CN102245539A - 板砖的制造方法及板砖 - Google Patents
板砖的制造方法及板砖 Download PDFInfo
- Publication number
- CN102245539A CN102245539A CN2009801502869A CN200980150286A CN102245539A CN 102245539 A CN102245539 A CN 102245539A CN 2009801502869 A CN2009801502869 A CN 2009801502869A CN 200980150286 A CN200980150286 A CN 200980150286A CN 102245539 A CN102245539 A CN 102245539A
- Authority
- CN
- China
- Prior art keywords
- plate brick
- quality
- aluminium
- oxidation
- resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011449 brick Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000007789 gas Substances 0.000 claims abstract description 63
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910017083 AlN Inorganic materials 0.000 claims description 57
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- 238000006703 hydration reaction Methods 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 239000004411 aluminium Substances 0.000 claims description 29
- 230000036571 hydration Effects 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 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 8
- 229910052863 mullite Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052845 zircon Inorganic materials 0.000 claims description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 32
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 238000010304 firing Methods 0.000 abstract description 17
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 238000007788 roughening Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- 229910010271 silicon carbide Inorganic materials 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229920003987 resole Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- -1 norbide Chemical compound 0.000 description 4
- 238000012384 transportation and delivery Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 229910018134 Al-Mg Inorganic materials 0.000 description 3
- 229910018467 Al—Mg Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910001374 Invar Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910026551 ZrC Inorganic materials 0.000 description 3
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910021365 Al-Mg-Si alloy Inorganic materials 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62665—Flame, plasma or melting treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—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
- C04B35/101—Refractories from grain sized mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—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
- C04B35/101—Refractories from grain sized mixtures
- C04B35/1015—Refractories from grain sized mixtures containing refractory metal compounds other than those covered by C04B35/103 - C04B35/106
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—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
- C04B35/101—Refractories from grain sized mixtures
- C04B35/103—Refractories from grain sized mixtures containing non-oxide refractory materials, e.g. carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—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
- C04B35/101—Refractories from grain sized mixtures
- C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3865—Aluminium nitrides
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/401—Alkaline earth metals
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—Aluminium
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/424—Carbon black
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/652—Reduction treatment
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
- C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
-
- 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
- C04B2235/721—Carbon content
-
- 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
- C04B2235/722—Nitrogen content
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- 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
- C04B2235/9684—Oxidation resistance
Abstract
本发明提供一种板砖的制造方法及板砖,在含有铝及/或铝合金的耐火原料配合物中添加有机结合剂后混匀,成形后,在氮气环境下,在1000℃以上1400℃以下进行烧成,至少在炉内环境温度为300℃以上时,为氮气环境,而且在炉内环境温度为1000℃以上时,使环境中的氧气浓度保持在100体积ppm以下,且一氧化碳气体浓度和二氧化碳气体浓度的合计保持在1.0体积%以下。由此,在板砖中生成很多细微、均匀的氮化铝,可防止碳化铝的生成引起的水化导致组织劣化,同时可抑制碳结合的氧化,提高抗表面粗糙性。
Description
技术领域
本发明涉及在用于控制熔融金属的流量的滑动水口装置中使用的板砖的制造方法及板砖。
背景技术
在钢的制造过程中,使用滑动水口装置来用于控制从浇包、浇口盘等熔融金属容器中排出的钢液的流量。在该滑动水口装置上使用2块或3块具有浇注孔的耐火材料制板砖。该板砖重叠,在表面施加有压力的状态下滑动,通过调节浇注孔的开度来调节钢液流量。
该板砖一般使用氧化铝·碳质材料,根据其制造方法而分为烧成型和非烧成型。烧成型比非烧成型的成本高,但是由于其强度优异,所以被用于比较大型的板砖。
在许多情况下,板砖的寿命根据作为工作面的滑动面所受的磨损而定。该板砖滑动面的磨损(以下称“表面粗糙”)原因一般被认为是热冲击所导致的组织松弛;与钢液发生化学反应所至;滑动导致的磨耗;或者碳结合的氧化等。
作为改善抗表面粗糙性的方法,例如为了提高耐热冲击性,采用了低热膨胀率的氧化锆莫来石或锆刚玉等耐火原料。而且,为了提高耐腐蚀性,正在研究讨论使用不易与熔渣发生反应的电熔刚玉等高纯度、致密原料以及碳的种类、碳含量的优化等。为了提高针对滑动的耐磨性,采用了如下方法,即通过优化所使用原料的粒度构成等而使组织致密化、高强度化,并且提高滑动面的研磨精度等方法。另外,为了防止氧化,添加碳化硅、碳化硼、氮化铝等防氧化剂。
如此,为了提高板砖的抗表面粗糙性,正在对各种耐火原料的组合进行研究讨论。同时还在研究讨论烧成条件等的制造方法的优化。
作为烧成型板砖的一般制造方法,例如存在如下方法:在含有硅等金属的耐火原料配合物中添加有机结合剂混匀,成形后,将成形体放入充满焦炭粒的容器内,在1000℃以上的温度下进行烧成。该烧成型板砖的结合组织的主体是碳结合和碳化硅结合,其中夹杂有氧化物的烧结结合等。碳结合与陶瓷结合相比具有低弹性率,耐热冲击性优异。而且,碳化硅结合具有赋予强度及耐氧化磨耗性的效果,由此构成抑制使用时磨损的优异的结合组织。但是,当碳化硅氧化后会成为SiO2,与FeO、CaO等外来成分发生反应,从而生成低融点物质,因此耐腐蚀性降低。而且,SiO2存在如下问题,在高温下容易作为SiO气体而消失,在长时间使用时效果难以保持。
而且,还知道在烧成型中除了硅以外还使用铝。例如在专利文献1中,公开了如下内容:使用包含铝的耐火原料配合物,通过在碳中的还原环境下进行烧成,可获得碳化铝、氮化铝的反应烧结结合。另外,还记载着与现有的碳结合类型相比,机械强度及耐腐蚀性优异。
但是,当将专利文献1所示的基于铝的添加而包含氮化铝结合的类型的板砖在碳中的还原环境下进行烧成时,会生成大量的碳化铝,因此存在抗水化性劣化的问题。具体而言,根据操作情况等因素而被拆下,再使用时等,由于被放置,在下次使用之前花费时间,所以会产生如下问题:碳化铝因大气中的水蒸气而被水合,从而砖的强度降低,耐用性降低。另外,在使用后回收,再利用的情况下等,由于将回收的砖再次进行研磨、加工,所以碳化铝因加工时的水而被水合,从而砖的强度降低,耐用性降低。在专利文献1中,还公开了一种在氮气环境下进行烧成的方法。但是,仅仅在氮气环境下进行烧成时,由于被烧成物即成形体中所含的酚醛树脂等结合剂分解而产生的挥发成分中的CO、CO2等气体,氮化铝的生成受到阻碍。因此,板砖的抗表面粗糙性的改善效果不充分,无法得到所期待程度的效果。
而且,作为烧成条件,在专利文献2中公开了在氧气分压为10~10000ppm下进行弱氧化环境烧成的技术。
但是,即使在专利文献2的烧成条件下,在烧结基于添加铝而包含氮化铝结合的板砖时,如前所述,由于被烧成物即成形体内所含的酚醛树脂等结合剂分解而产生的挥发成分中的CO、CO2等气体,氮化铝的生成受到阻碍。因此,氮化铝的收获率低,无法得到令人满意的抗氧化性(抗表面粗糙性)的改善效果。
而且,在专利文献2的烧成条件下,虽然容许存在CO及CO2(参照专利文献2的0022段),但是,如果在烧成环境中存在大量的CO及CO2,则会产生阻碍通过氮气和铝发生反应而生成氮化铝的问题。
如此,虽然板砖的抗表面粗糙性正在通过所使用的原料的组合以及烧成条件而逐渐得到改善,但是,在现有的技术上存在上述问题,即使是现在,影响板砖寿命的原因依然是表面粗糙。
专利文献1:日本特开昭57-27971号公报
专利文献2:日本特开2003-171187号公报
发明内容
本发明所要解决的课题是提高烧成型板砖尤其是具有氮化铝结合的板砖的抗氧化性,提高抗表面粗糙性。
本发明者根据对使用后的板砖的解析,认为作为防止表面粗糙的措施,必须抑制使用时的碳质原料、碳结合的氧化,抑制水化导致的组织劣化,为此,提高碳结合的抗氧化性是非常重要的。而且,由于氮化铝被认为比碳化硅或碳化硼作为防氧化剂的效果高,因此,为了提高板砖的抗氧化性,而着眼于具有氮化铝结合的板砖。而且,通过对其烧成环境进行各种各样的研究讨论,结果发现烧成过程中的氮气以外的微量气体对板砖的抗氧化性给予很大影响。
即,本发明提供一种板砖的制造方法,其特征在于,在含有铝及/或铝合金的耐火原料配合物中添加有机结合剂后混匀,成形后,在氮气环境下,在1000℃以上1400℃以下进行烧成,至少在炉内环境温度为300℃以上时,为氮气环境,而且在炉内环境温度为1000℃以上时,使环境中的氧气浓度保持在100体积ppm以下,且一氧化碳气体浓度和二氧化碳气体浓度的合计保持在1.0体积%以下。
下面,对本发明的特征进行具体说明。
在板砖的成形体中含有酚醛树脂等有机结合剂,当成形体被加热后,通过有机结合剂的缩合而产生水。并且,当温度上升后,硬化的有机结合剂的一部分会分解,产生水蒸气、一氧化碳气体、二氧化碳气体、碳化氢系气体等。另外,在烧成环境中随时都容易混入大气,在大气中含有氧气、二氧化碳气体、水蒸气等。氧气、一氧化碳气体或二氧化碳气体在烧成时会与板砖中的铝发生反应,生成氧化铝,阻碍氮化铝生成。
另外,在烧成时,从1000℃左右开始,在板砖中,铝的熔融物或气化物与氮气发生反应,开始生成氮化铝。因此,为了提高氮化铝的收获率,在1000℃以上时,需要降低阻碍生成氮化铝的气体即氧气、一氧化碳气体及二氧化碳气体的浓度。具体而言,使氧气浓度为100体积ppm以下,且使一氧化碳气体浓度和二氧化碳气体浓度的合计为1.0体积%以下。
由于氧气与铝的反应性较高,即使是微量也会对铝进行氧化,因此,其浓度越低越优选,即使为0也可以。氧气浓度如果超过100体积ppm,则氮化铝的生成量不充分,从而抗氧化性不充分。
一氧化碳气体及二氧化碳气体与氧气相比虽然反应性相当低,但是也会与铝发生反应,生成氧化铝,因此,其浓度越低越好,即使为0也可以。如果它们的合计超过1.0体积%,则氮化铝的生成量不充分,从而抗氧化性不充分。
另外,烧成温度不足1000℃时,氮化铝的生成不充分,如果烧成温度超过1400℃,则陶瓷结合过于发达,呈现高弹性化,导致耐热冲击性下降。
在这种条件下制造的板砖中,烧成过程中熔融的铝或者气化后的铝在基质上会与环境中的氮气发生反应,生成氮化铝。这一点通过以下内容可以明显看出,如对本发明的板砖进行SEM观察的结果即图1所示,氮化铝呈直径为0.1~0.2μm的微细纤维状,填充了组织中的空间。
本发明的板砖中的氮化铝以上述形态存在,所以活性非常高。即,在使用时,虽然在砖的工作面上,工作面的砖中的碳因钢液中的FeO等而被氧化,但此时生成的CO气体会立刻与氮化铝发生反应。于是,生成氧化铝和碳,因此形成由氧化铝和碳构成的新组织,使基质组织致密化。由于通过这样的机理,一时被氧化的碳会再生,而且表面的组织会致密化从而抑制FeO等的浸透,因此可以认为,碳结合的氧化受到抑制,提高了抗氧化性,进而赋予了抗表面粗糙性。
另一方面,像现有技术那样,当在耐火原料配合物中添加粉末状的氮化铝时,难以均匀分散,其粒径也较大。因此,与通过反应而生成的氮化铝相比,对提高抗氧化性所起的作用差,而且也不会形成结合组织。
另外,根据本发明的制造方法,能够使耐火原料配合物中含有4质量%以上20质量%以下的氧化锆、氧化锆莫来石及锆刚玉中的1种以上的ZrO2成分。
在埋设于焦炭粒中进行烧成的现有一般的板砖的制造方法中,如果在含有铝及/或铝合金的耐火原料配合物中使用含有氧化锆的原料,在烧成后则容易产生龟裂。虽然该理由尚不明确,但是,在高温下,焦炭粒中的氧气会与焦炭发生反应,生成一氧化碳气体,而且,在被烧成物中含有强还原剂即铝,因此,耐火砖的气孔中形成强还原环境。可以认为,在高温条件下、强还原环境下,氧化锆被还原,变为容易生成锆或碳化锆。推测锆或碳化锆由于进一步与微量的氧气进行伴随体积显著变化的强烈反应,因而生成氧化锆,产生龟裂。
另一方面,在本发明的制造方法中,即使使用含有氧化锆的原料,烧成后也不产生龟裂。可以认为其理由如下:烧成环境以氮气为主体,还原性气体即一氧化碳等的气体浓度较少,在1.0体积%以下,所以不会形成强还原环境,抑制了锆或碳化锆的生成。因此,采用本发明的制造方法制造的板砖能够通过含有氧化锆的原料提高耐热冲击性,所以抗表面粗糙性有了格外提高。
当耐火原料配合物中的氧化锆、氧化锆莫来石以及锆刚玉中的1种以上的ZrO2成分不足4质量%时,则不能充分获得提高耐热冲击性的效果,而如果超过20质量%,则存在耐FeO性降低、耐用性降低的情况。
并且,根据本发明的制造方法,还能够使耐火原料配合物中含有0.5~5质量%的硅。人们知道,添加铝后,如果含有碳,在烧成过程中熔融的铝和碳则会发生反应,生成部分碳化铝。碳化铝虽然容易发生水合,从而成为使组织崩溃的重要原因,但是人们知道,添加硅后,硅则会固溶于碳化铝,从而难以水合。由此,抗水化性得到改善。当硅不足0.5质量%时,则无法充分获得防止水化的效果,而如果超过5质量%,则存在耐FeO性及耐CaO性降低、耐用性降低的情况。
另一方面,本发明的板砖为,氮化铝的含量为1.5质量%以上7.0质量%以下,在用高压釜进行的水化试验中,在0.49MPa的加压条件下,在150℃下保持3小时后基于水合反应的重量增加率为0.5%以下。
配合在耐火原料配合物中的铝或铝合金、硅等金属,在烧成时生成碳化铝或氮化铝、氧化铝、碳化硅、氮化硅、二氧化硅等碳化物、氮化物和氧化物。
在上述物质中,氮化铝在使用时,会与砖中的碳因钢液中的FeO等而在砖的工作面上氧化后生成的CO气体立刻发生反应。并且,由于生成氧化铝和碳,所以使基质的组织致密化,因此抗氧化性的效果较高。氧化铝则无法得到该抗氧化性的效果,氮化铝的生成量越多,抗氧化性的效果便越高。当氮化铝生成量为1.5质量%以下时,则不能充分获得抗氧化性的效果。另一方面,虽然碳化铝也可以期待获得同样的抗氧化性效果,但是碳化铝会由于水合反应,产生甲烷、碳化物、乙炔等气体,生成氢氧化铝。通过该反应,体积会膨胀,从而产生龟裂,因此,砖会崩溃,难以作为耐火物使用。在碳化铝的水合反应中,由于生成氢氧化铝,所以重量增加。如果用高压釜进行水化试验时的重量增加率超过0.5%,在长期保管或者在实际炉中再使用、或再生使用时,将产生水合后的滑动面剥离、出现龟裂等故障,因此不能获得充分的效果。
氮化铝与碳化铝相比,虽然难以发生水合反应,但是当大量含有时,因水合反应会产生氨气,生成氢氧化铝。与碳化铝相同,在该水合反应中也会生成氢氧化铝,所以重量增加。如果氮化铝的含量超过7.0质量%,则基于水合反应的重量增加率将超过0.5%,在长期保管或者在实际炉中的再使用、或再生使用时,水合后的滑动面会剥离、出现龟裂等故障,因此不能获得充分的效果
而且,本发明的板砖,优选与氧浓度调节为30~120质量ppm且调节在1550℃~1650℃范围的钢液反应300分钟时的工作面的脱碳层厚度为1500μm以下。
该脱碳层的厚度是抗氧化性的指标,具体而言,采用日本特开2009-204594号公报中记载的抗氧化性评价方法,使氧浓度调节为30~120质量ppm且调节在1550℃~1650℃范围的钢液与耐火物反应300分钟,对工作面的脱碳层厚度的最大值进行评价。根据该抗氧化性评价方法,耐火物中的碳因钢液中的氧气而被氧化,形成脱碳层。当氮化铝的生成量多时,因氧化而生成的一氧化碳和氮化铝发生反应,形成致密的氧化铝层,并析出碳,因此抑制脱碳层的生成。当脱碳层的最大厚度为1500μm以下时,即使在实际炉中,虽然也可抑制滑动面氧化,减轻滑动面的磨损,但是当超过1500μm时,钢液中的氧气会推进脱炭程度,从而无法获得充分的效果。
另外,本发明的板砖可以通过上述的本发明的制造方法获得。
根据本发明而获得的板砖由于抗氧化性优异,因此可提高抗表面粗糙性,其结果,可提高板砖的耐用性。
附图说明
图1表示通过本发明的制造方法制造的板砖的SEM观察图。
图2是表示使用高频感应炉的抗氧化性的评价方法的说明图。
具体实施方式
如果是一般用于板砖的制造,铝及/或铝合金则无特别问题可以正常使用。作为铝合金,可以使用与硅或镁等的合金。其中,在合金的情况下,由于Al的含有率在50质量%以上的Al-Mg合金、Al-Si合金或者Al-Mg-Si合金的氮化铝的收获率高,因此优选。铝及/或铝合金如果使用其粒径在200μm以下的粉末状材料,则制造的板砖的抗氧化性更优异,因此优选。
优选铝及/或铝合金在耐火原料配合物中以Al换算含有1~10质量%,更优选含有2~5质量%。如果在1质量%以下,则存在生成的氮化铝不足、抗氧化性不足的情况。如果超过10质量%,则存在以下情况:氮化铝的生成过多,形成高强度高弹性率,耐热冲击性降低,而且抗水化性降低。而且,还存在烧成时的体积变化大,烧成后发生龟裂等问题。
在本发明的板砖的制造方法中,虽然使用含有铝及/或铝合金的耐火原料配合物,但是作为铝及铝合金以外的耐火原料,也可以使用在一般的板砖中使用的耐火原料。例如,可以以金属氧化物为主体,此外使用金属氮化物、金属碳化物、铝及铝合金以外的金属以及碳质原料中的1种以上。更优选使用80~98质量%的金属氧化物,金属氮化物、金属碳化物、铝及铝合金以外的金属以及碳质原料中的1种以上为1~10质量%。
作为金属氧化物,例如可使用氧化铝、莫来石、氧化锆莫来石、锆刚玉、氧化镁、尖晶石、粘土、玻璃以及砖屑等中的1种以上;作为金属氮化物,可使用氮化硅、氮化铝以及氮化硼等中的1种以上;作为金属碳化物,可使用碳化硅以及碳化硼等中的1种以上;作为铝以及铝合金以外的金属,可使用硅、镁、铁、镍以及它们的合金等中的1种以上;作为碳质原料,可使用沥青、焦油、炭黑以及石墨等中的1种以上。
作为金属氧化物,更优选使用50~80质量%的氧化铝。氧化铝可提高耐腐蚀性。而且,在需要重视耐腐蚀性的情况下,也可以使用氧化镁、尖晶石等金属氧化物。
关于有机结合剂,可使用为了在成形时赋予强度以及形成碳结合而一般使用于耐火物的有机结合剂,但是更优选使用热硬化性有机结合剂。具体而言,可使用将酚醛树脂、呋喃树脂在苯酚、乙二醇或乙醇等溶剂中稀释而调节粘度后的结合剂。而且,还可以并用或单独使用它们的粉末型树脂。
在本发明中,在含有铝及/或铝合金的耐火原料配合物中添加有机结合剂,并采用通常方法混匀、成形。在氮气环境下进行烧成。
关于烧成炉,无论是分批炉还是连续炉均可以使用。不论哪种情况,能够防止大气、燃烧气体等氮气以外的气体侵入,且能够控制氮气的供给量、炉内气体的排放量以及温度等即可。这些炉已作为耐火物或陶瓷的烧成炉而公知,可使用市场上销售的产品。
烧成时,为了防止被烧成物氧化,最低也要在环境温度为300℃以上时是氮气环境。不足300℃时虽然也可以是大气环境,但是,考虑到在烧成过程中改变环境的复杂性,更优选使烧成开始至烧成结束之间为氮气环境。
在升温过程中,在炉内环境不足1000℃之前的区域,由于结合剂中所含的气体会产生,因此,可一边排放炉内的气体,且一边供给氮气而进行。
在炉内的环境温度为1000℃以上时,以氮气的供给量和排气量来控制炉内环境,使环境中的氧气浓度为100体积ppm以下,并且使一氧化碳气体浓度和二氧化碳气体浓度的合计为1.0体积%以下。更优选的条件是:在环境温度为1000℃以上时,氧气浓度为10体积ppm以下,一氧化碳气体浓度和二氧化碳气体浓度的合计为0.1体积%以下。
炉内环境的最高温度是1000℃以上1400℃以下范围内的任意温度,在该范围的环境温度下,被烧成物保持1小时以上10小时以下的时间即可。
在降温过程中,从炉内的环境温度不足1000℃开始,为了防止炉外侵入的空气引起氧化,基本上是在氮气环境下进行,直至烧成结束为止。在该冷却时,由于不会产生来自被烧成物的气体,所以,能够在300℃为止的温度区域内抑制大气侵入炉内即可。作为此时炉内环境的标准,更优选使氧气浓度为1000体积ppm以下,并且使一氧化碳气体浓度和二氧化碳气体浓度的合计为1.0体积%以下。另外,节约氮气时,在不足300℃的温度下,即使导入大气进行冷却,氧化的影响也较小。
关于分批炉,在供给氮气时,更优选采用通常方法操作,将炉内环境置换为氮气。
在利用隧道窑等连续炉进行烧成时,可以供给氮气,以便形成从出口侧朝向入口侧的氮气流。通过这样做,由于在1000℃以下被烧成物所产生的气体会流向温度更低的低温侧,所以能够较高地保持1000℃以上的环境下的氮气浓度。关于连续炉,优选基本上在台车送入炉内的位置形成氮气环境。但是,节约氮气时,至少在环境温度达到300℃以上的地方是氮气环境,不足300℃的地方可以是大气环境。而且,在800℃以下的低温区域,为了除去被烧成物所产生的气体,最好设置脱脂带。
另外,作为有机结合剂,在使用酚醛树脂等热硬化性树脂时,为了预先除去因溶剂或反应而产生的水分,也可以在铝的氧化较小的300~100℃的范围内,在大气环境下使用其他的炉进行热处理。
而且,将成形体埋入焦炭粒等碳粒子内进行的烧成,由于氮化铝的生成少,而且在烧成时容易产生龟裂,因此,在本发明中不能采用。本发明不使用碳粒,仅使用氮气,在氧气、一氧化碳气体及二氧化碳气体极少的条件下进行烧成。
实施例1
表1表示本发明的实施例及对比例。在表1所示的耐火原料配合物中外掺添加酚醛树脂,混匀并用液压机获得板砖的成形体。
在表1所示的实施例1中,烧成是用密闭式的分批炉(电炉)进行的。将成形体放入炉内,并将炉内环境置换为氮气,在炉内的氧气浓度为1000体积ppm以下的条件下开始烧成。在升温过程中随时供给氮气,将炉内产生的气体、过剩的氮气排出炉外。随着烧成温度升高,虽然氧气浓度降低,由于酚醛树脂等的分解,一氧化碳气体浓度及二氧化碳气体浓度上升,但是,在升温途中的900℃下保持2小时,调节供气量和排气量,使氧气浓度为100体积ppm以下,一氧化碳气体浓度和二氧化碳气体浓度的合计为1.0体积%以下。然后,在该气体浓度条件下进行升温,在最高温度(烧成温度)1300℃下保持3小时。从室温升至1300℃用了20小时。然后停止加热,一边供给氮气以使炉内压力高于大气,一边在氧气浓度为100体积ppm以下、一氧化碳气体及二氧化碳气体的合计为1.0体积%以下的条件下冷却至150℃,在150℃下取出烧成物。在本实施例中,所使用的氮气为N2纯度99.99%以上,氧气浓度为5体积ppm以下,并且一氧化碳气体浓度和二氧化碳气体浓度的合计为100体积ppm以下。
炉内气体浓度的测量是通过将配管通入炉内收集气体而进行的。而且,使用电化学式的氧气浓度计及红外线二氧化碳气体分析装置,连续测量炉内气体浓度,控制供气量和排气量。而且,通过氧气或一氧化碳气体及二氧化碳气体的供给,控制氧气浓度和一氧化碳气体浓度及二氧化碳气体浓度。根据测量仪器的测量精度,氧气浓度的测量精度达到了1体积ppm,一氧化碳气体浓度及二氧化碳气体浓度的测量精度达到了0.1体积%。
另外,在表1中,氧气浓度、一氧化碳气体浓度及二氧化碳气体浓度的合计表示的是在1300℃下测量的结果。
在实施例2和3以及对比例1和2中,在上述实施例1的条件下,为了达到表中所示的浓度,从1000℃开始调节氮气的供给量和排气量,并且通过少量供给氧气控制了氧气浓度。在实施例4和5以及对比例3和4中,在上述实施例1的条件下,从1000℃开始供给将一氧化碳气体及二氧化碳气体按1比1调节的气体,调节至规定的浓度。实施例6~10以及对比例5的烧成条件与上述实施例1相同。在这些实施例2~10以及对比例1~5中,冷却是在与上述实施例1相同的条件下进行的。
对比例6是在其他的隧道式燃气烧成炉中使用碳化硅容器,并在将烧成体埋设在焦炭粉中的状态下进行烧成的,烧成温度与实施例相同。
表1中使用的电熔刚玉使用了99质量%的Al2O3,煅烧氧化铝使用了99质量%的Al2O3,氧化锆莫来石使用了55质量%的Al2O3,38质量%的ZrO2,17质量%的SiO2。Al粉、Al-Si粉以及Al-Mg粉使用了粒径在200μm以下的材料。另外,氧化锆莫来石在所有的例子中均配合了33质量%。即,各例的耐火原料配合物均含有13质量%的ZrO2成分。
氮化铝的生成量是根据X射线衍射的内部标准法进行定量的。另外,表1所示的氮化铝生成量是通过烧成而产生的量,但是,在耐火原料配合物内没有配合氮化铝的情况下,则相当于砖中的含量。
氮含量是使用氧氮同时分析装置(LECO公司制造)并采用热传导度法进行的定量。而且,碳含量是采用JISR2011中记载的耐火砖的化学分析方法进行的评价。
显气孔率是采用JISR2205中记载的耐火砖显气孔率的测量方法进行的评价。
抗氧化性是使用旋转炉在大气中以800℃的条件氧化2小时后,根据英国标准法,喷涂SiC磨粒,以实施例1为100进行了指数化。数值越小,抗氧化性越优异。
而且,还根据日本特开2009-204594号公报中记载的抗氧化性评价方法对抗氧化性进行了评价。即,如图2所示,使用高频感应炉,使内衬于该高频感应炉的反应容器(未图示)的样品即耐火物与钢液反应300分钟,该钢液被放入反应容器内,氧浓度调节为30~120质量ppm,且调节在1550℃~1650℃范围,对通过该反应而生成的工作面(钢浴部)脱碳层的最大厚度进行了评价。而且,在对该抗氧化性进行评价时,使用氧气浓度计测量钢液的氧浓度,使其氧浓度为30~120质量ppm。另外,用搅拌夹具对钢液进行搅拌。
另外,抗水化性是用高压釜根据重量变化率进行测量,并以实施例1为100进行了指数化。而且,作为抗水化性,在用高压釜进行的水化试验中,还调查了在0.49MPa的加压条件下,在150℃下保持3小时后基于水合反应的重量增加率。关于这些抗水化性的评价数值,其数值越小,抗水化性越优异。
另外,作为在实际炉中的表面粗糙的评价,用同一个炼钢厂的浇包使用5组表1的板砖,在使用3次后观察滑动面,根据表面粗糙的程度判断是否可以使用。5组使用次数的平均值如表1所示。
实施例1~3是在氧气浓度不同的条件下制造的例子,随着氧气浓度升高,虽然氮化铝的生成量减少,但是氮化铝的生成量在1.5质量%以上,即使是使用高频感应炉的抗氧化性评价,脱碳层厚度也较薄,在1500μm以下,结果良好。另一方面,在氧气浓度为本发明的范围外的对比例1和2中,氮化铝的生成量不足1.5质量%,即使是使用高频感应炉的抗氧化性评价,脱碳层厚度也较厚,超过1500μm,抗氧化性差。可以认为,对比例1和2之所以抗氧化性差,是由于铝因微量的氧气而形成氧化铝,阻碍了氮化铝的生成。在实际炉的表面粗糙评价结果中,在对比例1中是4.4次,对比例2是3.2次,也劣于实施例1~3的5.0~5.4次。而且,关于实施例1~3,氮化铝的生成量在7.0质量%以下,在用高压釜进行的水化试验中,重量增加率也是在0.5%以下,抗水化性也较优异。由此可知,炉内的氧气浓度以在100体积ppm以下为好。
在实施例4和5中,一氧化碳气体浓度和二氧化碳气体浓度的合计为0.5体积%及1.0体积%,在本发明的范围内。两个实施例的氮化铝的生成量均在1.5质量%以上,即使是使用高频感应炉的抗氧化性评价,脱碳层厚度也均较薄,在1500μm以下,结果良好。而且,关于实施例4和5,氮化铝的生成量在7.0质量%以下,在用高压釜进行的水化试验中,重量增加率也是在0.5%以下,抗水化性也较优异。如此,实施例4和5的抗氧化性及抗水化性优异,在实际炉中板砖的使用次数也是5.0次,结果良好。
另一方面,在对比例3和4中,一氧化碳气体浓度和二氧化碳气体浓度的合计为2.0体积%及5.0体积%,在本发明的范围外,氮化铝的生成量不足1.5质量%,即使是使用高频感应炉的抗氧化性评价,脱碳层厚度也超过1500μm,抗氧化性降低。而且,在用高压釜进行的水化试验中,重量增加率也超过了0.5%,不仅抗氧化性,抗水化性也降低了。由此,可以认为,虽然氮化铝的生成量在7.0质量%以下,但是生成了碳化铝。在实际炉中板砖的使用次数也是3.2次,成为很差的结果。
对比例5虽然未使用铝或铝合金,是在耐火原料配合物中添加了氮化铝粉末的例子,但是与各实施例相比,抗氧化性差,在实际炉中板砖的使用次数也较少。
对比例6虽然是在其他的隧道式燃气烧成炉中使用碳化硅容器,并在将成形体埋设在焦炭粉中的状态下进行烧成的,但是氮化铝的生成量不足1.5质量%,即使是使用高频感应炉的抗氧化性评价,脱碳层厚度也较厚,超过1500μm,抗氧化性较差。在用高压釜进行的水化试验中,重量增加率也超过了0.5%超。可以认为,虽然氮化铝的生成量在7.0质量%以下,但是生成了很多碳化铝。而且在烧成后还产生了龟裂,推测这种龟裂是由于在强还原环境下烧成而导致氧化锆还原引起的。
实施例6、7添加了Si粉,与实施例1相比,在用高压釜进行的水化试验中,重量增加率也在0.3%以下,可知抗水化性提高了。实施例8使用了Al-Si粉,实施例9使用了Al-Mg粉,与使用Al粉的情况相比,结果并不逊色。
实施例10是在与实施例1相同的烧成条件下增加了Al粉量。氮化铝的生成量在1.5质量%以上,在使用高频感应炉的抗氧化性评价中,脱碳层厚度较薄,在1500μm以下,结果良好,但是氮化铝的生成量超过了7.0质量%,在用高压釜进行的水化试验中,重量增加率超过了0.5%,抗水化性呈降低趋势。因此,可以说氮化铝的生成量优选抑制在7.0质量%以下。
表1
Claims (5)
1.一种板砖的制造方法,在含有铝及/或铝合金的耐火原料配合物中添加有机结合剂后混匀,成形后,在氮气环境下,在1000℃以上1400℃以下进行烧成的板砖的制造方法中,其特征在于,
在炉内环境温度为300℃以上时,为氮气环境,而且在炉内环境温度为1000℃以上时,使环境中的氧气浓度保持在100体积ppm以下,且一氧化碳气体浓度和二氧化碳气体浓度的合计保持在1.0体积%以下。
2.根据权利要求1所述的板砖的制造方法,其特性在于,耐火原料配合物含有4质量%以上20质量%以下的氧化锆、氧化锆莫来石及锆刚玉中的1种以上的ZrO2成分。
3.根据权利要求1或2所述的板砖的制造方法,其特性在于,耐火原料配合物含有0.5质量%以上5质量%以下的硅。
4.一种板砖,其特性在于,氮化铝的含量为1.5质量%以上7.0质量%以下,在用高压釜进行的水化试验中,在0.49MPa的加压条件下,在150℃下保持3小时后基于水合反应的重量增加率为0.5%以下。
5.根据权利要求4所述的板砖,其特征在于,与氧浓度调节为30~120质量ppm且调节在1550℃~1650℃范围的钢液反应300分钟时的工作面的脱碳层厚度为1500μm以下。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-322609 | 2008-12-18 | ||
JP2008322609 | 2008-12-18 | ||
PCT/JP2009/071124 WO2010071196A1 (ja) | 2008-12-18 | 2009-12-18 | プレートれんがの製造方法及びプレートれんが |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102245539A true CN102245539A (zh) | 2011-11-16 |
CN102245539B CN102245539B (zh) | 2015-06-17 |
Family
ID=42268863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200980150286.9A Active CN102245539B (zh) | 2008-12-18 | 2009-12-18 | 板砖的制造方法及板砖 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8609562B2 (zh) |
JP (1) | JP5565908B2 (zh) |
KR (1) | KR101246813B1 (zh) |
CN (1) | CN102245539B (zh) |
BR (1) | BRPI0922166B1 (zh) |
DE (1) | DE112009004278B4 (zh) |
GB (1) | GB2480165B (zh) |
WO (1) | WO2010071196A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113151707A (zh) * | 2021-03-30 | 2021-07-23 | 李功毕 | 一种泡沫铝及其制备工艺 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010071196A1 (ja) * | 2008-12-18 | 2010-06-24 | 黒崎播磨株式会社 | プレートれんがの製造方法及びプレートれんが |
JP6027405B2 (ja) * | 2012-11-12 | 2016-11-16 | 東京窯業株式会社 | スライディングノズル用のプレート再生品の製造方法 |
JP5880883B2 (ja) * | 2013-05-15 | 2016-03-09 | 品川リフラクトリーズ株式会社 | スライドプレート装置用プレートれんが及びその製造方法 |
JP6279068B2 (ja) * | 2014-02-28 | 2018-02-14 | 黒崎播磨株式会社 | 鋼の鋳造用耐火物,及びスライディングノズル装置用のプレート,並びに鋼の鋳造用耐火物の製造方法 |
JP2017083400A (ja) * | 2015-10-30 | 2017-05-18 | 黒崎播磨株式会社 | 耐火物の評価方法 |
CA3192681A1 (en) * | 2020-12-04 | 2022-06-09 | Refractory Intellectual Property Gmbh & Co. Kg | Method for the quantitative determination of al4c3 and apparatus for carrying out the method |
CN113004027B (zh) * | 2021-03-26 | 2022-05-17 | 福建安溪马斯特陶瓷有限公司 | 一种耐磨高性能陶瓷辊棒及其制备方法 |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3236663A (en) * | 1961-07-19 | 1966-02-22 | Union Carbide Corp | Method of producing refractory body bonded by an aluminum nitride-aluminum boride composition |
US3492153A (en) * | 1964-09-03 | 1970-01-27 | North American Rockwell | Silicon carbide-aluminum nitride refractory composite |
US4332755A (en) * | 1978-06-15 | 1982-06-01 | Kennecott Corporation | Sintered silicon carbide - aluminum nitride articles and method of making such articles |
ZA812568B (en) * | 1980-05-14 | 1982-06-30 | Dresser Ind | Refractory |
JPS5727971A (en) | 1980-07-22 | 1982-02-15 | Kurosaki Refractories Co | Plate brick for sliding nozzle |
JPS5727970A (en) * | 1980-07-22 | 1982-02-15 | Kurosaki Refractories Co | Plate brick for sliding nozzle |
JPS5727972A (en) * | 1980-07-22 | 1982-02-15 | Kurosaki Refractories Co | Plate brick for sliding nozzle |
FR2565964A1 (fr) * | 1984-06-13 | 1985-12-20 | Lafarge Refractaires | Nouveaux refractaires a haute teneur en alumine et leur procede d'obtention |
JPH03257062A (ja) * | 1990-03-05 | 1991-11-15 | Tokyo Yogyo Co Ltd | スライドゲート用プレートレンガ |
JPH0416547A (ja) * | 1990-05-08 | 1992-01-21 | Shinagawa Refract Co Ltd | 炭素含有耐火物 |
US5286685A (en) * | 1990-10-24 | 1994-02-15 | Savoie Refractaires | Refractory materials consisting of grains bonded by a binding phase based on aluminum nitride containing boron nitride and/or graphite particles and process for their production |
DE4109375A1 (de) * | 1991-03-22 | 1992-09-24 | Dolomitwerke Gmbh | Verfahren zur herstellung eines feuerfesten verbundwerkstoffs |
JPH0825786B2 (ja) * | 1993-01-13 | 1996-03-13 | 品川白煉瓦株式会社 | 連続鋳造用耐火物及びその製造方法 |
JP3031192B2 (ja) * | 1995-02-01 | 2000-04-10 | 住友金属工業株式会社 | スライディングノズル用プレート耐火物 |
JPH10139527A (ja) * | 1996-11-12 | 1998-05-26 | Kawasaki Refract Co Ltd | スライディングノズル用プレート耐火物の製造方法 |
JPH11278940A (ja) * | 1998-03-27 | 1999-10-12 | Kurosaki Refract Co Ltd | アルミナ−炭化珪素質耐火物 |
JP2000094121A (ja) * | 1998-09-22 | 2000-04-04 | Toshiba Ceramics Co Ltd | スライドゲート用プレートの製造方法 |
JP3395108B2 (ja) * | 1998-10-01 | 2003-04-07 | 東芝セラミックス株式会社 | スライドゲート用プレートの製造方法 |
JP2000319070A (ja) * | 1999-04-30 | 2000-11-21 | Nkk Corp | 衝撃に強い耐火物およびその製造方法 |
JP2000327401A (ja) * | 1999-05-13 | 2000-11-28 | Toshiba Ceramics Co Ltd | スライドゲート用プレート |
JP2003002742A (ja) * | 2001-06-19 | 2003-01-08 | Sumitomo Metal Ind Ltd | 電気伝導性に優れる耐火物 |
JP4009451B2 (ja) * | 2001-12-03 | 2007-11-14 | 黒崎播磨株式会社 | スライディングノズル装置用プレートれんがとその製造法 |
JP4119659B2 (ja) * | 2002-03-22 | 2008-07-16 | 黒崎播磨株式会社 | スライディングノズル装置用プレートれんがの製造方法 |
JP4245122B2 (ja) * | 2002-08-28 | 2009-03-25 | 黒崎播磨株式会社 | 窒化アルミニウム結合耐火れんがの製造方法 |
CN100519005C (zh) * | 2003-07-21 | 2009-07-29 | 宝山钢铁股份有限公司 | 一种采用不烧工艺生产的铝碳锆质滑动水口砖 |
CN100534954C (zh) * | 2007-02-09 | 2009-09-02 | 江苏苏嘉集团新材料有限公司 | 一种非氧化物复合低碳镁碳砖 |
JP5054572B2 (ja) | 2008-02-29 | 2012-10-24 | 黒崎播磨株式会社 | カーボン含有耐火物の耐酸化性評価方法 |
WO2010071196A1 (ja) * | 2008-12-18 | 2010-06-24 | 黒崎播磨株式会社 | プレートれんがの製造方法及びプレートれんが |
-
2009
- 2009-12-18 WO PCT/JP2009/071124 patent/WO2010071196A1/ja active Application Filing
- 2009-12-18 US US13/139,338 patent/US8609562B2/en active Active
- 2009-12-18 DE DE112009004278.3T patent/DE112009004278B4/de active Active
- 2009-12-18 BR BRPI0922166-2A patent/BRPI0922166B1/pt active IP Right Grant
- 2009-12-18 KR KR1020117012246A patent/KR101246813B1/ko active IP Right Grant
- 2009-12-18 CN CN200980150286.9A patent/CN102245539B/zh active Active
- 2009-12-18 GB GB1112159.7A patent/GB2480165B/en not_active Expired - Fee Related
- 2009-12-18 JP JP2010543011A patent/JP5565908B2/ja active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113151707A (zh) * | 2021-03-30 | 2021-07-23 | 李功毕 | 一种泡沫铝及其制备工艺 |
Also Published As
Publication number | Publication date |
---|---|
KR101246813B1 (ko) | 2013-03-26 |
WO2010071196A1 (ja) | 2010-06-24 |
DE112009004278B4 (de) | 2016-11-17 |
GB2480165B (en) | 2014-03-19 |
US8609562B2 (en) | 2013-12-17 |
JPWO2010071196A1 (ja) | 2012-05-31 |
US20110241267A1 (en) | 2011-10-06 |
CN102245539B (zh) | 2015-06-17 |
BRPI0922166B1 (pt) | 2020-02-18 |
DE112009004278T5 (de) | 2012-09-20 |
GB201112159D0 (en) | 2011-08-31 |
BRPI0922166A2 (pt) | 2015-12-29 |
KR20110081885A (ko) | 2011-07-14 |
JP5565908B2 (ja) | 2014-08-06 |
GB2480165A (en) | 2011-11-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102245539A (zh) | 板砖的制造方法及板砖 | |
US8349752B2 (en) | Plate brick and production method therefor | |
KR101722041B1 (ko) | 내화물 및 주조용 노즐 | |
EP2399879B1 (en) | Carbonaceous refractory material, process for producing same, and furnace bottom or side wall of blast furnace | |
CN102898154B (zh) | 一种碳化硅滑板及其制备方法 | |
CN101356136A (zh) | 防火模制品或材料及其生产方法 | |
JP3593101B2 (ja) | 炭素質耐火物及びその製造方法 | |
JP2015193511A (ja) | 鋳造用耐火物、並びにそれを使用した鋳造用ノズル及びスライディングノズル用プレート | |
EP3564201A1 (en) | Brick for blast furnace hearths and blast furnace hearth using same, and method for producing brick for blast furnace hearths | |
Thethwayo et al. | A review of carbon-based refractory materials and their applications | |
JP6193793B2 (ja) | 鋳造用耐火物、並びにそれを使用した鋳造用ノズル及びスライディングノズル用プレート | |
WO2011058811A1 (ja) | スライディングノズルプレート | |
JP6600729B1 (ja) | 真空脱ガス装置用スピネル−マグネシア−カーボンれんが及びこれを下部槽側壁にライニングした真空脱ガス装置 | |
JPH1129366A (ja) | 高炉出銑口閉塞用マッド材 | |
JP4245122B2 (ja) | 窒化アルミニウム結合耐火れんがの製造方法 | |
JP2003226583A (ja) | 溶銑用不定形耐火物 | |
JP5578680B2 (ja) | 炭素含有耐火物 | |
JP5388268B2 (ja) | スライディングノズルプレート用の耐火物及びその製造方法 | |
JP2021181113A (ja) | カーボン含有スライドプレート耐火物の製造方法 | |
KR101167157B1 (ko) | 마그네시아-흑연질 내화물 | |
JP2004017136A (ja) | スライディングノズル用プレート耐火物 | |
Moliné et al. | Carbon Trends | |
JPH05228594A (ja) | アルミナ・カ−ボン質スライディングノズルプレ−ト |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |