TWI606025B - 具高氧化鋯含量之耐火產品 - Google Patents
具高氧化鋯含量之耐火產品 Download PDFInfo
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- TWI606025B TWI606025B TW100103487A TW100103487A TWI606025B TW I606025 B TWI606025 B TW I606025B TW 100103487 A TW100103487 A TW 100103487A TW 100103487 A TW100103487 A TW 100103487A TW I606025 B TWI606025 B TW I606025B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title description 45
- 239000011521 glass Substances 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000010455 vermiculite Substances 0.000 claims description 16
- 229910052902 vermiculite Inorganic materials 0.000 claims description 16
- 235000019354 vermiculite Nutrition 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006060 molten glass Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 62
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000012768 molten material Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012926 crystallographic analysis Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- -1 oxynitrides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/481—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
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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
- C04B35/01—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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
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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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- 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
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- 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
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- 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
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Description
本發明係關於一種具有高氧化鋯含量之新穎熔鑄耐火產品。
在耐火產品中，熔鑄產品(已知用於構築玻璃熔爐)與燒結產品之間存在差別。
與燒結產品不同，熔鑄產品通常包括連接結晶顆粒之晶粒間玻璃相。因此，一般而言，燒結產品與熔鑄產品所遇到之問題及適用於解決該等問題之技術解決方案係不同。因此，經開發用於燒結產品之組合物本身不能先驗地用於製造熔鑄產品，且反之亦然。
熔鑄產品(通常稱為電熔產品)係藉由在電弧爐中熔化適宜的原材料混合物或任何其他適用於此等產品之技術獲得。隨後將熔融材料澆鑄於一鑄模中，此後所獲得之產品經歷控制冷卻循環，以在不破裂的情況下達到室溫。熟悉此項技術者將此操作稱為「退火」。
在熔鑄產品中，彼等具有高氧化鋯含量者(即包含85重量%以上的氧化鋯(ZrO2))之優點在於：其在不使所製造之玻璃著色及不產生缺陷下具有高度耐腐蝕性之品質。
通常，具有高氧化鋯含量之熔鑄產品亦包含氧化鈉(Na2O)，以防止自產品中存在之氧化鋯及矽石形成鋯石。此係由於鋯石形成係有害，因為其伴隨體積減少約20%，由此產生引發裂縫之機械應力。
由Saint-Gobain SEFPRO製造及售出及專利EP-B-403 387所提及之產品ER-1195目前係廣泛地用於玻璃熔爐中。其化學組成包括約94重量%氧化鋯、4至5重量%矽石、約1重量%氧化鋁、0.3重量%氧化鈉及小於0.05重量% P2O5。其係用於玻璃熔爐之具有高氧化鋯含量的典型產品。
FR 2 701 022揭示一種具有高氧化鋯含量之熔鑄產品，其包含0.05至1.0重量% P2O5及0.05至1.0重量%氧化硼B2O3。此等產品具有高電阻率。因此，玻璃電熔期間之能量消耗係有利地穩定，且最重要的是，可避免耐火產品中導致其快速劣化的任何短路問題。此係因為在玻璃電熔期間，某些電流流過耐火物。此等耐火物之電阻率一旦增加，則可藉此減少能夠流過其中之電流量。
WO 2009 027610揭示一種具有高氧化鋯含量之熔鑄產品，其針對6至12%之間的矽石含量，在選自Nb2O5及Ta2O5之至少一種氧化物的存在下顯示高電阻率。
WO 2007 099253揭示一種具有高氧化鋯含量之熔鑄產品，其在選自CrO3、Nb2O5、MoO3、Ta2O5及WO3之至少一種氧化物的存在下顯示高電阻率。此等產品包含小於1.5重量%的B2O3，且氧化鋁含量係在0.1至2.4%之間。
WO 2005 068393揭示一種具有高氧化鋯含量之熔鑄產品，其在顯示高電阻率的同時使BaO、SrO、MgO、CaO、P2O5、Na2O及K2O含量最小。此等產品包含0.1至1.2重量%的B2O3及0.8至2.5重量%的氧化鋁，然而未注意Al2O3/B2O3比例。此外，以上文獻中之實例皆不具有小於0.85%之氧化鋁含量，其以大於0.9%之氧化鋁含量較佳。
JP 63 285173揭示一種具有高氧化鋯含量之熔鑄產品，其在矽石含量低於6.5%時顯示良好的電阻率及抗裂性。
目前，極高品質玻璃(特定言之LCD平面螢幕)之開發使得對玻璃熔爐中之耐火物之需求增加。特定言之，需要在不要求使用摻雜劑下具有較高電阻率，同時仍具有耐玻璃腐蝕性之耐火物。
本發明之目標係滿足此需求。
更特定言之，本發明係關於一種熔鑄耐火產品，其基於氧化物之重量百分比及總共100%的氧化物包含：
ZrO2+Hf2O：補足至100%
4.5%<SiO2<6.0%
0.80%Al2O3<1.10%
0.3%<B2O3<1.5%
Ta2O5+Nb2O5<0.15%
Na2O+K2O<0.10%
K2O<0.04%
CaO+SrO+MgO+ZnO+BaO<0.4%
P2O5<0.05%
Fe2O3+TiO2<0.55%
視需要包含SnO2及/或CuO之其他氧化物種類(即當存在SnO2及/或CuO時，其係包含於該其他氧化物種類中)：<1.5%，且SnO2+CuO<0.05%，Al2O3/B2O3質量含量之A/B比例係在0.75至1.6之間。
如隨後可見，本發明者已令人驚訝地發現：儘管Ta2O5及/或Nb2O5摻雜劑之含量小於0.15%，但此組成可使得根據本發明之耐火產品顯示良好的電阻率及良好的耐腐蝕性。
根據本發明之耐火產品亦可包括一或多種以下視需要之特徵：- Al2O3/B2O3質量含量之A/B比例係小於或等於1.5，較佳小於或等於1.2，小於1.1或甚至小於1.0；- (ZrO2+HfO2)質量含量係小於95.5%，或甚至小於95.0%或甚至小於94.0%及/或大於90.0%，或大於91.0%或甚至大於92.0%；- 矽石SiO2之質量含量係大於4.6%，大於4.8%，大於4.9%，及/或小於5.8%，小於5.5%；- 氧化鋁Al2O3之質量含量係小於1.00%，小於0.90%；- 氧化鋁之質量含量係大於或等於0.85%；- B2O3質量含量係大於0.35%，或甚至大於0.40%或甚至大於0.45%；- B2O3質量含量係小於1.20%，或甚至小於1.0%，或甚至小於0.80%，小於0.70%或小於0.60%或小於0.55%；- (Ta2O5+Nb2O5)質量含量係小於0.10%，小於0.05%或甚至實質上為零；- (Na2O+K2O)質量含量係小於0.04%；- 氧化鐵及/或氧化鈦及/或氧化鈣及/或氧化鍶及/或氧化鋇及/或氧化鎂及/或氧化鋅及/或氧化磷僅作為雜質存在；- 氧化鐵及/或氧化鈦(Fe2O3+TiO2)之質量含量係小於0.4%，較佳小於0.3%，較佳小於0.2%；- 氧化鈣及/或氧化鍶及/或氧化鋇及/或氧化鎂及/或氧化鋅之質量含量係小於0.2%，較佳小於0.1%；- 氧化鈣及/或氧化鍶及/或氧化鋇及/或氧化鎂及/或氧化鋅(CaO+SrO+BaO+MgO+ZnO)之總質量含量係小於0.3%，較佳小於0.2%，小於0.1%，小於0.05%；- 「其他氧化物種類」之總質量含量係小於1.0%，小於0.6%，小於0.5%或甚至小於0.3%；- 「其他氧化物種類」僅構成雜質且「其他氧化物種類」之總質量含量係小於0.6%，小於0.5%或甚至小於0.3%；- 氧化釔Y2O3之質量含量係小於1.0%，較佳小於0.5%，更佳小於0.4%，或甚至小於0.3%，或小於0.25%。
本發明亦係關於一種用於製造本發明耐火產品之方法，其包括以下連續步驟：
a)將原材料混合以形成始料；
b)將該始料熔化以獲得熔融材料；及
c)澆鑄該熔融材料及藉由冷卻固化，以獲得耐火產品，此方法值得注意之處在於：選擇該等原材料以使該耐火產品係與本發明一致。
較佳地，必需具有最低含量之氧化物(尤其係ZrO2、SiO2、B2O3或此等氧化物之前驅物)係有系統及有條理地添加。較佳地，在其他氧化物來源中通常被視為雜質之此等氧化物之含量係考慮在內。
較佳係控制冷卻，以使其較佳在小於20℃/小時的速率，較佳約10℃/小時的速率下進行。
本發明亦係關於一種特定言之在欲與熔融玻璃接觸之區域中，包含根據本發明之耐火產品，或根據本發明之方法製造或可根據本發明之方法製造之耐火產品之玻璃熔爐。在根據本發明之熔爐中，該耐火產品可有利地形成用於藉由熔化(尤其係電熔)製造玻璃之槽之部份，其中該耐火產品係傾向於在1200℃以上的溫度下與熔融玻璃接觸。
根據工業中之通常慣例，氧化物之質量含量係關於以最穩定氧化物形式表示之各相應的化學元素之總體含量。此等因此包括次氧化物及視需要包括氮化物、氧氮化物、碳化物、碳氧化物、碳氮化物或甚至上述元素之金屬種類。
術語「熔融材料」應瞭解為意指為保持其形式而必須包含於容器中之液體物質。其可包含少量固體顆粒，但其量並不足以使其構成該物質。
術語「雜質」應瞭解為意指並非有意及必然隨原材料一起引入或源自與此等成份之反應之不可避免的成份。雜質並非必需成份，只不過容許存在。例如，屬於氧化物、氮化物、氧氮化物、碳化物、碳氧化物、碳氮化物及鐵、鈦、釩及鉻金屬種類之群的化合物係雜質。
術語「摻雜劑」在此係指Ta2O5及/或Nb2O5成份。
除非文中另外指出，否則所述及所主張之產品中之所有氧化物含量係基於氧化物之重量百分比計。
在根據本發明之熔鑄產品中，高氧化鋯ZrO2含量使得可在不使所製造之玻璃著色或產生損害此玻璃之品質的缺陷下滿足高耐腐蝕性之要求。
在藉由熔化所獲得之產品中，HfO2係不可自ZrO2化學解離。因此，在該產品之化學組成中，ZrO2+HfO2係指此兩種氧化物之總含量。然而，根據本發明，HfO2並非有意添加至始料中。因此，HfO2僅指微量的氧化鉿，此氧化物總是以一般低於2%之含量天然存在於氧化鋯來源中。為清楚明瞭起見，「氧化鋯及微量氧化鉿之含量」可無差別地以ZrO2+HfO2或以ZrO2或另外以「氧化鋯含量」表示。
在根據本發明之產品中，氧化鉿HfO2之含量係小於5%，一般係小於2%。
矽石SiO2之存在使得特定言之可形成能夠在其可逆同素異形變化期間(即當其自單斜相轉變成四方相時)有效地適應氧化鋯之體積變化之晶粒間玻璃相。
相反地，必須限制添加矽石以獲得高耐腐蝕性。此外，矽石含量過高會因釋放石塊(由於黏結力下降而產生之耐火產品碎片)而在玻璃中產生缺陷，此在本申請案中被視為不良行為。
氧化鋁之存在可促進穩定玻璃相的形成及改善產品在鑄模中之流動性。含量過高導致玻璃相不穩定(結晶形成)，此尤其在氧化硼的存在下對實用性具有負面影響。因此，氧化鋁質量含量必須保持低於1.10%。
B2O3之存在(其質量含量使得Al2O3/B2O3質量含量之A/B比例小於或等於1.6)可增加電阻。
氧化物Na2O及K2O對電阻率具有不利影響。因此，(Na2O+K2O)質量含量必須小於0.10%。特定言之，K2O含量必須小於0.04%。
根據本發明，(Fe2O3+TiO2)質量含量係小於0.55%及P2O5之質量含量係小於0.15%，較佳小於0.10%，甚至更佳小於0.05%。此係因為已知此等氧化物係有害，且其含量較佳必須限制為隨原材料以雜質引入之微量。
除非另外相反指出，否則「其他氧化物種類」係以上未列出之種類，即除ZrO2、Hf2O、SiO2、Al2O3、B2O3、Ta2O5、Nb2O5、Na2O、K2O、CaO、SrO、MgO、ZnO、BaO、P2O5、Fe2O3及TiO2以外之種類。在一實施例中，「其他氧化物種類」係限定為並非特別希望存在之種類，此等在原材料中一般係以雜質形式存在。
通常，在熔鑄產品中，氧化物占該產品質量之98.5%以上，99%以上或甚至實質上100%。此點在根據本發明之產品中同樣適用。
根據本發明之產品通常可根據以下所述之步驟a)至c)製造：
a)將原材料混合以形成始料；
b)將該始料熔化以獲得熔融材料；
c)藉由冷卻使該熔融材料固化，以獲得根據本發明之耐火產品。
在步驟a)中，原材料係經選擇以確保最終產品中之氧化物含量。
在步驟b)中，熔化較佳係藉由較長電弧(不產生還原作用)與攪拌(有利於產品之再氧化)之組合作用實施。
為使金屬表觀之節結形成最小化及避免在最終產品中形成裂縫或裂紋，較佳在氧化條件下實施熔化操作。
較佳地，使用法國專利第1,208,577號及其增補物75893及82310中所述之長弧熔化方法。
此方法包括利用電弧爐，其中電弧在電荷與遠離此電荷之至少一個電極之間跳躍；及包括調節弧長，以使其還原作用最小化，同時藉由攪拌熔融浴(通過電弧本身的作用或藉由將氧化氣體(例如空氣或氧氣)吹入該浴中)或另外藉由添加氧釋放物質(諸如過氧化物或硝酸鹽)至該浴中，在該熔融浴之上方保持氧化氣氛。
特定言之，該熔化可在2300℃以上的溫度下，較佳在2400℃至2500℃之間的溫度下實施。
在步驟c)中，冷卻較佳係以小於20℃/小時之速率，較佳約10℃/小時之速率實施。
由此製造之本發明產品係由經玻璃相圍繞之氧化鋯顆粒組成。80重量%以上，90重量%以上，99重量%以上或約100重量%的氧化鋯可係單斜晶。該玻璃相基於玻璃相之重量計可包括50重量%以上，或甚至70重量%以上的矽石，5重量%至20重量%的B2O3及1至20重量%的氧化鋁。矽石、B2O3及氧化鋁可占玻璃相質量之95%以上，97%以上或甚至約100%。
可利用用於製造欲應用於玻璃熔爐之以氧化鋯為主之熔融產品之任何習知方法，只要始料之組成允許獲得具有與本發明產品一致之組成之產品即可。
提供以下非限制性實例以用於闡述本發明之目的。
在此等實例中，使用以下原材料：- 平均主要包含98.5重量%(ZrO2+HfO2)、0.2重量%SiO2及0.02重量% Na2O之氧化鋯；- 包含33%矽石之鋯砂；及- 純度大於99%之氧化硼。
將原材料根據習知熔化方法於電弧爐中熔化及隨後澆鑄熔融材料，以獲得尺寸為220 mm×450 mm×150 mm之塊體。
實例1對應於由Saint-Gobain SEFPRO售出之產品ER1195並構成對照。
對於所獲得之所有產品而言，晶體學分析顯示經通常包含70%以上矽石的玻璃相圍繞之單斜晶氧化鋯。除氧化鋯以外，所有矽石及其他氧化物種類皆係在玻璃相中。
所獲得之產品之化學分析(即以重量百分比表示之平均總體化學組成)係示於表1中。
在下表1中，*表示該實例係在本發明之範圍外，而空白相當於0.05重量%或更少之含量。
直徑為30 mm及高度為30 mm之圓柱棒產品係取自所製造之不同塊體實例。此等棒係分別於1500℃及1600℃下，在100赫茲的頻率下，經受1伏特之電位差，以測量電阻率(R1500及R1600)。
結果顯示，經測試之本發明產品具有比產品ER1195(實例1)更高的電阻率。
實例2*與實例3或4之比較顯示：A/B比例之減小對電阻率具有相當積極的作用。
此外，已利用包含5.0%矽石、1.4% B2O3及0.80氧化鋁之產品(其A/B比例係0.57)實現補充測試：其玻璃相之黏度導致低耐滲出性。此係較佳將A/B比例保持在0.75或更大的值之原因。
最後，測量顯示本發明產品之耐熔融玻璃腐蝕性係與對照實例1*相當。
顯然，本發明並不限於該等實例之實施例，其係針對闡釋目的而提供。
Claims (19)
- 一種熔鑄耐火產品，其基於氧化物之重量百分比及總共100%的氧化物包含：ZrO2+Hf2O：補足至100% 4.5%<SiO2<6.0% 0.80%Al2O3<1.10% 0.3%<B2O3<1.5% Ta2O5+Nb2O5<0.15% Na2O+K2O<0.1% K2O<0.04% CaO+SrO+MgO+ZnO+BaO<0.4% P2O5<0.05% Fe2O3+TiO2<0.55%其他氧化物種類：<1.5%，Al2O3/B2O3質量含量之A/B比例係在0.75至1.6之間。
- 如請求項1之產品，其中該A/B比例係小於1.5。
- 如請求項2之產品，其中該A/B比例係小於1.2。
- 如請求項3之產品，其中該A/B比例係小於1.1。
- 如請求項1至4中任一項之產品，其中Nb2O5+Ta2O5<0.10%。
- 如請求項5之產品，其中Nb2O5+Ta2O5<0.05%。
- 如請求項1至4中任一項之產品，其中矽石SiO2之質量含量係大於4.8%。
- 如請求項1至4中任一項之產品，其中B2O3之質量含量係 小於0.80%。
- 如請求項1至4中任一項之產品，其中B2O3之質量含量係大於0.35%。
- 如請求項1至4中任一項之產品，其中Y2O3之質量含量係小於0.25%。
- 如請求項1至4中任一項之產品，其中Na2O+K2O之質量含量係小於0.04%，氧化鐵及/或氧化鈦(Fe2O3+TiO2)之質量含量係小於0.4%，P2O5之質量含量係小於0.05%，氧化鈣及/或氧化鍶及/或氧化鋇及/或氧化鎂及/或氧化鋅(CaO+SrO+BaO+MgO+ZnO)之總質量含量係小於0.3%及「其他氧化物種類」之總質量含量係小於0.6%。
- 如請求項11之產品，其中氧化鈣及/或氧化鍶及/或氧化鋇及/或氧化鎂及/或氧化鋅(CaO+SrO+BaO+MgO+ZnO)之總質量含量係小於0.05%。
- 如請求項1至4中任一項之產品，其中該其他氧化物種類之總質量含量係小於0.3%。
- 如請求項1至4中任一項之產品，其中矽石之質量含量係小於5.5%。
- 如請求項1至4中任一項之產品，其中Al2O3之質量含量係小於1.00%。
- 如請求項15之產品，其中Al2O3之質量含量係小於0.90%。
- 如請求項1至4中任一項之產品，其中Na2O+K2O<0.04%。
- 如請求項1至4中任一項之產品，其中該其他氧化物種類包含SnO2及/或CuO，且SnO2+CuO<0.05%。
- 一種玻璃熔爐，其在欲與熔融玻璃接觸之區域中包括如請求項1至18中任一項之產品。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1050601A FR2955578B1 (fr) | 2010-01-28 | 2010-01-28 | Produit refractaire a forte teneur en zircone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201136866A TW201136866A (en) | 2011-11-01 |
| TWI606025B true TWI606025B (zh) | 2017-11-21 |
Family
ID=42167616
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100103487A TWI606025B (zh) | 2010-01-28 | 2011-01-28 | 具高氧化鋯含量之耐火產品 |
| TW100103484A TWI535680B (zh) | 2010-01-28 | 2011-01-28 | 具高氧化鋯含量之耐火產品 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100103484A TWI535680B (zh) | 2010-01-28 | 2011-01-28 | 具高氧化鋯含量之耐火產品 |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US8796167B2 (zh) |
| EP (2) | EP2528878B1 (zh) |
| JP (3) | JP2013518026A (zh) |
| KR (2) | KR101790688B1 (zh) |
| CN (4) | CN102741194A (zh) |
| BR (2) | BR112012018402A2 (zh) |
| CA (2) | CA2787927A1 (zh) |
| EA (2) | EA023471B1 (zh) |
| FR (1) | FR2955578B1 (zh) |
| MX (2) | MX2012008646A (zh) |
| SG (2) | SG182723A1 (zh) |
| TW (2) | TWI606025B (zh) |
| WO (2) | WO2011092656A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2955578B1 (fr) | 2010-01-28 | 2014-06-13 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone |
| FR2955577B1 (fr) | 2010-01-28 | 2014-06-20 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone. |
| FR2969145B1 (fr) * | 2010-12-16 | 2013-01-11 | Saint Gobain Ct Recherches | Produit refractaire a haute teneur en zircone. |
| JP6140686B2 (ja) * | 2012-04-06 | 2017-05-31 | 旭硝子株式会社 | 高ジルコニア質電鋳耐火物 |
| TWI509077B (zh) * | 2012-05-10 | 2015-11-21 | China Steel Corp | Refractory coating for blast furnace castings for cooling pipes |
| FR3032963A1 (fr) * | 2015-02-20 | 2016-08-26 | Saint Gobain Ct Recherches | Produit fondu a forte teneur en zircone |
| TW201831410A (zh) * | 2017-01-03 | 2018-09-01 | 美商康寧公司 | 用於生產包含結晶氧化鋯的玻璃之裝置及方法 |
| WO2018162447A1 (en) | 2017-03-09 | 2018-09-13 | Merck Patent Gmbh | Organic semiconducting compounds |
| EP4253347A4 (en) * | 2020-11-24 | 2024-11-06 | Saint-Gobain TM K.K. | ELECTRO-MELTED REFRACTORY CASTING MATERIAL WITH HIGH ZIRCONIA CONTENT |
| CN113582731A (zh) * | 2021-08-20 | 2021-11-02 | 佛山石湾鹰牌陶瓷有限公司 | 一种哑光带立体感的数码干粒陶瓷砖及其制备方法 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1208577A (fr) | 1958-07-07 | 1960-02-24 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux |
| US3281137A (en) * | 1963-09-26 | 1966-10-25 | Corhart Refractories Co | Refractory and furnace lining |
| JPS6259576A (ja) * | 1985-09-10 | 1987-03-16 | 旭硝子株式会社 | 高ジルコニア質熱溶融耐火物 |
| JPH0694391B2 (ja) | 1987-05-18 | 1994-11-24 | 東芝モノフラックス株式会社 | 高ジルコニア鋳造耐火物 |
| FR2648455B1 (fr) * | 1989-06-15 | 1993-04-23 | Produits Refractaires | Produits refractaires fondus et coules a forte teneur en zircone |
| FR2701022B1 (fr) | 1993-02-03 | 1998-07-10 | Asahi Glass Co Ltd | Refractaires coules par fusion a forte teneur en zircone. |
| JP3518560B2 (ja) * | 1994-08-10 | 2004-04-12 | サンゴバン・ティーエム株式会社 | 高ジルコニア溶融耐火物 |
| JP4979047B2 (ja) * | 1999-04-22 | 2012-07-18 | サンゴバン・ティーエム株式会社 | 高ジルコニア鋳造耐火物 |
| JP2003292382A (ja) * | 2003-05-16 | 2003-10-15 | Saint-Gobain Tm Kk | 高ジルコニア溶融耐火物 |
| JP2004099441A (ja) * | 2003-11-25 | 2004-04-02 | Saint-Gobain Tm Kk | 高ジルコニア溶融耐火物 |
| RU2006124609A (ru) * | 2004-01-02 | 2008-01-20 | Везувиус Крусибл Компани (Us) | Огнеупорный материал |
| FR2897862B1 (fr) * | 2006-02-24 | 2008-05-09 | Saint Gobain Ct Recherches | Produit refractaire fondu et coule a forte teneur en zircone, presentant une resistivite electrique amelioree. |
| FR2897861B1 (fr) * | 2006-02-24 | 2008-06-13 | Saint Gobain Ct Recherches | Refractaire a forte teneur en zircone a grande resistivite |
| JP4658870B2 (ja) * | 2006-06-28 | 2011-03-23 | サンゴバン・ティーエム株式会社 | 高電気抵抗高ジルコニア鋳造耐火物 |
| FR2913013B1 (fr) * | 2007-02-23 | 2009-12-18 | Saint Gobain Ct Recherches | Bloc refractaire fondu et coule a forte teneur en zircone |
| FR2920153B1 (fr) | 2007-08-24 | 2010-11-26 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone dope. |
| JP5270913B2 (ja) * | 2007-12-26 | 2013-08-21 | サンゴバン・ティーエム株式会社 | 高電気抵抗高ジルコニア鋳造耐火物 |
| FR2932475B1 (fr) * | 2008-06-16 | 2010-09-03 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone |
| FR2942468B1 (fr) * | 2009-02-25 | 2012-06-29 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone. |
| FR2955577B1 (fr) | 2010-01-28 | 2014-06-20 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone. |
| FR2955578B1 (fr) | 2010-01-28 | 2014-06-13 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone |
-
2010
- 2010-01-28 FR FR1050601A patent/FR2955578B1/fr not_active Expired - Fee Related
-
2011
- 2011-01-28 CN CN2011800075905A patent/CN102741194A/zh active Pending
- 2011-01-28 TW TW100103487A patent/TWI606025B/zh active
- 2011-01-28 EP EP11705267.0A patent/EP2528878B1/fr active Active
- 2011-01-28 CN CN201611116090.6A patent/CN106986632A/zh active Pending
- 2011-01-28 BR BR112012018402A patent/BR112012018402A2/pt not_active IP Right Cessation
- 2011-01-28 EA EA201200970A patent/EA023471B1/ru not_active IP Right Cessation
- 2011-01-28 EP EP11704852.0A patent/EP2528877B1/fr active Active
- 2011-01-28 US US13/575,568 patent/US8796167B2/en active Active
- 2011-01-28 JP JP2012550552A patent/JP2013518026A/ja active Pending
- 2011-01-28 CN CN2011800075642A patent/CN102725246A/zh active Pending
- 2011-01-28 BR BR112012018404A patent/BR112012018404A2/pt not_active IP Right Cessation
- 2011-01-28 US US13/575,796 patent/US8859445B2/en active Active
- 2011-01-28 SG SG2012055075A patent/SG182723A1/en unknown
- 2011-01-28 CA CA2787927A patent/CA2787927A1/fr not_active Abandoned
- 2011-01-28 MX MX2012008646A patent/MX2012008646A/es not_active Application Discontinuation
- 2011-01-28 EA EA201200969A patent/EA201200969A1/ru unknown
- 2011-01-28 TW TW100103484A patent/TWI535680B/zh active
- 2011-01-28 CA CA2787925A patent/CA2787925A1/fr not_active Abandoned
- 2011-01-28 WO PCT/IB2011/050387 patent/WO2011092656A1/fr active Application Filing
- 2011-01-28 JP JP2012550551A patent/JP5837509B2/ja active Active
- 2011-01-28 CN CN201510408604.4A patent/CN105130462A/zh active Pending
- 2011-01-28 WO PCT/IB2011/050388 patent/WO2011092657A1/fr active Application Filing
- 2011-01-28 SG SG2012055059A patent/SG182721A1/en unknown
- 2011-01-28 MX MX2012008645A patent/MX2012008645A/es not_active Application Discontinuation
- 2011-01-28 KR KR1020127021015A patent/KR101790688B1/ko active Active
- 2011-01-28 KR KR1020127021013A patent/KR101779577B1/ko active Active
-
2015
- 2015-08-07 JP JP2015157045A patent/JP6100334B2/ja active Active
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