CN113454045B - 具有高含量氧化锆的耐火制品 - Google Patents
具有高含量氧化锆的耐火制品 Download PDFInfo
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- CN113454045B CN113454045B CN202080013867.4A CN202080013867A CN113454045B CN 113454045 B CN113454045 B CN 113454045B CN 202080013867 A CN202080013867 A CN 202080013867A CN 113454045 B CN113454045 B CN 113454045B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title description 30
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 229910052810 boron oxide Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 229910000449 hafnium oxide Inorganic materials 0.000 description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000012768 molten material Substances 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 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
- 230000035939 shock Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 oxynitrides Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001508691 Martes zibellina Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 238000000137 annealing Methods 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 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 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种熔铸耐火制品，以基于氧化物的重量百分比计且总计为100％，包含：‑ZrO2：至100％的余量；‑HfO2：<5％；‑SiO2：8.1％至12.0％；‑B2O3：0.20％至0.90％；‑Na2O+K2O：0.40％至0.80％；‑Al2O3：0.3％至2.0％；‑Y2O3：<2.0％；‑Fe2O3+TiO2：<0.6％；‑其他物质：<1.5％。
Description
技术领域
本发明涉及一种具有高氧化锆含量的熔凝耐火制品以及包括这种制品的玻璃熔炉。
背景技术
玻璃熔炉通常包括极其大量的耐火制品，这些耐火制品根据它们的特性而放置在不同的位置。对于熔炉的每个部位，所选择的制品将是不会引起使玻璃不可使用的缺陷(这会降低产量)，并且具有足够长的耐受时间以使熔炉具有令人满意的使用寿命的制品。
图1示意性地示出玻璃熔炉10的半个截面。可特别辨别的是槽12、金属结构14和上部结构16。
用于容纳熔融玻璃的槽12包括竖向侧壁22和底部24。侧壁22通常由在槽的整个高度上延伸直至上边缘25的侧槽块组成。
上部结构16通常包括在其基部的中间层18(通过该中间层，上部结构靠在金属结构上)、靠在中间层上的侧壁26、以及冠部28。未示出的燃烧器位于侧壁26中并交替运行。中间层18包括充填砖20，优选地由充填砖20组成。
上部结构部件经受各种热机械应力。首先，熔炉内部(在约1500℃的温度下)和冷却的外部(在接近环境温度的温度下，通常是由于鼓风冷却引起)之间存在高的热梯度。这种热梯度导致材料的与其热膨胀成比例的应变，因此这产生应力(该应变和材料的弹性模量的乘积)。由于熔炉的冷却或燃烧器系统的故障，这些部件也经受热冲击。因此，尽管热机械应力非常高，但上部结构部件必须经受住开裂。
上部结构还必须经受住熔炉的腐蚀性烟气和冷凝物的腐蚀。
为了经受住这些应力，上部结构由耐火制品制成的块组成。
在耐火制品中，区分熔凝块和烧结块。
与烧结块不同，熔凝块通常包括连接晶粒的晶间玻璃相。因此，烧结块和熔凝块所遇到的问题以及为解决这些问题所采用的技术方案通常是不同的。因此，为制造烧结块而研发的组合物不能先验地同样用于制造熔凝块，反之亦然。
熔凝块，通常称为“电熔”或“熔铸”块，是通过在电弧炉中或通过任何其他合适的技术将合适原材料的混合物熔化而获得的。然后通常将熔化的材料浇铸在模具中，然后凝固。通常，获得的产品然后经历受控的冷却循环以便在没有破裂的情况下达到环境温度。该操作被本领域技术人员称为“退火”。
目前，为了形成上部结构，主要利用熔凝块，特别是含有30％至45％的氧化锆的氧化铝-氧化锆-二氧化硅类型(简称AZS)的制品。
此外，已知具有非常高的氧化锆含量(VHZC)的熔凝块，其通常包含按重量计超过80％或超过85％的氧化锆。它们以其非常高的耐腐蚀性和不使生产的玻璃着色且不在生产的玻璃中产生缺陷的能力而闻名。
EP 403 387描述了具有高氧化锆含量的熔铸制品，其含有按重量百分比计4％至5％的SiO2、约1％的Al2O3、0.3％的氧化钠、和小于0.05％的P2O5。
FR 2 701 022描述了具有高氧化锆含量的熔铸制品，其含有按重量百分比计0.05％至1.0％的P2O5和0.05％至1.0％的硼氧化物B2O3。
FR 2 723 583描述了具有高氧化锆含量的熔铸制品，其含有按重量百分比计3％至8％的SiO2、0.1％至2.0％的Al2O3、0.05％至3.0％的硼氧化物B2O3、0.05％至3％的BaO+SrO+MgO、0.05％至0.6％的Na2O+K2O、和小于0.3％的Fe2O3+TiO2。
具有非常高的氧化锆含量的熔凝块，例如由SEFPRO公司生产和销售的ER 1195，如今被广泛用于玻璃熔炉中。然而，它们的高成本和它们的特性可能限制它们的使用，其主要集中在与玻璃接触的块上，特别是在槽的最大应力的区域中的块上。
需要具有耐腐蚀性和具有在机械应力下的断裂强度，使得它们适用于玻璃熔炉的上部结构中的耐火制品。
本发明旨在满足这种需求。
发明内容
本发明提供了一种熔铸耐火制品，以基于氧化物的重量百分比计且总计为100％，其包含：
如将在本说明书的其余部分更详细地看到的，这种组合物使熔凝制品在玻璃熔炉的上部结构的环境中具有显著的机械性能。测试也已证明了低渗出。因此，根据本发明的制品完全适用于上部结构中。
根据本发明的制品还可以具有以下任选特征中的一者或多者，当它与以下描述的特定实施方式一致时以及当这些任选的特征与所述特定的实施方式相容时包括：
-制品的总孔隙率小于10％、或者甚至小于5％；
-优选地，氧化物占制品重量的超过90％、超过95％、超过99％、或甚至基本上100％；
-ZrO2+HfO2的重量含量小于92.0％、或甚至小于90.0％、或甚至小于89.0％，和/或大于83.0％、或甚至大于84.0％、或大于85.0％；
-SiO2的重量含量大于8.4％、或甚至大于8.5％、或甚至大于8.6％、或甚至大于8.8％、或甚至大于9.1％，和/或小于11.5％、或甚至小于11.0％、或甚至小于10.8％、或甚至小于10.6％；
-硼氧化物B2O3、钠氧化物Na2O和钾氧化物K2O的重量含量之和大于0.65％、或甚至大于0.70％、或甚至大于0.75％，和/或小于1.20％、或甚至小于1.10％、或甚至小于1.00％；
-硼氧化物B2O3的重量含量大于0.25％、或甚至大于0.30％、或甚至大于0.35％、或甚至大于0.40％，和/或小于0.85％、小于0.80％、小于0.75％、小于0.70％、小于0.60％、或甚至小于0.55％；
-钠氧化物Na2O和钾氧化物K2O的重量含量之和大于0.45％，和/或小于0.75％、小于0.65％；
-Na2O的重量含量大于0.40％、或甚至大于0.45％、或甚至大于0.50％，和/或小于0.80％、或甚至小于0.70％、或甚至小于0.60％；
-K2O作为杂质存在或部分替代Na2O，并且K2O的重量含量小于0.70％、或甚至小于0.60％、或甚至小于0.50％、或甚至小于0.40％、或甚至小于0.30％；
-Al2O3的重量含量小于1.9％、或甚至小于1.8％、或小于1.7％，和/或大于0.5％、或甚至大于0.6％、或甚至大于0.7％、或甚至大于0.9％、大于1.0％、或甚至大于1.1％、或甚至大于1.2％；
-Y2O3的重量含量大于0.5％、或甚至大于0.7％、或甚至大于0.9％、或甚至大于1.0％、或甚至大于1.1％，和/或小于1.9％、或甚至小于1.8％、或甚至小于1.7％、或甚至小于1.6％；
-铁氧化物和钛氧化物Fe2O3+TiO2的重量含量之和小于0.4％、优选小于0.3％、优选小于0.2％；
-“其他物质”的总重量含量小于1.2％、或甚至小于1.0％、或甚至小于0.6％、或甚至小于0.5％、或甚至小于0.4％；
-“其他物质”仅由杂质组成；
-任一“其他物质”的重量含量小于0.40％、或甚至小于0.30％、或甚至小于0.20％；
-钙氧化物CaO、钡氧化物BaO、锶氧化物SrO和镁氧化物MgO的重量含量之和小于0.60％、小于0.50％、小于0.40％、或甚至小于0.30％；
-CaO的重量含量小于0.60％、或甚至小于0.40％、或甚至小于0.30％；
-BaO的重量含量小于0.60％、或甚至小于0.40％、或甚至小于0.30％、小于0.20％、小于0.10％、小于0.05％、或基本上为零；
-SrO的重量含量小于0.60％、或甚至小于0.40％、或甚至小于0.30％、小于0.20％、小于0.10％、小于0.05％、或基本上为零；
-MgO的重量含量小于0.60％、或甚至小于0.40％、或甚至小于0.30％；
-Ta2O5的重量含量小于0.20％、小于0.10％、小于0.05％、或基本上为零；
-Nb2O5的重量含量小于0.20％、小于0.10％、小于0.05％、或基本上为零。
根据一个特定的实施方式，本发明提供了一种熔铸耐火制品，以基于氧化物的重量百分比计，其包含：
根据一个特定的实施方式，本发明提供了一种熔铸耐火制品，以基于氧化物的重量百分比计，其包含：
根据一个特定的实施方式，本发明提供了一种熔铸耐火制品，以基于氧化物的重量百分比计，其包含：
本发明还涉及一种制造根据本发明的耐火制品的方法，包括以下依次进行的步骤：
a.混合原材料以形成进料，
b.将所述进料熔化直到获得熔化的材料，
c.将所述熔化的材料浇铸且通过冷却将所述熔化的材料凝固，以获得耐火制品，
该方法值得注意的是，选择所述原材料使得所述耐火制品符合本发明。
优选地，需要最低含量的氧化物或这些氧化物的前体被系统地且有条理地添加。优选地，考虑这些氧化物在它们作为杂质而存在的其他氧化物源中的含量。
优选地，控制冷却，优选以便以每小时小于20℃的速率，优选以每小时约10℃的速率进行冷却。
本发明还涉及包括根据本发明的耐火制品的玻璃熔炉，或涉及按照根据本发明的方法制造的或能够按照根据本发明的方法已被制造的耐火制品，特别是在不用于与熔融玻璃接触的区域中、特别是在上部结构中、特别是在冠部中的耐火制品。
定义
当制品通过执行进料的熔化直到获得熔化的材料，然后通过冷却凝固该材料的方法而获得时，该制品通常被称作是“熔凝的”。
块是这样的物体，其所有的尺寸都大于10mm，优选大于50mm，优选大于100mm，且与层不同，其通过包括模制且从模具中移出的操作的方法而获得。块可以例如具有总体平行六面体的形状或者适合其使用的特定形状。
除非另有说明，否则在根据本发明的制品中所有的氧化物的含量都是基于氧化物的重量百分比。根据工业惯例，金属元素的氧化物的重量含量涉及以最稳定氧化物形式表示的该元素的总含量。
HfO2不能与ZrO2化学分离。然而，根据本发明，HfO2不被有意添加到进料中。因此，HfO2仅表示痕量的铪氧化物，这种氧化物总是以通常小于5％、通常小于2％的含量天然存在于锆氧化物源中。在根据本发明的块中，HfO2的重量含量小于5％、优选小于3％、优选小于2％。为清楚起见，可以无区别地用“ZrO2”或“ZrO2+HfO2”表示锆氧化物和痕量铪氧化物的总含量。因此，HfO2不包括在“其他物质”中。
术语“杂质”理解为是指与原材料一起引入或由与这些成分反应产生的不可避免的成分。杂质不是必需的成分，而仅仅是可以接受的。例如，属于氧化物、氮化物、氮氧化物、碳化物、碳氧化物、碳氮化物的组的化合物和铁、钛、钒和铬的金属物质是杂质。
附图说明
本发明的其他特征和优点在阅读以下的详细说明和查阅附图后将变得更加明显，其中前言部分中描述的图1示意性地示出玻璃熔炉的半个截面。
具体实施方式
在根据本发明的熔铸制品中，高含量的ZrO2可以满足高耐腐蚀性的要求，而不会产生对玻璃质量有害的缺陷。
存在于根据本发明的制品中的铪氧化物HfO2是天然存在于ZrO2源中的铪氧化物。因此，其在根据本发明的制品中的含量小于5％，通常小于2％。
SiO2的存在尤其使得可以形成能够有效适应氧化锆骨架变形的晶间玻璃相。另一方面，SiO2的添加不应超过12％，因为这种添加是以氧化锆含量为代价进行的且因此会不利于耐腐蚀性。
Al2O3的存在对于稳定玻璃相的形成和熔化的材料在模具中的良好可铸性特别有用。然而，Al2O3的添加应该受到限制，因为太高的重量含量会导致玻璃相的不稳定性(莫来石晶体的形成)，特别是存在硼氧化物的情况下。
B2O3和Na2O+K2O的同时存在可以提高制品的可行性。B2O3对制品中锆石的形成有不利影响，其会对耐热循环性产生不利影响。因此，硼氧化物B2O3的重量含量应保持是限量的。
优选地，Na2O+K2O的重量含量被限制以限制原材料、特别是硼氧化物的挥发。在根据本发明的制品中，认为氧化物Na2O和K2O具有相似的效果。
在一个实施方式中，Na2O含量和K2O含量中的至少一者大于0.30％、优选大于0.35％、优选大于0.40％。
根据一个特定的实施方式：
-SiO2： 8.5％至10.8％
-B2O3： 0.30％至0.70％
-Al2O3： 1.0％至1.8％
Na2O含量和K2O含量中的至少一者大于0.30％、优选大于0.35％、优选大于0.40％。
应限制钇氧化物Y2O3的重量含量以保持良好的可行性。
根据本发明，Fe2O3+TiO2的重量含量小于0.50％、优选小于0.30％。优选地，P2O5的重量含量小于0.05％。具体而言，这些氧化物是有害的，它们的含量应限制为作为杂质随原材料引入的痕量。
“其他物质”是上面未列出的氧化物物质，即不同于ZrO2、HfO2、SiO2、Y2O3、B2O3、Al2O3、Na2O、K2O、TiO2和Fe2O3的物质。在一个实施方式中，“其他物质”限于其存在不是特别期望的且其通常作为原材料中的杂质存在的物质。
优选地，根据本发明的制品是块的形式。
根据本发明的制品的总孔隙率小于15％、或甚至小于10％、或甚至小于5％、或甚至小于2％、或甚至小于1％。
根据本发明的制品可以根据以下描述的步骤a至步骤c进行常规地制造：
a.混合原材料以形成进料，
b.将所述进料熔化直到获得熔化的材料，
c.通过冷却将所述熔化的材料凝固，以获得根据本发明的耐火制品。
在步骤a中，选择原材料以保证制成品中氧化物的含量。
在步骤b中，优选地通过不产生还原的相对长的电弧和促进制品再氧化的混合的联合作用进行熔化。
为了最小化金属外观的结核(nodule)的形成并防止在最终制品中狭缝或裂纹的形成，优选在氧化条件下进行熔化。
优选地，使用在法国专利No.1 208 577及其增补专利No.75893和No.82310中描述的长弧熔化工艺。
该工艺在于使用电弧炉，其中电弧在进料和与该进料分开的至少一个电极之间涌出，并调整电弧的长度以使其还原作用最小化，同时保持熔融浴上方的氧化气氛，并且通过电弧本身的作用，或通过向浴中鼓入氧化气体(例如空气或氧气)，或通过向浴中添加如过氧化物或硝酸盐的释放氧气的物质来混合所述熔融浴。
在步骤c中，冷却优选以小于20℃/小时的速率进行，优选以约10℃/小时的速率进行。
可以使用用于制造意在玻璃熔炉中应用的基于氧化锆的熔融制品的任何常规方法，条件是进料的组成能够获得具有与根据本发明的制品的组成一致的组成的制品。
在根据本发明的制品中，ZrO2基本上完全(通常超过其重量的95％)呈氧化锆的形式，SiO2和Al2O3基本上完全(通常超过其重量的95％)在玻璃相中。
实施例
出于说明本发明的目的给出以下的非限制性实施例。
在这些实施例中，使用了以下的原材料：
-平均含有99％的ZrO2+HfO2的氧化锆Q1，
-平均含有33％的SiO2和66％的ZrO2+HfO2的锆砂，
-平均含有99％的SiO2的“Sable BE01 Bédouin”(BE01 Bedouin砂)二氧化硅，
-平均含有98％的B2O3的硼氧化物，
-平均含有99.5％的Na2CO3作为Na2O源的碳酸钠，
-平均含有99％的Al2O3的AC34型氧化铝，
-平均含有99％的Y2O3的钇氧化物。
根据常规的电弧炉熔化工艺制备制品，然后浇铸以获得测量为996mm x203mm x800mm的块。
在表1给出所得制品的化学分析；它是平均化学分析，以重量百分比给出。
耐热机械应力性
为了研究制品承受上部结构的块所经受的热机械应力的能力，本发明人使用了将MOR/MOE比率与耐热冲击性联系起来的Kingery理论和将断裂能量与耐热冲击性联系起来的Hasselman理论。此外，在线性弹性力学中，热机械应力的严重程度与断裂模量(MOR)和弹性模量(MOE)之间的比率有关联。这个比率应该最大化，就像断裂能量一样，使得制品耐热机械源的开裂。将制品放置在1000℃，这基本上相当于块核心的温度。
MOR测量
断裂模量(MOR)是对于尺寸为150×25×15mm3的样品在1000℃空气中测量的最大应力，该样品放置在3点弯曲组件中，其中两个下支承件之间的距离为120mm，沿样品长度的一半提供上支承件的冲头(punch)的下降速率等于0.5毫米/分钟。MOR的值是三次连续测量的平均值。
MOE测量
为了测量MOE，使用与对于MOR描述的组件相同的组件和位移传感器来监测样品偏转的位移并确定MOE，即应力和由该应力引起的弹性应变之间的比率。
断裂能量测量
断裂能量是在1000℃下，在空气中，对于尺寸为150×25×25mm3且其中间具有60°角和25mm底边的三角形凹口的样品进行测量，该样品放置在4点弯曲组件中，其中两个下支承件之间的距离为120mm，两个上支承件之间的距离为40mm。上支承件的下降速率等于20μm/min。
耐腐蚀性测量
通过在1450℃的炉子中旋转(6rpm)的4个尺寸为110×100×30mm3的样品上方，以每小时180克的速度总计20千克，喷洒由50％的碎玻璃、15％的二氧化硅、5％的白云石和30％的碳酸钠组成的粉末，来测量耐腐蚀性(CR)。腐蚀体积通过3D扫描测量，该体积与初始体积相关。
渗出测量
耐渗出性(REx)是在空气中对尺寸为100×100×20mm3的样品进行测量。样品经历循环，在该循环期间样品以每小时100℃的速度升至1550℃，然后在1550℃保持6小时。REx是相对于样品的初始体积，在两个循环后从样品中逸出的硅酸盐相(在样品上(样品体积的增加)或者在坩埚的底部发现的)的体积的百分比。将样品放置在1550℃，这基本上相当于暴露于槽内部的块的表面的温度。
实施例1和实施例2分别对应于传统的AZS制品和具有高氧化锆含量的传统产品。
余量对应于ZrO2+HfO2的含量以及杂质(在这些实施例中杂质的含量总是小于0.5％)。
[表1]
| 1* | 2* | 3 | 4 | |
| SiO2 | 15.0 | 4.3 | 10.1 | 8.5 |
| Al2O3 | 50.9 | 1.2 | 1.7 | 1.6 |
| Na2O | 1.30 | 0.22 | 0.43 | 0.43 |
| B2O3 | <0.2 | <0.2 | 0.47 | 0.26 |
| Y2O3 | <0.2 | <0.2 | 0.51 | 1.19 |
| MOR/MOE | 1.80 | 1.40 | 3.16 | 2.13 |
| 断裂能量 | 0.4kJ/m2 | 0.5kJ/m2 | 4.0kJ/m2 | 1.2kJ/m2 |
| CR | 4.30％ | ND | <0.5％ | ND |
| REx | 4.78％ | 0.77％ | 0.71％ | 0.16％ |
*本发明之外
测试表明，相对于比较制品2，根据本发明的制品3和制品4具有改善的耐热机械应力性和更高的断裂能量。
根据本发明的制品的渗出程度极好。
显然，本发明因此提供了一种制品，其在玻璃熔炉上部结构的环境中具有显著的机械性能，并且在运行中具有低渗出。
当然，本发明不限于所描述和表示的实施方式，这些实施方式仅通过说明的方式提供。
Claims (9)
1.一种玻璃熔炉，所述玻璃熔炉包括位于上部结构中且由熔铸耐火制品制成的块，以基于氧化物的重量百分比计且总计为100％，所述熔铸耐火制品包含：
2.根据权利要求1所述的玻璃熔炉，其中，在所述熔铸耐火制品中：
-83.0％<ZrO2+HfO2；和/或
-8.4％<SiO2<11.5％；和/或
-0.25％<B2O3<0.75％；和/或
-0.45％<Na2O+K2O<0.75％；和/或
-0.6％<Al2O3<1.9％；和/或
-0.5％<Y2O3<1.9％；和/或
-Fe2O3+TiO2<0.4％；和/或
-其他物质<1.2％。
3.根据权利要求2所述的玻璃熔炉，其中，在所述熔铸耐火制品中：
-84.0％<ZrO2+HfO2<90.0％；和/或
-8.8％<SiO2<11.0％；和/或
-0.40％<B2O3<0.70％；和/或
-0.45％<Na2O+K2O<0.65％；和/或
-0.8％<Al2O3<1.7％；和/或
-0.7％<Y2O3<1.7％；和/或
-Fe2O3+TiO2<0.3％；和/或
-其他物质<1.0％。
4.根据权利要求3所述的玻璃熔炉，其中，在所述熔铸耐火制品中：
-85.0％<ZrO2+HfO2<90.0％；和/或
-9.1％<SiO2<10.8％；和/或
-0.40％<B2O3<0.60％；和/或
-0.9％<Al2O3<1.7％；和/或
-1.0％<Y2O3<1.6％；和/或
-Fe2O3+TiO2<0.2％；和/或
-不同于ZrO2、HfO2、SiO2、Y2O3、B2O3、Al2O3、Na2O、K2O、TiO2和Fe2O3的物质：<0.5％。
5.根据权利要求1所述的玻璃熔炉，其中，以基于氧化物的重量百分比计，所述熔铸耐火制品包含：
6.根据权利要求5所述的玻璃熔炉，其中，以基于氧化物的重量百分比计，所述熔铸耐火制品包含：
7.根据权利要求5所述的玻璃熔炉，其中，以基于氧化物的重量百分比计，所述熔铸耐火制品包含：
8.根据权利要求1至4中任一项所述的玻璃熔炉，其中，在所述熔铸耐火制品中：CaO+MgO+BaO+SrO<0.60％。
9.根据权利要求1至4中任一项所述的玻璃熔炉，其中，所述块的所有尺寸大于10mm。
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| FR1208577A (fr) | 1958-07-07 | 1960-02-24 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux |
| FR75893E (fr) | 1959-06-11 | 1961-08-18 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux |
| FR82310E (fr) | 1962-04-07 | 1964-01-24 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électro-fondus contenant des oxydes minéraux |
| 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. |
| US5679612A (en) | 1994-08-10 | 1997-10-21 | Toshiba Monofrax Co., Ltd. | High-zirconia fused refractories |
| US7598195B2 (en) | 2004-01-02 | 2009-10-06 | Refractory Intellectual Property Gmbh & Co. Kg | Fusion-cast refractory with high electrical resistivity |
| 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 |
| CN102369170B (zh) | 2009-04-06 | 2014-11-12 | 旭硝子株式会社 | 高氧化锆质耐火材料及熔融窑 |
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