WO2004101466A1 - ジルコニア質不定形耐火物 - Google Patents
ジルコニア質不定形耐火物 Download PDFInfo
- Publication number
- WO2004101466A1 WO2004101466A1 PCT/JP2004/006802 JP2004006802W WO2004101466A1 WO 2004101466 A1 WO2004101466 A1 WO 2004101466A1 JP 2004006802 W JP2004006802 W JP 2004006802W WO 2004101466 A1 WO2004101466 A1 WO 2004101466A1
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- WIPO (PCT)
- Prior art keywords
- particles
- glass
- refractory
- jirukonia
- zirconia
- Prior art date
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011823 monolithic refractory Substances 0.000 title claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 124
- 239000011521 glass Substances 0.000 claims abstract description 62
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 19
- 239000006060 molten glass Substances 0.000 abstract description 14
- 238000010186 staining Methods 0.000 abstract description 3
- 239000011819 refractory material Substances 0.000 description 18
- 238000010276 construction Methods 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000011396 hydraulic cement Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000002694 phosphate binding agent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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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
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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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
- C04B2235/50—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
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/61—Mechanical properties, e.g. fracture toughness, hardness, Young's modulus or strength
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
Definitions
- the present invention relates to an amorphous zirconia refractory, particularly to an amorphous zirconia refractory suitable for forming a hearth structure of a glass tank kiln.
- electrofused refractory materials such as zirconia are used as refractories in the area of direct contact with molten glass because of their corrosion resistance and non-contamination of the glass substrate.
- These electric refractories are large in size in order to minimize the contact between refractories (hereinafter referred to as joints).
- Refractories serving bases
- Refractories for supporting the electric refractories composing such joints and hearths (babes) are usually ramming materials, stamping materials, and tamping materials (hereinafter, referred to as these materials).
- pump material Cold material
- a 1 2 0 3 - Z R_ ⁇ 2 - S i O 2 (hereinafter, simply referred to as AZS) based molten ⁇ refractory particles 5 5-9 8 wt% alumina
- AZS a 1 2 0 3 - Z R_ ⁇ 2 - S i O 2
- An irregular-shaped refractory containing 1 to 5% by mass of hydraulic cement such as cement is proposed in Japanese Patent Publication No. 58-46475. Because the proposed method contains hydraulic cement, the unevenness of the construction surface becomes large when used as a sub-bead when it is used as a sub-bead. It must be used to smooth out surface irregularities.
- a mortar there is an alumina-zirconia mortar, but generally has poor corrosion resistance, permeation resistance and non-contamination of a glass base material, and thus may have a bad influence on the corrosion resistance of an electric refractory.
- the amorphous refractory in contact with the refractory be made of the same material, zirconia, because it is possible to avoid problems due to differences in the coefficient of thermal expansion, etc.
- AZS amorphous refractories proposed in 4 6 4 7 2 is not always satisfactory in that respect either.
- zirconia-based refractories are superior to AZS-based refractories in terms of corrosion resistance and penetration resistance to molten glass. It is rare.
- Japanese Unexamined Patent Publication (Kokai) No. 63-103869 proposes a refractory containing zirconium particles and alumina cement particles as a zirconium amorphous refractory for various kilns and molten metal contact members.
- alumina cement particles has the above-mentioned problems.
- incineration ash melting treatment, and incinerators 4.5 to 49.5% by mass of molten zirconium particles and 45 to 94% by mass of alumina particles %
- alumina cement particles of 0.3 to 10% by mass have been proposed in Japanese Patent Application Laid-Open No.
- molten zirconia particles is less than 50% by mass, so that the properties are not necessarily sufficient for glass tank kilns.
- Japanese Patent Application Laid-Open No. 7-293851 discloses , Zirconia for waste melting furnaces It is stated that those using fused zirconium particles as refractories can be used as amorphous refractories other than fired refractories, but there is no specific proposal for amorphous refractories. .
- An object of the present invention is to provide a zirconia amorphous refractory which has excellent corrosion resistance and penetration resistance to molten glass, is suitable as an amorphous refractory for a glass hearth, and has excellent workability.
- the present invention includes a Jirukonia particles (Z R_ ⁇ 2 equivalent) 7 0-9 5 wt%, and 2 to 1 2% by weight particulate alumina child, a coupling member 1 to 1 0 weight%, the glass content (in Jirukonia particles (If a glass phase is included, the glass phase is included in the glass phase.)
- the amorphous refractory containing 2 to 8% by mass, and the amorphous refractory contains substantially no alumina cement.
- Jirukonia quality monolithic refractory of the present invention (hereinafter, referred to as the irregular shaped refractory) is Jill Konia particles (Z r0 2 equivalent) 70 to 95 wt% (hereinafter abbreviated simply%), alumina particles 2
- An amorphous refractory comprising 12%, a binder 1 to 10%, and a glass component (if the glass phase is contained in the zirconia particles, the glass phase is included therein) 2 to 8%.
- Amorphous refractories are characterized by being substantially free of alumina cement.
- Z r 0 2 crystal phase as the Jirukonia particles containing at least monoclinic (hereinafter, simply referred to as Z R_ ⁇ 2 crystal phase) is not particularly limited as long as it contains.
- Z R_ ⁇ 2 crystal phase is substantially monoclinic, stable at room temperature, when the heat up for use, preferred because there is no volume change at low temperatures.
- zirconia particles examples include fused zirconia containing a glass phase and zirconia particles obtained by desiliconizing zircon.
- zirconia particles other than fused zirconia particles are collectively referred to as non-fused zirconia particles.
- a melt Jirukonia particles as Jirukonia particles content in the castable refractory is a minus glass phase since converting Z R_ ⁇ 2.
- molten zirconia particles as the zirconium particles, since the uneven distribution of glass content is small and the homogeneity is improved.
- Melting Jirukonia, as the particles more preferably with those containing a Z R_ ⁇ 2 forming phase 85 to 97% and glass phase 3% to 15%.
- Z R_ ⁇ 2 a Z R_ ⁇ 2 forming phase 85 to 97% and glass phase 3% to 15%.
- During melting Jirukonia particles against the molten glass Z r 0 2 crystal phase is less than 85% That corrosion resistance may become insufficient in terms of resistance to penetration, whereas Z r0 2
- the amount of the crystalline phase exceeds 9 7% glass phase becomes too small monoclinic, body product by transition square interdendritic The change may not be absorbed sufficiently.
- the constituent component of the glass phase of the molten zirconia particles be AZS-based, because improvement in corrosion resistance can be expected.
- the present amorphous refractory if a large amount of iron enters the zirconia particles for some reason such as a process of adjusting the particle size, the non-contamination property and permeation resistance of the glass material of the amorphous refractory may be reduced.
- the content of iron in Jirukonia particles is 0.15% or less by F e 2 ⁇ 3 terms, preferred in terms of corrosion resistance and the glass base material non-contaminating to glass.
- iron in Jirukonia particles is 10% or less 0.1 at F e 2 ⁇ 3 basis, and particularly preferably 0.08% or less.
- iron in the zirconia particles includes not only the case where iron is contained as a component of the zirconia particles, but also the case where iron particles are fixed to the surface of the zirconia particles.
- the content of iron is 0.15% or less Fe 2 0 3 in terms, preferred in terms of corrosion resistance and the glass base material non-contaminating to glass. More preferably the iron content is at most 10% 0.1 in F e 2 0 3 in terms of, and particularly preferably 0.08% or less.
- the particle diameter (hereinafter simply referred to as particle diameter) of the zirconium particles is not particularly limited as long as the particle diameter is 5 mm or less, but it is preferable to use those having a diameter of 5 mm to 30 m.
- Jirukonia particles having a particle size 5Mm ⁇ 300 (hereinafter, also referred to as the particle element Z 1) and a particle diameter 300 m or less of Jirukonia particles (hereinafter, the particles Z 2 refers Tomo) mass ratio of Z R_ ⁇ 2 Conversion ( particles Z 1 / Particle Z 2) is more preferably 0.5 to 2, and the mass ratio is particularly preferably 0.8 to 1.2.
- the zirconia particles not only act as aggregates but also act as fine particles in the binder portion between the aggregates to impart corrosion resistance and the like to the binder portion. Since non-molten zirconia particles are easily available as fine particles, if fusible zirconia particles are used as aggregate particles and non-molten zirconia particles are used as the fine particles used in the binder, both characteristics and economy can be achieved. Did not It is more preferable because it becomes a fixed refractory.
- the molten Jirukonia particles 8 0-9 5% Z r O 2 equivalent, particularly preferably a non-fused Jirukonia particles and 5-2 0% by Z R_ ⁇ 2 equivalent.
- the particle size of the fine particles is preferably 0.2 mm or less, and more preferably 0.15 mm or less.
- This amorphous refractory contains 2 to 8% of glass.
- the glass phase is included in the glass component.
- Glass content is mainly serves to absorb Z r 0 2 monoclinic, a volume change accompanying the transition of the tetragonal interdendritic.
- the glass component may include glass particles, or may be a glass phase in the molten zirconia particles.
- the diameter of the glass particles is preferably 0.2 mm or less, more preferably 0.1 mm or less.
- an AZS type or the like is preferable. It is preferable that the glass content in the amorphous refractory be derived from the glass phase of the molten zirconia particles, since the absorption of the volume change by the glass content becomes more effective.
- the glass component may be used in combination with the glass particles and the glass phase in the molten zirconia particles.
- This amorphous refractory contains 2 to 12% of alumina particles.
- alumina particles are not particularly limited, but a higher purity is preferred because shrinkage after heating is small and defects such as cracks do not occur in the construction of the amorphous refractory.
- the purity of the alumina particles is preferably 90% or more, and more preferably 95% or more.
- calcined alumina by-alumina obtained by calcining aluminum hydroxide obtained by the Bayer method or calcined alumina was further calcined.
- sintered alumina evening alumina
- colloidal alumina derived from alumina sol and the like can be mentioned.
- the alumina particles of the amorphous refractory sintered alumina is preferable in terms of corrosion resistance and the like.
- the particle size of the alumina particles is 100 m or less, the dispersibility can be improved with a small amount of addition, so that the workability is improved, which is preferable. More preferably, the particle size of the alumina particles is 75 xm or less, particularly preferably 45 xm or less.
- alumina particles mainly work as a dispersant, but the effect is remarkable especially when the binder contains phosphoric acid and Z or phosphate. This is because the isoelectric point of the zirconia particles is on the acidic side, and it is difficult to obtain sufficient dispersibility at the time of construction with phosphoric acid and / or phosphate binder alone, but the isoelectric point is on the alkaline side. It is thought that the use of the alumina particles in the above will improve the dispersibility of the zirconia particles, thereby improving workability.
- the content of alumina particles in the amorphous refractory is less than 2%, the effect of improving the workability of the amorphous refractory by adding alumina particles may not be sufficient.
- the content of alumina particles in the amorphous refractory exceeds 12%, the corrosion resistance and the penetration resistance may be insufficient. More preferably, the content of the amorphous refractory is 3 to 9%.
- the amorphous refractory contains silicide particles as a binder, because it can suppress an increase in viscosity at the time of construction and can promote hardening of the construction body after construction.
- the silica particles are not particularly limited, but those having a purity of 90% or more are preferable. Examples of such silica particles include fumed silica (silica flour), colloidal silica derived from white carbon, silica sol, and the like. When the particle size of the silica particles is 10 / m or less, the above-described effects are easily obtained, and it is more preferable that the particle size is 1 im or less.
- the addition amount of the sily particles is preferably 7% or less, more preferably 1 to 5%, and particularly preferably 2 to 4% of the present amorphous refractory.
- Substantially free of alumina cement means that the content of alumina cement is 0.1. % Or that the peak of alumina cement cannot be clearly identified by X-ray diffraction measurement.
- the binder is not particularly limited as long as it has a small amount of alkali, but if it contains phosphoric acid and / or phosphate, workability is improved and sufficient strength is obtained. Is preferred.
- the phosphoric acid include orthophosphoric acid (normal phosphoric acid), hypophosphorous acid, phosphorous acid, metaphosphoric acid, and pyrophosphoric acid. Orthophosphoric acid is preferably used.
- phosphate examples include orthophosphate, polyphosphate, and metaphosphate, such as sodium phosphate. It is preferable to use phosphate-phosphoric acid alone or in combination.
- the added amount of phosphoric acid, Z or phosphate is preferably at least 80% of the binder, more preferably at least 90% of the binder.
- the usual construction method of irregular-shaped refractory can be used as appropriate.
- the construction method include driving, vibration construction, pouring, and tamping, but are not particularly limited thereto.
- Examples 1 to 5 Each raw material was sampled so as to have a raw material mixing ratio (unit: parts by mass, hereinafter simply abbreviated to "parts") shown in Tables 1 and 2, and a kneaded product was obtained by mixing with a universal mixer. This kneaded material is poured into a mold with an inner size of 4 O mmX 4 O mmX 160.0 mm with a gavel, cured for a predetermined time, removed from the mold, cured at room temperature for 24 hours to obtain a test sample, workability and compression The strength was evaluated. Tables 1 and 2 show the composition and results.
- Particles Z 1 melt Jirukonia particles (. Glass phase 6%, F e 2 0 3 0 0 7%, the remainder Z r O 2 crystal phase), particle size:. 0 3 ⁇ 4. 7 6 mm .
- Particles Z 2 melt Jirukonia particles (. Glass phase 6% F e 2 ⁇ 3 0 0 8%, the remainder Z r 0 2 crystal phase), particle size:. 0 less than 3 mm.
- Particle Z 3 non-molten zirconia particles (Fukushima Steel Corp., trade name: BR-90G), Particle size: less than 0.105 mm.
- Particle A Sintered alumina, particle size less than 44.
- Particle S fumed silica (manufactured by Asahi Glass Ceramics Co., Ltd., trade name: LP-A), average particle size 0.8 xm.
- Phosphoric acid 75% orthophosphoric acid aqueous solution.
- Phosphate sodium metaphosphate
- Example 1 Example 2 Example 3 Example 4 Example 5
- Particle Z 1 38.0 38.0 38.0 38.0
- Compressive strength 180 150 270 190 160
- this amorphous refractory is a zirconium amorphous refractory containing about 80% or more of zirconium particles, it has excellent corrosion resistance to molten glass, permeation resistance, and non-contamination of the glass substrate, and has a glass content of 2%. Since it contains up to 8%, it is strong against defects caused by temperature changes.
- the zirconia particles contain fine particles of 0.1 mm or less, they improve the corrosion resistance of the binder between the aggregates, and further improve the corrosion resistance of the amorphous refractory to molten glass. I do.
- the amorphous refractory contains phosphoric acid and / or phosphate as a binder, it has excellent mechanical strength characteristics, corrosion resistance to molten glass, etc., and uniformity of characteristics due to the dispersion effect of alumina particles. The workability during construction is also excellent. Furthermore, since this amorphous refractory does not substantially contain alumina cement, it is suitable as an irregular refractory for glass hearths such as sub-beds because it has little unevenness of the construction and excellent surface properties.
- the amorphous refractory under a high-zirconia electrical refractory as a sub-tube, it prevents severe erosion by molten glass (glass base) and prevents foaming caused by reaction with molten glass.
- the lower portion of the electric refractory can be prevented from being eroded by molten glass circulated below the electric refractory, and the durability of the furnace can be improved.
- the use of the amorphous refractory is not limited to sub-vessels, etc., but may be used as the glass itself depending on the type and use of glass.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04732811A EP1810956A4 (en) | 2003-05-14 | 2004-05-13 | MONOLITHIC REFRACTORY MATERIAL BASED ON ZIRCONIA |
JP2005506243A JP4598672B2 (ja) | 2003-05-14 | 2004-05-13 | ジルコニア質不定形耐火物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2003-136124 | 2003-05-14 | ||
JP2003136124 | 2003-05-14 |
Publications (2)
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WO2004101466A1 true WO2004101466A1 (ja) | 2004-11-25 |
WO2004101466A8 WO2004101466A8 (ja) | 2008-03-13 |
Family
ID=33447207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2004/006802 WO2004101466A1 (ja) | 2003-05-14 | 2004-05-13 | ジルコニア質不定形耐火物 |
Country Status (4)
Country | Link |
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EP (1) | EP1810956A4 (ja) |
JP (1) | JP4598672B2 (ja) |
TW (1) | TW200502193A (ja) |
WO (1) | WO2004101466A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009215107A (ja) * | 2008-03-11 | 2009-09-24 | Kurosaki Harima Corp | スタンプ耐火物 |
JP2010501449A (ja) * | 2006-07-06 | 2010-01-21 | ベスビウス クルーシブル カンパニー | セメントを含まない耐火物 |
WO2013011927A1 (ja) * | 2011-07-21 | 2013-01-24 | 旭硝子株式会社 | 溶融ガラス搬送設備要素および溶融ガラス搬送設備要素の製造方法、ならびにガラス製造装置 |
WO2014073594A1 (ja) * | 2012-11-12 | 2014-05-15 | 旭硝子株式会社 | 溶融ガラス搬送設備要素、溶融ガラス搬送設備要素の製造方法、溶融ガラス搬送設備要素を含むガラス製造装置、およびガラス物品の製造方法 |
JP2016501815A (ja) * | 2012-11-28 | 2016-01-21 | コーニング インコーポレイテッド | ガラス製造装置および方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8505335B2 (en) * | 2007-06-19 | 2013-08-13 | Magneco/Metrel, Inc. | Refractoy composition for glass melting furnaces |
FR2943055B1 (fr) * | 2009-03-10 | 2011-04-08 | Saint Gobain Ct Recherches | Poudre de zircone |
FR2954768A1 (fr) * | 2009-12-24 | 2011-07-01 | Saint Gobain Ct Recherches | Poudre pour pise sec vitroceramique |
FR2978144B1 (fr) | 2011-07-22 | 2013-08-30 | Saint Gobain Ct Recherches | Bloc refractaire et four de fusion de verre |
EP3286157A4 (en) * | 2015-04-24 | 2018-12-05 | Corning Incorporated | Bonded zirconia refractories and methods for making the same |
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JPH05213676A (ja) * | 1992-01-31 | 1993-08-24 | Asahi Glass Co Ltd | ドライラミング用耐火材 |
JPH08104567A (ja) * | 1994-09-30 | 1996-04-23 | Toshiba Monofrax Co Ltd | ジルコニア耐火物 |
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US4552852A (en) * | 1984-06-27 | 1985-11-12 | Champion Spark Plug Company | Alumina ceramic comprising a siliceous binder and at least one of zirconia and hafnia |
EP0232095A3 (en) * | 1986-01-24 | 1988-12-07 | The Dow Chemical Company | Ceramic composites from chemically derived magnesium-aluminate and zirconium oxide |
JP2926966B2 (ja) * | 1989-11-28 | 1999-07-28 | 旭硝子株式会社 | 高ジルコニア質熱溶融鋳造耐火物 |
JPH05319919A (ja) * | 1992-05-21 | 1993-12-03 | Kurosaki Refract Co Ltd | 連続鋳造用ノズルの製造方法 |
JPH1160340A (ja) * | 1997-08-08 | 1999-03-02 | Toshiba Ceramics Co Ltd | キャスタブル耐火物 |
JP4297543B2 (ja) * | 1998-02-26 | 2009-07-15 | Agcセラミックス株式会社 | アルミナ・ジルコニア・シリカ質溶融鋳造耐火物およびそれを使用したガラス溶融窯 |
DE69901468T2 (de) * | 1998-02-26 | 2002-11-28 | Asahi Glass Co., Ltd. | Schmelzgegossenes Aluminiumoxid-Zirkonoxid-Siliziumoxid-Feuerfestmaterial und Glasschmelzofen, in den dieses eingesetzt wird |
ZA200309168B (en) * | 2002-12-10 | 2004-07-22 | Magneco Metrel Inc | Refractory system for glass melting furnaces. |
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2004
- 2004-05-13 WO PCT/JP2004/006802 patent/WO2004101466A1/ja active Application Filing
- 2004-05-13 EP EP04732811A patent/EP1810956A4/en not_active Withdrawn
- 2004-05-13 JP JP2005506243A patent/JP4598672B2/ja not_active Expired - Fee Related
- 2004-05-14 TW TW093113748A patent/TW200502193A/zh unknown
Patent Citations (2)
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JPH05213676A (ja) * | 1992-01-31 | 1993-08-24 | Asahi Glass Co Ltd | ドライラミング用耐火材 |
JPH08104567A (ja) * | 1994-09-30 | 1996-04-23 | Toshiba Monofrax Co Ltd | ジルコニア耐火物 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010501449A (ja) * | 2006-07-06 | 2010-01-21 | ベスビウス クルーシブル カンパニー | セメントを含まない耐火物 |
JP2009215107A (ja) * | 2008-03-11 | 2009-09-24 | Kurosaki Harima Corp | スタンプ耐火物 |
WO2013011927A1 (ja) * | 2011-07-21 | 2013-01-24 | 旭硝子株式会社 | 溶融ガラス搬送設備要素および溶融ガラス搬送設備要素の製造方法、ならびにガラス製造装置 |
WO2014073594A1 (ja) * | 2012-11-12 | 2014-05-15 | 旭硝子株式会社 | 溶融ガラス搬送設備要素、溶融ガラス搬送設備要素の製造方法、溶融ガラス搬送設備要素を含むガラス製造装置、およびガラス物品の製造方法 |
JPWO2014073594A1 (ja) * | 2012-11-12 | 2016-09-08 | 旭硝子株式会社 | 溶融ガラス搬送設備要素、溶融ガラス搬送設備要素の製造方法、溶融ガラス搬送設備要素を含むガラス製造装置、およびガラス物品の製造方法 |
US9446976B2 (en) | 2012-11-12 | 2016-09-20 | Asahi Glass Company, Limited | Molten glass conveying equipment element, method for manufacturing molten glass conveying equipment element, glass manufacturing apparatus comprising molten glass conveying equipment element and method for manufacturing glass product |
JP2016501815A (ja) * | 2012-11-28 | 2016-01-21 | コーニング インコーポレイテッド | ガラス製造装置および方法 |
US9890069B2 (en) | 2012-11-28 | 2018-02-13 | Corning Incorporated | Glass manufacturing apparatus and methods |
JP2019001712A (ja) * | 2012-11-28 | 2019-01-10 | コーニング インコーポレイテッド | ガラス製造装置および方法 |
Also Published As
Publication number | Publication date |
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TW200502193A (en) | 2005-01-16 |
WO2004101466A8 (ja) | 2008-03-13 |
EP1810956A1 (en) | 2007-07-25 |
JP4598672B2 (ja) | 2010-12-15 |
EP1810956A8 (en) | 2009-04-29 |
JPWO2004101466A1 (ja) | 2006-07-13 |
EP1810956A4 (en) | 2007-11-28 |
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