CN112442335B - Sealing material and sealing structure - Google Patents
Sealing material and sealing structure Download PDFInfo
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- CN112442335B CN112442335B CN202010893730.4A CN202010893730A CN112442335B CN 112442335 B CN112442335 B CN 112442335B CN 202010893730 A CN202010893730 A CN 202010893730A CN 112442335 B CN112442335 B CN 112442335B
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- 238000007789 sealing Methods 0.000 title claims abstract description 137
- 239000003566 sealing material Substances 0.000 title claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000011362 coarse particle Substances 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005192 partition Methods 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000005368 silicate glass Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- -1 alkali metal orthophosphate Chemical class 0.000 abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 6
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 description 36
- 238000011156 evaluation Methods 0.000 description 17
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000005365 phosphate glass Substances 0.000 description 5
- 238000004227 thermal cracking Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910004742 Na2 O Inorganic materials 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Abstract
The present invention relates to a sealing material and a sealing structure. A sealing material which exhibits excellent sealing properties when used for repairing a high-temperature device. 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 silicate, alkaline earth metal silicate, alkali metal orthophosphate and alkaline earth metal orthophosphate, the second component contains oxide particles, the particles 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, the fine particles content is in the range of 8 to 45 mass% relative to 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 salt contained in the first component to the total of the alkali metal component and the oxide of the alkaline earth metal component contained in the first component is in the range of 0.35 to 0.9 in terms of molar ratio.
Description
Technical Field
The present invention relates to a sealing material and a sealing structure.
Background
High temperature devices such as high temperature atmosphere furnaces having an internal space capable of atmosphere control are widely used in various fields.
In such a high-temperature apparatus, there is a case where the sealability of a sealing portion that seals the internal space from the outside is lowered during use of the high-temperature apparatus. In addition, in this case, it may often be necessary to repair the sealing 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 device, various sealing materials and sealing methods have been proposed so far (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-3313
Disclosure of Invention
Problems to be solved by the invention
In the in-situ repair of a high-temperature apparatus, it is required to provide a sealing material at a sealing portion in a high-temperature state, thereby sealing an internal space from the outside appropriately.
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 sealability at room temperature, it is often confirmed that the sealing material is degraded 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 adapted 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 that 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 sealing structure made of such a sealing material.
Means for solving the problems
The present invention provides a sealing material for sealing an internal space of a high-temperature device from the outside, wherein the sealing material comprises a first component and a second component, the first component is at least one metal salt selected from the group consisting of alkali metal silicate, alkaline earth metal silicate, alkali metal orthophosphate and alkaline earth metal orthophosphate, the second component comprises oxide-containing particles, the particles comprise 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, the content of the fine particles is in the range of 8 mass% to 45 mass% relative to the total mass of the coarse particles, the ratio of the total of the metal salt (SiO 2) and phosphoric acid component (P 2O5) contained in the first component relative to the total of the alkali metal component and alkaline earth metal component oxide reference contained in the first component is in the range of 1.5 to 3.5, and the mass ratio of the first component relative to the second component is in the range of 0.35 to 0.9.
In addition, the present invention provides a sealing material for sealing an internal space of a high-temperature device from the outside, wherein when the sealing material is provided in the sealing portion at 350 ℃, the sealing material is foamed to form a sealing structure, the sealing structure has a skeleton portion composed of film-shaped 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.
Further, the present invention provides a sealing structure provided in a sealing portion that blocks an internal space of a high-temperature apparatus from the outside, wherein the sealing structure has a skeleton portion made up 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 [ mu ] m to 5000 [ mu ] m.
Effects of the invention
The present invention can provide a sealing material that exhibits excellent sealing properties when applied to in-situ repair of high-temperature devices. In addition, the present invention can provide a sealing structure made of such a sealing material.
Drawings
Fig. 1 is a cross-sectional view schematically showing a sealing structure according to an embodiment of the present invention formed at a sealing portion of a high temperature apparatus.
Fig. 2 is an optical micrograph showing an example of a cross section of a sealing structure according to an embodiment of the present invention.
Fig. 3 is a diagram schematically showing the configuration of a test apparatus used in the seal performance evaluation test.
Fig. 4 is a graph showing the results of the seal performance evaluation test obtained in several samples.
Fig. 5 is an optical micrograph showing an example of a cross section of the sealing structure according to the 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 numerals
10. High temperature device
15. Gap of
20. Sealing part
30. First wall member
31. Second wall member
40. Interior space
42. Sealing member
100. Sealing structure
110. Skeleton part
120. Air holes
210. Test device
220. Metal container
226. Protruding part
230. Electric stove
240. Buffer tank
250. Sealing material (sealing structure)
360. Metal mould
362. Upper surface of
364. Lower surface of
366. Hole part
Detailed Description
An embodiment of the present invention will be described below.
In the present application, the "sealing material" refers to a material applied to a sealing portion of a high-temperature apparatus in order to seal an internal space of the high-temperature apparatus from the outside. In the present application, the "sealing structure" means a member formed in a high-temperature sealing portion of a high-temperature apparatus by disposing a "sealing material" in the sealing portion.
Therefore, when the "sealing material" is provided in the sealing portion in the high-temperature state of the high-temperature apparatus, the "sealing 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 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 silicate, alkaline earth metal silicate, alkali metal orthophosphate and alkaline earth metal orthophosphate,
The second component contains oxide-containing particles 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, the content of the fine particles is in the range of 8 to 45 mass% relative to the total mass of the coarse particles and the fine particles, the ratio of the total of the silicic acid component (SiO 2) and the phosphoric acid component (P 2O5) of the metal salt contained in the first component relative to the total of the alkali metal component and the oxide of the alkaline earth metal component contained in the first component is in the range of 1.5 to 3.5 in terms of a molar ratio, and the mass ratio of the first component relative to the second component is in the range of 0.35 to 0.9.
As described above, in the in-situ repair of a high-temperature apparatus, it is required to provide a sealing material in a sealing portion at a high temperature such as 200 to 600 ℃.
However, when a conventional sealing material is used, the following problems often occur: even if good sealability is exhibited at room temperature, very good sealability cannot be obtained in a high temperature region of 200 ℃ or higher. One of the reasons for this is considered to be that when the conventional sealing material is provided in a high-temperature sealing portion, the components contained in the sealing material shrink, and cracks are generated in the sealing structure.
In contrast, the sealing material according to one embodiment of the present invention has a first component that is at least one metal salt selected from the group consisting of alkali metal silicate, alkaline earth metal silicate, alkali metal orthophosphate, and alkaline earth metal orthophosphate. The first component can be foamed and bubbles can be generated at a high temperature in the range of 200 to 600 ℃.
Therefore, when the sealing material according to one embodiment of the present invention is applied to a sealing portion at a high temperature, shrinkage of the sealing material can be significantly suppressed by expansion caused by generation of bubbles. In addition, as a result, when the sealing material according to one embodiment of the present invention is applied to a sealing portion at a high temperature, cracks generated 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 bubbles, the size of bubbles, and the like. For example, when only the first component is added to the sealing material and the sealing material is applied, there is a possibility that unevenness occurs in the foaming region or extremely large bubbles are generated. The presence of such uneven foaming and large bubbles may cause through holes, which may become a factor that reduces the sealability and strength of the formed sealing structure.
Thus, the sealing material according to one embodiment of the present invention also has a second component. When a sealing structure is formed from the sealing material according to one embodiment of the present invention, the second component constitutes a majority of the skeleton portion in the sealing structure. In addition, the second component contains particles of an oxide having 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 μm to 1000 μm.
In the particles of the oxide, the fine particles function as base points at the time of foaming of the first component. 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 mass ratio of the fine particles to 8% or more with respect to the total of coarse particles and 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 a base point.
In addition, when the proportion of fine particles in the second component contained in the sealing material is too high, the strength of the resulting sealing structure may be lowered. In this case, cracks may be easily generated at the time of formation of the sealing structure or during use of the sealing structure after formation.
Therefore, in the sealing material according to an 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 strength of the sealing structure can be significantly suppressed.
By the above-described effects, when the sealing material according to one embodiment of the present invention is applied to the sealing portion of the high-temperature device, a sealing structure having better sealing performance than before can be formed.
(Sealing Structure according to one embodiment of the present invention)
Hereinafter, a sealing 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 cross-sectional view schematically showing a sealing structure according to an embodiment of the present invention formed at a sealing 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 apparatus 10 has a first wall member 30 and a second wall member 31, and an internal space 40 is formed inside the high temperature apparatus 10 by the first and second wall members 30, 31, and the like. However, a gap 15 exists between the first wall member 30 and the second wall member 31, and in order to seal the gap 15, a sealing member 42 is filled in the gap 15. Thus, the sealing portion 20 is formed to block 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 sealing structure 100 is provided for such in-situ repair. That is, by constructing the sealing structure 100 in the sealing portion 20, the sealing performance of the high-temperature apparatus 10 can be maintained.
The temperature of the sealing portion 20 to which the sealing structure 100 is applied varies according to the high temperature apparatus 10. In one example, the temperature of the sealing portion 20 to which the sealing structure 100 is applied is in the range of 200 to 600 ℃, preferably 300 to 500 ℃.
Fig. 2 shows an example of a cross-sectional photograph of the sealing structure 100 taken by an optical microscope.
As shown in fig. 2, the sealing structure 100 has a characteristic form. Specifically, the sealing structure 100 includes a skeleton portion 110 formed of film-like partition walls extending three-dimensionally in the longitudinal and transverse directions, and a plurality of air holes (closed holes) 120 separated by the partition walls.
Most of the air holes 120 are formed between the partition walls, but some of the air holes 120 are formed inside the partition walls.
In the sealing structure 100, the skeleton portion 110 includes at least one of silicate glass and phosphate glass. Silicate glass and phosphate glass may each comprise alkali metal salts and/or alkaline earth metal salts. In addition, the alkali metal salt may be Na 2 O and/or K 2 O. Furthermore, the alkaline earth metal salt may be MgO and/or CaO.
In the skeleton portion 110, the ratio of the total B of silicic acid (SiO 2) and phosphoric acid (P 2O5) to the total a of the alkali metal component and the alkaline earth metal component based on the oxide basis (i.e., the ratio B/a) is in the range of 1.5 to 3.5 in terms of a molar ratio. When the ratio B/A is less than 1.5, the viscosity of the sealing material becomes low and the foaming becomes unstable. If the ratio B/a is more than 3.5, the viscosity of the sealing material becomes high, and mixing with other members becomes difficult to perform the sealing portion. The ratio B/A is preferably in the range of 1.8 to 3.3 in terms of molar ratio.
The pores 120 have an average diameter of 30 μm to 5000 μm. 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) (corporation Mountech) can be used. The average diameter of the pores 120 is preferably in the range of 60 μm to 3000 μm.
The sealing structure 100 has excellent strength. Therefore, the occurrence of cracks in the sealing structure 100 can be significantly suppressed at the time of formation and during use of the sealing structure 100.
Therefore, the sealing portion 20 of the high temperature apparatus 10 can obtain good sealing properties for a long period of time.
The first wall member 30 and the second wall member 31 forming the sealing portion 20 in which the sealing structure 100 is provided may be made of any material having heat resistance, such as metal (for example, heat-resistant metal) and ceramic (for example, fire-resistant brick).
(Sealing Material according to one embodiment of the present invention)
Next, a sealing material according to an embodiment of the present invention for forming the sealing structure of the first sealing structure 100 described above will be described.
The sealing material according to an embodiment of the present invention (hereinafter, referred to as "first sealing material") has a first component and a second component.
The components are described in detail below.
(First component)
The first component is, for example, a substance which foams at a high temperature in the range of 200 to 600 ℃ to generate bubbles.
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 are not limited thereto. The first component may be used by mixing two or more of these metal salts.
Among these metal salts, the alkali metal may contain sodium and/or potassium, for example. In addition, the alkaline earth metal may comprise magnesium and/or calcium, for example.
The ratio of the total D of the silicic acid component (SiO 2) and the phosphoric acid component (P 2O5) contained in the first component to the total C of the alkali metal component and the alkaline earth metal component on the basis of the oxides is 1.5 to 3.5 in terms of a molar ratio. If the ratio D/C is less than 1.5, sufficient foaming may not be obtained. In addition, if the ratio D/C is more than 3.5, there is a possibility that uniform foaming cannot 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 shown below is in the range of 0.35 to 0.9 in terms of mass ratio. If the ratio V is less than 0.35, sufficient foaming may not be obtained. In addition, 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 a majority of the skeleton portion 110 in the first seal structure 100 formed of the first seal material. Here, the skeleton portion 110 in the sealing structure 100 is composed of a first component and a second component after foaming.
As described above, the first sealing structure 100 has the form of the partition wall made of the thin film. Accordingly, in the first sealing structure 100, the "skeleton portion 110" refers to a film-like partition wall portion.
The second component comprises particles comprising an oxide. Examples of the oxide include: silica, alumina, magnesia, calcia or zirconia, or a combination of at least two thereof, and the like, but are not limited to these.
In order to secure the strength of the skeleton portion, the second component preferably contains particles of 96 mass% or more of oxide, and more preferably contains particles of 98 mass% or more of oxide.
The particles of the oxide contained in the second component have fine particles having an average particle diameter of 10 μm or less and coarse particles having an average particle diameter of 200 μm to 1000 μm. In the present application, the average particle diameter is measured by a laser diffraction method.
The fine particles are added so that the mass ratio relative 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 mass%, it is difficult to sufficiently control the morphology 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 associated with the generation of through holes, which is one cause of reduced sealing performance, but may also become a factor of reduced strength. On the other hand, when the proportion of the fine particles is more than 45 mass%, there is a possibility that the strength of the obtained first sealing structure 100 may be lowered. The proportion of the fine particles is preferably in the range of 9 to 43 mass%.
(Others)
The first sealing material may further comprise water. By adding an appropriate amount of water, the fluidity of the first sealing material can be appropriately adjusted.
The amount of water to be added is not particularly limited, but is preferably in the range of 40% to 60% by weight based on the total weight of the sealing material.
(Application example of 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 ℃, bubbles are generated by the first component contained in the first sealing material. Therefore, when the first sealing material is applied to the high-temperature sealing portion 20, shrinkage (for example, shrinkage due to drying) of the first sealing material can be significantly suppressed by expansion caused by generation of bubbles. In addition, the occurrence of shrinkage cracks can thereby be significantly suppressed.
In addition, in the first sealing material, bubbles are generated particularly with fine particles contained in the second component as a base point, but the amount of fine particles contained in the second component has been adjusted to an appropriate range. Therefore, the first sealing material can be foamed in a controlled state, and as a result, a plurality of fine bubbles can be formed in a uniform manner. Therefore, the occurrence of the through hole adversely affecting the sealability can be significantly suppressed.
In the first sealing material, the first component after foaming and the second component together form the skeleton portion 110 of the sealing structure 100. That is, the sealing structure 100 formed after foaming the first sealing material 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 sealing structure 100 having significant strength can be formed.
When the sealing material is provided in the sealing portion 20 at 350 ℃, the sealing structure 100 is formed by foaming. In the sealing structure 100, the skeleton portion 110 includes silicate glass and/or phosphate glass, and the pores 120 have an average diameter of 30 μm to 5000 μm. The average diameter of the pores 120 is preferably in the range of 60 μm to 3000 μm.
By the above-described effects, when the sealing material according to one embodiment of the present invention is applied to the sealing portion 20 of the high-temperature apparatus 10, the sealing structure 100 having better sealing performance than before can be formed.
The method of disposing the first sealing material in the sealing portion 20 of the high temperature device 10 is not particularly limited. For example, a spatula, a scraper is used to fill the sealing portion 20 of the high temperature device 10 with the first sealing material. In the case where the sealing portion 20 is at a high temperature, for safety, a method such as a mortar injector or a spraying method may be employed in which the first sealing material can be provided from a relatively remote position.
The sealing material and the sealing structure according to the embodiment of the present invention are described above. These sealing materials and sealing structures can be applied to any high-temperature apparatus 10 that requires sealing at high temperatures.
The high temperature apparatus 10 is not limited to various kilns such as a coke oven including coal, a blast furnace including iron ore, a glass melting furnace, and a glass forming furnace.
Examples (example)
Next, an embodiment of the present invention will be described. 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 in the following manner.
As the first component, sodium silicate was used. Sodium silicate 1,2, 3, 4 and 5 (all manufactured by Fuji chemical Co., ltd.) were mixed in a predetermined amount so that the molar ratio of SiO 2/Na2 O, which is the ratio D/C, was 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 μm to 1000 μm is used. The proportion of the fine particles with respect to the whole of the 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 obtained 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, at least one of the molar ratio D/C of SiO 2/Na2 O in the first component, the ratio 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 this example 12, potassium silicate (potassium silicate No. 2 manufactured by Fuji chemical Co., ltd.) was used as the first component. In the first component, the molar ratio D/C, that is, siO 2/K2 O was 3. In example 12, the mass ratio V was set to 0.4.
Other conditions were the same as in example 1.
The obtained 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 this example 13, as the second component, mixed particles of silica and alumina were used instead of silica particles. Other conditions were the same as in example 1.
The obtained 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 this example 14, as the second component, mixed particles of silica and magnesia were used instead of silica particles. Other conditions were the same as in example 1.
The obtained 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 this example 15, glass particles were used as the second component instead of silica particles. As the glass particles, particles obtained by pulverizing fragments of soda lime glass composition are used. Other conditions were the same as in example 1.
The obtained sealing material was referred to as "sample of example 15".
The preparation conditions of the samples of examples 1 to 15 are summarized in table 1 below.
TABLE 1
(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 this 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 obtained 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 this example 31, as the first component, silica sol (Cataloid S-50L: manufactured by Nissan catalyst Co., ltd.) was used. 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 contains almost no alkali component, the above ratio D/C was not calculated.
The obtained 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 CASTER CA-13T: manufactured by AGC ceramics Co., ltd.) 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 the cement contains almost no alkali component, the ratio D/C was not calculated.
The obtained 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
(Evaluation)
(Test for evaluating sealing Properties)
Sealing performance evaluation tests were performed using each sample.
Fig. 3 schematically shows a test apparatus used in the evaluation. As shown in fig. 3, the test device 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 face of the metal container 220 is an opening having a rectangular shape of 150mm×20 mm. The volume of the inside of the metal container 220 is about 10L.
The metal container 220 is disposed in the electric furnace 230 such that the opening portion protrudes outward from the electric furnace 230. The length of the protruding portion 226 protruding from the electric furnace 230 is about 10mm. A further opening is provided in a part of the metal container 220, and the opening is connected to the buffer tank 240 for air.
At the time of the test, the electric furnace was warmed up to about 550 ℃. Thereby heating the protruding portion 226 of the metal container 220 to about 350 deg.c.
Next, any one of the above samples is filled into the metal container 220 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 be 20mm from the front end of the protrusion 226.
After 10 minutes from the filling of the sealing material 250, the buffer tank 240 was opened, and air was supplied to the inside of the metal container 220. At the moment when the pressure reaches 10000Pa, the buffer tank 240 is closed. The time at which the pressure in the metal container 220 was 10000Pa, which is the state, was set to 0 seconds, and the change in the internal pressure of the metal container 220 was measured. Further, the time until the internal pressure was reduced to 10Pa was measured.
The results obtained in the samples of examples 1 to 15 are summarized in the column "sealing performance" in table 3 below. Similarly, the results obtained in the samples of examples 21 to 32 are summarized in the column "sealing performance" in table 4 below.
TABLE 3 Table 3
TABLE 4 Table 4
In the column of "sealing performance" in table 4, "×" indicates that the time until the internal pressure was reduced to 10Pa was 5 seconds or less.
As is clear from table 4, in the samples of examples 21 to 32, the internal pressure was reduced to 10Pa or less within 5 seconds from the start of measurement. On the other hand, as shown in table 3, in the samples of examples 1 to 15, at least 60 seconds were required until the internal pressure became 10Pa or less.
Fig. 4 shows a time-dependent curve of the internal pressure obtained in the samples of examples 1, 4 and 23 as an example.
In fig. 4, the horizontal axis represents elapsed time (unit: seconds), and the vertical axis represents internal pressure.
From this graph, it is understood that the internal pressure rapidly decreases with the lapse of time and reaches 10Pa or less within a few seconds in the sample of example 23. From this result, it can be said that the sample of example 23 was not very good in sealability.
In contrast, the time required for the internal pressure of the samples of examples 1 and 4 to decrease to 10Pa or less was significantly prolonged as compared with the sample of example 23. In particular, the internal pressure of the sample of example 1 was 10Pa or lower, and a time of 1550 seconds was required.
From this, it was found that the samples of examples 1 to 15 had better high temperature sealability than the samples of examples 21 to 32.
(Tissue observation)
Each of the samples obtained after the above-mentioned sealing performance evaluation test was observed by SEM, and the foaming condition was evaluated.
The foaming conditions were 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 medium level of foaming was observed as a whole was evaluated as "Δ", and the case where only foaming was observed locally and the case where foaming was not generated were evaluated as "x".
In addition, in the sample in which foaming occurred, the average pore diameter was determined by image analysis. Specifically, in a cross-sectional photograph of a sample, a dark portion surrounded by a white-appearing skeleton portion is 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) (Inc. Mountech) was used for image analysis.
The results of evaluation of the foaming conditions obtained in the samples of examples 1 to 15 are summarized in the column "foaming conditions" in table 3. The values of the average pore diameters obtained in the sealed structures formed from the samples of examples 1 to 15 are shown in the column "average pore diameter".
Similarly, the results of evaluation of the foaming conditions obtained in the samples of examples 21 to 32 are summarized in the column "foaming conditions" in table 4. The values of the average pore diameters obtained in the sealed structures formed from the samples of examples 21 to 32 are shown in the column "average pore diameter".
From these results, it was found that little foaming occurred in the samples of examples 26 to 32. It is considered that, since the above ratio V of the samples of examples 26 to 28 is smaller than 0.35, the amount of the first component functioning as a foam is insufficient, and sufficient foaming is not generated. Further, since the above ratio V of the sample of example 29 was more than 0.9, the bubbles were excessively coarse, and proper foaming was not generated. Further, it is considered that the above ratio D/C of the sample of example 30 is more than 3.3 in terms of molar ratio, and therefore foaming is locally generated, but uniform foaming is not generated as a whole.
The samples of examples 31 to 32 did not contain the first component, and thus did not foam.
In contrast, the samples of examples 1 to 15 were all in a good foaming state. The results are consistent with those of the above-mentioned sealing performance evaluation test.
Fig. 2 shows an example of an optical microscopic photograph of a cross section of the sealing structure obtained after the sealing performance evaluation test of the sample of example 3. As shown in fig. 2, the sealing structure is composed of a plurality of film-like partition walls and air holes surrounded by the partition walls.
On the other hand, fig. 5 shows an example of an optical microscopic photograph of a cross section of the sealing structure obtained after the sealing performance evaluation test of the sample of example 26. As shown in fig. 5, in the sample of example 26, almost no pores were observed, and sufficient foaming was 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 a metal mold. As shown in fig. 6, the metal mold 360 has a circular upper surface 362 and a circular lower surface 364 opposite to each other, and a hole portion 366 penetrating the center of the metal mold 360 in the axial direction 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. The height H of the die 360 was 10mm.
The thermal crack evaluation test was performed by providing the metal mold 360 on an iron plate. Specifically, the sample is filled into the hole 366 of the die 360 in a state where the die 360 is heated to 200 ℃. Then, the sample was held at 200 ℃ for 1 hour in this state, thereby forming a sealing structure at the hole 366 of the metal mold 360. Then, the presence or absence of cracks was evaluated on the sealed structure obtained by naturally cooling the mold 360 to room temperature.
The evaluation results obtained in the sealed structures formed from the samples of examples 1 to 15 are summarized in the column "thermal cracking" of table 3. The evaluation results obtained in the sealed structures formed from the samples of examples 21 to 32 are shown in the column "thermal cracking" in table 4.
As is clear from table 4, thermal cracks were generated in the sealing structures formed by the samples of examples 21 to 26 and examples 29 to 30.
In the samples of examples 21 to 22, the proportion of fine particles in the second component was less than 8%, and thus foaming was not sufficiently controlled, and extremely large pores such as through holes were likely to be 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 atmospheric pores larger than the predetermined range were generated, and as a result, the strength was lowered.
In the samples of examples 23 to 25, since the proportion of the fine particles in the second component is more than 45%, it is considered that the seal structure cannot obtain sufficient strength in these cases.
On the other hand, thermal cracks were not generated in the sealing structures formed from the samples of examples 1 to 15.
Thereby confirming: by using the samples of examples 1 to 15, a sealing structure having good sealing performance and good strength was formed.
Claims (5)
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,
The second component contains particles of an oxide, the second component contains at least one selected from the group consisting of silica, alumina and magnesia, the particles have fine particles having an average particle diameter of 10 μm or less and coarse particles having an average particle diameter of 200 μm to 1000 μm, and the content of the fine particles is in the range of 10 mass% to 40 mass% relative to the total mass of the coarse particles and the fine particles,
The ratio of the content of SiO 2 which is the silicic acid component of the metal salt contained in the first component to the content of the oxide basis of the alkali metal component contained in the first component is 2.2 to 3.2 in terms of a molar ratio, and
The mass ratio of the first component to the second component is in the range of 0.4 to 0.8.
2. The sealing material of claim 1, wherein the first component comprises sodium and/or potassium.
3. The use of the sealing material according to claim 1 for forming a sealing structure for sealing off an inner 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 is foamed to become a sealing structure,
The sealing structure has a skeleton portion formed by film-like partition walls and a plurality of air holes,
The skeleton portion comprises silicate glass, and
The pores have an average diameter of 30 μm to 5000 μm.
4. A sealing structure provided in a sealing portion that blocks an internal space of a high-temperature apparatus from the outside, the sealing structure being formed by using the sealing material according to claim 1, wherein,
The sealing structure has a skeleton portion formed by film-like partition walls and a plurality of air holes,
The skeleton portion comprises silicate glass, and
The pores have an average diameter of 30 μm to 5000 μm.
5. The sealing structure according to claim 4, wherein the silicate glass contained in the skeleton portion contains alkali silicate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-162289 | 2019-09-05 | ||
| JP2019162289A JP2021038839A (en) | 2019-09-05 | 2019-09-05 | Seal material and seal structure |
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| CN112442335A CN112442335A (en) | 2021-03-05 |
| CN112442335B true CN112442335B (en) | 2024-06-21 |
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Citations (1)
| 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 |
Patent Citations (1)
| 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 |
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