TW202239719A - Member applied to part in contact with molten glass and manufacturing method of member - Google Patents

Abstract

Provided is a member which is applied, at a glass manufacturing facility, to a part in contact with molten glass. The member has: a refractory brick that has a first surface and a second surface and that has a porosity in the range of 10%-30%; a glass component filled on the first surface side of the refractory brick; and a metal film including platinum, provided on the first surface or the second surface of the refractory brick. The total amount of alumina and silica in the refractory brick is 50 mass% or more. The greatest penetration depth of the glass component from the first surface is 2000 [mu]m or more.

Description

Member suitable for part in contact with molten glass, and manufacturing method thereof

The present invention relates to a member suitable for a part in contact with molten glass in glass manufacturing equipment, and a manufacturing method thereof.

Glass manufacturing equipment for manufacturing glass products includes multiple devices such as melting furnaces, clarification furnaces, and forming devices. In such devices, refractory bricks are usually used for components in contact with high-temperature molten glass.

However, refractory bricks do not have sufficient durability against molten glass. Therefore, when refractory bricks are used for a long time, there may often be problems that the refractory bricks are corroded, or components of the refractory bricks are dissolved into molten glass, resulting in lower quality of glass products.

In order to deal with such a problem, it is proposed to use platinum which has favorable durability with respect to molten glass for the member which contacts molten glass (for example, patent document 1, 2). prior art literature patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2012-121740 Patent Document 2: International Publication No. WO2012/070508

[Problem to be solved by the invention]

It is known that bubbles are generated in molten glass when molten glass contacts platinum.

The reason for this is presumed to be that when the moisture contained in the high-temperature molten glass comes into contact with platinum, it decomposes into hydrogen and oxygen. That is, the generated hydrogen passes through the platinum and is released out of the system through the pores of the refractory brick. However, it is difficult for oxygen to permeate platinum, and it stays in molten glass as it is, resulting in generation of air bubbles.

If such air bubbles remain in molten glass, there exists a problem that the quality of the glassware manufactured will fall.

In addition, in order to cope with this problem, it is considered to use an electro-fused cast brick as a refractory brick. The reason for this is that, in general, the porosity of electro-fused cast bricks is as small as a few percent or less, and therefore it is presumed that when electro-fused cast bricks coated with platinum are used for parts in contact with molten glass, hydrogen does not easily permeate. However, electrocast bricks are not resistant to thermal shock and are not suitable for repeated heating/cooling devices.

In this way, in glass manufacturing equipment, if platinum is to be applied to components in contact with high-temperature molten glass, many problems may arise.

The present invention was made in view of such a background, and an object of the present invention is to provide a member suitable for a portion in contact with molten glass, which is resistant to thermal shock and can remarkably suppress generation of air bubbles. Furthermore, the object of the present invention is to provide a method for manufacturing such a member. [Technical means to solve the problem]

The present invention provides a member suitable for use in a portion of a glass manufacturing apparatus that is in contact with molten glass, and having: Refractory bricks having a first surface and a second surface, and having a porosity in the range of 10% to 30%; A glass component filled on the first surface side of the refractory brick; and A metal film provided on the first surface or the second surface of the refractory brick, and containing platinum; The total amount of alumina and silica in the above refractory bricks is 50% by mass or more, The maximum penetration depth of the above-mentioned glass component from the above-mentioned first surface is 2000 μm or more.

Furthermore, the present invention provides a manufacturing method, which is a method of manufacturing a member suitable for a part in contact with molten glass in glass manufacturing equipment, and includes: (1) On the above-mentioned first surface of the refractory brick having the first surface and the second surface, the total amount of alumina and silicon oxide is 50% by mass or more, and the porosity is in the range of 10% to 30%, glass is provided raw material steps; (2) Melting the above-mentioned glass raw material to form molten glass, impregnating the above-mentioned molten glass from the above-mentioned first surface of the above-mentioned refractory brick, and impregnating the above-mentioned molten glass so that the maximum penetration depth from the above-mentioned first surface becomes 2000 μm or more the steps of (3) A step of removing the above-mentioned glass raw material remaining on the above-mentioned first surface after the above-mentioned molten glass is solidified; and (4) A step of providing a metal film containing platinum on the first surface or the second surface of the refractory brick. [Effect of Invention]

The present invention can provide a member suitable for a portion in contact with molten glass, which is resistant to thermal shock and can remarkably suppress generation of air bubbles. In addition, the present invention can provide a method for manufacturing such a component.

One embodiment of the present invention will be described below.

One embodiment of the present invention provides a member suitable for a part in contact with molten glass in glass manufacturing equipment, and has: Refractory bricks having a first surface and a second surface, and having a porosity in the range of 10% to 30%; A glass component filled on the first surface side of the refractory brick; and A metal film provided on the first surface or the second surface of the refractory brick, and containing platinum; The total amount of alumina and silica in the above refractory bricks is 50% by mass or more, The maximum penetration depth of the above-mentioned glass component from the above-mentioned first surface is 2000 μm or more.

When constituting a member by placing platinum on refractory bricks as described above, there is a problem that water is decomposed and hydrogen is dissipated due to contact between platinum and molten glass, so that air bubbles are generated in the molten glass.

Also, in order to deal with the air bubble problem, when using an electro-fused cast brick with a small porosity as a refractory brick, there is a problem that, when the heating/cooling of the device is repeated, the electro-fused cast brick may be damaged due to thermal shock. damaged.

On the other hand, in one embodiment of the present invention, the member has a refractory brick having a porosity in the range of 10% to 30%, and a metal film containing platinum provided on the first or second surface of the refractory brick. .

When such a member is applied to a part in contact with molten glass, the existence of the metal film can significantly suppress the corrosion of the refractory brick due to the molten glass or the dissolution of components.

Furthermore, a member according to one embodiment of the present invention has a metal film. Therefore, when the member is in contact with high-temperature molten glass, the decomposition reaction of water as described above may occur.

However, in one Embodiment of this invention, the glass component is filled in the air hole of the 1st surface side of a refractory brick. In particular, in one embodiment of the present invention, the glass component penetrates to a maximum depth of 2000 μm or more from the first surface of the refractory brick.

In this case, the glass component can be used as a barrier to hydrogen diffusion. That is, even if the decomposition reaction of water occurs between the metal film and the molten glass, the generated hydrogen can be significantly suppressed from being released out of the system through the refractory brick by the glass component in the refractory brick. It is considered that as a result, the decomposition reaction of water can be suppressed, thereby significantly suppressing the generation of oxygen bubbles.

Furthermore, about the member which concerns on one Embodiment of this invention, the refractory brick contains the material whose porosity exists in the range of 10%-30%, and the total amount of silica and alumina is 50 mass % or more.

This kind of refractory brick is different from ordinary electric fused cast bricks, and has the property of heat shock resistance. Therefore, in one embodiment of this invention, even when heating/cooling is repeated to a member, deterioration of a refractory brick or damage can be suppressed remarkably.

Based on the above effects, one embodiment of the present invention can provide a thermal shock resistant member capable of remarkably suppressing generation of air bubbles.

Furthermore, when a platinum plate is provided on the surface of the refractory brick to form a component as described in Patent Document 1, the following problem may arise. Platinum deforms due to thermal expansion difference. Once the platinum plate is deformed in this way, the platinum plate may be damaged due to deformation, making it difficult to protect the refractory brick from the damage of molten glass.

However, in the member of one embodiment of the present invention, platinum is provided as a "metal film". In this case, even if the member is heated or cooled to deform the refractory brick, the metal film can follow the deformation of the refractory brick. Therefore, the member of one embodiment of the present invention can protect the refractory brick with the metal film for a long time.

(Member for glass manufacturing equipment according to one embodiment of the present invention) Next, the structure of the member for glass manufacturing facilities which concerns on one Embodiment of this invention is demonstrated in more detail, referring drawings.

FIG. 1 schematically shows a cross section of a member for glass manufacturing equipment (hereinafter, referred to as "first member") according to one embodiment of the present invention.

As shown in FIG. 1 , the first member 100 has a refractory brick 110 , a glass component 120 , and a metal film 130 .

The refractory brick 110 has a first surface 112 and a second surface 114 facing each other. The refractory brick 110 has a composition such that the total amount of silicon oxide and aluminum oxide becomes 50% by mass or more.

The glass component 120 is provided on the first surface 112 side of the refractory brick 110 . More specifically, the glass component 120 is provided so as to fill at least a part of the pores existing on the first surface 112 of the refractory brick 110 and its vicinity.

The metal film 130 is disposed on the first surface 112 of the refractory brick 110 . The metal film 130 includes platinum and has the function of protecting the refractory brick 110 from the damage of the molten glass.

Furthermore, in the example shown in FIG. 1 , a plurality of recesses 140 are formed on the first surface 112 of the refractory brick 110 , and the metal film 130 is also filled in the recesses 140 .

By providing such a concave portion 140, the adhesion between the metal film 130 and the first surface 112 of the refractory brick 110 can be improved.

However, this is only an example, and the recess 140 does not have to be necessarily provided.

Here, the first member 100 has a refractory brick 110 having a porosity within a range of 10% to 30%. This kind of refractory brick 110 is different from electro-fused cast bricks with lower porosity, and has relatively good thermal shock resistance. Therefore, the first member 100 can also be suitably used in a device that is repeatedly heated and cooled.

Moreover, the first member 100 has the glass component 120 filled in the pores of the refractory brick 110 . The glass component 120 reaches a maximum depth of 2000 μm or more from the first surface 112 of the refractory brick 110 .

In addition, below, the maximum distance of the glass component 120 from the 1st surface 112 of the refractory brick 110 in the depth direction is called "maximum depth _Dmax ". In the first member 100, the maximum depth D _max ≧2000 μm.

Such a glass component 120 functions as a barrier to hydrogen permeation. Therefore, although the first member 100 has the metal film 130 containing platinum and the refractory brick 110 with a porosity in the range of 10% to 30%, it can significantly suppress the contact between the molten glass and the metal film 130 due to water contact. The hydrogen produced by the decomposition reaction passes through the refractory brick 110 and is released out of the system.

It is considered that as a result, the decomposition reaction of water in the molten glass can be remarkably suppressed, so that the generation of oxygen gas in the form of bubbles in the molten glass can be remarkably suppressed.

According to the above effects, the first member 100 can obtain good thermal shock resistance, and can remarkably suppress generation of air bubbles when it comes into contact with molten glass.

Furthermore, platinum is used in the form of the metal film 130 in the first member 100 . In this case, even if the first member 100 is rapidly heated or cooled to cause deformation of the refractory brick 110 , the metal film 130 can follow the deformation of the refractory brick 110 .

Moreover, the refractory brick 110 contains a silicon oxide and/or alumina type material. For example, compared with a refractory brick containing zirconium, the difference in thermal expansion between the refractory brick 110 and platinum is smaller, so the possibility of delamination of the metal film 130 in use can be significantly suppressed.

(Constituent elements of members of one embodiment of the present invention) Next, each constituent element of a member of one embodiment of the present invention having the above-mentioned features will be described.

In addition, in the following description, for the sake of clarity, each constituent element will be described by taking the above-mentioned first member 100 as an example of a member of one embodiment of the present invention. Therefore, when expressing each component, the reference signs shown in FIG. 1 are used.

(refractory brick 110) The kind of refractory brick 110 will not be specifically limited as long as it has the above-mentioned characteristics. The refractory brick 110 can be, for example, a fired brick. Generally speaking, compared with electric fused cast bricks, sintered bricks have the characteristics of higher processability and thermal shock resistance.

The refractory brick 110 may include alumina-based, silica-based, or alumina-silica-based ceramics.

When the refractory brick 110 is an alumina system, the refractory brick 110 contains at least 50% by mass or more of alumina. The amount of alumina may be, for example, 60 mass % or more, and may be 70 mass % or more. The amount of alumina may also be 100% by mass.

When the refractory brick 110 is a silicon oxide system, at least 50% by mass or more of silicon oxide is contained in the refractory brick 110 . The amount of silicon oxide may be, for example, 60% by mass or more, or may be 70% by mass or more. The amount of silicon oxide may also be 100% by mass.

Moreover, when the refractory brick 110 is an alumina-silica system, the sum of the alumina and silicon oxide in the refractory brick 110 is at least 50 mass % or more. The sum of alumina and silicon oxide may be, for example, 60% by mass or more, or may be 70% by mass or more. Alternatively, the sum of alumina and silicon oxide in the refractory brick 110 may be 100% by mass. In this case, the amount of silicon oxide may be in the range of 10% by mass to 40% by mass.

The porosity of the refractory brick 110 is in the range of 10% to 30%, preferably below 20%.

(glass component 120) The composition of the glass component 120 filled in the pores of the refractory brick 110 is not particularly limited.

However, the glass component 120 is preferably glass in which the amount of alkaline components is suppressed. For example, in the glass component 120, the total amount of lithium, sodium, and potassium is preferably 5% by mass or less in terms of oxides.

When the amount of the alkaline component is suppressed, the reaction between the refractory brick and the glass component 120 can be significantly suppressed.

In addition, the glass component 120 preferably has a property that the position of the first member 100 does not largely shift during use. For example, the glass component 120 may have a viscosity of 10 ² -10 ⁴ Poise at 1400°C.

The maximum penetration depth D _max of the glass component 120 is at least 2000 μm. By setting the maximum infiltration depth _Dmax to 2000 μm or more, the permeation of hydrogen in the refractory brick 110 can be significantly suppressed.

Furthermore, among the pores in the refractory brick 110, there are open pores capable of gas communication with the first surface 112 and/or the second surface 114, and closed pores that are not connected to the surfaces 112 and 114. Among them, the closed pores do not participate in the movement of hydrogen. Therefore, it is sufficient for the pores filled with the glass component 120 to be only open pores.

Also, regarding the open pores, it is not necessary to fill all the open pores in the region from the first surface 112 to the maximum penetration depth D _max with the glass component 120 .

According to the experience of the inventors of this application, it is considered that although it also depends on the composition of the glass component 120, when the maximum penetration depth _Dmax is 5000 μm, about 30% of the open pores in the area from the surface to the depth of 5000 μm The above open pores are sealed, and there are substantially no open pores communicating from the first surface to the second surface.

The maximum penetration depth D _max is preferably at least 3000 μm, more preferably at least 5000 μm, and still more preferably at least 8000 μm.

(metal film 130) The composition of the metal film 130 is not limited as long as it contains 50% by mass or more of platinum. For example, the metal film 130 may include platinum or a platinum alloy. Platinum alloys can be platinum-gold alloys, platinum-rhodium alloys, or platinum-iridium alloys.

The metal film 130 may be a fusion film.

The thickness of the metal film 130 is not particularly limited. The metal film 130 may have a thickness ranging from 100 μm to 700 μm, for example.

Furthermore, the first member 100 has a concave portion 140 as shown in FIG.

The shape of the recess 140 is not particularly limited, and the recess 140 may be, for example, a groove extending in one direction, or a substantially circular hole. Such concave portion 140 can be formed by laser processing.

The depth of the concave portion 140 may be in the range of 100 μm˜500 μm, for example. Also, the aspect ratio of the concave portion 140 may be in the range of 0.5˜2.0. Here, the aspect ratio of the concave portion 140 is represented by the depth of the concave portion 140 relative to the minimum width (diameter in the case of a hole) of the concave portion 140 .

However, as described above, the concave portion 140 may be omitted.

(first member 100) The first member 100 is suitable for use in a portion of a glass manufacturing facility that is in contact with molten glass.

Such a location may be, for example, a melting furnace, a fining furnace, a supply pipe for molten glass, and/or a part of a forming device.

In particular, in glass manufacturing facilities, the process of removing air bubbles from molten glass is not often performed on the downstream side of the clarification furnace. Therefore, the first member 100 is preferably suitable for devices arranged downstream of the clarification furnace, such as molding devices.

(Member for glass manufacturing equipment according to another embodiment of the present invention) Next, the configuration of a member for glass manufacturing equipment according to another embodiment of the present invention will be described with reference to FIG. 2 .

FIG. 2 schematically shows a cross section of a member for glass manufacturing equipment (hereinafter referred to as "second member") according to another embodiment of the present invention.

As shown in FIG. 2 , the second member 200 has a refractory brick 210 , a glass component 220 , and a metal film 230 .

In the second member 200, the refractory brick 210 and the glass component 220 have the same configuration as the refractory brick 110 and the glass component 120 in the first member 100, respectively. However, in the second member 200 , the arrangement aspect of the metal film 230 is different from that of the first member 100 .

That is, in the second member 200, the metal film 230 is not arranged on the first surface 212 side of the refractory brick 210, but is arranged on the second surface 214 side. Also, a plurality of recesses 240 are formed on the second surface 214 of the refractory brick 210 . However, as described above, the concave portion 240 does not necessarily have to be provided.

The second member 200 is used so that the side of the metal film 230 is in contact with the molten glass.

Practitioners understand that the second component 200 can also obtain the same effect as the above-mentioned first component 100 .

That is, the second member 200 can also obtain good thermal shock resistance, and can remarkably suppress generation of air bubbles when it comes into contact with molten glass.

(Method for manufacturing glass manufacturing equipment member according to one embodiment of the present invention) Next, an example of the manufacturing method of the member for glass manufacturing facilities which concerns on one Embodiment of this invention is demonstrated with reference to FIGS. 3-7.

FIG. 3 schematically shows the flow of a manufacturing method (hereinafter, referred to as "first method") of a member for glass manufacturing equipment according to an embodiment of the present invention. As shown in Figure 3, the first method includes: The step of arranging glass raw materials on the first surface of the refractory brick having the first surface and the second surface, the total amount of alumina and silicon oxide being 50% by mass or more, and the porosity being in the range of 10% to 30% ( Step S110); A step of melting glass raw materials to form molten glass, and impregnating the molten glass from the first surface of the refractory brick (step S120); After the molten glass is solidified, the step of removing the remaining glass raw material on the first surface (step S130); and The step of providing a metal film containing platinum on the first surface of the refractory brick (step S140).

Hereinafter, each step will be described also with reference to FIGS. 4 to 7 .

In addition, here, for the sake of clarity, it is assumed that the first member 100 shown in FIG. 1 is a member to be manufactured. Therefore, the reference signs shown in FIG. 1 are used when expressing each constituent element of the member.

(step S110) First, refractory bricks 110 are prepared.

As mentioned above, the refractory brick 110 contains the material whose total amount of silica and alumina is 50 mass % or more, and the porosity exists in the range of 10%-30%. The refractory brick 110 may include silica-based, alumina-based, or silica-alumina-based ceramics.

The refractory brick 110 may be a fired brick.

The refractory brick 110 has an initial first surface 116 and an initial second surface 118 .

Next, glass raw material is provided on the initial first surface 116 of the refractory brick 110 .

FIG. 4 schematically shows the state in which the glass raw material 122 is provided on the initial first surface 116 of the refractory brick 110 .

The glass raw material 122 includes glass frit, a binder, and a solvent (such as water). Glass raw material 122 can be provided in a slurry state, for example.

(step S120) Next, the glass raw material 122 is melt-processed. The temperature and time of the melting treatment are appropriately determined based on the composition of the glass frit contained in the glass raw material 122 .

When the glass frit 122 is heated to a high temperature by melting, the solvent is vaporized and the glass frit melts. The binder vaporizes with the solvent or melts with the glass frit. The molten glass frit infiltrates from the initial first surface 116 of the refractory brick 110 into the interior. Thereby, the glass component 120 is impregnated in the pores existing on the initial first surface 116 of the refractory brick 110 and its vicinity.

FIG. 5 schematically shows the state in which the glass component 120 is impregnated in the pores of the refractory brick 110 .

Furthermore, the glass component 120 formed from the glass raw material 122 may not be completely impregnated in the pores of the refractory brick 110 . That is, as shown in FIG. 5 , a part of the glass component 120 remains on the initial first surface 116 of the refractory brick 110 as the glass layer 124 .

Then, the glass composition 120 is cured.

(step S130) Then, the glass layer 124 remaining on the initial first surface 116 of the refractory brick 110 is removed.

The glass layer 124 can be removed from the original first surface 116 by mechanical grinding of the refractory brick 110 . At this time, the initial first surface 116 of the refractory brick 110 may also be ground to form a ground surface. This ground surface can become the new surface (1st surface 112) of the refractory brick 110.

Thereby, a refractory brick 110 in which at least a part of the pores near the first surface 112 (or the initial first surface 116 ) is filled with the glass component 120 as shown in FIG. 6 can be obtained.

The maximum penetration depth D _max of the glass component 120 from the first surface 112 is 2000 μm or more.

(step S140) Next, a metal film 130 is provided on the first surface 112 of the refractory brick 110 . However, the concave portion 140 may be formed on the first surface 112 before this treatment.

FIG. 7 schematically shows the state where the recessed part 140 is formed in the 1st surface 112 of the refractory brick 110. As shown in FIG.

The recess 140 can be a plurality of grooves or a plurality of circular holes extending along a fixed direction. The recesses 140 may have a regular two-dimensional arrangement in plan view, or may be arranged randomly.

The minimum width of the concave portion 140 may be in the range of 100 μm˜200 μm, for example. Also, the aspect ratio represented by the depth of the recess relative to the minimum width of the recess may be in the range of 0.5 to 2.0.

The concave portion 140 can be formed by laser processing, for example.

Furthermore, the formation of the concave portion 140 is not specified.

Next, a metal film 130 is provided on the first surface 112 of the refractory brick 110 . As described above, metal film 130 contains platinum.

The method of disposing the metal film 130 is not particularly limited. The metal film 130 can be formed by, for example, a spray method.

The thickness of the metal film 130 is, for example, in the range of 100 μm˜500 μm.

Through the above steps, the first member 100 as shown in FIG. 1 can be manufactured. Furthermore, when there is no step of grinding the initial second surface 118 of the refractory brick 110 in the first method, the initial second surface 118 becomes the second surface 114 of the refractory brick 110 .

As mentioned above, the manufacturing method of the member which concerns on one Embodiment of this invention was demonstrated taking the 1st method as an example. However, practitioners understand that the components of an embodiment of the present invention can also be manufactured by other methods.

For example, in the case where the metal film 130 is formed on the initial second surface 118 of the refractory brick 110 in the above step S140, the second member 200 as shown in FIG. 2 can be manufactured. Various changes other than this are also possible. [Example]

Next, examples of the present invention will be described. In addition, in the following description, examples 1-5 are examples, and examples 11-12 are comparative examples.

(example 1) The member for evaluation was produced by the above-mentioned first method.

The size of the refractory brick is set to 50 mm in length, 50 mm in width and 15 mm in thickness. A surface of 50 mm in length and 50 mm in width is called the first surface.

The refractory brick A of the composition shown in the following Table 1 was used as a refractory brick.

[Table 1] Composition (mass%) Refractory brick A Refractory brick B SiO ₂ 21.4 12.0 Al ₂ O ₃ 77.7 85.5 _{Fe2O3 _} 0.08 - CaO 0.23 - Porosity(%) 16 22.2 The refractory brick A is a fired brick with a porosity of 16%.

Next, the glass component was filled in the refractory brick by the following method.

First, glass paste is coated on the first surface of the refractory brick. The glass paste includes water, binder and glass frit. The glass contained in the glass frit is called glass A. Moreover, the composition and softening point of glass A are shown in Table 2 below.

[Table 2] Composition (mass%) Glass A glass B Glass C glass SiO ₂ 70～80 58.1 81.0 72.4 Al ₂ O ₃ 10～20 18.8 2.0 1.9 B ₂ O ₃ 0～10 10.0 13.0 - MgO 0～10 2.6 - 3.8 CaO 0～10 1.7 - 8.3 SrO - 8.8 - - BaO - - - - Na2O _{＋ K2O} - - 4.0 13.7 Softening point (℃) 1068 950 821 729 Next, the refractory bricks were heated to 1450° C. in the air, kept at this temperature for 3 hours, and then slowly cooled. Thereby, glass A is filled in the air hole of the 1st surface vicinity of a refractory brick.

Then, the glass layer remaining on the first surface of the refractory brick is removed by mechanical grinding.

Then, on the first surface of the refractory brick, a large number of circular holes are formed in a staggered arrangement by laser processing. The diameter of the hole was set at about 300 μm, and the depth was set at about 300 μm. Therefore, the aspect ratio of the pores is about 1.0.

Then, a platinum film is formed on the first surface of the refractory brick by flame spraying method. The thickness of the platinum film was set at about 300 μm.

In this way, a member for evaluation (hereinafter referred to as "sample 1") was obtained.

(Example 2) A member for evaluation was produced by the same method as in Example 1. However, in this Example 2, glass B was used as the glass contained in the glass frit. The composition and softening point of glass B are shown in Table 2 above.

Hereinafter, the produced member for evaluation is referred to as "sample 2".

(Example 3) A member for evaluation was produced by the same method as in Example 1. However, in this Example 3, glass C was used as the glass contained in the glass frit. The composition and softening point of Glass C are shown in Table 2 above.

Hereinafter, the produced member for evaluation is referred to as "sample 3".

(Example 4) Samples for evaluation were produced by the same method as in Example 1. However, in this example 4, the refractory brick B which is 1 type of fired brick was used as a refractory brick. The composition and porosity of the refractory brick B are shown in Table 1 above. In addition, in this Example 4, glass C was used as the glass contained in the glass frit.

Hereinafter, the produced member for evaluation is referred to as "sample 4".

(Example 5) Samples for evaluation were produced by the same method as in Example 1. However, in this Example 5, glass D was used as the glass contained in the glass frit. The composition and softening point of glass D are shown in Table 2 above.

Hereinafter, the produced member for evaluation is referred to as "sample 5".

(Example 11) Samples for evaluation were produced by the same method as in Example 1. However, in this Example 11, the glass component was not filled in the refractory brick. That is, after performing laser processing on the 1st surface of a refractory brick without applying glass paste, a platinum film was sprayed and the sample for evaluation was produced.

Hereinafter, the produced member for evaluation is referred to as "sample 11".

(Example 12) Samples for evaluation were produced by the same method as in Example 1. However, in this Example 12, the coating amount of the glass paste was made into 1/10 of Example 1 in the filling process of a glass component.

Hereinafter, the produced member for evaluation is referred to as "sample 12".

(Measurement of penetration depth of glass components) In each of the above examples, the penetration depth of the glass component from the first surface of the refractory glass was measured before the circular hole was processed by laser.

The measurement is carried out by taking an EPMA (electron probe micro analyzer) map of silicon (Si) in a section obtained by cutting each refractory brick in a direction parallel to the thickness direction. That is, using the map of Si, the distance from the first surface of the refractory brick to the maximum depth where the glass component is located was obtained. The obtained distance was taken as the maximum depth D _max of the glass composition.

An example of the mapped image of Si in the cross section of the refractory brick before laser processing of Example 3 is shown in FIG. 8 . Moreover, an example of the mapping image of Si in the cross section of the refractory brick before the laser processing of Example 11 is shown in FIG.

It can be seen from Fig. 9 that no glass component was found in the depth direction of the refractory brick in Example 3. On the other hand, as can be seen from FIG. 8 , the refractory brick in Example 3 is filled with a glass component to a depth of at least 2000 μm from the surface.

Table 3 summarizes the types of refractory bricks in each sample, the type of glass filled, and the maximum depth D _max of the glass composition.

[table 3] sample Types of refractory bricks glass type The maximum penetration depth D _max of glass components (μm) 1 A A More than 5000 μm 2 A B More than 4000 μm 3 A C More than 2000 μm 4 B C More than 5000 μm 5 A D. More than 8000 μm 11 A - 0 12 A A Less than 1000 μm It can be seen from Table 3 that the maximum penetration depth D _max of the glass components of samples 1 to 5 exceeds at least 2000 μm. On the other hand, the maximum penetration depth D _max of sample 12 was not as high as 1000 μm.

(Evaluation) (Molten Glass Contact Test) The molten glass contact test was implemented using each sample.

The test was carried out as follows.

Firstly, a disk-shaped glass block is placed on the surface of the platinum film of the sample. Use Glass B as the glass block.

Next, the sample was heated to 1400° C. in the air to melt the glass brick. The contact area between the molten glass and the platinum film is about 150 mm ² . With the sample temperature maintained at 1400°C, the state in the molten glass, especially the presence or absence of bubbles was observed. The hold time at 1400°C was about 120 minutes.

(Thermal cycle test) A thermal cycle test was implemented using each sample.

The thermal cycle test was implemented by repeating three cycles of heating each sample to 1400° C., maintaining at this temperature for 10 minutes, and then air cooling. The test is carried out in the atmosphere.

After the test, evaluate the state of the sample. In particular, the presence or absence of damage to the refractory bricks and the presence or absence of peeling of the platinum film were evaluated.

(result) The results of the respective evaluation tests are collectively shown in Table 4 below.

[Table 4] sample Generation of Bubbles in Molten Glass Contact Test Thermal Cycle Test Results 1 none nothing unusual 2 none nothing unusual 3 none nothing unusual 4 none nothing unusual 5 few - 11 many peel off 12 many - As shown in Table 4, it can be seen that samples 11 and 12 generated a large number of bubbles in the molten glass contact test. On the other hand, samples 1 to 4 did not generate air bubbles in the molten glass contact test. Also, even in Sample 5, the amount of air bubbles was small.

In this way, it was confirmed that the generation of air bubbles was remarkably suppressed by setting the maximum penetration depth D _max of the glass component to be 2000 μm or more.

Also, in sample 11, the platinum film peeled off after the thermal cycle test. On the other hand, in Samples 1 to 4, no peeling of the platinum film was observed after the heat cycle test. Moreover, no abnormality in particular was found similarly about a refractory brick.

Thus, it was confirmed that samples 2 to 4 had favorable thermal shock resistance.

(additional test) A thermal shock test is performed using a plurality of refractory bricks.

The thermal shock test was implemented by heating each refractory brick to 1300°C in the air, and then putting it into water at 25°C.

Three kinds of refractory bricks from I to III are used as refractory bricks. The dimensions of the refractory bricks are all set to 40 mm in length x 40 mm in width x 100 mm in thickness.

The compositions of the refractory bricks used are summarized in Table 5 below.

[table 5] Composition (mass%) Refractory brick I Refractory brick II Refractory brick III SiO ₂ 21.4 33.0 4.0 Al ₂ O ₃ 77.7 0.6 - _ZrO2 - 65.0 94.5 _{Fe2O3 _} 0.08 0.3 - CaO 0.23 - - The refractory brick I is equivalent to the above-mentioned refractory brick A, and is an alumina-based fired brick. Refractory brick II series zirconia series fired brick. Also, refractory brick III series zirconia series electric fused cast brick (porosity 1%).

The state of each refractory brick after the thermal shock test is collectively shown in FIG. 10 .

It can be seen from Fig. 10 that the refractory brick III has produced relatively large cracks. Also, about the refractory brick II, similarly, cracks were found in a part.

On the other hand, no abnormalities such as cracks were found in the refractory brick 1 after the test.

Thus, it can be seen that alumina-based fired bricks have better thermal shock resistance than electroformed bricks and non-alumina-based fired bricks.

This case claims priority based on Japanese Patent Application No. 2021-060625 filed on March 31, 2021, and all content of the Japanese application is incorporated into this case by reference.

100: Member (first member) of one embodiment of the present invention 110: refractory brick 112: 1st surface 114: Second surface 116: Initial 1st surface 118: Initial 2nd surface 120: glass composition 122: glass raw material 124: glass layer 130: metal film 140: concave part 200: Member (second member) of one embodiment of the present invention 210: refractory brick 212: 1st surface 214: 2nd surface 220: glass composition 230: metal film 240: concave part

Fig. 1 is a cross-sectional view schematically showing the structure of a member according to an embodiment of the present invention. Fig. 2 is a cross-sectional view schematically showing the structure of another embodiment of the present invention. Fig. 3 is a diagram schematically showing the flow of a method for manufacturing a member for glass manufacturing equipment according to an embodiment of the present invention. Fig. 4 is a diagram schematically showing one step in a method of manufacturing a member for glass manufacturing equipment according to an embodiment of the present invention. Fig. 5 is a diagram schematically showing one step in a method of manufacturing a member for glass manufacturing equipment according to an embodiment of the present invention. Fig. 6 is a diagram schematically showing one step in a method of manufacturing a member for glass manufacturing equipment according to an embodiment of the present invention. Fig. 7 is a diagram schematically showing one step in a method of manufacturing a member for glass manufacturing equipment according to an embodiment of the present invention. FIG. 8 is a diagram showing an example of the mapping result of Si in the cross section of the refractory brick before laser processing of Example 3. FIG. FIG. 9 is a diagram showing an example of Si mapping results in a cross section of a refractory brick before laser processing in Example 11. FIG. Fig. 10 is a photograph collectively showing the states of various refractory bricks after thermal shock tests.

100: Member (first member) of one embodiment of the present invention

110: refractory brick

112: 1st surface

114: Second surface

120: glass composition

130: metal film

140: concave part

Claims (16)

A member suitable for use in a portion of glassmaking equipment in contact with molten glass, having: Refractory bricks having a first surface and a second surface, and having a porosity in the range of 10% to 30%; A glass component filled on the first surface side of the refractory brick; and A metal film provided on the first surface or the second surface of the refractory brick, and containing platinum; The total amount of alumina and silica in the above refractory bricks is 50% by mass or more, The maximum penetration depth of the above-mentioned glass component from the above-mentioned first surface is 2000 μm or more. The member according to claim 1, wherein the above-mentioned refractory bricks are alumina-based refractory bricks, and contain more than 50% by mass of alumina. The member according to claim 1 or 2, wherein the above-mentioned refractory bricks are fired bricks. The member according to any one of claims 1 to 3, wherein the metal film has a thickness in the range of 100 μm to 700 μm. The member according to any one of claims 1 to 4, wherein the metal film comprises platinum or a platinum alloy. The member according to any one of claims 1 to 5, wherein the metal film is a sprayed film. The member according to any one of claims 1 to 6, wherein the metal film is provided on the first surface of the refractory brick. The member according to any one of claims 1 to 7, wherein the surface of the above-mentioned refractory brick on which the above-mentioned metal film is provided has a concave portion. A manufacturing method, which is a manufacturing method of a member suitable for a portion in contact with molten glass in glass manufacturing equipment, and comprising: (1) On the first surface of the refractory brick having the first surface and the second surface, the total amount of alumina and silicon oxide is 50% by mass or more, and the porosity is in the range of 10% to 30%, glass is provided raw material steps; (2) Melting the above-mentioned glass raw material to form molten glass, impregnating the above-mentioned molten glass from the above-mentioned first surface of the above-mentioned refractory brick, and impregnating the above-mentioned molten glass so that the maximum penetration depth from the above-mentioned first surface becomes 2000 μm or more the steps of (3) A step of removing the above-mentioned glass raw material remaining on the above-mentioned first surface after the above-mentioned molten glass is solidified; and (4) A step of providing a metal film containing platinum on the first surface or the second surface of the refractory brick. The manufacturing method according to claim 9, wherein the above-mentioned refractory bricks are alumina-based refractory bricks, and contain more than 50% by mass of alumina. The manufacturing method according to claim 9 or 10, wherein the above-mentioned refractory bricks are fired bricks. The manufacturing method according to any one of claims 9 to 11, wherein the metal film has a thickness in the range of 100 μm to 700 μm. The manufacturing method according to any one of claims 9 to 12, wherein the metal film includes platinum or a platinum alloy. The manufacturing method according to any one of claims 9 to 13, wherein the metal film is formed by spraying. The manufacturing method according to any one of claims 9 to 14, further comprising the step of forming a concave portion on the surface on which the metal film is provided before the step (4). The manufacturing method according to any one of claims 9 to 15, wherein the metal film is provided on the first surface of the refractory brick.

Images