CN112442335A - Sealing material and sealed structure - Google Patents

Sealing material and sealed structure Download PDF

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Publication number
CN112442335A
CN112442335A CN202010893730.4A CN202010893730A CN112442335A CN 112442335 A CN112442335 A CN 112442335A CN 202010893730 A CN202010893730 A CN 202010893730A CN 112442335 A CN112442335 A CN 112442335A
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Prior art keywords
component
sealing material
sealing
alkaline earth
alkali metal
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CN202010893730.4A
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Inventor
谷井史朗
太田胜己
今成正明
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AGC Inc
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Asahi Glass Co Ltd
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Publication of CN112442335A publication Critical patent/CN112442335A/en
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/12—Materials for stopping leaks, e.g. in radiators, in tanks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B29/00—Other details of coke ovens
    • C10B29/06—Preventing or repairing leakages of the brickwork
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces

Abstract

The present invention relates to a sealing material and a sealed structure. A sealing material which exhibits excellent sealing properties when used for repairing a high-temperature device. The sealing material comprises a first component and a second component, wherein the first component is at least one metal salt selected from the group consisting of alkali metal silicates, alkaline earth metal silicates, alkali metal orthophosphates and alkaline earth metal orthophosphates, the second component comprises oxide particles, the particles comprise fine particles having an average particle size of 10 [ mu ] m or less and coarse particles having an average particle size of 200 [ mu ] m to 1000 [ mu ] m, the content of the fine particles is 8 to 45 mass% based on the total mass of the coarse particles and the fine particles, the ratio of the total of the silicic acid component and the phosphoric acid component of the metal salts contained in the first component to the total oxide-based alkali metal component and alkaline earth metal component contained in the first component is 1.5 to 3.5 in terms of molar ratio, and the mass ratio of the first component to the second component is 0.35 to 0.9.

Description

Sealing material and sealed structure
Technical Field
The present invention relates to a sealing material and a sealed structure.
Background
High temperature apparatuses having an internal space capable of controlling an atmosphere, such as a high temperature atmosphere furnace, are widely used in various fields.
In such a high-temperature apparatus, the sealing property of the sealing portion that seals the internal space from the outside may be reduced during use of the high-temperature apparatus. In addition, in this case, it may often be necessary to perform repair of the seal portion while maintaining the high-temperature device in a high-temperature state.
In order to perform so-called in-situ repair of such a high-temperature apparatus, various sealing materials and sealing methods have been proposed (for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-3313
Disclosure of Invention
Problems to be solved by the invention
In-situ repair of high-temperature devices, it is required to provide a sealing material in a sealing portion in a high-temperature state so as to appropriately seal an internal space from the outside.
However, in the conventional sealing material and sealing method, a sufficient sealing effect may not always be obtained in some cases. For example, even in the case of a sealing material exhibiting good sealing properties at room temperature, it is often confirmed that the sealing material deteriorates or cracks are generated in the sealing material in a high-temperature region of 200 ℃.
Accordingly, there is still a great need for a sealing material that can be suitable for in-situ repair of high temperature devices.
The present invention has been made in view of such a background, and an object of the present invention is to provide a sealing material which exhibits good sealing properties when applied to in-situ repair of a high-temperature device. Another object of the present invention is to provide a seal structure formed of such a sealing material.
Means for solving the problems
In the inventionA sealing material for a seal portion that seals an internal space of a high-temperature apparatus from the outside, wherein the sealing material has a first component and a second component, the first component is at least one metal salt selected from the group consisting of alkali metal silicates, alkaline earth metal silicates, alkali metal orthophosphates, and alkaline earth metal orthophosphates, the second component contains particles of an oxide having fine particles having an average particle diameter of 10 [ mu ] m or less and coarse particles having an average particle diameter of 200 [ mu ] m to 1000 [ mu ] m, and the content of the fine particles is in a range of 8 mass% to 45 mass% with respect to the total mass of the coarse particles and the fine particles, and a silicic acid component (SiO) of the metal salt contained in the first component is a silicic acid component (SiO) of the metal salt2) With phosphoric acid component (P)2O5) The ratio of the total of (a) to the total of the alkali metal component and the alkaline earth metal component contained in the first component is 1.5 to 3.5 in terms of a molar ratio, and the mass ratio of the first component to the second component is in the range of 0.35 to 0.9.
In addition, the present invention provides a sealing material for a sealing portion that blocks an internal space of a high-temperature apparatus from the outside, wherein the sealing material foams to form a sealed structure when the sealing material is provided in the sealing portion at 350 ℃, the sealed structure has a skeleton portion composed of film-like partition walls and a plurality of pores, the skeleton portion contains silicate glass and/or phosphate glass, and the pores have an average diameter of 30 μm to 5000 μm.
In addition, the present invention provides a seal structure provided in a seal portion that blocks an internal space of a high-temperature apparatus from the outside, wherein the seal structure has a skeleton portion formed of film-like partition walls and a plurality of pores, the skeleton portion contains silicate glass and/or phosphate glass, and the pores have an average diameter of 30 μm to 5000 μm.
Effects of the invention
The present invention can provide a sealing material that exhibits good sealing properties when applied to in-situ repair of a high-temperature device. In addition, the present invention can provide a seal structure formed of such a seal material.
Drawings
Fig. 1 is a sectional view schematically showing a seal structure according to an embodiment of the present invention formed at a seal portion of a high-temperature apparatus.
Fig. 2 is an optical microscope photograph showing an example of a cross section of a seal structure according to an embodiment of the present invention.
Fig. 3 is a view schematically showing the configuration of a test apparatus used in the sealing performance evaluation test.
Fig. 4 is a graph showing the results of the sealing performance evaluation test obtained in several samples.
Fig. 5 is an optical micrograph showing an example of a cross section of a seal structure according to a comparative example.
Fig. 6 is a perspective view schematically showing the shape of a metal mold used in the thermal cracking evaluation test.
Description of the reference symbols
10 high temperature device
15 gap
20 sealing part
30 first wall member
31 second wall member
40 inner space
42 sealing member
100 sealed structure
110 skeleton part
120 air hole
210 test device
220 metal container
226 projection
230 electric stove
240 buffer tank
250 sealing Material (sealing Structure)
360 metal mold
362 upper surface
364 lower surface
366 hole part
Detailed Description
Hereinafter, one embodiment of the present invention will be described.
In the present application, the "sealing material" refers to a material applied to a sealing portion of a high-temperature device in order to seal an internal space of the high-temperature device from the outside. In the present application, the term "seal structure" refers to a member formed in a high-temperature seal portion of a high-temperature device by providing a "seal material" in the seal portion.
Therefore, when the "sealing material" is provided in the sealing portion in a high-temperature state of the high-temperature apparatus, a "sealed structure" is formed from the "sealing material".
In one embodiment of the present invention, there is provided a sealing material for a sealing portion that blocks an internal space of a high-temperature apparatus from the outside, the sealing material having a first component of at least one metal salt selected from the group consisting of alkali metal silicates, alkaline earth metal silicates, alkali metal orthophosphates, and alkaline earth metal orthophosphates,
the second component contains oxide particles having a fine particle having an average particle diameter of 10 [ mu ] m or less and a coarse particle having an average particle diameter of 200 [ mu ] m to 1000 [ mu ] m, the content of the fine particle being in the range of 8% by mass to 45% by mass based on the total mass of the coarse particle and the fine particle, and a silicic acid component (SiO) of the metal salt contained in the first component2) With phosphoric acid component (P)2O5) The ratio of the total of (a) to the total of the alkali metal component and the alkaline earth metal component contained in the first component is 1.5 to 3.5 in terms of a molar ratio, and the mass ratio of the first component to the second component is in the range of 0.35 to 0.9.
As described above, in-situ repair of a high-temperature apparatus, it is required to provide a sealing material in a sealing portion in a high-temperature state such as 200 to 600 ℃, for example, so as to appropriately seal the internal space from the outside.
However, when a conventional sealing material is used, the following problems often occur: even if good sealing properties are exhibited at room temperature, very good sealing properties cannot be obtained in a high-temperature region of 200 ℃ or higher. One of the reasons for this is that, when a conventional sealing material is provided in a high-temperature sealing portion, the components contained in the sealing material shrink, and cracks occur in the sealed structure.
In contrast, the sealing material according to one embodiment of the present invention has the first component which is at least one metal salt selected from the group consisting of alkali metal silicates, alkaline earth metal silicates, alkali metal orthophosphates, and alkaline earth metal orthophosphates. The first component can be foamed at a high temperature in the range of 200 to 600 ℃, for example, to generate bubbles.
Therefore, when the sealing material according to one embodiment of the present invention is applied to a high-temperature sealing portion, shrinkage of the sealing material can be significantly suppressed by expansion caused by generation of bubbles. As a result, when the sealing material according to one embodiment of the present invention is applied to a high-temperature sealing portion, cracks caused by shrinkage can be significantly suppressed.
However, when the first component is foamed at a high temperature, it is difficult to accurately control the degree of foaming, the number of cells, the size of the cells, and the like. For example, when only the first component is added to the sealing material and the sealing material is applied, unevenness or extremely large bubbles may be generated in the foamed region. The presence of such uneven foaming, large bubbles, causes through holes, which may become a factor of reducing the sealability of the formed seal structure and reducing the strength thereof.
Thus, the sealing material according to an embodiment of the present invention also has a second component. When a seal structure is formed from the seal material according to one embodiment of the present invention, the second component constitutes a large part of the skeleton portion in the seal structure. The second component contains oxide particles having a fine particle size of 10 [ mu ] m or less and a coarse particle size having an average particle size in the range of 200 [ mu ] m to 1000 [ mu ] m.
In the particles of the oxide, the fine particles function as base points when the first component is foamed. Therefore, by appropriately adjusting the amount of fine particles contained in the sealing material as the second component, it is possible to control the generation of foaming, and to adjust the number and size of bubbles and the like to some extent.
Specifically, by setting the fine particles to 8% by mass or more relative to the total of the coarse particles and the fine particles in the second component contained in the sealing material, foaming can be uniformly generated as a whole, and a plurality of fine bubbles can be generated with the fine particles as base points.
In addition, when the proportion of the fine particles in the second component contained in the sealing material is excessively high, the strength of the resulting sealed structure may be reduced. In this case, cracks may easily occur at the time of formation of the seal structure or in use of the seal structure after formation.
Therefore, in the sealing material according to one embodiment of the present invention, the fine particles are added so that the mass ratio is 45% or less with respect to the total of the coarse particles and the fine particles in the second component. By setting the fine particles to such an upper limit, a decrease in the strength of the seal structure can be significantly suppressed.
As a result, when the sealing material according to one embodiment of the present invention is applied to a sealing portion of a high-temperature device, a sealed structure having better sealing performance than the conventional one can be formed.
(seal structure according to one embodiment of the present invention)
Hereinafter, a seal structure according to an embodiment of the present invention will be described in more detail with reference to the accompanying drawings.
Fig. 1 is a sectional view schematically showing a seal structure according to an embodiment of the present invention formed at a seal portion of a high-temperature apparatus.
As shown in fig. 1, a seal structure (hereinafter, referred to as a "first seal structure") 100 according to an embodiment of the present invention is provided at a seal portion 20 that blocks a gap 15 of a high-temperature apparatus 10.
More specifically, the high temperature device 10 has a first wall member 30 and a second wall member 31, and the internal space 40 is formed inside the high temperature device 10 by the first and second wall members 30, 31 and the like. However, there is a gap 15 between the first wall member 30 and the second wall member 31, and in order to seal this gap 15, a seal member 42 is filled in the gap 15. This forms the sealing portion 20, and blocks the internal space 40 from the outside.
However, for example, when the high-temperature apparatus 10 is used for a long time, the sealing member 42 deteriorates, and its sealing performance is lowered. In such a case, it may be necessary to repair the sealing member 42 in a state where the high-temperature apparatus 10 is used, that is, in a state where the sealing portion 20 is at a high temperature.
The seal structure 100 is provided for such in-situ repair. That is, by configuring the seal structure 100 in the seal portion 20, the sealing performance of the high temperature apparatus 10 can be maintained.
The temperature of the sealing portion 20 to which the seal structure 100 is applied varies depending on the high temperature apparatus 10. In one example, the temperature of the sealing portion 20 to which the seal structure 100 is applied is in the range of 200 to 600 ℃, preferably in the range of 300 to 500 ℃.
Fig. 2 shows an example of a cross-sectional photograph of the seal structure 100 taken by an optical microscope.
As shown in fig. 2, the seal structure 100 has a characteristic form. Specifically, the seal structure 100 includes a frame portion 110 formed of film-like partition walls extending three-dimensionally in three directions of vertical and horizontal depths, and a plurality of air holes (closed cells) 120 separated by the partition walls.
Although most of the air holes 120 are formed between the partition walls, some of the air holes 120 are formed inside the partition walls.
In the seal structure 100, the skeleton portion 110 includes at least one of silicate glass and phosphate glass. The silicate glass and the phosphate glass may each comprise an alkali metal salt and/or an alkaline earth metal salt. In addition, the alkali metal salt may be Na2O and/or K2And O. Further, the alkaline earth metal salt may be MgO and/or CaO.
In the skeleton portion 110, silicic acid (SiO)2) And phosphoric acid (P)2O5) The total of B with respect to oxygen of the alkali metal component and the alkaline earth metal componentThe ratio of the total A based on the compound (i.e., the ratio B/A) is in the range of 1.5 to 3.5 in terms of a molar ratio. When the B/A ratio is less than 1.5, the viscosity of the sealing material becomes low and foaming becomes unstable. When the ratio B/a is more than 3.5, the viscosity of the sealing material increases, and mixing with other members and application to the sealing portion become difficult. The ratio B/A is preferably in the range of 1.8 to 3.3 in terms of a molar ratio.
The pores 120 have an average diameter of 30 to 5000 μm. Here, the average diameter of the pores was obtained by image analysis of a cross-sectional photograph. As the image analysis software, Mac-view (version 4) (mount tech, ltd.) can be used. The average diameter of the pores 120 is preferably in the range of 60 to 3000. mu.m.
The seal structure 100 has good strength. Therefore, the occurrence of cracks in the seal structure 100 can be significantly suppressed at the time of formation and in use of the seal structure 100.
Therefore, the sealing portion 20 of the high-temperature apparatus 10 can obtain good sealing performance for a long period of time.
The first wall member 30 and the second wall member 31 forming the seal portion 20 in which the seal structure 100 is provided may be made of any material as long as it is a material having heat resistance, such as metal (for example, heat-resistant metal) or ceramic (for example, refractory brick).
(sealing Material according to one embodiment of the present invention)
Next, a description will be given of a sealing material according to an embodiment of the present invention for forming a seal structure such as the first seal structure 100 described above.
A sealing material according to an embodiment of the present invention (hereinafter, referred to as a "first sealing material") has a first component and a second component.
Hereinafter, each component will be described in detail.
(first component)
The first component is a substance that foams at a high temperature in the range of 200 ℃ to 600 ℃ to generate bubbles, for example.
Examples of such substances include: metal salts such as alkali metal silicate, alkaline earth metal silicate, alkali metal orthophosphate and alkaline earth metal orthophosphate, but not limited thereto. The first component may be used by mixing two or more of these metal salts.
In these metal salts, the alkali metal may comprise, for example, sodium and/or potassium. In addition, the alkaline earth metal may include magnesium and/or calcium, for example.
Silicic acid component (SiO) contained in the first component2) With phosphoric acid component (P)2O5) The ratio of the total D of (A) to the total C of the alkali metal component and the alkaline earth metal component on an oxide basis is 1.5 to 3.5 in terms of a molar ratio. When the ratio D/C is less than 1.5, sufficient foaming may not be obtained. When the ratio D/C is more than 3.5, uniform foaming may not be generated. The ratio D/C is preferably in the range of 1.8 to 3.3.
The ratio V of the first component to the second component, which is described below, is in the range of 0.35 to 0.9 by mass. When the ratio V is less than 0.35, sufficient foaming may not be obtained. When the ratio V is more than 0.9, uniform foaming may not be generated. The ratio V is preferably in the range of 0.4 to 0.85.
(second component)
The second component constitutes most of the skeleton portion 110 in the first seal structure 100 formed of the first seal material. Here, the skeleton portion 110 in the seal structure 100 is composed of a foamed component of the first component and the second component.
As described above, the first seal structure 100 has a form of partition walls made of a thin film. Therefore, in the first seal structure 100, the "skeleton portion 110" refers to a film-like partition wall portion.
The second component comprises particles of an oxide. Examples of the oxide include: silica, alumina, magnesia, calcia or zirconia, or a combination of at least two of them, and the like, but is not limited thereto.
In order to secure the strength of the skeleton portion, the second component preferably contains 96 mass% or more of particles of an oxide, and more preferably contains 98 mass% or more of particles of an oxide.
The particles of the oxide contained in the second component have fine particles having an average particle diameter of 10 [ mu ] m or less and coarse particles having an average particle diameter of 200 [ mu ] m to 1000 [ mu ] m. In the present application, the average particle size is measured by a laser diffraction method.
The fine particles are added so that the mass ratio of the fine particles to the total of the coarse particles and the fine particles is in the range of 8% to 45%. When the proportion of the fine particles is less than 8% by mass, it is difficult to sufficiently control the form of the first sealing material at the time of foaming. As a result, large bubbles may be generated or uneven foaming may occur. Large bubbles are not only involved in the generation of through holes, which is one cause of the deterioration of sealing performance, but also may be a factor of the reduction in strength. On the other hand, when the proportion of the fine particles is more than 45 mass%, the strength of the resulting first seal structure body 100 may decrease. The proportion of the fine particles is preferably in the range of 9 to 43 mass%.
(others)
The first sealing material may further include water. By adding an appropriate amount of water, the fluidity of the first sealing material can be appropriately adjusted.
The amount of water added is not particularly limited, and water is preferably added in the range of 40% to 60% by weight based on the total weight of the sealing material.
(application example of the first sealing Material)
For example, when the first sealing material is applied to the sealing portion 20 of the high-temperature apparatus 10 having a temperature in the range of 200 to 600 ℃, the first component contained in the first sealing material foams to generate bubbles. Therefore, when the first sealing material is applied to the high-temperature sealing portion 20, the first sealing material can be significantly inhibited from shrinking (for example, shrinking due to drying) due to expansion caused by the generation of air bubbles. In addition, this can significantly suppress the occurrence of shrinkage cracks.
In addition, in the first sealing material, bubbles are generated with the fine particles contained in the second component as base points, in particular, but the amount of the fine particles contained in the second component has been adjusted to an appropriate range. Therefore, in the first sealing material, foaming can be generated in a controlled state, and as a result, a plurality of fine bubbles can be formed in a uniform manner. Therefore, the occurrence of through holes that adversely affect the sealing performance can be significantly suppressed.
In addition, in the first sealing material, the foamed first component and the second component together constitute the skeleton portion 110 of the seal structure 100. That is, the seal structure 100 formed after the first sealing material is foamed has the skeleton portion 110 and the plurality of fine pores 120. The skeleton portion 110 contains a predetermined amount of coarse particles of the second component, and thus has a corresponding strength. Therefore, in the case of using the first sealing material, the seal structure 100 having a remarkable strength can be formed.
When the sealing material is provided in the sealing portion 20 at 350 ℃, it foams to become the sealing structure 100. In the seal structure 100, the skeleton portion 110 contains silicate glass and/or phosphate glass, and the pores 120 have an average diameter of 30 to 5000 μm. The average diameter of the pores 120 is preferably in the range of 60 to 3000. mu.m.
As a result of the above-described effects, when the sealing material according to the embodiment of the present invention is applied to the sealing portion 20 of the high-temperature device 10, the seal structure 100 having better sealing performance than the conventional one can be formed.
A method of disposing the first sealing material in the sealing portion 20 of the high temperature device 10 is not particularly limited. For example, the first sealing material is filled into the sealing portion 20 of the high temperature device 10 using a spatula or a scraper. When the sealing portion 20 is at a high temperature, a method of providing the first sealing material from a relatively distant position, such as a mortar injector or a spray method, may be employed for safety.
The sealing material and the sealed structure according to the embodiment of the present invention have been described above. These sealing materials and sealing structures can be applied to any high-temperature device 10 that requires sealing at high temperatures.
The high-temperature apparatus 10 includes, for example, various furnaces such as a coal coke oven, an iron ore blast furnace, a glass melting furnace, and a glass forming furnace, but is not limited to these.
[ examples ]
Next, examples of the present invention will be explained. In the following description, examples 1 to 15 are examples, and examples 21 to 32 are comparative examples.
(example 1)
The sealing material was prepared by mixing the first component with the second component by the following method.
As the first component, sodium silicate was used. As the sodium silicate, sodium silicate Nos. 1, 2, 3, 4 and 5 (all manufactured by Fuji chemical Co., Ltd.) were mixed in a predetermined amount so that the above ratio D/C, that is, SiO2/Na2The molar ratio of O was adjusted to 3.
As the second component, silica particles are used. As the silica particles, a mixture of fine particles having an average particle diameter of 10 μm or less and coarse particles having an average particle diameter in the range of 200 to 1000 μm is used. The proportion of the fine particles with respect to the entire second component was set to 30 mass%.
The mass ratio V of the mass of the first component to the mass of the second component was set to 0.52.
Further, 50% of water was mixed in the mixture of the first component and the second component, thereby obtaining a sealing material. The resulting sealing material was referred to as "sample of example 1".
(examples 2 to 11)
A sealing material was prepared in the same manner as in example 1.
However, in examples 2 to 11, SiO in the first component was used2/Na2At least one of the molar ratio D/C of O, the proportion of fine particles contained in the second component, and the mass ratio V of the mass of the first component to the mass of the second component was changed as compared with the case of example 1.
The obtained sealing materials were referred to as "samples of examples 2 to 11", respectively.
(example 12)
A sealing material was prepared in the same manner as in example 1.
However, in example 12, potassium silicate (No. 2 potassium silicate, manufactured by fuji chemical) was used as the first component. In the first component, the ratio D/C, i.e., SiO2/K2The molar ratio of O is 3.In example 12, the mass ratio V was set to 0.4.
Other conditions were the same as in example 1.
The resulting sealing material was referred to as "sample of example 12".
(example 13)
A sealing material was prepared in the same manner as in example 1.
However, in example 13, a mixed particle of silica and alumina was used as the second component in place of the silica particles. Other conditions were the same as in example 1.
The resulting sealing material was referred to as "sample of example 13".
(example 14)
A sealing material was prepared in the same manner as in example 1.
However, in example 14, a mixed particle of silica and magnesium oxide was used as the second component in place of the silica particle. Other conditions were the same as in example 1.
The resulting sealing material was referred to as "sample of example 14".
(example 15)
A sealing material was prepared in the same manner as in example 1.
In example 15, glass particles were used as the second component in place of silica particles. As the glass particles, particles obtained by pulverizing fragments made of soda-lime glass are used. Other conditions were the same as in example 1.
The resulting sealing material was referred to as "sample of example 15".
Table 1 below summarizes the preparation conditions of the samples of examples 1 to 15.
TABLE 1
Figure BDA0002657747990000151
(examples 21 to 29)
A sealing material was prepared in the same manner as in example 1.
However, in examples 21 to 29, the ratio of the fine particles contained in the second component and/or the mass ratio V of the mass of the first component to the mass of the second component was changed as compared with the case of example 1.
The obtained sealing materials were referred to as "samples of examples 21 to 29", respectively.
(example 30)
A sealing material was prepared in the same manner as in example 1.
However, in example 30, the ratio D/C in the first component was set to 3.4. In example 30, the mass ratio V was set to 0.44.
Other conditions were the same as in example 1.
The resulting sealing material was referred to as "sample of example 30".
(example 31)
A sealing material was prepared in the same manner as in example 1.
However, in example 31, silica sol (Catalogid S-50L: manufactured by Nikkiso Co., Ltd.) was used as the first component. In example 31, the mass ratio V was set to 0.52. Other conditions were the same as in example 1. Since the silica sol hardly contains an alkali component, the ratio D/C was not calculated.
The resulting sealing material was referred to as "sample of example 31".
(example 32)
A sealing material was prepared in the same manner as in example 1.
However, in this example 32, cement (Asahi case CA-13T: manufactured by AGC ceramics) was used as the first component. In example 32, the mass ratio V was set to 0.20. Other conditions were the same as in example 1. Since cement contains almost no alkali component, the ratio D/C was not calculated.
The resulting sealing material was referred to as "sample of example 32".
The preparation conditions of the samples of examples 21 to 32 are summarized in table 2 below.
TABLE 2
Figure BDA0002657747990000171
(evaluation)
(sealing Performance evaluation test)
The sealing performance evaluation test was performed using each sample.
Fig. 3 schematically shows a test apparatus used in the evaluation. As shown in fig. 3, the test apparatus 210 has a metal container 220 and an electric furnace 230 accommodating the metal container 220.
The metal container 220 is made of stainless steel and has a substantially rectangular parallelepiped shape. One surface of the metal container 220 is an opening having a rectangular shape of 150mm × 20 mm. The volume of the interior of the metal container 220 is about 10L.
The metal container 220 is disposed in the electric furnace 230 such that an opening portion protrudes outward from the electric furnace 230. The length of the projection 226 protruding from the fire 230 is about 10 mm. A part of the metal container 220 is provided with another opening, and the opening is connected to an air buffer tank 240.
During the test, the furnace was warmed to about 550 ℃. Thereby heating the protrusion 226 of the metal container 220 to about 350 deg.c.
Next, the metal container 220 is filled with any of the above samples from the vicinity of the protruding portion 226 of the metal container 220. Thereby disposing the sealing material 250 in the protrusion 226 and sealing the opening portion. The depth of the sealing material 250 is set to 20mm from the tip of the protrusion 226.
After 10 minutes from the filling of the sealing material 250, the buffer tank 240 was opened to supply air to the inside of the metal container 220. At the point when the pressure reaches 10000Pa, the buffer tank 240 is closed. The change in the internal pressure of the metal container 220 was measured with the time 0 second representing the state, i.e., the time when the pressure in the metal container 220 was 10000 Pa. Further, the time until the internal pressure was reduced to 10Pa was measured.
The results obtained for the samples of examples 1 to 15 are summarized in the column of "sealing performance" in table 3 below. Similarly, the results obtained for the samples of examples 21 to 32 are summarized in the column of "sealing performance" in table 4 below.
TABLE 3
Figure BDA0002657747990000181
TABLE 4
Figure BDA0002657747990000191
In the column of "sealing performance" in table 4, "×" indicates that the time until the internal pressure is reduced to 10Pa is 5 seconds or less.
As is clear from table 4, in the samples of examples 21 to 32, the internal pressure decreased to 10Pa or less within 5 seconds from the start of the measurement. In contrast, as shown in table 3, in the samples of examples 1 to 15, it took at least 60 seconds until the internal pressure reached 10Pa or less.
Fig. 4 shows, as an example, time-varying curves of the internal pressure obtained in the samples of examples 1, 4 and 23.
In fig. 4, the horizontal axis represents elapsed time (unit: seconds), and the vertical axis represents internal pressure.
As can be seen from this graph, in the sample of example 23, the internal pressure rapidly decreased with the passage of time, and reached 10Pa or less within a few seconds. From the results, it can be said that the sample of example 23 had poor sealing properties.
In contrast, the time required for the internal pressure of the samples of examples 1 and 4 to be reduced to 10Pa or less was significantly longer than that of the sample of example 23. In particular, it took 1550 seconds until the internal pressure of the sample of example 1 reached 10Pa or less.
From this, it is understood that the samples of examples 1 to 15 have better high-temperature sealing properties than the samples of examples 21 to 32.
(tissue observation)
Each sample obtained after the above-described sealing performance evaluation test was observed by SEM, and the foaming condition was evaluated.
The foaming status was classified and evaluated as follows: the case where a large amount of foaming was observed as a whole was evaluated as "o", the case where a moderate degree of foaming was observed as a whole was evaluated as "Δ", and the case where foaming was observed only partially and the case where no foaming was generated were evaluated as "x".
In addition, in the sample in which the foaming occurred, the average pore diameter was determined by image analysis. Specifically, in a cross-sectional photograph of the sample, dark portions surrounded by skeleton portions that appear white are recognized as pores, the sizes of the pores are measured, and the obtained sizes are averaged to calculate an average pore diameter. Mac-view (version 4) (Mountech, K.K.) was used for image analysis.
The column entitled "foaming status" in table 3 above summarizes the results of the evaluation of the foaming status obtained for the samples of examples 1 to 15. The column entitled "average pore diameter" collectively shows the values of the average pore diameters obtained in the seal structures formed from the samples of examples 1 to 15.
Similarly, the column entitled "foaming status" in table 4 above summarizes the results of the evaluation of the foaming status obtained for the samples of examples 21 to 32. The column entitled "average pore diameter" collectively shows the values of the average pore diameters obtained in the seal structures formed from the samples of examples 21 to 32.
From these results, it was found that foaming hardly occurred in the samples of examples 26 to 32. Among them, the samples of examples 26 to 28 had the ratio V of less than 0.35, and therefore the amount of the first component acting as a foam was insufficient, and sufficient foaming was not generated. It is also considered that the sample of example 29 had the ratio V of more than 0.9, and therefore the cells became excessively coarse, and no appropriate foaming occurred. Further, it is considered that the sample of example 30 has the above ratio D/C in terms of molar ratio of more than 3.3, and therefore, although foaming is locally generated, uniform foaming is not generated as a whole.
The samples of examples 31 to 32 did not contain the first component, and therefore, no foaming occurred.
On the other hand, the samples of examples 1 to 15 all had good foaming state. This result is in agreement with the result of the above-mentioned sealing performance evaluation test.
Fig. 2 shows an example of an optical micrograph of a cross section of the seal structure obtained after the test for evaluating the sealing performance of the sample of example 3. As shown in fig. 2, the seal structure is constituted by a plurality of film-like partition walls and pores surrounded by the partition walls.
On the other hand, fig. 5 shows an example of an optical micrograph of a cross section of the seal structure obtained after the sealing performance evaluation test of the sample of example 26. As shown in fig. 5, it is found that almost no pores are observed in the sample of example 26, and sufficient foaming is not generated.
(thermal cracking evaluation test)
Next, using each sample, a thermal cracking evaluation test was performed by the following method.
First, a metal mold having a ring shape is prepared.
Fig. 6 schematically shows the shape of the metal mold. As shown in fig. 6, the metal mold 360 has a circular upper surface 362 and a circular lower surface 364 facing each other, and further has a hole portion 366 axially penetrating the center of the metal mold 360 from the upper surface 362 to the lower surface 364. The hole portion 366 has a cylindrical shape. The upper surface 362 and the lower surface 364 of the metal mold 360 have an outer diameter of 130mm phi and an inner diameter of 100mm phi. Further, the height H of the metal mold 360 was 10 mm.
The thermal cracking evaluation test was performed by providing the metal mold 360 on an iron plate. Specifically, the sample is filled into the hole portion 366 of the metal mold 360 in a state where the metal mold 360 is heated to 200 ℃. Then, the sample is held at 200 ℃ for 1 hour in this state, thereby forming a seal structure at the hole portion 366 of the metal mold 360. Then, the presence or absence of cracks was evaluated for the sealed structure obtained by naturally cooling the metal mold 360 to room temperature.
The column entitled "thermal cracking" in table 3 above summarizes the evaluation results obtained for the seal structures formed from the samples of examples 1 to 15. The column entitled "thermal cracking" in table 4 above summarizes the evaluation results obtained for the seal structures formed from the samples of examples 21 to 32.
As is clear from table 4, thermal cracks occurred in the seal structures formed by the samples of examples 21 to 26 and 29 to 30.
In the samples of examples 21 to 22, the ratio of the fine particles in the second component was less than 8%, and therefore, the control of foaming was insufficient, and there was a possibility that extremely large pores such as through holes were generated. In fact, in the samples of examples 21 to 22, the average pore diameter was 5000 μm or more. Therefore, it is considered that in the samples of examples 21 to 22, the large pores larger than the predetermined range are generated, and as a result, the strength is lowered.
In the samples of examples 23 to 25, the proportion of the fine particles in the second component was more than 45%, and it is considered that in these cases, the seal structure could not obtain sufficient strength.
On the other hand, no thermal cracking occurred in the seal structures formed from the samples of examples 1 to 15.
Thereby confirming that: a seal structure having good sealing performance and good strength was formed by using the samples of examples 1 to 15.

Claims (8)

1. A sealing material for a sealing portion that blocks an internal space of a high-temperature device from the outside, wherein,
the sealing material has a first component and a second component,
the first component is at least one metal salt selected from the group consisting of alkali metal silicates, alkaline earth metal silicates, alkali metal orthophosphates and alkaline earth metal orthophosphates,
the second component contains oxide particles having a fine particle having an average particle diameter of 10 [ mu ] m or less and a coarse particle having an average particle diameter of 200 [ mu ] m to 1000 [ mu ] m, and the content of the fine particle is in the range of 8% by mass to 45% by mass relative to the total mass of the coarse particle and the fine particle,
a silicic acid component (SiO) of the metal salt contained in the first component2) With phosphoric acid component (P)2O5) Of (2)The ratio of the alkali metal component to the total oxide basis of the alkaline earth metal component in the first component is 1.5 to 3.5 in terms of molar ratio, and
the mass ratio of the first component to the second component is in the range of 0.35 to 0.9.
2. The sealing material according to claim 1, wherein the second component contains at least one selected from the group consisting of silica, alumina, magnesia, calcia and zirconia.
3. The sealing material according to claim 1 or 2, wherein the first component is an alkali metal silicate and comprises sodium and/or potassium.
4. The sealing material according to any one of claims 1 to 3, wherein a silicic acid component (SiO) of the metal salt contained in the first component2) With phosphoric acid component (P)2O5) Is 1.8 to 3.3 in terms of a molar ratio relative to the total of the alkali metal component and the alkaline earth metal component contained in the first component, based on an oxide.
5. A sealing material for a sealing portion that blocks an internal space of a high-temperature device from the outside, wherein,
when the sealing material is provided at the sealing portion at 350 ℃, the sealing material foams to become a sealed structure,
the seal structure has a skeleton portion formed of film-like partition walls and a plurality of pores,
the skeleton portion contains silicate glass and/or phosphate glass, and
the pores have an average diameter of 30 to 5000 [ mu ] m.
6. A sealing structure provided in a sealing portion that blocks an internal space of a high-temperature apparatus from the outside, wherein,
the seal structure has a skeleton portion formed of film-like partition walls and a plurality of pores,
the skeleton portion contains silicate glass and/or phosphate glass, and
the pores have an average diameter of 30 to 5000 [ mu ] m.
7. The seal structure according to claim 6, wherein the silicate glass contained in the skeleton portion contains an alkali metal silicate and/or an alkaline earth metal silicate.
8. The seal structure according to claim 6 or 7, wherein the phosphate glass contained in the skeleton portion contains an alkali metal phosphate and/or an alkaline earth metal phosphate.
CN202010893730.4A 2019-09-05 2020-08-31 Sealing material and sealed structure Pending CN112442335A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5795104A (en) * 1995-08-30 1998-08-18 Schanze Rudolf Waterglass-based material for sealing purposes and processes for hardening waterglass materials
JPH1135924A (en) * 1997-07-18 1999-02-09 Nitto Denko Corp Cutoff sealing material
JP2012036283A (en) * 2010-08-05 2012-02-23 Toshiba Corp Ceramic seal material and method of using the same

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Publication number Priority date Publication date Assignee Title
JP6049213B2 (en) 2014-06-19 2016-12-21 品川リフラクトリーズ株式会社 Coke oven joint repair material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5795104A (en) * 1995-08-30 1998-08-18 Schanze Rudolf Waterglass-based material for sealing purposes and processes for hardening waterglass materials
JPH1135924A (en) * 1997-07-18 1999-02-09 Nitto Denko Corp Cutoff sealing material
JP2012036283A (en) * 2010-08-05 2012-02-23 Toshiba Corp Ceramic seal material and method of using the same

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