TWI411593B - 具有高氧化鋯含量之高電阻耐火物質 - Google Patents
具有高氧化鋯含量之高電阻耐火物質 Download PDFInfo
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- TWI411593B TWI411593B TW096106366A TW96106366A TWI411593B TW I411593 B TWI411593 B TW I411593B TW 096106366 A TW096106366 A TW 096106366A TW 96106366 A TW96106366 A TW 96106366A TW I411593 B TWI411593 B TW I411593B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 44
- 239000002019 doping agent Substances 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910001610 cryolite Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 239000006060 molten glass Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 abstract description 7
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 abstract 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 abstract 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract 1
- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 abstract 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 abstract 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 74
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000035899 viability Effects 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
- C04B35/484—Refractories by fusion casting
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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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- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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Description
本發明係關於一種新穎之具有高氧化鋯含量之經熔合和鑄造的耐火產物。
耐火產物包括經熔合和鑄造的產物,熟知其用於玻璃熔爐和燒結產物之建構。
與燒結產物不同地,經熔合和鑄造的產物通常包括連接晶粒之顆粒間的玻璃相。因此,與燒結產物及經熔合和鑄造的產物有關的問題及克服這些問題的技術解決方案通常不同。所以,以前開發之用於燒結產物之組成物本身無法用於經熔合和鑄造的產物,反之亦然。
經熔合和鑄造的產物常被稱為電熔合產物,係藉由在電弧爐中熔合適當的起始物之混合物或藉適用於該產物的任何其他技巧而得。熔合的液體於之後在模具中鑄造,且所得的產物被施以經控制的冷卻循環,以於無破裂的情況下到達常溫。此技術中,將此操作稱為"退火"。
經熔合和鑄造的產物包括具有高氧化鋯含量(即,包含高於85重量%的氧化鋯(ZrO2
))之電熔合產物,已知其品質具有極高耐蝕性,且不會使得所製得的玻璃著色,且不會產生裂紋。
通常,具有高氧化鋯含量之經熔合和鑄造的產物亦包括氧化鈉(Na2
O),以防止自存在於產物內的氧化鋯和氧化矽形成鋯石。鋯石之形成非所所欲者,此因其伴隨著體積降低約20%,因而製造出導致破裂之機械應力之故。
產品EPR-1195,其由SocitEuropenne des Produits Rfractaires生產和銷售並揭示於EP-B 0 403 387,其於目前被廣泛用於玻璃熔爐。其化學組成包含約94重量%氧化鋯、4%至5重量%氧化矽、約1重量%氧化鋁、0.3重量%氧化鈉和低於0.05重量%P2
O5
。其為典型之用於玻璃爐之高氧化鋯含量產物。
法國專利案FR-A-2 701 022描述具有高氧化鋯含量之經熔合和鑄造的產物,其含有0.05%至1.0重量%P2
O5
和0.05%至1.0重量%氧化硼B2
O3
。該產物具有高電阻。它們可以有利地安定電力玻璃熔合期間內之電力消耗,且特別可防止耐火物中之短路而造成們迅速損壞的問題。在電力玻璃熔合期間內,一部分電流通過耐火物。此耐火產物的電阻值之提高會減低可通過的電流量。
國際專利案WO-2005 068393描述經熔合和鑄造的產物,其具有高電阻值,具高氧化鋯含量且儘量減少BaO、SrO、MgO、CaO、P2
O5
、Na2
O和K2
O的量。這些產物含有0.1%至1.2重量%B2
O3
。
目前之發展朝向非常高品質的玻璃,特別是用於LCD型平面螢幕的玻璃,此提高了對於源自於玻璃熔爐之耐火產物之需求。特別地,對於具有進一步改良之電阻且維持對於熔合玻璃之良好耐蝕性之耐火產物有需求存在。
本發明滿足此需求。
更特別地,本發明提供具有高氧化鋯含量之經熔合和鑄造的產物,以相對於氧化物之重量%計,其包括以下的量超過98.5%,高於99%較佳,高於99.5%更佳:.ZrO2
+Hf2
O:>85%.SiO2
:1%至10%.Al2
O3
:0.1%至2.4%.B2
O3
:<1.5%,且.摻雜物,選自V2
O5
、CrO3
、Nb2
O5
、MoO3
、Ta2
O5
、WO3
和它們的混合物,其加權量以下列式(1)表示:0.2%2.43V2
O5
+8.84CrO3
+1.66Nb2
O5
+6.14MoO3
+Ta2
O5
+3.81WO3
較佳者以下列式(2)表示:0.2%2.43V2
O5
+4.42CrO3
+1.66Nb2
O5
+3.07MoO3
+Ta2
O5
+1.91WO3
令人訝異地,如下所示者,本發明之耐火產物具有顯著的電阻性並維持良好之抗熔合玻璃的腐蝕性。
較佳地,本發明之耐火產物亦具有下列可選用的特徵之一或多者(以多者為佳):.摻雜物的加權量是0.5%或以上,以0.6%或以上為佳,1.2%或以上更佳,和/或3%或以下,以2.5%或以下為佳,1.4%或以下更佳;.摻雜物選自V2
O5
、Nb2
O5
、Ta2
O5
、WO3
和它們的混合物,以Nb2
O5
、Ta2
O5
和它們的混合物為佳;.氧化矽SiO2
的量是2%或以上,以3%或以上為佳,3.8%或以上更佳,和/或8%或以下;.Al2
O3
/SiO2
比例低於0.5,以低於0.3為佳,低於0.25更佳。氧化矽含量低於2%時,此性質特別有利。
.B2
O3
的量高於0.05%,以高於0.1%為佳,和/或低於1%。當SiO2
<3%時,B2
O3
的量高於0.1%,或甚至高於0.2%,或甚至高於0.25%特別有用。
.此產物不包含V2
O5
。
.氧化釔Y2
O3
的量是1%或以下,以低於0.5%為佳,低於0.2%更佳;.氧化硼B2
O3
的量是1%或以下,以低於0.50%為佳;.氧化鋯(ZrO2
+Hf2
O)的量是90%或以上,以93%或以上為佳;.氧化鋁Al2
O3
的量是0.5%或以上,以0.6%或以上為佳,和/或1.5%或以下,以1%或以下為佳,0.85%或以下更佳;.耐火產物具有下列組成,ZrO2
+Hf2
O補足100%:.SiO2
:3.8%至4.8%.B2
O3
:<0.25%,.Al2
O3
:0.65%至0.85%.Y2
O3
:<0.45%.介於0.8%和1.2%之間的Ta2
O5
,或介於0.4%和0.9%之間的Nb2
O5
。
.雜質(主要是鐵、鈦、磷和鈣的氧化物)的量低於6%,以低於0.3%為佳。
有利地,這些特性可以進一步改良本發明之產物的電阻性和耐蝕性。
較佳地,本發明之耐火產物於100Hz[赫茲]頻率、1500℃的電阻值是200歐姆.公分或以上,以400歐姆.公分或以上為佳,600歐姆.公分或以上更佳。於950℃的電阻值可為至少10,000歐姆.公分,以至少20,000歐姆.公分為佳,至少25,000歐姆.公分更佳。其甚至可高於28,000歐姆.公分。
本發明亦提供玻璃熔爐,其包括本發明之耐火產物或根據本發明之方法製得或可製得之耐火產物,特別是位於欲與熔融玻璃接觸的區域。
本發明之爐中,有利地,此耐火產物可以是用以藉熔合(特別是電力熔合)而製造玻璃之槽的一部分,可於此處接觸溫度高於1200℃的熔融玻璃。
本發明之耐火產物不欲與溫度低於1100℃的熔融玻璃接觸。
本發明亦係關於電解槽,例如用以電解鋁者,其中,其包含多個耐火區塊,該區塊之至少一者係根據本發明之耐火產物或根據本發明之方法製得或可製得之耐火產物。特別地,此產物可為槽之側壁部分。其可位於與熔融的冰晶石接觸的區域。
最後,本發明提出製造本發明之耐火產物之方法,此方法包含下列順序的步驟:.混合起始物,包括引入摻雜物,以形成起始進料;.熔合該起始進料,以得到熔合的液體;和.鑄造和藉由經控制之冷卻而固化該熔合的液體,以得到耐火產物;.該方法之特徵在於選擇該起始物,以使得耐火產物係根據本發明。
此處所謂摻雜物的量或"加權"量指定其量為:2.43V2
O5
+8.84CrO3
+1.66Nb2
O5
+6.14MoO3
+Ta2
O5
+3.81WO3
較佳地,其量為:2.43V2
O5
+4.42CrO3
+1.66Nb2
O5
+3.07MoO3
+Ta2
O5
+1.91WO3
其中,氧化物的量以重量%表示。
除非特別聲明,否則本描述中之所有的百分比係相對於氧化物之重量%。
在本發明之經熔合和鑄造的產物中,高氧化鋯含量,即ZrO2
>85%,有助於滿足高耐蝕性及不會使製得的玻璃著色和產生缺陷(其會損及玻璃的品質)之需求。
存在於本發明之產物中之氧化鉿Hf2
O,是自然存在於氧化鋯來源中之氧化鉿。因此,其於本發明之產物中之含量是5%或以下,通常是2%或以下。
氧化矽之存在為形成顆粒間的玻璃相所必須者,顆粒間的玻璃相可以有效地容納氧化鋯於其可逆的同素異形轉變作用期間(即,在由單斜晶相轉變成四角錐相之變化期間)之體積變化。相對地,添加的氧化矽必須不超過10%,此因其添加將損及氧化鋯含量而導致耐蝕性降低之故。
氧化鋁之存在為形成安定的玻璃相和產物在模具中具有良好的流動性質所必須者。過量會使得玻璃相變得不安定(晶體形成)。
較佳地,本發明之產物包含的B2
O3
量為0.5%或以下。氧化硼事實上不利於產物中的鋯石之形成。此成份可改良產物的可行性。
氧化釔Y2
O3
對於電阻具有所不欲之影響,其存在的容忍量低於1%,以低於0.5%為佳,低於0.2%更佳。
摻雜物必須存在於本發明之產物中,以改良電阻性。然而,較佳地,該氧化物的總加權含量必須不超過4%,以使得氧化鋯的百分比維持於夠高的程度,以確保對於熔合玻璃腐蝕之良好耐受性及維持玻璃相安定。
本發明者已證實所有的五價摻雜物於相同的莫耳量時具有實質上相同的效果。此亦適用於所有的六價摻雜物。此外,本發明者已觀察到六價摻雜物M6+
的莫耳效率約是五價摻雜物M5+
的兩倍。不希望為特別的理論所限,本發明者以摻雜物扮演在氧化鋯中之氧空缺的角色來解釋此差異。事實上,六價摻雜物M6+
補償兩個氧空缺,而五價摻雜物M5+
則是補償一個氧空缺。因此,一莫耳五價摻雜物M2
O5
的氧化物所具有的效果與一莫耳六價摻雜物MO3
的氧化物相同。
摻雜物加權含量亦將摻雜物的莫耳質量之間的差異列入考慮。因此,1.66克Ta2
O5
所具有的效果等同於1克Nb2
O5
。
以其他物種將本發明之產物的組成補足至100%。所謂的"其他物種"是指其存在非特別所欲且通常以雜質形式存在於起始物中之物種。
舉例而言,可為鹼金屬氧化物,特別是氧化鈉Na2
O和氧化鉀K2
O,其可被容許但不應超過0.5%,以0.1%為佳,僅微量存在更佳。否則,電阻值將會因為玻璃相之提高的導電性而降低。也已經知道鐵、鈦和磷之氧化物有不利的影響,且它們的量必須限制於以雜質形式與起始物一起引入的微量。較佳地,Fe2
O3
+TiO2
的量低於0.55%且P2
O5
的量低於0.05%。
本發明之產物可於下文所描述的步驟a)至c)中製造:a)混合起始物,包括引入摻雜物,以形成起始進料;b)熔合該起始進料,以得到熔合的液體;和c)藉由經控制之冷卻而固化該熔合的液體,以得到根據本發明之耐火產物。
步驟a)中,添加摻雜物以確保在本發明之最終產物中之摻雜物量。
步驟b)中,熔合以藉比較長的電弧、無還原反應、攪動之合併作用進行為佳,以增進產物之再氧化反應。
欲儘可能減少具有金屬外觀的小瘤(nodule)形成及防止在最終產物中之破裂或裂紋形成,以於氧化性條件下進行熔合為佳。
較佳地,使用法國專利案第FR-A-1208577號及其追加案第75893和82310號中所描述的長弧熔合法。
該方法包含:使用電弧爐,其中的電弧介於進料和與該進料有一段距離的至少一個電極之間;調整該弧的長度,使其還原作用降至最低,並在熔合的熔融物上方維持氧化性環境;及藉弧本身的作用或藉由將氧化性氣體(例如,空氣或氧)通入熔融物中方式或藉由將釋出氧的物質(如,過氧化物)加至熔融物中的方式,攪動該熔融物步驟c)中,較佳地,冷卻速率低於20℃/小時,速率約10℃/小時更佳。
可以實施任何慣用的製造用於玻璃熔爐之以氧化鋯為基礎之熔合產物之方法,只要起始進料之組成可製得具有根據本發明之產物組成之產物即可。
以下列非限制例說明本發明。
實例中,使用下列起始物:.氧化鋯,基本上含有(以重量平均計):98.5%ZrO2
+Hf2
O,0.2%SiO2
和0.02%Na2
O;.含有33%氧化矽的鋯石砂;.AC44型氧化鋁,由Pechiney銷售且平均含有99.4%氧化鋁Al2
O3
;和.硼的氧化物、釔的氧化物、鉭的氧化物Ta2
O5
和鈮的氧化物Nb2
O5
,其純度超過99%。
產物1至39係使用慣用之電弧爐熔合法製得,之後鑄造得到尺寸為220x450x150毫米的塊狀物。
產物40至43係使用FR 1 430 962中所描述之藉由感應(迴圈直徑是275毫米,功率介於100和1000千瓦之間,藉非週期性的發電機輸送的頻率介於50和250kHz之間)而熔合之方法所製造。
所得產物之化學分析列於表1:此化學分析係以重量%表示。
此表中,空格對應於其量為0.05重量%或以下。(*
)代表樣品非屬本發明之範圍內。
製得之許多塊狀物的例子中,圓柱條直徑30毫米且高30毫米的產物於1伏特的電位差、頻率100赫茲、1500℃下測定電阻值R。
這些實例顯示,當摻雜物的總加權含量(Ta2
O5
+1.66Nb2
O5
)超過相對於氧化物重量計之0.2%(超過0.5重量%較佳)時,添加摻雜物可以明顯提高具有高氧化鋯含量之經熔合和鑄造的耐火產物之電阻值。因此,本發明之產物的電阻值高於200歐姆.公分。
表1的例子亦顯示多種摻雜物的莫耳當量。比較實例7和8或12和14的(Ta2
O5
+1.66Nb2
O5
)值和電阻值R之時,此當量特別清楚。
其他試驗顯示,當摻雜物的總加權含量提高超過3重量%,電阻值並未進一步提高。更佳地,將摻雜物的總加權含量限制於3重量%,使得氧化鋯的百分比維持於夠高的程度,以確保對於熔融玻璃之腐蝕的極佳耐受性。
實例(特別是相當於較佳組成的實例23)亦顯示摻雜物的總加權含量在0.5重量%至2重量%的範圍內時,添加摻雜物的效果最大。
實例19*
與實例9和10或23和24之比較顯示,提高氧化矽含量有利於改良產品的電阻值。因此,相對於氧化物之重量百分比,氧化矽含量必須大於2%,以大於3%為佳。
吾等亦觀察到,有利的情況為產物中之B2
O3
含量高於0.05%,高於0.1%較佳,高於0.2%更佳,特別是SiO2
<3%之時。
實例13*
相較於實例23和24及較低程度的實例26指出,若欲改良產物的電阻性,則提高氧化釔含量較為不利。
也必須注意到,將Na2
O含量值限制於0.1%或以下為佳,0.05%或以下更佳。較佳地,本發明之產物僅包括微量的Na2
O。如由實例15和16之比較可見者,氧化鈉Na2
O之存在,將因為玻璃相的低電阻而損及電阻性。
最後,由實例40至43亦可觀察到,使用感應爐也會導致良好的電阻性。令人訝異地,其他測試已證實使用感應爐,以連續熔合和固化(如FR 1 430 162中所描述者),得以製造氧化鋯含量特別均勻的產物。有利地提高使用壽命和此使用壽命的可預知性。
此外,其他試驗顯示,根據本發明之摻雜物存在時,認知之關於高氧化鋯材料的其他性質(特別是耐蝕性)並未惡化。
本發明之產物可以有利地用於要求耐火產物展現高電阻之任何其他應用。特別地,該產物可用以構築氧化鋁電解槽,此槽藉由在含有熔融冰晶石的浴液中,在溶液中之氧化鋁之電解作用而以工業方式產製金屬鋁。
電解質浴液正統上盛裝於電解槽中。此槽包含側壁和底部。底部由耐火底部塊體和陰極塊體及(在較低的部分)絕緣區塊所構成。側壁由側邊的耐火塊體所構成,其被金屬包裹物或封套所環繞,而或多或少地絕緣。
此區塊使用溫度是950℃或以下。
因此,以本發明之實例18於950℃的電阻值與以碳化矽(SiC)為基礎之參考用的塊體(被氮化矽基質(Si3
N4
)所圍住),根據與前述相同的程序,但於950℃作比較。
實例18於950℃的電阻值是30,000歐姆.公分,參考用的塊體則是6,000歐姆.公分。
使實例18的樣品和參考用的塊體(截面為25毫米x25毫米)在1030℃的熔融冰晶石浴中維持20小時,藉此評估被冰晶石所腐蝕的耐受程度。實例18的樣品之被腐蝕的體積(因腐蝕而減少的體積)是參考用的塊體的一半。
因此,本發明之耐火產物可以完美地用於電解槽,特別是用於鋁者,特別地,作為該槽之側壁部分和/或會與熔融的冰晶石接觸的區域。
顯然,本發明不限於此處以非限制例所描述和作為代表之執行方式。
Claims (29)
- 一種具有高氧化鋯含量之經熔合和鑄造的耐火產物,以相對於氧化物之重量%計,其包括以下的量高於98.5%:.ZrO2 +Hf2 O:>85%.SiO2 :1%至10%.Al2 O3 :0.1%至2.4%.B2 O3 :<1.5%,和.摻雜物,選自CrO3 、Nb2 O5 、MOO3 、Ta2 O5 、WO3 和它們的混合物,其加權量使得:0.2%8.84CrO3 +1.66Nb2 O5 +6.14MoO3 +Ta2 O5 +3.81WO3 。
- 根據申請專利範圍第1項之耐火產物,其中該加權量使得:0.2%4.42CrO3 +1.66Nb2 O5 +3.07MoO3 +Ta2 O5 +1.91WO3 。
- 根據申請專利範圍第1或2項之耐火產物,其中氧化矽SiO2 的量是2%或以上。
- 根據申請專利範圍第1或2項之耐火產物,其中Al2 O3 /SiO2 比例低於0.5。
- 根據申請專利範圍第1或2項之耐火產物,其中Al2 O3 /SiO2 比例低於0.3。
- 根據申請專利範圍第1或2項之耐火產物,其中摻雜物的加權量是0.5%或以上,和/或3%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其中摻雜物的加權量是0.6%或以上,和/或1.4%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其中摻雜物選自Nb2 O5 、Ta2 O5 、WO3 和它們的混合物。
- 根據申請專利範圍第1或2項之耐火產物,其中摻雜物選自Nb2 O5 、Ta2 O5 和它們的混合物。
- 根據申請專利範圍第1或2項之耐火產物,其中氧化矽SiO2 的量是3%或以上和/或8%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其中B2 O3 的量高於0.05%,和/或低於1%。
- 根據申請專利範圍第1或2項之耐火產物,其中B2 O3 的量高於0.1%。
- 根據申請專利範圍第11項之耐火產物,其中SiO2 的量低於3%。
- 根據申請專利範圍第1或2項之耐火產物,其中Y2 O3 的量是1%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其具有的電阻值於1500℃是至少200歐姆.公分,和/或於950℃是至少10,000歐姆.公分。
- 根據申請專利範圍第1或2項之耐火產物,其具有電阻值於1500℃是至少400歐姆.公分,和/或於950℃是至少25,000歐姆.公分。
- 根據申請專利範圍第1或2項之耐火產物,其中以相對於氧化物之重量%計,具有的氧化鋁含量(Al2 O3 )是1%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其中以相對於氧化物之重量%計,具有的氧化鋁含量(Al2 O3 )是0.85%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其中Na2 O含量是0.1%或以下。
- 根據申請專利範圍第1或2項之耐火產物,其具有下列組成,且ZrO2 +Hf2 O和雜質補足100%:.SiO2 :3.8%至4.8%.B2 O3 :<0.25%.Al2 O3 :0.65%至0.85%.Y2 O3 :<0.45%.介於0.8%和1.2%之間的Ta2 O5 ,或介於0.4%和0.9%之間的Nb2 O5 。
- 一種製造根據前述申請專利範圍任一項之耐火產物之方法,其包含下列順序的步驟:a)混合起始物,以形成起始進料;b)熔合該起始進料,以得到熔合的液體;c)鑄造和藉由經控制之冷卻而固化該熔合的液體,以得到耐火產物;該方法之特徵在於選擇該起始物,以使得耐火產物係根據前述申請專利範圍任一項。
- 根據申請專利範圍第21項之方法,其中熔合係於氧化性條件下進行。
- 根據申請專利範圍第21或22項之方法,其中熔合係以感應電爐或以長電弧進行。
- 根據申請專利範圍第21或22項之方法,其中,於步驟c),冷卻係以低於20℃/小時的速率進行。
- 一種玻璃熔爐,其特徵在於包括根據申請專利範圍第1至20項任一項之耐火產物或藉申請專利範圍第21至24項任一項製造或可藉其製造之耐火產物。
- 如申請專利範圍第25項之玻璃熔爐,該耐火產物係用於電力熔合製造玻璃之槽的一部分,可於此處接觸溫度高於1200℃的熔融玻璃。
- 一種包含多個耐火區塊的電解槽,其特徵在於該區塊之至少一者係根據申請專利範圍第1至20項任一項之耐火產物或藉申請專利範圍第21至24項任一項所製造或可藉其製造之耐火產物。
- 根據申請專利範圍第27項之電解槽,其中該耐火產物可接觸熔融的冰晶石。
- 根據申請專利範圍第27或28項之電解槽,其中該耐火產物係該槽之側壁的一部分。
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FR0601661A FR2897862B1 (fr) | 2006-02-24 | 2006-02-24 | Produit refractaire fondu et coule a forte teneur en zircone, presentant une resistivite electrique amelioree. |
FR0654305A FR2897861B1 (fr) | 2006-02-24 | 2006-10-16 | Refractaire a forte teneur en zircone a grande resistivite |
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TW200738580A TW200738580A (en) | 2007-10-16 |
TWI411593B true TWI411593B (zh) | 2013-10-11 |
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US (2) | US7687422B2 (zh) |
EP (1) | EP1986979B1 (zh) |
JP (1) | JP5519153B2 (zh) |
KR (1) | KR101389419B1 (zh) |
AT (1) | ATE538077T1 (zh) |
AU (1) | AU2007220395A1 (zh) |
BR (1) | BRPI0708085A2 (zh) |
CA (1) | CA2643334A1 (zh) |
EA (1) | EA013484B1 (zh) |
FR (1) | FR2897861B1 (zh) |
MX (1) | MX2008010850A (zh) |
TW (1) | TWI411593B (zh) |
WO (1) | WO2007099253A2 (zh) |
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FR2897861B1 (fr) * | 2006-02-24 | 2008-06-13 | Saint Gobain Ct Recherches | Refractaire a forte teneur en zircone a grande resistivite |
FR2907116B1 (fr) * | 2006-10-16 | 2008-12-19 | Saint Gobain Ct Recherches | Produit fritte a base de zircon+nb2o5 ou ta2o5 |
FR2910467B1 (fr) * | 2006-12-21 | 2010-02-05 | Saint Gobain Ct Recherches | Produit fritte dope a base de zircon et de zircone |
FR2913013B1 (fr) * | 2007-02-23 | 2009-12-18 | Saint Gobain Ct Recherches | Bloc refractaire fondu et coule a forte teneur en zircone |
FR2920152B1 (fr) * | 2007-08-24 | 2009-12-04 | Saint Gobain Ct Recherches | Refractaire a fortre teneur en zircone et teneur en silice elevee. |
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 |
FR2929941B1 (fr) * | 2008-04-15 | 2011-03-04 | Saint Gobain Ct Recherches | Produit fritte dope a base de zircon |
FR2940276B1 (fr) * | 2008-12-22 | 2011-02-04 | Saint Gobain Ct Recherches | Bloc refractaire et four de fusion de verre |
FR2942468B1 (fr) * | 2009-02-25 | 2012-06-29 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone. |
EP2418189B1 (en) | 2009-04-06 | 2016-08-17 | Asahi Glass Company, Limited | Highly zirconia-based refractory and its use for a melting furnace |
FR2953825B1 (fr) * | 2009-12-16 | 2013-12-20 | 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 |
KR20140000668A (ko) | 2010-10-06 | 2014-01-03 | 아사히 가라스 가부시키가이샤 | 고지르코니아질 전기 주조 내화물 |
EP2626339B1 (en) * | 2010-10-06 | 2018-06-06 | Asahi Glass Company, Limited | High zirconia refractory product |
FR2969145B1 (fr) * | 2010-12-16 | 2013-01-11 | Saint Gobain Ct Recherches | Produit refractaire a haute teneur en zircone. |
ITRM20110593A1 (it) * | 2011-11-09 | 2013-05-10 | Antonio Naddeo | Procedimento di fabbricazione di prodotti ignifughi |
FR2984878B1 (fr) | 2011-12-21 | 2014-02-28 | Saint Gobain Ct Recherches | Produit refractaire a forte teneur en zircone. |
US9725349B2 (en) * | 2012-11-28 | 2017-08-08 | Corning Incorporated | Glass manufacturing apparatus and methods |
JP6030953B2 (ja) | 2012-12-28 | 2016-11-24 | Agcセラミックス株式会社 | 高ジルコニア質電鋳耐火物 |
US11028001B2 (en) | 2016-11-08 | 2021-06-08 | Corning Incorporated | High temperature glass melting vessel |
JP7099898B2 (ja) | 2017-09-08 | 2022-07-12 | Agcセラミックス株式会社 | 高ジルコニア質電鋳耐火物及びその製造方法 |
EP3453689B1 (en) | 2017-09-08 | 2020-08-26 | AGC Ceramics Co., Ltd. | High-zirconia electrocast refractory and method for manufacturing the same |
FR3092579B1 (fr) * | 2019-02-11 | 2023-04-14 | Saint Gobain Ct Recherches | Produit refractaire a haute teneur en zircone |
JPWO2022114022A1 (zh) | 2020-11-24 | 2022-06-02 |
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- 2007-02-23 EP EP07731661A patent/EP1986979B1/fr active Active
- 2007-02-23 US US12/280,166 patent/US7687422B2/en active Active
- 2007-02-23 MX MX2008010850A patent/MX2008010850A/es active IP Right Grant
- 2007-02-23 JP JP2008555852A patent/JP5519153B2/ja active Active
- 2007-02-23 EA EA200801715A patent/EA013484B1/ru not_active IP Right Cessation
- 2007-02-23 AU AU2007220395A patent/AU2007220395A1/en not_active Abandoned
- 2007-02-23 KR KR1020087020509A patent/KR101389419B1/ko active IP Right Grant
- 2007-02-23 AT AT07731661T patent/ATE538077T1/de active
- 2007-02-23 BR BRPI0708085-9A patent/BRPI0708085A2/pt not_active IP Right Cessation
- 2007-02-23 CA CA002643334A patent/CA2643334A1/fr not_active Abandoned
- 2007-02-26 TW TW096106366A patent/TWI411593B/zh active
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Publication number | Publication date |
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US7687422B2 (en) | 2010-03-30 |
MX2008010850A (es) | 2008-09-05 |
CA2643334A1 (fr) | 2007-09-07 |
JP2009527454A (ja) | 2009-07-30 |
FR2897861B1 (fr) | 2008-06-13 |
BRPI0708085A2 (pt) | 2011-05-17 |
WO2007099253A2 (fr) | 2007-09-07 |
KR101389419B1 (ko) | 2014-04-25 |
EP1986979A2 (fr) | 2008-11-05 |
EP1986979B1 (fr) | 2011-12-21 |
US7655587B2 (en) | 2010-02-02 |
ATE538077T1 (de) | 2012-01-15 |
EA013484B1 (ru) | 2010-04-30 |
TW200738580A (en) | 2007-10-16 |
WO2007099253A3 (fr) | 2007-11-15 |
US20080076659A1 (en) | 2008-03-27 |
KR20080104124A (ko) | 2008-12-01 |
JP5519153B2 (ja) | 2014-06-11 |
US20090038936A1 (en) | 2009-02-12 |
FR2897861A1 (fr) | 2007-08-31 |
EA200801715A1 (ru) | 2008-12-30 |
AU2007220395A1 (en) | 2007-09-07 |
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