TW201228995A - 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 DEG C, the method for producing a ceramic member having a step for performing a heat treatment at a temperature of 1500 DEG 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

201228995 VI. Description of the Invention: [The invention relates to a method for manufacturing a ceramic member, a ceramic member produced by the method, and a molten glass having the ceramic member. A manufacturing apparatus, a manufacturing method of the glazing glass using the manufacturing apparatus, a manufacturing apparatus of the glass article including the ceramic member, and a manufacturing method of the glass article using the manufacturing apparatus.

L·ittr U BACKGROUND OF THE INVENTION For example, a glass product such as a glass plate is obtained by molding a molten glass from a glass raw material and then molding the molten glass by a molding apparatus. In order to improve the quality of the formed glass product, there is a proposal to use a vacuum defoaming device for the purpose of removing the bubbles generated in the molten glass after melting the glass raw material by the melting tank and before forming the forming device. (for example, Patent Document 1). The vacuum defoaming device is provided with a decompression defoaming tank which is internally maintained at a predetermined degree of decompression, and when the molten glass passes through the decompression defoaming tank, the bubbles contained in the molten glass are made shorter. The time is grown, and the bubble A which is greatly grown is floated on the surface of the molten glass by buoyancy, and bubbles are removed from the molten glass. The temperature of the molten glass flowing out of the smelting tank is as high as 1200~1600 °C, and the temperature of the molten glass introduced into the vacuum defoaming device is 1 为了 in order to effectively decompress and defoam. 〇~15〇 (about Tc, and introduced to minus & 3 201228995 The temperature of the molten glass of the defoaming tank is about 1 〇〇〇~1400 °c. In the vacuum defoaming device, the decompression defoaming tank The member that is in contact with the molten glass crucible must have good heat resistance and corrosion resistance to the molten glass, so ceramic members such as electroforming bricks are used. In order to further suppress the remnant caused by the molten glass, it is proposed to In the method of coating a cast iron with a metal film, in the following Patent Document 2, there is described a method in which a recess for fixing is formed on the surface of an electroformed brick and a metal sprayed film is formed by embedding a recessed portion. The adhesion strength between the electroforming brick and the metal film is increased, and the peeling of the metal film is suppressed. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: International Publication No. 2009/125750 Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-121073 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, in the method described in Patent Document 2, the adhesion strength between the electroformed brick and the metal film is not sufficient. According to the findings of the present inventors, in terms of the fixing effect of the concave portion, The effect of improving the adhesion strength of the tensile force in the thickness direction of the metal film is too large. J. The present invention is based on the above-mentioned situation, and is a method of manufacturing a ceramic substrate such as an electrocast brick and covering the surface thereof. A method of manufacturing a ceramic member of a metal spray film, and an object of the invention is to provide a method for producing a ceramic member having excellent adhesion strength between the ceramic base material and the metal nozzle film. Further, it is an object of the present invention to provide a method for producing a ceramic member. Ceramic member produced by the production method, apparatus for producing molten glass including the ceramic member, method for producing molten glass using the same, apparatus for producing glass article including the ceramic member, and glass using the same Method for producing an article. Means for solving the problem The inventors of the present invention have repeatedly studied intensively and found that: After the metal sprayed film is formed on the ceramic substrate containing a predetermined amount or more of the glass phase, and then heat-treated under specific conditions, the ceramic substrate and the metal, which are particularly opposed to the tensile force in the thickness direction of the metal sprayed film, can be greatly improved. The adhesion strength of the sprayed film is also found: as long as the heat treatment is performed, the minute space at the interface between the ceramic substrate and the metal sprayed film becomes a state in which the glass phase is filled, and the present invention is completed. The method is used for manufacturing a ceramic component having a temperature lower than 1500 ° C in use, and is characterized in that it has the following steps: sintering from a glass phase containing 3 to 30% by mass and electroforming brick or zircon as a main component a step of heat-treating at a temperature of 1500 ° C or higher after forming a metal sprayed film on a ceramic substrate made of bricks, and the metal sprayed film is selected from a platinum group metal and one or more platinum group metals A spray film of at least one metal selected from the group consisting of alloys of the main component. In the method for producing a ceramic member of the present invention, the temperature at the time of use is preferably 1400 ° C or lower. A regular fixing recess is formed on the surface of the ceramic base material, and the metal spray film is preferably formed on the fixing recess. 5 201228995 The ceramic member of the present invention is obtained by the above-described production method of the present invention, characterized in that the interface space between the ceramic substrate and the metal spray film is filled with a glass phase. The ceramic member of the present invention has a ceramic base material and a metal sprayed film provided on the surface thereof, and has a low temperature M150 (rc) in use, wherein the metal is selected from the group consisting of platinum group metals and a metal of at least one of the group consisting of an alloy containing a platinum group metal as a main component; the ceramic substrate is sintered by a glass containing 3 to 30 mass ❶/〇 of a glass phase and containing electroforming brick or zircon as a main component The brick is formed; and the interface space between the ceramic material and the metal tilting film is filled with the glass phase. The temperature of the ceramic component of the present invention is preferably used in the following. It is preferable that the surface of the surface is formed with a regular S1 recessed portion, and the metal sprayed film is finely formed by the recessed portion. The present invention provides a device for manufacturing a glazed glass which is lower than The 1500 eni glass-contacting member uses the shouting member of the present invention. In the present month, the member that is in contact with the molten glass of 14 〇〇C or less is preferably a ceramic member using the present invention. Manufacturing device Using a sintered glass material containing 3 3hS% glass phase and containing electric material or wrong; 5 as the main component, the H substrate 'construction of the fused glass is connected with the melting glass below C. At least a part of the part is at 15 〇〇. (: The above-mentioned shouting substrate is formed with a metal spray film, in which at least the above-mentioned manufacturing equipment of the glazed glass is manufactured by heat treatment. 201228995 The metal spray coating film is selected from the group consisting of a sprayed film of at least one metal selected from the group consisting of a family of metals and an alloy containing one or more platinum group metals as a main component. The present invention provides a molten glass. a manufacturing apparatus using a ceramic substrate composed of a sintered brick containing 3 to 30% by mass of a glass phase and comprising electroforming brick or zircon as a main component to constitute a device for manufacturing molten glass and less than 1500 C. At least a part of the fused glass contact portion, and a metal spray film formed on the ceramic substrate of the structure, and then at least 1500 ° C or higher to make at least the smelting glass manufacturing device Ceramic substrate formed with the aforementioned metal spray film In the heat treatment, the metal sprayed film is selected from the group consisting of a sprayed film of at least one of the group consisting of a metal of the group and an alloy containing one or more of the metals of the group. The present invention provides a method for producing a molten glass which is produced by using the apparatus for producing a molten glass of the present invention. The present invention provides a manufacturing apparatus for a glass article, comprising: a mechanism for manufacturing molten glass; A forming mechanism for forming a glass; and a cold-cooling mechanism for cooling the formed glass; and a member for contacting the molten glass of less than 1500 °C uses the ceramic member of the present invention. The present invention has: a mechanism for manufacturing molten glass; a forming mechanism for forming the obtained molten glass; and a 'cold cooling mechanism for cooling the formed glass; and the member contacting the molten glass of 1400 C or less is used according to the present invention. Ceramic components are preferred. The present invention provides an apparatus for producing a glass article, comprising: a device for producing molten glass; a glass forming device for molding molten glass; and 201228995 a cold cooling device for forming a glass after cooling; and manufacturing of the molten glass A ceramic substrate composed of a sintered brick containing 3 to 30% by mass of a glass phase and an electroforming brick or zircon as a crucible is used to form a portion of the molten glass manufacturing apparatus that is in contact with the molten glass of less than 1503⁄4. At least a part of the molten glass manufacturing apparatus is at least a part of the above-mentioned molten glass manufacturing apparatus, and the shingling substrate is formed into a sprayed film, and the metal spray is formed. The coating film is selected from at least a bismuth spray film of a group consisting of a metal and an alloy containing a platinum group metal as a main component. Jinquanjuan provides a manufacturing device for glass articles, which comprises: manufacturing glass for n (four) glass forming of glass forming; and cooling device for forming cold after forming; The system uses a sintered brick containing 3 to 3 〇 mass% of the glass phase and is made of electroformed brick or smectite, and is constructed to produce (4) (4) and a molten glass phase of less than 15 GGt. At least a portion of the joint portion forms a metal nozzle film on the (four) substrate of the portion of the structure, and the contact is made at a temperature of 1500 ° C or higher to cause the formation of the (four) glass to be formed. At least the metal spray film is selected from the group consisting of (4) metals and alloys composed of the above-mentioned alloys, and at least the metal of the group. membrane. The present invention provides a method of producing a glass article, which is a glass article manufactured using the apparatus for manufacturing a glass article. According to the present invention, a spray film surface space in which a metal having a surface of a ceramic substrate having a glass phase and a metal spray film is reinforced by a surface thereof is filled with the aforementioned glass docking phase a ceramic member having a good adhesion strength between the ceramic substrate and the metal coating film. The gas-making device of the molten glaze beer of the present invention is a member in which the metal spray coating is contacted with the molten glass. Then, the ./5 β clothing is excellent in corrosion resistance to molten glass, and because of the long-lasting nature of the metal, it is difficult to separate, so it has good resistance to use by using the molten molten glass and glass articles of the present invention. Slope manufacturing apparatus, stable manufacturing drawings, sectional view for explaining the embodiment, Fig. 1 showing one of the ceramic members of the present invention, and Fig. 2 showing the section along the BB line in the fixing recess system (a) Fig. - (a) is a plan view '(b) Fig. 3 is a longitudinal sectional view showing the sleek form of the present invention. Fig. 4 is a view showing the manufacture of a device for sloping soil. Fig. 4 shows the break of the present invention. Manufacture of continuation Fig. 5 is a view showing a method of measuring the adhesion strength. Fig. 6 is a graph showing the measurement results of the adhesion strength. The paste is obtained in the example i, and (a) before the heat treatment and (b) The system is executed. The surface map is -, after, the (a') is displayed (the map is mapped in the uniform, and the (b) is not called the map_phase. 9 201228995 8 The figure is a cross-sectional view of the ceramic member obtained in Example 2, (a) before heat treatment and (b) after heat treatment; (b,) is enlarged to show the main part of (b). The cross-sectional picture of the ceramic member obtained in Comparative Example 1 is (a) before heat treatment and (b) after heat treatment; (b,) is enlarged to show the main portion of (b). Fig. 10 is shown in the examples. 3 is a graph showing the thermal history of melting and solidifying a glass raw material in a container made of a ceramic member. Fig. 11 shows the result of Example 3, and (a) is in a container composed of a ceramic member. A cross-sectional image of the cured glass, (b) is a graph showing the measurement results of the cold-OH value. Figure 12 shows Comparative Example 2 As a result, (a) is a cross-sectional image of the glass solidified in the container composed of the ceramic member, and (b) is a graph showing the measurement result of the cold-OH value. Fig. 13 shows the result of Comparative Example 3, (a A cross-sectional image of a glass solidified in a container composed of a ceramic member, and (b) a graph showing a measurement result of a cold-OH value. Fig. 14 is a ceramic member produced in Reference Example 1. Fig. 15 is a cross-sectional view showing the result of measurement of the call-OH value of Reference Example 1. C Embodiment 3 Form for carrying out the invention <Ceramic member> The figure shows a section of an embodiment of the ceramic component of the present invention.

S 10 201228995 Illustration. The symbol 1 is the surface: coffin, (4) 2, the gold number 3 indicates the fixing recess, the ceramic member of the present invention has the ceramic substrate 丨, and the composite metal spray film 2, the money smash 1 and the metal spray The surface of _2 is filled with a glass phase (not shown) which is infiltrated from the H substrate. 1 2 middle <ceramic substrate> tile pure enamel uses bricks containing 3 to 30% by mass of the surface

It is better to use the high-sensitivity ', ', XT >^T# m-T'+' - for the purpose of the smelting of the glass, and in this view, the use of the escaping is the main cause of the oxidization error. The electric brick is the main component of the sintered brick. When the content of the right glass phase is less than 3% by mass, it is difficult to cause the glass phase to ooze out from the squeezing substrate when the heat treatment described later is performed. If it exceeds (4)% by mass, there is a problem that the amount of exudation of the glass phase increases and the metal spray film is easily swollen. [Electro-casting brick] The electric-faced brick is selected from at least one group consisting of oxidized, oxidized, sulphuric acid, shoal _ Tian Shao, · column, 5 I 11 and titanium oxide. As a monument that constitutes a knife and completely smashes the raw materials in an electric furnace, it is essentially composed of a crucible day and a glass transition. In the present invention, <from the known electric scale bricks, the content of the glass phase is selected to be 3 to 3 % by mass. The glass phase content in the ceramic substrate of the present invention is obtained by calculating the area ratio of the glass phase of the total area of the BB phase and the glass phase based on the cross-sectional image and converting this into a mass ratio. For the value m, it is within the surface of the dense surface 5 () of the m-coated material of the coated metal spray film.

The layer of S 11 201228995 was obtained by binarizing the glass phase and the crystal phase using a reflection electron image (group imaging) taken at 5 〇 to 1 〇〇 times by an electron microscope. For the specific example of the electroformed brick used in the present invention, for example, there are: AZS (Al2〇3-Si〇2-Zr〇2) brick, high gasified knot brick having improved cerium oxide content, and the like. In these cases, it is difficult to form AZS bricks because of the difficulty in generating cracks caused by heating or thermal fluctuations. The glass phase content of the AZS brick is preferably 10 to 25% by mass, and 15 to 2% by mass is preferably 0. The glass phase content of the AZS monument can be adjusted by the blending ratio of the raw materials. The composition of the AZS brick is preferably 40-55 mass% of Al2〇3'1〇~15 mass0/〇 of Si〇2, 30~45 mass0/〇 of Zr02, and 0.5 to 2.5% by mass of Na2〇. The other components are preferably 2% or less, more preferably 1% or less, such as various metal oxides constituting the glass phase and unavoidable impurities. The glass phase content of the high oxidized enamel brick is preferably 2 to 20% by mass, preferably 4 to 15% by mass. The glass phase content of the highly oxidized malform brick can be adjusted by blending. ° The composition of the high oxidized enamel brick is preferably 0.5 to 20% by mass of 丨2〇3, 2 to 1 〇% by mass of 丨〇2, and 8 〇 to 96% by mass of B 1*〇2. Other components - such as various metal oxides and unavoidable impurities constituting the glass phase, are preferably 3% or less, and preferably 2% or less. [Sintered brick with zircon as the main component] The sintered brick with the main component of the wrong stone contains zircon ~% by mass. / 〇 The sintered brick consists essentially of a crystalline phase and a glass phase. In the present invention, the spoon T is selected from the group consisting of the known sapphire as the main component, and the glazed phase is used in an amount of 3 to 30% by mass. 12 201228995 The glass phase content of the sintered brick mainly composed of conical stone is preferably 3 to 1 〇 mass / 〇, and 4 to 10% by mass. The glass phase content of the sintered monument having zircon as a main component can be adjusted by the blending ratio of the raw material powder. The composition of the sintered brick containing zircon as a main component is preferably 3 〇 to β mass%, Zr 〇 2 is 50 to 70% by mass, and the other metal oxide is 5% by mass or less. [Fixed recess] A regular fixing recess 3 is preferably formed on the surface of the ceramic base material 1. By providing the fixing recess 3, the adhesion strength between the ceramic substrate 丨 and the metal spray film 2 can be improved. In particular, the adhesion strength with respect to the tensile stress in the direction parallel to the surface of the ceramic substrate 1 can be improved. Fig. 2 is a cross-sectional view taken along line b-B in (a) a plan view and (b) a line (a) in a plan view showing the shape of the fixing recess 3. In the fixing recessed portion 3 of this example, a plurality of straight grooves g having a rectangular cross-sectional shape in a lattice shape are provided. The side surface of each groove g is perpendicular to the surface of the ceramic substrate 且 and the groove width W is constant. In order to obtain a fixing effect effectively, the groove constituting the fixing recess 3 must have a certain depth. However, if the depth is too deep, the strength of the surface portion of the ceramic base material is lowered to make processing difficult. For example, the depth of the groove g is preferably about 50 to 350 #m, preferably about 15 〇 25 〇 / / m. 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 (the distance between the grooves, the distance between the center lines of the grooves of the adjacent grooves) p, in order to disperse the stress and To reduce the stress applied to one place, it is preferable to reduce the groove pitch p. Considering the stress durability of the metal spray film 2 and the strength of the porcelain substrate 1 , the groove pitch is preferably about 2,5,111,111 or less, preferably about 1.5 mm or less. In the same way, the groove width is also preferably narrower, and in terms of maintaining the strength of the surface portion of the ceramic substrate 1, it is also preferable to narrow the width of the substrate. However, if the groove width w is smaller than the particle diameter of the metal particles to be sprayed, the groove cannot be filled with the sprayed particles. Therefore, the groove width w needs to be set to be larger than the particle diameter of the sprayed particles. For example, the groove width is preferably 丨(8) above the claw, and preferably about i5 〇#m or more. In order to maintain the strength of the convex portion between the adjacent grooves g to be resistant to stress, it is necessary to ensure the width of the convex portion according to the stress (= the interval between the grooves - that is, the difference between the groove width - the groove width w). The thicker the thickness m of the metal sprayed film 2 formed on the ceramic substrate, the greater the tensile stress applied from the metal sprayed film 2 in the direction parallel to the surface of the ceramic substrate. In this regard, the width of the convex portion is preferably about 4 times or more the thickness 〇1 of the metal sprayed film 2. Further, in consideration of the narrowing of the groove pitch P, the ideal convex portion width X is about 2.5 to 5 times the thickness m of the film. The deeper the stress applied to the side of the groove g is, the deeper the depth of the groove (i.e., the larger the side surface), the more the stress may be dispersed to the entire side surface and the convex portion is hard to be broken. Therefore, the smaller the ratio (p/d) of the groove pitch p to the depth d of the groove, the higher the dispersibility of the stress, and the more easily the peeling of the metal spray film 2 is suppressed. It is preferable to calculate the p/d value for appropriately distributing the stress based on the above-described appropriate groove pitch p and the depth d of the groove, and it is preferably about 3 to 8. Further, the fixing recess is not limited to the shape shown in FIG. Regularly, a slightly cylindrical hole can also be formed regularly. When the intermittent hole is formed as the groove 3 as shown in Fig. 2

In the case of the S 14 201228995 substitute, it is preferable to form a hole at the intersection of the orthogonal lattice (checker mesh). Or arranging in a position of a thousand birds (Staggered Layout) to make the hole spacing distance uniform. For example, the hole pitch distance is preferably about 0.7 to 2.5 mm, preferably about 1.0 to 1.6 mm. The diameter of the hole is preferably from about 2 〇〇 to 500 Å, and the value is from 300 to 400 //m. The depth of the hole is about 2 to 600 / zm, preferably about 300 to 500 / zm. In the formation of the fixing recess 3, when the fixing recess 3 is formed in a groove shape, it can be mechanized by using a boring machine that mounts a grinding knives such as a grindstone or a diamond blade. Or it can be carried out using a high energy beam such as a laser or a high pressure water stream. When the fixing recess 3 has a hole shape, it can be carried out using a polishing tool such as a pin-drill or a high-energy beam or a high-pressure water stream such as a laser. Before the fixing recessed portion 3 is formed, the surface of the ceramic base material 1 is prepared to have a high-precision plane by cutting by a grinder or the like, and it is preferable to prevent the metal sprayed film 2 from being peeled off by the unevenness of the outer surface. In the present invention, the fixing recess 3 may optionally be a groove shape or a hole shape, and the hole may be relatively narrowed by a hole shape to close the space enclosed by the metal spray film (the space inside the hole), and One hole is formed to form a closed space, so that the adhesion strength due to the tensile force in the thickness direction of the metal spray film 2 is increased by filling the glass phase at the interface between the base material 1 and the metal nozzle film 2 At the point where the effect is greater, it is ideal. On the other hand, because the groove shape will increase the closed space enclosed by the metal spray sputum (the inner side of the ditch)

The space is formed by a larger groove, so that the above effect is relatively reduced. S <Metal Spray Film> 15 201228995 The metal spray film 2 is a metal film formed by a spray coating method. In the spraying method, the metal teaching piece heated at a high temperature is emitted onto the substrate, and the deposited film of the metal particles is formed into a film n, so that the metal film is different from the cured film by coating of a molten metal or the like. Etc., on the other side, the structure can be stacked in a granular shape. The metal may be at least one selected from the group consisting of a group metal and an alloy containing one or more kinds of metal compounds as a main component. The platinum group metal is, for example, platinum (Pt), iridium (Ir), ruthenium (Ru), and rhodium (Rh). Alloys based on the alloy of the Ming family include Pt_5%Au alloy, Pt-l〇%Ir alloy, and platinum alloy such as Pt-10°/〇Rh alloy. <Manufacturing Method of Ceramic Member> First, the metal spray film 2 is formed on the ceramic base material 1. When the fixing recess 3 is provided on the surface of the ceramic substrate i, the metal spray film 2 is formed so as to cover the fixing recess 3. As the spraying method, a known spraying method such as a laser spraying method, a wire frame nozzle coating method, an electric nozzle coating method, an arc spraying method, or an oxyhydrogen flame spraying method can be suitably used. The particle diameter (flying spray particle diameter) of the metal particles emitted by the spray coating method is preferably a short diameter, and the type of the spray method can be reduced to about 4 〇//〇1 or about 50 to 150//. m or so. The metal particles emitted by the spray coating are deposited on the surface of the ceramic substrate 1 to form the metal spray film 2. When the fixing recess 3 is formed on the surface of the ceramic substrate, the metal particles emitted by the spraying method fill the recess 3 and deposit on the surface to form the metal spray film 2. The thickness m of the metal spray film 2 can be appropriately adjusted depending on the amount of spray. The thicker, then

S 16 201228995 The strain of the tensile stress in the direction parallel to the surface of the ceramic substrate 1 is increased. Therefore, the thickness m of the sprayed film 2 (the thickness of the portion having no concave portion when there is a concave portion) is 丨00~ It is preferably about 400 ym, and the ideal range is 200 to 35 〇α m. The temperature of the emitted metal particles is about 7〇〇~i5〇〇°c. If the heating (ie, preheating) is performed in advance, the temperature of the ceramic substrate during the spraying is increased to reduce the temperature of the metal particles and the ceramic substrate. It is preferable that the adhesion between the metal spray film 2 and the ceramic substrate 1 can be improved. At this time, it is preferable to carry out the spraying under the condition of heating (preheating) the Tauman substrate 1 and then cooling it to normal temperature. The temperature (preheating temperature) of the ceramic substrate 1 at the time of spraying is preferably below the solidification temperature of the emitted metal particles, specifically, about 200 to 500 ° C, preferably 300 to 40 (TC. The cooling rate is as slow as possible, and is preferably 1 〇 ° C / min or less. Next, in a state where the metal spray film 2 has been formed on the ceramic base material 1, the heat treatment is performed at a temperature of 1500. By performing the heat treatment, the glass phase can be ooze out from the ceramic substrate to a small space in the interface between the ceramic substrate 1 and the metal nozzle film 2, and the state in which the glass phase is filled in the space can be obtained. Because, once heated to a high temperature of 1500 C or higher, the glass phase in the ceramic substrate can be easily flowed, and the glass phase is squeezed into a small space by the difference in thermal expansion between the glass phase and the ceramic phase. In the present invention, the state in which the interface space between the ceramic substrate 1 and the metal spray film 2 is filled with a glass phase means that glass is present between the ceramic substrate 1 and the metal spray film 2 Phase 'and at least a portion of the glass phase and the ceramic base Material 丨 and gold £ 17 201228995 It is a state in which both sides of the spray 臈 2 are connected. Some space may remain in the interface between the ceramic substrate 金属 and the metal spray film 2, but in order to obtain the ceramic substrate i and the metal spray film 2 The good adhesion strength is preferably not left as much as possible. For example, in the cross-sectional picture after the heat treatment, there is no relative area of the space in the interface between the ceramic substrate 1 and the metal spray film 2 The space remaining in the glass phase is preferably 20 area% or less, preferably 10 area ° / ◦ or less, and 0 area % is optimal. - The heat treatment temperature is lower than 1500. (:, it is difficult to obtain a glass phase filled with ceramics The state of the interface space between the substrate 1 and the metal spray film 2. This is because the flow state of the glass phase is insufficient, and it cannot be wet-slip in the space in a short time, and since the ceramic phase and the glass phase pass over time The reaction is carried out, so that the state in which the space is filled with the glass phase cannot be obtained even if the heating time is increased. On the other hand, the upper limit of the heat treatment temperature must be lower than the melting point of the metal constituting the spray film 2. Therefore, the heat treatment temperature is The melting point of the sprayed film 2 is preferably set so that the interface space between the ceramic substrate 1 and the metal sprayed film 2 can be filled with a glass phase in an appropriate heat treatment time to be described later. The appropriate heat treatment temperature depends on the ceramic substrate 1 The composition of the components varies, for example, but it is preferably, for example, 1500 to 170 (about TC, preferably about 1500 to 1600 ° C. As long as the heat treatment temperature is within the ranges, the flowability of the glass phase is south, and thus the The reaction of the glass phase has a low effect on the effect of filling the interface space between the ceramic substrate 1 and the metal spray film 2 with the glass phase. Once the heat treatment time is too short, it will be in the interface between the ceramic substrate 1 and the metal spray film 2. There is a lot of space left. On the other hand, once the heat treatment time increases,

S 18 201228995 After the passage of time, the reaction of the ceramic phase with the glass phase makes it difficult to squeeze the glass phase into the interface space between the ceramic substrate 1 and the metal nozzle film 2. ^ So it is advisable to set the heat treatment time in such a way that it does not cause such problems. For example, it is preferably about 1 to 100 hours, and preferably 10 to 50 hours. According to the manufacturing method of the present invention, the ceramic member of the present invention in which the interface space between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase derived from the ceramic substrate can be obtained. <Use of Ceramic Member> The ceramic member of the present invention has a temperature of less than 1,500 when used. (The structure of 17 is used for the temperature when it is used. It is not expected to be 1500. (: The above part is because the use temperature is 15〇 (in the component above rc, even if it is not in the stone month) 15仃c As a result of the above heat treatment, the same effect as the present invention can be obtained. Therefore, the demand of the present invention is low in the member. From the above reasons, the ceramic member of the present invention preferably has a temperature below 〇c in use. 14〇〇 (a member having a thickness of 5 c or less is preferable. Since the ceramic member of the present invention is provided with a metal spray film 1 on the ceramic substrate 1), it is excellent in corrosion resistance to the molten glass. Therefore, it is used for manufacturing a molten slope. In the glass device, the ceramic member of the present invention can be suitably used as a member that comes into contact with molten glass of less than 1500 C. Further, in the device for producing a glazed glass, the ceramic member of the present invention is suitably used as the 1450. A member that is in contact with the glazed glass below 0, and is more suitably used as a member that is in contact with the glazed glass below 1400. 19 201228995 Specifically, the molten glass flowing out of the melting tank is desirably used as a defoaming device by decompression And in the flow path before the delivery of the forming device, the member that is in contact with the glazed glass of less than 1 〇〇 适当 is suitably used. Further, the molten glass flowing out from the melting tank is preferably used as a defoaming under reduced pressure. A member that is in contact with the molten glass of 1450 ° C or lower in the flow path before the delivery of the molding apparatus is suitably used as a member that is in contact with the molten glass of 1400 ° C or less. a member for depressing the inner wall of the bubble tank, a member constituting the inner wall of the molten riser pipe provided upstream of the decompression defoaming tank, or a member constituting the inner wall of the downcomer provided downstream of the decompression defoaming tank. The ceramic member of the present invention is ceramic Since the metal spray film 2 is provided on the surface of the substrate crucible, even if it is in contact with the molten glass, the erosion of the ceramic substrate 1 can be suppressed. Further, as will be described later, the substrate 1 and the metal are ceramics. The spray film 2 has excellent joint strength. Therefore, the metal spray film 2 is difficult to peel off and has good durability. Further, when the ceramic member of the present invention is used as a member in contact with the molten glass, the ceramic substrate is used. In the state in which the interface space of the metal spray film is filled with the glass phase, the effect of suppressing the generation of bubbles in the molten glass can be obtained. That is, once the water present in the molten glass acts on the metal spray by the catalyst of the platinum group metal The surface of the film is decomposed into oxygen and hydrogen, in which hydrogen penetrates the metal spray film but oxygen does not penetrate the metal spray film and remains on the surface. At this time, as long as hydrogen remains in the metal spray film, it will be combined with metal. The oxygen on the surface of the spray film is combined again to form water, so that oxygen does not become bubbles. However, in the conventional ceramic member, there is a small space in the interface between the metal tantalum coating and the underlying Tauman substrate. Penetrating metal spray

S 20 201228995 The hydrogen in the membrane moves through this space, so that hydrogen cannot remain in the metal spray film. Therefore, the oxygen on the surface of the metal spray film cannot be combined with hydrogen to become bubbles. Since the ceramic member of the present invention is filled with a surface phase in the interface space t between the metal spray film and the ceramic substrate, hydrogen can remain in the metal spray film and recombine with oxygen to form water. _, can prevent oxygen from changing. <Manufacturing Apparatus of Molten Glass> The apparatus for producing a smelting glass of the present invention is a member (four) in contact with a refining glass lower than the boot. X. The apparatus for producing molten glass of the present invention is preferably used in a member which is in contact with a molten glass under 14 thieves, and is more preferably used. The member in contact with the molten glass below C uses the ceramic member of the present invention. Further, the apparatus for producing molten glass of the present invention comprises a ceramic base material comprising a sintered monument having a glass phase of 3 to 30% by mass and electroforming a monument or a streak as a main component, and is configured to manufacture a molten glass. At least a portion of the 1500 π junction portion, and at least the ceramic substrate of the apparatus for manufacturing the molten glass is heat-treated at a temperature of t or higher, wherein the ceramic substrate forms a metal spray film, and The metal spray film is selected from the group consisting of a spray film of at least one metal selected from the group consisting of a platinum group metal and an alloy containing one or more platinum group metals. Further, the apparatus for producing molten glass of the present invention contains 3 to 30 masses. /. The glass-phase and the Tauman substrate composed of the electro-cast brick or vermiculite-based sintered bricks constitute a device for melting glass and is preferably less than 15 °C 21 201228995, preferably below 1450 ° C. At least a part of the molten glass contact portion of 1400 t or less, and a metal spray film is formed on the ceramic substrate of the structure, and then at 1500. (The above-mentioned metal sprayed film is selected from the group consisting of a platinum group metal and one or more kinds of the ceramic base material in which the molten metal is produced in the apparatus for producing molten glass; A sprayed film of at least one metal selected from the group consisting of alloys containing a platinum group metal as a main component. Fig. 3 is a longitudinal cross-sectional view showing an embodiment of a device for producing molten glass of the present invention. The apparatus is roughly configured by the following elements: that is, the melting tank U, the glass raw material is melted, and the molten glass is homogenized and clarified; and the vacuum defoaming device 12 sets the internal air pressure to be lower than atmospheric pressure and from the refining tank 11 The bubble in the supplied molten glass floats and breaks; the first conduit 13 connects the melting tank 11 and the vacuum defoaming device 12; and the second conduit 14 serves to melt the molten material from the vacuum defoaming device 12. The glass is sent to the forming mechanism of the lower step through the cooling bath 15. The symbol G in the figure indicates the molten glass. The first duct U is provided with the cooling mechanism na and the feeding mechanism nb, and the molten glass flowing out of the melting tank 11 is at the i-th. Conduit 13 cooling 1〇〇〇. 匸 above and below l5〇〇C, it is introduced into the vacuum defoaming device 12. The decompression/shaw/package device 12 is provided with a decompression defoaming tank 12a, and a decompression defoaming tank 12a. The upstream side communicates with the conduit 13 through the riser 12b, and the downstream side of the depressurization defoaming tank 12a passes through the downcomer to communicate with the second conduit M. The decompression defoaming tank 12a, the riser 12b' and the downcomer 12e The internal system is maintained in a reduced pressure environment, and the inside of the second conduit 13 is melted through the riser 12b by the siphon effect.

S 22 201228995 Boseshaw and the inside of the decompression defoaming tank 12a. Further, the portion after the conduit 14 is connected to the forming mechanism through the cold 15 . In the apparatus of the present embodiment, the members of the vacuum degassing tank 12a, the riser 12b, the downcomer 12c, and the inner wall of the cooling tank 15 constituting the vacuum defoaming device 12 are formed of the ceramic member of the present invention. A ceramic substrate having a metal spray film is formed by heat treatment. That is, the inner walls of the depressurization defoaming tank 12a, the riser 12b, the downcomer 12c, and the cooling tank 15 are composed of a ceramic base material whose inner surface has been coated with a metal spray coating, and are used for the ceramic base material and the metal sprayed film. The tiny space of the interface is filled with a glass phase. The vacuum defoaming device 12 and the cooling bath 15 are manufactured by first forming a vacuum degassing tank 12a, a riser 12b, a downcomer 12c, and a ceramic base material coated with a metal spray coating in advance. And the inner wall of the cooling tank 15 is assembled into a series of shapes from the decompression defoaming device 12 to the cooling tank 15, and then a series of structures including the decompression defoaming device 12 and the cooling tank 15 are connected at a predetermined temperature of 1500 C or higher. After the internal heat treatment, it is cooled to below the use temperature. Further, the decompression defoaming tank 12a, the riser 12b, the downcomer 12c, and the inner wall of the cooling tank 15 can be formed by the ceramic member of the present invention, and can be assembled into a series from the decompression defoaming device 12 to the cooling tank 15. shape. Further, after the vacuum degassing tank 12a, the riser 12b, the downcomer 12c, and the inner wall of the cooling bath 15 are formed by the ceramic base material, a metal spray may be formed on the surface on the side in contact with the molten glass of the base material. The membrane ' then takes 1500. (The above temperature is to heat-treat the ceramic substrate on which the metal sprayed film is formed. After the apparatus is manufactured by the above method, it is used at a use temperature lower than 1500 ° C. Further, after the apparatus is manufactured as described above, It is used at a temperature of 1450. (the following 23 201228995 is used, and it is more preferable to use 0 at a use temperature of 14 ° C or less, and the assembly order of each part or the part using the ceramic member of the present invention is not limited to the above. For example, since the temperature of the molten glass in the cooling bath 15 is lower than the upstream portion, it is also possible to use only the portion using the ceramic component of the present invention as the vacuum defoaming device 12 without using the cooling tank 15 Alternatively, the portion of the vacuum defoaming device 12 to which the ceramic member of the present invention is used may be a reduced pressure defoaming tank 12a, or only the riser 12b and the downcomer 12c, or only the downcomer 12c. Further, the ceramic member of the present invention may be used for the inner walls of the first duct 13 and the second duct 14. <Method for Producing Molten Glass> The method for producing the molten glass of the present invention is less than 15 〇〇. : molten glass The member to be contacted 'is a method of manufacturing a molten glass using the manufacturing apparatus of the ceramic member of the present invention. Further, the method for producing the molten glass of the present invention is preferably a member that is in contact with molten glass of 1450 ° C or less. A method of manufacturing a molten glass by a manufacturing apparatus of a ceramic member. Further, the method for producing a molten glass of the present invention is preferably a manufacturing apparatus using the ceramic member of the present invention for a member that is in contact with a glazing glass of 14 〇〇〇c or less. For example, in the method of producing molten glass using the apparatus for producing molten glass shown in Fig. 3, the molten glass flowing out of the melting tank u is cooled to 1 in the first guide 13 After 〇〇C or more and less than 15〇〇〇c, it is introduced into the decompression/short bubble device 12. Further, the (four) glass from the smelting tank (4) should be cooled to 1GGG °C or higher in the i-th guide 13 And 145 (Γ (: after α, then import and subtract

S 24 201228995 Pressure defoaming device 12. Further, it is preferable that the glazed glass that has flowed out of the smelting tank 11 is cooled to 10 ° C or more and 1400 ° C or less in the first duct 13 and then introduced into the vacuum defoaming device 12 . Since the decompression defoaming tank 12a, the riser 12b, the downcomer 12c, and the inner wall of the cooling tank 15 of the vacuum defoaming device 12 are in contact with the molten glass of i〇〇〇〇c or more and less than 15〇〇°c, Further, since the surface (i.e., the inner surface) of the ceramic base material constituting the inner wall is covered with the metal spray film, it is excellent in the contact resistance to the glazed glass. Further, since the ceramic substrate and the metal spray film have excellent adhesion strength, the spray film is difficult to peel off and has excellent durability. In addition, since the interface between the metal spray film and the underlying ceramic substrate is filled with a glass phase, even if the moisture in the glass is decomposed into oxygen and hydrogen on the surface of the metal spray film, the hydrogen can be left on the metal spray film. . Therefore, as described above, the hydrogen can be recombined with the oxygen generated in the decomposition of water to form water, and the phenomenon in which bubbles are generated in the molten glass due to the oxygen can be suppressed. &lt;Production Apparatus and Manufacturing Method of Glass Article&gt; The apparatus for producing a glass article of the present invention includes: a mechanism for producing molten glass; a molding mechanism for molding the obtained molten glass; and cooling the formed glass The refrigerant element of the present invention is used in a member that is in contact with the molten glass below 1500 ° C. Further, the apparatus for producing a glass article of the present invention comprises: a mechanism for producing molten glass; a forming mechanism for forming the obtained molten glass; and a cold-cooling mechanism for cooling the formed glass; and preferably at 1450 ° C The following members in contact with the molten glass use the ceramic member of the present invention. Further, the manufacturing apparatus of the glass article of the present invention has: a mechanism for manufacturing molten glass; forming the obtained molten glass

The forming mechanism of S 25 201228995; and the cold-cooling mechanism for cooling the formed glass; and preferably at 1400. The member in contact with the molten glass below uses the ceramic member of the present invention. The mechanism for producing molten glass is preferably the manufacturing apparatus of the molten glass of the present invention. For example, it can be configured as shown in Fig. 3, that is, a molding mechanism for forming molten glass downstream of the flow direction of the molten glass of the apparatus for manufacturing molten glass, and having a cooling mechanism for cooling the formed glass downstream thereof. mechanism. A processing mechanism for cutting or grinding may be provided downstream of the Xu cold mechanism. Although there is no such formation mechanism, various mechanisms such as a known floating glass method, an overflow down extraction method, and a melting method can be used. Xu Leng institutions and processing organizations can also use well-known technologies. Fig. 4 is a flow chart showing an example of a method for producing a glass article using the apparatus for producing a glass article of the present invention. According to the method shown in Fig. 4, the glass article is preferably produced by obtaining the molten glass G by the glass melting step si of the molten glass manufacturing apparatus of Fig. 3, and then passing the molten glass G to the forming mechanism and forming it. After the forming step S2 of the shape, the cooling is performed by the cold cooling step S3. Thereafter, the glass article G5 is obtained by post-processing such as cutting or grinding in the post-processing step % as an embodiment. The present invention will be further described in detail below using examples, but the invention is not limited by the implementation. For example. [Example 1] In this example, the AZS (Al2〇3_Si〇2-Zr〇2) monument was used as the ceramic base 26 201228995, and the surface of the brick was subjected to a regular configuration as follows. A metal film is sprayed to obtain a substrate with a metal film, and a heat treatment is applied to the substrate of the metal film to produce a ceramic member. Hereinafter, a substrate on which a metal sprayed film is formed on the surface of the ceramic substrate is also referred to as a metal film-attached material. Table 1 shows the results of measuring the composition of the ceramics used in the ceramics by X-ray fluorescence analysis. Further, the content of the glass phase calculated based on the cross-sectional image of the base material to which the metal film was attached before the heat treatment was collectively shown in Table 1 (hereinafter, the same applies to Example 2 and Comparative Example 1). The calculation of the glass phase content was carried out in the following manner. The electron beam microscope was used to take a 50-fold reflection electron image (composition image) of an electron microscope from the surface of the substrate to a position of 20 mm from the surface of the substrate before the heat treatment. Calculate the total area of the crystal phase and the glass phase in the obtained image, calculate the area ratio of the glass phase relative to the image, and convert the area ratio into a mass ratio to obtain the content of the glass phase (unit). :quality%). First, the AZS monument was cut into a 50 mm x 50 mm x 10 mm high monument. Then, a fiber laser was used to form a fixing recess on one of the 50 mm x 50 mm faces of the tablet. The fixing recess is a slightly cylindrical hole having a hole diameter of 300 / / m, a hole depth of 400 / m, and a hole pitch of 1 mm. Next, the tile is heated to 300 ° C in an atmospheric environment, and the spray of platinum is started on the surface on which the hole is formed by the wire frame spraying method (the flying sprayed particle is about 100/zm, and the temperature is about 1〇〇°〇. Continue to spray until the platinum film. The film thickness becomes 300; after czm, the tile is cooled to room temperature to obtain a substrate with a metal film. 27 201228995 Two pieces are produced under the same conditions. The base material of the metal film was attached, and the base material of the metal film attached to one of the substrates was heat-treated at 1500 ° C for 1 hour in an electric furnace to obtain a ceramic member. The base material of the other metal film was directly subjected to heat treatment as an untreated sample. [Example 2] A metal was obtained in the same manner except that the ceramic substrate of Example 1 was changed to a high zirconia brick. The substrate of the film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. Further, as a control, an untreated sample to which no heat treatment was applied was produced in the same manner as in Example 1. Example 1] In addition to the ceramic substrate of Example 1. A substrate with a metal film was prepared in the same manner except for the α/3 alumina brick, and the substrate of the metal film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. An untreated sample 0 to which no heat treatment was applied was produced in the same manner as in Example 1. Table 1 Composition of ceramic substrate (% by mass) Content of glass phase (% by mass) Si02 Zr02 Al2〇3 Na20 Example 1 AZS brick 12.0 41.0 45.8 0.4 17 Example 2 High zirconia brick 4.0 94.5 0.8 1.0 6 Comparative example 1 a 泠 alumina brick 0.8 0.0 95.0 3.5 1 [Evaluation method] (bonding strength)

S 28 201228995 Each of the ceramic members obtained in each of the examples and the untreated samples were each cut into three plate-shaped pieces each having a length of I4 mm x a width of 14 mm x a height of 10 mm, and as shown in Fig. 5, at 14 mm x 14 mm A test piece was produced by adhering the stretching jigs 24 and 25 to the both surfaces with a thermosetting epoxy adhesive 23, respectively. In the figure, reference numeral 21 denotes a ceramic substrate, and 22 denotes a metal spray film. Using a tensile strength tester (TSE DuPont, product name: AUTOCOM/AC · 50KN-C), the stretching jigs 24, 25 are stretched away from each other at a speed of _·5 _ / min to determine The load when the ceramic substrate and the metal spray film 22 are peeled off. The adhesion strength (P/s, in MPa) was calculated from the load value (ρ) at the time of peeling and the area (S) of the plate piece (ceramic member). The result is shown in Fig. 6. As shown in the results of Fig. 6, in the comparative example, the splicing strength of the untreated sample and the Tauman member was substantially the same. On the other hand, the adhesion strength of the Tauman members in Examples 1 and 2 was three times or more the adhesion strength of the untreated sample, and it was confirmed that the adhesion strength was greatly improved by the heat treatment. (Sectional Structure) In each of the examples, a base material of a metal film to be attached before the heat treatment at the time of manufacturing the ceramic member, and a cross-sectional view of the ceramic member after heat treatment were taken. Fig. 7 is a picture obtained in the first embodiment, and Fig. 8 is a picture obtained in the second embodiment. Fig. 9 is a picture obtained in Comparative Example 1. Reference numeral 21 denotes a ceramic substrate, and 22 denotes a metal spray film. In Fig. 7, '(a) is a cross-sectional picture before heat treatment, (15) is a cross-sectional picture after heat treatment, and (a') is a map showing the broken glass in the picture of (a)' (b) The glass phase is mapped to the display in the picture of (b). I·* 29 201228995 In Fig. 8 and Fig. 9, (a) is a picture of the scraped surface before heat treatment, and a picture of the cross section after heat treatment, (b,) is an enlarged display of (b) Ml ϋβ J^r (indicated by symbol B in the figure). The surface of the attached metal film is minute. As shown in (a) of Fig. 7 to Fig. 9, in the hard front substrate, the boundary between the ceramic substrate 21 and the metal spray film 22 is space). On the other hand, as shown in Fig. 7 and Fig. 8(b), the (4) member towel after the reduction of the embodiment 1 '2 has no gap at the interface between the H substrate 21 and the metal spray film 22. As shown in Figures 7 and 8, it shows that there is a glass phase along the interface. In contrast, as shown in FIG. 9(b), in the ceramic member after the heat treatment of the comparative example, there is a gap between the ceramic substrate 21 and the metal sprayed crucible 22, and as shown in FIG. It is shown in (b') that no bleeding of the broken glass phase to the interface was observed. [Example 3] In this example, a container for glass refining composed of a ceramic member was produced as a device for producing molten glass, and the glass raw material was melted at a temperature of 1400 ° C in the container. Cool it down. Then, the amount of moisture in the glass near the inner wall of the container and the presence or absence of bubbles were investigated by the evaluation method described later. First, 'the outer diameter of 75 mm and the outer wall height of 55 mm were produced by using a high-zirconia tablet of the same material as that used in Example 2 and having a fixing recess on one side as in the first embodiment. A bottomed cylindrical container having an inner diameter of 50 mm and an inner wall depth of 40 mm. The surface provided with the fixing recess is used as the inner surface.

S 30 201228995 Next, the sHai container was heated to 3 ° C in an atmosphere ring, and a metal spray film having a film thickness of 300 / / 111 was formed on the inner surface in the same manner as in the first embodiment. A container composed of a substrate with a metal film is prepared. Then, put the far-field device into the electric furnace under the atmosphere and take 16 〇〇. The heat treatment was carried out for 5 hours to obtain a container composed of a ceramic member. In the practice of the above-mentioned Embodiment 3, the obtained container was placed in a heating furnace, and the heat history shown by the first command was applied under normal pressure. The vertical axis of Fig. 1 indicates the ambient temperature in the furnace. First, put the glass material of borax acid glass into the container at a temperature of 4 hours and 4 minutes from normal temperature to 1400 C ', and then at 14:00, and then heat the glass with l40 (rc heating for hrs). The raw material was melted. After that, it was rapidly cooled to 72 (TC and 72 〇χ: after 1 hour, it was cooled to 60 (TC in 2 hours), then cooled to room temperature for 3 hours and then made in the volume. [Comparative Example 2] A glass which was cured in a container (4) was obtained in the same manner as in Example 3 except that the container composed of the substrate with the metal film in Example 3 was not subjected to heat treatment. f L Comparative Example 3] except that the material of the ceramic substrate in Example 3 was made from the high oxidation error and the use of the compound (4) in the comparative example (4) in the same manner as in the external father example 3 A container composed of a container of a metal film and a container having the same heat treatment as in Example 3 was applied to the container. The container was used in the same manner as in Example 3 in the container.

31

S 201228995 Cured glass. [Evaluation method] (Presence of moisture content and air bubbles) The OH value of the glass was measured as an index of the moisture content in the glass. The glass--OH value (unit: mm-i) can measure the absorbance of light for a wavelength of 2.75 to 2.95/zm for a glass sample, and recall the maximum value by the thickness (mm) of the glass sample. Seek. The glass which had been solidified in the container prepared in the above examples was cut along with the container along the cut surface in the direction of the scent, and a longitudinal section sample having a thickness of 1 mm was cut. In the central portion in the height direction of the container of the longitudinal section sample obtained, i.e., the region near the interface between the inner wall of the container and the solidified glass, the _OH value was measured by the above method. And take a picture of the area. The results of Example 3 are shown in the figure, the results of Comparative Example 2 are shown in Fig. 12, and the results of Comparative Example 3 are shown in Fig. 13. (a) of each figure is a cross-sectional picture, and the reference position of the interface is indicated by an arrow. In the figure, the symbol indicates a ceramic substrate, 22 indicates a metal spray film, and 3 indicates a glass crucible. Each figure (b) is a graph showing the measurement result of the point-OH value, and the horizontal axis represents the distance in the width direction of the image of the section (a) (unit: #m), and the vertical axis represents the seven digits: mm·1) . The position corresponding to the reference position of the interface is indicated by an arrow. [Reference Example 1] The container composed of the metal bismuth of each of the above-mentioned Example 3 and Comparative Examples 2 and 3 has a metal spray film under the layer of a ceramic substrate: However, in this example, the moisture content in the case where the lower layer of the metal spray film is composed of glass is measured as follows.曰 32 201228995 That is, in the third embodiment, after the container composed of the ceramic member was placed in a heating furnace, it reached 14 〇〇. (: At the time point, when the glass raw material of the borosilicate glass is put into the container, a part of the glass raw material to be input is directly put into the container composed of the ceramic material, and the remaining part of the glass raw material is released. After the preparation was separately made, the object was placed in the container. In the same manner as in Example 3, the solidified glass was produced in the container. Fig. 14 is a view showing a longitudinal section thereof. It is known that in the container 31 composed of the ceramic member, the crucible 32 is filled in the solidified glass 30, and both the inner surface and the outer surface of the crucible 32 are in contact with the solidified glass. The cut surface of the direction, together with the container and the crucible, cut the glass which has been solidified in the container prepared in this example, and cut a longitudinal section sample having a thickness of 1 mm. The center of the depth direction, that is, the inner surface of the crucible and the area outside the glass interface (indicated by symbol 33 in Fig. 14) - the /3-OH value is measured by the above method. Figure. The horizontal axis represents the 14th figure The distance in the width direction of the face image indicates that the vertical axis represents the point-OH value. In Fig. 15, the position corresponding to the side wall of the hanging frame is indicated by the arrow. However, in the longitudinal profile sample used for the determination of the value of the _0H value. No bubbles were found in the glass. As shown in Fig. 12(b) and Fig. 13(b), the moisture content (cold_〇H value) in the glass in Comparative Examples 2 and 3 was adjacent to The area of the metallized film is reduced. Further, as shown in Fig. 12 (4) and Fig. 13 (4), bubbles are found in the glass in the region adjacent to the metal spray film. Thus, it is known from 201228995, The moisture generated in the molten glass by the decomposition of the surface of the metal sprayed film did not regenerate water, but instead became bubbles. In Comparative Example 2, a high oxidized brick containing 6% by mass of the glass phase was used. Ceramic substrate, but it has not been subjected to 15 〇 (heat treatment of rc before use). Therefore, even if it is heated at 140 °C during use, it is still observed at the interface between the metal spray film and the ceramic substrate in the cross-sectional picture. Tiny gap. Comparative Example 3 contains only glass phase due to the ceramic substrate. Since it is 8 mass%, even if it is subjected to the heat treatment of ISOOt: before use, a small gap is observed in the cross-sectional picture at the interface between the metal spray film and the ceramic substrate. From the above, in Comparative Example 2, In the third embodiment, the hydrogen generated in the molten glass through the decomposition of the metal on the surface of the metal sprayed film penetrates the metal sprayed film and moves through the interface space between the metal sprayed film and the ceramic substrate without leaving the metal. On the other hand, as shown in Fig. 15, in the reference example, in the region adjacent to the metal spray film, the moisture content (cold_〇H value) in the glass is not lowered, and As a result of Fig. 11, the moisture content (/3-OH value) was hardly lowered in Example 3. Further, in Reference Example 3 and Example 3, no bubble generation in the glass was observed. From this, it is understood that the moisture generated in the molten glass through the decomposition of the oxygen generated on the surface of the metal sprayed film is again combined with hydrogen to form water, and thus no bubbles are generated. Further, in the cross-sectional view of Example 3, a glass phase was present at the interface between the metal spray film and the ceramic substrate, and no gap was observed. As described above, the effect of the same bubble suppression as that of the reference example can be obtained in the third embodiment, and it is understood that the glass at the interface between the metal sprayed film and the ceramic substrate is opposed to the gas in the molten glass.

S 34 201228995 The bubble suppression system contributes. INDUSTRIAL APPLICABILITY According to the present invention, a ceramic member having excellent adhesion strength between a ceramic base material and a metal sprayed film can be obtained, and the ceramic member is excellent in corrosion resistance to molten glass, and is used as a manufacturing device for molten glass. The component system is quite useful. And the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2010-262591, the entire disclosure of which is hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a ceramic member of the present invention. Fig. 2 is a view showing an example of a fixing recess, (a) is a plan view, and (b) is a plan view along line B-B in (a). Fig. 3 is a longitudinal plan view showing an embodiment of a manufacturing apparatus for a glazed glass of the present invention. Fig. 4 is a block diagram showing an example of a method of producing a glass article of the present invention. Fig. 5 is a view showing a method of measuring the adhesion strength. Fig. 6 is a graph showing the measurement results of the adhesion strength. Figure 7 is a cross-sectional view of the ceramic member obtained in Example ,, (a) before heat treatment and (b) after heat treatment; (a,) shows that the glass phase is mapped in (a), and (b) ') shows the mapping of the glassy phase in (b). Fig. 8 is a cross-sectional view of the ceramic member obtained in Example 2, 0) before the heat treatment and (b) after the heat treatment; (b,) is the main part of the enlarged display of 201228995. Fig. 9 is a cross-sectional view of the ceramic member obtained in Comparative Example 1, (a) before heat treatment and (b) after heat treatment; and (b') is enlarged to show the main portion of (b). Fig. 10 is a graph showing the heat history used in the case where the glass raw material is melt-solidified in the container composed of the ceramic member in the third embodiment. Fig. 11 is a view showing the results of Example 3, wherein (a) is a sectional view of a glass which has been solidified in a container made of a ceramic member, and (b) is a graph showing a result of measurement of a cold-OH value. Fig. 12 is a view showing the results of Comparative Example 2, wherein (a) is a sectional view of a glass which has been solidified in a container composed of a ceramic component, and (b) is a graph showing a measurement result of a/5-OH value. Fig. 13 is a view showing the results of Comparative Example 3, wherein (a) is a sectional view of a glass which has been solidified in a container made of a ceramic member, and (b) is a graph showing a result of measurement of a 5-OH value. Fig. 14 is a cross-sectional view of a glass which has been solidified in a container composed of a ceramic member, which was obtained in Reference Example 1. Fig. 15 is a graph showing the results of measurement of the cold--0H value of Reference Example 1 [Main element symbol description 1, 21... Ceramic base material 2, 22... Metal spray film 3... Fixing recess 11... Melting groove 12... Pressure defoaming device 12a···pressure defoaming tank 12b·.·rise pipe 12c···down pipe 13...first pipe 13a···cooling mechanism

S 36 201228995 13b...Stirring mechanism 14···Second conduit 15...Cooling tank 23...Thermosetting epoxy adhesive 24,25···Stretching jig 30...Glass 31···Container 32···Shabu-shabu 33...the center of the depth direction of the crucible (the inner surface of the crucible and the outer surface and the area near the glass interface) d...depth g...groove G...molten glass m...thickness p...groove spacing w...groove width X...convex width £37

Claims (1)

201228995 VII. Patent application scope: 1. A method for manufacturing a ceramic member, which is used for manufacturing a ceramic member having a temperature lower than 1500 ° C in use, and characterized in that it has the following steps: 3 to 30% by mass in the content a step of heat-treating at a temperature of 1500 ° C or higher after forming a metal sprayed film on a ceramic substrate composed of a sintered glass of electroforming brick or zircon as a main component, and the metal sprayed film is A spray film selected from at least one metal selected from the group consisting of a platinum group metal and an alloy containing one or more platinum group metals as a main component. 2. The method for producing a ceramic member according to the first aspect of the invention, wherein the temperature at the time of use is 1400 ° C or lower. 3. The method of producing a ceramic member according to the first or second aspect of the invention, wherein the surface of the ceramic substrate is formed with a regular fixing recess, and the metal spray film is formed on the fixing recess. A ceramic member obtained by the production method according to any one of claims 1 to 3, characterized in that the interface space between the ceramic substrate and the metal spray film is filled with glass. phase. 5. A ceramic member having a ceramic substrate and a metal spray film disposed on the surface thereof, and having a temperature of less than 1500 ° C when used, wherein: the metal is selected from the group consisting of platinum group metals And at least one metal in the group consisting of an alloy containing one or more platinum group metals as a main component; the ceramic substrate is composed of a glass phase containing 3 to 30% by mass and mainly composed of electric or monumental stones The sintered monument is configured, and a portion of the glass phase is filled in an interface space between the ceramic substrate and the metal spray film. 6. The ceramic member according to item 5 of the patent application, wherein the temperature at the time of use is 1400 ° C or lower. 7. The ceramic member according to any one of claims 4 to 6, wherein the surface of the ceramic substrate is formed with a regular fixing recess, and the metal spray film is used for embedding the fixing recess. Way to form. A device for manufacturing a molten glass, which is in contact with a molten glass of less than 1500 ° C, is a ceramic member according to any one of claims 4 to 7. A device for manufacturing a molten glass, which is in contact with a molten glass of 1400 ° C or lower, is a ceramic member according to any one of claims 4 to 7. 10. A device for producing molten glass, which is a low-cost manufacturing apparatus for a molten glass using a ceramic base material comprising 3 to 30% by mass of a glass phase and an electroconductive brick or zircon as a main component. And at least a part of the molten glass contacting portion at 1500 ° C, and heat-treating at least the ceramic substrate of the molten glass manufacturing apparatus at a temperature of 1500 ° C or higher, wherein the ceramic substrate is formed with a metal spray The metal sprayed film is selected from the group consisting of a sprayed film of at least one metal composed of a platinum group metal and an alloy containing one or more platinum group metals as a main component. 11. A device for producing molten glass, which comprises a ceramic substrate comprising a sintered glass having 3 to 30% by mass of a glass phase and consisting of an electroforming brick or vermiculite as a main component, and is used in a manufacturing apparatus for molten glass. At least part of the fused glass interface portion at 1500 ° C 39 201228995, and a metal spray _ is formed on the Tauman substrate of the portion of the composition, and then at 150 (). (At the above temperature, at least (4) of the (four) glass manufacturing apparatus is heat-treated with the H substrate having the metal spray film, and the metal spray film is selected from the group consisting of a hard metal and a (4) a spray film of at least one metal selected from the group consisting of alloys containing a metal as a main component. 12. A method for producing a glass of the Hyun (5) glass, which is used in any of the items 8 to 11 of the patent application scope. The manufacturing equipment of the sloping glass is used to manufacture the smelting glass. 13. - a glass material (4) manufacturing device, having: a mechanism for making a molten glass; a forming mechanism for forming the obtained molten glass; and, after forming the glass And the member which is in contact with the molten glass of the lower than i5〇〇t&gt;c is a ceramic member according to any one of claims 4 to 7. 14. A glass article manufacturing The apparatus includes: a mechanism for manufacturing molten glass; a molding mechanism for forming the obtained molten glass; and a cold-cooling mechanism for cooling the formed glass; and the member that is in contact with the molten glass of 140 〇t: or less is used. If you apply for a special A ceramic member according to any one of items 4 to 7. 15. A device for producing a glass article, comprising: a device for producing molten glass according to claim 10 or 11; a glass forming device for molding molten glass And a cold-cooling device for cooling the formed glass. S 40 201228995 16. A method for producing a glass article, which is produced by using a manufacturing apparatus for a glass article according to any one of claims 13 to 15. Glass 41