JPWO2015005208A1 - Protective structure of high temperature apparatus and method for recovering metal element - Google Patents

Abstract

The object of the present invention is to suppress oxidative deterioration and oxidative volatilization even when used in an atmosphere where oxygen is present in a high temperature region, and extend the life of a high temperature device and easily recover metals such as platinum group metals. It is an object of the present invention to provide a protection structure for a high-temperature device and a method for recovering a metal element that can be performed. The protection structure for a high-temperature device according to the present embodiment is a protection structure for a high-temperature device used in a high-temperature region of 1200 ° C. or higher. A part or all of the outer surface of the high-temperature device 1 includes a metal oxide as a main component. Covered with a ribbon-shaped molded body 2 and fixed in a state where the molded body 2 is not fixed to the outer surface of the high-temperature apparatus 1, and the molded body 2 suppresses contact between the outer surface of the high-temperature apparatus 1 and the outside air. is doing.

Description

  The present invention relates to a protective structure for a high temperature device used in a high temperature range of 1200 ° C. or higher and a method for recovering a metal element.

  As a high temperature apparatus used in a high temperature range of 1200 ° C. or higher, for example, there is an apparatus for manufacturing glass for liquid crystal display, optical glass, or oxide single crystal. In these high-temperature devices, the heat-resistant component that becomes high temperature is usually formed of a metal or an oxide.

  However, when the high temperature device is made of metal, there is a problem that the metal is oxidized in an atmosphere where oxygen is present in a high temperature region, the strength is lowered due to oxidative deterioration and oxidation volatilization, and the product life is shortened. Furthermore, when an expensive metal such as a platinum group metal is used, there is a problem that its recovery becomes difficult. On the other hand, when the high temperature apparatus is formed of an oxide, the oxide is stable in an atmosphere where oxygen is present in a high temperature range, but contamination of impurities due to the reaction between molten glass or the molten oxide and the oxide, or There was a problem of contamination of impurities due to oxide chips or oxide particles falling off.

  As a method for suppressing volatilization loss due to high-temperature oxidation of a platinum group metal, a method is disclosed in which a coating layer made of stabilized zirconia is formed on the outer surface of a high-temperature apparatus by thermal spraying (see, for example, Patent Document 1). . A base material made of iridium or an iridium alloy, and an alloy layer including a base material component and a passive oxide film forming element on a part or all of the base material surface, the iridium in the alloy layer being the base material interface An oxidation-resistant iridium alloy having a composition gradient continuously from the surface to the surface is disclosed (see, for example, Patent Document 2).

  By the way, a zirconia green sheet containing a zirconia powder and a binder and molded by a doctor blade method and a zirconia sheet obtained by firing the zirconia green sheet are known (for example, see Patent Document 3 or 4).

JP 2012-132071 A JP 2008-280597 A JP 2006-290707 A JP 2012-87046 A

  However, in Patent Document 1, due to the difference in thermal expansion coefficient between the metal forming the high temperature device and the stabilized zirconia of the coating layer, the coating layer peels off when expansion and contraction are repeated in the use in a high temperature range, or There is a problem that cracks occur in the coating layer, and it cannot be said that the effect of suppressing the oxidative deterioration and oxidation volatilization of the metal forming the high temperature device is sufficient. Moreover, in patent document 2, since the iridium base material and the alloy layer are integrated, it is difficult to isolate | separate and refine | purify each metal element.

  The object of the present invention is to suppress oxidative deterioration and oxidation volatilization of a metal forming a high temperature device even when used in an atmosphere where oxygen is present in a high temperature region. It is an object of the present invention to provide a protection structure for a high-temperature device and a method for recovering a metal element that can easily recover an expensive metal such as the above.

  A protective structure for a high-temperature device according to the present invention is a protective structure for a high-temperature device used in a high-temperature region of 1200 ° C. or more, wherein a part or all of the outer surface of the high-temperature device contains a metal oxide as a main component. Covered with a ribbon-like, ribbon-like, string-like or woven-like molded body, and the molded body is fixed to the outer surface of the high-temperature device, and the molded body is fixed to the outer surface of the high-temperature device. It is characterized by suppressing contact with the outside air.

  In the protection structure for a high-temperature apparatus according to the present invention, the high-temperature apparatus includes a glass manufacturing furnace, a pipe connected to the glass manufacturing furnace, a stirring component used in the glass manufacturing furnace, or the glass manufacturing furnace. Attached jigs; crucibles; or forms that are single crystal growth containers.

  In the protection structure for a high-temperature device according to the present invention, the high-temperature device is formed using one of elements selected from (1) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W, (2) It is formed using an alloy containing two or three elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W, or (3) Ir, Pt, Rh , Ru, Mo, Re, Nb, Ta and W are preferably formed using an alloy containing one or two elements selected from the group consisting of Pd and Au. The material of the high temperature apparatus can be selected according to the purity and quality of the target product.

  In the protective structure for a high-temperature device according to the present invention, the metal species of the metal oxide of the compact is preferably at least one selected from Zr, Y, Hf, Mg, Ca, Al, Si, Ti, and Th. . Oxidation degradation and oxidation volatilization of the metal forming the high temperature device can be further suppressed.

  In the protective structure of the high temperature device according to the present invention, a diffusion prevention layer, in order from the side close to the outer surface of the high temperature device, between a part or all of the outer surface of the high temperature device and the molded body, and A metal or alloy layer is preferably disposed. The high temperature apparatus can be made stronger.

  In the protective structure of the high-temperature device according to the present invention, the diffusion prevention layer contains an oxide as a main component, and the elements bonded to oxygen of the oxide are Zr, Y, Hf, Mg, Ca, Al, Si, Ti. And at least one selected from Th. It is possible to more efficiently suppress the diffusion of the material of the high temperature device and the material of the metal or alloy layer.

  In the protective structure of the high-temperature device according to the present invention, the metal or alloy layer is formed using one of elements selected from Ru, Mo, Re, Nb, Ta and W, or Ru, Mo, Re, It is preferably formed using an alloy containing two or more elements selected from Nb, Ta and W. High temperature equipment can be thinned.

  In the protective structure for a high temperature device according to the present invention, the metal or alloy layer is preferably a reinforcing layer of the high temperature device. The high temperature device can be formed with a thin wall, and the cost can be further reduced when an expensive metal such as a platinum group metal is used for the high temperature device.

  In the protective structure for a high-temperature device according to the present invention, it is preferable that a metal oxide film, a metal nitride film, a boron nitride film, or a silicon nitride film is fixed to a part or all of the outer surface of the high-temperature device. Oxidation degradation and oxidation volatilization of the metal forming the high temperature device can be further suppressed.

  In the protective structure for a high-temperature apparatus according to the present invention, the film is preferably formed by a thermal spraying method, a CVD method, a PVD method, a coating pyrolysis method, a spray pyrolysis method, or a spray pyrolysis method. An appropriate film can be selected according to the shape or application of the high-temperature apparatus.

  In the protection structure for a high-temperature device according to the present invention, the molded body is wound with a Pt line, a Pt-Rh line, an Ir line, or an Ir-Rh line, and the Pt line, Pt-Rh line, Ir line, or Ir- It is preferred that the end of the Rh line is tied to a high temperature device or welded. The molded body can be reliably fixed at a predetermined position on the outer surface of the high temperature apparatus.

  In the protection structure for a high temperature device according to the present invention, it is preferable that the molded body is further fixed in a state where it is not fixed to a portion of the inner surface of the high temperature device that is exposed to outside air. Oxidation deterioration and oxidation volatilization of the material forming the high temperature device can be further suppressed.

  The metal element recovery method according to the present invention was used in the step 1 of taking out the molded body used in the protective structure of the high temperature apparatus according to the present invention from the high temperature apparatus and / or in the protective structure of the high temperature apparatus according to the present invention. A removal step for removing the diffusion prevention layer from the high temperature apparatus and the metal or alloy layer 2 and a metal adhering to or adhering and diffusing into the molded body and / or diffusion prevention layer taken out in the removal step A recovery step of recovering the element.

  The present invention can suppress oxidative degradation and oxidation volatilization of a metal that forms a high-temperature device even when used in an atmosphere where oxygen exists in a high-temperature region. It is possible to provide a protection structure for a high-temperature apparatus and a method for recovering a metal element that can easily recover a metal.

It is a figure which shows an example of the protection structure of the high temperature apparatus which concerns on this embodiment, and shows the case where a high temperature apparatus is a pipe connected to the furnace for glass manufacture. FIG. 2 is a sectional view taken along line XX in FIG. 1. The modification of the XX broken sectional view of Drawing 1 is shown. It is a figure which shows an example of the protection structure of the high temperature apparatus which concerns on this embodiment, and shows the case where a high temperature apparatus is a crucible. It is a figure which shows an example of the protection structure of the high temperature apparatus which concerns on this embodiment, and shows the case where a high temperature apparatus is a furnace for glass manufacture. It is a photograph which shows the 1st example of the specific form of the protection structure of the high temperature apparatus which concerns on this embodiment. It is a photograph which shows the 2nd example of the specific form of the protection structure of the high temperature apparatus which concerns on this embodiment. It is a photograph which shows the 3rd example of the specific form of the protection structure of the high temperature apparatus which concerns on this embodiment. It is a photograph which shows the 1st example of the combination of a high temperature apparatus, a diffusion prevention layer, and a metal or alloy layer. It is a photograph which shows the 2nd example of the combination of a high temperature apparatus, a diffusion prevention layer, and a metal or alloy layer. The result of the thermogravimetric analysis about Ir is shown. The EDX analysis spectrum when not arrange | positioning a sheet | seat is shown. The EDX analysis spectrum at the time of arrange | positioning a sheet | seat is shown.

  Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these descriptions. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.

  FIG. 1 is a view showing an example of a protection structure for a high temperature apparatus according to the present embodiment, and shows a case where the high temperature apparatus is a pipe connected to a glass manufacturing furnace. 2 is a sectional view taken along line XX in FIG. The protection structure for a high-temperature device according to the present embodiment is a protection structure for a high-temperature device used in a high-temperature region of 1200 ° C. or higher. A part or all of the outer surface of the high-temperature device 1 includes a metal oxide as a main component. Covered with a ribbon-shaped molded body 2 and fixed in a state where the molded body 2 is not fixed to the outer surface of the high-temperature apparatus 1, and the molded body 2 suppresses contact between the outer surface of the high-temperature apparatus 1 and the outside air. doing.

  The high temperature apparatus 1 is an apparatus used in a high temperature range of 1200 ° C. or higher. For example, a glass manufacturing furnace, a pipe connected to a glass manufacturing furnace, a stirring component used in a glass manufacturing furnace, or a glass manufacturing apparatus. It includes an auxiliary jig for a furnace; a crucible; or a form that is a container for growing a single crystal. In FIG. 1, the high temperature apparatus 1 showed the form which is a pipe connected to the furnace for glass manufacture as an example. The present embodiment is not limited to the shape and application of the high temperature apparatus 1.

  The protective structure according to the present embodiment can suppress the oxidative deterioration and oxidation volatilization of the metal forming the high temperature device even when the high temperature device 1 is used in an atmosphere where oxygen exists in a high temperature range of 1200 ° C. or higher. . Therefore, even when the protective structure according to this embodiment is applied to a device used at a temperature lower than 1200 ° C., it is possible to naturally suppress oxidative deterioration and oxidative volatilization of the device.

  The upper limit of the temperature at which the high temperature apparatus 1 is used varies depending on the material of the high temperature apparatus 1. For example, when the high temperature apparatus 1 is made of Pt, the upper limit of the temperature at which the high temperature apparatus 1 is used is preferably 1600 ° C. or less, and more preferably 1500 ° C. or less. When the high temperature apparatus 1 is made of Ir, the upper limit of the temperature at which the high temperature apparatus 1 is used is preferably 2300 ° C. or less, and more preferably 2100 ° C. or less.

  In the high-temperature device protection structure according to the present embodiment, is the high-temperature device 1 formed using one of elements selected from (1) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta, and W? (2) formed of an alloy containing two or three elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W, or (3) Ir, Pt, It is preferably formed using an alloy containing one or two elements selected from Rh, Ru, Mo, Re, Nb, Ta and W and at least one element of Pd or Au. The material of the high temperature apparatus 1 can be selected according to the purity and quality of the target product. When the target product requires high purity such as a single crystal used in applications such as optical glass, liquid crystal display glass, various optical or electronic elements, the high temperature apparatus 1 is expensive such as platinum group metals. However, since the protective structure of the high-temperature device according to the present embodiment can suppress oxidative volatilization and oxidative degradation of expensive metals such as platinum group metals, the device can have a long life. it can. Moreover, in the protection structure of the high temperature apparatus 1 which concerns on this embodiment, the inner surface of the high temperature apparatus 1 has the above-mentioned metal or alloy of (1)-(3) exposed, and the target product Can be manufactured stably.

  The high temperature apparatus 1 is formed using one kind of element selected from (1) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W. A dispersion strengthened alloy in which an oxide or nitride is dispersed may be used. The oxide is, for example, zirconium oxide, hafnium oxide, yttrium oxide, magnesium oxide, titanium oxide, or aluminum oxide. The nitride is, for example, boron nitride, silicon nitride, zirconium nitride, tantalum nitride, niobium nitride, hafnium nitride, or yttrium nitride. Ceramics may be used alone or in combination of two or more.

  The form in which the high temperature apparatus 1 is formed using an alloy containing two or three elements selected from (2) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W is mainly Ir. Binary alloy or ternary alloy as a component, binary alloy or ternary alloy mainly containing Pt, binary alloy or ternary alloy mainly containing Rh, binary alloy or ternary alloy mainly containing Ru Binary alloy, binary alloy or ternary alloy containing Mo as a main component, binary alloy or ternary alloy containing Re as a main component, binary alloy or ternary alloy containing Nb as a main component, Ta as a main component A binary alloy or a ternary alloy, or a binary alloy or a ternary alloy containing W as a main component. In this specification, Ir as a main component means that the content of Ir is the largest among the metal components constituting the alloy, and more preferably, the content of Ir in the alloy is 50% by mass or more. In this specification, an alloy containing Ir as a main component is sometimes referred to as “Ir-M (“ M ”represents a metal other than the element described at the top (in this case, Ir).)”. The same applies to the case where other metal is the main component. Preferred examples of the alloy include Ir—Pt, Ir—Rh, Ir—Ru, Ir—Re, Ir—Mo, Ir—W, Pt—Ir, Pt—Rh, Pt—Ru, Pt—Re, Pt— Mo, Pt—W, Rh—Ir, Rh—Pt, Rh—Ru, Rh—Mo, Rh—Re, Rh—W, Mo—Re, Mo—W, Mo—Nb, Mo—Ta or W—Re is there. Alternatively, a dispersion strengthened alloy in which an oxide or nitride is dispersed in each alloy may be used.

  The high-temperature apparatus 1 includes (3) one or two elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta, and W (hereinafter, sometimes referred to as metal group A group) and Pd. Alternatively, the form formed using an alloy containing at least one kind of Au (hereinafter sometimes referred to as a metal species B group) has a metal species A group as a main component if the melting point is, for example, 1400 ° C. or higher. Or an alloy mainly composed of metal group B may be used. Among these, it is more preferable that it is an alloy which has metal group A group as a main component. Preferred specific examples of the alloy include Ir—Pd, Pt—Pd, Rh—Pd, Ru—Pd, Pt—Au, Rh—Au, Ir—Pt—Pd, Ir—Rh—Pd, Pt—Rh—Pd, Ir-Pt-Au or Ir-Rh-Au. Alternatively, a dispersion strengthened alloy in which an oxide or nitride is dispersed in each alloy may be used.

  Among Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta, and W, Mo is more likely to be oxidized and volatilized in an atmosphere where oxygen is present in a high temperature region than other elements. For this reason, it can be said that the protective structure according to the present embodiment is particularly effective in suppressing oxidative degradation and oxidative volatilization when the high-temperature device 1 is formed using Mo. Ir, Pt, Rh, Ru, Re, Nb, Ta, and W are not as high as Mo, but oxidatively deteriorate and oxidize and volatilize. Therefore, the high-temperature apparatus 1 is Ir, Pt, Rh, Ru, Re, Nb, Ta, or W. In this case, it goes without saying that the effect of suppressing oxidative degradation and oxidative volatilization can be obtained by protecting the protective structure according to the present embodiment. When the high temperature apparatus 1 is formed using an alloy containing (2) two or three elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta, and W, the high temperature apparatus 1 Is formed using an alloy containing (1) one or two elements selected from Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W and at least one element of Pd or Au. The same is true.

  In the present embodiment, it is more preferable that the high-temperature apparatus 1 is made of Ir, Pt, Mo, or W, or an alloy containing Ir, Pt, Mo, or W as a main component and Rh added.

  The molded body 2 contains a metal oxide as a main component. The metal species of the metal oxide of the molded body 2 is preferably at least one selected from Zr, Y, Hf, Mg, Ca, Al, Si, Ti, and Th. The metal oxide of the molded body 2 may be a single metal oxide having one kind of metal or a composite metal oxide having two or more kinds of metal. The composite metal oxide may form a solid solution. These oxides have high heat resistance. Contact between the outer surface of the high temperature apparatus 1 and the outside air can be efficiently suppressed, and oxidation deterioration and oxidation volatilization of the metal or alloy forming the high temperature apparatus 1 can be further suppressed. More preferable form of the molded body 2 is a form in which the metal oxide is zirconia, and the metal oxide is at least one oxide selected from the group consisting of zirconia and scandium oxide, yttrium oxide and ytterbium oxide. 3 to 12 mol% of stabilized zirconia with respect to zirconia, metal oxide is stabilized zirconia with Si oxide, Al oxide, Ge oxide, Sn oxide, Ti oxidation And at least one oxide selected from the group consisting of oxides, Sb oxides, Ta oxides, Nb oxides and Bi oxides. The thickness of the molded body 2 is preferably 0.07 to 2.5 mm, and more preferably 0.1 to 1.0 mm.

  The molded body 2 only needs to have heat resistance at the temperature at which the high temperature apparatus 1 is used, and the oxide used for the molded body 2 is selected according to the operating temperature of the high temperature apparatus 1. For example, when the high-temperature device 1 is made of Pt, the melting point of Pt is 1768 ° C., so that the operating temperature of the high-temperature device 1 is sufficiently lower than 1768 ° C. (for example, 1600 ° C. or less), Zr, Y, Hf , Mg, Ca, Al, Si, Ti, and an oxide containing at least one selected from Th each have a melting point of 1800 ° C. or more and have sufficient heat resistance. Further, when the high-temperature device 1 is made of Ir, the melting point of Ir is 2447 ° C., so that it may be used at a higher use temperature (for example, more than 1600 ° C. and 2300 ° C. or less) than the high-temperature device made of Pt. Thus, when the high-temperature apparatus 1 is used in an ultrahigh temperature range such as exceeding 1600 ° C. and not exceeding 2300 ° C., an oxide containing Zr, Hf, Mg, or Th is used as the oxide used for the molded body 2. Is preferred. Since these oxides have a melting point of 2500 ° C. or higher, they have sufficient heat resistance even in a super-high temperature range such as a temperature exceeding 1600 ° C. and 2300 ° C. or lower.

  The molded body 2 covers part or all of the outer surface of the high temperature apparatus 1. In FIG. 1, a form in which the molded body 2 covers the entire outer surface of the high temperature apparatus 1 is shown. The form (not shown) in which the molded body 2 covers a part of the outer surface of the high temperature apparatus 1 is, for example, a form that covers only a part that is likely to become high temperature and is concerned about oxidation deterioration and oxidation volatilization. When the portion is in contact with the target product or its raw material, only the portion not in contact with the target product or its raw material (for example, the shaft portion of the stirring component) is covered.

  The molded body 2 is fixed in a state where it is not fixed to the outer surface of the high temperature apparatus 1. Here, the state in which the molded body 2 is not fixed is formed as long as the molded body 2 is not damaged due to a difference in thermal expansion coefficient between the high temperature apparatus 1 and the molded body 2 in addition to the form in which the high temperature apparatus 1 and the molded body 2 are not bonded. It includes a form in which a part of the body 2 is bonded to the high temperature apparatus 1 for the purpose of fixing.

  In the present embodiment, the molded body 2 is damaged due to the difference in thermal expansion coefficient between the high temperature apparatus 1 and the molded body 2 by the configuration that the molded body 2 is fixed without being fixed to the outer surface of the high temperature apparatus 1. Can be prevented. In the present embodiment, the molded body 2 is fixed to the outer surface of the high-temperature device 1 at least when the production of the protective structure with the protective structure attached to the high-temperature device 1 is completed and before the high-temperature device 1 is used in a high temperature range. As long as it is not in a state. After the temperature of the high temperature apparatus 1 is increased and the high temperature apparatus 1 is thermally expanded, the molded body 2 may not be fixed to the outer surface of the high temperature apparatus 1 or may have a fixed portion. More preferably, even after the temperature of the high temperature apparatus 1 is increased, the molded body 2 is not fixed to the outer surface of the high temperature apparatus 1.

  Next, an example of a method for fixing the molded body 2 in a state where it is not fixed to the outer surface of the high temperature apparatus 1 will be described. First, the raw material of the molded body 2 containing a metal oxide powder as a main component, a binder, a solvent, and various additives such as a plasticizer, a dispersant, a surfactant or an antifoaming agent added as necessary. The slurry containing the above is stretched into a thin ribbon shape with a coating machine such as a doctor blade and dried to produce a green sheet having plasticity. The shape of the green sheet is not limited to a ribbon shape, and is a matter that is appropriately selected according to the shape of the high-temperature apparatus 1, and may be, for example, a sheet shape, a string shape, or a fabric shape. The green sheet may be formed on a plastic film as a carrier tape. Moreover, you may use the green sheet described in patent document 3 or 4 or the commercially available green sheet as a green sheet.

  Next, as shown in FIG. 1, a green sheet is wound around the outer surface of the high-temperature device 1, for example, in a spiral shape to cover the outer surface of the high-temperature device 1, thereby forming a molded body 2. The method of winding the green sheet is not limited to this as long as the outer surface of the high temperature apparatus 1 can be covered with the molded body 2. The molded body 2 is spirally wound so that the green sheets overlap with each other, so that the molded body 2 is deformed so that the overlapping portion of the spiral is displaced even if the high temperature apparatus 1 is thermally expanded, and the suppression of contact with the outside air is maintained. It is. In the protection structure for a high-temperature device according to the present embodiment, it is preferable that the molded body 2 is wound around the Pt wire 3 and the end portion of the Pt wire 3 is tied to the high-temperature device 1 or welded. . In FIG. 1, as an example, a form in which the terminal portion of the Pt line 3 is bound to the high temperature apparatus 1 is shown. By winding with the Pt wire 3, the molded body 2 can be reliably fixed at a predetermined position on the outer surface of the high temperature apparatus 1. The method of winding the Pt wire 3 is not particularly limited as long as the molded body 2 can be fixed to the outer surface of the high temperature apparatus 1. In FIG. 1, the form in which the Pt wire 3 is wound so as to fix the winding end portion 2a of the green sheet is shown, but the form in which the Pt wire 3 is wound spirally along the molded body 2 (not shown) is also possible. Good.

  Finally, the molded body 2 is sintered. The sintering temperature is preferably 1200 to 1500 ° C. and more preferably 1300 to 1450 ° C. when the molded body 2 is zirconia-based. For sintering, a sintering process may be performed separately, but when the high temperature apparatus 1 is, for example, a glass manufacturing furnace, a pipe connected to a glass manufacturing furnace, or an auxiliary jig for a glass manufacturing furnace, for glass manufacturing. You may sinter by the heating at the time of operation of a furnace. Since the green sheet loses plasticity and is solidified by sintering, the molded body 2 may be fixed to the outer surface of the high-temperature apparatus 1 by itself. As shown in FIG. 2, it is preferable to provide a gap between the molded body 2 and the outer surface of the high temperature apparatus 1. It is possible to prevent the molded body 2 from being damaged by the thermal expansion of the high temperature apparatus 1.

  In this specification, “the molded body contains a metal oxide as a main component” means that the molded body contains a component that can be mixed in the process of producing the molded body in addition to the metal oxide. It is. The component that can be mixed in the process of producing the molded body is, for example, a binder derived from a green sheet, a solvent, or various additives.

  Although not shown, in the protection structure for a high-temperature device according to the present embodiment, a metal oxide film, a metal nitride film, a boron nitride film, or a silicon nitride film is fixed to part or all of the outer surface of the high-temperature device 1. Also good. Oxidation degradation and oxidation volatilization of the metal forming the high temperature device 1 can be further suppressed. The metal species of the metal oxide or metal nitride is preferably at least one selected from, for example, Zr, Y, Hf, Mg, Ca, Al, Si, Ti, and Th. The film is preferably formed by thermal spraying, CVD, PVD, coating pyrolysis, spray pyrolysis, or spray pyrolysis. An appropriate film can be selected according to the shape or application of the high-temperature apparatus. The upper limit of the film thickness is preferably 2 mm or less. More preferably, it is 1 mm or less. Although the minimum of the thickness of a film | membrane is not specifically limited, It is preferable that it is 50 nm or more, and it is more preferable that it is 100 micrometers or more.

  FIG. 3 shows a modification of the XX fracture cross-sectional view of FIG. In FIG. 1, the form in which the molded body 2 is directly arranged on the outer surface of the high temperature apparatus 1 is shown. However, in the protection structure for a high temperature apparatus according to the present embodiment, as shown in FIG. It is preferable to arrange the diffusion prevention layer 4 and the metal or alloy layer 5 in order from the side close to the outer surface of the high temperature apparatus 1 between a part or all of the above and the molded body 2.

  In the protective structure of the high temperature device according to the present embodiment, the metal or alloy layer 5 is a layer made of a metal or alloy, and is formed using one kind of element selected from Ru, Mo, Re, Nb, Ta, and W. Or an alloy containing two or more elements selected from Ru, Mo, Re, Nb, Ta, and W. Preferred specific examples of the alloy include Ru—Mo, Mo—Ru, Mo—Re, Mo—Ta, Mo—Nb, Mo—W, W—Ru, W—Re, W—Ta, and W—Nb. The high temperature apparatus can be thinned, and the cost can be further suppressed. The alloy may be a binary alloy or a multicomponent alloy such as a ternary alloy or a quaternary alloy. Further, a metal oxide film, a metal nitride film, a boron nitride film, or a silicon nitride film may be fixed to part or all of the outer surface of the metal or alloy layer 5.

  The protective structure according to the present embodiment suppresses oxidative deterioration and oxidative volatilization by reducing the chance that the metal or alloy layer 5 comes into contact with oxygen by arranging the molded body 2 outside the metal or alloy layer 5. There is an effect. Among Ru, Mo, Re, Nb, Ta, and W, Mo is more likely to be oxidized and volatilized in an atmosphere where oxygen is present in a high temperature range as compared with other elements. For this reason, when the metal or alloy layer 5 is formed using Mo, it can be said that the effect which suppresses oxidation deterioration and oxidation volatilization is especially large. Ru, Re, Nb, Ta, and W are not as bad as Mo, but oxidatively deteriorate and oxidize and volatilize. Therefore, even when the metal or alloy layer 5 is Ru, Re, Nb, Ta, or W, the outer side of the metal or alloy layer 5 It goes without saying that the effect of suppressing oxidative degradation and oxidative volatilization can be obtained by arranging the molded body 2 on the surface. This is the same when the metal or alloy layer 5 is made of an alloy.

  In the protection structure for a high temperature device according to this embodiment, the metal or alloy layer 5 is preferably a reinforcing layer of the high temperature device 1. The high temperature apparatus 1 can be formed with a thin wall, and the cost can be further reduced when a noble metal is used for the high temperature apparatus 1. As a preferable embodiment when the metal or alloy layer 5 is a reinforcing layer of the high temperature apparatus 1, the high temperature apparatus 1 is formed of one of elements selected from Ir, Pt, Rh and Au, or two alloys The high-temperature apparatus 1 has a thickness of 0.1 to 10 mm, and the metal or alloy layer 5 has a thickness of 3 to 15 mm. The thickness of the high temperature apparatus 1 is more preferably 0.3 to 5 mm. Further, the thickness of the metal or alloy layer 5 is more preferably 5 to 8 mm.

  In the protection structure of the high-temperature device according to the present embodiment, the diffusion prevention layer 4 includes an oxide as a main component, and elements that combine with oxygen in the oxide are Zr, Y, Hf, Mg, Ca, Al, Si, Ti. And at least one selected from Th. The oxide of the diffusion preventing layer 4 may be a single oxide in which one element that combines with oxygen is a single oxide, or may be a complex oxide in which two or more elements that combine with oxygen. The composite oxide may form a solid solution. The diffusion prevention layer 4 has a role of preventing the material of the high temperature device 1 and the material of the metal or alloy layer 5 from adhering due to diffusion. The diffusion preventing layer 4 only needs to prevent diffusion bonding between the two, and may be disposed over the entire boundary portion between the high temperature apparatus 1 and the metal or alloy layer 5 or may be partially disposed as a spacer. The upper limit of the thickness of the diffusion preventing layer 4 is more preferably 2 mm or less. More preferably, it is 1 mm or less. More preferably, it is 200 μm or less. The lower limit of the thickness of the diffusion preventing layer 4 is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, and further preferably 100 μm or more. In this embodiment, it does not ask | require whether the diffusion prevention layer 4 adhere | attaches with respect to the high temperature apparatus 1 or the metal or alloy layer 5. FIG.

  When the diffusion prevention layer 4 is disposed on the entire boundary portion between the high temperature device 1 and the metal or alloy layer 5, the diffusion prevention layer 4 becomes a physical wall between the high temperature device 1 and the metal or alloy layer 5. By preventing the movement of elements between them, a diffusion preventing effect can be obtained. Further, when the diffusion prevention layer 4 is partially disposed at the boundary portion between the high temperature apparatus 1 and the metal or alloy layer 5, the diffusion prevention layer 4 becomes a physical wall at a portion where the diffusion prevention layer 4 is interposed. Thus, the movement of elements between the high temperature apparatus 1 and the metal or alloy layer 5 is prevented, and there is a space between the high temperature apparatus 1 and the metal or alloy layer 5 at a portion where the diffusion prevention layer 4 is not interposed. The apparatus 1 and the metal or alloy layer 5 are prevented from being diffusion bonded. Thus, the diffusion prevention by the diffusion prevention layer 4 is due to a physical wall or space, and is not a phenomenon depending on the element type of the high temperature apparatus 1 and the metal or alloy layer 5.

  The diffusion preventing layer 4 only needs to have heat resistance at the temperature at which the high temperature apparatus 1 is used, and the oxide used for the diffusion preventing layer 4 is selected according to the operating temperature of the high temperature apparatus 1. For example, when the high-temperature device 1 is made of Pt, the melting point of Pt is 1768 ° C., so that the operating temperature of the high-temperature device 1 is sufficiently lower than 1768 ° C. (for example, 1600 ° C. or less), Zr, Y, Hf , Mg, Ca, Al, Si, Ti, and an oxide containing at least one selected from Th each have a melting point of 1800 ° C. or more and have sufficient heat resistance. Further, when the high temperature apparatus 1 is made of Ir, the melting point of Ir is 2447 ° C., so the high temperature apparatus 1 may be used at a higher use temperature (for example, more than 1600 ° C. and less than 2300 ° C.) than the container made of Pt. is there. As described above, when the high temperature apparatus 1 is used in an ultrahigh temperature range such as higher than 1600 ° C. and lower than 2300 ° C., an oxide containing Zr, Hf, Mg, or Th is used as the oxide used for the diffusion prevention layer 4. It is preferable. Since these oxides have a melting point of 2500 ° C. or higher, they have sufficient heat resistance even in a super-high temperature range such as a temperature exceeding 1600 ° C. and 2300 ° C. or lower.

  The diffusion preventing layer 4 and the metal or alloy layer 5 may be formed by, for example, a method in which a green sheet of the diffusion preventing layer 4 is sandwiched between the high temperature apparatus 1 and the metal or alloy layer 5 and sintered. A method of coating the raw material on the outer surface of the high temperature apparatus 1 or the surface of the metal or alloy layer 5, and slurry containing the raw material of the diffusion preventing layer 4 between the outer surface of the high temperature apparatus 1 and the surface of the metal or alloy layer 5 It is a method of applying and sintering. For sintering, a sintering process may be performed separately, but when the high temperature apparatus 1 is, for example, a glass manufacturing furnace, a pipe connected to a glass manufacturing furnace, or an auxiliary jig for a glass manufacturing furnace, for glass manufacturing. You may sinter by the heating at the time of operation of a furnace.

  In the present embodiment, at least when the protection structure having the protection structure attached to the high temperature device 1 is completed and before the high temperature device 1 is used in the high temperature region, the diffusion prevention layer 4 is formed on the high temperature device 1 and / or The metal or alloy layer 5 is preferably not fixed. After the container is used in a high temperature range, the diffusion preventing layer 4 may not be fixed to the high temperature apparatus 1 and / or the metal or alloy layer 5 or may have a fixed part. More preferably, even after the container is used in a high temperature range, the diffusion preventing layer 4 is not fixed to the high temperature apparatus 1 and / or the metal or alloy layer 5.

  In this specification, "the diffusion preventing layer contains an oxide as a main component" means that the diffusion preventing layer contains a component that can be mixed in the step of forming the diffusion preventing layer in addition to the oxide. Meaning. The component that can be mixed in the step of forming the diffusion preventing layer is, for example, a binder derived from a green sheet, a solvent, or various additives.

  When the protective structure includes the diffusion prevention layer 4 and the metal or alloy layer 5, when a metal oxide film, a metal nitride film, a boron nitride film, or a silicon nitride film is provided, the metal oxide film, the metal nitride A diffusion prevention layer 4 and a metal or alloy layer 5 are sequentially disposed on the outer surface of the high temperature apparatus 1 to which the film, boron nitride film or silicon nitride film is fixed.

  FIG. 4 is a diagram showing an example of the protection structure for a high temperature device according to the present embodiment, and shows a case where the high temperature device is a crucible. A crucible 10 shown in FIG. 4 has an upper surface opening portion 11, a body portion 12, and a bottom portion 13. The present embodiment is not limited to the shape of the crucible 10. When the high-temperature apparatus has a curved portion like the bottom portion 13 of the crucible 10 shown in FIG. 4, the ribbon-shaped molded body 2 is vertically arranged and covered on the curved portion (bottom portion 13), and the ribbon is formed thereon. The whole outer surface can be covered by winding the shaped molded body 2 in the lateral direction. In FIG. 4, one Pt line 3 is wound in the longitudinal direction along the trunk portion 12 and the bottom portion 13, and the end portions 3 a and 3 b are welded to the upper surface opening portion 11 of the crucible 10, thereby crucible. 10 is fixed.

  FIG. 5 is a diagram showing an example of a protective structure for a high temperature apparatus according to the present embodiment, and shows a case where the high temperature apparatus is a glass manufacturing furnace. The glass manufacturing furnace 20 shown in FIG. 5 includes an upper surface opening 21, a flange portion 21 a extending from the upper surface opening 21, a body portion 22, a bottom portion 23, and a pipe 24 connected to the central portion of the bottom portion 23. And have. The present embodiment is not limited to the shape of the glass manufacturing furnace 20. In the case where the high temperature apparatus has a reduced diameter portion such as a boundary portion 23a between the bottom portion 23 and the pipe 24 of the glass manufacturing furnace 20 shown in FIG. By winding in the shape, the entire outer surface can be covered without exposing the outer surface of the glass manufacturing furnace 20 with the reduced diameter portion (boundary portion 23a). In FIG. 5, a plurality of Pt wires 3 are wound radially from the center of the bottom portion 23 toward the body portion 22, and the terminal portions (not shown) are flange portions of the glass manufacturing furnace 20. It is being fixed to the furnace 20 for glass manufacture by welding to the lower surface (surface not shown) of 21a.

  In the high-temperature device protection structure according to the present embodiment, it is preferable that the molded body 2 is further fixed in a state where it is not fixed to a portion of the inner surface of the high-temperature device 1 that is exposed to the outside air. Oxidation degradation and oxidation volatilization of the metal forming the high temperature device 1 can be further suppressed. The portion of the inner surface of the high-temperature apparatus 1 that is exposed to the outside air is, for example, the portion of the inner surface of the crucible or glass manufacturing furnace that does not contact the target product or its raw material, or the inner surface of the crucible or glass manufacturing furnace. Among these, it is the vicinity of an upper surface opening part. A method for fixing the molded body 2 in a state where it is not fixed to the inner surface of the high-temperature apparatus 1 and being exposed to the outside air is not particularly limited. However, the crucible 10 in FIG. There is a method of folding along the inner surface through the upper end opening 11.

  The protective structure according to the present embodiment is formed by attaching the protective structure in the manufacturing process of the high-temperature device 1 or in a subsequent process of the manufacturing process, or forming the protective structure by retrofitting the existing device as the high-temperature device 1. Also good.

  Up to this point, the form in which the formed body 2 has a ribbon shape has been described as an example. However, in the present embodiment, the formed body 2 may have a sheet shape, a string shape, or a fabric shape. When the molded body 2 has a sheet shape, for example, the outer surface of the high-temperature apparatus 1 is wrapped and covered with a sheet-shaped molded body (not shown). When the molded body 2 has a string shape, for example, a string-shaped molded body (not shown) is wrapped around the outer surface of the high temperature apparatus 1 to cover it. When the molded body 2 is woven, for example, the outer surface of the high temperature apparatus 1 is wrapped and covered with a woven molded body (not shown).

  Although one Pt line 3 (FIG. 1 or FIG. 4) or a plurality of Pt lines 3 (FIG. 5) is shown, the Pt line 3 may be knitted in a net shape and put on the high temperature apparatus 1. In this embodiment, a Pt-Rh line, an Ir line, or an Ir-Rh line may be used instead of the Pt line 3. In the Pt—Rh line, Ir line, or Ir—Rh line, the ratio of each metal in the alloy is not particularly limited.

  6 to 8 show examples of specific forms of the protective structure according to this embodiment. These are only specific examples, and the present invention is not limited to these. As a first example of a concrete form, as shown in FIG. 6, the outer surface of a glass melting pipe made of Pt as a high temperature apparatus 1 is covered with a zirconium oxide ribbon as a molded body 2, and a Pt wire 3 is wound around It is a fixed form. As a second example of the specific form, as shown in FIG. 7, the outer surface of a high temperature member pipe made of Ir as the high temperature apparatus 1 is covered with a zirconium oxide sheet as the molded body 2. As a third example of the specific form, as shown in FIG. 8, the outer surface of an Ir crystal growth container (crucible) as the high temperature apparatus 1 is covered with a zirconium oxide fabric as the molded body 2.

  9 and 10 show examples of combinations of a high-temperature device, a diffusion prevention layer, and a metal or alloy layer. These are only specific examples, and the present invention is not limited to these. 9 and 10, the molded body is not shown. As shown in FIGS. 9 and 10, when the high temperature apparatus 1 is a crucible, a crucible having a size capable of accommodating the crucible to be the high temperature apparatus 1 may be used as the metal or alloy layer 5. As an example of a specific form, as shown in FIG. 9, an Ir crucible (outer diameter φ (diameter) 79 mm × h (height) 55 mm × t (thickness) 0.5 mm) and metal or A Mo crucible (outer diameter φ85 mm × h57 mm × t2.5 mm) is nested as the alloy layer 5, and a zirconium oxide sheet (t0...) Is used as a diffusion prevention layer (not shown) between the high temperature apparatus 1 and the metal or alloy layer 5. 1 mm). As another example of a specific form, as shown in FIG. 10, a Pt crucible (outer diameter φ (diameter) 145 mm × h (height) 149 mm × t (thickness) 0.5 mm) is used as the high temperature apparatus 1. And a crucible made of Mo (outer diameter φ150 mm × h150 mm × t1.0 mm) as the metal or alloy layer 5 and zirconium oxide as a diffusion preventing layer (not shown) between the high temperature apparatus 1 and the metal or alloy layer 5 It is the form which has arrange | positioned the sheet | seat (t0.1mm).

  The metal element recovery method according to the present embodiment is a process 1 for taking out the molded body 2 used in the protection structure of the high temperature apparatus according to the present embodiment from the high temperature apparatus 1 and the molded body 2 taken out from the high temperature apparatus 1. Or a step of recovering the metal element adhering and diffusing into the inside. In the protection structure for a high temperature device according to the present embodiment, the molded body 2 is fixed without being fixed to the outer surface of the high temperature device 1, so that the molded body 2 can be easily detached from the high temperature device 1. It is possible to recover the metal element that is slightly adhered to the molded body 2 or adhered and diffused to the inside.

  The metal element recovery method according to the present embodiment includes the step 2 of taking out the diffusion prevention layer 4 used in the protective structure of the high temperature device according to the present embodiment from the high temperature device 1 and the metal or alloy layer 5, and the high temperature device 1 and the metal. Or a step of recovering the metal element adhering to the diffusion preventing layer 4 taken out from the alloy layer 5 or adhering and diffusing into the inside. In the protection structure for a high temperature device according to the present embodiment, in particular, when the diffusion prevention layer 4 is fixed without being fixed to the outer surface of the high temperature device 1 and the inner surface of the metal or alloy layer 5, the diffusion prevention layer 4. Can be easily removed from the high temperature apparatus 1 and the metal or alloy layer 5. It is possible to collect a slight amount of the metal element adhering to the diffusion preventing layer 4 or adhering and diffusing to the inside.

  The metal element recovery method according to the present embodiment is performed by performing only step 1 and recovering the metal element only from the formed body 2, performing only step 2 and recovering the metal element only from the diffusion prevention layer 4, or You may collect | recover a metal element from both the molded object 2 and the diffusion prevention layer 4 by performing both the process 1 and the process 2. FIG. When performing both step 1 and step 2, the order of performing step 1 and step 2 does not matter. Further, the step of recovering the metal from the molded body 2 and the step of recovering the metal from the diffusion preventing layer 4 may be performed together in one step or may be performed in separate steps. In the present specification, the concept of “diffusing into the interior” includes entering into the hole when the molded body 2 or the diffusion preventing layer 4 has a hole. A method for recovering the metal element from the molded body 2 and / or the diffusion preventing layer 4 is a dry method or a wet method.

  As the dry method, for example, a technique described in JP 2012-509987A can be used. Moreover, as a wet method, the technique using strong acids, such as aqua regia well-known conventionally, can be utilized, for example.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.

  Prior to the test, the test conditions were selected as follows. Thermogravimetric analysis was performed on Ir. As a sample for thermogravimetric analysis, 79.63 mg of plate-shaped Ir having a length of 3 mm, a width of 5.9 mm, and a thickness of 0.2 mm was used. The results are shown in FIG. As shown in FIG. 11, it was confirmed that the oxidation and volatilization of Ir becomes remarkable from about 1000 ° C. For this reason, a test at 1500 ° C. in the atmosphere was performed as an accelerated test. Even at a temperature lower or higher than 1500 ° C., the volatilization and depletion of metal species that form a high-temperature device such as Pt and Ir can be suppressed by reducing the chance of contact with oxygen by the molded body.

When the high temperature apparatus was made of Ir or Pt, a test for confirming the volatilization preventing effect by the molded body was performed. A plate made of Pt having a length of 10 mm × width of 10 mm × thickness of 0.2 mm or an Ir plate having the same dimensions is regarded as a high-temperature device, and the entire plate made of Pt or Ir is used as a molded body. Wrapped in a 0.1 mm thick zirconium oxide sheet, the mass change after 24 hours at 1500 ° C. in the atmosphere was measured, and the mass loss per unit area was determined. Here, the mass reduction per unit area means the amount of mass reduction (unit: g) by the surface area (total area of front, back and side surfaces) (unit: cm ² ) of a Pt plate or an Ir plate. It is the value divided. The test also included a sample that was not wrapped with a zirconium oxide sheet. The results are shown in Table 1. By wrapping with a compact, the precious metals such as Pt and Ir are less likely to come into contact with oxygen in nitrogen gas or oxygen remaining in the tube furnace, and volatile depletion is reduced to about one third for Pt and about one sixth for Ir. The amount could be reduced.

Next, the test which confirms the volatilization prevention effect by a molded object was done about the case where a high temperature apparatus consists of Mo. A Mo plate measuring 10 mm long × 10 mm wide × 0.2 mm thick is regarded as a high-temperature device, and the entire Mo plate is wrapped in a zirconium oxide sheet having a thickness of 0.1 mm as a molded body, after 24 hours at 1500 ° C. The mass change of was measured, and the mass loss per unit area was determined. Here, the mass loss per unit area is a value obtained by dividing the mass reduction amount (unit: g) by the surface area of the Mo plate (total area of the front surface, back surface, and side surface) (unit: cm ² ). . Since Mo is so oxidized and depleted that it cannot be tested in the same air atmosphere as noble metals such as Ir and Pt, the test was performed in an atmosphere in which a nitrogen flow rate of 1 L / min was supplied into the tubular furnace. The test also included a sample that was not wrapped with a zirconium oxide sheet. The results are shown in Table 2. By wrapping with the compact, Mo became difficult to come into contact with oxygen in nitrogen gas or oxygen remaining in the tubular furnace, and the amount of volatile depletion could be reduced to about one fifth.

  Next, an Ir plate (hereinafter referred to as an Ir plate) having a length of 10 mm × width 10 mm × thickness 2 mm is referred to as a high-temperature device, and a Mo plate having a length of 10 mm × width 10 mm × thickness 10 mm (hereinafter referred to as Mo plate). ) Was regarded as a metal layer, and a test for confirming the anti-diffusion effect of the anti-diffusion layer was conducted.

  A zirconium oxide sheet having a length of 15 mm, a width of 15 mm, and a thickness of 0.1 mm is disposed between the Ir plate and the Mo plate as a diffusion preventing layer, and is left in a tubular furnace at 1500 ° C. for 24 hours. Surface analysis by EDX was performed on the side surface. Since Mo is so exhausted that oxidation is impossible in an air atmosphere at 1500 ° C., a nitrogen flow rate of 1 L / min was supplied into the furnace. In the test, a sample without a zirconium oxide sheet was also provided. FIG. 12 shows an EDX analysis spectrum when no sheet is arranged, and FIG. 13 shows an EDX analysis spectrum when a sheet is arranged. When the zirconium oxide sheet was not disposed, Mo was strongly detected from the surface of Ir that was in contact with Mo as shown in FIG. On the other hand, when the zirconium oxide sheet was arranged, Mo was hardly detected from the surface of Ir as shown in FIG. 13, and the function as a diffusion preventing layer was confirmed.

  The following tests were conducted on the recovery of metal elements. A high temperature apparatus was produced in which a zirconium oxide sheet was disposed as a diffusion preventing layer between an Ir high temperature apparatus and a Mo metal layer. This high temperature apparatus was used for about one year as an aluminum oxide single crystal growing apparatus. It was found that the returned high temperature device did not join Ir and Mo, and diffusion was suppressed. Moreover, when the taken-out zirconium oxide sheet was grind | pulverized and analyzed, 1.3% Ir was detected and it confirmed that collection | recovery of a noble metal was possible.

DESCRIPTION OF SYMBOLS 1 High temperature apparatus 2 Forming body 2a Winding end part 3 Pt wire 3a, 3b End part 4 Diffusion prevention layer 5 Metal or alloy layer 10 Crucible 11 Upper surface opening part 12 Body part 13 Bottom part 20 Glass manufacturing furnace 21 Upper surface opening part 21a Flange part 22 trunk 23 bottom 24 pipe 23a boundary

Claims (13)

In the protection structure of the high temperature device used in the high temperature range of 1200 ° C or higher,
A part or all of the outer surface of the high-temperature device is covered with a sheet-like, ribbon-like, string-like, or woven-like molded body containing a metal oxide as a main component, and the molded body is outside the high-temperature device. It is fixed without sticking to the surface,
A protection structure for a high-temperature device, wherein the molded body suppresses contact between an outer surface of the high-temperature device and outside air.   The high-temperature apparatus is a glass manufacturing furnace, a pipe connected to the glass manufacturing furnace, a stirring part used in the glass manufacturing furnace, or an auxiliary jig for the glass manufacturing furnace; a crucible; or for growing a single crystal The protective structure for a high-temperature device according to claim 1, wherein the protective structure is a container.   Whether the high-temperature device is formed using one of elements selected from (1) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and W, or (2) Ir, Pt, Rh, Ru, Or an alloy containing two or three elements selected from Mo, Re, Nb, Ta and W, or (3) Ir, Pt, Rh, Ru, Mo, Re, Nb, Ta and The protective structure for a high-temperature device according to claim 1 or 2, wherein the protective structure is formed using an alloy containing one or two elements selected from W and at least one element of Pd or Au.   The metal species of the metal oxide of the molded body is at least one selected from Zr, Y, Hf, Mg, Ca, Al, Si, Ti, and Th. The protection structure of the high temperature apparatus as described in one.   A diffusion prevention layer and a metal or alloy layer are arranged in order from the side close to the outer surface of the high-temperature device between a part or all of the outer surface of the high-temperature device and the compact. The protective structure for a high-temperature device according to any one of claims 1 to 4.   The diffusion preventing layer contains an oxide as a main component, and the element bonded to oxygen of the oxide is at least one selected from Zr, Y, Hf, Mg, Ca, Al, Si, Ti, and Th. The protection structure for a high-temperature device according to claim 5, wherein the protection structure is a high-temperature device.   The metal or alloy layer is formed using one kind of element selected from Ru, Mo, Re, Nb, Ta and W, or two elements selected from Ru, Mo, Re, Nb, Ta and W. The protective structure for a high-temperature device according to claim 5 or 6, wherein the protective structure is formed using an alloy containing at least a seed.   The protective structure for a high temperature device according to claim 5, wherein the metal or alloy layer is a reinforcing layer of the high temperature device.   9. A metal oxide film, a metal nitride film, a boron nitride film, or a silicon nitride film is fixed to a part or all of the outer surface of the high temperature device. The protective structure of the high temperature apparatus as described in 1.   The high temperature apparatus protective structure according to claim 9, wherein the film is formed by a thermal spraying method, a CVD method, a PVD method, a coating pyrolysis method, a spray pyrolysis method, or a spray pyrolysis method.   The molded body is wound with at least one kind of Pt line, Pt-Rh line, Ir line or Ir-Rh line, and at least one kind of Pt line, Pt-Rh line, Ir line or Ir-Rh line The protection structure for a high-temperature device according to any one of claims 1 to 10, wherein the end portion is bound to or welded to the high-temperature device.   The high-temperature apparatus according to any one of claims 1 to 11, wherein the molded body is further fixed in a state where it is not fixed to an inner surface of the high-temperature apparatus and a portion that is exposed to outside air. Protective structure. The process 1 which takes out the molded object used with the protection structure of the high temperature apparatus as described in any one of Claims 1-12 from this high temperature apparatus, and / or the high temperature as described in any one of Claims 5-8. A removal step of performing step 2 of removing the diffusion prevention layer used in the protective structure of the device from the high temperature device and the metal or alloy layer;
And a recovery step of recovering the metal element adhering or adhering and diffusing into the molded body and / or the diffusion preventing layer taken out in the taking-out step.