the untreated sample, and it is recognized that the adhesion strength has been remarkably improved by heat treatment. .

(Cross-sectional structure)
When manufacturing the ceramic member in each example, a cross-sectional photograph of the substrate with the metal film before heat treatment and the ceramic member after heat treatment was taken. 7 is a photograph obtained in Example 1, FIG. 8 is a photograph obtained in Example 2, and FIG. 9 is a photograph obtained in Comparative Example 1. Reference numeral 21 denotes a ceramic substrate, and 22 denotes a metal sprayed film.
In FIG. 7, (a) is a cross-sectional photograph before the heat treatment, (b) is a cross-sectional photograph after the heat treatment, (a ′) is a mapping of the glass phase shown in the photograph (a), (b ′) Is a mapping of the glass phase in the photograph of (b).
8 and 9, (a) is a cross-sectional photograph before heat treatment, (b) is a cross-sectional photograph after heat treatment, and (b ′) is an enlarged view of a main part (indicated by symbol B in the drawing) of (b). It is shown.

As shown in FIGS. 7A to 9A, in the base material with the metal film before the heat treatment, there is a minute gap (space) at the interface between the ceramic base material 21 and the metal sprayed film 22. On the other hand, as shown in FIGS. 7 and 8 (b), in the ceramic members after the heat treatment of Examples 1 and 2, there is no gap at the interface between the ceramic base material 21 and the metal sprayed film 22, and FIGS. As shown in (b ′), a glass phase exists along the interface.
On the other hand, as shown in FIG. 9B, in the ceramic member after the heat treatment of Comparative Example 1, there is a gap at the interface between the ceramic base material 21 and the metal sprayed film 22, and FIG. As shown in b '), no oozing of the glass phase to the interface is observed.

[Example 3]
In this example, as a molten glass manufacturing apparatus, a glass melting container made of a ceramic member was prepared as described below, and the glass raw material was melted at 1400 ° C. in the container and then cooled. Thereafter, the moisture content in the glass and the presence or absence of bubbles in the vicinity of the inner wall of the container were examined by an evaluation method described later.
First, using a ceramic base material made of a high zirconia brick of the same material as used in Example 2 and provided with anchor recesses on one side in the same manner as in Example 1, the outer diameter is 75 mm and the height of the outer wall is high. A bottomed cylindrical container having a thickness of 55 mm, an inner diameter of 50 mm, and an inner wall depth of 40 mm was prepared. The surface provided with the anchor recess was made the inner surface.
Subsequently, this container was heated to 300 ° C. in an air atmosphere, and a metal sprayed film having a film thickness of 300 μm was formed on the inner surface in the same manner as in Example 1 to obtain a container made of a substrate with a metal film. .
Subsequently, this container was placed in an electric furnace under the atmosphere and subjected to heat treatment at 1600 ° C. for 5 hours to obtain a container made of a ceramic member.

In carrying out the above Example 3, the obtained container was placed in a heating furnace, and the thermal history shown in FIG. 10 was added under normal pressure. The vertical axis | shaft of FIG. 10 shows the atmospheric temperature in a heating furnace. First, the temperature is raised from room temperature to 1400 ° C. over 4 hours and 40 minutes. When the temperature reaches 1400 ° C., the glass raw material of borosilicate glass is put into the container and heated at 1400 ° C. for 1 hour to melt the glass raw material. I let you. Thereafter, the glass was rapidly cooled to 720 ° C. and held at 720 ° C. for 1 hour, then the temperature was lowered to 600 ° C. over 2 hours and further cooled to room temperature over 3 hours to obtain a glass solidified in the container. .

[Comparative Example 2]
In Example 3, glass solidified in the container was obtained in the same manner as in Example 3 except that the container made of the metal film-coated substrate was not subjected to heat treatment.
[Comparative Example 3]
In Example 3, the material of the ceramic substrate was changed from a high zirconia brick to the same αβ alumina brick as used in Comparative Example 1, and was made of a substrate with a metal film in the same manner as in Example 3. A container was obtained, and the same heat treatment as in Example 3 was performed on the container to prepare a container made of a ceramic member.
Using this container, a glass solidified in the container was obtained in the same manner as in Example 3.

[Evaluation methods]
(Moisture content and presence of bubbles)
The β-OH value of the glass was measured as an indicator of the water content in the glass. The β-OH value (unit: mm ⁻¹ ) of the glass was measured by measuring the absorbance of the glass sample with respect to light having a wavelength of 2.75 to 2.95 μm, and determining the maximum value β _max as the thickness (mm) of the glass sample. It can be obtained by dividing.
The glass solidified in the container obtained in each of the above examples was cut along with the container along a cut surface along the height direction, and a longitudinal section sample having a thickness of 1 mm was cut out. The β-OH value was measured by the above method for the region of the obtained longitudinal section sample at the center in the height direction of the container and in the vicinity of the interface between the inner wall of the container and the solidified glass. A photograph of the area was taken.
The results of Example 3 are shown in FIG. 11, the results of Comparative Example 2 are shown in FIG. 12, and the results of Comparative Example 3 are shown in FIG. (A) of each figure is a cross-sectional photograph, and the reference position of the interface is indicated by an arrow. In the figure, reference numeral 21 denotes a ceramic substrate, 22 denotes a metal sprayed film, and 30 denotes glass. (B) of each figure is a graph showing the measurement result of β-OH value, the horizontal axis shows the distance (unit: μm) in the horizontal direction of the cross-sectional photograph of (a), and the vertical axis shows β-OH value (unit). : Mm ⁻¹ ). A position corresponding to the reference position of the interface is indicated by an arrow.

[Reference Example 1]
In the container made of the base material with the metal film of each of the examples 3 and comparative examples 2 and 3 described above, the lower layer of the metal sprayed film is made of a ceramic base material. The water content when the lower layer of glass was made of glass was measured.
That is, in Example 3, when a glass material of borosilicate glass is introduced into the container when the temperature reaches 1400 ° C. after the container made of the ceramic member is placed in the heating furnace, A part of the glass raw material was directly put into a container made of the ceramic member, and the remainder of the glass raw material was put in a separately prepared platinum rhodium crucible, and the crucible was put in the container. Other than that obtained the glass solidified in the container like Example 3. FIG. FIG. 14 is a photograph showing the longitudinal section. In this example, the crucible 32 is embedded in the solidified glass 30 in the container 31 made of a ceramic member, and both the inner surface and the outer surface of the crucible 32 are in contact with the solidified glass.

The glass solidified in the container obtained in this example was cut along the height direction along with the container and the crucible, and a longitudinal cross-sectional sample having a thickness of 1 mm was cut out. About the area | region (it shows with the code | symbol 33 in FIG. 14) in the center part of the depth direction of a crucible of the obtained longitudinal cross-section sample, and the vicinity of the interface of the inner surface and outer surface of a crucible, and glass. The β-OH value was measured at
The results are shown in FIG. The horizontal axis indicates the distance in the horizontal direction of the cross-sectional photograph of FIG. 14, and the vertical axis indicates the β-OH value. In FIG. 15, the position corresponding to the side wall of the crucible is indicated by an arrow.
In the longitudinal section sample used for measuring the β-OH value, no bubbles were observed in the glass.

As shown in the results of FIGS. 12B and 13B, in Comparative Examples 2 and 3, the water content (β-OH value) in the glass decreases in the region adjacent to the metal sprayed film. ing. Further, as shown in FIGS. 12A and 13A, generation of bubbles was observed in the glass in a region adjacent to the metal sprayed film. From this, it can be seen that the oxygen generated by the decomposition of the water present in the molten glass on the surface of the metal sprayed film became bubbles without generating water again.
Moreover, although the comparative example 2 used the high zirconia brick containing 6 mass% of glass phases as a ceramic base material, since it did not heat-process at 1500 degreeC before use, even if it heats at 1400 degreeC for 1 hour at the time of use In the cross-sectional photograph, a minute gap was observed at the interface between the metal sprayed film and the ceramic substrate.
In Comparative Example 3, since the ceramic base material contains only 0.8% by mass of the glass phase, even if heat treatment at 1500 ° C. is performed before use, there is a minute amount at the interface between the metal sprayed film and the ceramic base material in the cross-sectional photograph. A gap was observed.
From these facts, in Comparative Examples 2 and 3, the hydrogen generated by the decomposition of the water present in the molten glass on the surface of the metal sprayed film permeates the metal sprayed film, and the metal sprayed film and the ceramic substrate It is thought that it moved through the space of the interface and did not stay on the metal sprayed film.

On the other hand, as shown in the results of FIG. 15, in Reference Example 1, the water content (β-OH value) in the glass does not decrease in the region adjacent to the metal sprayed film, and is also shown in the results of FIG. As in Example 3, the water content (β-OH value) hardly decreased. In Reference Example 1 and Example 3, the generation of bubbles in the glass was not observed. From this, it is considered that the oxygen generated by the decomposition of the water present in the molten glass on the surface of the metal sprayed film was combined with hydrogen again to generate water, and thus bubbles were not generated.
Further, in the cross-sectional photograph of Example 3, there was a glass phase at the interface between the metal sprayed film and the ceramic substrate, and no gap was observed. As described above, since the bubble suppression effect equivalent to that of Reference Example 1 was obtained in Example 3, the glass phase at the interface between the metal spray coating and the ceramic substrate contributed to bubble suppression in the molten glass. I understand that.

ADVANTAGE OF THE INVENTION According to this invention, the ceramic member excellent in the adhesive strength of a ceramic base material and a metal sprayed film can be obtained, This ceramic member is excellent in the corrosion resistance with respect to molten glass, and the ceramic member for the manufacturing apparatus of molten glass Useful as.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-262591 filed on Nov. 25, 2010 are incorporated herein as the disclosure of the present invention. .

DESCRIPTION OF SYMBOLS 1,21 Ceramic base material 2,22 Metal spray film 3 Anchor recessed part 11 Melting tank 12 Depressurization defoaming apparatus 12a Depressurization defoaming tank 12b Rising pipe 12c Downfalling pipe 13 First conduit 14 Second duct 15 Cooling tank 30 Glass G Molten glass

Claims (16)

A method for producing a ceramic member having a temperature of less than 1500 ° C. during use,
On a ceramic substrate made of sintered brick mainly containing electrocast brick or zircon containing 3 to 30% by mass of glass phase,
After forming a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals,
A method for producing a ceramic member, comprising a step of heat-treating at a temperature of 1500 ° C. or higher. The method for producing a ceramic member according to claim 1, wherein the temperature during use is 1400 ° C or lower. The method for producing a ceramic member according to claim 1 or 2, wherein a regular anchor recess is formed on the surface of the ceramic substrate, and the metal sprayed film is formed on the anchor recess. A ceramic member obtained by the production method according to any one of claims 1 to 3,
A ceramic member, wherein a glass phase is filled in a space at an interface between the ceramic base and the metal sprayed film. A ceramic member having a ceramic substrate and a metal sprayed coating provided on the surface thereof, the temperature at the time of use being less than 1500 ° C.,
The metal is at least one metal selected from the group consisting of a platinum group metal and an alloy mainly composed of at least one platinum group metal;
The ceramic substrate is composed of electrocast brick or sintered brick mainly composed of zircon, containing 3 to 30% by mass of a glass phase,
A ceramic member, wherein a part of the glass phase is filled in a space at an interface between the ceramic base and the metal sprayed film. The ceramic member according to claim 5, wherein the temperature during use is 1400 ° C or lower. The regular anchor recesses are formed on the surface of the ceramic substrate, and the metal sprayed film is formed so as to fill the anchor recesses. The ceramic member as described. An apparatus for producing molten glass, wherein the ceramic member according to any one of claims 4 to 7 is used as a member that contacts molten glass having a temperature of less than 1500 ° C. An apparatus for producing molten glass, wherein the ceramic member according to any one of claims 4 to 7 is used as a member that contacts molten glass at 1400 ° C or lower. An electroformed brick comprising 3 to 30% by mass of a glass phase, on which a thermal spray film of at least one metal selected from the group consisting of platinum group metals and alloys containing at least one platinum group metal as a main component is formed. Using a ceramic base material composed of sintered bricks mainly composed of zircon, constituting at least a part of the molten glass manufacturing apparatus in contact with the molten glass of less than 1500 ° C., and at least the molten glass manufacturing apparatus An apparatus for producing molten glass obtained by heat-treating a ceramic substrate at a temperature of 1500 ° C. or higher. At least one of the portions in contact with the molten glass of less than 1500 ° C. of the molten glass manufacturing apparatus using a ceramic base material composed of electrocast brick or sintered brick mainly composed of zircon containing 3 to 30% by mass of the glass phase. A sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys containing as a main component one or more of platinum group metals is formed on the ceramic substrate of the configured part. An apparatus for producing molten glass, which is formed and then heat-treated at a temperature of 1500 ° C. or higher at least on the ceramic substrate on which the metal sprayed film is formed. A method for producing molten glass, comprising producing molten glass using the apparatus for producing molten glass according to any one of claims 8 to 11. A member having a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after molding, and a member that contacts the molten glass of less than 1500 ° C. An apparatus for producing a glass article, wherein the ceramic member according to any one of 4 to 7 is used. A member having a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the molded glass, and a member that contacts the molten glass at 1400 ° C. or lower. An apparatus for producing a glass article, wherein the ceramic member according to any one of 4 to 7 is used. An apparatus for producing a glass article, comprising the apparatus for producing molten glass according to claim 10 or 11, a glass forming apparatus for forming molten glass, and a slow cooling apparatus for gradually cooling the glass after forming. A method for manufacturing a glass article, wherein the glass article is manufactured using the glass article manufacturing apparatus according to any one of claims 13 to 15.

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