TW201940439A - Molten glass stirring chamber - Google Patents

Abstract

A stirring chamber includes a stirring vessel configured to receive molten glass; a cover on the stirring vessel; and a stirrer configured to pass through the cover and stir the molten glass. The cover includes a porous heat-resistant body and an inorganic ceramic layer covering a surface of the porous heat-resistant body.

Description

Molten glass stirring chamber

This application claims the priority right of Korean Patent Application No. 10-2018-0011606 in accordance with the Patent Law. The Korean patent application was filed on January 30, 2018. This article relies on the content of the Korean patent application and the The Korean patent application is incorporated herein by reference in its entirety.

The present disclosure is about a molten glass stirring chamber, which can reduce defects in a glass sheet formed of molten glass.

An apparatus for manufacturing a flat glass sheet includes a stirring apparatus for stirring molten glass.

The stirring device includes: a stirring container assembled to contain molten glass; a cover member assembled to cover the stirring container; and a stirring blade positioned in the stirring container. Over time, the platinum-based heat source disposed inside the cover reacts with oxygen in the atmosphere. Oxidized platinum is undesirably incorporated into the glass as platinum precipitates, thus causing defects in the glass sheet.

The disclosure of this case provides a molten glass stirring chamber capable of reducing defects occurring from a cover.

According to one or more embodiments, a stirring chamber may include: a stirring container assembled to receive molten glass; a cover positioned on the stirring container; and a stirrer passing through the cover and assembled to stir the molten glass The cover includes a cover main body and an inorganic ceramic layer, the inorganic ceramic layer covers a surface of the cover main body, and the cover main body is porous.

The inorganic ceramic layer may include a glass layer. The glass layer may include about 80% to about 90% by weight of silicon dioxide (SiO ₂ ), about 1% to about 3% by weight boron oxide (B ₂ O ₃ ), and about 2% to about 5% by weight Aluminum oxide (Al ₂ O ₃ ), about 1% to about 3% by weight sodium oxide (Na ₂ O), about 2% to about 4% by weight potassium oxide (K ₂ O), about 2% by weight To about 6% by weight of zinc oxide (ZnO), and about 0.1 to about 2% by weight of zirconia (ZrO ₂ ).

The cover body may include a groove and a heat source disposed within the groove. The heat source may remain in the groove surrounded by the inorganic filler. The inorganic ceramic layer may cover at least a top surface and a bottom surface of the cover body, and an exposed portion of the inorganic filler. The inorganic filler may be cement.

The cover may further include a noble metal coating layer covering at least a top surface and a bottom surface of the cover body, and the noble metal coating layer is disposed on the inorganic ceramic layer. The cover may further include a refractory oxide layer covering the surface of the precious metal coating layer facing the inside of the stirring container.

The cover may have a central hole through which the agitator passes, and the cover may be divided into a first body and a second body along a boundary region, wherein the first body includes horizontally protruding along the boundary region in a longitudinal direction. The piece section. The sheet portion may at least partially overlap the second body. The sheet portion may be disposed on a lower portion of the first body facing the inside of the stirring container.

According to one or more embodiments, a stirring chamber may include: a stirring container assembled to receive molten glass; a cover on the stirring container; and a stirrer passing through the cover and assembled to stir the molten glass, wherein The cover includes a cover body having a center hole and the agitator passes through the center hole. The cover body is porous, wherein the cover body includes a first body and a first body along a boundary region. Two main bodies, and wherein the first main body includes a sheet portion that protrudes horizontally along a boundary region in a longitudinal direction.

The sheet portion may at least partially overlap the second body. The surface of each of the first body and the second body may be covered by an inorganic ceramic layer. A lower portion of the first body includes a precious metal coating, and the sheet is partially attached to a surface of the precious metal coating.

According to one or more embodiments, a stirring chamber may include: a stirring container assembled to receive molten glass; a cover on the stirring container; and a stirrer passing through the cover and assembled to stir the molten glass, Wherein the cover includes a noble metal coating, the noble metal coating is at least on the lower surface of the cover, wherein the surface of the noble metal coating facing the molten glass is covered by a refractory oxide layer, the refractory oxide layer comprising: from about 3% to about 5 wt% of CaO, from about 0.2% to about 1 wt% of SiO _2, from about 0.2% to about 1 wt% of Al ₂ O _3, from about 0.5 wt% to about 3.5 HfO _{2 by} weight and the balance of ZrO ₂ .

The refractory oxide layer may further include about 0.01% by weight to about 0.3% by weight of Fe ₂ O ₃ and about 0.01% by weight to about 0.9% by weight of MgO.

The refractory oxide layer may have a thickness of about 2 mils to about 8 mils.

The cover may include a cover body having a central hole through which the agitator body is divided, wherein the cover is divided into a first body and a second body along a boundary area, the boundary area extending through the center hole, The surface of each of the first body and the second body is covered by an inorganic ceramic layer, and a sheet portion protruding horizontally across the boundary region is disposed on the first body.

Exemplary embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, the patent application scope may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that the disclosure of this case is thorough and complete, and will fully convey the exemplary implementation to those with ordinary knowledge in the technical field to which the invention belongs.

In the drawings, the dimensions of the layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or element, it can be directly on the other layer or element, or intervening layers may also be present. In addition, it should also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. The same element symbol indicates the same element throughout.

As used herein, the term "and / or" (or and / or) includes any and all combinations of one or more of the associated listed items. For example, the term "or" is not exclusive and can be understood to have the same meaning as "and / or". When there is an expression such as "at least one" in front of a list of elements, the expression is to modify the entire list of elements without modifying the individual elements of the list.

Although terms such as "first", "second", etc. may be used to describe various components, these components should not be limited to the above terms. The above terms are only used to distinguish one component from another. For example, the first component discussed below may be referred to as the second component, and similarly, the second component may be referred to as the first component without departing from the teachings of the disclosure of the present case.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. An expression used in the singular encompasses the expression in the plural, unless it has a clearly different meaning in the context. It should be understood that when used in this specification, terms such as "including" and / or "including" designate the existence of stated features, integers, steps, operations, elements, components, and / or groups described above, but not Exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components, and / or groups of the foregoing.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It will be further understood that terms such as those defined in commonly used dictionaries should be interpreted to have meanings consistent with their meaning in the context of the relevant field, and should not be interpreted as idealized or overly formal, unless it is clearly so Define.

The operations of all methods described herein can be performed in any suitable order unless otherwise specified herein or otherwise clearly contradicted by context. The embodiments are not limited to the described sequence of operations. For example, two successively described processes may be performed substantially simultaneously or in a reverse order to the described order.

In this regard, differences in the illustrated shapes due to, for example, manufacturing techniques and / or tolerances can be expected. Therefore, the embodiments should not be construed as being limited to the specific shape of the regions described herein, but include, for example, shape deviations caused by manufacturing.

FIG. 1 is a diagram of an exemplary glass manufacturing apparatus 1 according to various embodiments.

Referring to FIG. 1, the glass manufacturing apparatus 1 may include a melting container 100, a clarification container 200, a molten glass stirring chamber 300, a delivery container 500, and a forming apparatus 700. According to some embodiments, the glass manufacturing apparatus 1 may manufacture sheet glass, however, in other embodiments, the glass manufacturing apparatus may manufacture various other glass articles, including glass rods, glass tubes, glass containers, and glass envelopes.

The melting container 100, the clarification container 200, the molten glass stirring chamber 300, the delivery container 500, and the forming apparatus 700 may be glass manufacturing process stations connected in series. The predetermined processes for manufacturing glass products are performed at these stations. According to some embodiments, the manufacturing process performed by the glass manufacturing equipment may include a down-draw process, a slot-draw fusion forming process (including a double fusion process), a float glass forming process, and a rolling process.

According to some embodiments, each of the melting vessel 100, the clarification vessel 200, the molten glass stirring chamber 300, the delivery vessel 500, and the forming apparatus 700 may include a platinum-containing metal such as platinum or platinum-rhodium, platinum-iridium, and the above A combination of materials. According to some embodiments, each of the melting vessel 100, the clarification vessel 200, the molten glass stirring chamber 300, the delivery vessel 500, and the forming apparatus 700 may include palladium, osmium, ruthenium, and osmium, and other metals. According to some embodiments, the forming apparatus 700 may include a ceramic material or a glass-ceramic material.

The melting vessel 100 receives a batch 11 from a storage vessel 10. The batch 11 is inserted into the melting container 100 through a batch delivery device 13, which is powered by a driving device 15. The selective controller 17 may be assembled to operate the driving device 15 to introduce a desired amount of the batch 11 into the melting vessel 100, as indicated by arrow a1. According to some embodiments, the glass liquid height probe 19 may be used to measure the liquid height of the molten glass MG in the standpipe 21 and transmit the measured liquid height of the molten glass MG to the controller 17 through the communication line 23.

According to some embodiments, the clarification vessel 200 is connected to the melting vessel 100 by a first conduit 150. The first duct 150 includes a passage through which the molten glass MG flows. The second duct 250 and the third duct 350 described below also provide a passage through which the molten glass MG flows. The first conduit 150 may include a material that is conductive and can be used under high temperature conditions. According to some embodiments, the first catheter may include a platinum-containing metal, such as platinum, platinum-rhodium, platinum-iridium, or a combination of the foregoing materials. According to some embodiments, the first to third conduits may include a metal, such as molybdenum, palladium, hafnium, tantalum, titanium, tungsten, ruthenium, hafnium, zirconium, or an alloy of the above metals, and / or zirconium dioxide.

The clarification container 200 functions as a refining tube. The clarification vessel 200 is located downstream of the melting vessel 100. The clarification container 200 receives the molten glass MG from the melting container 100. According to some embodiments, a high temperature process may be performed in the clarification container 200 to remove air bubbles (ie, gaseous inclusions) from the molten glass MG. According to some embodiments, the clarification container 200 is assembled to remove bubbles from the molten glass MG by heating the molten glass MG while the molten glass MG passes through the clarification container 200. According to some embodiments, when the molten glass MG is heated in the clarification container 200, the clarifier contained in the molten glass MG may initiate a redox reaction, thereby causing oxygen and other gases to be removed from the molten glass MG. Specifically, the bubbles contained in the molten glass MG may include oxygen, carbon dioxide, and / or sulfur dioxide, and may be combined with oxygen generated in the reduction reaction of the fining agent, and thus the volume of the bubbles may increase. The growing bubbles may float toward the free surface of the molten glass MG in the clarification container 200, thereby being separated from the molten glass MG. The air bubbles can be discharged to the outside of the clarification container 200 through the gas phase space in the upper part of the clarification container 200.

According to some embodiments, the molten glass stirring chamber 300 is located downstream of the clarification vessel 200. The molten glass stirring chamber 300 can homogenize the molten glass MG supplied from the clarification container 200. A stirrer 310 may be provided in the molten glass stirring chamber 300 to rotate relative to the molten glass stirring chamber 300 so that the molten glass MG flows and mixes in the molten glass stirring chamber 300. The stirrer 310 may stir the molten glass MG to homogenize the molten glass MG before leaving the stirring chamber 300.

The delivery container 500 may be located downstream of the molten glass stirring chamber 300. The delivery container 500 is connected to the molten glass stirring chamber 300 by a third conduit 350. The outlet conduit 600 is connected to a delivery container 500. The molten glass MG is transferred through the outlet duct 600 to the inlet 650 of the forming apparatus 700.

The forming apparatus 700 receives the molten glass MG from the delivery container 500. The forming apparatus 700 may form the molten glass MG into a sheet-type glass product, however, in a further embodiment, the forming apparatus may form the molten glass into other shapes of objects, such as rods, tubes, envelopes, and the like. For example, the forming apparatus 700 may include a fusion traction machine for forming the molten glass MG into a continuous glass ribbon. The molten glass MG flowing into the forming apparatus 700 may overflow in the forming apparatus 700. The overflowing molten glass MG is moved in a downward direction by a combination of gravity and appropriately arranged rolls such as an edge roll 750 and a drawing roll 800 to form a molten glass ribbon.

FIG. 2 is a perspective view of a molten glass stirring chamber 300 according to an embodiment.

Referring to FIG. 2, the molten glass stirring chamber 300 may include: a stirring container 320 assembled to receive the molten glass MG in the stirring container 320; a cover 330 disposed on the stirring container 320; and a stirrer 310 penetrating the cover 330 and Assembled into a stirred molten glass MG.

The stirring vessel 320 may be connected to the second and third ducts 250 and 350. As described above, the molten glass MG is introduced into the stirring container 320 through the second conduit 250 and is discharged from the stirring container 320 through the third conduit 350.

The agitator 310 may include a stirring rod 314 and a plurality of blades 312 attached to the stirring rod 314.

The cover 330 is assembled to cover the opening of the stirring container 320. A center hole 338 through which the stirring rod 314 passes may be provided in the center of the cover 330. A heat source 332 may be provided inside the cover 330.

The cover 330 may include two bodies, a first body 330a and a second body 330b. The first body 330a and the second body 330b may be separated from each other, and a boundary area is disposed between the first body 330a and the second body 330b and the boundary area intersects the center hole 338. Although FIG. 2 illustrates an example in which the cover 330 is divided into two bodies, in another embodiment, the cover 330 may be divided into three or more bodies.

The first body 330a and the second body 330b may each include a cover body 334 and a heat source 332 embedded in the body.

The heat source 332 includes platinum or a platinum alloy, and heat may be generated when power is supplied to the heat source 332. In detail, the heat source 332 may include pure platinum or a platinum alloy. The platinum alloy may be an alloy of platinum and at least one of the following metals: rhodium (Rh), iridium (Ir), ruthenium (Ru), palladium (Pd), and osmium (Os).

The cover body 334 may include a refractory material. In some embodiments, the cover body 334 may include a porous material. For example, the cover body 334 may include materials such as Crystallite HF339 (available from BUCHER Emhart Glass) or AN485 (available from Saint Gobain).

FIG. 3 is a perspective view of the first body 330a of the cover 330 according to an embodiment, and FIG. 4 illustrates a cross section taken along a line IV-IV 'of FIG. Although the following description focuses on the first body 330a, those having ordinary knowledge in the technical field to which the invention pertains will understand that the description can be equally applied to the second body 330b, or the cover 330 is divided into three or more Extra subjects in the examples.

Referring to FIGS. 3 and 4, the cover body 334 may be provided with a groove 334R, which is assembled to receive the heat source 332. The groove 334R may extend in the line of sight direction of FIG. 4, or may extend in another direction, such as the circumferential or radial direction of the cover body 334. The heat source 332 may be received in the groove 334R.

The heat source 332 may be embedded and fixed in the groove 334R surrounded by the inorganic filler 334f. The inorganic filler 334f may be, for example, cement.

As illustrated in FIG. 4, the inorganic filler 334 f may be at least partially exposed from the cover body 334. In some embodiments, the surface of the inorganic filler 334f may be coplanar with the surface of the cover body 334.

The surface of the cover body 334 may be covered with an inorganic ceramic layer 336. In one embodiment, the inorganic ceramic layer 336 as used herein is an inorganic compound between a metal and a non-metal element, for which the interatomic bond is completely ionic (or mainly ionic), and the inorganic ceramic The material included in the layer has a crystalline, partially crystalline, or non-crystalline (ie, glass) structure. In some embodiments, the inorganic ceramic layer 336 may be a glass layer including silicon dioxide as a main component. For example, the inorganic ceramic layer 336 may include about 80% to about 90% by weight of silicon dioxide (SiO ₂ ), about 1% to about 3% by weight boron oxide (B ₂ O ₃ ), and about 2% by weight to about 5 wt.% alumina (Al ₂ O _3),% by weight to about 3% by weight of sodium oxide of about 1 (Na ₂ O), from about 2 wt.% to about 4 wt% of potassium oxide (K ₂ O), About 2% to about 6% by weight of zinc oxide (ZnO) and about 0.1% to about 2% by weight of zirconia (ZrO ₂ ).

In some embodiments, the inorganic ceramic layer 336 may cover the upper surface of the cover body 334. In some embodiments, the inorganic ceramic layer 336 may cover the lower surface of the cover body 334. In some embodiments, the inorganic ceramic layer 336 may cover the exposed surface of the inorganic filler 334f.

It is desirable to prevent or reduce oxygen from coming into contact with the platinum contained in the heat source 332, because otherwise platinum may be oxidized due to contact with oxygen at high temperatures and lost in gaseous PtO ₂ . Undesirably, such gaseous PtO ₂ may be deposited as a condensate at undesired locations, including as an inclusion in the molten glass MG in the stirring chamber 300. The inorganic ceramic layer 336 may prevent or reduce the contact of platinum and oxygen included in the heat source 332.

The thickness of the inorganic ceramic layer 336 may be in a range of about 1 mm to about 5 mm. If the thickness of the inorganic ceramic layer 336 is too large, particles may be generated due to the peeling of the layer 336. On the other hand, if the thickness of the inorganic ceramic layer 336 is too small, the effect of preventing the oxidation of platinum included in the heat source 332 may be insufficient.

On the other hand, when the cover body 334 is porous, the interface between the cover body 334 and the inorganic ceramic layer 336 may be blurred. In other words, the inorganic ceramic layer 336 may partially penetrate into the pores of the cover body 334 in a region in contact with the porous cover body 334.

FIG. 5 is a diagram conceptually illustrating a method of defining an interface between the cover body 334 and the inorganic ceramic layer 336 with respect to a cross section cut along a line VT ′ of FIG. 4. In FIG. 5, the horizontal axis represents a position along a line VT ′ in FIG. 4, and the vertical axis represents a mass fraction of a material constituting the inorganic ceramic layer 336 and a material constituting the cover body 334. Referring to FIG. 5, there may be a section in which the mass fraction of the cover body 334 and the inorganic ceramic layer 336 gradually changes around the interface IF, at which the cover body 334 is in contact with the inorganic ceramic layer 336. A virtual interface where the masses of the cover body 334 and the inorganic ceramic layer 336 are about 0.5, respectively, may be defined as the interface between the cover body 334 and the inorganic ceramic layer 336.

FIG. 6 is a side sectional view of a first body 330a 'according to another embodiment. The first body 330a 'of FIG. 6 is different from the first body 330a of FIG. 4 in that the inorganic ceramic layer 336a is formed only on the lower surface of the cover body 334. Therefore, in the following, these differences will be mainly described, and redundant descriptions will be omitted.

Referring to FIG. 6, the inorganic ceramic layer 336 a is not formed on the entire surface of the cover body 334. In some embodiments, the inorganic ceramic layer 336a may coat only the surface of the cover body 334 on which the heat source 332 is provided. In some embodiments, the inorganic ceramic layer 336a may cover the exposed surface of the inorganic filler 334f. In some embodiments, the inorganic ceramic layer 336a may cover the surface of the cover body 334, which is substantially coplanar with the exposed surface of the inorganic filler 334f. In some embodiments, the inorganic ceramic layer 336a may not cover a surface of the cover body 334 that is not coplanar with the exposed surface of the inorganic filler 334f.

Since the shortest way for oxygen to oxidize platinum in the heat source 332 is from the surface on the side where the inorganic filler 334f is located, even if the inorganic ceramic layer 336a is formed on only one surface (that is, only the surface on which the groove 334R is formed) The effect of preventing platinum oxidation and loss as shown in FIG. 4 can also be obtained similarly. Furthermore, the first body 330a 'in the embodiment of Fig. 6 uses a smaller amount of the inorganic ceramic layer 336a than the embodiment of Fig. 4, so the first body 330a' is relatively more cost-effective and easier to manufacture. In addition, since the first body 330a 'may be lighter in weight than the first body 330a of FIG. 4 (due to a smaller amount of the inorganic ceramic layer 336), the sagging of the cover 330 may be less likely at the operating temperature. occur.

7A to 7C are side sectional views sequentially explaining a method of manufacturing the first bodies 330a and 330a 'according to the embodiment.

Referring to FIG. 7A, a groove 334R is formed on a lower surface of the cover body 334. The groove 334R may have a size sufficient to receive the heat source 332 (see FIG. 7B) in the groove 334R.

Referring to FIG. 7B, the heat source 332 may be disposed in the groove 334R, and a space between the inner surface of the groove 334R and the heat source 332 may be filled with an inorganic filler 334f. Since the material of the inorganic filler 334f has been described in detail above, further detailed description of the material is omitted.

Referring to FIG. 7C, an inorganic ceramic material layer 336p is formed on the surfaces of the cover body 334 and the inorganic filler 334f. The inorganic ceramic material layer 336p may be, for example, a slurry layer in which the inorganic ceramic material is dispersed in a dispersion medium. In some embodiments, the inorganic ceramic material layer 336p may include a mixture in which a solid powder is mixed with a dispersion medium such as water at a weight ratio of about 1: 2 to about 2: 1, the solid powder includes: about 80% by weight To about 90% by weight of silicon dioxide (SiO ₂ ), about 1% to about 3% by weight of boron oxide (B ₂ O ₃ ), and about 2% to about 5% by weight of alumina (Al ₂ O ₃ ), About 1% to about 3% by weight of sodium oxide (Na ₂ O), about 2% to about 4% by weight of potassium oxide (K ₂ O), and about 2% to about 6% by weight of zinc oxide (ZnO) and about 0.1% to about 2% by weight of zirconia (ZrO ₂ ).

The inorganic ceramic material layer 336p may be formed by brush coating, spray coating, dip coating, or spin coating, but the embodiments disclosed in this case are not limited thereto.

Subsequently, the inorganic ceramic material layer 336 p is annealed at a temperature of about 800 ° C. to about 2000 ° C. for about 10 seconds to about 60 minutes to form an inorganic ceramic layer 336 a, and a first body 330 a illustrated in FIG. 4 can be obtained.

The first body 330a 'illustrated in FIG. 6 may be manufactured by the same method as described with reference to FIGS. 7A to 7C, except that the inorganic ceramic material layer 336p is formed only on the cover body 334 in FIG. On the lower surface.

8 is a side sectional view of a first body 330a "according to another embodiment. The first body 330a" of Fig. 8 is different from the first body 330a of Fig. 4 in that the first body 330 "further includes a noble metal coating 333 and refractory oxide layer 337, the refractory oxide layer is on one surface of the noble metal cladding layer 333. Therefore, in the following, this difference will be mainly described, and redundant description will be omitted.

The noble metal cladding layer 333 may be formed on at least the upper surface 333US or the lower surface 333LS of the noble metal cladding layer 333. Precious metals are defined as metals that are resistant to corrosion and oxidation, such as platinum (Pt), gold (Au), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir) , Copper (Cu), and rhenium (Re). In some embodiments, a noble metal cladding layer 333 may be formed on the upper and lower surfaces of the cover body 334. In some embodiments, the noble metal cladding layer 333 may also be formed on the inner surface of the center hole 338 (corresponding to the side wall portion SW of FIG. 8).

The noble metal cladding layer 333 may include, for example, platinum or a platinum alloy. For example, the platinum alloy may be an alloy of platinum and at least one of the following metals: rhodium (Rh), iridium (Ir), ruthenium (Ru), palladium (Pd), and osmium (Os).

The refractory oxide layer 337 may be disposed on the lower surface 333LS of the noble metal cladding layer 333. The refractory oxide layer 337 is made of a highly heat-resistant oxide material. The lower surface 333LS may be a surface facing the stirring container 320. The refractory oxide layer 337 covers platinum or platinum alloy exposed to high temperature to reduce the area of the exposed area, thereby reducing the redox reaction of platinum and the possibility of condensation of reaction products on the inner surface of the cover and the stirring container At this inner surface, reaction products may fall into the molten glass MG. This makes it possible to reduce product defects caused by such inclusions.

The thickness of the refractory oxide layer 337 may range from about 1 mil (= 0.001 inches) to about 10 mils. In some embodiments, the thickness of the refractory oxide layer 337 may be in a range of about 2 mils (= 0.002 inches) to about 8 mils.

The lower surface 333LS of the noble metal cladding layer 333 formed with the refractory oxide layer 337 thereon may be roughened. In some embodiments, when measured by the BS EN ISO 4287: 2000 standard, the roughness Ra of the lower surface 333LS of the precious metal cladding layer 333 may be in a range of about 0.1 μm to about 50 μm. Here, Ra is an arithmetic mean roughness, and is an arithmetic mean difference of a roughness distribution curve. If the roughness Ra is too large, the flatness after the refractory oxide layer 337 is formed may be insufficient. If the roughness Ra is too small, adhesion between the refractory oxide layer 337 and the precious metal cladding layer 333 may be insufficient.

9A and 9B are perspective views illustrating a method of forming a refractory oxide layer 337 on a surface of a first body 330a according to an embodiment.

Referring to FIG. 9A, an outer surface of the first body 330 a may be covered with an inorganic ceramic layer 336. The noble metal cladding layer 333 may be provided on the upper and lower surfaces of the first body 330a. In addition, the noble metal cladding layer 333 may be at least partially provided on the sidewall SW of the first body 330a.

Subsequently, the lower surface 333LS of the noble metal cladding layer 333 may be roughened. In FIG. 9A, for easy understanding, the first body 330 a is turned upside down so that the lower surface 333LS faces upward. The roughening may be performed by, for example, sand blasting, but is not limited thereto. Thus, a roughened lower surface 333SB can be obtained.

Referring to FIG. 9B, a refractory oxide layer 337 is formed on the roughened lower surface 333SB of the noble metal cladding layer 333.

The refractory oxide layer 337 may be a material layer including zirconia (ZrO ₂ ) as a main component. In some embodiments, the refractory 337 may include an oxide layer: wt% to about 1% to about 5% by weight to about 3% by weight of calcium oxide (CaO), from about 0.2 weight silicon dioxide (SiO _2), about 0.2 Alumina (Al ₂ O ₃ ) by weight% to about 1% by weight, hafnium oxide (HfO ₂ ) from about 0.5% to about 3.5% by weight, and the rest are zirconia (ZrO ₂ ) and inevitable impurities. The refractory oxide layer 337 may further include about 0.01% to about 0.3% by weight of iron oxide (Fe ₂ O ₃ ) and about 0.01% to about 0.9% by weight of magnesium oxide (MgO).

In some embodiments, the refractory oxide layer 337 may include: about 1% to about 2% by weight hafnium oxide (HfO ₂ ), about 2.5% to about 4.5% by weight calcium oxide (CaO), and about 0.2% by weight. % To about 1.0% by weight of silicon dioxide (SiO ₂ ), about 0.3% to about 1.2% by weight of alumina (Al ₂ O ₃ ), and about 0.01% to about 0.2% by weight of iron oxide (Fe ₂ O ₃ ), about 0.05% by weight to about 0.2% by weight of titanium dioxide (TiO ₂ ), and about 0.01% by weight to about 0.1% by weight of magnesium oxide (MgO), and the rest are zirconia (ZrO ₂ ) and inevitable impurities.

In some embodiments, the refractory oxide layer 337 may be formed by melting the source powder with a plasma and spraying the molten source powder. FIG. 9B illustrates an exposed portion of the lower surface 333SB to show that the refractory oxide layer 337 can be formed on the lower surface 333SB. However, in other embodiments, the refractory oxide layer 337 may be formed on the entirety of the roughened lower surface 333SB.

FIG. 10 illustrates a first body 331a of a cover 330 according to an embodiment. The first body 331a may constitute the cover 330 together with the second body 331b.

Referring to FIG. 10, a sheet portion 339 protruding along a boundary region BD between the first body 331 a and the second body 331 b may be disposed under the refractory oxide layer 337.

Although the sheet portion 339 is attached to the lower surface of the first body 331a, the protruding portion of the sheet portion 339 may at least partially overlap the second body 331b. In other words, the sheet portion 339 may substantially completely cover the boundary region BD other than the center hole 338. In some embodiments, the width G1 of the sheet portion 339 protruding from the first body 331a toward the second body 331b may be larger than the gap G2 between the first body 331a and the second body 331b.

The sheet portion 339 may include a metal or an inorganic material. In some embodiments, the sheet portion 339 may include a metal, such as platinum or a platinum alloy. In some embodiments, the sheet portion 339 may include a silicon dioxide-based inorganic material, a zirconia-based inorganic material, or an alumina-based inorganic material. In some embodiments, the sheet portion 339 may include an alloy of platinum and rhodium.

11A and 11B are cross-sectional views of first bodies 331a 'and 331a "of a cover according to other embodiments.

Referring to FIG. 11A, the sheet portion 339 may be directly attached to the surface of the inorganic ceramic layer 336. The first body 331a 'of FIG. 11A may be substantially the same as the first body 331a in the embodiment of FIG. 10, except that the refractory oxide layer 337 and the noble metal cladding layer 333 are omitted.

Referring to FIG. 11B, the sheet portion 339 may be directly attached to the surface of the precious metal cladding layer 333. The first body 331 a ″ in FIG. 11B may be substantially the same as the first body 331 a in the embodiment of FIG. 10, except that the refractory oxide layer 337 is omitted.

In the following, the composition and effects of the disclosure in this case will be described in more detail with reference to specific examples and comparative examples. However, these examples are only intended to clarify the disclosure in this case, not to limit the scope of the disclosure in this case.

FIG. 12 is a diagram illustrating a helium gas leak test apparatus for testing the performance of an inorganic ceramic layer according to an embodiment.

Referring to FIG. 12, the chamber 51 includes an opening 54 on one side, and the sample SA is fixed in the opening 54 of the chamber 51. The inlet valve 52 is opened so that helium (He) is supplied at a predetermined pressure in a state where no leakage occurs between the sample SA and the chamber 51, and the outlet valve 53 is closed.

If more gas can pass through the path of the sample SA, the amount of helium leakage detected by the helium sensor 43 will increase. Conversely, if there are fewer gas paths that can pass through the sample SA, the amount of helium leak detected by the helium sensor 43 will decrease.

An inorganic ceramic layer was formed to a thickness of about 3 mm on a porous AN485 (available from Saint Gobain) sample. The inorganic ceramic layer includes: about 85.05% by weight of silicon dioxide (SiO ₂ ) and about 2.25% by weight of boron oxide (B ₂ O ₃ ), about 3.25% by weight of alumina (Al ₂ O ₃ ), about 1.7% by weight of sodium oxide (Na ₂ O), about 2.5% by weight of potassium oxide (K ₂ O), and about 4.1% by weight Zinc oxide (ZnO) and about 1.15% by weight of zirconia (ZrO ₂ ).

A sample with an inorganic ceramic layer (Example 1) and a sample without an inorganic ceramic layer (Comparative Example 1) were fixed at the opening of the chamber, and a helium leak test was performed thereon.

As a result, it was found that when the inorganic ceramic layer was formed, the leakage of gas was reduced to less than 1/4 of the leakage when there was no inorganic ceramic layer, as illustrated in FIG. 13. Therefore, it can be seen that the inorganic ceramic layer can prevent the platinum contained in the heat source from being oxidized.

14A and 14B are exploded perspective views of samples for the comparative relaxation test of Examples 2 and 3 and Comparative Examples 2 and 3. FIG.

A longitudinal groove 61r is formed on the surface of the strip-shaped body sample 61, a heat source (not shown) and an inorganic filler 63 are formed in the groove 61r, and then an inorganic ceramic layer 67 is formed thereon (Example 2). A sample was manufactured in the same manner as in Example 2 except that the extending direction of the groove 61r was changed to a direction perpendicular to the longitudinal direction. The samples of Comparative Examples 2 and 3 were manufactured, and these samples were substantially the same as the samples of Examples 2 and 3 except that the inorganic ceramic layer 67 was not formed for comparison.

These samples were supported on two supports 69 spaced apart from each other at a predetermined interval, and then left at 1,500 ° C for 3 days. Then, the sag length at the center between the two supports 69 was measured to obtain the result shown in FIG. 15. The sag length is the height difference at the center between the original height and the height after heating at 1,500 ° C for 3 days.

Referring to FIG. 15, it can be seen that the inorganic ceramic layer 67 also helps to reduce sagging of the sample regardless of the extending direction of the groove. The sagging length of Example 2 is less than one third of the sagging length of Comparative Example 2. The sagging length of Example 3 is about half of the sagging length of Comparative Example 3.

Although the present disclosure has been specifically shown and described with reference to the embodiments of the disclosure, it should be understood that various changes can be made in form and detail without departing from the spirit and scope of the appended claims.

10‧‧‧Storage Container

11‧‧‧ batch

15‧‧‧Drive

17‧‧‧controller

19‧‧‧ glass liquid height probe

21‧‧‧Standpipe

23‧‧‧communication line

43‧‧‧helium sensor

51‧‧‧ chamber

52‧‧‧Inlet valve

53‧‧‧outlet valve

54‧‧‧ opening

61‧‧‧sample

61r‧‧‧groove

63‧‧‧ inorganic filler

67‧‧‧Inorganic ceramic layer

69‧‧‧ support

100‧‧‧melt container

150‧‧‧ the first catheter

200‧‧‧clarification container

250‧‧‧Second catheter

300‧‧‧ molten glass stirring chamber

310‧‧‧ Stirrer

312‧‧‧blade

314‧‧‧Stirring rod

320‧‧‧ stirred container

330‧‧‧ Cover

330a, 330a ’, 330a" ‧‧‧ the first subject

330b‧‧‧Second Subject

331a, 331a ’, 331a" ‧‧‧ the first subject

331b‧‧‧Second Subject

332‧‧‧heat source

333‧‧‧Precious metal coating

333US‧‧‧ Top surface

333LS‧‧‧Lower surface

333SB‧‧‧Roughened lower surface

334‧‧‧cover body

334R‧‧‧Groove

334f‧‧‧Inorganic filler

336, 336a, 336p‧‧‧‧Inorganic ceramic layer

337‧‧‧ Refractory oxide layer

338‧‧‧Center hole

339‧‧‧ film section

350‧‧‧ third conduit

500‧‧‧ delivery container

600‧‧‧ Outlet Conduit

650‧‧‧ entrance

700‧‧‧ forming container

750‧‧‧Edge roller

G1‧‧‧Width

G2‧‧‧ Clearance

IF‧‧‧ interface

MG‧‧‧ Molten Glass

SA‧‧‧ Sample

SW‧‧‧Side wall part

The embodiments disclosed in this case will be more clearly understood from the following detailed descriptions and the accompanying drawings, in which:

FIG. 1 is a diagram of a glass manufacturing apparatus according to an embodiment of the disclosure;

2 is a perspective view of a molten glass stirring chamber according to an embodiment of the disclosure;

3 is a perspective view of a first body of a cover according to an embodiment of the present disclosure;

FIG. 4 shows a section taken along line IV-VI 'of FIG. 3;

5 is a diagram conceptually showing a method of defining an interface between a cover body and an inorganic ceramic layer with respect to a cross section taken along a line V-V 'of FIG. 4;

6 is a side cross-sectional view of a first body of a cover according to another embodiment of the disclosure;

7A to 7C are side sectional views sequentially showing a method of manufacturing a first body of a cover according to an embodiment of the content disclosed in this case;

8 is a side cross-sectional view of a first body of a cover according to another embodiment of the disclosure;

9A and 9B are perspective views showing a method of forming a refractory oxide layer on a surface of a first body of a cover according to an embodiment of the present disclosure;

FIG. 10 illustrates a first body of a cover according to an embodiment of the disclosure;

11A and 11B are cross-sectional views of a first body of a cover according to other embodiments of the present disclosure;

FIG. 12 is a conceptual diagram showing a test device for testing the performance of an inorganic ceramic layer according to an embodiment of the present disclosure;

13 is a graph showing the results of performing a helium leak test on Example 1 and Comparative Example 1;

14A and 14B are exploded perspective views of samples of the relaxation comparison test of Examples 2 and 3 and Comparative Examples 2 and 3; and

FIG. 15 is a graph showing the results of performing a relaxation comparison test on Examples 2 and 3 and Comparative Examples 2 and 3. FIG.

Domestic storage information (please note in order of storage organization, date, and number)
no

Information on foreign deposits (please note according to the order of the country, institution, date, and number)
no

Claims (20)

A stirring chamber includes: A stirring container is assembled to receive molten glass; a cover is positioned on the stirring container; and a stirrer passes through the cover and is assembled to stir the molten glass, wherein the cover includes a cover body and a An inorganic ceramic layer covering one surface of the cover body, and the cover body is porous. The stirring chamber according to claim 1, wherein the inorganic ceramic layer comprises a glass layer. The stirring chamber according to claim 2, wherein the glass layer comprises: about 80% to about 90% by weight of silicon dioxide (SiO ₂ ), and about 1% to about 3% by weight of boron oxide (B ₂ O ₃ ), about 2% to about 5% by weight of alumina (Al ₂ O ₃ ), about 1% to about 3% by weight of sodium oxide (Na ₂ O), and about 2% to about 4% by weight Of potassium oxide (K ₂ O), about 2% to about 6% by weight of zinc oxide (ZnO), and about 0.1% to about 2% by weight of zirconia (ZrO ₂ ). The stirring chamber according to claim 1, wherein the cover body includes a groove and a heat source disposed in the groove. The agitating chamber according to claim 4, wherein the heat source is retained in the groove surrounded by an inorganic filler. The stirring chamber according to claim 5, wherein the inorganic ceramic layer covers at least a top surface and a bottom surface of the cover body, and an exposed portion of the inorganic filler. The stirring chamber according to claim 6, wherein the inorganic filler is a cement. The stirring chamber according to claim 1, wherein the cover further comprises a noble metal coating layer, the noble metal coating layer covers at least a top surface and a bottom surface of the cover body, and the noble metal coating layer is disposed at On the inorganic ceramic layer. The stirring chamber according to claim 8, wherein the cover further comprises a refractory oxide layer covering the surface of the precious metal coating layer facing the inside of the stirring container. The stirring chamber according to claim 1, wherein the cover has a central hole, the stirrer passes through the central hole, and the cover is divided into a first body and a second body along a boundary area, Wherein, the first body includes a portion protruding horizontally along the boundary region in the longitudinal direction. The stirring chamber according to claim 10, wherein the sheet partially overlaps the second body at least partially. The stirring chamber according to claim 11, wherein the sheet portion is provided on a lower portion of the first body facing the inside of the stirring container. A stirring chamber includes: A stirring container assembled to receive molten glass; A cover on the mixing container; and A stirrer that passes through the cover and is assembled to stir the molten glass, Wherein the cover includes a cover body, the cover body has a central hole, and the agitator passes through the center hole, the cover body is porous, The cover body includes a first body and a second body along a boundary area, and Wherein, the first body includes a portion protruding horizontally along the boundary region in the longitudinal direction. The stirring chamber according to claim 13, wherein the sheet partially overlaps the second body at least partially. The stirring chamber according to claim 13, wherein a surface of each of the first body and the second body is covered by an inorganic ceramic layer. The stirring chamber according to claim 15, wherein a lower portion of the first body includes a precious metal coating, and the sheet is partially attached to a surface of the precious metal coating. A stirring chamber includes: a stirring container assembled to receive molten glass; a cover on the stirring container; and a stirrer passing through the cover and assembled to stir the molten glass, wherein the cover includes A noble metal coating layer on at least the lower surface of the cover, wherein a surface of the noble metal coating layer facing the molten glass is covered by a refractory oxide layer, the refractory oxide layer includes : from about 3% to about 5 wt% of CaO, from about 0.2% to about 1 wt% of SiO _2, from about 0.2% to about 1 wt% of Al ₂ O _3, from about 0.5 wt% to about 3.5 wt% HfO ₂ and the balance of ZrO ₂ . The stirring chamber of claim 17, wherein the refractory oxide layer further comprises about 0.01% to about 0.3% by weight of Fe ₂ O ₃ and about 0.01% to about 0.9% by weight of MgO. The stirring chamber of claim 17, wherein the refractory oxide layer has a thickness of about 2 mils to about 8 mils. The stirring chamber according to claim 17, wherein the cover includes a cover body having a central hole, the agitator body passes through the center hole, and the cover is divided into a first body along a boundary area and A second body, the boundary region extending through the central hole, One surface of each of the first body and the second body is covered by an inorganic ceramic layer, and a portion protruding horizontally across the boundary region is disposed on the first body.