JP2016141598A - Monolithic refractory composition for metal casting and manufacturing method therefor, cured article of monolithic refractory composition for metal casting - Google Patents
Monolithic refractory composition for metal casting and manufacturing method therefor, cured article of monolithic refractory composition for metal casting Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000005058 metal casting Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011823 monolithic refractory Substances 0.000 title abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 36
- 239000008119 colloidal silica Substances 0.000 claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 21
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000000292 calcium oxide Substances 0.000 claims abstract description 15
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 9
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 29
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 37
- 239000002184 metal Substances 0.000 abstract description 37
- 238000001035 drying Methods 0.000 abstract description 14
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- 239000000835 fiber Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical class C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- -1 ethyleneimine compound Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BYCHPAAGFQAEOD-UHFFFAOYSA-N ethenamine;hydrochloride Chemical compound Cl.NC=C BYCHPAAGFQAEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- KWQCSIPJQQXVEQ-UHFFFAOYSA-N n'-ethenylprop-2-enimidamide;hydrochloride Chemical compound Cl.C=CC(N)=NC=C KWQCSIPJQQXVEQ-UHFFFAOYSA-N 0.000 description 1
- ILCQQHAOOOVHQJ-UHFFFAOYSA-N n-ethenylprop-2-enamide Chemical compound C=CNC(=O)C=C ILCQQHAOOOVHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
Abstract
Description
本発明は、アルミニウム、亜鉛、マグネシウム等の鋳造装置において、金属溶湯と直接接する部位に使用し得る金属鋳造用不定形耐火組成物及びその製造方法、金属鋳造用不定形耐火組成物の硬化物に関する。 The present invention relates to an amorphous refractory composition for metal casting that can be used in a portion in direct contact with a molten metal in a casting apparatus for aluminum, zinc, magnesium, and the like, a manufacturing method thereof, and a cured product of the amorphous refractory composition for metal casting. .
アルミニウム等の非鉄金属の鋳造装置、例えば樋、溶湯保持炉、取鍋等において、溶湯と接触する内張材として、不定形耐火組成物を施工し乾燥又は焼成させた断熱壁が利用されている。また、内張材には不定形耐火組成物の他に耐火成形体が用いられており、不定形耐火組成物にて耐火成形体の目地部を埋め、断熱壁とする場合もある。 In a non-ferrous metal casting apparatus such as aluminum, for example, a firewood, a molten metal holding furnace, a ladle, etc., a heat insulating wall obtained by applying an amorphous refractory composition and drying or firing is used as a lining material in contact with the molten metal. . In addition to the amorphous refractory composition, a refractory molded body is used for the lining material, and the joint portion of the refractory molded body may be filled with the amorphous refractory composition to form a heat insulating wall.
金属溶湯と直接接触する部位に使用される断熱壁は、使用時における金属溶湯との反応や金属溶湯の浸透によって表面に金属が貼り付いてしまい、この表面に貼り付いた金属を剥がそうとすると、断熱壁も一緒に剥がれて、損傷を引き起こすという技術課題が存在していた。 Insulating walls used in areas that come into direct contact with the molten metal will stick to the surface due to reaction with the molten metal during use and penetration of the molten metal, and if you try to peel off the adhered metal on this surface In addition, there was a technical problem that the insulation wall was peeled off together, causing damage.
特許文献１には、金属溶湯の浸透や表面反応による金属の貼り付きが抑制された金属鋳造用不定形耐火組成物が記載されている。 Patent Document 1 describes an amorphous refractory composition for metal casting in which penetration of molten metal and adhesion of metal due to surface reaction are suppressed.
しかしながら、特許文献１に記載の金属鋳造用不定形耐火組成物は、乾燥又は焼成して得られる硬化物（断熱壁）の強度が弱いという問題があった。
本発明は、上記課題に鑑み、施工性及び乾燥又は焼成時における金属溶湯の貼り付き耐性を担保できると共に、乾燥又は焼成時における強度を向上できる金属鋳造用不定形耐火組成物及びその硬化物を提供すること、前記金属鋳造用不定形耐火組成物を簡便に製造する方法を提供することを目的とする。
However, the amorphous refractory composition for metal casting described in Patent Document 1 has a problem that the strength of a cured product (heat insulating wall) obtained by drying or firing is weak.
In view of the above problems, the present invention provides an amorphous refractory composition for metal casting and a cured product thereof capable of ensuring the workability and the adhesion resistance of the molten metal during drying or firing and improving the strength during drying or firing. It is an object of the present invention to provide a method for easily producing the amorphous refractory composition for metal casting.
本発明によれば、以下の金属鋳造用不定形耐火組成物及びその硬化物、金属鋳造用不定形耐火組成物の製造方法が提供される。
１．固形分中に、
無機繊維を１５〜７５質量％と、
コロイダルシリカをシリカ換算で２１〜６５質量％と、
フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上であるイオン結合性物質を４〜４０質量％と
を含む金属鋳造用不定形耐火組成物。
２．固形分中において前記無機繊維を２０〜７０質量％と、前記コロイダルシリカをシリカ換算で２５〜５５質量％と、前記イオン結合性物質を５〜３０質量％とを含む１記載の金属鋳造用不定形耐火組成物。
３．ちょう度が１００〜４００（１／１０ｍｍ）である１又は２記載の金属鋳造用不定形耐火組成物。
４．無機繊維１５〜７５質量％と、
コロイダルシリカをシリカ換算で２１〜６５質量％と、
フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上であるイオン結合性物質４〜４０質量％とを混合する金属鋳造用不定形耐火組成物の製造方法。
５．１〜３のいずれか記載の金属鋳造用不定形耐火組成物を硬化させた硬化物。
According to this invention, the manufacturing method of the following amorphous refractory compositions for metal casting, its hardened | cured material, and the amorphous refractory composition for metal castings is provided.
1. In the solids,
15 to 75% by mass of inorganic fiber,
Colloidal silica is 21 to 65% by mass in terms of silica,
4 to 40% by mass of an ion-binding substance that is at least one selected from calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof, magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate An amorphous refractory composition for metal casting, comprising:
2. 2. The metal casting defect according to 1, comprising 20 to 70% by mass of the inorganic fiber, 25 to 55% by mass of the colloidal silica in terms of silica, and 5 to 30% by mass of the ion binding substance in a solid content. A regular refractory composition.
3. The amorphous refractory composition for metal casting according to 1 or 2, having a consistency of 100 to 400 (1/10 mm).
4). 15 to 75% by mass of inorganic fibers,
Colloidal silica is 21 to 65% by mass in terms of silica,
4-40% by mass of an ion-binding substance that is at least one selected from calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof, magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate. A method for producing an amorphous refractory composition for metal casting to be mixed.
5. Hardened | cured material which hardened the amorphous refractory composition for metal casting in any one of 1-3.
本発明によれば、施工性及び乾燥又は焼成時における金属溶湯の貼り付き耐性を担保できると共に、乾燥又は焼成時における強度を向上できる不定形耐火組成物及びその硬化物を提供することができる。また、前記不定形耐火組成物を簡便に製造する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while being able to ensure the workability and the adhesion tolerance of the molten metal at the time of drying or baking, the amorphous refractory composition which can improve the intensity | strength at the time of drying or baking, and its hardened | cured material can be provided. Moreover, the method of manufacturing the said amorphous refractory composition simply can be provided.
本発明の不定形耐火組成物は、固形分中に、無機繊維を１５〜７５質量％、コロイダルシリカをシリカ換算で２１〜６５質量％、フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上の結合性物質を４〜４０質量％含む。 The amorphous refractory composition of the present invention comprises 15 to 75% by mass of inorganic fibers and 21 to 65% by mass of colloidal silica in terms of silica, calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof in the solid content. 4 to 40% by mass of one or more binding substances selected from magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate.
無機繊維は、得られる不定形耐火組成物の骨材としての機能を発揮するものであり、この機能を発揮するものであれば特に制限されないが、例えば、ガラス繊維、グラスウール、セラミックウール、ロックウール、アルミナ質繊維、ジルコニア質繊維、アルミノシリケート繊維、生体溶解性無機繊維等から選ばれる１種以上を挙げることができる。 Inorganic fiber exhibits the function as an aggregate of the obtained amorphous refractory composition, and is not particularly limited as long as it exhibits this function. For example, glass fiber, glass wool, ceramic wool, rock wool And one or more selected from alumina fiber, zirconia fiber, aluminosilicate fiber, biosoluble inorganic fiber, and the like.
本発明において、生体溶解性無機繊維とは、４０℃における生理食塩水溶解率が１％以上である無機繊維を意味する。例えば、ＳｉＯ２とＡｌ２Ｏ３とＺｒＯ２とＴｉＯ２との合計が５０〜８２質量％、ＣａＯとＭｇＯとの合計が１８〜５０質量％である無機繊維、ＳｉＯ２５０〜８２質量％、ＣａＯとＭｇＯとの合計が１０〜４３質量％である無機繊維、ＳｉＯ２０〜８２質量％、ＣａＯ１〜９質量％、ＭｇＯ１０〜２９質量％、Ａｌ２Ｏ３３質量％未満である無機繊維、ＳｉＯ２７０〜８２質量％、ＣａＯ１０〜２９質量％、ＭｇＯ１質量％以下、Ａｌ２Ｏ３３質量％未満である無機繊維、ＳｉＯ２７３．６質量％〜８５．９質量％、ＭｇＯ．０質量％〜２１．３質量％、ＣａＯ５．１質量％〜１２．４質量％、Ａｌ２Ｏ３０質量％以上２．３質量％未満、Ｆｅ２Ｏ３０質量％〜０．５０質量％である無機繊維、ＳｉＯ２７３．６質量％〜８５．９質量％、ＭｇＯ９．０質量％〜１５．０質量％、ＣａＯ５．１質量％〜１２．４質量％。、Ａｌ２Ｏ３０質量％以上２．３質量％未満、Ｆｅ２Ｏ３０質量％〜０．５０質量％、ＳｒＯ０．１質量％未満である無機繊維等を挙げることができる。 In the present invention, the biosoluble inorganic fiber means an inorganic fiber having a physiological saline dissolution rate at 40 ° C. of 1% or more. For example, SiO 2 and Al 2 O 3 and ZrO 2 and total 50-82% by weight of TiO 2, inorganic fibers sum of CaO and MgO is 18 to 50 wt%, SiO 2 50 to 82 wt%, Inorganic fiber whose total of CaO and MgO is 10 to 43% by mass, SiO 2 0 to 82% by mass, CaO 1 to 9% by mass, MgO 10 to 29% by mass, Al 2 O 3 less than 3% by mass, SiO 2 70 to 82% by mass, CaO 10 to 29% by mass, MgO 1% by mass or less, Al 2 O 3 less than 3% by mass inorganic fiber, SiO 2 73.6% by mass to 85.9% by mass, MgO. 0% by mass to 21.3% by mass, CaO 5.1% by mass to 12.4% by mass, Al 2 O 3 0% by mass to less than 2.3% by mass, Fe 2 O 3 0% by mass to 0.50% by mass Inorganic fibers, SiO 2 73.6% by mass to 85.9% by mass, MgO 9.0% by mass to 15.0% by mass, CaO 5.1% by mass to 12.4% by mass. Al 2 O 3 0% by mass or more and less than 2.3% by mass, Fe 2 O 3 0% by mass to 0.50% by mass, SrO less than 0.1% by mass, and the like.
無機繊維の平均繊維径や平均繊維長は、特に制限されないが、平均繊維径は例えば１〜１０μｍであり、無機繊維の平均繊維長は、例えば１〜５０ｍｍである。
なお、本発明において、平均繊維径は、電子顕微鏡による観察画像にて、繊維２００本の直径を測定したときの平均値を意味する。また、平均繊維長は、繊維２００本の繊維長をノギスで測定したときの平均値を意味する。
The average fiber diameter and average fiber length of the inorganic fibers are not particularly limited, but the average fiber diameter is, for example, 1 to 10 μm, and the average fiber length of the inorganic fibers is, for example, 1 to 50 mm.
In addition, in this invention, an average fiber diameter means the average value when the diameter of 200 fibers is measured by the observation image by an electron microscope. Moreover, an average fiber length means the average value when the fiber length of 200 fibers is measured with a caliper.
本発明の不定形耐火組成物において、無機繊維は、１５〜７５質量％含まれ、２０〜７０質量％含まれることが好ましく、２５〜６０質量％含まれることがより好ましい。
無機繊維の含有割合が１５〜７５質量％であることにより、乾燥速度が速く施工性に優れた不定形耐火組成物を提供することができ、さらに強度及び耐侵食性を有しつつ、保温性（断熱性）及び軽量性に優れた不定形耐火組成物の硬化物を提供することができる。
In the amorphous refractory composition of the present invention, the inorganic fiber is contained in an amount of 15 to 75% by mass, preferably 20 to 70% by mass, and more preferably 25 to 60% by mass.
When the content ratio of the inorganic fiber is 15 to 75% by mass, it is possible to provide an amorphous refractory composition having a high drying speed and excellent workability, and further having heat resistance while having strength and erosion resistance. The hardened | cured material of the amorphous refractory composition excellent in (heat insulation) and lightweight property can be provided.
無機繊維は軽量で低密度であるといった性質を有することから、従来、不定形耐火組成物の構成材料として用いた場合、機械強度的に脆く、アルミニウム等の金属溶湯の侵食を受け易い不定形耐火組成物の硬化物しか得られないと考えられていた。しかしながら、イオン結合性物質及びコロイダルシリカとともに所定量の無機繊維を不定形耐火組成物の構成材料として用いることにより、強度及び耐侵食性を有しつつ、保温性（断熱性）に優れ、軽量化された不定形耐火組成物の硬化物を作製し得る。 Since inorganic fibers have the property of being lightweight and low density, conventionally, when used as a constituent material for an amorphous refractory composition, it is brittle in mechanical strength and is susceptible to corrosion by a molten metal such as aluminum. It was thought that only a cured product of the composition could be obtained. However, by using a certain amount of inorganic fiber together with the ion-binding substance and colloidal silica as the constituent material of the amorphous refractory composition, it has excellent heat retention (heat insulation) and light weight while having strength and erosion resistance. A cured product of the formed amorphous refractory composition can be produced.
本発明で用いるコロイダルシリカとしては、シリカ粒子又はその水和物が水中にコロイド状に分散された、メディアン径（Ｄ５０）が０．１μｍ未満、９０％積算径（Ｄ９０）が０．２μｍ未満であるものが好ましく、メディアン径（Ｄ５０）が０．０１μｍ以上０．１μｍ未満、９０％積算径（Ｄ９０）が０．０２μｍ以上０．２μｍ未満であるものがより好ましい。 As colloidal silica used in the present invention, silica particles or hydrates thereof are colloidally dispersed in water, the median diameter (D50) is less than 0.1 μm, and the 90% cumulative diameter (D90) is less than 0.2 μm. Some are preferable, and those having a median diameter (D50) of 0.01 μm or more and less than 0.1 μm and a 90% integrated diameter (D90) of 0.02 μm or more and less than 0.2 μm are more preferable.
コロイダルシリカは、不定形耐火組成物を乾燥又は焼成して得られる硬化物に十分な保形性及び強度を付与するものであり、硬化後に無機繊維同士を結着させる機能を発揮するとともに、金属溶湯への酸素供給源として、硬化物と金属溶湯が接触する界面で、金属溶湯の酸化膜（金属がアルミニウムの場合、酸化アルミニウム膜）形成機能を発揮する。コロイダルシリカのメディアン径（Ｄ５０）が０．１μｍ未満、９０％積算径（Ｄ９０）が０．２μｍ未満であると、硬化後にシリカの表面積が大きくなって、還元力の高い金属溶湯とシリカの酸化還元反応が素早く進み易くなり、耐火物表面に酸化膜が迅速に形成され易くなる。一方、コロイダルシリカのメディアン径（Ｄ５０）が０．１μｍ以上であったり、９０％積算径（Ｄ９０）が０．２μｍ以上であると、酸化膜が迅速に形成し難くなり、得られる硬化物表面に金属が貼り付き易くなる。 Colloidal silica imparts sufficient shape retention and strength to a cured product obtained by drying or firing an irregular refractory composition, and exhibits a function of binding inorganic fibers to each other after curing. As an oxygen supply source to the molten metal, an oxide film (aluminum oxide film when the metal is aluminum) forming function of the molten metal is exhibited at the interface where the cured product and the molten metal are in contact. When the median diameter (D50) of the colloidal silica is less than 0.1 μm and the 90% cumulative diameter (D90) is less than 0.2 μm, the surface area of the silica increases after curing, and the metal melt having high reducing power and the oxidation of the silica The reduction reaction easily proceeds quickly, and an oxide film is easily formed on the surface of the refractory. On the other hand, when the median diameter (D50) of colloidal silica is 0.1 μm or more or the 90% cumulative diameter (D90) is 0.2 μm or more, it becomes difficult to form an oxide film quickly, and the surface of the cured product obtained It becomes easy for metal to stick to.
本発明において、メディアン径（Ｄ５０）とは、粒度分布に対して、細かい方から積算で５０％になる粒径を言い、９０％積算径（Ｄ９０）とは、粒度分布に対して、細かい方から積算で９０％になる粒径を意味する。コロイダルシリカの粒径は、粒子から散乱した光強度分布から粒度分布（粒径）を算出するレーザ回析・散乱法により求めることができる。 In the present invention, the median diameter (D50) refers to a particle size that is 50% integrated from the finer with respect to the particle size distribution, and the 90% integrated diameter (D90) is smaller with respect to the particle size distribution. Means a particle size that is 90% integrated. The particle size of colloidal silica can be determined by a laser diffraction / scattering method for calculating the particle size distribution (particle size) from the light intensity distribution scattered from the particles.
本発明の不定形耐火組成物において、コロイダルシリカは、固形分中にシリカ換算で、２１〜６５質量％含まれ、２５〜５５質量％含まれることが好ましく、３０〜５０質量％含まれることがより好ましい。 In the amorphous refractory composition of the present invention, the colloidal silica is contained in an amount of 21 to 65% by mass in terms of silica, preferably 25 to 55% by mass, and preferably 30 to 50% by mass. More preferred.
コロイダルシリカは、シリカ粒子又はその水和物が水中に分散したコロイド状物であるが、本発明において、上記コロイダルシリカの含有割合は、不定形耐火組成物の固形分全体に占めるシリカ換算した質量割合を意味する。 Colloidal silica is a colloidal product in which silica particles or hydrates thereof are dispersed in water. In the present invention, the content of the colloidal silica is the mass in terms of silica in the total solid content of the amorphous refractory composition. Mean percentage.
コロイダルシリカの含有割合が、シリカ換算で２１質量％未満であると、硬化後の強度が不十分である。また、６５質量％を超えるとちょう度が高くなり、施工時にペースト状の組成物が垂れ、また、乾燥による目地等の施工物の収縮が大きくなる。
ところで、コロイダルシリカの含有割合がシリカ換算で２１質量％以上であると製造効率が低下（具体的には、多量のコロイダルシリカを混合することによりコロイダルシリカとイオン結合性物質などの粉体が凝集しやすくなることによる分散不足）する可能性がある。そこで、本発明では、例えば、コロイダルシリカを混合する前に無機繊維とイオン結合性物質などの粉体を事前混合することにより、コロイダルシリカとイオン結合性物質などの粉体の凝集を起きにくくし、分散不足を解消することができる。
When the content of colloidal silica is less than 21% by mass in terms of silica, the strength after curing is insufficient. Moreover, when it exceeds 65 mass%, the consistency will become high, a paste-like composition drips at the time of construction, and shrinkage | contraction of construction materials, such as a joint by drying, will become large.
By the way, production efficiency falls that the content rate of colloidal silica is 21 mass% or more in conversion of a silica (specifically, powders, such as colloidal silica and an ion binding substance, aggregate by mixing a lot of colloidal silica. There is a possibility of insufficient dispersion due to the fact that Therefore, in the present invention, for example, before mixing the colloidal silica, the inorganic fiber and the powder such as the ion-binding substance are premixed, thereby making it difficult for the colloidal silica and the powder such as the ion-binding substance to aggregate. , The lack of dispersion can be resolved.
本発明の不定形耐火組成物は、イオン結合性物質として、フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上を含んでいる。イオン結合性物質としては、フッ化カルシウムが最もイオン結合性が強いため、好適である。 The amorphous refractory composition of the present invention is selected from calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof, magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate as an ion binding substance. Contains one or more. As the ion binding substance, calcium fluoride is preferred because it has the strongest ion binding ability.
酸化カルシウムの前駆体としては、炭酸カルシウムが挙げられる。また、酸化マグネシウムの前駆体としては、炭酸マグネシウムが挙げられる。また、酸化バリウムの前駆体としては、炭酸バリウムが挙げられる。これらの前駆体は加熱により容易に分解するため、焼成後の硬化物中において、それぞれ、酸化カルシウム、酸化マグネシウム、酸化バリウムとして存在することになる。 An example of the calcium oxide precursor is calcium carbonate. Moreover, magnesium carbonate is mentioned as a precursor of magnesium oxide. Moreover, barium carbonate is mentioned as a precursor of barium oxide. Since these precursors are easily decomposed by heating, they are present as calcium oxide, magnesium oxide, and barium oxide, respectively, in the cured product after firing.
イオン結合性物質は、接触する溶湯金属の酸化物、例えば、酸化アルミニウムと同等以上の強いイオン結合性を有しており、不定形耐火組成物の硬化物と金属溶湯が接触する界面で、金属溶湯の酸化膜を形成させる目的で使用される。イオン結合性物質は、イオン結合性が強いほど酸化膜形成効果が大きいため、混合物中の含有量が少量であっても充分な酸化膜形成効果を発現することができる。 The ion-binding substance has a strong ion-bonding property equivalent to or higher than that of the molten metal oxide, for example, aluminum oxide, and is a metal at the interface between the cured product of the amorphous refractory composition and the molten metal. Used for the purpose of forming a molten oxide film. Since the ion binding substance has a larger oxide film forming effect as the ion binding property is stronger, even if the content in the mixture is small, a sufficient oxide film forming effect can be exhibited.
イオン結合性物質は、粒径が小さいものが好ましく、具体的には、平均粒径０．１５ｍｍ以下のものが好ましく、平均粒径０．１０ｍｍ以下のものがより好ましく、平均粒径０．０５０ｍｍ以下のものがさらに好ましい。また、上記平均粒径は、０．００１ｍｍ以上であることが好ましい。
粒径の小さなイオン結合性物質を使用した場合には、イオン結合性物質の比表面積を全体として大きくすることができるため、適度な剥離性を有する酸化膜を不定形耐火組成物の硬化物表面に迅速に形成することができる。
The ion-binding substance preferably has a small particle diameter, specifically, an average particle diameter of 0.15 mm or less is preferable, an average particle diameter of 0.10 mm or less is more preferable, and an average particle diameter of 0.050 mm. The following are more preferable. Moreover, it is preferable that the said average particle diameter is 0.001 mm or more.
When an ion-binding substance having a small particle size is used, the specific surface area of the ion-binding substance can be increased as a whole, so an oxide film having an appropriate peelability is formed on the surface of the cured refractory composition. Can be formed quickly.
なお、本発明において、イオン結合性物質の平均粒径は、粒度分布計を用いてレーザ回折・散乱法により測定した値を意味する。 In the present invention, the average particle diameter of the ion-binding substance means a value measured by a laser diffraction / scattering method using a particle size distribution meter.
また、イオン結合性物質は純度９０％以上のものを使用することが好ましく、純度９９％以上のものを使用することがさらに好ましい。 Moreover, it is preferable to use an ion-binding substance having a purity of 90% or more, and it is more preferable to use a substance having a purity of 99% or more.
本発明の組成物において、イオン結合性物質は、４〜４０質量％含まれ、５〜３０質量％含まれることが好ましく、５〜２５質量％含まれることがより好ましい。 In the composition of the present invention, the ion-binding substance is contained in an amount of 4 to 40% by mass, preferably 5 to 30% by mass, and more preferably 5 to 25% by mass.
イオン結合性物質の含有割合が、４質量％未満であると、不定形耐火組成物の硬化物と金属溶湯が接触する界面に金属溶湯の酸化膜を迅速に形成させ難くなる。また、４０質量％を超えると、イオン結合性の強い材料は、一般に加熱による体積膨張が大きいため、耐熱衝撃性が低下して、熱衝撃により硬化物が割れ易くなる。本発明の組成物は、イオン結合性物質とコロイダルシリカとを特定の割合で含むことによって、得られる硬化物と金属溶湯が接触する界面に金属溶湯の酸化膜を迅速に形成することができる。 When the content of the ion-binding substance is less than 4% by mass, it becomes difficult to quickly form an oxide film of the molten metal at the interface where the cured product of the amorphous refractory composition and the molten metal are in contact. On the other hand, when the content exceeds 40% by mass, a material having strong ionic bonding generally has a large volume expansion due to heating, so that the thermal shock resistance is lowered and the cured product is easily cracked by thermal shock. The composition of the present invention can rapidly form an oxide film of the molten metal at the interface where the obtained cured product and the molten metal are in contact with each other by containing the ion binding substance and the colloidal silica in a specific ratio.
本発明の不定形耐火組成物は、好ましくは、無機繊維、コロイダルシリカ、イオン結合性物質を合わせて固形分の８０質量％以上、８５質量％以上、９０質量％以上又は９５質量％以上含むようにしてもよい。 The amorphous refractory composition of the present invention preferably contains 80 mass% or more, 85 mass% or more, 90 mass% or more, or 95 mass% or more of the solid content in combination with inorganic fibers, colloidal silica, and ion-binding substances. Also good.
本発明の不定形耐火組成物は、任意成分として、充填材や骨材、被覆層形成剤、増粘剤、分散剤、防腐剤を含むことができる。 The amorphous refractory composition of the present invention can contain a filler, an aggregate, a coating layer forming agent, a thickener, a dispersant, and an antiseptic as optional components.
充填材や骨材としては、シリカ、アルミナ、シャモット、チタニア、ジルコニア、窒化珪素、炭化珪素、コージェライト、ワラストナイト等が挙げられる。 Examples of the filler and aggregate include silica, alumina, chamotte, titania, zirconia, silicon nitride, silicon carbide, cordierite, and wollastonite.
被覆層形成剤としては、リン酸塩、モリブデン化合物、亜鉛化合物等の無機化合物、ポリアミジン化合物、エチレンイミン化合物等の有機化合物が挙げられる。上記リン酸塩としては、トリポリリン酸アルミニウム、トリポリリン酸二水素アルミニウム、メタリン酸アルミニウム、リン酸亜鉛、リン酸カルシウム等が挙げられ、上記モリブデン化合物としては、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム、リンモリブデン酸カルシウム、リンモリブデン酸アルミニウム等が挙げられ、上記亜鉛化合物としては酸化亜鉛が挙げられ、上記ポリアミジン化合物としては、アクリルアミド、アクリロニトリル、Ｎ−ビニルアクリルアミジン塩酸塩、Ｎ−ビニルアクリルアミド、ビニルアミン塩酸塩、Ｎ−ビニルホルムアミド共重合体等が挙げられ、上記エチレンイミン化合物としては、アミノエチレン、ジメチレンイミン等が挙げられる。 Examples of the coating layer forming agent include inorganic compounds such as phosphates, molybdenum compounds, and zinc compounds, and organic compounds such as polyamidine compounds and ethyleneimine compounds. Examples of the phosphate include aluminum tripolyphosphate, aluminum dipolyphosphate, aluminum metaphosphate, zinc phosphate, and calcium phosphate. Examples of the molybdenum compound include zinc molybdate, aluminum molybdate, calcium molybdate, phosphorus, and the like. Examples of the zinc compound include zinc oxide. Examples of the polyamidine compound include acrylamide, acrylonitrile, N-vinylacrylamidine hydrochloride, N-vinylacrylamide, and vinylamine hydrochloride. N-vinylformamide copolymer and the like, and examples of the ethyleneimine compound include aminoethylene and dimethyleneimine.
本発明の不定形耐火組成物において、無機繊維として生体溶解性無機繊維を用いる場合、被覆層形成剤を配合することにより、生体溶解性無機繊維の表面に速やかに被覆層が形成されて、水等の液体媒体と接触による劣化を抑制することができる。 In the amorphous refractory composition of the present invention, when a biosoluble inorganic fiber is used as the inorganic fiber, a coating layer is quickly formed on the surface of the biosoluble inorganic fiber by adding a coating layer forming agent, It is possible to suppress deterioration due to contact with a liquid medium such as.
増粘剤としては、ヒドロキシエチルセルロース、アクリル酸ナトリウム重合物等を挙げることができ、分散剤としては、カルボン酸類、多価アルコール、アミン類等を挙げることができ、防腐剤としては、窒素原子又は硫黄原子を有する無機化合物又は有機化合物を挙げることができる。 Examples of the thickener include hydroxyethyl cellulose and sodium acrylate polymer, examples of the dispersant include carboxylic acids, polyhydric alcohols and amines, and examples of the preservative include a nitrogen atom or Mention may be made of inorganic or organic compounds having a sulfur atom.
本発明の不定形耐火組成物において、不定形状は特に限定されない。不定形状は、例えば、所定の固形分（例えばシリカ粒子）を分散させてなる液体（例えばコロイダルシリカ）とその他固形分とを互いに混合してなるペースト状や、固形分に液体媒体を混合してなるペースト状として構成することができる。 In the irregular refractory composition of the present invention, the irregular shape is not particularly limited. The indefinite shape is, for example, a paste formed by mixing a liquid (for example, colloidal silica) in which a predetermined solid content (for example, silica particles) is dispersed and other solid content, or a liquid medium mixed with the solid content. Can be configured as a paste.
ペースト状物を形成する液体媒体としては、特に制限されないが、水及び極性有機溶媒が挙げられ、極性有機溶媒としては、エタノール、プロパノール等の１価のアルコール類、エチレングリコール等の２価のアルコール類が挙げられる。これ等の液体媒体のうち、作業環境や環境負荷を考慮すると、水が好ましい。また、水としては特に制限されず、蒸留水、イオン交換水、水道水、地下水、工業用水等が挙げられる。 Although it does not restrict | limit especially as a liquid medium which forms a paste-like thing, Water and a polar organic solvent are mentioned, As a polar organic solvent, monovalent alcohols, such as ethanol and propanol, Divalent alcohols, such as ethylene glycol, are mentioned. Kind. Of these liquid media, water is preferable in consideration of the working environment and environmental load. Moreover, it does not restrict | limit especially as water, Distilled water, ion-exchange water, tap water, groundwater, industrial water etc. are mentioned.
本発明の不定形耐火組成物のちょう度は好ましくは１００〜４００（１／１０ｍｍ）であり、より好ましくは１００〜３５０（１／１０ｍｍ）である。 The consistency of the amorphous refractory composition of the present invention is preferably 100 to 400 (1/10 mm), more preferably 100 to 350 (1/10 mm).
ちょう度が１００（１／１０ｍｍ）未満であると不定形耐火組成物の柔軟性が低下するので施工性が悪くなる。また、ちょう度が４００（１／１０ｍｍ）を超えると施工時にペースト状の組成物が垂れ、また、乾燥による目地等の施工物の収縮が大きくなる。
なお、不定形耐火組成物のちょう度は、不定形耐火組成物に含まれる固形分を除く溶媒量（例えばコロイダルシリカに含まれる水分量やその他液体媒体量）や無機繊維量によって調整・制御され得る。具体的には、前記溶媒量を増加又は無機繊維量を低下させるとちょう度は高くなる一方で、前記溶媒量を低下又は無機繊維量を増加させるとちょう度は低くなる。本発明では、不定形耐火組成物のちょう度を上記範囲（１００〜４００（１／１０ｍｍ））にすべく、不定形耐火組成物の固形分を１００質量部としたときの溶媒量が３１〜９７質量部、かつ、無機繊維量が７５〜１５質量％であるように構成することができる。また好ましくは、不定形耐火組成物のちょう度を１００〜３５０（１／１０ｍｍ）にすべく、不定形耐火組成物の固形分を１００質量部としたときの溶媒量が３１〜９０質量部、かつ、無機繊維量が７５〜２５質量％であるように構成することができる。
When the consistency is less than 100 (1/10 mm), the flexibility of the amorphous refractory composition is lowered, so that the workability is deteriorated. On the other hand, if the consistency exceeds 400 (1/10 mm), the paste-like composition drips during construction, and the shrinkage of construction such as joints due to drying increases.
The consistency of the amorphous refractory composition is adjusted and controlled by the amount of solvent excluding solids contained in the amorphous refractory composition (for example, the amount of water contained in colloidal silica and the amount of other liquid media) and the amount of inorganic fibers. obtain. Specifically, when the amount of the solvent is increased or the amount of the inorganic fibers is decreased, the consistency is increased, while when the amount of the solvent is decreased or the amount of the inorganic fibers is increased, the consistency is decreased. In the present invention, the amount of solvent when the solid content of the amorphous refractory composition is 100 parts by mass is set to 31 to 3 so that the consistency of the amorphous refractory composition is in the above range (100 to 400 (1/10 mm)). It can be configured such that 97 parts by mass and the amount of inorganic fiber is 75 to 15% by mass. Also preferably, the amount of solvent is 31 to 90 parts by weight when the solid content of the amorphous refractory composition is 100 parts by weight, so that the consistency of the amorphous refractory composition is 100 to 350 (1/10 mm). And it can comprise so that inorganic fiber amount may be 75-25 mass%.
本発明の不定形耐火組成物は、例えば、樋、溶湯保持炉、取鍋等の溶湯と接触する部材の内張材及び目地材として使用され、乾燥又は焼成することにより、任意形状を有する硬化物とすることができる。この硬化物は、イオン結合性の高いイオン結合性物質とシリカとを所定量含む材料からなるものであることから、還元力の高い金属溶湯と金属溶湯への酸素供給源であるシリカの酸化還元反応が素早く進み、硬化物表面に金属酸化膜を迅速に形成することができる。その結果、金属溶湯の浸透が生じる前に硬化物表面に金属酸化物が形成されるため、硬化物に対する金属の貼り付きを抑制し得るとともに、硬化物に対する金属溶湯の浸透が抑制され、更に金属酸化物自体、剥がれ易いものであるために、硬化物へ生じる損傷を抑制することができる。 The amorphous refractory composition of the present invention is used, for example, as a lining material and joint material for members that come into contact with molten metal such as firewood, molten metal holding furnaces, ladles, etc., and has a desired shape by drying or firing. It can be a thing. This cured product is made of a material containing a predetermined amount of an ion-binding substance having a high ion-binding property and silica, so that the metal redox having a high reducing power and the redox of silica that is an oxygen supply source to the metal molten metal. The reaction proceeds quickly, and a metal oxide film can be rapidly formed on the surface of the cured product. As a result, the metal oxide is formed on the surface of the cured product before the penetration of the molten metal occurs, so that the adhesion of the metal to the cured product can be suppressed, and the penetration of the molten metal to the cured product is suppressed. Since the oxide itself is easily peeled off, damage to the cured product can be suppressed.
次に、本発明の不定形耐火組成物を製造する方法について説明する。
本発明の不定形耐火組成物を製造する方法としては、上記無機繊維、コロイダルシリカ、イオン結合性物質等の構成材料を、上記の量で混合することにより製造することができる。
Next, a method for producing the amorphous refractory composition of the present invention will be described.
As a method for producing the amorphous refractory composition of the present invention, it can be produced by mixing constituent materials such as the inorganic fiber, colloidal silica, and ion-binding substance in the above amounts.
本発明の不定形耐火組成物の好ましい製造方法としては、無機繊維とイオン結合性物質、所望により充填材や骨材、被覆層形成剤を混合し、その後、コロイダルシリカを加え、さらに所望により増粘剤、防腐剤等他の配合成分を添加する方法が好ましい。
また、液体媒体を使用する場合は、液体媒体と被覆層形成剤の混合液に、無機繊維を添加し、その後、コロイダルシリカ、イオン結合性物質を加え、さらに所望により増粘剤、防腐剤等他の配合成分を添加する方法が好ましい。
As a preferred method for producing the amorphous refractory composition of the present invention, inorganic fibers and an ion-binding substance, if necessary, a filler, an aggregate, and a coating layer forming agent are mixed, and then colloidal silica is added. The method of adding other compounding ingredients, such as a sticking agent and a preservative, is preferable.
In addition, when using a liquid medium, inorganic fibers are added to the liquid mixture of the liquid medium and the coating layer forming agent, and then colloidal silica and an ion-binding substance are added. Further, if necessary, thickeners, preservatives, etc. A method of adding other compounding components is preferred.
上記構成材料の混合方法としては、ニーダーや加圧ニーダー等の混練装置で混練する方法を挙げることができる。 Examples of the method for mixing the constituent materials include a method of kneading with a kneader such as a kneader or a pressure kneader.
本発明の不定形耐火組成物を乾燥又は焼成することにより硬化物が得られる。この硬化物は、熱に曝されていてもよい。
なお、本発明の不定形耐火組成物及びその硬化物は、アルミニウム、亜鉛、マグネシウム等の鋳造装置において金属溶湯と直接接する部位に使用し得るものであり、前記金属に特に限定はないが、例えばアルミニウム鋳造用や亜鉛鋳造用である。
A cured product is obtained by drying or baking the amorphous refractory composition of the present invention. This cured product may be exposed to heat.
In addition, the amorphous refractory composition of the present invention and the cured product thereof can be used in a portion that is in direct contact with the molten metal in a casting apparatus such as aluminum, zinc, and magnesium, and the metal is not particularly limited. For aluminum casting and zinc casting.
次に、実施例を挙げて、本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。
なお、以下の実施例及び比較例において、コロイダルシリカの粒径及びフッ化カルシウムの平均粒径は、ナノ粒子径分布測定装置 ＳＡＬＤ−７１００（測定範囲；０．０１〜３００μｍ）（島津製作所製）を使用し、レーザ回折・散乱法により測定したものである。また、曲げ強度（ＭＰａ）はＪＩＳ Ｒ ２５５３に準じて測定したものであり、ちょう度はＪＩＳ Ｋ２２２０に準じて測定したものである。ただし、円錐が試料に進入しにくいことを考慮し、１５０ｇの錘を載せて測定したものである。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.
In the following examples and comparative examples, the colloidal silica particle size and the average particle size of calcium fluoride were measured using a nanoparticle size distribution measuring device SALD-7100 (measurement range; 0.01 to 300 μm) (manufactured by Shimadzu Corporation). And measured by the laser diffraction / scattering method. The bending strength (MPa) is measured according to JIS R 2553, and the consistency is measured according to JIS K2220. However, taking into account that the cone is difficult to enter the sample, the measurement was made with a 150 g weight.
実施例１
表１に示すように、アルミノシリケート繊維（ニチアス（株）製、ファインフレックスバルクファイバー）４０質量％、メディアン径（Ｄ５０）が０．０２μｍで９０％積算径（Ｄ９０）が０．０４μｍのコロイダルシリカをシリカ換算で３０質量％、フッ化カルシウム（平均粒径４５μｍ）１９質量％、アルミナ粉末１０質量％、増粘剤１質量％からなる固形分１００質量部に対し、水を１５質量部加えて混練し、ペースト（不定形耐火組成物）を作製した。混練直後のちょう度は、２５０（１／１０ｍｍ）であった。
Example 1
As shown in Table 1, 40% by mass of aluminosilicate fiber (manufactured by NICHIAS, fine flex bulk fiber), colloidal silica having a median diameter (D50) of 0.02 μm and a 90% integrated diameter (D90) of 0.04 μm 15 parts by mass of water is added to 100 parts by mass of solid content consisting of 30% by mass in terms of silica, 19% by mass of calcium fluoride (average particle size 45 μm), 10% by mass of alumina powder, and 1% by mass of thickener. It knead | mixed and produced the paste (amorphous refractory composition). The consistency immediately after kneading was 250 (1/10 mm).
得られたペーストを成形型へ充填し、１００℃で２４時間乾燥した後に脱型し、乾燥体（硬化物）を得た。乾燥体を加熱炉中で、空気雰囲気下、７００℃で３時間焼成して焼成体（硬化物）を得た。この焼成体の嵩密度は０．９ｇ／ｃｍ３であり、曲げ強度は２．０ＭＰａであった。 The obtained paste was filled into a mold, dried at 100 ° C. for 24 hours, and then demolded to obtain a dried product (cured product). The dried body was fired in a heating furnace at 700 ° C. for 3 hours in an air atmosphere to obtain a fired body (cured product). The fired body had a bulk density of 0.9 g / cm 3 and a bending strength of 2.0 MPa.
実施例２〜８、比較例１〜５
表１，２に示す原料を用いて、実施例１と同様にしてペースト（不定形耐火組成物）及びその乾燥体、焼成体を製造し、評価した。結果を表１，２に示す。
尚、実施例５〜８、比較例４，５の焼成体については、アルミ溶湯性を以下の方法で測定した。結果を表２に示す。
Examples 2-8, Comparative Examples 1-5
Using the raw materials shown in Tables 1 and 2, a paste (amorphous refractory composition), a dried product and a fired product thereof were produced and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
In addition, about the sintered body of Examples 5-8 and Comparative Examples 4 and 5, the molten aluminum property was measured with the following method. The results are shown in Table 2.
＜アルミ溶湯浸漬試験（アルミ溶湯性）＞
試験体をアルミニウム溶湯に浸漬させ、その後試験体を引き上げた後、アルミニウムが試験体に貼り付くか否かを評価した。
先ず、るつぼ状の電気炉内に、アルミニウムを投入した後、７００℃で溶解させた。溶解したアルミニウムに、角柱状の試験体を浸漬させる。この時、試験体上面部はアルミニウム溶湯面から出すようにする。浸漬中、電気炉は７００℃に保持し、浸漬開始２４時間後に試験体を引き上げ、引き上げた試験体を室温で冷却し、目視確認することにより、次のとおり評価した。
アルミ溶湯浸漬試験において、試験体にアルミニウムの貼り付きが観察されない場合、「「○」（無し）」と評価し、試験体にアルミニウムの貼り付きが観察される場合、「「×」（全面貼り付き）」と評価した。
<Aluminum melt immersion test (aluminum melt properties)>
After immersing the test body in molten aluminum and then pulling up the test body, it was evaluated whether or not aluminum adhered to the test body.
First, aluminum was put into a crucible-shaped electric furnace and then melted at 700 ° C. The prismatic specimen is immersed in the melted aluminum. At this time, the upper surface portion of the test body is projected from the molten aluminum surface. During immersion, the electric furnace was maintained at 700 ° C., the test specimen was pulled up 24 hours after the start of immersion, and the pulled up specimen was cooled at room temperature and visually checked to evaluate as follows.
In the molten aluminum immersion test, when aluminum sticking is not observed on the test specimen, it is evaluated as “O” (none), and when aluminum sticking is observed on the specimen, “×” (full sticking) Attached) ”.
本発明の産業上の利用可能性の分野は、特に限定されない。本発明の不定形耐火組成物及びその硬化物は、例えば、アルミニウム、亜鉛、マグネシウム等の非鉄金属の鋳造装置において、例えば樋、溶湯保持炉、取鍋等の溶湯と接触する部材を構築するための内張材および目地材として利用され得る。 The field of industrial applicability of the present invention is not particularly limited. The amorphous refractory composition of the present invention and the cured product thereof are, for example, for constructing a member that comes into contact with a molten metal such as a firewood, a molten metal holding furnace, a ladle, etc., in a non-ferrous metal casting apparatus such as aluminum, zinc, and magnesium. It can be used as a lining material and joint material.
Claims (5)
無機繊維を１５〜７５質量％と、
コロイダルシリカをシリカ換算で２１〜６５質量％と、
フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上であるイオン結合性物質を４〜４０質量％と
を含む金属鋳造用不定形耐火組成物。 In the solids,
15 to 75% by mass of inorganic fiber,
Colloidal silica is 21 to 65% by mass in terms of silica,
4 to 40% by mass of an ion-binding substance that is at least one selected from calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof, magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate An amorphous refractory composition for metal casting, comprising:
コロイダルシリカをシリカ換算で２１〜６５質量％と、
フッ化カルシウム、フッ化マグネシウム、酸化カルシウム又はその前駆体、酸化マグネシウム又はその前駆体、酸化バリウム又はその前駆体及び硫酸バリウムから選ばれる１種以上であるイオン結合性物質４〜４０質量％とを混合する金属鋳造用不定形耐火組成物の製造方法。 15 to 75% by mass of inorganic fibers,
Colloidal silica is 21 to 65% by mass in terms of silica,
4-40% by mass of an ion-binding substance that is at least one selected from calcium fluoride, magnesium fluoride, calcium oxide or a precursor thereof, magnesium oxide or a precursor thereof, barium oxide or a precursor thereof and barium sulfate. A method for producing an amorphous refractory composition for metal casting to be mixed.
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| JPS58104059A (en) * | 1981-12-15 | 1983-06-21 | ニチアス株式会社 | Fibrous formed body composition |
| JP2011093726A (en) * | 2009-10-28 | 2011-05-12 | Nichias Corp | Molded refractory for metal casting, method for manufacturing molded refractory for metal casting, castable refractory composition, and holding member of molten metal for metal casting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020051030A (en) * | 2018-09-21 | 2020-04-02 | ニチアス株式会社 | Incombustible back-up material and manufacturing method thereof |
| JP7176905B2 (en) | 2018-09-21 | 2022-11-22 | ニチアス株式会社 | Incombustible backup material and its manufacturing method |
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