WO2012070508A1 - Élément en céramique et son procédé de fabrication, dispositif et procédé pour la production de verre fondu, et dispositif et procédé pour la fabrication d'un article en verre - Google Patents

Élément en céramique et son procédé de fabrication, dispositif et procédé pour la production de verre fondu, et dispositif et procédé pour la fabrication d'un article en verre Download PDF

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WO2012070508A1
WO2012070508A1 PCT/JP2011/076730 JP2011076730W WO2012070508A1 WO 2012070508 A1 WO2012070508 A1 WO 2012070508A1 JP 2011076730 W JP2011076730 W JP 2011076730W WO 2012070508 A1 WO2012070508 A1 WO 2012070508A1
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Prior art keywords
glass
molten glass
ceramic
metal
producing
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PCT/JP2011/076730
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English (en)
Japanese (ja)
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泰成 石川
和雄 浜島
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旭硝子株式会社
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Priority to CN201180055948.1A priority Critical patent/CN103221570B/zh
Priority to JP2012545730A priority patent/JP5928340B2/ja
Priority to KR1020137011162A priority patent/KR101768262B1/ko
Publication of WO2012070508A1 publication Critical patent/WO2012070508A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
    • C03B5/1672—Use of materials therefor
    • C03B5/1675—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining
    • C03B5/2252—Refining under reduced pressure, e.g. with vacuum refiners
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
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    • C04B35/16—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 silicates other than clay
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    • 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
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/94—Products characterised by their shape
    • C04B2235/945—Products containing grooves, cuts, recesses or protusions

Definitions

  • the present invention relates to a method for producing a ceramic member, a ceramic member obtained by the production method, a production apparatus for molten glass provided with the ceramic member, a production method for molten glass using the production apparatus, and a glass article comprising the ceramic member.
  • the manufacturing apparatus of this invention and the manufacturing method of the glass article using this manufacturing apparatus.
  • a glass product such as a glass plate is obtained by producing molten glass from a glass raw material and molding the molten glass with a molding apparatus.
  • a method using a vacuum degassing device was proposed to remove bubbles generated in the molten glass after melting the glass raw material in the melting tank and before molding with the molding device (For example, Patent Document 1).
  • Such a vacuum degassing apparatus includes a vacuum degassing tank whose inside is maintained at a predetermined degree of vacuum, and when the molten glass passes through the vacuum degassing tank, the bubbles contained in the molten glass are compared.
  • the temperature of the molten glass flowing out of the melting tank is, for example, about 1200 to 1600 ° C. in the case of soda lime glass, but the temperature of the molten glass introduced into the vacuum degassing apparatus for effective vacuum degassing. Is about 1000 to 1500 ° C., and the temperature of the molten glass introduced into the vacuum degassing vessel is about 1000 to 1400 ° C.
  • a ceramic member such as an electroformed brick is used.
  • a method of coating an electroformed brick with a metal film has also been proposed.
  • a concave portion for anchor is formed on the surface of the electroformed brick.
  • a method is described in which a metal sprayed film is formed so as to fill the concave portion, thereby improving the adhesion strength between the electroformed brick and the metal film and suppressing the peeling of the metal film.
  • the adhesion strength between the electroformed brick and the metal film is not necessarily sufficient.
  • the anchor effect by the recesses has a small effect of improving the adhesion strength against the tensile force in the thickness direction of the metal film.
  • the present invention has been made in view of the above circumstances, and is a method of manufacturing a ceramic member having a ceramic base material such as an electroformed brick and a metal sprayed coating covering the surface thereof. It aims at providing the manufacturing method of the ceramic member excellent in the improvement effect of the adhesive strength with a film
  • the present invention also provides a ceramic member obtained by such a manufacturing method, a manufacturing apparatus for molten glass provided with the ceramic member, a manufacturing method for molten glass using the manufacturing apparatus, a manufacturing apparatus for glass articles provided with the ceramic member, And it aims at providing the manufacturing method of the glass article using this manufacturing apparatus.
  • the inventors of the present invention formed a metal sprayed film on a ceramic substrate containing a glass phase of a predetermined amount or more, and then heat-treated under specific conditions, in particular, the thickness of the metal sprayed film. It has been found that the adhesion strength between the ceramic substrate and the metal sprayed film against the tensile force in the direction is remarkably improved. Moreover, when this heat processing was performed, it also discovered that it became the state with which the glass phase was filled in the micro space of the interface of a ceramic base material and a metal sprayed film, and came to complete this invention.
  • the method for producing a ceramic member according to the present invention is a method for producing a ceramic member having a temperature of less than 1500 ° C. in use, and comprises electrocast brick or zircon as a main component containing 3 to 30% by mass of a glass phase. After forming a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys mainly composed of one or more platinum group metals on a ceramic base material composed of sintered bricks, It has the process of heat-processing at the temperature of 1500 degreeC or more.
  • the temperature during use is preferably 1400 ° C. or lower. It is preferable that a regular anchor recess is formed on the surface of the ceramic substrate, and the metal sprayed film is formed on the anchor recess.
  • the ceramic member of the present invention is a ceramic member obtained by the manufacturing method of the present invention, wherein a glass phase is filled in a space at an interface between the ceramic base material and the metal sprayed film.
  • the ceramic member of the present invention is a ceramic member having a ceramic base material and a metal sprayed film provided on the surface of the ceramic member, and the temperature at the time of use is less than 1500 ° C., wherein the metal is a platinum group metal.
  • the ceramic member of the present invention preferably has a temperature during use of 1400 ° C. or lower. It is preferable that a regular anchor recess is formed on the surface of the ceramic substrate, and the metal sprayed film is formed so as to fill the anchor recess.
  • the present invention provides a molten glass manufacturing apparatus in which the ceramic member of the present invention is used as a member that contacts molten glass of less than 1500 ° C. In the present invention, it is preferable that the ceramic member of the present invention is used for a member that contacts molten glass of 1400 ° C. or lower.
  • the present invention includes 3 to 30% by mass of a glass phase in which a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is formed.
  • a ceramic substrate made of electrocast brick or sintered brick mainly composed of zircon constituting at least a part of a portion of the molten glass manufacturing apparatus in contact with the molten glass of less than 1500 ° C.
  • manufacturing the molten glass Provided is an apparatus for producing molten glass obtained by heat-treating at least the ceramic substrate of the apparatus at a temperature of 1500 ° C. or higher.
  • the present invention uses a ceramic base material composed of electrocast bricks or sintered bricks mainly composed of zircon containing 3 to 30% by mass of a glass phase, and is in contact with molten glass of less than 1500 ° C. in a molten glass production apparatus.
  • At least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is provided on at least a part of the ceramic base material.
  • a molten glass manufacturing apparatus obtained by heat-treating at least a ceramic substrate on which a metal sprayed film is formed in a molten glass manufacturing apparatus at a temperature of 1500 ° C. or higher.
  • This invention provides the manufacturing method of a molten glass which manufactures a molten glass using the manufacturing apparatus of the molten glass of this invention.
  • the present invention has a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after molding, and a member that contacts the molten glass at a temperature lower than 1500 ° C. Furthermore, a glass article manufacturing apparatus in which the ceramic member of the present invention is used is provided.
  • the present invention has a means for manufacturing molten glass, a forming means for forming the obtained molten glass, and a slow cooling means for gradually cooling the glass after forming, and a member that contacts the molten glass at 1400 ° C. or lower.
  • the ceramic member of the present invention includes 3 to 30% by mass of a glass phase in which a sprayed film of at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is formed.
  • a ceramic substrate made of electrocast brick or sintered brick mainly composed of zircon constituting at least a part of a portion of the molten glass manufacturing apparatus in contact with the molten glass of less than 1500 ° C., manufacturing the molten glass An apparatus for producing molten glass obtained by heat-treating at least the ceramic substrate of the apparatus at a temperature of 1500 ° C.
  • the present invention uses a ceramic base material composed of electrocast bricks or sintered bricks mainly composed of zircon containing 3 to 30% by mass of a glass phase, and is in contact with molten glass of less than 1500 ° C. in a molten glass production apparatus. At least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is provided on at least a part of the ceramic base material.
  • a molten glass manufacturing apparatus is formed by heat-treating a ceramic substrate on which at least the metal sprayed film of the molten glass manufacturing apparatus is formed at a temperature of 1500 ° C. or higher.
  • a glass article manufacturing apparatus having a glass forming apparatus for performing cooling and a slow cooling apparatus for gradually cooling the formed glass. This invention provides the manufacturing method of a glass article which manufactures a glass article using the manufacturing apparatus of the glass article of this invention.
  • a part of the glass phase is present in a space at the interface between the ceramic base material having a glass phase and a metal spray coating (hereinafter also referred to as a metal spray coating) covering the surface thereof.
  • a metal spray coating hereinafter also referred to as a metal spray coating
  • the apparatus for producing molten glass of the present invention is excellent in corrosion resistance against molten glass because the surface of the member in contact with the molten glass is coated with the metal sprayed film, and the metal sprayed film is difficult to peel off. Excellent. By using the apparatus for producing molten glass of the present invention, it is possible to stably produce molten glass and glass articles.
  • Example 3 it is a graph which shows the heat history used when melting and solidifying a glass raw material within the container which consists of a ceramic member.
  • the results of Example 3 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of ⁇ -OH values.
  • the results of Comparative Example 2 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of ⁇ -OH values.
  • Comparative Example 3 The results of Comparative Example 3 are shown, in which (a) is a cross-sectional photograph of glass solidified in a container made of a ceramic member, and (b) is a graph showing measurement results of ⁇ -OH values. It is a cross-sectional photograph of the glass solidified in the container which consists of a ceramic member obtained in Reference Example 1. 6 is a graph showing the measurement result of ⁇ -OH value in Reference Example 1.
  • FIG. 1 is a cross-sectional view showing an embodiment of the ceramic member of the present invention.
  • Reference numeral 1 denotes a ceramic base material
  • reference numeral 2 denotes a metal sprayed film
  • reference numeral 3 denotes an anchor recess.
  • the ceramic member of the present invention has a ceramic base material 1 and a metal sprayed film 2 provided on the surface thereof, and oozes out from the ceramic base material into a space at the interface between the ceramic base material 1 and the metal sprayed film 2.
  • the filled glass phase (not shown) is filled.
  • ⁇ Ceramic substrate> As the ceramic substrate 1, a brick containing 3 to 30% by mass of a glass phase is used. In order to obtain corrosion resistance to the molten glass, bricks having high density are preferable. From this viewpoint, electrocast bricks mainly composed of zirconia and the like described below or sintered bricks mainly composed of zircon are used. When the content of the glass phase is less than 3% by mass, a phenomenon that the glass phase exudes from the ceramic substrate 1 hardly occurs when heat treatment described later is performed. If it exceeds 30% by mass, the amount of oozing out of the glass phase increases and the metal sprayed film tends to swell.
  • An electroformed brick is a brick that has at least one component selected from the group consisting of zirconia, alumina, silicate alumina, zircon-mullite, silica, and titania, and is cast by melting these raw materials completely in an electric furnace. , Consisting essentially of a crystal phase and a glass phase. In the present invention, one having a glass phase content of 3 to 30% by mass can be selected from known electroformed bricks.
  • the content of the glass phase in the ceramic substrate in the present invention is a value obtained by obtaining the area ratio of the glass phase relative to the total area of the crystal phase and the glass phase based on the cross-sectional photograph and converting this to the mass ratio. It is.
  • a glass phase and a crystal Obtained by binarizing the phase are formed by binarizing the phase.
  • the electroformed brick used in the present invention include AZS (Al 2 O 3 —SiO 2 —ZrO 2 ) brick, high zirconia brick with increased zirconia content, and the like. Of these, AZS bricks are preferred because cracks that occur during heating or heat fluctuation are unlikely to occur.
  • the content of the glass phase of the AZS brick is preferably 10 to 25% by mass, and more preferably 15 to 20% by mass.
  • the content of the glass phase of the AZS brick can be adjusted by the mixing ratio of the raw materials.
  • the composition of the AZS brick is preferably 40 to 55% by mass of Al 2 O 3 , 10 to 15% by mass of SiO 2 , 30 to 45% by mass of ZrO 2 , and 0.5 to 2.5% by mass of Na 2 O. .
  • Other components such as various metal oxides and inevitable impurities constituting the glass phase are preferably 2% or less, more preferably 1% or less.
  • the content of the glass phase of the high zirconia brick is preferably 2 to 20% by mass, and more preferably 4 to 15% by mass.
  • the content of the glass phase of the high zirconia brick can be adjusted by blending.
  • Al 2 O 3 is preferably 0.5 to 20% by mass
  • SiO 2 is 2 to 10% by mass
  • ZrO 2 is preferably 80 to 96% by mass.
  • the other components include, for example, various metal oxides and inevitable impurities constituting the glass phase, including Na 2 O, preferably 3% or less and more preferably 2% or less.
  • the sintered brick mainly composed of zircon is a sintered brick containing 80 to 96% by mass of zircon, and substantially consists of a crystal phase and a glass phase.
  • one having a glass phase content of 3 to 30% by mass can be selected from among known sintered bricks mainly composed of zircon.
  • the content of the glass phase in the sintered brick mainly composed of zircon is preferably 3 to 10% by mass, and more preferably 4 to 10% by mass. Content of the glass phase of the sintered brick which has a main component of zircon can be adjusted with the compounding ratio of raw material powder.
  • the composition of the sintered brick mainly composed of zircon is preferably 30 to 45% by mass of SiO 2 , 50 to 70% by mass of ZrO 2 and 5% by mass or less of other metal oxides.
  • a regular anchor recess 3 is formed on the surface of the ceramic substrate 1.
  • the adhesion strength between the ceramic substrate 1 and the metal sprayed film 2 is further improved.
  • the adhesion strength against tensile stress in the direction parallel to the surface of the ceramic substrate 1 is improved.
  • 2A and 2B show an example of the shape of the anchor recess 3.
  • FIG. 2A is a plan view
  • FIG. 2B is a cross-sectional view taken along line BB in FIG.
  • the anchor recess 3 of this example is provided with a plurality of linear grooves g having a rectangular cross-sectional shape in a lattice shape.
  • each groove g is perpendicular to the surface of the ceramic substrate 1, and the groove width w is constant.
  • the groove g constituting the anchor recess 3 needs to have a certain depth. However, if the depth is too deep, the strength of the surface layer portion of the ceramic substrate 1 is reduced and processed. It is also difficult.
  • the depth d of the groove g is preferably about 50 to 350 ⁇ m, more preferably about 150 to 250 ⁇ 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 (inter-groove interval, which indicates the distance between the center lines of adjacent grooves) p. It is preferable to reduce the groove pitch p in order to reduce the stress applied to one place by dispersing the above.
  • the groove pitch p is preferably about 2.5 mm or less, more preferably about 1.5 mm or less.
  • the groove width w is narrow, and the groove width w is preferably narrow also from the viewpoint of maintaining the strength of the surface layer portion of the ceramic substrate 1.
  • the groove width w is set to be equal to or larger than the particle size of the spray particles.
  • the groove width w is preferably 100 ⁇ m or more, and more preferably about 150 ⁇ m or more.
  • the tensile stress applied from the metal spray film 2 in the direction parallel to the surface of the ceramic substrate 1 increases as the thickness m of the metal spray film 2 formed on the ceramic substrate 1 increases.
  • the width x of the convex portion is preferably about 4 times or more the thickness m of the metal sprayed film 2. Further, considering the point that the groove pitch p is reduced, the preferable width x of the convex portion is about 2.5 to 5 times the thickness m of the film.
  • the p / d value at which the stress is appropriately dispersed is obtained based on the above-mentioned preferable groove pitch p and groove depth d, it is preferably about 3 to 8.
  • the anchor recess is not limited to the shape shown in FIG.
  • substantially cylindrical holes may be regularly formed.
  • intermittent holes are formed as an alternative to the grooves 3 as shown in FIG. 2, it is preferable to form holes at crossing positions of the orthogonal lattice (cross grid).
  • it is preferably arranged at a staggered (staggered layout) position such that the hole pitch distance is uniform.
  • the hole pitch distance is preferably about 0.7 to 2.5 mm, more preferably about 1.0 to 1.6 mm.
  • the pore diameter is preferably about 200 to 500 ⁇ m, more preferably 300 to 400 ⁇ m.
  • the depth of the hole is preferably about 200 to 600 ⁇ m, more preferably about 300 to 500 ⁇ m.
  • the anchor recess 3 can be formed mechanically using a grinder equipped with a grinding blade composed of, for example, a grindstone or a diamond blade. Or you may carry out using high energy beams, such as a laser, and a high voltage
  • the anchor recess 3 is hole-shaped, it can be formed using a grinding tool in the form of a pin drill or the like, or a high energy beam such as a laser or a high-pressure water stream. If the surface of the ceramic substrate 1 is adjusted to a highly accurate surface by cutting with a grinder or the like in advance before forming the anchor recess 3, the metal sprayed film 2 can be prevented from peeling off due to unexpected unevenness. This is preferable.
  • the anchor recess 3 may be either a groove shape or a hole shape.
  • the hole shape the closed space (inside space of the hole) closed by the metal sprayed film is relatively small, and the hole has a uniform shape. Since the closed space can be formed one by one, the adhesion strength against the tensile force in the thickness direction of the metal sprayed film 2 is improved by filling the interface between the ceramic substrate 1 and the metal sprayed film 2 with a glass phase. It is preferable in that the effect is large.
  • the groove-shaped direction has a relatively large closed space (inner space in the groove) closed by the metal sprayed film, and the closed space is constituted by a large groove, so the above effect is relatively low.
  • the metal sprayed film 2 is a metal film formed by a spraying method.
  • the thermal spraying method is a method in which metal particles heated to a high temperature are injected onto a substrate and a coating film is formed by deposition of the metal particles. Therefore, the metal sprayed film has a granular deposited structure in the cross section, unlike a solidified film formed by applying molten metal or the like.
  • the metal at least one metal selected from the group consisting of platinum group metals and alloys composed mainly of one or more platinum group metals is used.
  • the platinum group metal include platinum (Pt), iridium (Ir), ruthenium (Ru), and rhodium (Rh).
  • the alloy containing a platinum group metal as a main component include platinum alloys such as a Pt-5% Au alloy, a Pt-10% Ir alloy, and a Pt-10% Rh alloy.
  • the metal sprayed film 2 is formed on the ceramic substrate 1.
  • the anchor recess 3 is provided on the surface of the ceramic substrate 1, the metal sprayed film 2 is formed so as to cover the anchor recess 3.
  • a thermal spraying method a known thermal spraying method such as a laser spraying method, a wire frame spraying method, a plasma spraying method, an arc spraying method, an oxyhydrogen flame spraying method, or the like can be appropriately used.
  • the particle diameter of the metal particles (flying spray particle diameter) injected in the thermal spraying method is preferably finer and can be reduced to about 40 ⁇ m depending on the type of thermal spraying method, but is generally about 50 to 150 ⁇ m.
  • the metal particles injected by the thermal spraying method are deposited on the surface of the ceramic substrate 1 to form the metal sprayed film 2.
  • the metal particles injected by the thermal spraying method fill the recess 3 and further deposit on the surface to form the metal sprayed film 2.
  • the thickness m of the metal sprayed film 2 can be appropriately adjusted depending on the amount of spraying. The greater the thickness, the greater the strain due to the tensile stress in the direction parallel to the surface of the ceramic substrate 1, so the thickness m of the sprayed film 2 (if there is a recess, the thickness at the portion without the recess) is 100 to 400 ⁇ m. The preferred range is 200 to 350 ⁇ m.
  • the temperature of the ceramic substrate during the thermal spraying is increased, for example, by preheating (that is, preheating). It is preferable to reduce the temperature difference from the base material because the adhesion between the metal sprayed film 2 and the ceramic base material 1 is improved. In this case, it is preferable that after the thermal spraying in a state where the ceramic substrate 1 is heated (preheated), it is gradually cooled to room temperature.
  • the temperature (preheating temperature) of the ceramic substrate 1 at the time of thermal spraying is preferably not higher than the solidification temperature of the injected metal particles, specifically about 200 to 500 ° C., more preferably 300 to 400 ° C.
  • the cooling rate during slow cooling should be as slow as possible, preferably about 10 ° C./min or less.
  • heat treatment is performed at a temperature of 1500 ° C. or higher with the metal sprayed film 2 formed on the ceramic substrate 1.
  • the glass phase oozes out from the ceramic base material 1 into a minute space at the interface between the ceramic base material 1 and the metal sprayed film 2, and a state in which the glass phase is filled in the space is obtained. .
  • This is because when heated to a high temperature of 1500 ° C. or higher, the glass phase in the ceramic substrate easily flows, and due to the difference in thermal expansion between the glass phase and the ceramic phase, the glass phase is extruded into a minute space, It is thought that it spreads in the space.
  • the state in which the glass phase is filled in the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 means that the glass phase exists between the ceramic substrate 1 and the metal sprayed film 2 and the glass At least a part of the phase refers to a state in contact with both the ceramic substrate 1 and the metal sprayed film 2. Although some space may remain at the interface between the ceramic substrate 1 and the metal sprayed film 2, such space does not remain as much as possible in order to obtain good adhesion strength between the ceramic substrate 1 and the metal sprayed film 2. It is preferable.
  • the remaining space without the glass phase is 20 area% or less with respect to the entire area of the space existing at the interface between the ceramic substrate 1 and the metal sprayed film 2. It is preferably 10 area% or less, and most preferably 0 area%.
  • the heat treatment temperature is lower than 1500 ° C., it is difficult to obtain a state where the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase. This is because the flow state of the glass phase is insufficient, so that it cannot spread in the space in a short time, and the ceramic phase and the glass phase react with the passage of time. It is considered that a state where the space is filled with the glass phase cannot be obtained.
  • the upper limit of the heat treatment temperature needs to be lower than the melting point of the metal constituting the sprayed film 2.
  • the heat treatment temperature is preferably set so that the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase in a preferable heat treatment time described later, which is lower than the melting point of the sprayed film 2.
  • the preferred heat treatment temperature varies depending on the component composition of the ceramic substrate 1, but is preferably about 1500 to 1700 ° C, and more preferably about 1500 to 1600 ° C. Since the glass phase has high fluidity when the heat treatment temperature is within these ranges, the influence of the reaction between the ceramic phase and the glass phase on the effect of filling the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 with the glass phase is low. .
  • the heat treatment time is too short, a large amount of space remains at the interface between the ceramic substrate 1 and the metal sprayed film 2.
  • the ceramic phase and the glass phase react with the passage of time, so that the phenomenon in which the glass phase is extruded into the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 does not easily proceed. Therefore, it is preferable to set the heat treatment time so that these disadvantages do not occur. For example, it is preferably about 1 to 100 hours, and more preferably 10 to 50 hours.
  • the ceramic member of the present invention in which the space at the interface between the ceramic substrate 1 and the metal sprayed film 2 is filled with the glass phase derived from the ceramic substrate is obtained.
  • the ceramic member of the present invention is a member having a temperature of less than 1500 ° C. during use. That is, it is used for a portion where the temperature during use is not assumed to be 1500 ° C. or higher. In a member whose operating temperature is 1500 ° C. or higher, there is a possibility that the same effect as that of the present invention may be obtained as a result without performing heat treatment at 1500 ° C. or higher before use, and the present invention is applied to such a member. This is because the necessity is low. For this reason, the ceramic member of the present invention is preferably a member having a temperature of 1450 ° C. or lower, more preferably a member having a temperature of 1400 ° C. or lower.
  • the ceramic member of the present invention is excellent in corrosion resistance against molten glass. Therefore, the ceramic member of this invention is used suitably as a member which contacts the molten glass below 1500 degreeC in the apparatus used for manufacture of molten glass.
  • the ceramic member of the present invention is more preferably used as a member that contacts molten glass at 1450 ° C. or lower, and more preferably as a member that contacts molten glass at 1400 ° C. or lower in an apparatus used for manufacturing molten glass. Used.
  • the molten glass that has flowed out of the melting tank is preferably used as a member that comes into contact with the molten glass at a temperature of less than 1500 ° C., preferably through a vacuum degassing apparatus and sent to the molding apparatus.
  • the molten glass that has flowed out of the melting tank is more preferably used as a member that contacts the molten glass at 1450 ° C. or lower in the flow path until it is sent to the molding device through a vacuum degassing device, It is more suitably used as a member that contacts molten glass at 1400 ° C. or lower.
  • a member constituting the inner wall of the vacuum degassing tank a member constituting the inner wall of the melting riser pipe provided upstream of the vacuum degassing tank, or a member constituting the inner wall of the downcomer pipe provided downstream of the vacuum degassing tank Is mentioned.
  • the metal sprayed film 2 is provided on the surface of the ceramic substrate 1, erosion of the ceramic substrate 1 can be suppressed even when it comes into contact with molten glass. Moreover, since the adhesion strength between the ceramic substrate 1 and the metal sprayed film 2 is excellent as shown in the examples described later, the metal sprayed film 2 is hardly peeled off and excellent in durability.
  • the ceramic member of the present invention when used as a member that comes into contact with molten glass, bubbles are generated in the molten glass because the glass phase is filled in the space between the ceramic substrate and the metal sprayed film.
  • the effect which suppresses is acquired. That is, when moisture present in the molten glass is decomposed into oxygen and hydrogen on the surface of the metal spray film by the catalytic action of the platinum group metal, hydrogen passes through the metal spray film and oxygen passes through the metal spray film. It remains on its surface without. At this time, if hydrogen stays on the metal sprayed film, it combines with oxygen on the surface of the metal sprayed film to generate water, so that oxygen does not become bubbles.
  • the apparatus for producing molten glass of the present invention uses the ceramic member of the present invention as a member that contacts molten glass of less than 1500 ° C.
  • the ceramic member of the present invention is preferably used for a member that contacts the molten glass at 1450 ° C. or lower, and the present invention is preferably applied to a member that contacts the molten glass at 1400 ° C. or lower. More preferably, the ceramic member is used.
  • the apparatus for producing molten glass of the present invention comprises a glass phase in which a sprayed film of at least one metal selected from the group consisting of a platinum group metal and an alloy containing at least one platinum group metal as a main component is formed. 3 to 30% by mass, using a ceramic base material made of electrocast brick or sintered brick mainly composed of zircon, less than 1500 ° C., preferably 1450 ° C. or less, more preferably 1400 ° C. of a molten glass production apparatus. It constitutes at least a part of a portion in contact with the molten glass having a temperature of not higher than ° C., and at least the ceramic substrate of the molten glass manufacturing apparatus is heat treated at a temperature of 1500 ° C.
  • the apparatus for producing molten glass of the present invention is an apparatus for producing molten glass using a ceramic base material comprising 3-30% by mass of a glass phase and comprising a sintered brick mainly composed of electroformed brick or zircon. It constitutes at least a part of a part in contact with the molten glass of less than 1500 ° C., preferably 1450 ° C. or less, more preferably 1400 ° C.
  • FIG. 3 is a longitudinal sectional view showing an embodiment of the apparatus for producing molten glass according to the present invention.
  • the apparatus of this embodiment is a melting tank 11 for melting glass raw materials and homogenizing and clarifying molten glass.
  • the internal pressure is set to be lower than atmospheric pressure, and bubbles in the molten glass supplied from the melting tank 11 are floated.
  • the vacuum degassing device 12 for breaking the bubbles, the first conduit 13 connecting the melting tank 11 and the vacuum degassing device 12, and the molten glass flowing out from the vacuum degassing device 12 through the cooling tank 15 in the next step And a second conduit 14 for feeding to the forming means.
  • symbol G in a figure shows a molten glass.
  • the first conduit 13 is provided with a cooling means 13a and a stirring means 13b, and the molten glass flowing out of the melting tank 11 is cooled to 1000 ° C. or more and less than 1500 ° C. in the first conduit 13, It is introduced into the vacuum degassing device 12.
  • the vacuum degassing apparatus 12 includes a vacuum degassing tank 12a.
  • the upstream side of the vacuum degassing tank 12a communicates with the first conduit 13 through the riser 12b, and is downstream of the vacuum degassing tank 12a.
  • the side communicates with the second conduit 14 via the downcomer 12c.
  • the insides of the vacuum degassing tank 12a, the rising pipe 12b, and the lowering pipe 12c are maintained in a vacuum environment, and the molten glass in the first conduit 13 is sucked up to the vacuum degassing tank 12a through the rising pipe 12b by the siphon effect. It is configured as follows. Further, the conduit 14 and subsequent parts are connected to the forming means via the cooling tank 15.
  • the members constituting the inner walls of the reduced pressure defoaming tank 12a, the rising pipe 12b, the lowering pipe 12c, and the cooling tank 15 of the reduced pressure defoaming apparatus 12 are ceramic members or metal according to the present invention. It consists of what heat-processes the ceramic base material in which the sprayed film was formed. That is, the inner walls of the vacuum degassing tank 12a, the riser pipe 12b, the downfall pipe 12c, and the cooling tank 15 are made of a ceramic base material whose inner surface is coated with a metal sprayed film. A glass phase is filled in a minute space at the interface.
  • the vacuum degassing apparatus 12 and the cooling tank 15 are first formed of a ceramic base material in which the inner walls of the vacuum degassing tank 12a, the ascending pipe 12b, the descending pipe 12c, and the cooling tank 15 are previously coated with a metal sprayed film. Then, after assembling into a series of shapes from the vacuum degassing apparatus 12 to the cooling tank 15, the inside of the series of structures including the vacuum degassing apparatus 12 and the cooling tank 15 is subjected to heat treatment at a predetermined temperature of 1500 ° C. or more, Subsequently, it is manufactured by a method of cooling below the use temperature.
  • the ceramic member of the present invention forms the inner wall of the vacuum degassing tank 12a, the rising pipe 12b, the descending pipe 12c, and the cooling tank 15, and assembles into a series of shapes from the vacuum degassing apparatus 12 to the cooling tank 15. You can also. Further, the inner walls of the vacuum degassing tank 12a, the rising pipe 12b, the downfalling pipe 12c, and the cooling tank 15 are formed of a ceramic base material, and a metal sprayed film is formed on the surface of the base material on the side in contact with the molten glass. Then, the ceramic base material on which the metal sprayed film is formed can be heat-treated at a temperature of 1500 ° C. or higher.
  • the device After the device is manufactured in this way, it is used at a use temperature of less than 1500 ° C. Moreover, after manufacturing an apparatus in this way, it is preferably used at a use temperature of 1450 ° C. or less, and more preferably used at a use temperature of 1400 ° C. or less.
  • part using the ceramic member of this invention are not limited to said example. For example, since the molten glass temperature in the cooling bath 15 is lower than that in the upstream portion, the portion using the ceramic member of the present invention may be only the vacuum degassing device 12 and not used in the cooling bath 15.
  • the portion of the vacuum degassing apparatus 12 that uses the ceramic member of the present invention may be only the vacuum degassing tank 12a, only the rising pipe 12b and the lowering pipe 12c, or only the lowering pipe 12c. Further, the ceramic member of the present invention may be used for the inner walls of the first conduit 13 and the second conduit 14.
  • the manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass using the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts the molten glass below 1500 degreeC. Moreover, the manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass which uses the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts 1450 degrees C or less molten glass. Furthermore, the manufacturing method of the molten glass of this invention is a method of manufacturing a molten glass more preferable to use the manufacturing apparatus with which the ceramic member of this invention is used for the member which contacts 1400 degrees C or less molten glass. .
  • the molten glass that has flowed out of the melting tank 11 is 1000 ° C. or more and less than 1500 ° C. in the first conduit 13. After being cooled, it is introduced into the vacuum deaerator 12. Moreover, it is preferable that the molten glass flowing out from the melting tank 11 is introduced into the vacuum degassing apparatus 12 after being cooled to 1000 ° C. or higher and 1450 ° C. or lower in the first conduit 13. Furthermore, it is more preferable that the molten glass flowing out from the melting tank 11 is introduced into the vacuum degassing apparatus 12 after being cooled to 1000 ° C. or higher and 1400 ° C.
  • the inner walls of the reduced pressure defoaming tank 12a, the rising pipe 12b, the descending pipe 12c, and the cooling tank 15 of the vacuum degassing apparatus 12 are in contact with molten glass at 1000 ° C. or more and less than 1500 ° C., but the ceramic base constituting the inner wall Since the surface (that is, the inner surface) of the material is coated with the metal sprayed film, the corrosion resistance to the molten glass is excellent. Further, since the adhesion strength between the ceramic substrate and the metal sprayed film is excellent, the sprayed film is hardly peeled off and excellent in durability.
  • the hydrogen can remain on the metal spray coating. Therefore, as described above, the hydrogen can be recombined with oxygen generated by the decomposition of moisture to generate water, so that generation of bubbles in the molten glass due to the oxygen is suppressed. be able to.
  • the apparatus for producing a glass article of the present invention comprises a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, and is less than 1500 ° C.
  • the ceramic member of this invention is used for the member which contacts molten glass.
  • the apparatus for producing a glass article of the present invention has a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, and 1450 ° C. It is preferable that the ceramic member of this invention is used for the member which contacts the following molten glass.
  • the apparatus for producing a glass article of the present invention comprises a means for producing molten glass, a shaping means for shaping the obtained molten glass, and a slow cooling means for gradually cooling the glass after shaping, at 1400 ° C. It is more preferable that the ceramic member of the present invention is used for the following member that contacts the molten glass.
  • the means for producing molten glass is preferably the molten glass production apparatus of the present invention.
  • the apparatus has a forming means for forming molten glass downstream of the molten glass flow direction of the molten glass manufacturing apparatus, and a slow cooling means for gradually cooling the glass after forming downstream thereof. Can do.
  • a processing means for further cutting and polishing may be provided downstream of the slow cooling means.
  • FIG. 4 is a flowchart showing an example of a glass article manufacturing method using the glass article manufacturing apparatus according to the present invention.
  • a molten glass G is obtained by a glass melting step S1 using the molten glass manufacturing apparatus of FIG. 3, and the molten glass G is sent to a forming means. After passing through the forming step S2 for forming into a shape, it is gradually cooled in the slow cooling step S3. Thereafter, the glass article G5 can be obtained by post-processing such as cutting and polishing in the post-processing step S4 as necessary.
  • Example 1 In this example, AZS (Al 2 O 3 —SiO 2 —ZrO 2 ) brick is used as the ceramic substrate, and the surface of the brick is subjected to drilling with a regular arrangement as described below, and then metal spraying is performed. A substrate with a metal film was obtained, and the substrate with a metal film was subjected to heat treatment to produce a ceramic member.
  • the base material on which the metal sprayed film is formed on the surface of the ceramic base material is also referred to as a base material with a metal film.
  • Table 1 shows the results of measuring the component composition of the ceramic substrate used by fluorescent X-ray analysis. Further, the glass phase content obtained based on the cross-sectional photograph of the base material with the metal film before the heat treatment is shown in Table 1 (the same applies to Example 2 and Comparative Example 1 below). The glass phase content is calculated by the following method. Using an electron microscope, a 50-fold backscattered electron image (composition image) of the cross section of the base material with a metal film before heat treatment is taken from the base material surface to the position of 20 mm toward the inside of the base material. To do.
  • AZS bricks were cut into 50 mm long ⁇ 50 mm wide ⁇ 10 mm high brick pieces, and anchor concave portions were formed on one side of the brick pieces using a fiber laser.
  • the anchor recess was a substantially cylindrical hole, the hole diameter was 300 ⁇ m, the hole depth was 400 ⁇ m, and the hole pitch distance was 1 mm. Subsequently, the brick piece was heated to 300 ° C.
  • Example 2 In Example 1, except that the ceramic substrate was changed to high zirconia brick, a substrate with a metal film was obtained in the same manner, and the substrate with the metal film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. did. As a control, an untreated sample not subjected to heat treatment was prepared in the same manner as in Example 1.
  • Example 1 In Example 1, except that the ceramic base material was changed to ⁇ alumina brick, a base material with a metal film was obtained in the same manner, and the base material with the metal film was subjected to the same heat treatment as in Example 1 to produce a ceramic member. did. As a control, an untreated sample not subjected to heat treatment was prepared in the same manner as in Example 1.
  • the load when the metal sprayed film 22 peeled off was measured. From the value (P) of the load at the time of peeling and the area (S) of the plate-like piece (ceramic member), the adhesion strength (P / S, unit is MPa) was determined. The result is shown in FIG.
  • FIG. 7 is a photograph obtained in Example 1
  • FIG. 8 is a photograph obtained in Example 2
  • FIG. 9 is a photograph obtained in Comparative Example 1.
  • Reference numeral 21 denotes a ceramic substrate
  • 22 denotes a metal sprayed film.
  • FIG. 7 (a) is a cross-sectional photograph before the heat treatment
  • (b) is a cross-sectional photograph after the heat treatment
  • (a ′) is a mapping of the glass phase shown in the photograph (a)
  • (b ′) Is a mapping of the glass phase in the photograph of (b).
  • FIGS. 7A to 9A in the base material with the metal film before the heat treatment, there is a minute gap (space) at the interface between the ceramic base material 21 and the metal sprayed film 22.
  • FIGS. 7 and 8 (b) in the ceramic members after the heat treatment of Examples 1 and 2, there is no gap at the interface between the ceramic base material 21 and the metal sprayed film 22, and FIGS.
  • FIG. 9B in the ceramic member after the heat treatment of Comparative Example 1, there is a gap at the interface between the ceramic base material 21 and the metal sprayed film 22, and FIG. As shown in b '), no oozing of the glass phase to the interface is observed.
  • Example 3 As a molten glass manufacturing apparatus, a glass melting container made of a ceramic member was prepared as described below, and the glass raw material was melted at 1400 ° C. in the container and then cooled. Thereafter, the moisture content in the glass and the presence or absence of bubbles in the vicinity of the inner wall of the container were examined by an evaluation method described later. First, using a ceramic base material made of a high zirconia brick of the same material as used in Example 2 and provided with anchor recesses on one side in the same manner as in Example 1, the outer diameter is 75 mm and the height of the outer wall is high.
  • a bottomed cylindrical container having a thickness of 55 mm, an inner diameter of 50 mm, and an inner wall depth of 40 mm was prepared.
  • the surface provided with the anchor recess was made the inner surface.
  • this container was heated to 300 ° C. in an air atmosphere, and a metal sprayed film having a film thickness of 300 ⁇ m was formed on the inner surface in the same manner as in Example 1 to obtain a container made of a substrate with a metal film. .
  • this container was placed in an electric furnace under the atmosphere and subjected to heat treatment at 1600 ° C. for 5 hours to obtain a container made of a ceramic member.
  • Example 3 In carrying out the above Example 3, the obtained container was placed in a heating furnace, and the thermal history shown in FIG. 10 was added under normal pressure.
  • shaft of FIG. 10 shows the atmospheric temperature in a heating furnace.
  • the temperature is raised from room temperature to 1400 ° C. over 4 hours and 40 minutes.
  • the glass raw material of borosilicate glass is put into the container and heated at 1400 ° C. for 1 hour to melt the glass raw material. I let you. Thereafter, the glass was rapidly cooled to 720 ° C. and held at 720 ° C. for 1 hour, then the temperature was lowered to 600 ° C. over 2 hours and further cooled to room temperature over 3 hours to obtain a glass solidified in the container. .
  • Example 3 glass solidified in the container was obtained in the same manner as in Example 3 except that the container made of the metal film-coated substrate was not subjected to heat treatment.
  • the material of the ceramic substrate was changed from a high zirconia brick to the same ⁇ alumina brick as used in Comparative Example 1, and was made of a substrate with a metal film in the same manner as in Example 3.
  • a container was obtained, and the same heat treatment as in Example 3 was performed on the container to prepare a container made of a ceramic member. Using this container, a glass solidified in the container was obtained in the same manner as in Example 3.
  • the ⁇ -OH value of the glass was measured as an indicator of the water content in the glass.
  • the ⁇ -OH value (unit: mm ⁇ 1 ) of the glass was measured by measuring the absorbance of the glass sample with respect to light having a wavelength of 2.75 to 2.95 ⁇ m, and determining the maximum value ⁇ max as the thickness (mm) of the glass sample. It can be obtained by dividing.
  • the glass solidified in the container obtained in each of the above examples was cut along with the container along a cut surface along the height direction, and a longitudinal section sample having a thickness of 1 mm was cut out.
  • the ⁇ -OH value was measured by the above method for the region of the obtained longitudinal section sample at the center in the height direction of the container and in the vicinity of the interface between the inner wall of the container and the solidified glass. A photograph of the area was taken.
  • the results of Example 3 are shown in FIG. 11, the results of Comparative Example 2 are shown in FIG. 12, and the results of Comparative Example 3 are shown in FIG. (A) of each figure is a cross-sectional photograph, and the reference position of the interface is indicated by an arrow.
  • reference numeral 21 denotes a ceramic substrate
  • 22 denotes a metal sprayed film
  • 30 denotes glass.
  • (B) of each figure is a graph showing the measurement result of ⁇ -OH value, the horizontal axis shows the distance (unit: ⁇ m) in the horizontal direction of the cross-sectional photograph of (a), and the vertical axis shows ⁇ -OH value (unit). : Mm ⁇ 1 ).
  • a position corresponding to the reference position of the interface is indicated by an arrow.
  • the lower layer of the metal sprayed film is made of a ceramic base material.
  • the water content when the lower layer of glass was made of glass was measured. That is, in Example 3, when a glass material of borosilicate glass is introduced into the container when the temperature reaches 1400 ° C. after the container made of the ceramic member is placed in the heating furnace, A part of the glass raw material was directly put into a container made of the ceramic member, and the remainder of the glass raw material was put in a separately prepared platinum rhodium crucible, and the crucible was put in the container. Other than that obtained the glass solidified in the container like Example 3.
  • FIG. FIG. 14 is a photograph showing the longitudinal section. In this example, the crucible 32 is embedded in the solidified glass 30 in the container 31 made of a ceramic member, and both the inner surface and the outer surface of the crucible 32 are in contact with the solidified glass.
  • the glass solidified in the container obtained in this example was cut along the height direction along with the container and the crucible, and a longitudinal cross-sectional sample having a thickness of 1 mm was cut out.
  • a longitudinal cross-sectional sample having a thickness of 1 mm was cut out.
  • region (it shows with the code
  • the ⁇ -OH value was measured at The results are shown in FIG.
  • the horizontal axis indicates the distance in the horizontal direction of the cross-sectional photograph of FIG. 14, and the vertical axis indicates the ⁇ -OH value.
  • the position corresponding to the side wall of the crucible is indicated by an arrow.
  • the longitudinal section sample used for measuring the ⁇ -OH value no bubbles were observed in the glass.
  • the comparative example 2 used the high zirconia brick containing 6 mass% of glass phases as a ceramic base material, since it did not heat-process at 1500 degreeC before use, even if it heats at 1400 degreeC for 1 hour at the time of use In the cross-sectional photograph, a minute gap was observed at the interface between the metal sprayed film and the ceramic substrate.
  • Comparative Example 3 since the ceramic base material contains only 0.8% by mass of the glass phase, even if heat treatment at 1500 ° C. is performed before use, there is a minute amount at the interface between the metal sprayed film and the ceramic base material in the cross-sectional photograph. A gap was observed.
  • the ceramic member excellent in the adhesive strength of a ceramic base material and a metal sprayed film can be obtained, This ceramic member is excellent in the corrosion resistance with respect to molten glass, and the ceramic member for the manufacturing apparatus of molten glass Useful as.
  • the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-262591 filed on Nov. 25, 2010 are incorporated herein as the disclosure of the present invention. .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un élément en céramique comportant un substrat céramique tel qu'une brique électrofondue, et un film métallique déposé par pulvérisation recouvrant la surface de la brique, le procédé améliorant considérablement la résistance d'adhérence entre l'élément en céramique et le film métallique déposé par pulvérisation. Ledit élément en céramique est destiné à être utilisé à des températures inférieures à 1500 °C. Le procédé de fabrication d'un élément en céramique comprend une étape consistant à effectuer un traitement thermique à une température d'au moins 1500 °C après qu'un film métallique déposé par pulvérisation (2), qui est choisi dans le groupe constitué par les métaux du groupe du platine et les alliages ayant comme principal composant un ou plusieurs types de métaux du groupe du platine, a été formé sur un substrat céramique (1) comprenant une brique frittée dont le principal composant est une brique électrofondue ou de la zircone, et dont 3-30 % en masse se trouvent à l'état vitreux.
PCT/JP2011/076730 2010-11-25 2011-11-18 Élément en céramique et son procédé de fabrication, dispositif et procédé pour la production de verre fondu, et dispositif et procédé pour la fabrication d'un article en verre WO2012070508A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201180055948.1A CN103221570B (zh) 2010-11-25 2011-11-18 陶瓷构件及其制造方法、熔融玻璃的制造装置及制造方法以及玻璃物品的制造装置及玻璃物品的制造方法
JP2012545730A JP5928340B2 (ja) 2010-11-25 2011-11-18 セラミック部材およびその製造方法、溶融ガラスの製造装置および製造方法、ならびにガラス物品の製造装置およびガラス物品の製造方法
KR1020137011162A KR101768262B1 (ko) 2010-11-25 2011-11-18 세라믹 부재 및 그 제조 방법, 용융 유리의 제조 장치 및 제조 방법, 그리고 유리 물품의 제조 장치 및 유리 물품의 제조 방법

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JP2010-262591 2010-11-25
JP2010262591 2010-11-25

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WO2020067493A1 (fr) * 2018-09-28 2020-04-02 新和工業株式会社 Procédé de traitement de céramiques et élément céramique
JP2021042453A (ja) * 2019-09-13 2021-03-18 株式会社東芝 コーティング方法及びコーティング構造
KR20230165752A (ko) 2021-03-31 2023-12-05 에이지씨 가부시키가이샤 용융 유리와 접촉하는 부분에 적용되는 부재 및 그 제조 방법

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JPH11240725A (ja) * 1998-02-26 1999-09-07 Asahi Glass Co Ltd 溶融ガラスの減圧脱泡装置
JP2008121073A (ja) * 2006-11-13 2008-05-29 Asahi Glass Co Ltd 金属被膜付き電鋳煉瓦及びその製造方法

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JP2000203972A (ja) * 1999-01-18 2000-07-25 Tanaka Kikinzoku Kogyo Kk 白金被覆耐火物製品の表面処理方法
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US7071135B2 (en) * 2004-09-29 2006-07-04 Corning Incorporated Ceramic body based on aluminum titanate and including a glass phase
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JPH11240725A (ja) * 1998-02-26 1999-09-07 Asahi Glass Co Ltd 溶融ガラスの減圧脱泡装置
JP2008121073A (ja) * 2006-11-13 2008-05-29 Asahi Glass Co Ltd 金属被膜付き電鋳煉瓦及びその製造方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020067493A1 (fr) * 2018-09-28 2020-04-02 新和工業株式会社 Procédé de traitement de céramiques et élément céramique
JP6745424B1 (ja) * 2018-09-28 2020-08-26 新和工業株式会社 セラミックの処理方法及びセラミック部材
JP2021042453A (ja) * 2019-09-13 2021-03-18 株式会社東芝 コーティング方法及びコーティング構造
JP7309544B2 (ja) 2019-09-13 2023-07-18 株式会社東芝 コーティング方法及びコーティング構造
KR20230165752A (ko) 2021-03-31 2023-12-05 에이지씨 가부시키가이샤 용융 유리와 접촉하는 부분에 적용되는 부재 및 그 제조 방법

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KR101768262B1 (ko) 2017-08-14
TW201228995A (en) 2012-07-16
JP5928340B2 (ja) 2016-06-01
CN103221570A (zh) 2013-07-24
KR20130140700A (ko) 2013-12-24
CN103221570B (zh) 2015-05-20

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