JP3520190B2 - Shape adjustment method of lightweight refractory having glass film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adjusting the shape of a lightweight refractory material having a glass film, and more particularly to repairing a highly accurate glass film constructed (formed) on the lightweight refractory material. .

[0002]

2. Description of the Related Art Conventionally, lightweight refractory materials have been coated with a glass film. For example, an inorganic fiber-based lightweight refractory used in a space shuttle has a glass film on its surface.

[0003]

However, a glass film formed on a lightweight refractory made of an inorganic fiber such as that conventionally used in a space shuttle has a through hole, a crack, etc. which reach the lightweight refractory. Some of them had serious defects. The lightweight refractory coated with the glass film having such a serious defect cannot be used for the space shuttle because of the following reasons, and thus is a defective product.

One of the purposes of applying a glass film to a lightweight refractory material is to prevent entry of moisture such as rainwater into the lightweight refractory material. The lightweight refractory containing water will be broken down because the water becomes ice due to heat insulation / condensation at the time of launch. In addition, lightweight refractory that escaped destruction is
The orbit is re-entry while containing ice, and the refractory is destroyed due to extreme sublimation expansion of the ice due to aerodynamic heating. Therefore,
For the glass film of a light-weight refractory material, through holes, cracks, etc. to the refractory material are serious defects.

Conventionally, no suitable means for repairing defects such as through holes and cracks in the light-weight refractory has been found in the glass film covering the light-weight refractory, so that the glass film has the above-mentioned defects. The lightweight refractory became defective and reduced the yield.

The present invention solves the above-mentioned problems of the prior art, repairs the above-mentioned defects in the glass film formed on the lightweight refractory, and improves the yield of the lightweight refractory having the glass film formed thereon. An object of the present invention is to provide a shape adjusting method for a lightweight refractory having a glass film, a lightweight refractory having a glass film, and a shape adjusting material for the lightweight refractory.

[0007]

As a shape modifier for a lightweight refractory having a glass film, the inventor of the present invention said that the emissivity is lower than that of the glass film covering the lightweight refractory, so that heat can be easily accumulated and melted easily. When the starting material of the glass film is used and the starting material of the glass is melted on the glass film,
It has been found that the shape of the glass film can be adjusted by selectively melting only the starting material of the glass and fusing it to the glass film without deforming or melting the glass film, thus completing the present invention. Came to do.

That is, according to the first aspect of the present invention, the surface of a glass refractory material having a glass film is attached to the surface of the glass film.
The glass film for repairing defects or without defects
Has a glass film to give the desired shape to the surface of
Fusion of shape-regulating agent to the surface of lightweight refractory
Then, it has a surface shape adjusting step of adjusting the surface shape, and the starting material of the glass film is used as the shape adjusting agent.
A shape adjusting agent containing as a main component, said starting material
Fee is shape adjustment method of lightweight refractories having a glass film to use a radiation rate enough to retain the shape of the glass film during the welding is lower than the glass film.

In the surface shape adjusting step, the melted shape adjusting agent obtained by selectively heating the shape adjusting agent retained on the surface of at least one of the glass film and the lightweight refractory is used as the glass film. The surface shape of the lightweight refractory can be adjusted by fusion bonding to the surface of the lightweight refractory. In the surface shape adjusting step, a molten shape adjusting agent obtained by locally heating the shape adjusting agent retained on the surface of at least one of the glass film and the lightweight refractory is a light weight having the glass film. The surface shape of the lightweight refractory can be adjusted by fusion bonding to the surface of the refractory.

The method of adjusting the shape of a lightweight refractory having a glass film includes a fusing step of fusing a shape adjusting agent melted to defects in the glass film (particularly the surface of the glass film). A surface shape adjusting step of adjusting the surface shape of the lightweight refractory by filling a shape adjusting agent into defects (particularly on the surface of the glass film) can be included. As the shape adjusting agent, a shape adjusting agent containing, as a main component, a glass frit and a reaction-cured glass obtained by firing a crystal inhibitor of the glass frit can be used. As the lightweight refractory material, a high porosity lightweight refractory material mainly composed of inorganic fibers can be used.

According to a second aspect of the present invention, there is provided a lightweight refractory having a glass film whose shape is adjusted by the method for adjusting the shape of the lightweight refractory having the glass film of the present invention.

According to a third aspect of the present invention, containing as a main component reaction curing glass obtained by firing a crystal inhibitor of glass frit and the glass frit, claim
1. A method for adjusting the shape of a lightweight refractory having a glass film according to 1.
The shape adjusting agent applied as the shape adjusting agent in 1. Upper Symbol shape modifier may contain B ₂ O _3. In addition, in the present invention, the description of the numerical range includes not only both end values but also all arbitrary intermediate values included therein. Also, 1 kgf / cm ² = 0.098MP
a.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Method for adjusting the shape of a lightweight refractory having a glass film]

[Lightweight refractory having glass film] The object of the shape adjusting method of the present invention is a lightweight refractory having a glass film. The thickness of the glass film may be such that the glass film does not peel off from the lightweight refractory material, for example, 0.
It can be 2 to 0.4 mm. The light-weight refractory having a glass film is preferably a light-weight refractory having a coating layer (usually a dry coating layer) containing a starting material for forming the glass film and an organic binder. It can be obtained by a glass film forming step in which a glass film is formed by baking the glass film on a lightweight refractory material by heat treatment at a predetermined temperature.

The starting material for forming the glass film may be any material that forms a glass film by heat treatment in the glass film forming step, and generally has an average particle size of 0.5 to 50 μm (preferably, an average particle size of 0.5 to 50 μm). Particles having a particle shape of 0.5 to 20 μm) can be preferably used. As the organic binder, one that can maintain the shape of the coating layer can be used, and preferably methyl cellulose, ethyl cellulose, polyvinyl alcohol, or the like can be used.

The range of the weight ratio of the starting material to the organic binder for forming the glass film in the coating layer is preferably 99.0 to 99.99: 1.0 to 0.01 (more preferably 99). 9.9-99.99: 0.1-0.0
Set to 1). The coating layer is preferably formed by applying a slurry containing particles of a starting material for forming a glass film, an organic binder and an organic solvent to a lightweight refractory and then drying (that is, removing the organic solvent). Get what you got. The particle size of the particles of the starting material for forming the glass film, which are not dissolved in the organic solvent, is preferably 0.
The thickness is 5 to 50 μm (more preferably 0.5 to 20 μm). Before applying the slurry to the lightweight refractory, preferably, the surface of the lightweight refractory to be applied with the organic solvent such as ethanol is sufficiently wetted.

As a lightweight refractory, the general characteristics are:
Any material can be used as long as it can withstand the heat treatment temperature (glass coating film baking temperature) in the glass film forming step, and generally a ceramic material can be considered. For example, there is a porous lightweight refractory having high porosity in which inorganic fibers are bonded with a glassy binder phase. Further, US Pat.
The reusable surface heat insulating material (RSI) of the porous silica structure described in No. 7,771, a foamed silica sintered body, etc.
Some have fire resistance up to 500 ° C and low temperature resistance up to -100 ° C.

Other concrete lightweight refractory materials include, for example, JP-A-62-9181 and JP-B-64-10.
No. 469, Japanese Patent Publication No. 5-72341, and Japanese Patent Laid-Open No.
No. 0-231453, Japanese Patent Publication No. 1-55222, Japanese Patent Application Laid-Open No. 4-119995, and Japanese Patent Publication No. 4-286.
There are lightweight refractories described in Japanese Patent No. 66, Japanese Patent Application Laid-Open No. 4-119959, Japanese Patent Application Laid-Open No. 6-172010, and the like.

[Surface shape adjusting step] The surface shape adjusting step is a step of adjusting the surface shape of the lightweight refractory having a glass film, and includes a specific fusing step. That is, in this fusion step, the melted shape-regulating agent is fused to the surface of the lightweight refractory having the glass film, that is, the surface of the lightweight refractory itself and one or more surfaces of the glass film. It is a process. Then, as the shape adjusting agent, the emissivity is such that the shape of the glass film can be maintained during fusion, and the starting material of the glass film having a lower emissivity than the glass film is used as a main component (at least, of the entire shape adjusting agent. The shape adjusting agent is used so that the emissivity is lower than that of the glass film (preferably at least 5%, more preferably at least 10%).

Further, the shape adjusting material is mainly composed of the starting material of the glass film having the above-mentioned specific emissivity (preferably 80% by weight or more, more preferably 90% by weight or more, further preferably 99% by weight or more). ) A shape adjusting material to be contained can be used. The shape adjusting material is 100% by weight of the starting material of the glass film having the specific emissivity.
What is contained can be used. For shape adjustment material,
1.0% by weight or less (more preferably 0.5 to 0.01% by weight, further preferably 0.1 to 0.01% by weight) of an organic binder can be contained, and also an organic binder is contained. You can choose not to let it happen.

The starting material for the glass film in the shape control agent preferably has an emissivity of 5 than that of the glass film.
% Or more (more preferably 10% or more) lower is used. The emissivity can be adjusted by changing the content rate of the inorganic pigment (preferably, a heat-resistant substance that mainly develops black). For example, the addition of an inorganic pigment (preferably a heat-resistant black pigment such as silicon boride) increases the emissivity of glass.

When the glass film whose shape is to be adjusted contains an inorganic pigment (for example, a heat-resistant black pigment), the shape adjusting agent containing only the starting material of the glass film (the inorganic pigment is It is contained at substantially the same content ratio as the glass film). Further, as long as the effect of the present invention is not impaired, a shape adjusting agent having a content of the inorganic pigment lower than that of the glass film whose shape is adjusted can be used as the shape adjusting agent. Preferably, the main component is the starting material of the glass film excluding the inorganic pigment (preferably 80% by weight or more, more preferably 90% by weight or more, further preferably 99% by weight or more, particularly preferably 100% by weight). The shape modifier contained can be used.

However, when the surface shape of a glass film containing an inorganic pigment (for example, a heat resistant black pigment such as silicon boride) is adjusted, the area of the defective portion of the glass film whose shape is adjusted is large, and so on. When coloring such as black is required, the starting material of the glass film (the content of the inorganic pigment, which is a heat-resistant black pigment such as silicon boride, is the same) is used as the shape adjusting agent. it can. In this case, for example, the shape adjusting agent is heated at a higher temperature (for example, by increasing the burner flame temperature (heat power) by 100 to 200 ° C.) than when the starting material for the glass film containing no inorganic pigment is heated. Can be melted to repair defects in the glass film without impairing the effects of the present invention.

The heating conditions (for example, the maximum temperature and the holding time at that temperature, the type of atmosphere, etc.) for locally fusing the shape-regulating agent retained on the surface of the lightweight refractory having a glass film are as follows: It can be appropriately set according to the type of glass film to be formed. Moreover, the area to be locally heated is set to an area that does not impair the shape of the glass film already formed on the surface of the lightweight refractory, and is preferably 25.
cm ² or less (more preferably 10 cm ² or less, further preferably 0.1 to ¹ cm ² ).

The light-weight refractory having a glass film may be either a glass film having a defect or a glass film having no defect. When the glass film has a defect, the surface shape of the lightweight refractory material is adjusted so that the defect is filled with a melted shape adjusting agent and fused to repair the defect (make the defect flat). be able to. In addition, when the glass film has no defects, a desired shape (eg, a shape in which a convex portion having a desired shape is formed) is obtained by fusing a melted shape adjusting agent to the glass film (for example, the surface of the glass film). Moreover, the surface shape of the lightweight refractory material can be adjusted.

The molten shape-adjusting agent is obtained by heating and melting a solid (preferably powder) shape-adjusting agent which is held in advance on the surface of a lightweight refractory material having a glass film (for example, a defective portion of the glass film). Can be obtained. In order to make the surface of a lightweight refractory material having a glass film (for example, a defective portion of the glass film) retain a solid (preferably powder) shape adjusting agent, the surface of the lightweight refractory material having a glass film (for example, a defect of the glass film). Part), a means for applying a solid (preferably powder) shape adjusting agent together with an organic solvent such as ethanol and drying, and a solid (preferably powder) shape adjusting agent, an organic solvent and an organic binder. There is a means for applying and drying the slurry thus formed. In this case, the particle size of the solid (preferably powder) shape adjusting agent is preferably 0.5 to 20 μm (more preferably 0.5 to 10 μm).
m, more preferably 0.5 to 5 μm).

Further, the molten shape adjusting agent obtained by heating the solid shape adjusting agent is supplied to the surface of the lightweight refractory material having the glass film (for example, defective portion of the glass film) (for example, coating). Or lightly) and fused to the surface of the lightweight refractory.

[Lightweight Refractory Having a Glass Film] The lightweight refractory having a glass film of the present invention is a lightweight refractory having a shape adjusted by a method for adjusting the shape of a lightweight refractory having a glass film of the present invention. . The thickness of the glass film is preferably 0.2 to 0.4 mm, but can be further appropriately selected in consideration of usage conditions, material and the like.

[Shape Adjusting Material for Lightweight Refractory Material] The shape adjusting material for a lightweight refractory material of the present invention contains a glass frit and a reaction-cured glass obtained by firing a crystal inhibitor of the glass frit as a main component (at least Shape adjustment to contain the emissivity of the entire shape modifier lower than that of the glass film on the surface of the lightweight refractory (preferably 5% or more, more preferably 10% or more) It is a material.
The ratio of the glass frit crystallization inhibitor to the glass frit is preferably 6% by weight or more (more preferably 8 to 13% by weight).

The reaction-cured glass has a lower emissivity than a glass film obtained by heat-treating the reaction-cured glass (in particular, one containing an inorganic pigment (for example, a heat-resistant black pigment such as silicon boride)). (That is, the emissivity is low enough to maintain the shape of the glass film during fusion bonding), so that it is easier to melt than the glass film already formed on the surface of the lightweight refractory. Therefore, while maintaining the shape of the glass film already formed on the surface of the lightweight refractory (for example, without melting or deforming the glass film), the shape adjusting material of the present invention is formed on the surface of the lightweight refractory having the glass film. Can be fused.

The shape-adjusting material of the lightweight refractory material of the present invention comprises, as a component other than the main component, the above-mentioned specific reaction-cured glass 1
For example, B ₂ O ₃ is preferably 30 parts by weight with respect to 00 parts by weight.
It may be contained in an amount of not more than 20 parts by weight (more preferably not more than 20 parts by weight, further preferably not more than 10 parts by weight).

When the glass film whose shape is to be adjusted contains an inorganic pigment, the shape adjusting agent of the present invention is preferably
The specific reaction-cured glass containing no inorganic pigment as a main component (preferably 80% by weight or more, more preferably 90% by weight or more).
% By weight or more, more preferably 99% by weight or more), and most preferably a shape adjusting agent consisting essentially of the specific reaction-hardened glass.

Further, the shape-adjusting material of the lightweight refractory material of the present invention may contain an inorganic pigment within a range that does not impair the effects of the present invention. That is, the shape adjusting agent of the present invention is an inorganic pigment (preferably a heat resistant black pigment such as silicon boride).
The emissivity is higher in the case of containing no. Than in the case of not containing the inorganic pigment. Therefore, the shape adjusting material of the present invention preferably contains all the inorganic pigments (for example, a heat resistant black pigment such as silicon boride) contained in the glass film portion near the portion whose shape is to be adjusted. The inorganic pigment is contained in a content not more than the total content.

For example, when the surface shape of a glass film containing an inorganic pigment (for example, a heat-resistant black pigment such as silicon boride) is adjusted, the area of the defective portion of the glass film whose shape is adjusted is large. When coloring such as black is required, use the starting material of the glass film (the content of the inorganic pigment, which is a heat-resistant black pigment such as silicon boride, is the same) as the shape-adjusting agent. You can In this case, for example, the burner flame temperature (fire power) is set to 1 as compared with the case where the starting material of the glass film containing no inorganic pigment is heated.
It is possible to repair the defects of the glass film without increasing the effect of the present invention by raising the temperature by 0 to 200 ° C. to melt the shape adjusting agent.

When the shape adjusting material of the present invention is mounted on the surface of a lightweight refractory and used, for example, it is made of 100% by weight of the reaction-cured glass (or the reaction-cured glass and the inorganic pigment) (for example, Powder). Further, the shape-adjusting material of the present invention is a form in which an organic solvent (for example, ethanol or the like) is mixed with the reaction-cured glass (or the reaction-cured glass and the inorganic pigment) so as to be easily retained on the surface of the lightweight refractory, Alternatively, it can be supplied to the surface of the lightweight refractory material in the form of a slurry containing the reaction-cured glass (or the reaction-cured glass and the inorganic pigment), an organic solvent and an organic binder.

In the former case, the organic solvent is preferably 20 to 50 parts by weight (more preferably 30 to 50 parts by weight) with respect to 100 parts by weight of the reaction cured glass (or the reaction cured glass and the inorganic pigment). , And more preferably 40
˜50 parts by weight). In the latter case,
The organic solvent is preferably 20 to 50 parts by weight (more preferably 30 to 50 parts by weight, further preferably 40 to 50 parts by weight) with respect to 100 parts by weight of the reaction-cured glass (or the reaction-cured glass and the inorganic pigment). In addition, the amount of the organic binder may be preferably 1.0 to 0.01 parts by weight (more preferably 0.1 to 0.01 parts by weight).

[Examples of Preferred Embodiments] As a starting material for forming a glass film, a reaction hardening glass mainly composed of a high-silica glass frit and a crystal inhibitor of the glass frit is used as a shape adjusting material. The case of using a shape adjusting material containing the reaction-cured glass as a main component will be described.

As a starting material for forming the glass film, a reaction-hardened glass mainly composed of a high-silica glass frit and a crystal inhibitor (preferably boron oxide powder) of the glass frit can be used. In addition, various pigments (for example, black pigments such as silicon borides) may be added. In this case, the ratio of boron oxide in the reaction-cured glass when boron oxide is used as the crystallization inhibitor is preferably 8 to 13% by weight. As the silicon boride used as the black pigment, silicon tetraboride or a mixture of one or more of silicon tetraboride and other silicon boride can be used.

In order to impart high temperature resistance and thermal shock resistance to the coated glass film, the glass frit as the main raw material is preferably a high silica glass frit. Generally, the silica content is preferably 96% by weight or more. The impurities contained in the glass frit are N
It is desirable that impurities that deteriorate the heat resistance of the glass of an alkali metal such as a and K or an alkaline earth metal such as Mg and Ca are not contained as much as possible, and most of the impurities are preferably boron oxide or alumina.

For the glass frit, the silica content is preferably as high as possible for the reason described above, and there is a glass frit having a high silica content of 98% by weight silica as known in quartz glass, but the availability is high. From the viewpoint of cost, it is possible to use a porous glass frit containing 96 wt% silica as a standard value. However, although alumina and boron oxide are acceptable as the main impurities contained in the glass frit,
It is preferable that the total amount of other impurities, especially those that deteriorate the heat resistance of the glass, be less than 1% by weight. Such impurities that reduce heat resistance include alkali metals such as Na and K, and Mg and Ca.
Such as alkaline earth metals, Fe, and Ti.

As a high-silica glass frit, Vycol glass manufactured by Corning Inc. of the United States is known. However, these high-silica glasses generally have an acid washing step for removing impurities in the manufacturing process and are acid-washed. There are porous glass having pores generated at that time and dense glass in which pores are removed by heat treatment after acid cleaning. If the heat treatment temperature (glass baking temperature) in the glass film forming process is set too high, the entire light weight refractory material is likely to be distorted, which causes inconvenience. It is desirable that the silica be high silica and at the same time be porous with high activity.

As the lightweight refractory used in the example of the present embodiment, those repeatedly used in a high temperature atmosphere are also specifically intended. The higher the porosity is, the more preferable it is, but in consideration of the balance with strength, it is appropriate to use 80 to 90% by weight or more, preferably 90% by weight or more, and particularly 90 to 96% by weight. For that purpose, it is preferable to add a glass crystallization inhibitor so that the glass does not crystallize even when it is repeatedly used in a high temperature atmosphere.

Boron is known as a glass crystallization inhibitor, and boron oxide can be effectively used in the example of the present embodiment. Boron oxide added to a glass frit that is high in silica and porous is preferably as pure as possible in terms of removing impurities in order to ensure high temperature resistance and thermal shock resistance, similar to glass frit. From the viewpoint of easiness and cost, it is preferable to use a high-purity boron oxide powder of 5 nines (99.999% by weight or more).

Regarding the ratio of boron oxide to glass frit, US Pat. No. 4,093,771 recommends _{2 to} 4% by weight of B ₂ O ₃ . However, from the viewpoint of reducing the amount of strain, it is preferable to select B ₂ O _{3 in} which the ratio of boron oxide to the glass frit is 6% by weight or more, particularly 8 to 13% by weight. It should be noted that when the ratio of boron oxide to the glass frit is 8% by weight or more, the temperature at the time of heat treatment (at the time of glass baking) becomes appropriate and it is effective in reducing the strain amount
If it is higher than 13% by weight, the high temperature resistance tends to be deteriorated and it may be inappropriate, so caution is required.

In order to uniformly mix the glass frit and the high-purity boron oxide powder, the glass frit is homogeneously dispersed in an aqueous solution of boron oxide in which the boron oxide powder is dissolved and dispersed in ion-exchanged water, and then a hot plate is used. Alternatively, the water is removed by stirring while heating with a mantle heater or the like. Further, after removing excess water in a drying oven, it is pulverized and classified with # 16 mesh. Mix the classified glass frit and boron oxide at 1000 to 1100 ° C.
The glass frit and the boron oxide are reacted by firing at the temperature of 2 hours. At a temperature lower than 1000 ° C., the reaction between glass frit and boron oxide is insufficient,
If the temperature is higher than 0 ° C., the glass frit and boron oxide will react and melt, which is inappropriate. After firing, it is ground with a ball mill and classified with # 330-300 mesh to obtain reaction-cured glass. If a mesh coarser than # 300 mesh is used in the classification, a reaction-hardened glass having a large average particle diameter is obtained, and a highly accurate glass coating film tends not to be formed. Moreover, the classification operation becomes complicated even if the mesh is classified with a finer mesh than the # 330 mesh.

Silicon boride was added to the reaction-cured glass obtained as described above, and then ethanol as a dispersion medium and a 2 wt% methylcellulose aqueous solution as a binder were mixed in a ball mill for 3 to 6 hours to form a slurry (for forming a glass film). Slurry). In order to obtain a sufficient black glass film, silicon boride is added to the reaction hardening glass. The silicon boride to be added is preferably silicon tetraboride, silicon hexaboride,
Other silicon boride compounds such as silicon diboride or mixtures or composites thereof (including solid solutions), or molybdenum disilicide can be used although the black coloration is not as good as silicon tetraboride. . Silicon tetraboride is a special silicon boride compound.
Obtained in a grade of 1088.

Silicon boride (particularly silicon tetraboride as a main component) is preferably blended in an amount of 2.5% by weight or more based on the total amount of the reaction-cured glass and the silicon boride compound. If the addition rate of the silicon boride compound is lower than 2.5% by weight, there is a tendency that a black color is formed or predetermined optical characteristics cannot be obtained. Moreover, since silicon tetraboride such as boron tetrasilicide is a special boron silicide compound and is an expensive raw material, it is not economically advantageous to use it in a large amount.
The most desirable is 2.5 to 5.0% by weight.

An organic solvent is suitable as a dispersion medium for forming a slurry. Lightweight refractories with glass membranes have a high porosity, especially those with a porosity of 80 to 90% or more are intended to absorb a large amount of dispersion medium, but have a high evaporation temperature such as water. With the medium, the dispersion medium that has penetrated into the lightweight refractory is difficult to evaporate, and the glass film tends to be damaged during heat treatment (glass baking) in the drying or glass film forming step. Further, when a dispersion medium such as water is used, it may react with silicon tetraboride and decompose, which is inappropriate. Although ethanol was selected as the dispersion medium in the examples of the present invention in view of the above points, the affinity of the glass frit, and the ease of availability, other volatile organic solvents such as methanol and isopropyl alcohol can also be used.

An organic binder is used for maintaining the shape (up to firing) of the glass paste film obtained by coating the slurry on a lightweight refractory, and an aqueous solution of methylcellulose is added as an example. The concentration of the aqueous methylcellulose solution is not particularly limited, but if the concentration is high, it is difficult to prepare and it is disadvantageous. In the examples of the present invention, a standard 2% by weight aqueous solution of methylcellulose was adopted. In general, the aqueous methyl cellulose solution is basically dissolved in ethanol (mixed)
Not to do so, Methocel E, F, J, K manufactured by 3M Company in the United States
Methyl cellulose having a hydroxypropyl group, which has improved solubility in an organic solvent, such as SH type manufactured by Shin-Etsu Chemical Co., Ltd. is preferable. As the organic binder for retaining the shape of the frit slurry, other known materials such as ethyl cellulose and polyvinyl alcohol can be used.

The slurry obtained as described above was filled in a spray gun, and the compressor pressure was 4 kgf / c.
m ² or less, to set the pressure when the trigger is pulled the spray gun so that the 3 kgf / cm ² or less. If spray coating is performed at a pressure higher than this, in the case of a general-purpose spray gun used, care should be taken as the compressed air from the spray gun may cause the coating surface to wavy and it may not be possible to apply a highly accurate coating film. . It is preferable that the lightweight refractory to be coated with the slurry be sufficiently wet with the same ethanol as that used for the slurry in advance. Since the lightweight refractory is porous, spray coating it while it is dry will only absorb ethanol, which is the solvent, into the lightweight refractory, which will roughen the coating surface.

After spray coating, the product is dried at room temperature for a predetermined time (for example, 16 hours or more) to remove ethanol, and then dried in an oven at a predetermined temperature (for example, 70 ° C.) (for example, 3 hours or more) to remove the remaining solvent. Sufficiently remove (ethanol).

A light-weight refractory having a coating layer (dry layer containing reaction-cured glass particles, silicon boride and methylcellulose) formed as described above can be obtained.

When the reaction-cured glass and the black pigment such as silicon boride are used as the starting material for forming the glass film, the heat treatment in the glass film forming step is preferably nitrogen gas, argon gas or other inert gas. It is performed by gradual heating and gradual cooling in a gas atmosphere.

The heat treatment temperature (baking temperature of the glass film) for heat-treating the light-weight refractory having the coating layer formed thereon (the baking temperature of the glass film) is preferably a holding temperature of 1200 to 1260 ° C., preferably 1 to 3 hours. (More preferably 1 to
Hold for 2 hours. The temperature rising rate up to the holding temperature is preferably 500 to 700 ° C./hour (more preferably 600 to 650 ° C./hour), and the temperature lowering rate from the holding temperature to room temperature is preferably 20 to 100 ° C./hour. (More preferably 20 to 40 ° C./hour).

The reaction-hardened glass is supplied to the surface (for example, the defective portion of the glass film) of the lightweight refractory material having the glass film obtained as described above. The reaction-hardened glass preferably has a particle size of 0.5 to 50 μm (more preferably a particle size of 0.1 μm).
5 to 20 μm, more preferably 0.5 to 10 μm
m) into powder.

Usually, the reaction-cured glass powder is mixed with an organic solvent such as ethanol, methanol, or isopropyl alcohol to disperse the reaction-cured glass powder in the organic solvent. Supply to the defective portion of the film). In the dispersion liquid, the organic solvent is preferably 20 to 50 parts by weight (more preferably 30 to 50 parts by weight) with respect to 100 parts by weight of the reaction-cured glass powder.

When the base material of the light-weight refractory material (for example, white base material) is visible because the glass film is sharply broken, the reaction-cured glass powder, various pigments (preferably black pigment), and the organic solvent (preferably ethanol) are used. ) And an organic binder are mixed to disperse the reaction hardening glass powder, and the slurry is supplied to the surface of the lightweight refractory material (for example, a defective portion of the glass film).

In the above slurry, reaction-cured glass 1
The organic solvent is preferably 20 to 50 parts by weight with respect to 00 parts by weight.
The amount is more preferably 30 to 50 parts by weight, and the organic binder is preferably 1.0 to 0.01 parts by weight (more preferably 0.1 to 0.01 parts by weight). The various pigments (preferably black pigments) preferably have a particle size of 0.5 to 20 μm (more preferably a particle size of 0.5 to 10).
μm, and more preferably, a powder having a particle size of 0.5 to 5 μm).

The lightweight refractory supplied with the dispersion or the slurry containing the reaction hardening glass powder is dried.
The drying temperature is preferably 50 to 100 ° C. (more preferably 70 to 80 ° C.), and the drying time may be any time that allows sufficient drying, preferably 60 minutes or longer (more preferably 120 minutes or longer). ), For example, 60 to
It can be 120 minutes.

The dried product obtained by drying the dispersion liquid or the slurry and adhering to the lightweight refractory is locally heated by using, for example, a gas burner or the like to melt the dried product and fuse it to a glass film. Then, the surface shape of the lightweight refractory material having the glass film is adjusted to a desired shape (for example, so as to repair a defective portion). The heating temperature is preferably 1
700-3000 ° C (more preferably 1800-300)
0 ° C, more preferably 2000 to 3000 ° C).

The gas burner has, for example, a maximum flame temperature of 1400 to 3000 ° C. (preferably 1600 to 1).
800 ° C.), gas pressure 1.0 to 10 kgf / cm ² (preferably 4 to 7 kgf / cm ² ), nozzle diameter 0.2 to
A 2.0 mm (preferably 0.5-1.0 mm) oxygen welding burner can be used.

[0062]

[Example 1] <Glass film coating step> 37 g of boron oxide powder (5N manufactured by Furuuchi Chemical Co., Ltd.) is completely dissolved in 272 cc of ion-exchanged water heated to 85 ° C. Ethanol (special grade reagent manufactured by Kanto Scientific Co., Ltd.) 137
g and 400 g of glass frit (Vaicor # 7930, manufactured by Corning International Co., Ltd., SiO ₂ : 96% by weight). Stir while keeping the temperature at 85 ° C on a hot plate to remove ethanol and water. When the slurry becomes too viscous to stir, remove residual ethanol and water in an oven at 70 ° C. The dried product is pulverized, classified with # 16 mesh, filled in a silica container, and baked at 1100 ° C. for 2 hours. After firing, it is ground again and classified with # 330 mesh to obtain a reaction curable glass (reaction cured glass).

234 g of reaction curable glass, 6.0 g of silicon tetraboride (B-1088 manufactured by CERAC, USA), 386 g of ethanol, 2% methyl cellulose aqueous solution (methyl cellulose: Metroze 65SH manufactured by Shin-Etsu Chemical Co., Ltd.).
-4500) 39.2 g is put in an alumina pot together with alumina boulders and mixed on a pot stand for 5 hours. The slurry obtained by mixing was filled in a spray gun, compressor pressure: 3.0 kgf / cm ² , spray pressure:
2.5 kgf / cm ² , a slightly curved plate shape (thickness: about 25 mm, width (short side): 200 mm, as shown in FIG. 1)
The light-weight refractory having a length (long side) of 250 mm was coated on the upper end surface (convex surface having a radius of curvature R of 1000 mm) and four side surfaces, a total of 5 surfaces, and the concave surface was not coated. At that time, the surface of the lightweight refractory material was sufficiently wetted with ethanol as a pretreatment for coating.

After coating, it was dried at room temperature for 16 hours,
It was dried in an oven at 70 ° C. for 3 hours. The light-weight refractory after drying was placed in an atmosphere furnace, and nitrogen gas was supplied to the atmosphere furnace at a rate of 10 l / min for 30 minutes before heating, and the atmosphere in the atmosphere furnace was replaced with nitrogen. After 30 minutes of gas inflow, heating was started and 610 ° C./hr. The temperature was raised at 1215 ° C. and maintained at 1215 ° C. for 1 hour and 30 minutes, and then 600 ° C./hr. It was cooled in the furnace.

<Repair Step of Defects in Glass Film> When defects such as through holes and scratches occur in the glass film produced in the above glass film coating step, repair is performed by the following method.

A reaction-curable glass is produced by the above method. Reaction-curable glass mixed with ethanol is applied as a repair material to the defective portion of the glass film. Dry thoroughly in oven at 70 ° C. for 15 minutes. Maximum flame temperature 3000 ° C, gas pressure 5-10kgf / c
Using an oxygen welding burner with a m ² nozzle diameter of 0.9 mm, the reaction curable glass applied with a burner flame of 2000 to 3000 ° C. is melted to repair defects in the glass film.

[0067] In addition, large sharp glass film, if the matrix of light refractory (white) is seen, as repair material, instead of the reaction-curable glass is mixed with ethanol and four in the reaction-curable glass Silicon boride (US CERA
A slurry prepared by mixing B-1088 manufactured by Company C and ethanol, and a 2% methylcellulose aqueous solution (methylcellulose: Metroze 65SH-4500 manufactured by Shin-Etsu Chemical Co., Ltd.) at a predetermined mixing ratio in the above glass film coating step is used.

[0068]

The method of adjusting the shape of a lightweight refractory having a glass film according to claims 1 to 6 is for repairing defects in the glass refractory having the glass film, and
Gives the desired shape to the surface of the glass film without defects
To protect the surface of a lightweight refractory with a glass film,
A shape containing the starting material of the glass film as a main component as the shape adjusting agent, by fusing the shape adjusting agent melted and fused to adjust the surface shape.
A Jo modifier, since the emissivity to the extent that the starting material can hold a shape of the glass film during the fusing used lower than the glass film, it is possible to achieve the following basic effects it can.

That is, the surface shape of the lightweight refractory material having the glass film can be adjusted to a desired shape without deformation or melting of the glass film. In particular, defects in the glass film can be repaired without deformation or melting of the glass film, so that the yield of the lightweight refractory material having the glass film can be improved.

Since the method for adjusting the shape of a lightweight refractory having a glass film according to claims 2 to 6 is further provided with each of the above constitutions, the above-mentioned basic effects are remarkable.

Light weight resistance having the glass film according to claim 1.
It is applied as a shape adjusting agent in the shape adjusting method of fire
Shape modifier according to claim 8-9 that is one containing a reaction cured glass obtained by firing a crystal inhibitor of glass frit and the glass frit as the main component, having a glass film of the present invention It can be suitably used as a shape adjusting agent in the shape adjusting method of a lightweight refractory.

[Brief description of drawings]

FIG. 1 is a view of a slightly curved plate-shaped lightweight refractory viewed from a direction perpendicular to a thickness direction.

(72) Inventor Shinji Kato, 1-3-1, Noritake Shinmachi, Nishi-ku, Nagoya, Aichi Prefecture Noritake Company Limited, 36-1 (72) Inventor, Kenji Yano 3--1, Noritake Shinmachi, Nishi-ku, Nagoya, Aichi Prefecture No. 36 Noritake Company Limited (72) Inventor Kazuhiro Horimi 3-1, Noritake Shinmachi, Nishi-ku, Nagoya-shi, Aichi Prefecture No. 36 Noritake Company Limited (72) Inventor Yoshiki Kato Nishi-ku, Nagoya-shi, Aichi Prefecture Noritake Company Limited 1-336 Noritake Company Limited (72) Inventor Takamitsu Isoya Noritake Company Limited 3-36 Noritake Company Limited Nishi-ku, Aichi Prefecture Noritake Company Limited Limited (72) Inventor Masayoshi Hiyoshi Aichi Noritake Company Limited 1-36-36, Noritake Shinmachi, Nishi-ku, Nagoya, Japan (72) Inventor Takamitsu Fukui 3-36-3, Noritake Shinmachi, Nishi-ku, Nagoya, Aichi Prefecture (56) Reference JP 11-199353 (JP, A) JP 7-291770 (JP, A) JP 5-221755 (JP, A) JP 63-72786 ( JP, A) JP 59-174585 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C04B 41/80-41/91

Claims (9)

(57) [Claims] 1. A surface of a lightweight refractory material having a glass film, for repairing defects in the glass film, or for repairing defects of the glass film.
Not to give the desired shape to the surface of the glass film
Melts against the surface of a lightweight refractory with a glass film
And a surface shape adjusting step of adjusting the surface shape by fusing the shape adjusting agent, and the starting material of the glass film is mainly formed as the shape adjusting agent.
A shape adjustment agent containing as a frequency, and characterized by using the emissivity enough to retain the shape of the glass film during the starting material <br/> fused those lower than the glass film For adjusting the shape of a lightweight refractory having a glass film to be used. 2. The molten shape adjusting agent obtained by selectively heating the shape adjusting agent retained on at least one surface of the glass film and the lightweight refractory in the surface shape adjusting step, The method for adjusting the shape of a lightweight refractory material having a glass film according to claim 1, wherein the lightweight refractory material having a film is fused to the surface thereof. 3. In the surface shape adjusting step, a molten shape adjusting agent obtained by locally heating the shape adjusting agent retained on the surface of at least one of the glass film and the lightweight refractory is used as the glass. The method for adjusting the shape of a lightweight refractory having a glass film according to claim 1, wherein the lightweight refractory having a film is fused to the surface of the refractory. 4. The surface shape of the lightweight refractory material is adjusted by filling a defect in the glass film with a shape adjusting agent, which includes a fusing step of fusing a shape adjusting agent melted to the defect in the glass film. The method for adjusting the shape of a lightweight refractory having a glass film according to claim 1, further comprising a surface shape adjusting step. 5. The shape adjusting agent containing a glass frit and a reaction-cured glass obtained by firing a crystal inhibitor of the glass frit as a main component is used as the shape adjusting agent. 5. A method for adjusting the shape of a lightweight refractory material having the glass film according to any one of to 4. 6. The shape of a lightweight refractory having a glass film according to claim 1, wherein a high porosity lightweight refractory having inorganic fibers as a main component is used as the lightweight refractory. Adjustment method. 7. A lightweight refractory having a glass film, the shape of which is adjusted by the method for adjusting the shape of a lightweight refractory having the glass film according to any one of claims 1 to 6. 8. The glass film according to claim 1, which contains glass frit and a reaction-cured glass obtained by firing a crystal inhibitor of the glass frit as a main component. Shape adjustment in the shape adjustment method of the lightweight refractory
A shape adjusting agent applied as a conditioning agent . 9. shape modifier according to claim 8, characterized in that it contains B ₂ O _3.