CN105683099A - Conduit for glass melt, container for glass melt, method for producing same, glass article production device, and glass article production method - Google Patents

Conduit for glass melt, container for glass melt, method for producing same, glass article production device, and glass article production method Download PDF

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Publication number
CN105683099A
CN105683099A CN201480058174.1A CN201480058174A CN105683099A CN 105683099 A CN105683099 A CN 105683099A CN 201480058174 A CN201480058174 A CN 201480058174A CN 105683099 A CN105683099 A CN 105683099A
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China
Prior art keywords
overlay film
glass melting
thermal spraying
platinum
melting thing
Prior art date
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Granted
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CN201480058174.1A
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Chinese (zh)
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CN105683099B (en
Inventor
岛崎刚
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AGC Inc
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Asahi Glass Co Ltd
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    • 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
    • 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
    • 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
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The present invention pertains to a method for producing a conduit for a glass melt or a container for a glass melt by forming, on at least a portion of the inner surface of a platinum or platinum alloy hollow tube, a coating obtained by thermal spraying and satisfying conditions (1)-(4) below, and subsequently exposing the coating to an oxygen-containing atmosphere at 1300-1800 DEG C. (1) The average film thickness of the coating is 0.1-0.5 mm; (2) A starting material containing a platinum alloy and at least one element selected from the group consisting of zirconium (Zr) and yttrium (Y) is used in the formation of the coating; (3) The platinum alloy in (2) is an alloy of platinum (Pt) and at least one element selected from the group consisting of rhodium (Rh), iridium (Ir), gold (Au), palladium (Pd), and ruthenium (Ru), and the total content of the element(s) other than platinum is 5-40 mass% relative to the total mass of the platinum alloy; (4) In the starting material in (2), the total content of the element(s) other than the platinum alloy relative to the total mass of the platinum alloy is 0.05-3 mass%.

Description

Glass melting thing conduit, glass melting thing container, its manufacture method, glass article manufacture device and glass article manufacture method
Technical field
The present invention relates to the glass melting thing conduit of the conduit being used as glass melting thing in glass article manufacture device or glass melting thing container and manufacture method thereof.
Moreover, it relates to the glass article employing this glass melting thing conduit or glass melting thing container manufactures device.
Additionally, the present invention relates to the glass article manufacture method employing this glass manufacturing apparatus.
Background technology
As glass manufacturing apparatus (melting channel, defecator, regulating tank, agitator tank, cooling bath, other and they connecting path) constituent material, the alloy using platinum or platinum and other precious metal element such as rhodium (Rh), gold (Au), palladium (Pd), iridium (Ir) and ruthenium (Ru) is (following, in this manual, platinum and platinum alloy are referred to as alloy platinum material). Alloy platinum material is used to be because as their constituent material: the fusing point of alloy platinum material is high, it is formed without oxide skin(coating) in an atmosphere therefore not deteriorate, the probability deform during plant running, damaged is low, and chemical stability is also excellent in addition, and the probability of the glass polluting molten condition is low.
Unit temp in glass manufacture operation is different according to its process content, but is under the hot environment of more than about 900 DEG C. Even if alloy platinum material due to above-mentioned characteristic under such hot environment without the glass melting thing within polluting device, it is possible to the sufficient durability of long term maintenance.
But, for the glass manufacturing apparatus employing alloy platinum material, when manufacturing glass, there is the such problem of bubble producing to be caused by the moisture in glass melting thing at the interface of alloy platinum material. This is to be contacted with alloy platinum material by moisture contained in glass melting thing and decompose caused by generation hydrogen and oxygen. Think: hydrogen discharges to outside through alloy platinum material, and oxygen can not pass through alloy platinum material, remain in the concentration of the oxygen in glass melting thing when exceeding solubility limit, in the interface of alloy platinum material generation bubble (referring to patent documentation 1,2). When the gas bubbles left so produced is in the glass product manufactured so that the quality of glass product declines.
When especially for the alkali-free glass substrate being substantially free of alkali metal oxide of liquid crystal display (LCD), organic electroluminescent-display (OLED), inorganic EL-display etc., owing to alkali-free glass fusing point is high, viscosity height compared with alkali-containing glass, therefore the bubble in glass melting thing is difficult to float, thus being difficult to suppress bubble.
In order to solve the problems referred to above, it is proposed that at the diffusion impervious layer (referring to patent documentation 1,2) of the not hydrogen permeability overlay film of surface configuration densification of alloy platinum material, reduction or the diffusion suppressing hydrogen. In patent documentation 1, as the material of fine and close not hydrogen permeability overlay film, list glass, pottery, metal etc. In patent documentation 2, employ the diffusion impervious layer containing iridium.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2004-523449 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2009-523696 publication
Summary of the invention
Invent problem to be solved
The fine and close overlay film of the not hydrogen permeability recorded in patent documentation 1 is conceived to the molecular diameter of hydrogen, ionic diameter, intention utilizes the overlay film that hydrogen permeability material does not arrange densification by coating etc. to be therefore prevented from hydrogen through overlay film to outside release, but the generation of bubble when can not reduce manufacture glass fully. For the overlay film arranged at the outer surface not contacted with glass melting thing of alloy platinum material, think: for may not necessarily form the film of desired densification, because using the deterioration of caused overlay film in high temperature environments, because of reasons such as the overlay film strippings caused by the difference of alloy platinum material and the thermal coefficient of expansion of overlay film, hydrogen discharges to outside.
Additionally, for in patent documentation 2 record containing iridium diffusion impervious layer, think: iridium is expensive material, therefore not only the manufacturing cost of equipment increases, and the iridium being oxidized easily in high temperature environments compared with alloy platinum material due in high temperature environments use and oxidized, therefore can not play intended effect chronically. It addition, compared with alloy platinum material, iridium has hard and crisp characteristic, therefore, it is difficult to processing.
In order to solve the problems referred to above, the glass article it is an object of the invention to provide the generation that can effectively and stably prevent bubble when manufacturing glass, being possible to prevent the residual of bubble in manufactured glass article manufactures device and glass article manufacture method and manufactures the glass melting thing conduit or glass melting thing container and their manufacture method that use in device at this glass article.
Means for solving the above
To achieve these goals, the present invention provides the manufacture method of a kind of glass melting thing conduit or glass melting thing container, wherein, platinum system or the hollow pipe of platinum alloy inner surface at least some of on form utilization and meet the overlay film of thermal spraying of following condition (1)～(4), then above-mentioned overlay film is exposed in the oxygen-containing atmosphere of 1300～1800 DEG C
(1) average film thickness of above-mentioned overlay film is 0.1～0.5mm.
(2) in the formation of above-mentioned overlay film, the raw material containing platinum alloy with at least one element in the group selecting free zirconium (Zr) and yttrium (Y) to form is used.
(3) platinum alloy of (2) be platinum (Pt) and select free rhodium (Rh), iridium (Ir), golden (Au), palladium (Pd) and ruthenium (Ru) to form group in the alloy of at least one element, the total content of the element beyond platinum is 5～40 mass % relative to platinum alloy gross mass.
(4) in the raw material of (2), the total content of element beyond platinum alloy be 0.05～3 mass % relative to platinum alloy gross mass.
In the glass melting thing conduit of the present invention or the manufacture method of glass melting thing container, it is preferable that above-mentioned overlay film is formed by plasma thermal spraying.
Additionally, the present invention provides a kind of glass melting thing conduit or glass melting thing container, its have platinum system or platinum alloy hollow pipe and above-mentioned hollow pipe inner surface at least some of on utilize the overlay film of the thermal spraying meeting following condition (1)～(5).
(1) average film thickness of above-mentioned overlay film is 0.1～0.5mm.
(2) above-mentioned overlay film has pore, and the porosity of this overlay film is 8 more than volume % relative to the cumulative volume of this overlay film.
(3), after the raw material thermal spraying of the above-mentioned overlay film at least one element in using the group formed containing platinum alloy and the free zirconium of choosing (Zr) and yttrium (Y), it is exposed in the oxygen-containing atmosphere of 1300～1800 DEG C.
(4) platinum alloy of (3) be platinum (Pt) and select free rhodium (Rh), iridium (Ir), golden (Au), palladium (Pd) and ruthenium (Ru) to form group in the alloy of at least one element, the total content of the element beyond platinum is 5～40 mass % relative to platinum alloy gross mass.
(5) in the raw material of (3), the total content of element beyond platinum alloy be 0.05～3 mass % relative to platinum alloy gross mass.
In the glass melting thing conduit or glass melting thing container of the present invention, preferred: in above-mentioned overlay film, the particle of this overlay film stacking interface each other forms the Rotating fields extended substantially in parallel relative to the formation face of this overlay film, pore in above-mentioned overlay film be present between above-mentioned stacking interface at least partially, between above-mentioned stacking interface exist the pore average distance on above-mentioned layer direction each other be less than 50 μm.
In the glass melting thing conduit or glass melting thing container of the present invention, preferred: above-mentioned overlay film is formed at using at least some of of glass melting thing conduit or the position (position A) contacted during glass melting thing container and the position (position B) of exposing in atmosphere with glass melting thing among the inner surface of above-mentioned hollow pipe, contact with each other with at the position B overlay film formed at the position A overlay film formed, at the area C (cm of the above-mentioned position A overlay film formed2) and at the above-mentioned position A overlay film formed and the interface area D (cm at the above-mentioned position B overlay film formed2) area ratio (D/C) be more than 0.0005.
It addition, the present invention provides a kind of glass article to manufacture device, it uses at least some of as glass melting thing conduit of the glass melting thing conduit of the present invention.
It is preferred that the glass article of the present invention manufactures device: at least have the melting channel melted by frit and the glass melting thing supplied from above-mentioned melting channel carries out the defecator clarified, and uses the glass melting thing conduit conduit as the side farther downstream of the flow export than above-mentioned defecator of the present invention.
It addition, the present invention provides a kind of glass article manufacture method, it uses the glass article manufacture device of the present invention that frit fusing is obtained glass melting thing, and is undertaken clarifying thus obtaining glass article by above-mentioned glass melting thing.
Invention effect
According to the present invention it is possible to provide the generation that can effectively and stably prevent bubble when manufacturing glass, be possible to prevent the glass article of the residual of bubble in manufactured glass article to manufacture device and glass article manufacture method. It addition, according to the present invention it is possible to provide and manufacture, at this glass article, the glass melting thing conduit or glass melting thing container and their manufacture method that use in device.
Accompanying drawing explanation
Fig. 1 indicates that glass article manufactures the schematic diagram of a configuration example of device.
Fig. 2 is the generalized section of a configuration example of the glass melting thing conduit of the present invention.
Fig. 3 is the generalized section of another configuration example of the glass melting thing conduit of the present invention.
Fig. 4 is the generalized section of a configuration example of the glass melting thing container of the present invention.
Fig. 5 is the flow chart of the manufacture method of the glass melting thing conduit of the present invention.
The cross sectional photograph of the thermal spraying overlay film after heat treatment when Fig. 6 is to contain platinum alloy as raw material in the formation of thermal spraying overlay film.
The cross sectional photograph of the thermal spraying overlay film before heat treatment when Fig. 7 is to contain platinum alloy and zirconium (Zr) element as raw material in the formation of thermal spraying overlay film.
The cross sectional photograph of the thermal spraying overlay film after heat treatment when Fig. 8 is to contain platinum alloy and zirconium (Zr) element as raw material in the formation of thermal spraying overlay film.
The cross sectional photograph of the thermal spraying overlay film after heat treatment when Fig. 9 is that oxide containing platinum and zirconium (Zr) is as raw material in the formation of thermal spraying overlay film.
The cross sectional photograph of the thermal spraying overlay film after heat treatment when Figure 10 is to contain platinum and zirconium (Zr) element as raw material in the formation of thermal spraying overlay film.
Figure 11 is the schematic diagram of the release way of gas.
Detailed description of the invention
Hereinafter, the present invention will be described.
The glass melting thing conduit of the present invention manufactures the conduit being used as glass melting thing in device at glass article. The glass melting thing container of the present invention manufactures the container being used as glass melting thing in device at glass article. Container at this so-called glass melting thing refers to such as frit melts and keeps the crucible of obtained glass melting thing therein.
Fig. 1 indicates that glass article manufactures the schematic diagram of a configuration example of device. Glass article shown in Fig. 1 manufactures device 1 to be had: the melting channel 2 melted by frit, the defecator 3 arranged in the downstream of melting channel 2, the regulating tank 4 temperature conditions of glass melting thing, processing condition being adjusted for subsequent handling arranged in the downstream of defecator 3 and the forming device 5 arranged in the downstream of regulating tank 4, melting channel 2, defecator 3, regulating tank 4 and forming device 5 connect respectively through the conduit 6,7,8 being used for making glass melting logistics logical.
Melting channel 2 is provided with burner, electrode etc., it is possible to melted by frit. It is formed with the flow export of glass melting thing in the downstream of melting channel 2, makes melting channel 2 connect with defecator 3 via the conduit 6 being upstream extremity with this flow export.
Defecator 3 is the position of the clarification being substantially carried out glass. In defecator 3, for instance small bubble contained in glass melting thing is floated by the fining gases that discharged by clarifier, and removing from glass melting thing. Additionally, as defecator 3, can be vacuum deaerator groove as described below: be held in inside regulation degree of decompression reduced atmosphere under import glass melting thing, make the bubble parameters in glass melting thing, and make it float up to glass melting thing surface broken bubble and remove.
It is formed with the flow export of glass melting thing in the downstream of defecator 3, makes defecator 3 connect with regulating tank 4 via the conduit 7 using this flow export as upstream extremity.
Regulating tank 4 is the position utilizing agitator etc. to be stirred by glass melting thing as required and homogenizing and glass melting thing is cooled down. It is formed with flow export in the downstream of regulating tank 4, makes regulating tank 4 connect with forming device 5 via the conduit 8 using this flow export as upstream extremity. Sometimes also the position being stirred of regulating tank 4 is called agitator tank, the position carrying out cooling down is called cooling bath.
Forming device 5 is main by the position that forming of glass is desired shape, suitably selects according to the shape of the glass product manufactured. Such as, when glass product is the glass substrate of flat faced display, use float forming device, drop-down forming device etc. By using float forming device, drop-down forming device etc., obtain being preferably below 0.7mm, be more preferably below 0.5mm, more preferably below 0.3mm, be particularly preferably the glass plate of the thickness of below 0.1mm.
In the glass manufacturing apparatus 1 shown in Fig. 1, the conduit 6,7,8 of glass melting thing requires to be capable of withstanding by the thermostability of hot environment, durability and the corrosion resistance to glass melting thing, therefore platinum system or platinum-gold alloy, platinum-rhodium alloy, the such platinum alloy system of platinum-iridium alloy are used (below, in this manual, they are referred to as " alloy platinum material system ") hollow pipe. Alternatively, it is also possible to be used in platinum or platinum alloy be dispersed with ZrO2、Y2O3The strengthening platinum of such metal oxide particle is as alloy platinum material.
It addition, in the glass manufacturing apparatus 1 shown in Fig. 1, regulating tank 4 or as the agitator tank of regulating tank 4 and cooling bath in can also use the hollow pipe of alloy platinum material.
Therefore, in the glass melting thing conduit in the present invention, except the conduit 6,7,8 of the glass manufacturing apparatus 1 shown in Fig. 1, also include regulating tank 4 or as the agitator tank of regulating tank 4 and cooling bath.
It should be noted that the container of above-mentioned glass melting thing can also use the hollow pipe of alloy platinum material.
Position, the purposes of the container of glass melting thing that the shape of the hollow pipe of alloy platinum material, size use according to the conduit as glass melting thing suitably select. As the shape of hollow pipe, the shape recorded in Japanese Unexamined Patent Publication 2006-315894 publication, it is possible to be that face shaping has irregular shape, it is also possible to the shape recorded in Japan again No. 2010/067669 publication of table, for having the shape of arm.
In the glass melting thing conduit of the present invention or the manufacture method of glass melting thing container, alloy platinum material hollow pipe inner surface at least some of on formed by steps described below and to utilize the overlay film (hereinafter referred to as " thermal spraying overlay film ") of thermal spraying.
Fig. 2 is the generalized section of a configuration example of the glass melting thing conduit of the present invention. In fig. 2, the inner surface of the hollow pipe 10 of alloy platinum material forms thermal spraying overlay film 20. In figure, symbol G represents the glass melting thing (Fig. 3 is also same) of circulation in conduit. Glass melting thing conduit shown in Fig. 2 can apply to the conduit 6,7,8 of the such as glass manufacturing apparatus 1 shown in Fig. 1. Conduit shown in Fig. 2 is connected with other conduit, regulating tank etc. The gap at the position of this connection is narrow as well, is generally up to about 30mm. Be formed with thermal spraying overlay film 20 at the position of this connection, therefore the thermal spraying overlay film 20 of this part with conduit outside atmosphere. This position is called position B (40). It addition, the thermal spraying overlay film with B (40) place, this position is connected (in the present embodiment for connection) and is called position A (30) with the region of the glass melting thing G thermal spraying overlay film contacted. This position A (30) is set to area C (not shown) with the glass melting thing G area contacted. The connecting portion of the conduit of Fig. 2 forms flange, and glass melting thing G penetrates into gap between. Thus, the temperature of this part is low, therefore glass melting thing G solidification, and glass melting thing G will not from conduit clearance leakage each other. In fig. 2, the junction section that the part represented with dotted line 50 near connecting portion is position A (30) Yu position B (40), is comprise the interface area D (area of the section of the thermal spraying overlay film of interface office. Not shown) region. This junction section be formed gas (think mainly in glass melting thing produce oxygen. Same below) the part of release way.
Fig. 3 is the generalized section of another configuration example of the glass melting thing conduit of the present invention. In Fig. 3, a part for the hollow pipe 10 of alloy platinum material forms longitudinal hollow pipe, and its upper space (space on the top of glass melting thing) is open, bottom lock, different from Fig. 2 in this. Therefore, towards the thermal spraying overlay film 20 of upper space and atmosphere. This part is position B (40). It addition, the thermal spraying overlay film with B (40) place, this position is connected (in the present embodiment for connection) and is called position A (30) with the region of the glass melting thing G thermal spraying overlay film contacted. This position A (30) is set to area C (not shown) with the glass melting thing G area contacted. In figure 3, the junction section that the part represented with dotted line 50 is position A (30) Yu position B (40), is comprise the interface area D (area of the section of the thermal spraying overlay film of interface office. Not shown) region. This junction section is the part of the release way forming gas. Glass melting thing conduit shown in Fig. 3 can apply to the regulating tank 4 of the such as glass manufacturing apparatus 1 shown in Fig. 1 or as the agitator tank of regulating tank 4 or cooling bath.
Fig. 4 is the generalized section of a configuration example of the glass melting thing container of the present invention. In Fig. 4, the hollow pipe 10 of alloy platinum material is formed with the shape of bottom tube-like, and within it surface is formed with thermal spraying overlay film 20. For hollow pipe 10, its upper space (space on the top of glass melting thing) is open, towards thermal spraying overlay film 20 and the atmosphere of upper space. This part is position B (40). It addition, the thermal spraying overlay film with B (40) place, this position is connected (in the present embodiment for connection) and is called position A (30) with the region of the glass melting thing G thermal spraying overlay film contacted. This position A (30) is set to area C (not shown) with the glass melting thing G area contacted). In the diagram, the junction section that the part represented with dotted line 50 is position A (30) Yu position B (40), is comprise the interface area D (area of the section of the thermal spraying overlay film of interface office. Not shown) region. This junction section is the part of the release way forming gas. Glass melting thing container shown in Fig. 4 can apply to obtain frit fusing the crucible of glass melting thing.
Figure 11 is the schematic diagram of gas release way.
Fig. 5 is the flow chart of the manufacture method of the glass melting thing conduit of the present invention. Details is described further below, in the manufacture method of the glass melting thing conduit of the present invention, after producing the hollow pipe of alloy platinum material, to the inner surface thermal spraying platinum alloy of this hollow pipe thus forming thermal spraying overlay film. Then, the hollow pipe defining thermal spraying overlay film is carried out heat treatment in oxygen-containing atmosphere.
The thermal spraying overlay film formed on the inner surface of the hollow pipe of alloy platinum material requires to be capable of withstanding the thermostability by hot environment and the corrosion resistance to glass melting thing. The formation purpose of thermal spraying overlay film is in that, by the different element of mother metal imported and form thermal spraying overlay film, makes the composition of mother metal tilt, thus the raising intensity on mother metal surface, durability, corrosion resistance etc. Accordingly, with respect to glass melting thing originally durability, corrosion resistance is high and expensive alloy platinum material hollow pipe, it is often used without the alloy platinum material raw material as thermal spraying overlay film. But, in the present invention, based on the opinion of following description, in the raw material of thermal spraying overlay film, employ alloy platinum material. In the present invention, have employed the alloy platinum material raw material as thermal spraying overlay film, therefore, different from other thermal spray feedstock, the corrosion resistance of thermal spraying overlay film, durability will not come into question, therefore, it is possible to effectively and stably prevent the generation of bubble.
In the present invention, in the formation of thermal spraying overlay film, use the raw material containing platinum alloy with at least one element (following, to be called " elements A " in this manual) in the group selecting free zirconium (Zr) and yttrium (Y) to form.
Use the reason of raw material possibly together with elements A except platinum alloy as described below.
With platinum alloy for raw material form thermal spraying overlay film when, in forming thermal spraying overlay film immediately after, between the particle stacking interface each other of thermal spraying overlay film, there is a large amount of pore. But, it is generally the case that when thermal spraying overlay film is exposed in the oxygen-containing atmosphere of high temperature, the major part of pore blocks because of the growth of crystal grain, and the pore of residual is also present in thermal spraying overlay film randomly. It is thus impossible to formed for making the oxygen produced in glass melting thing, hydrogen (think the oxygen primarily as gas. Same below) the gas release way of release in atmosphere. Namely, it is impossible to formed as use described later except platinum alloy possibly together with the raw material of elements A time gas release way.
The cross sectional photograph with the multiplying power of 50, the state of the thermal spraying overlay film after heat treatment when with platinum alloy for raw material formation thermal spraying overlay film shot shown in Fig. 6 and obtain. It should be noted that the oxygen-containing atmosphere of high temperature specifically refers to 1300～1800 DEG C, is preferably the oxygen-containing atmosphere of 1300～1500 DEG C. In this manual, sometimes the heat treatment being called in oxygen-containing atmosphere in the oxygen-containing atmosphere of 1300～1800 DEG C, preferably 1300～1500 DEG C will be exposed to.
On the other hand, when using except platinum alloy except possibly together with the raw material of elements A, a part for elements A is dispersed in the alloy crystal of the platinum alloy of formation thermal spraying overlay film. It addition, the another part of elements A is dispersed in the grain boundaries of the platinum alloy forming thermal spraying overlay film. When thermal spraying overlay film is carried out heat treatment by later-mentioned step in oxygen-containing atmosphere, elements A is oxidized and becomes oxide. Such as, when elements A is Zr, form ZrO2. Now, the elements A being dispersed in alloy crystal produces dislocation by forming oxide in alloy crystal. Thus, it is suppressed that the growth of crystal grain. Additionally, it is believed that the elements A being dispersed in grain boundaries also forms oxide thereby inhibiting the growth of crystal grain. The effect of grain growth is suppressed by these, between the particle of thermal spraying overlay film stacking interface each other, a large amount of pore is there is also after sintering, and, these pores maintain the state that closely exists, and this pore can be formed for making the oxygen produced in glass melting thing, hydrogen to the gas release way of release in atmosphere. The cross sectional photograph using the multiplying power of 100 state of the thermal spraying overlay film before heat treatment when employing except platinum alloy possibly together with zirconium (Zr) as the raw material of elements A shot shown in Fig. 7 and obtain. Shown in Fig. 8 using the multiplying power of 50 to except platinum alloy possibly together with zirconium (Zr) as the raw material of elements A when heat treatment after the state of thermal spraying overlay film shoot and the cross sectional photograph that obtains.
Zr, Y of elements A has the growth inhibiting effect of crystal grain. The fusing point of the alloy particularly formed by platinum alloy and Zr when Zr is solid-solution in platinum alloy on a small quantity raises (conversely, for Y, platinum alloy the fusing point of the alloy become declines) with Y shape, and therefore elements A is more preferably Zr.
On the other hand, the raw material of thermal spraying overlay film contains the oxide of elements A, also it is in the alloy crystal that the part of the oxide of elements A is dispersed in the platinum alloy forming thermal spraying overlay film, another part of the oxide of elements A is dispersed in the grain boundaries of the platinum alloy forming thermal spraying overlay film, and this point is as described above. But, owing to being dispersed in alloy crystal with the form of the oxide of elements A from the beginning, when therefore carrying out heat treatment in oxygen-containing atmosphere, dislocation will not be produced in alloy crystal. Therefore, it does not have suppress the growth of crystal grain. Although it is believed that the oxide being dispersed in the elements A of grain boundaries suppresses the growth of crystal grain, but as thermal spraying overlay film on the whole, with employ containing compared with the situation of the raw material of elements A, it is suppressed that the effect step-down of grain growth. As a result of which it is, when thermal spraying overlay film being carried out heat treatment in oxygen-containing atmosphere, most pores block because of the growth of crystal grain, and the pore of residual is also present in thermal spraying overlay film randomly. It is thus impossible to form the gas release way for making the oxygen produced in glass melting thing, hydrogen discharge in atmosphere. Even if above-mentioned platinum alloy is replaced as platinum, the state of this thermal spraying overlay film is also roughly the same state. The cross sectional photograph using the multiplying power of 50 state of the thermal spraying overlay film after heat treatment when employing except platinum possibly together with the oxide of zirconium (Zr) as the raw material of the oxide of elements A shot shown in Fig. 9 and obtain.
When using platinum rather than platinum alloy as raw material, even if using the raw material containing elements A, the effect of above-mentioned suppression grain growth is also without giving full play to, and the major part of pore blocks because of the growth of crystal grain, and the pore of residual is also present in thermal spraying overlay film randomly. Its reason is as described below.
In platinum alloy, it is known that thus causing solution strengthening by adding other precious metal elements such as Rh to platinum, material is hardening. When being only platinum, above-mentioned phenomenon will not occurring, therefore the ductility of material is high. This is presumably because in platinum crystal, be susceptible to the dislocation of platinum element, diffusion, movement. Further, since in platinum crystal the dislocation of platinum element, diffusion, mobile fast, the therefore fast growth of crystal grain when heat treatment. Therefore, when being only platinum, it is believed that during even with raw material containing elements A, the effect of above-mentioned suppression grain growth is also low.
Further, when being only platinum, the major part blocking of the pore in thermal spraying overlay film, the pore of residual is also present in thermal spraying overlay film randomly. It is thus impossible to form the gas release way for making the oxygen produced in glass melting thing, hydrogen discharge in atmosphere. The cross sectional photograph using the multiplying power of 50 state of the thermal spraying overlay film after heat treatment when employing except platinum possibly together with zirconium (Zr) as the raw material of elements A shot shown in Figure 10 and obtain.
In the present invention, the total content of the elements A in thermal spraying overlay film raw material is 0.05～3 mass % relative to platinum alloy gross mass. When the total content of elements A is lower than 0.05 mass %, the effect of above-mentioned suppression grain growth is low, and when thermal spraying overlay film being carried out heat treatment in oxygen-containing atmosphere, most pores block because of the growth of crystal grain, and the pore of residual is also present in thermal spraying overlay film randomly. It is thus impossible to form the gas release way for making the oxygen produced in glass melting thing, hydrogen discharge in atmosphere.
On the other hand, when the total content of elements A is more than 3 mass %, the change in volume caused because of the oxidation of elements A increases, thus hindering the combination of the crystal of platinum alloy, therefore the intensity of platinum alloy significantly reduces. It addition, the kind according to elements A, owing to exceeding the solid solubility limit in platinum alloy, therefore not can contain.
The total content of the elements A in thermal spraying overlay film raw material is preferably 0.1～1 mass %, is more preferably 0.1～0.5 mass %.
In the present invention, the platinum alloy used in the raw material of thermal spraying overlay film be platinum (Pt) and select free rhodium (Rh), iridium (Ir), golden (Au), palladium (Pd) and ruthenium (Ru) to form group at least one element (below, in this manual, be called " element B ") alloy. In this platinum alloy, the total content of element B is 5～40 mass % relative to platinum alloy gross mass. When the total content of element B is lower than 5 mass %, the effect of above-mentioned suppression grain growth is low, and when thermal spraying overlay film being carried out heat treatment in oxygen-containing atmosphere, most pores block because of the growth of crystal grain, and the pore of residual is also present in thermal spraying overlay film randomly. It is thus impossible to form the gas release way for making the oxygen produced in glass melting thing, hydrogen discharge in atmosphere.
On the other hand, when the total content of element B is more than 40 mass %, the hardness of platinum alloy becomes too high because of solution strengthening, it is difficult to processing.
The platinum alloy of preferred hollow pipe and the platinum alloy except elements A in thermal spraying overlay film are identical platinum alloy. This is because: when the platinum alloy of hollow pipe is different from the platinum alloy except elements A in thermal spraying overlay film, when having the constituting parts that glass melting thing contacts with hollow pipe and thermal spraying overlay film, local cell is formed, it is possible in glass melting thing, produce bubble between hollow pipe and thermal spraying overlay film.
In the present invention, the average film thickness of the thermal spraying overlay film formed on the inner surface of the hollow pipe of alloy platinum material is 0.1～0.5mm. When the average film thickness of thermal spraying overlay film is less than 0.1mm, the area of above-mentioned gas release way diminishes, it is impossible to show its function.
On the other hand, when the average film thickness of thermal spraying overlay film is more than 0.5mm, although being regarded to the function played fully as gas release way in the area of above-mentioned gas release way, but owing to the thickness of overlay film increases, thermal spraying overlay film becomes to be easily peeled off, it is therefore possible to the function as gas release way can not be shown. Additionally, processing cost increases because the thickness of overlay film increases.
The average film thickness of thermal spraying overlay film is preferably 0.2～0.3mm.
The hot spray process used when the formation of thermal spraying overlay film is not particularly limited, for instance can use flame heat spray method or Plasma thermal spray. Among these, Plasma thermal spray due to the overlay film that is usually formed also high with the adaptation of base material it is preferred to. It addition, compared with flame heat spray method, the thermal spraying material of Plasma thermal spray is high temperature, therefore the oxidation of elements A during heat treatment is easily promoted, it is thus preferred to.
Thermal spraying condition during the formation of overlay film is not particularly limited, when flame heat spray, it is preferable that be carry out thermal spraying at 700～1500 DEG C and with 100～150m/s in flame temperature; When plasma thermal spraying, it is preferable that be carry out thermal spraying at 2000～3000 DEG C and with 100～300n/s at gas phase temperature.
In the manufacture method of the glass melting thing conduit of the present invention, after forming thermal spraying overlay film by above-mentioned steps on the inner surface of the hollow pipe of alloy platinum material, this thermal spraying overlay film is exposed in the oxygen-containing atmosphere of 1300～1800 DEG C, preferably 1300～1500 DEG C (carrying out heat treatment in oxygen-containing atmosphere). Heat treatment time is preferably more than 20 hours, is more preferably more than 50 hours, more preferably more than 200 hours. It should be noted that by the heat treatment carrying out more than 20 hours, it is possible to play the effect of the present invention. It should be noted that the heat treatment being not necessarily implemented in as independent step in oxygen-containing atmosphere, it is also possible to heat what implemented before manufacturing glass article as the heat treatment in oxygen-containing atmosphere. Thus, the elements A of grain boundaries be dispersed in the elements A in the alloy crystal of the platinum alloy forming thermal spraying overlay film, being dispersed in the platinum alloy forming thermal spraying overlay film is oxidized and forms oxide, has played the effect of above-mentioned suppression grain growth. Its result is, after heat treatment in oxygen-containing atmosphere, a large amount of pore is there is also between the particle stacking interface each other of thermal spraying overlay film, and, these pores maintain the close to each other and state that exists, and this pore can be formed for making the oxygen produced in glass melting thing, hydrogen to the gas release way of release in atmosphere.
From as being used for making the oxygen produced glass melting thing, hydrogen to the gas release way of release in atmosphere and the aspect of function considers, the porosity of thermal spraying overlay film is 8 more than volume % preferably with respect to the cumulative volume of thermal spraying overlay film, is more preferably 12 more than volume %.
It should be noted that can also be that the different thermal spraying overlay film of the porosity is multilayer laminated and formed. In this case, the porosity of thermal spraying overlay film is also be preferably 8 more than volume %, be more preferably 12 more than volume % relative to the cumulative volume of overlapping thermal spraying overlay film.
Additionally, from as being used for making the oxygen produced glass melting thing, hydrogen to the gas release way of release in atmosphere and the aspect of function considers, the pore existed between the stacking interface of the cambium layer structure average distance on its layer of direction each other is preferably less than 50 μm, is more preferably less than 40 μm, more preferably less than 30 μm.
In the present invention, the inner surface of the hollow pipe of the alloy platinum material as glass melting thing conduit is formed thermal spraying overlay film be in order to as make the oxygen produced in glass melting thing, hydrogen to the gas release way of release in atmosphere function. It should be noted that in order to make the inner surface of glass melting thing conduit as gas release way function, it is also possible to for being formed without other method of thermal spraying overlay film. Such as, as the means using the raw material forming same with present invention film composition and forming the film with said function, have: known employ metal dust or metallic fiber sintering, add sept after remove the sept method of sept, foamable molten method that combustion synthesis method, injection gas are sintered, the precursor methods that blowing promotor is sintered of adding, carry out continuous band fusion method, the etching etc. that cast to motlten metal importing nitrogen. Effect for these films, it is possible to observed by the microscope of the structure of film, the experiment shown in embodiment described later or measure the oxygen transmission rate etc. of film and confirm.
At this, when a part of open, melten glass and the atmosphere of hollow pipe as shown in Figure 3, the part towards air becomes the part exposed in atmosphere. When hollow pipe as shown in Figure 2 is not directly to atmosphere opening, as it has been described above, by connecting portion etc. with hollow pipe outside the part of atmosphere become the part exposed in atmosphere.
Therefore, among the inner surface of the hollow pipe of alloy platinum material, it is necessary to form thermal spraying overlay film when using glass melting thing conduit at position (position A) place contacted with glass melting thing. In order to prevent the bubble at the whole position contacted with glass melting thing of hollow pipe, form thermal spraying overlay film at the whole position contacted with glass melting thing. On the other hand, in order to prevent the bubble at the position of the part contacted with glass melting thing of hollow pipe, form thermal spraying overlay film at the position of this part.
It addition, among the inner surface of the hollow pipe of alloy platinum material, it is necessary to the position (position B) exposed in atmosphere when using glass melting thing conduit at least some of on also form thermal spraying overlay film.
Furthermore, it is necessary to make to contact with each other with at the position B thermal spraying overlay film formed at the position A thermal spraying overlay film formed. At this, from as being used for making the oxygen produced glass melting thing, hydrogen to the gas release way of release in atmosphere and the aspect of function considers, at the area C (cm of the position A thermal spraying overlay film formed2) and at the above-mentioned position A thermal spraying overlay film formed and the interface area D (cm at the above-mentioned position B thermal spraying overlay film formed2) area ratio (D/C) be preferably more than 0.0005.
This area ratio (D/C) is more preferably more than 0.001, more preferably more than 0.002.
It should be noted that thermal spraying overlay film can be formed on the whole inner surface of the hollow pipe of the alloy platinum material as glass melting thing conduit.
The glass melting thing conduit of the glass article manufacture device use present invention of the present invention manufactures at least some of of the conduit of the glass melting thing of device as composition glass article. Such as, when the glass article shown in Fig. 1 manufactures device 1, use the glass melting thing conduit of the present invention as at least some of in the conduit 6,7,8 being used for making glass melting logistics logical or as regulating tank 4 or as the agitator tank of regulating tank 4 or cooling bath.
As it has been described above, in the glass melting thing conduit of the present invention, the gas release way that the stomatal limiting value existed in the thermal spraying overlay film formed on the inner surface of the hollow pipe of alloy platinum material discharges in atmosphere for making the oxygen produced in glass melting thing, hydrogen. Thus, it is suppressed that with the generation of the inner surface of the hollow pipe of the interface of alloy platinum material, more specifically alloy platinum material Yu the bubble of the interface of glass melting thing. As a result of which it is, the quality of manufactured glass article improves.
Manufacture in device 1 at the glass article shown in Fig. 1, use the glass melting thing conduit of the present invention as, at least one of situation in conduit 6,7,8, which conduit the glass melting thing conduit of the present invention being used for and is not particularly limited. Therefore, it can be used for the glass melting thing conduit of the present invention in conduit 6,7,8 only any one, it is also possible to the glass melting thing conduit of the present invention is used for the whole of conduit 6,7,8. Furthermore it is also possible to the glass melting thing conduit of the present invention is used for any two in conduit 6,7,8. But, from the viewpoint of passing through to suppress the bubble with the interface of alloy platinum material to produce thus improving the quality of manufactured glass article, it is preferable that the glass melting thing conduit of the present invention is used for the conduit 7 or 8 than defecator 3 side farther downstream. Alternatively, it is also possible to the glass melting thing of the present invention is used as regulating tank 4 or as the agitator tank of regulating tank 4 or cooling bath with conduit. The downstream of conduit 8 is provided with forming device 5.
In the glass article manufacture method of the present invention, the glass article except with the present invention of described above manufactures beyond this point of device same. Therefore, manufacture to the glass article shown in Fig. 1 the melting channel 2 of device adds and carried out allocating to form the frit of desired glass composition, and make the glass melting thing obtained by adding heat fusing using conduit 6, defecator 3, conduit 7, as the order of the regulating tank 4 of agitator tank or cooling bath, conduit 8 and forming device 5 by thus obtaining the glass article of desired shape.
The glass manufactured in the present invention preferably without alkali glass, be more preferably following alkali-free glass.
Represent with the quality percentage based on oxide, containing the glass of following compositions:
SiO2: 54～73%
Al2O3: 10～23%
B2O3: 0～12%
MgO:0～12%
CaO:0～15%
SrO:0～16%
BaO:0～15%
MgO+CaO+SrO+BaO:8～26%
The strain point of above-mentioned alkali-free glass is preferably more than 650 DEG C, is more preferably more than 670 DEG C, more preferably more than 700 DEG C. When strain point is more than 670 DEG C, B2O3Be preferably 0～5%, be more preferably 0～3%, more preferably 0～2.5%, be further preferably 0～2%, be particularly preferably 0～1.5%.
The T of above-mentioned alkali-free glass2(glass viscosity reaches 102Temperature during dPa s) it is preferably 1620～1820 DEG C, is more preferably 1630～1770 DEG C, more preferably 1640～1720 DEG C.
Embodiment
(example 1 (evaluation of the porosity))
In this example, in order to the state of the thermal spraying overlay film after sintering is studied, refractory brick is formed thermal spraying overlay film, after exposing 5 hours in the oxygen-containing atmospheres of 1400 DEG C (air atmosphere), by following step, the state of the tissue of thermal spraying overlay film is observed. Observation is by thermal spraying overlay film is cut out section, is ground, and implements etching, then utilizes optical microscope to amplify 50 times and carry out. The porosity of the state of expression tissue is to calculate after brightness binaryzation with the area ratio in pore portion. During this binaryzation, make length and width respectively 0.6mm and the 0.3mm of object area. During calculating, choose five randomly from the section of thermal spraying overlay film, adopt its meansigma methods.
Additionally, in order to the state of the thermal spraying overlay film after long-time sintering is studied, the tissue of thermal spraying overlay film is observed by the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C and the thermal spraying overlay film after exposing 600 hours by same step.
The raw material of thermal spraying overlay film and the heat spraying method of use are as described below.
Raw material A: platinum, heat spraying method: flame heat spray
Raw material B: the platinum alloy of platinum and Rh and Rh are 10 mass %, heat spraying method relative to platinum alloy gross mass: flame heat spray
Raw material C: the platinum alloy of platinum and Rh and Zr and Rh are 10 mass %, Zr relative to platinum alloy gross mass is 0.2 mass %, heat spraying method relative to platinum alloy gross mass: plasma thermal spraying
Raw material D: platinum and Zr and Zr are 0.2 mass %, heat spraying method relative to platinum gross mass: flame heat spray
Raw material E: platinum and ZrO2, and ZrO2It it is 0.2 mass %, heat spraying method relative to platinum gross mass: flame heat spray
For only using platinum as the raw material A of the raw material of thermal spraying overlay film, the size of the grain growth to 5～40 μm in thermal spraying overlay film after exposing 5 hours in the oxygen-containing atmospheres of 1500 DEG C (air atmosphere). The pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 4.9 volume % relative to the cumulative volume of thermal spraying overlay film. The pore existed is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, being grown in of crystal grain carries out, and is 30～200 μm. The pore existed in thermal spraying overlay film reduces, and the porosity of thermal spraying overlay film is 1.2 volume %. The major part of the pore existed is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 600 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, being grown in of crystal grain carries out, and is 30～200 μm. The pore existed in thermal spraying overlay film reduces further, and the porosity of thermal spraying overlay film is 1.1 volume %. The major part of the pore existed is present in grain boundaries randomly.
Only use platinum alloy (platinum and Rh) as the size of the grain growth to 5～40 μm in the thermal spraying overlay film that the situation of the raw material B of the raw material of thermal spraying overlay film is also after exposing 5 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C. The pore existed in thermal spraying overlay film reduces, and the porosity of thermal spraying overlay film is 7.2 volume % relative to the cumulative volume of thermal spraying overlay film. The major part of the pore existed is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, being grown in of crystal grain carries out, and is 20～100 μm. The pore existed in thermal spraying overlay film reduces further, and the porosity of thermal spraying overlay film is 3.9 volume %. The major part of the pore existed is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 600 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, being grown in of crystal grain carries out, and is 20～100 μm. The pore existed in thermal spraying overlay film reduces further, and the porosity of thermal spraying overlay film is 3.0 volume %. The major part of the pore existed is present in grain boundaries randomly.
On the other hand, for using platinum alloy (platinum and Rh) and Zr as the raw material C of the raw material of thermal spraying overlay film, the growth of the crystal grain in thermal spraying overlay film after exposing 5 hours in the oxygen-containing atmospheres of 1500 DEG C (air atmosphere) is suppressed, and is the size of 5～30 μm. There is a large amount of pore in thermal spraying overlay film, the porosity of thermal spraying overlay film is 9.8 volume % relative to the cumulative volume of thermal spraying overlay film. It addition, there is a large amount of pore between the particle stacking interface each other of thermal spraying overlay film, the pore average distance on layer direction each other existed between the stacking interface of cambium layer structure is less than 50 μm.
For the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, the growth of crystal grain is also suppressed, and is 10～40 μm. The porosity of thermal spraying overlay film is 13.5 volume %, is less than 50 μm constituting the pore average distance on layer direction each other existed between the stacking interface of Rotating fields.
For the thermal spraying overlay film after exposing 600 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, the growth of crystal grain is also suppressed, and is 10～40 μm. The porosity of thermal spraying overlay film is 14.4 volume %, is less than 50 μm constituting the pore average distance on layer direction each other existed between the stacking interface of Rotating fields.
On the other hand, for using platinum and Zr as the raw material D of the raw material of thermal spraying overlay film, the growth of the crystal grain in thermal spraying overlay film after exposing 5 hours in the oxygen-containing atmospheres of 1500 DEG C (air atmosphere) is suppressed, it it is the size of 5～30 μm, but the pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 6.2 volume % relative to the cumulative volume of thermal spraying overlay film. The major part of the pore that additionally, there are is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, the growth of crystal grain is also suppressed, and is less than 40 μm, but the pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 7.4 volume %. The major part of the pore that additionally, there are is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 600 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, the growth of crystal grain is suppressed, and is less than 40 μm, but the pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 7.2 volume %. The major part of the pore that additionally, there are is present in grain boundaries randomly.
For using platinum and ZrO2As the raw material E of the raw material of thermal spraying overlay film, the size of the grain growth to 5～30 μm in thermal spraying overlay film after exposing 5 hours in the oxygen-containing atmospheres of 1500 DEG C (air atmosphere). The pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 4.9 volume % relative to the cumulative volume of thermal spraying overlay film. The major part of the pore that additionally, there are is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, the size of grain growth to 10～50 μm. The pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 4.9 volume %. The major part of the pore that additionally, there are is present in grain boundaries randomly.
For the thermal spraying overlay film after exposing 600 hours in the oxygen-containing atmospheres of 1500 DEG C (air atmosphere), crystal grain also grows to the size of 10～50 μm. The pore existed in thermal spraying overlay film is few, and the porosity of thermal spraying overlay film is 6.0 volume %. The major part of the pore that additionally, there are is present in grain boundaries randomly.
(example (evaluation of OTR oxygen transmission rate))
The surface of aluminum plectane is formed thermal spraying overlay film, afterwards, dissolves and remove aluminum plectane, thus obtaining the plectane sample only formed by thermal spraying overlay film. This plectane sample being exposed 20 hours in the oxygen-containing atmosphere (air atmosphere) of 1500 DEG C, then carrying out cutting processing to measuring required size, thus obtaining sample.
The mensuration of the OTR oxygen transmission rate of thermal spraying overlay film uses and is undertaken by the method for JISk-7126 the 1st-differential pressure method-GC (gas chromatogram) law regulation. Condition determination be set as dry atmosphere, 30 DEG C.
The size of the raw material of thermal spraying overlay film and heat spraying method and sample is as described below.
Raw material B: platinum and the platinum alloy of Rh, Rh are 10 mass %, heat spraying method relative to platinum alloy gross mass: flame heat spray, size: diameter 58mm, thickness 0.30mm
Raw material C: the platinum alloy of platinum and Rh and Zr, Rh are 10 mass %, Zr relative to platinum alloy gross mass is 0.2 mass %, heat spraying method relative to platinum alloy gross mass: plasma thermal spraying, size: diameter 35mm, thickness 0.33mm
Raw material D: platinum and Zr, Zr are 0.2 mass %, heat spraying method relative to platinum gross mass: flame heat spray, size: diameter 58mm, thickness 0.30mm
Raw material F: the platinum alloy of platinum and Rh and Zr, Rh are 10 mass %, Zr relative to platinum alloy gross mass is 0.2 mass %, heat spraying method relative to platinum alloy gross mass: flame heat spray, size: diameter 58mm, thickness 0.33mm
For raw material B, oxygen transmission rate is 1.95 × 10-18mol·m/m2·s·Pa。
For raw material C, oxygen transmission rate is 7.00 × 10-10mol·m/m2·s·Pa。
For raw material D, oxygen transmission rate is 4.49 × 10-11mol·m/m2·s·Pa。
For raw material F, oxygen transmission rate is 5.32 × 10-11mol·m/m2·s·Pa。
Oxygen transmission rate is preferably 5 × 10-11mol·m/m2More than s Pa, it is more preferably 10-10mol·m/m2More than s Pa, more preferably 5 × 10-10mol·m/m2More than s Pa.
It should be noted that can be the different thermal spraying overlay film multiple-layer overlapped of oxygen transmission rate and be formed. In this case, the oxygen transmission rate of thermal spraying overlay film with the overall form of overlapping thermal spraying overlay film preferably in above-mentioned preferable range.
(example 2 (inhibition 1 of bubble))
Using above-mentioned raw materials C, the outer surface at aluminum cylindrical die forms thermal spraying overlay film. Afterwards, dissolve and remove aluminium-making mould, obtain only being had bottom tube-like container by what thermal spraying overlay film was formed. The opening diameter of container is 30mm, is highly 0.3mm for 30mm, thickness.
In this container, put into cullet, be heated under the following conditions making cullet melt. Cullet are following alkali-free glass, and the water quantities β-OH in glass is 0.5mm-1。
Represent with the quality percentage based on oxide,
SiO2: 60%,
Al2O3: 17%,
B2O3: 8%,
MgO:3%,
CaO:4%,
SrO:8%
(incipient melting condition)
Heat up 2 hours from room temperature to 300 DEG C with the programming rate of 150 DEG C/h. Afterwards, from 300 DEG C to 1500 DEG C with programming rate 10 hours (absolute humidity 78g/m of intensification of 120 DEG C/h3). It addition, keep 5 hours (absolute humidity 78g/m after arriving 1500 DEG C3)。
After implementing the deaeration in glass melting thing under this condition, under the following conditions the generation of glass melting thing Yu the bubble of the interface of container wall is evaluated.
(formal test condition)
Heat up 4 hours (absolute humidity 2g/m from room temperature to 1350 DEG C with the programming rate of 330 DEG C/h3). Then, 2 hours (absolute humidity 2g/m are kept after arriving 1350 DEG C3)。
Unconfirmed to the generation at glass melting thing Yu the bubble of the interface of container wall.
On the other hand, using raw material A, implement step similar to the above, results verification is in the generation of glass melting thing Yu a large amount of bubbles of the interface of container wall.
(example 3 (inhibition 2 of bubble))
Use above-mentioned raw materials C, form thermal spraying overlay film in the side except bottom surface of the inner side having bottom tube-like container of platinum. The width of container is 45mm, the degree of depth is that 45mm, highly peristome for 45mm and top are shaped as rectangle. Thickness at the thermal spraying overlay film being internally formed is 0.3mm.
In container, add cullet, under above-mentioned incipient melting condition, cullet are melted. The degree of depth of melten glass is 15mm. Then, when above-mentioned formal test, the generation of glass melting thing Yu the bubble of the interface of container wall is evaluated.
As a result of which it is, confirm the generation of a large amount of bubble in the bottom surface of inner side and the interface of glass melting thing that do not form thermal spraying overlay film, in the generation to bubble unconfirmed of the side of the inner side of the container defining thermal spraying overlay film and the interface of glass melting thing.
(example 4 (inhibition 3 of bubble))
By the step same with example 3, only form thermal spraying overlay film in the bottom surface of the inner side of platinum container. By step similar to the above, the generation of glass melting thing Yu the bubble of the interface of container wall is evaluated.
Its result is to have confirmed the generation of bubble in the bottom surface of the inner side of container and the interface of side and glass melting thing.
(example 5 (inhibition 4 of bubble))
By the step same with example 4, only form thermal spraying overlay film in the bottom surface of the inner side of platinum container. Afterwards, on the bottom surface of platinum container, the hole that two place's diameters are 0.5mm is only formed in the mode of not perforate on the thermal spraying overlay film of bottom surface.
At this, it is formed at the area 2025mm that area C is bottom surface contacted with glass melting thing of the thermal spraying overlay film of the position A that glass melting thing contacts with thermal spraying overlay film2(45mm × 45mm). It is formed in the thermal spraying overlay film of position A, with the area 0.3927mm of the bottom that interface area D is two holes of the thermal spraying overlay film being formed at the position B exposed in atmosphere via two holes2(0.25mm × 0.25mm × π × 2). In this case, it is formed at the thermal spraying overlay film of position B and is absent from only belonging to the thermal spraying overlay film of position B, for being formed at a part for the thermal spraying overlay film of position A. Area ratio (D/C) is 0.000194. By step similar to the above, the generation of glass melting thing Yu the bubble of the interface of container wall is evaluated.
Its result is to confirm the generation of bubble in the bottom surface of the inner side of container and the interface of side and glass melting thing, have also discovered the generation of bubble in the position defining hole of container bottoms.
(example 6 (inhibition 5 of bubble))
By the step same with example 4, whole of a side in the bottom surface and four sides of the inner side of platinum container forms thermal spraying overlay film. At this, for the area C contacted with glass melting thing of the position A contacted with thermal spraying overlay film at the glass melting thing thermal spraying overlay film formed, owing to adding the melten glass of 15mm, therefore bottom surface and the face contacted with melten glass in side add up to 2700mm2(45mm × 45mm+45mm × 15mm). The degree of depth (or width) of side is carried out, with the thickness of thermal spraying overlay film, the area 13.5mm obtained that is multiplied by the interface area D of the thermal spraying overlay film and the thermal spraying overlay film being formed at the position B exposed in atmosphere that are formed at position A2(45mm × 0.3mm). Area ratio (D/C) is 0.005. By step similar to the above, the generation of glass melting thing Yu the bubble of the interface of container wall is evaluated.
As a result of which it is, in inner side, confirmed the generation of bubble in the interface in the face Yu glass melting thing that do not form thermal spraying overlay film. But, in inner side, in the bottom surface place generation to bubble unconfirmed in the face and container that define thermal spraying overlay film.
In detail and describe the present invention with reference to specific embodiment, can carrying out various changes and modifications without departing from the spirit and scope of the present invention, this will be apparent to those skilled in the art.
The Japanese patent application 2013-219984 that the application proposed based on October 23rd, 2013, using its content as with reference to being incorporated herein.
Accompanying drawing labelling
1: glass article manufactures device
2: melting channel
3: defecator
4: regulating tank
5: forming device
6,7,8: conduit
10: alloy platinum material hollow pipe
20: thermal spraying overlay film
30: position A
40: position B
50: comprise the section of interface area D
G: glass melting thing

Claims (8)

1. the manufacture method of a glass melting thing conduit or glass melting thing container, wherein, platinum system or the hollow pipe of platinum alloy inner surface at least some of on form utilization and meet the overlay film of thermal spraying of following condition (1)～(4), then described overlay film is exposed in the oxygen-containing atmosphere of 1300～1800 DEG C
(1) average film thickness of described overlay film is 0.1～0.5mm;
(2) in the formation of described overlay film, the raw material containing platinum alloy with at least one element in the group selecting free zirconium (Zr) and yttrium (Y) to form is used;
(3) platinum alloy of (2) be platinum (Pt) and select free rhodium (Rh), iridium (Ir), golden (Au), palladium (Pd) and ruthenium (Ru) to form group in the alloy of at least one element, the total content of the element beyond platinum is 5～40 mass % relative to platinum alloy gross mass;
(4) in the raw material of (2), the total content of element beyond platinum alloy be 0.05～3 mass % relative to platinum alloy gross mass.
2. the manufacture method of glass melting thing conduit as claimed in claim 1 or glass melting thing container, wherein, described overlay film is formed by plasma thermal spraying.
3. a glass melting thing conduit or glass melting thing container, its have platinum system or platinum alloy hollow pipe and described hollow pipe inner surface at least some of on utilize the overlay film of thermal spraying meeting following condition (1)～(5)
(1) average film thickness of described overlay film is 0.1～0.5mm;
(2) described overlay film has pore, and the porosity of this overlay film is 8 more than volume % relative to the cumulative volume of this overlay film;
(3), after the raw material thermal spraying of the described overlay film at least one element in using the group formed containing platinum alloy and the free zirconium of choosing (Zr) and yttrium (Y), it is exposed in the oxygen-containing atmosphere of 1300～1800 DEG C;
(4) platinum alloy of (3) be platinum (Pt) and select free rhodium (Rh), iridium (Ir), golden (Au), palladium (Pd) and ruthenium (Ru) to form group in the alloy of at least one element, the total content of the element beyond platinum is 5～40 mass % relative to platinum alloy gross mass;
(5) in the raw material of (3), the total content of element beyond platinum alloy be 0.05～3 mass % relative to platinum alloy gross mass.
4. glass melting thing conduit as claimed in claim 3 or glass melting thing container, wherein, in described overlay film, the particle of this overlay film stacking interface each other forms the Rotating fields extended substantially in parallel relative to the formation face of this overlay film, pore in described overlay film be present between described stacking interface at least partially, between described stacking interface exist the pore average distance on described layer direction each other be less than 50 μm.
5. glass melting thing conduit as described in claim 3 or 4 or glass melting thing container, wherein, described overlay film is formed at using at least some of of glass melting thing conduit or the position (position A) contacted during glass melting thing container and the position (position B) of exposing in atmosphere with glass melting thing among the inner surface of described hollow pipe, contact with each other with at the position B overlay film formed at the position A overlay film formed, at the area C (cm of the described position A overlay film formed2) and at the described position A overlay film formed and the interface area D (cm at the described position B overlay film formed2) area ratio (D/C) be more than 0.0005.
6. glass article manufactures a device, and it uses at least some of as glass melting thing conduit of glass melting thing conduit according to any one of claim 3～5.
7. a glass article manufactures device, it at least has the melting channel melted by frit and the glass melting thing supplied from described melting channel carries out the defecator clarified, and uses the glass melting thing conduit according to any one of claim 3～5 as the conduit of the side farther downstream of the flow export than described defecator.
8. a glass article manufacture method, wherein, uses the glass article described in claim 6 or 7 to manufacture device and frit fusing is obtained glass melting thing, and undertaken clarifying thus obtaining glass article by described glass melting thing.
CN201480058174.1A 2013-10-23 2014-10-23 Glass melting thing conduit, glass melting thing container, its manufacture method, glass article manufacture device and glass article manufacture method Active CN105683099B (en)

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JP2013219984 2013-10-23
JP2013-219984 2013-10-23
PCT/JP2014/078249 WO2015060398A1 (en) 2013-10-23 2014-10-23 Conduit for glass melt, container for glass melt, method for producing same, glass article production device, and glass article production method

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JP6414071B2 (en) 2018-10-31
KR20160074496A (en) 2016-06-28

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Address after: Tokyo, Japan

Patentee after: AGC Corporation

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Patentee before: Asahi Glass Co., Ltd.