JP2007528331A - 多孔性セラミックス発熱体及びその製造方法 - Google Patents
多孔性セラミックス発熱体及びその製造方法 Download PDFInfo
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- JP2007528331A JP2007528331A JP2005509249A JP2005509249A JP2007528331A JP 2007528331 A JP2007528331 A JP 2007528331A JP 2005509249 A JP2005509249 A JP 2005509249A JP 2005509249 A JP2005509249 A JP 2005509249A JP 2007528331 A JP2007528331 A JP 2007528331A
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- Prior art keywords
- heating element
- mixture
- ceramic heating
- porous ceramic
- binder
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- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000010438 heat treatment Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 16
- 239000011147 inorganic material Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002612 dispersion medium Substances 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 238000009628 steelmaking Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical group [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- QGBLCIBATKETJC-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;manganese(2+) Chemical compound [Mn+2].O1B([O-])OB2OB([O-])OB1O2 QGBLCIBATKETJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 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
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 229910001562 pearlite Inorganic materials 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- -1 polysiloxane Polymers 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
- C04B35/6316—Binders based on silicon compounds
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1328—Waste materials; Refuse; Residues without additional clay
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
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- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/19—Alkali metal aluminosilicates, e.g. spodumene
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- C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
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- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
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Abstract
本発明の多孔性セラミックス発熱体は、９９．００〜９９．９２ｗｔ％の、無機質材料と、粘結剤と、導電性材料と、硬化剤と、結合剤と、分散媒とを混合した混合物に、０．０８〜１．００ｗｔ％の気泡剤が添加されて混合される。このような構成の多孔性セラミックス発熱体は、セラミックス発熱体に形成した多孔性気泡の結合力が強くなるため、全体として構造が硬化する効果がある。
Description
本発明は多孔性セラミックス発熱体及びその製造方法に関し、特に無機質材料として製鉄所から排出される製鋼スラグ及び高炉スラグをリサイクルして用い、多孔性を持たせるための気泡剤（ｆｏａｍｉｎｇ ａｇｅｎｔ）としてメチルハイドロゲンポリシロキサン（ｍｅｔｈｙｌ ｈｙｄｒｏｇｅｎ ｐｏｌｙｓｉｌｏｘａｎｅ）を添加した多孔性セラミックス発熱体、及びこのような原料により低温で多孔性セラミックス発熱体を製造する多孔性セラミックス発熱体の製造方法に関する。
一般に、多孔性セラミックスは、セラミックスの内部に人工的に多数の気孔を形成したものであって、比重が小さく軽いことから特定の範囲内において軽量の建築材として用いられ、さらに各種のフィルタ、焼成用の具材、脱臭剤、断熱材、防音材、発熱材等の様々な用途で用いられている。
このような多孔性セラミックス発熱体及びその製造方法として、従来では次のような多孔性セラミックス発熱体及びその製造方法が通常採用されていた。
まず、従来の多孔性セラミックス発熱体は、アルミノケイ酸塩ヒドロゲルと、炭化物、窒化物又は酸化物等のセラミック粉末と、０．１〜０．２％程度のアルミニウム粒子と、界面活性剤である０．４〜０．８％程度のシリコングリコール及びゲル強化剤である１〜４％程度のシリカとを混合してなる混合物である。
このような多孔性セラミックス発熱体の製造方法は、粉末状の金属とアルカリ溶液とを反応させた後、前記混合物をアルミン酸塩スラリーに入れ、所望の形状に成形する。
すると、前記成形体においては、水素が発生しつつ多孔性セラミックス発熱体となり、後に水で洗浄してアルカリを除去し焼結すると、所望の多孔性セラミックス発熱体が得られる。
ところが、このような従来の多孔性セラミックス発熱体は、内部に形成した多数の気孔の結合力が弱く、全体として多孔性セラミックス発熱体構造の機械的強度が弱く、熱を保存する機能が低下してしまうという問題点を有している。
また、このような従来の多孔性セラミックス発熱体の製造方法は、多孔性を持たせるために有機物をセラミックススラリーと混合した後、焼成プロセスを経て多孔性を得たものである。
ところが、このような多孔性セラミックス発熱体は、高温で加熱した時に、添加した有機性の気泡剤が炭化しながら有毒ガスを発生する。
そして、１１００℃以上の高い焼結温度の条件と工程の複雑性から、形状の制限と経済面で不利であるという問題点を有している。
本発明は前記問題点に鑑みなされたものであり、セラミックス発熱体に形成した気孔の結合力を増加させて、全体として機械的強度及び蓄熱性能が向上できる多孔性セラミックス発熱体を提供することを目的とする。
また、本発明の他の目的は、低温で前記ような多孔性セラミックス発熱体が製造できる多孔性セラミックス発熱体の製造方法を提供することにある。
前記目的を達成するために、本発明の多孔性セラミックス発熱体は、９９．００〜９９．９２ｗｔ％の、無機質材料と、粘結剤（バインダ）と、導電性材料と、硬化剤と、結合剤と、分散媒とを混合した混合物に、０．０８〜１．００ｗｔ％の気泡剤が添加されて混合される。
ここで、前記無機質材料は、製鋼スラグと、高炉スラグと、アルミナと、ムライトと、炭化ケイ素と、炭化チタンと、窒化ケイ素と、窒化アルミニウムと、長石と、ゼオライトと、カオリンと、絹雲母と、滑石と、雲母と、イライトと、パーライトと、蛭石と、海泡石と、珪藻土との少なくとも一つの成分を含んだものであり、前記混合物の４０〜６６ｗｔ％であることが好ましい。
また、前記粘結剤はケイ酸ジルコニウムであり、前記混合物の２〜６ｗｔ％であることが好ましい。
また、前記導電性材料は黒鉛であり、前記混合物の８〜１２ｗｔ％であることが好ましい。
また、前記硬化剤はホウ酸亜鉛と、ホウ酸マンガン及びホウ酸マグネシウムのいずれかであり、前記混合物の３〜３３ｗｔ％であることが好ましい。
また、前記結合剤はアルカリ金属ケイ酸塩であり、前記混合物の１６〜３７ｗｔ％であることが好ましい。
また、前記分散媒は水であり、前記混合物の１〜８ｗｔ％であることが好ましい。
また、前記気泡剤はメチルハイドロゲンポリシロキサンであることが好ましい。
また、前記結合剤及び硬化剤は重縮合反応を行うことが好ましい。
そして、前記多孔性セラミックス発熱体を製造する方法は、（１）無機質材料と、前記無機質材料に粘結性を持たせる粘結剤と、気泡を形成する気泡剤と、強度増加のための硬化剤とを１次混合する工程と、（２）前記１次混合した混合物が相互結合するようにする結合剤と、前記結合剤に流動性を持たせるための分散媒を添加して２次混合及び混練する工程と、（３）前記２次混合及び混練した混合物をモールドに装入する工程と、（４）前記モールドに装入した混合物を常温で定置して、前記混合物中に気孔を形成する工程と、（５）前記気孔が形成された混合物を１次乾燥する工程と、（６）前記１次乾燥した混合物を前記モールドから脱型させる工程と、及び（７）前記モールドから脱型した前記１次乾燥混合物を２次乾燥する工程と、を含む。
ここで、前記１次乾燥温度は３０℃〜１２０℃の範囲であることが好ましい。
また、前記２次乾燥温度は８０〜３５０℃の範囲であることが好ましい。
本発明の多孔性セラミックス発熱体及びその製造方法によれば、次のような効果が得られる。
第一に、製鉄所から排出される製鋼スラグと高炉スラグを無機質材料として用いることで、資源のリサイクル及び環境親和の利得が得られる。
第二に、セラミックス発熱体中に形成した多孔性気泡の結合力が強くなり、全体の構造が硬化する多孔性セラミックス発熱体を提供することができる。
第三に、気泡剤としてメチルハイドロゲンポリシロキサンを用いることで、気泡の生成を促進し、低温での焼成作業時に有害ガスの排出を抑制することができる。
本発明の多孔性セラミックス発熱体は、９９．００〜９９．９２ｗｔ％の、無機質材料と、粘結剤と、導電性材料と、硬化剤と、結合剤と、分散媒とを混合した混合物９９．００〜９９．９２ｗｔ％に、０．０８〜１．００ｗｔ％の気泡剤が添加されて混合されたものである。
ここで、前記結合剤と硬化剤は重縮合反応により四面体の構造を有し、この四面体の構造は金属と架橋したり、金属を固定したりしてケイ酸ゲルを形成する。
前記無機質材料は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％中に４０〜６６ｗｔ％が含まれた不燃材であり、最終成形物の骨格のための充填物である。
この無機質材料は、製鋼スラグ（ｓｔｅｅｌ ｓｌａｇ）及び高炉スラグ（ｂｌａｓｔ−ｆｕｒｎａｃｅ ｓｌａｇ）等の産業副産物や；金属酸化物系のアルミナ（Ａｌ２Ｏ３）、ムライト（ｍｕｌｌｉｔｅ；３Ａｌ２Ｏ３・２ＳｉＯ２）；金属炭化物系の炭化ケイ素（ＳｉＣ）、炭化チタン（ＴｉＣ）；金属窒化物系の窒化ケイ素（Ｓｉ３Ｎ４）、窒化アルミニウム（ＡｌＮ）；アルカリ土類金属系の長石（ｆｅｌｄｓｐａｒ）、ゼオライト（ｚｅｏｌｉｔｅ）、カオリン（ｋａｏｌｉｎ）、絹雲母（ｓｅｒｉｃｉｔｅ）、滑石（ｔａｌｃ）、雲母（ｍｉｃａ）等と；軽量の材料であるイライト（ｉｌｌｉｔｅ）、パーライト（ｐｅａｒｌｉｔｅ）、蛭石（ｖｅｒｍｉｃｕｌｉｔｅ）、海泡石（ｓｅｐｉｏｌｉｔｅ）、珪藻土（ｄｉａｔｏｍａｃｅｏｕｓ ｅａｒｔｈ）等を単独又は２種以上混合して用いることができる。
特に、本発明において用いられる製鋼スラグと高炉スラグとは、下表１のような成分を含む。この表１は光陽製鉄所（Ｋｗａｎｇｙａｎｇ Ｉｒｏｎ Ｗｏｒｋｓ ｏｆ ＰＯＳＣＯ）から提供したものである。下表の成分中、ＣａＯはアルカリと反応すれば硬化するような潜在水硬性の特性があり、ＳｉＯ２、Ａｌ２Ｏ３、ＭｎＯは遠赤外線を放射する特性があるため、本発明の最終成形物の骨格をなすための原料として用いることが好ましい。
そして、前記製鋼スラグ及び高炉スラグは、その粒度が様々に排出されるが、その中でも粒度が０．２ｍｍ以下の大きさを有するものを用いることが好ましい。もし粒度の大きさが０．２ｍｍを超えると、粒子と粒子間の孔隙が大きく形成されて後述する気泡の結合断面積が小さく、外部の圧力に多少弱まる現象が現れ、さらに粒子の比重により気泡力が低下する。
前記粘結剤は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％中に２〜６ｗｔ％が含まれたケイ酸ジルコニウムであり、これらの粒子間に粘結性を持たせるためのものである。このケイ酸ジルコニウムは、アルカリ金属ケイ酸塩と混合して１００℃以上の乾燥温度で気泡が早く成長することを防止する役割と、機械的、熱的強度及び耐化学性を増大させる目的で用いる。そして、ケイ酸ジルコニウムの平均粒度は、粘結性の良い１μｍ以下のものを用いることが好ましい。
前記導電性材料は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％の中に８〜１２ｗｔ％含まれた黒鉛である。この黒鉛は投入量が増加するほど抵抗値が減少して低電圧でも電流の流れが良いが、摩擦係数が少ないことから、投入し過ぎると結合力が減少して機械的強度が低下するので、８〜１２ｗｔ％含まれることが好ましい。
前記硬化剤は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％中に３〜３３ｗｔ％が含まれたホウ酸亜鉛、ホウ酸マンガン、ホウ酸マグネシウムのいずれかの成分である。この硬化剤はアルカリ金属ケイ酸塩の硬化反応のためのものであり、平均粒度は０．０１〜０．０２ｍｍであることが好ましい。
前記結合剤は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％中に１６〜３７ｗｔ％が含まれたアルカリケイ酸塩である。このアルカリケイ酸塩は無機質材料を結合するためのものであり、Ｎａ２Ｏ・ｎＳｉＯ２［ｎ＝２．２〜３．４］・Ｈ２ＯのＮａ−ケイ酸塩、Ｌｉ２Ｏ・ｎＳｉＯ２［ｎ＝２．５〜８．５］・Ｈ２ＯのＬｉ−ケイ酸塩、Ｋ２Ｏ・ｎＳｉＯ２［ｎ＝１．５〜５．１］・Ｈ２ＯのＫ−ケイ酸塩を単独又は併用して用いることができる。ここで、ｎはモル比を示す。好ましくは、産業現場で汎用的に多用し、１．３８（２５℃）以上の比重と３．０〜３．４モル比の規格を有した安価のＮａ−ケイ酸塩である。
前記分散媒は、前記混合物を１００ｗｔ％とした時、この混合物１００ｗｔ％中に１〜８ｗｔ％含まれた水である。
前記気泡剤は、反応性のシリコンオイルの一種であるメチルハイドロゲンポリシロキサンであって、繊維撥水剤の原料油、消火器粉末や化粧品用粉体の撥水処理、金属、ガラス、陶磁器、カーボン抵抗器等の表面処理のために用い、加熱や、微量の酸又はアルカリ金属等により水素を発生しながら粘度が漸増してゲル化する特性を有する。従って、前記混合物に添加すると、水素が発生して常温で徐々に気泡が形成されつつ成長するが、全体の成形組成物の体積が５〜６０％増加するようになる。そして、このメチルハイドロゲンポリシロキサンは、熱処理プロセスにおいて疏水性のメチル基が水を撥ねるため、最終成形物は撥水性をも有するようになる。
このような成分を有した多孔性セラミックス発熱体の製造方法は、図１に示した通りである。
図面を参照すれば、前記成分比を有した無機質材料と、粘結剤と、気泡剤と、硬化剤とを１次混合する（Ｓ１０）。このように混合した混合物が相互結合するように結合剤を入れ、この結合剤に流動性を持たせるために分散媒を添加した後、２次混合する（Ｓ２０）。そして、この混合物内に気孔が形成されるようにモールドに装入（Ｓ３０）して常温で定置させる（Ｓ４０）。このように混合物内に気孔を成長させた後、３０〜１２０℃で１次乾燥する（Ｓ５０）。そして、前記モールドから脱型（Ｓ６０）させて８０〜３５０℃で２次乾燥する（Ｓ７０）。このように１，２次の乾燥プロセスを経れば、混合物内に形成した気孔が骨格を備えるようになる。その後、所望の方向に表面加工や色相をコートするようになる（Ｓ８０）。
このような本発明を実施形態により説明すると次の通りであるが、本発明は下記の実施形態により限定されるものではない。
次の実施形態において、物性の項目中、圧縮強度試験はＫＳＦ４００４、即ち、中空のコンクリートブロックの圧縮強度試験法に基づいた。
前記実施形態のＡ、Ｂ、Ｃは、気泡剤であるメチルハイドロゲンポリシロキサンの成分だけを変化させたものである。
前記実施形態において、Ａ、Ｂ、Ｃの物性項目を参照すると、気泡剤の添加量が増加するほど過剰の気泡が発生して、即ち、平均気孔率が増加して、圧縮強度が低下することが判る。そして、面積抵抗値が急激に高まるが、このことは、気泡剤特有の撥水能力により気孔間の界面が緻密とならないためである。このように面積抵抗値が高い多孔性セラミックス発熱体を暖房発熱体として用いる場合、１２０ボルト以上の高い電圧値を要する。このため、１．００ｗｔ％未満の気泡剤を用いることが好ましい。
前記実施形態のＤ、Ｅ、Ｆは、分散媒である水の成分だけを変化させたものである。
前記実施形態のＤ、Ｅ、Ｆの物性項目を参照すると、水の添加量が増加するほど圧縮強度が低下することが判る。このことは、水の添加によりこれらの組成物の流動性が増加するためである。このため、分散媒としての水は、前記混合物を１００％とした時、８ｗｔ％未満を添加することが好ましい。
図２及び図３は前記実施形態のＡについての走査電子顕微鏡写真を示したのである。
写真を参照すると、前記実施形態のＡの成分比による多孔性セラミックス発熱体は、相互連結した気孔を有し、平均気孔の大きさが２０μｍで気孔の大きさガが一様であることが確認できる。そして、平均気孔率は４８％であるが、これは１−（多孔性セラミックス発熱体の密度／原料粒子の密度）により算出されたものである。
このような多孔性セラミックス発熱体は、上述した構成成分で前記製造方法により製造すれば、従来の高温加熱時における有機性の気泡剤による有毒ガスの発生が無くなり、かつ低温の焼結温度及び工程の簡素化から、安価で様々な形状の多孔性セラミックス発熱体を製造することができる。
上述したように、本発明の多孔性セラミックス発熱体及びその製造方法は、発熱材、断熱材、防音材等軽量の建築材を作製する分野等において有効に用いられる。
Claims (12)
- ９９．００〜９９．９２ｗｔ％の、無機質材料と、粘結剤と、導電性材料と、硬化剤と、結合剤と、分散媒とを混合した混合物に、０．０８〜１．００ｗｔ％の気泡剤が添加されて混合されたことを特徴とする多孔性セラミックス発熱体。
- 前記無機質材料は、製鋼スラグと、高炉スラグと、アルミナと、ムライトと、炭化ケイ素と、炭化チタンと、窒化ケイ素と、窒化アルミニウムと、長石と、ゼオライトと、カオリンと、絹雲母と、滑石と、雲母と、イライトと、パーライトと、蛭石と、海泡石と、珪藻土との少なくとも一つの成分を含んだものであり、前記混合物の４０〜６６ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記粘結剤はケイ酸ジルコニウムであり、前記混合物の２〜６ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記導電性材料は黒鉛であり、前記混合物の８〜１２ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記硬化剤はホウ酸亜鉛と、ホウ酸マンガン及びホウ酸マグネシウムのいずれかであり、前記混合物の３〜３３ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記結合剤はアルカリ金属ケイ酸塩であり、前記混合物の１６〜３７ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記分散媒は水であり、前記混合物の１〜８ｗｔ％であることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記気泡剤はメチルハイドロゲンポリシロキサンであることを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 前記結合剤及び硬化剤は、重縮合反応を行うことを特徴とする請求項１記載の多孔性セラミックス発熱体。
- 多孔性セラミックス発熱体の製造方法であって、
無機質材料と、前記無機質材料に粘結性を持たせる粘結剤と、気泡を形成する気泡剤と、強度増加のための硬化剤とを１次混合する工程と、
前記１次混合した混合物が相互結合するようにする結合剤と、前記結合剤に流動性を持たせるための分散媒を添加して２次混合及び混練する工程と、
前記２次混合及び混練した混合物をモールドに装入する工程と、
前記モールドに装入した混合物を常温で定置して、前記混合物中に気孔を形成する工程と、
前記気孔が形成された混合物を１次乾燥する工程と、
前記１次乾燥した混合物を前記モールドから脱型させる工程と、及び
前記モールドから脱型した前記１次乾燥した混合物を２次乾燥する工程と、
を含むことを特徴とする多孔性セラミックス発熱体の製造方法。 - 前記１次乾燥温度は、３０〜１２０℃の範囲であることを特徴とする請求項１０記載の多孔性セラミックス発熱体の製造方法。
- 前記２次乾燥温度は、８０〜３５０℃の範囲であることを特徴とする請求項１０記載の多孔性セラミックス発熱体の製造方法。
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| KR1020040062267A KR100595011B1 (ko) | 2004-08-07 | 2004-08-07 | 다공성 세라믹스 발열체 및 그 제조방법 |
| PCT/KR2004/002502 WO2006016730A1 (en) | 2004-08-07 | 2004-09-24 | Porous ceramic heating element and method of manufacturing thereof |
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| Publication Number | Publication Date |
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| JP2007528331A true JP2007528331A (ja) | 2007-10-11 |
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| Country | Link |
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| US (1) | US7619187B2 (ja) |
| JP (1) | JP2007528331A (ja) |
| KR (1) | KR100595011B1 (ja) |
| CN (1) | CN1308263C (ja) |
| HK (1) | HK1084933A1 (ja) |
| WO (1) | WO2006016730A1 (ja) |
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| WO2019102530A1 (ja) * | 2017-11-21 | 2019-05-31 | アレブリオ合同会社 | ゼオライト含有組成物、ゼオライト含有硬化体、ゼオライト含有組成物の製造方法及びゼオライト含有硬化体の製造方法 |
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| US8196320B2 (en) | 2007-10-22 | 2012-06-12 | Nike, Inc. | Article of footwear with interchangeable bootie |
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| TWI554488B (zh) * | 2010-10-18 | 2016-10-21 | 國立聯合大學 | 廢棄泥灰再利用製備多孔陶瓷之方法 |
| KR101524637B1 (ko) * | 2013-04-19 | 2015-06-03 | 주식회사 진인 | 마이크로파에 의해 발열되는 발열체 조성물, 이를 포함하는 마이크로파에 의해 발열되는 균일 발열 장치 및 그 시공 방법 |
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- 2004-09-24 CN CNB2004800005071A patent/CN1308263C/zh not_active Expired - Fee Related
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018514500A (ja) * | 2015-05-06 | 2018-06-07 | エン−テック コーポレーションＥｎ−Ｔｅｃｈ Ｃｏｒｐｏｒａｔｉｏｎ | 非ポルトランドのセメント系材料の作製及び適用の為のシステム及び方法 |
| WO2019102530A1 (ja) * | 2017-11-21 | 2019-05-31 | アレブリオ合同会社 | ゼオライト含有組成物、ゼオライト含有硬化体、ゼオライト含有組成物の製造方法及びゼオライト含有硬化体の製造方法 |
| JPWO2019102530A1 (ja) * | 2017-11-21 | 2020-12-17 | アレブリオ合同会社 | ゼオライト含有組成物、ゼオライト含有硬化体、ゼオライト含有組成物の製造方法及びゼオライト含有硬化体の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070003750A1 (en) | 2007-01-04 |
| KR20060013618A (ko) | 2006-02-13 |
| US7619187B2 (en) | 2009-11-17 |
| HK1084933A1 (en) | 2006-08-11 |
| CN1697791A (zh) | 2005-11-16 |
| WO2006016730A1 (en) | 2006-02-16 |
| KR100595011B1 (ko) | 2006-06-30 |
| CN1308263C (zh) | 2007-04-04 |
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