CN103221570B - Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article - Google Patents

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

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Publication number
CN103221570B
CN103221570B CN201180055948.1A CN201180055948A CN103221570B CN 103221570 B CN103221570 B CN 103221570B CN 201180055948 A CN201180055948 A CN 201180055948A CN 103221570 B CN103221570 B CN 103221570B
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base material
melten glass
glass
ceramic
component
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CN103221570A (en
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石川泰成
浜岛和雄
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/16—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
    • C04B35/18—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 rich in aluminium oxide
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
    • C04B41/5122—Pd or Pt
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
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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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    • C04B2235/00—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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/945—Products containing grooves, cuts, recesses or protusions

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  • Chemical & Material Sciences (AREA)
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  • Ceramic Engineering (AREA)
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  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
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  • 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)
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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

The manufacturing installation of ceramic component and manufacture method thereof, melten glass and the manufacturing installation of manufacture method and glass article and the manufacture method of glass article
Technical field
The ceramic component the present invention relates to the manufacture method of ceramic component, being obtained by this manufacture method, manufacturing installation, the manufacture method that uses the manufacture method of the melten glass of this manufacturing installation, possess the manufacturing installation of the glass article of described ceramic component, use the glass article of this manufacturing installation of melten glass possessing this ceramic component.
Background technology
Such as, the glasswork such as sheet glass obtains by being formed by this melten glass building mortion after manufacturing melten glass by frit.In order to improve the quality of the glasswork after shaping, before proposing after by the melting of frit melting channel, forming with building mortion, remove the method (such as patent documentation 1) of the bubble produced in melten glass with vacuum degassing apparatus.
Described vacuum degassing apparatus possesses the vacuum deaerator groove that inside is held in specified vacuum degree, when melten glass passes through in this vacuum deaerator groove, bubble growth within a short period of time contained in melten glass, the bubble of having grown up floats up to the surface of melten glass by its buoyancy and breaks, thus bubble is removed from melten glass.
The temperature of the melten glass flowed out from melting channel is about 1200 ~ 1600 DEG C when such as soda-lime glass, in order to effectively carry out vacuum deaerator, the temperature importing the melten glass of vacuum degassing apparatus is set to about 1000 ~ 1500 DEG C, and the melten glass temperature importing vacuum deaerator groove is set to about 1000 ~ 1400 DEG C.
In vacuum degassing apparatus, vacuum deaerator groove etc. need thermotolerance and good to the solidity to corrosion of melten glass, so use the ceramic components such as electroforming brick with the component of melten glass.
In addition, the erosion caused to suppress melten glass further, also proposed the method being coated to electroforming brick with metallic membrane, following method is also described: by forming grappling recess on the surface of electroforming brick in following patent documentation 2, the meltallizing film of metal is formed in the mode of this recess of landfill, thus improve the dhering strength of electroforming brick and metallic membrane, suppress the stripping of metallic membrane.
Prior art document
Patent documentation
Patent documentation 1: International Publication No. 2009/125750 text
Patent documentation 2: Japanese Patent Laid-Open 2008-121073 publication
The summary of invention
Invent technical problem to be solved
But in the method that patent documentation 2 is recorded, the dhering strength of electroforming brick and metallic membrane might not be enough.
According to the knowledge that the present inventor grasps, in the anchoring effect produced by recess, little relative to the raising effect of the dhering strength of the drawing force in thickness of metal film direction.
The present invention is the invention completed in view of the foregoing, its object is to the manufacture method that ceramic component is provided, it is the method for the ceramic component manufacturing the metal meltallizing film with the ceramic base materials such as electroforming brick and its surface coating, and the raising of the dhering strength of this ceramic base material and metal meltallizing film is respond well.
In addition, the present invention also aims to provide the manufacturing installation of the ceramic component obtained by described manufacture method, the melten glass possessing this ceramic component, use the manufacture method of the melten glass of this manufacturing installation, possess the manufacturing installation of the glass article of described ceramic component and use the manufacture method of glass article of this manufacturing installation.
The technical scheme that technical solution problem adopts
The present inventor is the conscientiously rear discovery of research repeatedly, if heat-treated by specific condition form the meltallizing film of metal on the ceramic base material containing glassy phase more than specified amount after, then significantly improve relative to the ceramic base material of the drawing force of the thickness direction of metal meltallizing film and the dhering strength of metal meltallizing film.In addition, if also find to carry out described thermal treatment, be then filled with the state of glassy phase in the short space forming the interface of ceramic base material and metal meltallizing film, thus complete the present invention.
Namely, the manufacture method of ceramic component of the present invention manufactures the method for temperature when using lower than the ceramic component of 1500 DEG C, comprise following operation: by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or being on the ceramic base material that formed of the vitrified brick of main component with zircon, formed and be selected from platinum metals and with after the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, heat-treat at the temperature more than 1500 DEG C.The temperature when manufacture method of ceramic component of the present invention is better described use is below 1400 DEG C.
Be better form well-regulated grappling recess on the surface of described ceramic base material, this grappling recess is formed the meltallizing film of described metal.
Ceramic component of the present invention is the ceramic component obtained by described manufacture method of the present invention, it is characterized in that, is filled with glassy phase in the space at the interface of the meltallizing film of described ceramic base material and described metal.
Ceramic component of the present invention is that temperature when having ceramic base material and be located at the meltallizing film of the metal on the surface of this ceramic base material and use is lower than the ceramic component of 1500 DEG C, it is characterized in that, described metal is be selected from platinum metals and with at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, described ceramic base material, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or being that the vitrified brick of main component is formed with zircon, is filled with a part for described glassy phase in the space at the interface of the meltallizing film of described ceramic base material and described metal.Temperature when ceramic component of the present invention is better described use is below 1400 DEG C.
Be better form well-regulated grappling recess on the surface of described ceramic base material, be formed with the meltallizing film of described metal in the mode of filling up this grappling recess.
The invention provides the manufacturing installation that the component contacted with the melten glass lower than 1500 DEG C adopts the melten glass of ceramic component of the present invention.The present invention is better that the component contacted with the melten glass of less than 1400 DEG C adopts ceramic component of the present invention.
The invention provides the manufacturing installation of melten glass, it is characterized in that, use be formed be selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, the part contacted with the melten glass lower than 1500 DEG C forming the manufacturing installation of melten glass at least partially, is heat-treated and forms to temperature more than 1500 DEG C of the described ceramic base material of the manufacturing installation of melten glass described in major general.
The invention provides the manufacturing installation of melten glass, it is characterized in that, use by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form the part contacted with the melten glass lower than 1500 DEG C of the manufacturing installation of melten glass at least partially, the ceramic base material of this part formed is formed and is selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, heat-treat to temperature more than 1500 DEG C of the ceramic base material being formed with the meltallizing film of described metal of the manufacturing installation of melten glass described in major general again and form.
The invention provides the manufacture method using the manufacturing installation of melten glass of the present invention to manufacture the melten glass of melten glass.
The invention provides the manufacturing installation of glass article, it has the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, and the component contacted with the melten glass lower than 1500 DEG C adopts ceramic component of the present invention.The present invention has the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, and the component that the melten glass with less than 1400 DEG C contacts adopts ceramic component of the present invention.
The invention provides the manufacturing installation of glass article, it has the manufacturing installation of melten glass, the building mortion formed melten glass, the annealing device of annealing to the glass after being shaped; The manufacturing installation of described melten glass use be formed be selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, the part contacted with the melten glass lower than 1500 DEG C forming the manufacturing installation of melten glass at least partially, is heat-treated and forms to temperature more than 1500 DEG C of the described ceramic base material of the manufacturing installation of melten glass described in major general.
The invention provides the manufacturing installation of glass article, it has the manufacturing installation of melten glass, the building mortion formed melten glass, the annealing device of annealing to the glass after being shaped, the manufacturing installation of described melten glass uses by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form the part contacted with the melten glass lower than 1500 DEG C of the manufacturing installation of melten glass at least partially, the ceramic base material of this part formed is formed and is selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, heat-treat to temperature more than 1500 DEG C of the ceramic base material being formed with the meltallizing film of described metal of the manufacturing installation of melten glass described in major general again and form.
The invention provides the manufacture method using the manufacturing installation of glass article of the present invention to manufacture the glass article of glass article.
The effect of invention
If employing the present invention, can obtain and be filled with a part for described glassy phase at the ceramic base material with glassy phase and the space at the interface of the meltallizing film (hereinafter also referred to metal meltallizing film) of the metal on its surface coating, the ceramic component that the dhering strength of this ceramic base material and metal meltallizing film is good.
The manufacturing installation of melten glass of the present invention is coated to by metal meltallizing film due to the surface of the component contacted with melten glass, therefore good to the solidity to corrosion of melten glass, and this metal meltallizing film is not easily peeled off, so weather resistance is good.
The manufacturing installation of the melten glass of the application of the invention, Absorbable organic halogens ground manufactures melten glass and glass article.
The simple declaration of accompanying drawing
Fig. 1 is the sectional view of a kind of embodiment representing ceramic component of the present invention.
Fig. 2 is the figure of the example representing grappling recess, and (a) is vertical view, and (b) is the sectional view of the B-B line in (a).
Fig. 3 is the longitudinal sectional view of a kind of embodiment of the manufacturing installation representing melten glass of the present invention.
Fig. 4 is the block diagram of an example of the manufacture method representing glass article of the present invention.
Fig. 5 is the explanatory view of the measuring method of dhering strength.
Fig. 6 is the chart of the measurement result representing dhering strength.
Fig. 7 is the cross sectional photograph of the ceramic component obtained in embodiment 1, a () is the photo before thermal treatment, b () is the photo after thermal treatment, (a ') for carrying out distributional analysis to glassy phase in (a) and the photo illustrated, (b ') for carrying out distributional analysis to glassy phase in (b) and the photo illustrated.
Fig. 8 is the cross sectional photograph of the ceramic component obtained in embodiment 2, and (a) is the photo before thermal treatment, and (b) is the photo after thermal treatment, (b ') for the integral part of (b) being amplified the photo represented.
Fig. 9 is the cross sectional photograph of the ceramic component obtained in comparative example 1, and (a) is the photo before thermal treatment, and (b) is the photo after thermal treatment, (b ') for the integral part of (b) being amplified the photo represented.
The chart of the thermal process that Figure 10 uses when being and representing in embodiment 3 and make frit melting, solidification in the container formed by ceramic component.
Figure 11 is the figure of the result representing embodiment 3, and (a) is the cross sectional photograph of the glass solidified in the container formed by ceramic component, and (b) is the chart of the measurement result representing β-OH value.
Figure 12 is the figure of the result representing comparative example 2, and (a) is the cross sectional photograph of the glass solidified in the container formed by ceramic component, and (b) is the chart of the measurement result representing β-OH value.
Figure 13 is the figure of the result representing comparative example 3, and (a) is the cross sectional photograph of the glass solidified in the container formed by ceramic component, and (b) is the chart of the measurement result representing β-OH value.
Figure 14 is the cross sectional photograph of the glass solidified in the container formed by ceramic component obtained in reference example 1.
Figure 15 is the chart of the measurement result of the β-OH value representing reference example 1.
The mode carried out an invention
< ceramic component >
Fig. 1 is the sectional view of a kind of embodiment representing ceramic component of the present invention.Symbol 1 represents ceramic base material, and symbol 2 represents metal meltallizing film, and 3 represent grappling recess.
The metal meltallizing film 2 that ceramic component of the present invention has ceramic base material 1 and is located on the surface of this ceramic base material 1, is filled with at ceramic base material 1 and the space at the interface of metal meltallizing film 2 glassy phase (not shown) oozed out from ceramic base material.
< ceramic base material >
As ceramic base material 1, the brick comprising 3 ~ 30 quality % glassy phases can be used.In order to obtain the solidity to corrosion for melten glass, being better the brick that compactness is high, can using according to this viewpoint following based on the electroforming brick of zirconium white etc. or take zircon as the vitrified brick of main component.
If the content of glassy phase is lower than 3 quality %, then when carrying out thermal treatment described later, be difficult to the phenomenon that generation glassy phase oozes out from ceramic base material 1.If more than 30 quality %, then the seepage discharge of glassy phase is many, easily produces the problem that metal meltallizing film expands.
[electroforming brick]
That electroforming brick is that to be selected from zirconium white, aluminum oxide, hydrated aluminium silicate, zircon-mullite, silicon oxide and titanium oxide at least a kind be constituent, these raw material electric furnaces are melted completely and the brick cast, formed by crystallization phases and glassy phase in fact.In the present invention, can select from known electroforming brick the content of glassy phase be 3 ~ 30 quality % brick use.
The content of the glassy phase in ceramic base material of the present invention is based on cross sectional photograph, obtains the area occupation ratio of the glassy phase of the area summation relative to crystallization phases and glassy phase, is scaled quality rate and the value obtained.Specifically, in top layer within 50mm the compact surfaces of the ceramic base material from coated metal meltallizing film, use the reflected electron image (composition diagram picture) taken with 50 ~ 100 times by electron microscope, glassy phase and crystallization phases binaryzation are tried to achieve.
As the object lesson of electroforming brick used in the present invention, AZS (Al can be exemplified 2o 3-SiO 2-ZrO 2) brick, improve the Higly oxidized zirconia brick etc. of zirconic content.The crack that AZS brick wherein produces when not easily there is heating or thermal distortion, therefore preferably.
The content of the glassy phase of AZS brick is better 10 ~ 25 quality %, is more preferably 15 ~ 20 quality %.The content of the glassy phase of AZS brick adjusts by the proportioning of raw material.
As the composition of AZS brick, be better Al 2o 3be 40 ~ 55 quality %, SiO 2be 10 ~ 15 quality %, ZrO 2be 30 ~ 45 quality %, Na 2o is 0.5 ~ 2.5 quality %.Other composition such as various metal oxide and inevitable impurity such as forming glassy phase is better be more preferably below 1% below 2%.
The content of the glassy phase of Higly oxidized zirconia brick is better 2 ~ 20 quality %, is more preferably 4 ~ 15 quality %.The content of the glassy phase of Higly oxidized zirconia brick is by adjusting.
As the composition of Higly oxidized zirconia brick, be better Al 2o 3be 0.5 ~ 20 quality %, SiO 2be 2 ~ 10 quality %, ZrO 2be 80 ~ 96 quality %.Other composition such as various metal oxide and inevitable impurity such as forming glassy phase comprises Na 2o is better be more preferably below 2% below 3% interior.
[taking zircon as the vitrified brick of main component]
Take zircon as the vitrified brick of main component be the vitrified brick comprising 80 ~ 96 quality % zircons, formed by crystallization phases and glassy phase in fact.In the present invention, can from known be the vitrified brick of main component, select the content of glassy phase to be that the brick of 3 ~ 30 quality % uses with zircon.
Take zircon as the content of the glassy phase in the vitrified brick of main component be better 3 ~ 10 quality %, be more preferably 4 ~ 10 quality %.Be that the content of the glassy phase of the vitrified brick of main component adjusts by the proportioning of raw material powder with zircon.
As the composition of vitrified brick taking zircon as main component, be better SiO 2be 30 ~ 45 quality %, ZrO 2be 50 ~ 70 quality %, other metal oxide is at below 5 quality %.
[grappling recess]
Better form well-regulated grappling recess 3 on the surface of ceramic base material 1.By arranging grappling recess 3, ceramic base material 1 improves further with the dhering strength of metal meltallizing film 2.Particularly improve relative to the dhering strength of the tensile stress in the direction parallel with the surface of ceramic base material 1.
Fig. 2 is the figure of the example representing grappling recess 3, and (a) is vertical view, and (b) is the sectional view of the B-B line in (a).
The grappling recess 3 of this example is provided with many straight line ditch g that section shape is rectangle in reticulation.The side of each ditch g is vertical relative to the surface of ceramic base material 1, and furrow width w fixes.
In order to effectively obtain anchoring effect, form the ditch g needs degree of depth to a certain degree of grappling recess 3, if but excessively dark, then make the strength degradation of the surface part of ceramic base material 1, processing is difficulty also.Such as, the degree of depth d of ditch g is better about 50 ~ 350 μm, is more preferably about 150 ~ 250 μm.
The dispersity of the stress produced between metal meltallizing film 2 and ceramic base material 1 (is interval between dactylotome according to ditch spacing, distance between adjacent ditch center line separately) p and changing, reducing the stress putting on a place in order to dispersive stress, is better reduce ditch spacing p.If consider the stress weather resistance of metal meltallizing film 2 and the intensity of ceramic base material 1, ditch spacing p is better at below about 2.5mm, is more preferably at below about 1.5mm.Based on identical reason, furrow width w is also advisable with narrow, and from keeping the angle of intensity of surface part of ceramic base material 1, furrow width w is also advisable with narrow.But, if furrow width w is less than the metallics of institute meltallizing, then cannot use the particle-filled ditch of meltallizing, so furrow width w is set to more than the particle diameter of meltallizing particle.Such as, furrow width w is better more than 100 μm, is more preferably more than about 150 μm.
Have in order to ensure the protuberance between adjacent ditch g and its intensity that can not break is made to resistance to stress, must guarantee and protuberance width x that stress the is corresponding difference of interval, ditch spacing p and furrow width w (between=ditch).The thickness m being formed at the metal meltallizing film 2 on ceramic base material 1 is larger, larger from the tensile stress in the direction parallel with the surface of ceramic base material 1 that metal meltallizing film 2 applies.From this point of view, the width x of protuberance is better more than about 4 times of the thickness m at metal meltallizing film 2.In addition, reduce ditch spacing p this point if considered, the width x of preferred protuberance is about 2.5 ~ 5 times of the thickness m of film.
For the stress that the side of ditch g is born, ditch darker (that is, side is larger), then stress is scattered in side entirety, and protuberance not easily breaks.Therefore, less relative to the ratio (p/d) of the ditch spacing p of the degree of depth d of ditch, the dispersiveness of stress is higher, more easily suppresses the stripping of metal meltallizing film 2.If the degree of depth d based on described preferred ditch spacing p and ditch obtains the p/d value that stress suitably disperses, and is better about 3 ~ 8.
Grappling recess is not limited to the shape shown in Fig. 2.Such as, approximate columned hole can be formed with regularly.
Forming continuous print hole when replacing ditch g as shown in Figure 2, is better form hole at the crossover location of orthogonal grid (checker).Or, be better the position being configured at spination (staggered: Staggered Layout) in the mode that pitch of holes is homogeneous.Such as, pitch of holes is better about 0.7 ~ 2.5mm, is more preferably about 1.0 ~ 1.6mm.Bore dia is better about 200 ~ 500 μm, is more preferably 300 ~ 400 μm.The degree of depth in hole is better about 200 ~ 600 μm, is more preferably about 300 ~ 500 μm.
For the formation of grappling with recess 3, grappling with recess 3 in trench when, such as mechanically can carry out with the shredder being provided with the grinding knife formed with emery wheel, diamond tool etc.Or, the high-energy light beam guidings such as laser or High-Pressure Water can be used to carry out.Grappling recess 3, in when poroid, can use the high-energy light beam guidings such as the abrasive tool of the forms such as pin drill or laser or High-Pressure Water to be formed.Form grappling with before recess 3, if in advance by adopting the cutting etc. of shredder to be high-precision plane by the surfacing of ceramic base material 1, then the concavo-convex metal meltallizing film 2 caused because being difficult to expectation can be avoided to peel off, so preferably.
In the present invention, grappling recess 3 can be trench, poroid in any one, but when poroid, relatively little with the enclosed space of metal meltallizing membrane closure (internal space in hole), enclosed space can be formed by hole one by one, therefore because ceramic base material 1 and the interface of metal meltallizing film 2 are filled with glassy phase, large relative to the raising effect of the dhering strength of the drawing force of the thickness direction of metal meltallizing film 2, so preferably.On the other hand, when trench, relatively large with the enclosed space of metal meltallizing membrane closure (internal space in hole), form enclosed space with major groove, therefore above-mentioned effect is relatively little.
< metal meltallizing film >
Metal meltallizing film 2 is the metallic membrane formed by plasma spraying.Plasma spraying to be heated to the metallics injection of high temperature on base material, to be formed the method for tunicle by the accumulation of this metallics.Therefore, metal meltallizing film from adopt the coating etc. of molten metal and the cured film that formed etc. are different, in section visible particulate packed structures.
As metal, can use and be selected from platinum metals and with at least a kind of metal of the platinum metals of more than the a kind alloy that is main component.
As platinum metals, platinum (Pt), iridium (Ir), ruthenium (Ru), rhodium (Rh) can be exemplified.As the alloy taking platinum metals as main component, the platinum alloy such as such as Pt-5%Au alloy, Pt-10%Ir alloy, Pt-10%Rh alloy can be exemplified.
The manufacture method > of < ceramic component
First, ceramic base material 1 forms metal meltallizing film 2.When the surface of ceramic base material 1 is provided with grappling recess 3, form metal meltallizing film 2 in the mode covering this grappling recess 3.Meltallizing method suitably can adopt the known meltallizing methods such as laser plasma spraying, flame wire rod plasma spraying, plasma spray method, electric arc plasma spraying, oxyhydrogen flame plasma spraying.
The particle diameter (flight meltallizing particle diameter) of the metallics emitted by plasma spraying is advisable with little, according to the kind of meltallizing method, can be decreased to about 40 μm, be roughly about 50 ~ 150 μm.
The surface that the metallics penetrated by plasma spraying is deposited in ceramic base material 1 forms metal meltallizing film 2.When the surface of ceramic base material 1 is formed with grappling recess 3, the metallics penetrated by plasma spraying fills this grappling recess 3, and then piles up from the teeth outwards and form metal meltallizing film 2.
The thickness m of metal meltallizing film 2 suitably adjusts by meltallizing amount.Thicker, the strain that the tensile stress in the direction parallel with the surface of ceramic base material 1 causes is larger, therefore the thickness m (having when recess is the thickness without the position of recess) of metal meltallizing film 2 is better about 100 ~ 400 μm, and preferred scope is 200 ~ 350 μm.
The temperature of emitted metallics is roughly about 700 ~ 1500 DEG C, if so heat (namely in advance, preheating) etc. operation, the temperature of ceramic base material when making enforcement meltallizing rises, reduce the temperature head of metallics and ceramic base material, then metal meltallizing film 2 improves, so preferably with the adaptation of ceramic base material 1.In this situation, be better under the state that ceramic base material 1 is heated (preheating), carry out meltallizing after annealing to normal temperature.
The temperature (preheating temperature) of the ceramic base material 1 during meltallizing, below the temperature of solidification of emitted metallics, is specifically better about 200 ~ 500 DEG C, is more preferably 300 ~ 400 DEG C.Cooling rate during annealing is better slow as far as possible, it is desirable to below about 10 DEG C/min.
Then, the temperature in more than 1500 DEG C under state ceramic base material 1 being formed with metal meltallizing film 2 is heat-treated.
By carrying out described thermal treatment, at the short space of ceramic base material 1 with the interface of metal meltallizing film 2, glassy phase oozes out from ceramic base material 1, can obtain the state that this space is filled with glassy phase.After this can think to be heated to the high temperature of more than 1500 DEG C, the glassy phase in ceramic base material becomes easy flowing, and due to the thermal expansion difference of glassy phase and ceramic phase, this glassy phase is extruded to short space, infiltration spread in this space.
In the present invention, the state that the space at the interface of ceramic base material 1 and metal meltallizing film 2 is filled with glassy phase refers to there is glassy phase between ceramic base material 1 and metal meltallizing film 2, the state simultaneously connected with ceramic base material 1 and metal meltallizing film 2 at least partially of this glassy phase.Ceramic base material 1 can leave space slightly with the interface of metal meltallizing film 2, but obtains the angle of good dhering strength from ceramic base material 1 and metal meltallizing film 2, is better do not leave described space as far as possible.Such as, in cross sectional photograph after thermal treatment, relative to the total area in the space that ceramic base material 1 exists with the interface of metal meltallizing film 2, be better there is not glassy phase and residual space at 20 below area %, be more preferably at 10 below area %, preferably 0 area %.
If thermal treatment temp is lower than 1500 DEG C, then the state that the space being difficult to the interface obtaining ceramic base material 1 and metal meltallizing film 2 is full of by glassy phase.This flow state being considered to glassy phase is not enough, therefore cannot short period of time infiltration spread in this space, and ceramic phase and glassy phase are passed in time and reacted, even if thus extend heat-up time, also cannot obtain the state that this space is full of by glassy phase.
On the other hand, the upper limit of thermal treatment temp must be lower than the fusing point of the metal forming meltallizing film 2.
Therefore, thermal treatment temp is better the fusing point lower than meltallizing film 2, is set by the condition that glassy phase is full of with the space of ceramic base material in preferred heat treatment time described later 1 with the interface of metal meltallizing film 2.Preferred thermal treatment temp to be also grouped into etc. according to the one-tenth of ceramic base material 1 and different, such as, be better about 1500 ~ 1700 DEG C, be more preferably about 1500 ~ 1600 DEG C.If thermal treatment temp is within the scope of these, then the mobility of glassy phase is high, and therefore the reaction of ceramic phase and glassy phase is little with the impact of the effect in the space at the interface of metal meltallizing film 2 for being full of ceramic base material 1 with glassy phase.
If heat treatment time is too short, then remain large quantity space at ceramic base material 1 and the interface of metal meltallizing film 2.On the other hand, if heat treatment time is long, then ceramic phase and glassy phase are passed in time and are reacted, and the phenomenon that glassy phase is extruded not easily occurs in ceramic base material 1 and the space at the interface of metal meltallizing film 2.
Therefore, there is not the condition setting of these problems in heat treatment time.Such as, be better 1 ~ 100 hours, be more preferably 10 ~ 50 hours.
If adopt manufacture method of the present invention, then can obtain and be filled with the ceramic component of the present invention of the glassy phase deriving from ceramic base material at ceramic base material 1 and the space at the interface of metal meltallizing film 2.
The purposes > of < ceramic component
Ceramic component of the present invention is that temperature when using is lower than the component of 1500 DEG C.That is, the position that the temperature envisioned when using can not reach more than 1500 DEG C is used to.
Even if this is because the component that use temperature reaches more than 1500 DEG C does not carry out the thermal treatment of more than 1500 DEG C before use, also likely finally obtain the effect same with the present invention, described component adopts necessity of the present invention low.
Thus, the component of temperature below 1450 DEG C when ceramic component of the present invention is better use, is more preferably the component of temperature below 1400 DEG C during use.
Ceramic component of the present invention is provided with metal meltallizing film 2 on ceramic base material 1, therefore good to the solidity to corrosion of melten glass.Therefore, ceramic component of the present invention is preferably used as the component that contacts with the melten glass lower than 1500 DEG C in for the manufacture of the device of melten glass.In addition, ceramic component of the present invention is more preferably used as the component contacted with the melten glass of less than 1450 DEG C in for the manufacture of the device of melten glass, is more preferably used as the component contacted with the melten glass of less than 1400 DEG C further.
Specifically, the melten glass flowed out from melting channel is better the component being used as the stream till delivering to building mortion through vacuum degassing apparatus to contact with the melten glass lower than 1500 DEG C.In addition, the component contacted with the melten glass of less than 1450 DEG C is used as, further more preferably as the component contacted with the melten glass of less than 1400 DEG C the stream that the melten glass flowed out from melting channel is more preferably till delivering to building mortion through vacuum degassing apparatus.Such as, the component of the inwall forming vacuum deaerator groove can be exemplified, form the component that the component of being located at the inwall of the melting upcast of the upstream of vacuum deaerator groove or formation are located at the inwall of the downtake in the downstream of vacuum deaerator groove.
Ceramic component of the present invention is provided with metal meltallizing film 2 on the surface of ceramic base material 1, even if therefore contact with melten glass, the erosion of ceramic base material 1 is also inhibited.In addition, as shown in embodiment described later, ceramic base material 1 is good with the dhering strength of metal meltallizing film 2, and therefore this metal meltallizing film 2 is not easily peeled off, and weather resistance is good.
In addition, when ceramic component of the present invention is used for the component contacted with melten glass, the space at the interface of ceramic base material and metal meltallizing film is filled with glassy phase, so can obtain the effect suppressing the bubble in melten glass to produce.
That is, if be present in the moisture in melten glass to be broken down into oxygen and hydrogen by the katalysis of platinum metals on the surface of metal meltallizing film, then hydrogen is through metal meltallizing film, and oxygen does not stay its surface through metal meltallizing film.At this moment, if hydrogen is stranded in metal meltallizing film, then be again combined with the oxygen on metal meltallizing film surface and generate water, therefore oxygen can not form bubble.
But in ceramic component in the past, there is small space at metal meltallizing film and the interface of the ceramic base material being positioned at its lower floor, the hydrogen through metal meltallizing film passes through this spatial movement, and hydrogen can not be stranded in metal meltallizing film.Therefore, the oxygen on metal meltallizing film surface cannot be combined with hydrogen again, thus forms bubble.
Ceramic component of the present invention is filled with glassy phase in the space at the interface of described metal meltallizing film and ceramic base material, and therefore hydrogen is stranded in metal meltallizing film, can again be combined with oxygen and generate water.Therefore, bubble can be formed by anti-block.
The manufacturing installation > of < melten glass
The manufacturing installation of melten glass of the present invention is the device that the component contacted with the melten glass lower than 1500 DEG C adopts ceramic component of the present invention.In addition, the manufacturing installation of melten glass of the present invention is better that the component contacted with the melten glass of less than 1450 DEG C adopts ceramic component of the present invention, is more preferably the component contacted with the melten glass of less than 1400 DEG C and adopts ceramic component of the present invention.
In addition, the manufacturing installation of melten glass of the present invention uses to be formed and is selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form melten glass manufacturing installation with lower than 1500 DEG C, it is better less than 1450 DEG C, be more preferably the part of the melten glass contact of less than 1400 DEG C at least partially, heat-treat to temperature more than 1500 DEG C of the described ceramic base material of the manufacturing installation of melten glass described in major general and form.
In addition, the manufacturing installation of melten glass of the present invention uses by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form melten glass manufacturing installation with lower than 1500 DEG C, it is better less than 1450 DEG C, be more preferably the part of the melten glass contact of less than 1400 DEG C at least partially, the ceramic base material of this part formed is formed and is selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, heat-treat to temperature more than 1500 DEG C of the ceramic base material being formed with described metal meltallizing film of the manufacturing installation of major general's melten glass again and form.
Fig. 3 is the longitudinal sectional view of a kind of embodiment of the manufacturing installation representing melten glass of the present invention.The device of present embodiment is roughly floated by the melting channel 11 homogenizing with clarify of the fusing and melten glass of carrying out frit, the inner air pressure bubble be set in the melten glass making lower than normal atmosphere to supply from melting channel 11 and the vacuum degassing apparatus 12 broken, be connected melting channel 11 and vacuum degassing apparatus 12 the first conduit 13, form for the second conduit 14 melten glass flowed out from vacuum degassing apparatus 12 being delivered to the forming unit of subsequent processing by cooling tank 15.Symbol G in figure represents melten glass.
First conduit 13 is provided with cooling unit 13a and agitating unit 13b, from melting channel 11 flow out melten glass be cooled to more than 1000 DEG C by the first conduit 13, lower than 1500 DEG C after, importing vacuum degassing apparatus 12.
Vacuum degassing apparatus 12 possesses vacuum deaerator groove 12a, and the upstream side of vacuum deaerator groove 12a is communicated with the first conduit 13 by upcast 12b, and the downstream side of vacuum deaerator groove 12a is communicated with the second conduit 14 by downtake 12c.The inner sustain of vacuum deaerator groove 12a, upcast 12b, downtake 12c in reduced pressure atmosphere, with by siphonic effect by the first conduit 13 melten glass be situated between formed in mode upcast 12b being drawn to vacuum deaerator groove 12a.In addition, be connected with forming unit by cooling tank 15 after the second conduit 14.
In the device of present embodiment, form vacuum deaerator groove 12a, the upcast 12b of vacuum degassing apparatus 12, the component that the ceramic base material being formed with metal meltallizing film is heat-treated maybe forms by ceramic component of the present invention by the component of inwall of downtake 12c and cooling tank 15.That is, the inwall of vacuum deaerator groove 12a, upcast 12b, downtake 12c and cooling tank 15 is formed by the ceramic base material that metal meltallizing film is coating by inner face, and the short space at the interface of ceramic base material and metal meltallizing film is filled with glassy phase.
Described vacuum degassing apparatus 12 and cooling tank 15 are manufactured by following method: first, the inwall of vacuum deaerator groove 12a, upcast 12b, downtake 12c and cooling tank 15 is formed with the ceramic base material be coated to metal meltallizing film in advance, be assembled into after a series of shape till vacuum degassing apparatus 12 to cooling tank 15, thermal treatment is implemented with the specified temperature of more than 1500 DEG C in the inside comprising a series of works of vacuum degassing apparatus 12 and cooling tank 15, then is cooled to below use temperature.In addition, also can be formed the inwall of vacuum deaerator groove 12a, upcast 12b, downtake 12c and cooling tank 15 by ceramic component of the present invention, be assembled into a series of shape till vacuum degassing apparatus 12 to cooling tank 15.In addition, the inwall of vacuum deaerator groove 12a, upcast 12b, downtake 12c and cooling tank 15 can also be formed with ceramic base material, form metal meltallizing film at the side surface contacted with melten glass of these base materials, then heat-treat at the temperature of the ceramic base material being formed with described metal meltallizing film more than 1500 DEG C.
After such manufacturing installation, use under lower than the use temperature of 1500 DEG C.In addition, be better after such manufacturing installation, use under the use temperature below 1450 DEG C, use under being more preferably the use temperature below 1400 DEG C.
The number of assembling steps of each several part and the position of use ceramic component of the present invention are not limited in above-mentioned example.Such as, can be that the melten glass temperature in cooling tank 15 is lower than its upstream portion, therefore use the position of ceramic component of the present invention be only vacuum degassing apparatus 12 and be not used in the structure of cooling tank 15.Or, also can the position of ceramic component of the present invention be used to be only vacuum deaerator groove 12a in vacuum degassing apparatus 12, or be only upcast 12b and downtake 12c, again or be only downtake 12c.In addition, ceramic component of the present invention can also be used for the inwall of the first conduit 13, second conduit 14.
The manufacture method > of < melten glass
The manufacture method of melten glass of the present invention uses the component contacted with the melten glass lower than 1500 DEG C to adopt the manufacturing installation of ceramic component of the present invention to manufacture the method for melten glass.In addition, the manufacture method of melten glass of the present invention is better the method using the component contacted with the melten glass of less than 1450 DEG C to adopt the manufacture melten glass of the manufacturing installation of ceramic component of the present invention.In addition, the manufacture method of melten glass of the present invention is more preferably the method using the component contacted with the melten glass of less than 1400 DEG C to adopt the manufacture melten glass of the manufacturing installation of ceramic component of the present invention.
Such as, use the manufacturing installation of the melten glass shown in Fig. 3 to manufacture in the method for melten glass, the melten glass flowed out from melting channel 11 be cooled to more than 1000 DEG C by the first conduit 13, lower than after 1500 DEG C, importing vacuum degassing apparatus 12.In addition, be better, after the melten glass flowed out from melting channel 11 is cooled to more than 1000 DEG C, less than 1450 DEG C by the first conduit 13, import vacuum degassing apparatus 12.In addition, be more preferably after being cooled to more than 1000 DEG C, less than 1400 DEG C from the melten glass of melting channel 11 outflow by the first conduit 13, import vacuum degassing apparatus 12.
The inwall of vacuum deaerator groove 12a, the upcast 12b of vacuum degassing apparatus 12, downtake 12c and cooling tank 15 with more than 1000 DEG C, contact lower than the melten glass of 1500 DEG C, but form the surface of the ceramic base material of this inwall (namely, inner face) be coated to by metal meltallizing film, therefore good to the solidity to corrosion of melten glass.In addition, the dhering strength of ceramic base material and metal meltallizing film is good, and therefore this meltallizing film is not easily peeled off, and weather resistance is good.
In addition, metal meltallizing film is filled with glassy phase with the interface of the ceramic base material that is positioned at its lower floor, even if the moisture therefore in glass is broken down into oxygen and hydrogen on the surface of metal meltallizing film, this hydrogen also can be reserving at metal meltallizing film.Therefore, as mentioned above, the oxygen that this quinhydrones and the decomposition by moisture generate again is combined and generates water, and the situation being produced bubble by described oxygen in melten glass therefore can be suppressed to occur.
The manufacturing installation of < glass article and manufacture method >
The manufacturing installation of glass article of the present invention has the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, and the component contacted with the melten glass lower than 1500 DEG C adopts ceramic component of the present invention.In addition, the manufacturing installation of glass article of the present invention is better have the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, and the component that the melten glass with less than 1450 DEG C contacts adopts ceramic component of the present invention.In addition, the manufacturing installation of glass article of the present invention is more preferably has the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, and the component that the melten glass with less than 1400 DEG C contacts adopts ceramic component of the present invention.
The unit manufacturing melten glass is better the manufacturing installation of melten glass of the present invention.Such as, the forming unit that the downstream of the flow direction of the melten glass of the manufacturing installation at melten glass as shown in Figure 3 can be adopted to have form melten glass, the structure to the annealing unit that the glass after being shaped is annealed being positioned at its downstream.The downstream of annealing unit can arrange the machining cell carrying out cutting or grinding further.As forming unit, can adopt known float glass process, under draw the various method such as method, scorification, but not shown.Annealing unit and machining cell also can adopt known technology.
Fig. 4 is the schema of an example of the manufacture method of the glass article representing the manufacturing installation using glass article of the present invention.
When manufacturing glass article according to the method shown in Fig. 4, better the glass melting operation S1 acquisition melten glass G of the melten glass manufacturing installation by using Fig. 3, melten glass G is delivered to forming unit after the forming process S2 being configured as target shape, annealed by annealing operation S3.Then, carry out as required cutting in post-treatment operation S4 or the post-treatment such as grinding, thus glass article G5 can be obtained.
Embodiment
Below, the present invention will be described in more detail to use embodiment, but the present invention is not limited in these embodiments.
[embodiment 1]
In this example, ceramic base material adopts AZS (Al 2o 3-SiO 2-ZrO 2) brick, the surface to this brick as described below is implemented the laggard row metal meltallizing of hole machined of the well-regulated configuration of tool and obtains the base material being with metallic membrane, implements thermal treatment manufacture ceramic component to the base material of this band metallic membrane.Below, this is formed with the base material of base material also referred to as band metallic membrane of metal meltallizing film on the surface of ceramic base material.
The result that the one-tenth of the ceramic base material used by fluorescent x-ary analysis mensuration is grouped into and obtains is shown in table 1.In addition, the content of the glassy phase that the cross sectional photograph based on the base material of the band metallic membrane before thermal treatment is tried to achieve is shown in table 1 (following, in embodiment 2 and comparative example 1 too) in the lump.The calculating of the content of glassy phase is undertaken by following method.Use the reflected electron image (composition diagram picture) taking the electron microscope of 50 times from substrate surface to the inner scope to 20mm position of base material of the section of the base material of electron microscope band metallic membrane before heat treatment.For the image of gained, the area summation obtaining crystallization phases and glassy phase and the area occupation ratio relative to its glassy phase, this area occupation ratio is scaled quality rate and the value that obtains as the content (unit: quality %) of glassy phase.
First, by the brick bat of AZS brick cut growth 50mm × wide 50mm × high 10mm, use optical fiber laser to form grappling recess in the one side of the 50mm × 50mm of this brick bat.Grappling recess forms approximate columned hole, and bore dia is 300 μm, and the degree of depth in hole is 400 μm, and pitch of holes is 1mm.
Then, brick bat is heated to 300 DEG C in air atmosphere, the face defining hole starts with flame wire rod plasma spraying the meltallizing (flight meltallizing particle diameter: about 100 μm, temperature about 100 DEG C) of platinum.Continue after meltallizing to the thickness of platinum tunicle reaches 300 μm, brick bat is annealed to normal temperature and obtains the base material of band metallic membrane.
Make the base material of 2 pieces of band metallic membranes with identical condition, in 1500 DEG C of enforcement thermal treatment of 100 hours, ceramic component is obtained by electric furnace to the base material of one piece of band metallic membrane under air.
In addition, in contrast, thermal treatment is not implemented to the base material of another block band metallic membrane and directly as untreated samples.
[embodiment 2]
In embodiment 1, except being changed into by ceramic base material except Higly oxidized zirconia brick, similarly obtaining the base material of band metallic membrane, thermal treatment similarly to Example 1 being implemented to the base material of this band metallic membrane and makes ceramic component.In addition, in contrast, make similarly to Example 1 and do not implement heat treated untreated samples.
[comparative example 1]
In embodiment 1, except ceramic base material being changed into α βAl2O3 matter brick, similarly obtain the base material of band metallic membrane, thermal treatment is similarly to Example 1 implemented to the base material of this band metallic membrane and makes ceramic component.In addition, in contrast, make similarly to Example 1 and do not implement heat treated untreated samples.
[table 1]
[evaluation method]
(dhering strength)
The ceramic component obtained from each example and untreated samples cut out the plate-like tile of each 3 long 14mm × wide 14mm × high 10mm respectively, as shown in Figure 5, use the bonding stretching tool 24,25 of heat cured epoxy caking agent 23 on the two sides of 14mm × 14mm respectively and make test film.Symbol 21 in figure represents ceramic base material, and 22 represent metal meltallizing film.
(Tai Shite company (TSE society) makes to use tensile strength tester, goods name: AUTOCOM/AC50KN-C), with the velocity conditions of 0.5mm/ minute, stretching tool 24,25 is drawn in the direction away from each other, measure loading when ceramic base material 21 is peeled off with metal meltallizing film 22.Dhering strength (P/S, unit is MPa) is tried to achieve according to the value (P) of loading when peeling off and the area (S) of plate-like tile (ceramic component).The results are shown in Fig. 6.
As shown in the result of Fig. 6, in comparative example 1, the dhering strength of untreated samples and ceramic component is almost equal.In contrast, the dhering strength of the ceramic component in embodiment 1,2, at more than 3 times of dhering strength of untreated samples, confirms that dhering strength significantly improves by implementing thermal treatment.
(section tissue)
When manufacturing ceramic component in each example, take the cross sectional photograph of the base material of band metallic membrane before heat-treating and the ceramic component after it is heat-treated respectively.Fig. 7 is the photo obtained in embodiment 1, and Fig. 8 is the photo obtained in embodiment 2, and Fig. 9 is the photo obtained in comparative example 1.Symbol 21 represents ceramic base material, and 22 represent metal meltallizing film.
In Fig. 7, a () is the cross sectional photograph before thermal treatment, b () is the cross sectional photograph after thermal treatment, (a ') for carrying out distributional analysis to glassy phase in the photo of (a) and the photo illustrated, (b ') for carrying out distributional analysis to glassy phase in the photo of (b) and the photo illustrated.
In Fig. 8,9, a () is the cross sectional photograph before thermal treatment, b () is the cross sectional photograph after thermal treatment, (b ') for the integral part (representing to meet B in figure) of the photo of (b) is amplified the photo represented.
As shown in (a) of Fig. 7 ~ 9, in the base material of the band metallic membrane before thermal treatment, there is small gap (space) at ceramic base material 21 and the interface of metal meltallizing film 22.On the other hand, as Fig. 7,8 (b) shown in, in the ceramic component after the thermal treatment of embodiment 1,2, very close to each other with the interface of metal meltallizing film 22 at ceramic base material 21, as Fig. 7,8 (b ') shown in, there is glassy phase along this interface.
In contrast, as shown in (b) of Fig. 9, in the ceramic component after the thermal treatment of comparative example 1, there is gap at ceramic base material 21 and the interface of metal meltallizing film 22, as shown in (b ') of Fig. 9, do not find glassy phase oozing out to this interface.
[embodiment 3]
In this example, as described below, as the manufacturing installation of melten glass, make the container of the glass melting formed by ceramic component, frit is cooled in this container after 1400 DEG C of meltings.Then, the moisture content in investigating near container inner wall glass by evaluation method described later and the presence or absence of bubble.
First, use by be formed with the Higly oxidized zirconia brick of the identical material of brick used in embodiment 2 and at the ceramic base material being simultaneously provided with grappling recess similarly to Example 1, make the container of bottomed cylindrical of external diameter 75mm, height 55mm, the internal diameter 50mm of outer wall, the degree of depth 40mm of inwall.The face being provided with grappling recess is set to inner face.
Then, this container is heated to 300 DEG C in air atmosphere, inner face is formed metal meltallizing film that thickness is 300 μm similarly to Example 1, obtain the container formed by the base material of band metallic membrane.
Then, this container is put into electric furnace under air, obtain in 1600 DEG C of enforcement thermal treatment of 5 hours the container formed by ceramic component.
In the enforcement of above-described embodiment 3, the container of gained is put into process furnace, apply the thermal process shown in Figure 10 at ambient pressure.The longitudinal axis of Figure 10 represents the atmosphere temperature in process furnace.First, be warming up to 1400 DEG C with 4 hours 40 minutes from normal temperature, when reaching 1400 DEG C, the frit of borosilicate glass dropped in container, within 1 hour, make frit melting 1400 DEG C of heating.Then, be chilled to 720 DEG C, after keeping 1 hour at 720 DEG C, cooled the temperature to 600 DEG C with 2 hours, then be annealed to normal temperature with 3 hours, obtain the glass solidified in container.
[comparative example 2]
In embodiment 3, except the container do not formed the base material by band metallic membrane is implemented, except thermal treatment, to obtain the glass solidified in container similarly to Example 3.
[comparative example 3]
In embodiment 3, except the material of ceramic base material changes into except the α βAl2O3 matter brick identical with the material used comparative example 1 from Higly oxidized zirconia brick, obtain the container formed by the base material of band metallic membrane similarly to Example 3, thermal treatment is similarly to Example 3 implemented to this container and makes the container formed by ceramic component.
This container is used to obtain the glass solidified in container similarly to Example 3.
[evaluation method]
(presence or absence of moisture content and bubble)
As the index of the moisture content in glass, the β-OH measuring glass is worth.β-the OH of glass is worth (unit: mm -1) by measuring the absorbancy to the light of wavelength 2.75 ~ 2.95 μm to glass specimen, by its maximum value β maxtry to achieve divided by the thickness (mm) of this glass specimen.
By cutting together with container with the cut surface along short transverse at the glass solidified in container of obtaining in above-mentioned each example, cut out the longitudinal profile sample of thick 1mm.For the region of the container inner wall of central part of the short transverse of the container of the longitudinal profile sample of gained and the near interface of the glass of solidification, measure β-OH value by above-mentioned method.In addition, the photo in this region is taken.
The result of embodiment 3 is shown in Figure 11, and the result of comparative example 2 is shown in Figure 12, and the result of comparative example 3 is shown in Figure 13.(a) of each figure is cross sectional photograph, and the reference position at interface represents with arrow.Symbol 21 in figure represents ceramic base material, and 22 represent metal meltallizing film, and 30 represent glass.(b) of each figure is the chart of the measurement result representing β-OH value, and transverse axis represents the distance (unit: μm) of the transverse direction of the cross sectional photograph of (a), and the longitudinal axis represents β-OH value (unit: mm -1).The position corresponding with the reference position at interface represents with arrow.
[reference example 1]
In the container formed by the base material of band metallic membrane of each example of the above embodiments 3, comparative example 2,3, the lower floor of metal meltallizing film is formed by ceramic base material, in this example, as described below, the moisture content when lower floor of mensuration metal meltallizing film is formed by glass.
Namely, in embodiment 3, after the container formed by ceramic component is put into process furnace, when reaching 1400 DEG C, a part for the frit that should drop into when being dropped in container by the frit of borosilicate glass directly drops into the container formed by this ceramic component, in the crucible of the platinum rhodium prepared in addition, add this remaining frit simultaneously, this crucible is put into this container.In addition, the glass solidified in container is obtained similarly to Example 3.Figure 14 is the photo representing its longitudinal profile.In this example, in the container 31 formed by ceramic component, in the glass 30 of solidification, imbedded crucible 32, obtain the inner face of crucible 32 and outside all with the state of the glass contact of solidification.
By cutting together with crucible with container with the cut surface along short transverse at the glass solidified in container of obtaining in this example, cut out the longitudinal profile sample of thick 1mm.For the region (representing with symbol 33 in Figure 14) of the inner face of the crucible of the central part of the depth direction of the crucible of the longitudinal profile sample of gained and the near interface of outside and glass, measure β-OH value by above-mentioned method.
Result is shown in Figure 15.Transverse axis represents the distance of the transverse direction of the cross sectional photograph of Figure 14, and the longitudinal axis represents β-OH value.In Figure 15, the position corresponding with the sidewall of crucible represents with arrow.
In longitudinal profile sample for the mensuration of β-OH value, do not find that the bubble in glass occurs.
As shown in the result of Figure 12 (b), Figure 13 (b), in comparative example 2,3, the moisture content (β-OH is worth) in glass declines in the region adjacent with metal meltallizing film.In addition, as shown in Figure 12 (a), Figure 13 (a), in the area discover glass adjacent with metal meltallizing film, bubble is produced.It can thus be appreciated that the oxygen that the moisture be present in melten glass is decomposed on the surface of metal meltallizing film and produces again can not generate water and form bubble.
In addition, use the Higly oxidized zirconia brick containing 6 quality % glassy phases as ceramic base material in comparative example 2, but do not carry out the thermal treatment of 1500 DEG C before using, even if 1400 DEG C of heating 1 hour when therefore using, there is minim gap in the interface also observing metal meltallizing film and ceramic base material in cross sectional photograph.
In comparative example 3, ceramic base material is only containing 0.8 quality % glassy phase, even if carry out the thermal treatment of 1500 DEG C before therefore using, the interface also observing metal meltallizing film and ceramic base material in cross sectional photograph exists minim gap.
Can think thus, in comparative example 2,3, the hydrogen that the moisture be present in melten glass is decomposed on the surface of metal meltallizing film and produces, through metal meltallizing film, by the spatial movement at the interface of metal meltallizing film and ceramic base material, is not stranded in metal meltallizing film.
On the other hand, as shown in the result of Figure 15, in reference example 1, the moisture content (β-OH value) in the region glass adjoined with metal meltallizing film does not decline, and as shown in the result of Figure 11, in embodiment 3, almost there is no the decline of moisture content (β-OH value) yet.In addition, in reference example 1 and embodiment 3, do not find that the bubble in glass produces yet.Can think thus, the oxygen that the moisture be present in melten glass is decomposed on the surface of metal meltallizing film and produces again is combined with hydrogen and generates water, does not therefore produce bubble.
In addition, in the cross sectional photograph of embodiment 3, there is glassy phase in the interface of metal meltallizing film and ceramic base material, does not observe gap.As mentioned above, the bubble inhibition equal with reference example 1 is obtained in embodiment 3, it can thus be appreciated that the bubble that the glassy phase at the interface of metal meltallizing film and ceramic base material is conducive in melten glass suppresses.
The possibility that industry utilizes
If employing the present invention, then can obtain the ceramic component that the dhering strength of ceramic base material and metal meltallizing film is good, described ceramic component is good for the solidity to corrosion of melten glass, can be used as the ceramic component of the manufacturing installation of melten glass.
Quote the announcement of all the elements as specification sheets of the present invention of the specification sheets of No. 2010-262591, the Japanese patent application that on November 25th, 2010 files an application, claims, accompanying drawing and summary here.
The explanation of symbol
1,21 ceramic base materials
2,22 metal meltallizing films
3 grappling recesses
11 melting channels
12 vacuum degassing apparatus
12a vacuum deaerator groove
12b upcast
12c downtake
13 first conduits
14 second conduits
15 cooling tanks
30 glass
G melten glass

Claims (15)

1. the manufacture method of ceramic component, it manufactures temperature when using lower than the method for the ceramic component of 1500 DEG C, it is characterized in that, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or being on the ceramic base material that formed of the vitrified brick of main component with zircon,
Formed and be selected from platinum metals and with after the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component,
Heat-treat at temperature more than 1500 DEG C, fill a part for described glassy phase in the space at the interface of the meltallizing film of described ceramic base material and described metal.
2. the manufacture method of ceramic component as claimed in claim 1, is characterized in that, temperature during described use is below 1400 DEG C.
3. the manufacture method of ceramic component as claimed in claim 1 or 2, it is characterized in that, the surface of described ceramic base material forms well-regulated grappling recess, and this grappling recess is formed the meltallizing film of described metal.
4. ceramic component, it be have ceramic base material and be located at the metal on the surface of this ceramic base material meltallizing film and use time temperature lower than the ceramic component of 1500 DEG C, it is characterized in that,
Described metal is be selected from platinum metals and with at least a kind of metal of the platinum metals of more than the a kind alloy that is main component,
Described ceramic base material by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or being that the vitrified brick of main component is formed with zircon,
A part for described glassy phase is filled with in the space at the interface of the meltallizing film of described ceramic base material and described metal.
5. ceramic component as claimed in claim 4, is characterized in that, temperature during described use is below 1400 DEG C.
6. the ceramic component as described in claim 4 or 5, is characterized in that, the surface of described ceramic base material forms well-regulated grappling recess, and the meltallizing film of described metal is formed in the mode of this grappling recess of landfill.
7. the manufacturing installation of melten glass, is characterized in that, the component contacted with the melten glass lower than 1500 DEG C adopts the ceramic component described in any one in claim 4 ~ 6.
8. the manufacturing installation of melten glass, is characterized in that, the component contacted with the melten glass of less than 1400 DEG C adopts the ceramic component described in any one in claim 4 ~ 6.
9. the manufacturing installation of melten glass, it is characterized in that, use to be formed and be selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form the part contacted with the melten glass lower than 1500 DEG C of the manufacturing installation of melten glass at least partially, heat-treat to temperature more than 1500 DEG C of the described ceramic base material of the manufacturing installation of melten glass described in major general, fill a part for described glassy phase in the space at the interface of the meltallizing film of described ceramic base material and described metal and form.
10. the manufacturing installation of melten glass, it is characterized in that, use by comprising the electroforming brick of 3 ~ 30 quality % glassy phases or taking zircon as the ceramic base material that the vitrified brick of main component is formed, form the part contacted with the melten glass lower than 1500 DEG C of the manufacturing installation of melten glass at least partially, the ceramic base material of this part formed is formed and is selected from platinum metals and with the meltallizing film of at least a kind of metal of the platinum metals of more than the a kind alloy that is main component, heat-treat to temperature more than 1500 DEG C of the ceramic base material being formed with the meltallizing film of described metal of the manufacturing installation of melten glass described in major general again, fill a part for described glassy phase in the space at the interface of the meltallizing film of described ceramic base material and described metal and form.
The manufacture method of 11. melten glass, is characterized in that, uses the manufacturing installation of the melten glass described in any one in claim 7 ~ 10 to manufacture melten glass.
The manufacturing installation of 12. glass articles, it is characterized in that, have the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, the component contacted with the melten glass lower than 1500 DEG C adopts the ceramic component described in any one in claim 4 ~ 6.
The manufacturing installation of 13. glass articles, it is characterized in that, have the unit manufacturing melten glass, the forming unit formed the melten glass of gained, the annealing unit of annealing to the glass after being shaped, the component contacted with the melten glass of less than 1400 DEG C adopts the ceramic component described in any one in claim 4 ~ 6.
The manufacturing installation of 14. glass articles, is characterized in that, the glass forming apparatus have the manufacturing installation of the melten glass described in claim 9 or 10, forming to melten glass, the annealing device of annealing to the glass after being shaped.
The manufacture method of 15. glass articles, is characterized in that, uses the manufacturing installation of the glass article described in any one in claim 12 ~ 14 to manufacture glass article.
CN201180055948.1A 2010-11-25 2011-11-18 Ceramic member and method for producing same, device and method for producing molten glass, and device and method for producing glass article Active CN103221570B (en)

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