KR101768262B1 - Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article - Google Patents

Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article Download PDF

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KR101768262B1
KR101768262B1 KR1020137011162A KR20137011162A KR101768262B1 KR 101768262 B1 KR101768262 B1 KR 101768262B1 KR 1020137011162 A KR1020137011162 A KR 1020137011162A KR 20137011162 A KR20137011162 A KR 20137011162A KR 101768262 B1 KR101768262 B1 KR 101768262B1
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glass
molten glass
metal
ceramic
producing
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KR20130140700A (en
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야스나리 이시카와
가즈오 하마시마
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아사히 가라스 가부시키가이샤
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
    • C03B5/1672—Use of materials therefor
    • C03B5/1675—Platinum group metals
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    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
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    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

A method for producing a ceramic member having a ceramic base material such as an electroformed brick or the like and a metal thermal sprayed film covering the surface of the ceramic base material and a method for producing the ceramic member having an excellent effect of improving the adhesion strength between the ceramic base material and the metal thermal sprayed film.
A method of producing a ceramic member having a temperature at the time of use of less than 1500 ° C, comprising the steps of: forming a ceramic base member (1) comprising a ceramic base (1) composed of an electroformed brick or a zircon as a main component containing 3 to 30 mass% (2) of a metal selected from the group consisting of an alloy containing at least one element selected from the group consisting of platinum group metals and an alloy containing at least one element selected from the group consisting of platinum group metals as a main component, followed by heat treatment at a temperature of 1500 캜 or higher.

Description

TECHNICAL FIELD [0001] The present invention relates to a ceramic member and a manufacturing method thereof, a manufacturing apparatus and a manufacturing method of a molten glass, a manufacturing apparatus of a glass article, and a manufacturing method of a glass article PRODUCING GLASS ARTICLE}

The present invention relates to a manufacturing method of a ceramic member, a ceramic member obtained by the manufacturing method, a manufacturing apparatus for a molten glass including the ceramic member, a manufacturing method of a molten glass using the manufacturing apparatus, And a manufacturing method of a glass article using the manufacturing apparatus.

For example, a glass product such as a glass plate is obtained by preparing a molten glass from a glass raw material and molding the molten glass in a molding apparatus. There has been proposed a method of using a vacuum degassing apparatus for the purpose of removing the bubbles generated in the molten glass before the glass raw material is melted in the melting tank and molded in the molding apparatus in order to improve the quality of the glass product after molding For example, Patent Document 1).

Such a vacuum degassing apparatus is provided with a vacuum degassing apparatus in which the interior of the vacuum degassing apparatus is maintained at a predetermined reduced pressure. When the molten glass passes through the vacuum degassing apparatus, the bubbles contained in the molten glass grow in a relatively short time, The bubbles float up to the surface of the molten glass by the buoyancy force and are ruptured, so that the bubbles are removed from the molten glass.

For example, in the case of soda lime glass, the temperature of the molten glass flowing out of the molten bath is about 1200 to 1600 DEG C. In order to effectively perform the vacuum degassing, the temperature of the molten glass introduced into the vacuum degassing apparatus is preferably 1000 to 1500 DEG C , And the temperature of the molten glass introduced into the vacuum degassing vessel is considered to be about 1000 to 1400 ° C.

In the vacuum degassing apparatus, a ceramic member such as an electroformed brick or the like is used because a member in contact with a molten glass such as a vacuum degassing vessel needs to have excellent heat resistance and corrosion resistance to molten glass.

In order to further suppress the erosion by the molten glass, a method of covering the electroformed brick with a metal film has been proposed. In addition, in Patent Document 2, a recess for an anchor is formed on the surface of an electroformed brick, And a metal spray film is formed so as to fill the concave portion so as to improve the adhesion strength between the electroformed brick and the metal film to suppress the peeling of the metal film.

International Publication No. 2009/125750 pamphlet Japanese Patent Application Laid-Open No. 2008-121073

However, with the method described in Patent Document 2, it can not be said that the adhesion strength between the electroformed brick and the metal film is necessarily sufficient.

According to the knowledge of the present inventors, the effect of improving the adhesion strength to the tensile force in the thickness direction of the metal film is small with the anchor effect by the concave portion.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing a ceramic member having a ceramic base material such as an electroformed brick and a metal thermal sprayed film covering the surface thereof, And an object of the present invention is to provide a method of manufacturing a ceramic member.

The present invention also relates to a ceramic member obtained by such a manufacturing method, an apparatus for manufacturing a molten glass including the ceramic member, a method for producing molten glass using the apparatus, a method for manufacturing a glass article with the ceramic member And a process for producing a glass article using the production apparatus.

As a result of intensive studies, the inventors of the present invention have found that when a thermal sprayed coating of a metal on a ceramic substrate containing a predetermined amount or more of a glass phase is heat-treated under specific conditions, The adhesion strength between the substrate and the metal thermal sprayed coating is remarkably improved. It has also been found that when such a heat treatment is performed, the glass phase is filled in a minute space at the interface between the ceramic base material and the metal coating film. Thus, the present invention has been accomplished.

That is, the method for producing a ceramic member of the present invention is a method for producing a ceramic member having a temperature of less than 1500 ° C at the time of use, comprising a step of forming an electroconductive brick or a sintered brick comprising zircon as a main component A step of forming a thermal sprayed film of at least one kind of metal selected from the group consisting of a platinum group metal and an alloy mainly composed of at least one platinum group metal on a ceramic substrate and then performing a heat treatment at a temperature of 1500 캜 or more . In the method for producing a ceramic member of the present invention, the temperature at the time of use is preferably 1400 DEG C or lower.

It is preferable that a regular anchor recess is formed on the surface of the ceramic base, and a thermal sprayed film of the metal is formed on the recess for the anchor.

The ceramic member of the present invention is a ceramic member obtained by the manufacturing method of the present invention as described above, and is characterized in that a space in the interface between the ceramic base material and the metal is filled with a glass phase.

The ceramic member of the present invention is a ceramic member having a ceramic base material and a thermal sprayed film of a metal formed on the surface thereof and having a temperature of 1,500 ° C or less at the time of use, wherein the metal contains at least one of a platinum group metal and a platinum group metal as a main component And the ceramic base material is composed of an electroformed brick or a sintered brick comprising zircon as a main component containing 3 to 30 mass% of a glass phase, wherein the ceramic base material and the ceramic base material And a part of the glass phase is filled in the space at the interface of the metal thermal sprayed film. In the ceramic member of the present invention, it is preferable that the temperature at the time of use is 1400 占 폚 or less.

It is preferable that a regular anchor recessed portion is formed on the surface of the ceramic base material and a metal thermal sprayed film is formed so as to fill the recessed portion for the anchor.

The present invention provides an apparatus for producing a molten glass in which a ceramic member of the present invention is used in a member which contacts molten glass at a temperature lower than 1500 deg. In the present invention, it is preferable that the ceramic member of the present invention is used in a member that contacts molten glass at 1400 DEG C or less.

The present invention relates to an electroformed brick or an electroformed brick containing 3 to 30 mass% of a glass phase, in which a thermal sprayed film of 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 is formed, Wherein at least a part of a portion of the apparatus for manufacturing a molten glass contacting with the molten glass at a temperature lower than 1500 캜 is constituted by using a ceramics base material composed of a sintered brick mainly composed of zircon, Lt; 0 > C or higher.

The present invention relates to a method for producing a molten glass, which comprises using a ceramic base comprising an electroformed brick or a sintered brick mainly composed of zircon, containing a glass phase at 3 to 30 mass% And forming a thermal sprayed film of at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one of the platinum group metals as a main component, The present invention also provides an apparatus for manufacturing a molten glass, which is obtained by heat-treating a ceramic base material on which at least a metal thermal spraying film is formed at a temperature of 1500 ° C or higher.

The present invention provides a method for producing molten glass for producing molten glass using the apparatus for producing molten glass of the present invention.

The present invention relates to a method for producing a molten glass comprising a means for producing a molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the molten glass after molding, Is used in the production of a glass article. The present invention relates to a method for producing a molten glass comprising a means for producing a molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the molten glass after molding, Is preferably used.

The present invention relates to an electroformed brick or an electroformed brick containing 3 to 30 mass% of a glass phase, in which a thermal sprayed film of 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 is formed, Wherein at least a part of a portion of the apparatus for manufacturing a molten glass contacting with the molten glass at a temperature lower than 1500 캜 is constituted by using a ceramics base material composed of a sintered brick mainly composed of zircon, A glass forming apparatus for forming a molten glass, and an apparatus for producing a glass article having a cooling apparatus for thawing the glass after molding.

The present invention relates to a method for producing a molten glass, which comprises using a ceramic base comprising an electroformed brick or a sintered brick mainly composed of zircon, containing a glass phase at 3 to 30 mass% And forming a thermal sprayed film of at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one of the platinum group metals as a main component, The present invention relates to a manufacturing apparatus for a molten glass which is obtained by heat-treating at least a ceramic base material on which a thermal sprayed film of a metal is formed at a temperature of 1500 ° C or higher, a glass molding apparatus for molding a molten glass, A production apparatus for a glass article is provided.

The present invention provides a method for producing a glass article for producing a glass article using the apparatus for producing a glass article of the present invention.

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

The apparatus for producing a molten glass according to the present invention is excellent in corrosion resistance to molten glass because the surface of the member to be in contact with the molten glass is covered with the metal thermal sprayed film and the metal thermal sprayed film is not easily peeled off, great.

By using the apparatus for producing a molten glass of the present invention, molten glass and a glass article can be stably produced.

1 is a cross-sectional view showing an embodiment of a ceramic member of the present invention.
2 (a) is a plan view, and Fig. 2 (b) is a cross-sectional view taken along line BB in Fig. 2 (a).
3 is a longitudinal sectional view showing an embodiment of an apparatus for producing a molten glass of the present invention.
4 is a block diagram showing an example of a method of manufacturing a glass article of the present invention.
5 is a view for explaining a method of measuring the adhesion strength.
6 is a graph showing the measurement result of the adhesion strength.
FIG. 7 is a cross-sectional photograph of the ceramic member obtained in Example 1, wherein (a) shows a state before heat treatment, (b) shows a state after heat treatment, (a ') shows a glass phase mapped in (a) Is a map of the glass phase in (b).
Fig. 8 is a cross-sectional photograph of the ceramic member obtained in Example 2, wherein (a) shows before heat treatment, (b) after heat treatment, and (b ') shows an enlarged view of a main part of (b).
Fig. 9 is a cross-sectional photograph of the ceramic member obtained in Comparative Example 1, wherein (a) shows before heat treatment, (b) after heat treatment, and (b ') shows an enlarged view of a main part of (b).
10 is a graph showing a thermal history used in Example 3 for melting and solidifying a glass raw material in a container made of a ceramic member.
11 is a graph showing the results of Example 3, wherein (a) is a cross-sectional photograph of a glass solidified in a container made of a ceramic member, and (b) is a graph showing the measurement results of the? -OH value.
12 is a graph showing the results of Comparative Example 2, wherein (a) is a cross-sectional photograph of a glass solidified in a container made of a ceramic member, and (b) is a graph showing the results of measurement of the? -OH value.
Fig. 13 shows the results of Comparative Example 3, wherein (a) is a cross-sectional photograph of a glass solidified in a container made of a ceramic member, and (b) is a graph showing the results of measurement of the? -OH value.
14 is a cross-sectional photograph of a glass solidified in a container made of a ceramic member obtained in Reference Example 1. Fig.
15 is a graph showing the results of measurement of? -OH value in Reference Example 1. Fig.

<Ceramic member>

1 is a cross-sectional view showing an embodiment of a ceramic member of the present invention. Reference numeral 1 denotes a ceramic base, reference numeral 2 denotes a metal coating film, and reference numeral 3 denotes a recess for an anchor.

A ceramic member according to the present invention comprises a ceramic base material 1 and a metal thermal sprayed coating 2 formed on the surface thereof and is provided with a honeycomb structural body 1 in the space between the ceramic base material 1 and the metal thermal sprayed coating 2, (Not shown) is charged.

<Ceramic substrate>

As the ceramic substrate 1, a brick containing 3 to 30 mass% of a glass phase is used. In order to obtain corrosion resistance against molten glass, bricks having high denseness are preferable, and from this viewpoint, electroformed bricks mainly made of zirconia or the like or sintered bricks mainly composed of zircon are used.

When the content of the glass phase is less than 3% by mass, the glass phase is not easily broken out from the ceramic base 1 when the heat treatment to be described later is performed. When the amount exceeds 30% by mass, the amount of the glass phase leaking out is increased, and the problem of swelling of the metal thermal sprayed film tends to occur.

[Electroformed brick]

The electroformed brick is a brick which comprises at least one member selected from the group consisting of zirconia, alumina, alumina silicate, zircon-mullite, silica, and titania as constituent components, and completely dissolves these raw materials in an electric furnace to cast them, It is made of crystal phase and glass phase. In the present invention, among the known electroformed bricks, those having a glass phase content of 3 to 30% by mass can be selected and used.

The content of the glassy phase in the ceramic base material in the present invention is a value obtained by calculating the area ratio of the glassy phase to the sum of the crystalline phase and the glassy phase area based on the cross-sectional photograph and converting it into mass ratio. Specifically, using a reflection electron image (composition image) taken at 50 to 100 times by an electron microscope in a surface layer within 50 mm from the dense surface of the ceramic base covering the metal thermal sprayed film, the glass phase and the crystal phase are binarized .

Specific examples of the electroformed bricks used in the present invention include AZS (Al 2 O 3 -SiO 2 -ZrO 2 ) bricks and high-zirconia bricks having an increased content of zirconia. Of these, AZS bricks are preferable because cracks generated at the time of heating or heat change are not generated well.

The glass phase content of the AZS brick is preferably 10 to 25 mass%, more preferably 15 to 20 mass%. The glass phase content of AZS brick can be adjusted by mixing ratio of raw materials.

The composition of the AZS brick is preferably 40 to 55 mass% of Al 2 O 3 , 10 to 15 mass% of SiO 2 , 30 to 45 mass% of ZrO 2 , and 0.5 to 2.5 mass% of Na 2 O. The content of other components such as various metal oxides and inevitable impurities constituting the glass phase is preferably 2% or less, more preferably 1% or less.

The glass phase content of the high-zirconia quality brick is preferably 2 to 20% by mass, more preferably 4 to 15% by mass. The glass phase content of high zirconia quality bricks can be adjusted by combination.

As the composition of the high-zirconia quality brick, it is preferable that Al 2 O 3 is 0.5 to 20 mass%, SiO 2 is 2 to 10 mass%, and ZrO 2 is 80 to 96 mass%. As other components, for example, various metal oxides and inevitable impurities constituting the glass phase include Na 2 O, more preferably 3% or less and 2% or less.

[Zircon-based sintered brick]

A sintered brick mainly composed of zircon is a sintered brick containing 80 to 96 mass% of zircon, and is substantially composed of a crystalline phase and a glass phase. In the present invention, among the sintered bricks comprising a known zircon as a main component, those having a glass phase content of 3 to 30 mass% can be selected and used.

The content of the glass phase in the sintered brick mainly composed of zircon is preferably 3 to 10% by mass, more preferably 4 to 10% by mass. The content of the glass phase of the sintered brick mainly composed of zircon can be adjusted by the blending ratio of the raw material powder.

The composition of the sintered brick mainly composed of zircon is preferably 30 to 45 mass% of SiO 2 , 50 to 70 mass% of ZrO 2 , and 5 mass% or less of other metal oxide.

[Recess for anchor]

It is preferable that regular recesses 3 for anchors are formed on the surface of the ceramic base material 1. By forming the anchoring recesses 3, the adhesion strength between the ceramic base material 1 and the metal thermal sprayed film 2 is further improved. The adhesion strength to the tensile stress in the direction parallel to the surface of the ceramic base 1 is improved.

2 (a) is a plan view, and FIG. 2 (b) is a cross-sectional view taken along the line B-B in FIG. 2 (a).

In the anchor recess 3 of the present embodiment, a plurality of straight grooves g having a rectangular sectional shape are formed in a lattice pattern. The side surface of each groove g is perpendicular to the surface of the ceramic base 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 a certain depth, but if it is too deep, the strength of the surface layer portion of the ceramic base 1 is lowered and processing is also difficult. For example, the depth d of the groove g is preferably about 50 to 350 占 퐉, and more preferably about 150 to 250 占 퐉.

The degree of dispersion of the stress generated between the metal thermal sprayed film 2 and the ceramic base 1 is changed according to the groove pitch p (the distance between the center lines of the adjacent grooves as intervals between the grooves) p, It is preferable to reduce the groove pitch p in order to reduce the stress applied to one point. Considering the stress durability of the metal thermal sprayed coating 2 and the strength of the ceramic base 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. Also, in terms of maintaining the strength of the surface layer portion of the ceramic base material 1, the groove width w is preferably narrow. However, if the groove width w is narrower than the diameter of the metal particles to be sprayed, the grooves can not be filled with the sprayed particles, so that the groove width w is set to be equal to or larger than the particle diameter of the sprayed particles. For example, the groove width w is preferably 100 占 퐉 or more, and more preferably about 150 占 퐉 or more.

It is necessary to secure the convex portion width x (= the interval between the grooves, the difference between the groove pitch p and the groove width w) in accordance with the stress so that the convex portion between the neighboring grooves g will not break due to the stress. The tensile stress in the direction parallel to the surface of the ceramic substrate 1 applied from the metal thermal sprayed film 2 becomes larger as the thickness m of the metal thermal sprayed film 2 formed on the ceramic substrate 1 becomes larger. In this regard, it is preferable that the width x of the convex portion is about four times or more of the thickness m of the metal thermal sprayed film 2. Also, considering the point at which the groove pitch p is made small, the width x of the convex portion is preferably about 2.5 to 5 times the thickness m of the film.

The stress applied to the side surface of the groove g is such that as the groove is deeper (i.e., the side surface is larger), the stress is distributed over the entire side surface, and the convex portion is not broken well. Therefore, the smaller the ratio (p / d) of the groove pitch p to the depth d of the groove is, the higher the dispersibility of the stress is, and the peeling of the metal thermal sprayed film 2 can be easily suppressed. The p / d value at which the stress is appropriately dispersed is preferably about 3 to 8 on the basis of the above-described preferable groove pitch p and groove depth d.

The anchor recesses are not limited to those shown in Fig. For example, a substantially circular hole may be regularly formed.

In the case of forming intermittent holes by replacing the grooves g shown in Fig. 2, it is preferable to form holes at the intersections of the orthogonal grids (checkerboards). Or arranged at a position of a staggered shape (a staggered layout) so that the hole pitch distance becomes uniform. For example, the distance of the hole pitch 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 mu m, more preferably 300 to 400 mu m. The depth of the hole is preferably about 200 to 600 mu m, more preferably about 300 to 500 mu m.

The recess 3 for the anchor can be formed mechanically by using a grinder equipped with a grinding blade made of, for example, a grinding stone, a diamond blade or the like when the recess 3 for the anchor is in a groove shape. Alternatively, a high energy beam such as a laser beam or a high-pressure water stream may be used. When the recess 3 for the anchor is in the form of a hole, 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 base material 1 is arranged in a plane with high precision beforehand by cutting with a grinder or the like before forming the recess 3 for the anchor, the metal thermal sprayed coating 2 is peeled off due to unexpected unevenness It is preferable from the viewpoint of avoidance.

In the present invention, the recess 3 for the anchor may be either a groove or a hole, but the closed space (the space inside the hole) in which the hole is sealed by the metal thermal spraying film is relatively small, It is possible to improve the adhesion strength to the tensile force in the thickness direction of the metal thermal sprayed film 2 by filling the glass phase at the interface between the ceramic base material 1 and the metal thermal sprayed film 2 Is preferable. On the other hand, the above-mentioned effect is relatively low because a closed space (a space inside the groove) sealed by the metal thermal sprayed film is relatively large and a closed space is formed by a large groove.

<Desert for Metal>

The metal thermal sprayed film 2 is a metal film formed by a spraying method. The spraying method is a method in which metal particles heated at a high temperature are injected onto a substrate, and a coating film is formed by depositing the metal particles. Therefore, unlike a solidified film or the like due to the application of molten metal or the like, the metal thermal sprayed film can have a granular sedimentary structure in cross section.

As the metal, at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one of platinum group metals as a main component is used.

Examples of the platinum group metals 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 Pt-5% Au alloy, Pt-10% Ir alloy and Pt-10% Rh alloy.

&Lt; Manufacturing Method of Ceramic Member &

First, the metal thermal sprayed coating 2 is formed on the ceramic base material 1. When the anchor recess 3 is formed on the surface of the ceramic base 1, the metal thermal sprayed coating 2 is formed so as to cover the recess 3 for the anchor. As the spraying method, known spraying methods such as laser spraying, wire frame spraying, plasma spraying, arc spraying, and oxy-flame spraying can be suitably used.

The particle size of the metal particles to be injected in the spraying method (flying spray particle size) is preferably fine, and may be reduced to about 40 탆, depending on the spraying method, but is usually about 50 to 150 탆.

The metal particles injected by the spraying method are deposited on the surface of the ceramic base material 1 to form the metal thermal sprayed film 2. [ In the case where the anchor recess 3 is formed on the surface of the ceramic base 1, the metal particles injected by the spraying method fill the recess 3 for the anchor and are deposited on the surface, (2).

The thickness m of the metal thermal sprayed coating 2 can be appropriately adjusted by the amount of the solvent. The thickness m of the metal thermal sprayed coating 2 (in the case where the recessed portion exists, the thickness at the portion where the recessed portion is present) is in the range of 100 to 100 mm, since deformation due to tensile stress in the direction parallel to the surface of the ceramic base material 1 becomes larger. Preferably about 400 탆, and more preferably about 200 to 350 탆.

Since the temperature of the metal particles to be injected is generally about 700 to 1500 ° C, the temperature of the ceramic base material at the time of spraying is raised, for example, by preheating (i.e., preheating) in advance to reduce the temperature difference between the metal particles and the ceramic base material It is preferable because adhesion between the metal thermal sprayed film 2 and the ceramic base 1 is improved. In this case, it is preferable that the ceramic base material 1 is heated (pre-heated) and then subjected to spraying and then cooled to room temperature.

The temperature (preheating temperature) of the ceramic base material 1 at the time of spraying is preferably not more than the coagulation temperature of the metal particles to be injected, specifically 200 to 500 ° C, more preferably 300 to 400 ° C. The cooling rate at the time of cooling is preferably as low as possible, preferably at about 10 ° C / minute or less.

Then, in the state that the metal thermal sprayed coating 2 is formed on the ceramic base 1, the heat treatment is performed at a temperature of 1500 DEG C or higher.

By performing such a heat treatment, a glass phase is escaped from the ceramic base material 1 in a minute space at the interface between the ceramic base material 1 and the metal thermal sprayed film 2, and a glass phase is filled in the space. This is considered to be because when the glass substrate is heated to a high temperature of 1500 DEG C or more, the glass phase in the ceramic substrate is easily flowed and the glass phase is pushed out into the minute space due to the difference in thermal expansion between the glass phase and the ceramics phase, .

In the present invention, the state in which the glass phase is filled in the space between the ceramic base material 1 and the metal thermal sprayed film 2 means that a glass phase exists between the ceramic base material 1 and the metal thermal sprayed film 2, Refers to a state in which both of the ceramic base material 1 and the metal thermal sprayed film 2 are in contact with each other. A small amount of space may remain at the interface between the ceramic base material 1 and the metal thermal sprayed film 2. In order to obtain good adhesion strength between the ceramic base material 1 and the metal thermal sprayed film 2, desirable. For example, in the cross-sectional photograph after the heat treatment, it is preferable that the space remaining without the glass phase is 20% by area or less with respect to the total area of the space existing at the interface between the ceramic base material 1 and the metal thermal sprayed film 2 , More preferably 10 percent by area or less, and most preferably 0 percent by area.

If the heat treatment temperature is lower than 1500 deg. C, it is difficult to obtain a state in which the space between the ceramic base material 1 and the metal thermal sprayed film 2 is filled with glass. This is due to the insufficient flow state of the glass phase, so that it diffuses into the space in a short time and is not wettable. Since the ceramic phase and the glass phase react with the lapse of time, even if the heating time is prolonged, .

On the other hand, the upper limit of the heat treatment temperature is required to be lower than the melting point of the metal constituting the thermal sprayed coating 2.

Therefore, it is preferable that the heat treatment temperature is set to be less than the melting point of the thermal sprayed film 2 so that the space at the interface between the ceramic base material 1 and the metal thermal sprayed film 2 is filled with the glass phase at a preferable heat treatment time described later. The preferable heat treatment temperature varies depending on the composition of the ceramic base material 1 and the like, and is preferably, for example, about 1,500 to 1,700 ° C, more preferably about 1,500 to 1,600 ° C. Since the fluidity of the glass phase is high when the heat treatment temperature is within this range, the reaction effect of the ceramic phase and the glass phase on the effect of filling the space of the interface between the ceramic base material 1 and the metal thermal sprayed film 2 into the glass phase is low.

If the heat treatment time is too short, a lot of space remains at the interface between the ceramic base material 1 and the metal thermal sprayed film 2. On the other hand, when the heat treatment time becomes longer, the glass phase reacts with the glass phase with the lapse of time, so that the phenomenon that the glass phase is pushed out into the space between the ceramic base 1 and the metal thermal sprayed film 2 does not proceed well .

Therefore, it is preferable to set the heat treatment time such that these problems do not occur. For example, about 1 to 100 hours is preferable, and 10 to 50 hours is more preferable.

According to the manufacturing method of the present invention, the ceramic member of the present invention in which the glass phase derived from the ceramic base material is filled in the space between the interface between the ceramic base member 1 and the metal thermal sprayed film 2 is obtained.

&Lt; Use of Ceramic Member &

The ceramic member of the present invention is a member whose temperature at the time of use is lower than 1500 占 폚. That is, it is used in a region where the temperature at the time of use is not assumed to be 1500 ° C or higher.

A member having a use temperature of 1500 deg. C or higher may have the same effect as that of the present invention without heat treatment at 1500 deg. C or higher before use, and the necessity of applying the present invention to such members is low.

In this respect, the ceramic member of the present invention is preferably a member having a temperature of 1450 DEG C or less at the time of use, and more preferably a member having a temperature of 1400 DEG C or less.

The ceramic member of the present invention is excellent in corrosion resistance against molten glass because the metal thermal sprayed film 2 is formed on the ceramic base 1. Therefore, the ceramic member of the present invention is preferably used as a member which is in contact with molten glass of less than 1500 DEG C in an apparatus used for producing molten glass. The ceramic member of the present invention is preferably used as a member which is in contact with molten glass at 1450 DEG C or lower in a device used for producing molten glass and is preferably a member which contacts molten glass at 1400 DEG C or lower Is used.

Specifically, it is preferably used as a member which is in contact with molten glass of less than 1,500 占 폚 in the flow path from the molten bath to the point where it is sent to the molding apparatus through the vacuum degassing apparatus. The molten glass flowing out of the molten bath is more preferably used as a member which contacts the molten glass at 1450 DEG C or lower in the flow path from the molten glass to the molding apparatus through the vacuum degassing apparatus, Of the molten glass. For example, the member constituting the inner wall of the vacuum degassing apparatus, the member constituting the inner wall of the melting uprising pipe formed upstream of the vacuum degassing apparatus, or the member constituting the inner wall of the downfalling pipe formed downstream of the vacuum degassing apparatus .

In the ceramic member of the present invention, since the metal thermal sprayed film 2 is formed on the surface of the ceramic base 1, erosion of the ceramic base 1 is suppressed even in contact with the molten glass. Further, as shown in the examples described later, since the adhesion strength between the ceramic base material 1 and the metal thermal sprayed film 2 is excellent, the metal thermal sprayed film 2 is not peeled off well and the durability is excellent.

Further, when the ceramic member of the present invention is used for a member in contact with the molten glass, since the glass phase is filled in the space between the ceramic substrate and the metal thermal sprayed film, the effect of suppressing the generation of bubbles in the molten glass is obtained Loses.

That is, when moisture present in the molten glass is decomposed into oxygen and hydrogen on the surface of the metal thermal sprayed film by the catalytic action of the platinum group metal, hydrogen permeates through the metal thermal spray film and oxygen remains on the surface thereof . At this time, when hydrogen is left in the metal thermal sprayed film, oxygen is bubbled because it forms water by binding again with oxygen on the surface of the metal thermal sprayed film.

However, in the conventional ceramic member, since there is a minute space at the interface between the metal thermal sprayed film and the underlying ceramic substrate, hydrogen permeating through the metal thermal sprayed film moves through the space, and hydrogen does not stay in the metal thermal sprayed film . For this reason, oxygen on the surface of the metal desert can not be bonded again with hydrogen, and becomes bubbles.

In the ceramic member of the present invention, since the glass phase is filled in the space at the interface between the metal thermal sprayed coating and the ceramic substrate, hydrogen can remain in the metal thermal sprayed coating and can combine with oxygen to produce water. Therefore, oxygen can be prevented from becoming bubbles.

&Lt; Manufacturing apparatus of molten glass &

In the apparatus for producing a molten glass of the present invention, the ceramic member of the present invention is used in a member which is in contact with molten glass of less than 1500 ° C. The apparatus for producing a molten glass of the present invention preferably uses the ceramic member of the present invention in a member which is in contact with molten glass at 1450 DEG C or lower. In the member which is in contact with the molten glass at 1400 DEG C or lower, It is more preferable that the member is used.

The apparatus for producing a molten glass according to the present invention is characterized in that a glass phase in which a thermal sprayed film of at least one kind of metal selected from the group consisting of a platinum group metal and an alloy mainly composed of at least one kind of platinum group metal is formed, %, Preferably 1450 占 폚 or lower, and more preferably 1400 占 폚 or lower of a production apparatus for a molten glass, using a ceramic base material composed of an electroformed brick or a sintered brick containing zircon as a main component And at least the ceramic base material of the apparatus for manufacturing a molten glass is heat-treated at a temperature of 1500 ° C or higher.

Further, the apparatus for producing a molten glass of the present invention is a device for producing a molten glass, which comprises a ceramic base comprising an electroformed brick or a sintered brick containing zircon as a main component and containing a glass phase in an amount of 3 to 30 mass% Preferably at least 1450 DEG C, more preferably at most 1400 DEG C, and at least a part of a portion of the ceramic base material constituting the part is made of a platinum group metal and at least one platinum group metal as a main component And at least one metal selected from the group consisting of alloys, and then heat-treating the ceramic base having at least the above-described metal of the above-mentioned metal of the apparatus for manufacturing a molten glass at a temperature of 1500 ° C or higher.

3 is a longitudinal sectional view showing an embodiment of an apparatus for producing a molten glass of the present invention. The apparatus of the present embodiment is characterized in that the melting vessel 11 for allowing the glass raw material to melt and homogenize and purify the molten glass is set to a pressure lower than the atmospheric pressure and the bubbles in the molten glass fed from the melting vessel 11 are lifted The first conduit 13 connecting the melting vessel 11 and the vacuum degassing apparatus 12 and the molten glass flowing out from the vacuum degassing apparatus 12 are introduced into the cooling bath 15, And a second conduit (14) for sending the liquid to the molding means of the next process via the second conduit (14). In the figure, G denotes a molten glass.

The first conduit 13 is provided with a cooling means 13a and an agitating means 13b and the molten glass flowing out of the melting vessel 11 is heated to a temperature of 1000 占 폚 or more and less than 1500 占 폚 After cooled, it is introduced into the vacuum degassing apparatus 12.

The vacuum degassing apparatus 12 is provided with a vacuum degassing vessel 12a and the upstream side of the vacuum degassing vessel 12a is in communication with the first conduit 13 via an uprising pipe 12b, And the downstream side of the second conduit 12a communicates with the second conduit 14 via the downfalling pipe 12c. The inside of the decompression deaerator 12a, the uprising pipe 12b and the downfalling pipe 12c is maintained in a reduced-pressure environment and the molten glass in the first conduit 13 is discharged through the uprising pipe 12b And is sucked up into the deodorization tank 12a. Further, after the second conduit 14, it is connected to the molding means via the cooling bath 15.

The apparatus constituting the inner wall of the decompression deaerator 12a, the uprising pipe 12b, the downfalling pipe 12c and the cooling bath 15 of the vacuum degassing apparatus 12 according to the present embodiment, A ceramic member, or a ceramics base material on which a thermal sprayed coating of metal is formed. That is, the inner walls of the vacuum degassing apparatus 12a, the uprising pipe 12b, the downfalling pipe 12c, and the cooling bath 15 are made of a ceramic base whose inner surface is covered with a metal thermal sprayed film, A glass phase is filled in a minute space at the interface.

Such a vacuum degassing apparatus 12 and the cooling bath 15 are formed by first coating the inner walls of the vacuum degassing vessel 12a, the uprising pipe 12b, the downfalling pipe 12c and the cooling bath 15 with a metal thermal spraying film And then assembled into a series of shapes from the vacuum degassing apparatus 12 to the cooling tank 15 and thereafter the inside of the series of structures including the vacuum degassing apparatus 12 and the cooling tank 15 Treated at a predetermined temperature of 1500 ° C or higher, and then cooled to a temperature not higher than the use temperature. The inner wall of the vacuum degassing vessel 12a, the uprising pipe 12b, the downfalling pipe 12c and the cooling bath 15 is formed by the ceramic member of the present invention, 15). &Lt; / RTI &gt; The inner wall of the decompression / deaeration tank 12a, the uprising pipe 12b, the downfalling pipe 12c and the cooling bath 15 is formed of a ceramic base material and a metal sprayed film is formed on the surface of the base material in contact with the molten glass And then the ceramic base material having the above-mentioned metal thermal sprayed film formed thereon may be heat-treated at a temperature of 1500 ° C or higher.

After the apparatus is manufactured in this way, it is used at a service temperature of less than 1500 ° C. Further, after the apparatus is manufactured in this manner, it is preferably used at a use temperature of 1450 DEG C or lower, and more preferably at a use temperature of 1400 DEG C or lower.

Also, the assembling steps of the parts and the parts using the ceramic member of the present invention are not limited to the above examples. For example, since the temperature of the molten glass in the cooling bath 15 is lower than that in the upstream portion, only the portion where the ceramic member of the present invention is used is the vacuum degassing apparatus 12, . Alternatively, only the vacuum degassing apparatus 12a may be used in the vacuum degassing apparatus 12 where the ceramic member of the present invention is used, only the uprising pipe 12b and the downfalling pipe 12c or only the downfalling pipe 12c . The ceramic member of the present invention may be used for the inner wall of the first conduit 13 and the second conduit 14. [

&Lt; Process for producing molten glass >

The method for producing a molten glass of the present invention is a method for producing a molten glass by using a production apparatus in which the ceramic member of the present invention is used for a member which contacts molten glass of less than 1500 ° C. The method for producing a molten glass of the present invention is a method for producing a molten glass in which a production apparatus using the ceramic member of the present invention is preferably used for a member contacting molten glass at 1450 DEG C or lower. The method for producing a molten glass of the present invention is a method for producing a molten glass in which a manufacturing apparatus in which the ceramic member of the present invention is used is preferably used for a member contacting molten glass at 1400 ° C or lower.

For example, in the method for producing molten glass using the apparatus for producing molten glass shown in FIG. 3, the molten glass flowing out of the molten bath 11 is heated at a temperature of 1000 ° C or higher, 1500 ° C or higher , And then introduced into the vacuum degassing apparatus (12). It is preferable that the molten glass flowing out of the molten bath 11 is introduced into the vacuum degassing apparatus 12 after the molten glass is cooled in the first conduit 13 at a temperature of not lower than 1000 캜 and not higher than 1450 캜. It is more preferable that the molten glass flowing out of the molten bath 11 is introduced into the vacuum degassing apparatus 12 after the molten glass has been cooled in the first conduit 13 at a temperature of not lower than 1000 占 폚 and not higher than 1400 占 폚.

The inner wall of the decompression deaerator 12a, the uprising pipe 12b, the downfalling pipe 12c and the cooling bath 15 of the vacuum degassing apparatus 12 is in contact with the molten glass at 1000 deg. Since the surface (i.e., the inner surface) of the ceramic base material constituting the inner wall is covered with the metal thermal sprayed coating, the corrosion resistance to the molten glass is excellent. In addition, since the adhesion strength between the ceramic base material and the metal thermal sprayed film is excellent, the thermal sprayed coating is not easily peeled off, and the durability is excellent.

Further, since the interface between the metal thermal sprayed coating and the underlying ceramic substrate is filled with the glass phase, even if the moisture in the glass is decomposed into oxygen and hydrogen on the surface of the metal thermal sprayed coating, the hydrogen can stay in the metal thermal sprayed coating. Therefore, as described above, the hydrogen can be recombined with oxygen generated by the decomposition of water to produce water, so that generation of bubbles in the molten glass due to such oxygen can be suppressed.

&Lt; Device and method for manufacturing glass articles >

An apparatus for producing a glass article according to the present invention comprises means for producing a molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the glass after molding, , The ceramic member of the present invention is used. The apparatus for producing a glass article of the present invention comprises means for producing a molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the glass after molding, It is preferable that the ceramic member of the present invention is used in the member. Further, the apparatus for producing a glass article of the present invention comprises means for producing a molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the glass after molding, It is more preferable that the ceramic member of the present invention is used for the member.

It is preferable that the means for producing the molten glass is an apparatus for producing the molten glass of the present invention. For example, a configuration may be employed in which a forming means for forming a molten glass in the downstream of the molten glass flow direction of the molten glass producing apparatus shown in Fig. 3, and a threating means for thawing the molten glass downstream of the molten glass. A processing means for further cutting or polishing may be formed downstream of the quenching means. Although not shown, various means such as a known float method, a down-draw method, and a fusion method can be used as the forming means. The quenching means and the processing means can also use known techniques.

4 is a flowchart showing an example of a method of manufacturing a glass article using the apparatus for manufacturing a glass article according to the present invention.

When manufacturing the glass article according to the method shown in Fig. 4, preferably, the molten glass G is obtained by the glass melting step S1 using the molten glass producing apparatus of Fig. 3, and the molten glass G is sent to the molding means, , Followed by cooling in the quenching step S3. Thereafter, if necessary, a post-process such as cutting or polishing is carried out in the post-processing step S4 to obtain a glass article G5.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]

In the present example, AZS (Al 2 O 3 -SiO 2 -ZrO 2 ) bricks are used as the ceramic base, holes are formed on the surfaces of the bricks with regular arrangement, To obtain a coated substrate, and the coated substrate was heat-treated to produce a ceramic member. Hereinafter, a substrate having a metal coating film formed on the surface of the ceramic substrate is also referred to as a metal film coating substrate.

The composition of the used ceramic base material was measured by fluorescent X-ray analysis and the results are shown in Table 1. Table 1 also shows the content of the glass phase obtained on the basis of the cross-sectional photograph of the metal film-clad substrate before the heat treatment (the same applies to Example 2 and Comparative Example 1 hereinafter). The glass phase content is calculated in the following manner. Using a scanning electron microscope, a reflected electron image (composition image) of a 50 times magnification electron microscope is taken from the cross section of the metal film-coated substrate before the heat treatment to the position of 20 mm from the substrate surface toward the substrate interior. With respect to the obtained image, the sum of the crystal phase and the glass phase area and the glass phase area ratio are obtained, and the value obtained by converting the area ratio into the mass ratio is defined as the glass phase content (unit: mass%).

First, AZS bricks were cut into brick pieces of 50 mm in length × 50 mm in length × 10 mm in height, and recesses for anchors were formed on one surface of 50 mm × 50 mm of the brick pieces by using a fiber laser. The recesses for the anchors were approximately circumferential holes, the hole diameter was 300 mu m, the hole depth was 400 mu m, and the hole pitch was 1 mm.

Then, the brick pieces were heated up to 300 DEG C in an atmospheric environment, and spraying of platinum was initiated on the surface having the holes formed by the wire-frame spraying method (flying spray diameter: about 100 mu m, temperature: about 100 DEG C). The spraying was continued until the thickness of the platinum film became 300 m, and the brick pieces were then cooled to room temperature to obtain a metal film-coated substrate.

Two metal film-coated substrates were produced under the same conditions, and one of the metal film-coated substrates was subjected to a heat treatment at 1500 ° C for 100 hours by an electric furnace under the atmosphere to obtain a ceramic member.

As a control, the other metal film-coated substrate was not subjected to the heat treatment, but was directly treated as an untreated sample.

[Example 2]

A metallic film-coated base material was obtained in the same manner as in Example 1 except that the ceramic base material was changed to a high-zirconia brick, and the same heat treatment as in Example 1 was performed on the metal film-coated base material to produce a ceramic member. As a control, untreated samples without heat treatment were prepared in the same manner as in Example 1.

[Comparative Example 1]

A metal film-coated substrate was obtained in the same manner as in Example 1 except that the ceramic base was changed to?? Alumina brick, and the same heat treatment as in Example 1 was performed on the metal film-coated base material to prepare a ceramic member. As a control, untreated samples without heat treatment were prepared in the same manner as in Example 1.

Figure 112013038112003-pct00001

[Assessment Methods]

(Adhesion strength)

Three sheet pieces each having a size of 14 mm x 14 mm x 10 mm in height were cut out from each of the ceramic member and the untreated sample obtained in the respective examples. On both sides of 14 mm x 14 mm as shown in Fig. 5, A thermosetting epoxy adhesive 23 was used, and tensile jigs 24 and 25 were bonded to produce a test piece. In the figure, reference numeral 21 denotes a ceramic base, and reference numeral 22 denotes a metal thermal sprayed film.

The tensile jigs 24 and 25 were pulled in the direction away from each other at a speed of 0.5 mm / min using a tensile strength tester (product name: AUTOCOM / AC · 50KN-C manufactured by TSE) And the load when the metal thermal sprayed film 22 was peeled off was measured. The adhesion strength (P / S, unit: MPa) was determined from the value of the load (P) at the time of peeling and the area (S) of the plate-like piece (ceramic member). The results are 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 the same. On the other hand, it was confirmed that the adhesion strength of the ceramic member in Examples 1 and 2 was three times or more of the adhesion strength of the untreated sample, and the adhesion strength was remarkably improved by the heat treatment.

(Cross-sectional organization)

Sectional photographs of the metal film-coated substrate before the heat treatment and the ceramic member after the heat treatment were taken at the time of manufacturing the ceramic member in each example. Fig. 7 is a photograph obtained in Example 1, Fig. 8 is Example 2, and Fig. 9 is Comparative Example 1. Fig. Reference numeral 21 denotes a ceramic base, and reference numeral 22 denotes a metal thermal sprayed film.

(A ') is a graph showing a glass phase mapped in the photograph of (a), and FIG. 7 (b' In the photograph, the glass phase is mapped.

8A and 9B are cross-sectional photographs before heat treatment, after heat treatment, and FIG. 8B is an enlarged view of main parts (indicated by B in the figure) of the photograph of FIG. 8B and FIG.

As shown in Figs. 7 to 9 (a), in the metal film-coated base material before the heat treatment, a minute gap (space) exists at the interface between the ceramic base material 21 and the metal thermal sprayed film 22. 7 and 8 (b), in the ceramic member after the heat treatment in Examples 1 and 2, there is no gap in the interface between the ceramic base material 21 and the metal thermal sprayed film 22, There is a glass phase along the interface as shown in (b ') of FIG.

In contrast, as shown in Fig. 9 (b), in the ceramic member after the heat treatment in Comparative Example 1, there is a gap between the interface between the ceramic base 21 and the metal thermal sprayed film 22, As a result, it is not confirmed that the glass phase oozes out at the interface.

[Example 3]

In this example, as described below, a glass melting vessel made of a ceramic member was manufactured as a molten glass production apparatus, and the glass raw material was melted at 1400 캜 in the vessel and then cooled. Then, the moisture content and the presence of bubbles in the glass in the vicinity of the inner wall of the container were examined by an evaluation method to be described later.

First, a ceramic base having an anchor recess was formed on one surface of a high zirconia brick having the same material as that used in Example 2, and an outer diameter of 75 mm, an outer wall height of 55 mm, 50 mm, and a depth of the inner wall of 40 mm. And the surface on which the concave portion for the anchor was formed became the inner surface.

Subsequently, this container was heated to 300 캜 in an atmospheric environment, and a metal sprayed film having a thickness of 300 탆 was formed on the inner surface in the same manner as in Example 1 to obtain a container made of a metal film coated substrate.

Subsequently, the container was placed in an electric furnace under the atmosphere, and subjected to heat treatment at 1600 占 폚 for 5 hours to obtain a container made of a ceramic member.

In carrying out Example 3, the obtained container was placed in a heating furnace and the thermal history shown in Fig. 10 was applied under atmospheric pressure. The vertical axis in Fig. 10 represents the atmospheric temperature in the heating furnace. First, over a period of 4 hours and 40 minutes, the temperature was raised from room temperature to 1400 ° C, and when the temperature reached 1400 ° C, a glass raw material of borosilicate glass was charged into a container, and the glass raw material was melted by heating at 1400 ° C for 1 hour. Thereafter, the mixture was quenched to 720 占 폚, maintained at 720 占 폚 for 1 hour, lowered to 600 占 폚 over 2 hours, and further cooled to room temperature over 3 hours to obtain a solidified glass in the container.

[Comparative Example 2]

In Example 3, a glass solidified in a container was obtained in the same manner as in Example 3, except that the heat treatment was not performed on the container made of the metal film coated substrate.

[Comparative Example 3]

A container made of a metal film-clad substrate was obtained in the same manner as in Example 3 except that the material of the ceramic base material in Example 3 was changed from the high-zirconia brick to the same?? Alumina brick used in Comparative Example 1 , The container was subjected to the same heat treatment as in Example 3 to prepare a container made of a ceramic member.

Using this container, a solidified glass was obtained in the same manner as in Example 3.

[Assessment Methods]

(Water content and presence of bubbles)

The? -OH value of the glass as an indicator of the water content in the glass was measured. The β-OH value (unit: mm -1 ) of the glass can be obtained by measuring the absorbance of the glass sample with respect to light having a wavelength of 2.75 to 2.95 μm and dividing the maximum value β max by the thickness (mm) of the glass sample .

Samples of longitudinal sections of 1 mm in thickness were cut out by cutting the entire container at the cut surface along the height direction of the glass solidified in the containers obtained in the above examples. The value of? -OH was measured in the above-described manner for the center of the obtained longitudinal section sample in the height direction of the container and the area near the interface between the inner wall of the container and the solidified glass. A photograph of the area was also 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. In each drawing, (a) is a cross-sectional photograph, and the reference position of the interface is indicated by an arrow. In the drawing, reference numeral 21 denotes a ceramic base, 22 denotes a metal thermal sprayed film, and 30 denotes a glass. The horizontal axis represents the distance (unit: 占 퐉) in the lateral direction of the cross-sectional photograph of (a), and the vertical axis represents the? -OH value : Mm -1 ). The position corresponding to the reference position of the interface is indicated by an arrow.

[Referential Example 1]

In the container made of the metal film-clad substrate of each example of the above-mentioned Example 3, Comparative Examples 2 and 3, the lower layer of the metal thermal sprayed film is made of the ceramic base. In this example, The moisture content in the case where it was made was measured.

That is, in Example 3, when a container made of a ceramic member was placed in a heating furnace, and a glass raw material of borosilicate glass was charged into the container at a point of time when it reached 1400 ° C, And the remainder of the glass raw material was placed in a separately prepared crucible made of platinum rhodium, and the crucible was placed in the vessel. Other than that, the same procedure as in Example 3 was carried out to obtain a solidified glass in a container. 14 is a photograph showing a longitudinal section thereof. 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 Is obtained.

The container and the entire crucible were cut at the cut surface along the height direction of the glass solidified in the container obtained in the present example to cut off a longitudinal section sample having a thickness of 1 mm. The value of? -OH was measured by the above-described method for the central portion of the obtained longitudinal section sample in the depth direction of the crucible, and the area near the interface between the inner and outer surfaces of the crucible and the glass (indicated by reference numeral 33 in FIG.

The results are shown in Fig. The abscissa represents the distance in the lateral direction of the cross-sectional photograph of Fig. 14, and the ordinate represents the beta -OH value. In Fig. 15, the position corresponding to the sidewall of the crucible is indicated by an arrow.

In addition, bubble formation in the glass was not confirmed in the longitudinal section samples used for the measurement of the? -OH value.

As shown in Fig. 12 (b) and Fig. 13 (b), in Comparative Examples 2 and 3, the water content (? -OH value) in the glass is lowered in the region adjacent to the metal thermal sprayed film. As shown in Figs. 12 (a) and 13 (a), the occurrence of bubbles in the glass in the region adjacent to the metal thermal sprayed film was confirmed. At this point, 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 thermal sprayed film does not generate water again, but becomes bubbles.

In Comparative Example 2, a high-zirconia brick containing 6% by mass of a glass phase was used as the ceramic base material. However, since the heat treatment was not carried out at 1500 ° C before use, even if heated at 1400 ° C for 1 hour in use, Minute gaps were observed at the interface between the metal thermal sprayed coating and the ceramic substrate.

In Comparative Example 3, since the ceramic base contained only 0.8% by mass of the glass phase, a minute gap was observed at the interface between the metal thermal sprayed coating and the ceramic base material in the cross-sectional photograph, even if the heat treatment was performed at 1500 ° C before use.

In these points, in Comparative Examples 2 and 3, hydrogen generated as a result of decomposition of the water present in the molten glass on the surface of the metal thermal sprayed film permeated through the metal thermal sprayed film, and interposed between the metal thermal sprayed film and the ceramic base And it is thought that it did not stay in the metal dragon desert.

On the other hand, as shown in the results of FIG. 15, in Reference Example 1, the moisture content (? -OH value) in the glass did not decrease in the region adjacent to the metal thermal sprayed film. In Example 3, the moisture content (? -OH value) was not lowered. In Reference Examples 1 and 3, generation of bubbles in the glass was not observed. At this point, it can be considered that bubbles are not generated because oxygen generated by decomposition of water present in the molten glass on the surface of the metal thermal sprayed film again combines with hydrogen to generate water.

In the cross-sectional photograph of Example 3, a glass phase was present at the interface between the metal thermal sprayed coating and the ceramic substrate, and no gap was observed. As described above, it can be seen that the glass phase at the interface between the metal thermal sprayed coating and the ceramic base contributes to the suppression of bubbles in the molten glass since the bubble suppression effect equivalent to that of Reference Example 1 was obtained in Example 3.

Industrial availability

According to the present invention, a ceramic member having excellent adhesion strength between the ceramic base material and the metal thermal sprayed film can be obtained. Such a ceramic member is excellent in corrosion resistance to molten glass and is useful as a ceramic member for a molten glass production apparatus.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2010-262591 filed on November 25, 2010 are hereby incorporated herein by reference as if fully set forth herein.

1, 21: Ceramic substrate
2, 22: Desert for metals
3: recess for anchor
11:
12: Vacuum-defoaming device
12a:
12b: riser
12c: Downward pipe
13: First conduit
14: second conduit
15: Cooling tank
30: Glass
G: molten glass

Claims (16)

A method of producing a ceramic member having a temperature at use of less than 1500 ° C,
On a ceramic base material comprising an electroformed brick or a sintered brick mainly composed of zircon, containing 3 to 30 mass% of a glass phase,
After forming a thermal sprayed film of at least one metal selected from the group consisting of platinum group metals, and alloys containing at least one of a platinum group metal as a main component,
Treating the ceramic substrate at a temperature of 1500 DEG C or higher to fill a space of the interface between the ceramic substrate and the metal with a part of the glass phase. The method according to claim 1,
Wherein the temperature at the time of use is 1400 DEG C or lower. 3. The method according to claim 1 or 2,
Wherein a regular anchor recess is formed on a surface of the ceramic base, and a thermal sprayed film of the metal is formed on the recess for the anchor. delete A ceramic member having a ceramic base material and a metal sprayed film formed on the surface thereof and having a temperature at the time of use lower than 1500 占 폚,
Wherein the metal is at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one of a platinum group metal as a main component,
Wherein the ceramic base comprises an electroformed brick or a sintered brick containing zircon as a main component containing 3 to 30 mass% of a glass phase,
Wherein a part of the glass phase is filled in a space at an interface between the ceramic base material and the metal thermal sprayed film. 6. The method of claim 5,
Wherein a ceramic anisle recess is formed on a surface of the ceramic base, and a metal thermal sprayed film is formed to embed the anchor recess. The method according to claim 5 or 6,
Wherein the temperature at the time of use is 1400 DEG C or lower. Wherein the ceramic member according to claim 5 or 6 is used for a member which is in contact with the molten glass at a temperature lower than 1500 占 폚. Wherein the ceramic member according to claim 7 is used for a member which contacts molten glass at 1400 DEG C or lower. An electroformed brick or zircon as a main component containing 3 to 30 mass% of a glass phase, in which a sprayed film of at least one kind of metal selected from the group consisting of a platinum group metal and an alloy mainly composed of at least one kind of platinum group metal is formed At least a part of a portion of the apparatus for manufacturing a molten glass which is in contact with the molten glass at a temperature lower than 1500 ° C is used and at least the ceramic substrate of the apparatus for manufacturing a molten glass is heated at a temperature of 1500 ° C or higher And a part of the glass phase is filled in a space at an interface between the ceramic base material and the metal thermal sprayed film by heat treatment. delete A method for producing a molten glass for producing a molten glass by using the apparatus for producing molten glass according to claim 8. A method for producing a molten glass, comprising the steps of: preparing a molten glass; shaping means for shaping the obtained molten glass; and a thoriating means for thawing the formed glass, Wherein the ceramic member is used. A ceramic member according to claim 7 is used in a member having a means for producing molten glass, a molding means for molding the obtained molten glass, and a threating means for thawing the molten glass after the molding and contacting the molten glass at 1400 DEG C or lower Wherein the glass article is a glass article. An apparatus for producing a glass article having the apparatus for producing a molten glass according to claim 10, a glass molding apparatus for molding a molten glass, and a cooling apparatus for thawing the glass after molding. A method for manufacturing a glass article, wherein the glass article is manufactured using the apparatus for manufacturing a glass article according to claim 13.
KR1020137011162A 2010-11-25 2011-11-18 Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article KR101768262B1 (en)

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