CN117326864B - 高电阻率高锆砖及其制备方法 - Google Patents
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- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 48
- 239000011449 brick Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000011819 refractory material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011651 chromium Substances 0.000 description 10
- 239000012768 molten material Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 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
- 230000008859 change Effects 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
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Abstract
本发明涉及一种高电阻率高锆砖及其制备方法，涉及耐火材料的技术领域。本发明的高电阻率高锆砖通过电熔铸造而成并且以重量百分比计包含：86.1‑91.0％的ZrO2、7.5‑10.5％的SiO2、1.2‑2.1％的Al2O3、0.01‑0.10％的Na2O、0.12‑0.20％的K2O、0.30‑0.70％的Cr2O3，并且其他成分的含量小于0.20％，Al2O3/Cr2O3的比值为3～4；所述高锆砖的晶相结构由斜锆石和玻璃相组成，所述玻璃相的含量为9.0～13.0％，斜锆石的含量为87.0～91.0％。本发明的高电阻率高锆砖进一步提高了高温条件下的电阻率，降低了抗玻璃液侵蚀的速率，有利于确保玻璃窑炉的安全运行，同时也减少了电熔砖对玻璃的污染，适用于高品质玻璃的生产，例如可用于生产液晶玻璃基板等。
Description
技术领域
本发明涉及耐火材料的技术领域，涉及一种高温使用条件下具有高电阻率且耐腐蚀性优异的高电阻率高锆砖及其制备方法。
背景技术
熔铸耐火材料具有优越的抗侵蚀性，而且化学稳定性、高温热稳定性良好，玻璃相渗出温度高，对玻璃液的污染小等一系列优点，被广泛应用于玻璃窑炉的制备中，是玻璃窑炉的关键材料。与烧结产品不同，熔铸产品通常包括连接晶粒的晶间玻璃相，具有更高的密度以及对熔融玻璃更为优异的耐蚀性。熔铸耐火材料是将原料组分添加到电弧炉中融化，然后通过浇铸、退火得到的产品。
含有80wt％以上氧化锆的熔铸耐火材料被称为高锆耐火材料，其具有对所有种类的熔融玻璃的高耐侵蚀性，特别适合于高品质玻璃的制备。近年来随着玻璃窑炉的大型化发展，玻璃窑炉火焰温度的升高，对高锆耐火材料的性能提出了更高的要求。尤其是对于液晶玻璃基板玻璃生产窑炉的池壁、铺面、通道支撑等部位，需要更高的电阻率以及更低的抗玻璃液侵蚀速度、更低的玻璃相渗出量的高锆砖。
发明内容
为了满足玻璃窑炉以及极高品质玻璃生产的性能需求，本发明的目的在于提供一种高温使用条件下具有高电阻率且耐腐蚀性优异的高锆砖及其制备方法。
本发明的第一方面涉及一种高电阻率高锆砖，所述高锆砖通过电熔铸造而成并且以重量百分比计包含：86.1-91.0％的ZrO2、7.5-10.5％的SiO2、1.2-2.1％的Al2O3、0.01-0.10％的Na2O、0.12-0.20％的K2O、0.30-0.70％的Cr2O3，并且其他成分的含量小于0.20％，Al2O3/Cr2O3的比值为3～4；所述高锆砖的晶相结构由斜锆石和玻璃相组成，所述玻璃相的含量为9.0～13.0％，斜锆石的含量为87.0～91.0％。
其中，所述ZrO2中含有天然存在的HfO2，并且HfO2的含量为2％以下。
其中，所述高电阻率高锆砖基本不含有SrO和BaO，所述SrO的含量小于0.01％，所述BaO的含量小于0.01％。
其中，所述高电阻率高锆砖基本不含有P2O5和B2O3，所述P2O5的含量小于0.01％，B2O3的含量小于0.01％。
其中，所述高电阻率高锆砖基本不含有MgO和CaO，所述MgO的含量小于0.01％，所述CaO的含量小于0.01％。
其中，所述其他成分中TiO2+Fe2O3的含量小于0.20％。
其中，所述高锆砖在1650℃和100Hz频率的条件下，电阻率≥230Ω·cm；所述高锆砖在1500℃和100Hz频率的条件下，电阻率≥500Ω·cm。
其中，所述高锆砖在1500℃×24h条件下抗玻璃液侵蚀速度≤0.8mm。
其中，所述高锆砖在1500℃×4h条件下，玻璃相渗出量≤0.4。
本发明的第二方面还涉及上述高电阻率高锆砖的制备方法，所述制备方法包括以下步骤：
(1)将提供ZrO2、SiO2、Al2O3、Na2O、K2O和Cr2O3的起始原料混合均匀得到混合料；
(2)将所述混合料在电弧炉中加热熔化得到熔融液体；
(3)将所述熔融液体浇铸到铸型中凝固，保温退火，并加工得到所述高锆砖。
与现有技术相比，本发明的高电阻率高锆砖具有以下有益效果：
本发明的高电阻率高锆砖进一步提高了高温条件下的电阻率，降低了抗玻璃液侵蚀的速率，不仅降低了制备过程中的电力损耗，也有利于确保玻璃窑炉的安全运行，提高使用寿命；同时也减少了电熔砖对玻璃的污染，适用于高品质玻璃的生产，例如可用于生产液晶玻璃基板等。
具体实施方式
以下将结合具体实施例对本发明的高电阻率高锆砖做进一步的阐述，以帮助本领域的技术人员对本发明的技术方案有更完整、准确和深入的理解。
本发明提供一种高电阻率高锆砖，所述高锆砖通过熔铸而成，以重量百分比计包含：86.1-91.0％的ZrO2、7.5-10.5％的SiO2、1.2-2.1％的Al2O3、0.01-0.10％的Na2O、0.12-0.20％的K2O、0.30-0.70％的Cr2O3，并且其他成分的含量小于0.20％，Al2O3/Cr2O3的比值为3～4。所述高锆砖的晶相结构由斜锆石和玻璃相组成，所述玻璃相的含量为9.0～13.0％，斜锆石的含量为87.0～91.0％。
所述ZrO2中含有天然存在的HfO2，并且HfO2的含量为2％以下；在本发明中所述ZrO2是形成斜锆石相的主要成分，为了提供足够优异的耐熔融玻璃腐蚀性，ZrO2的含量至少为86.1％，优选至少为88％，当然如果ZrO2的含量如果高于91.0％，则玻璃相的含量不足，从而难以吸收由于斜锆石晶体的转变而导致的膨胀收缩，从而容易导致裂纹的形成。SiO2的存在对于晶间玻璃相的形成是必须的，在本发明的组成体系中，如果SiO2的含量低于7.5％，则形成的玻璃相不足，而当SiO2的含量超过10.5％时，则会劣化耐火材料的耐腐蚀性。Al2O3可降低玻璃相的熔化温度，而且能够抑制玻璃相中ZrO2组分的浓度，防止在玻璃相中ZrO2·SiO2的晶体，为此，Al2O3的含量至少应为1.2％，但当Al2O3的含量超过2.1％时，则在玻璃相中有形成晶体沉淀的趋势。Na2O和K2O有利于降低玻璃基质的粘度，而且抑制玻璃相中ZrO2·SiO2的形成，但引入Na2O会导致电阻率的降低，虽然K2O的引入也会导致电阻率的降低，但其对电阻率的影响较小。而在本发明中，引入含量在0.30-0.70％的Cr2O3会抑制Na+、K+的迁移，从而可以屏蔽Na+、K+对电阻率的影响，从而能够获得高的电阻率。在本发明中，Al2O3/Cr2O3的比值在3～4之间时，不仅有利于保证玻璃相的含量，而且能够防止沉淀的形成，抑制残余体积变化的影响，从而有利于减少玻璃相渗出量，并且降低抗玻璃液侵蚀速度。本发明的高电阻率高锆砖基本不含有SrO和BaO，所述SrO的含量小于0.01％，所述BaO的含量小于0.01％。SrO和BaO主要存在于玻璃相中，其不仅可能影响耐火材料的耐玻璃腐蚀性，而且可能形成Sr或Ba的硅酸盐化合物，使得玻璃相不稳定。P2O5和B2O3的引入虽然可以降低玻璃相的粘度，但会导致耐熔融玻璃腐蚀性的降低。在本发明中，所述高电阻率高锆砖基本不含有P2O5和B2O3，所述P2O5的含量小于0.01％，B2O3的含量小于0.01％。所述高电阻率高锆砖基本不含有MgO和CaO，所述MgO的含量小于0.01％，所述CaO的含量小于0.01％。MgO和CaO的引入会导致高温电阻率降低。TiO2和Fe2O3在高锆砖中是有害的，因而应当它们随原料而引入的量，在本发明中，所述TiO2+Fe2O3的含量小于0.20％。本发明的高锆砖通过熔铸方法制备，将提供ZrO2、SiO2、Al2O3、Na2O、K2O和Cr2O3起始原料基于氧化物的预定配比混合，混合均匀后加入电弧炉中，并使其熔化并在模具中铸造，并一起包埋于氧化铝粉末中，逐渐冷却至室温，然后通过加工得到所需尺寸的高锆砖。本发明中，所述高锆砖在1650℃和100Hz频率的条件下，电阻率≥230Ω·cm；所述高锆砖在1500℃和100Hz频率的条件下，电阻率≥500Ω·cm；所述高锆砖在1500℃×24h条件下抗玻璃液侵蚀速度≤0.8mm；所述高锆砖在1500℃×4h条件下，玻璃相渗出量≤0.4。
在本发明中，所述电阻率通过四端子法测量，并且在频率为1500℃、1650℃的条件下测定电阻率(单位为Ω·cm)。玻璃相渗出量在1500℃×4h检测条件下，依据标准JC/T493-2015测定。在1500℃的普通钠盖玻璃熔液条件下，依据标准JC/T806-2013测量静态下的抗玻璃液侵蚀速度(mm/24h)。
实施例
本发明实施例采用的原料包括脱硅锆石、石英、氧化铝、碳酸钠、碳酸钾和三氧化二铬。脱硅锆石中ZrO2≥93.5％,SiO2≤5.5％,TiO2≤0.10％,Fe2O3≤0.10％。石英中SiO2≥99.8％，Fe2O3≤0.05％；氧化铝中Al2O3≥99.5％，TiO2≤0.10％,Fe2O3≤0.10％；碳酸钠中Na2CO3≥98.5％,碳酸钾中K2CO3≥98.5％,三氧化二铬中Cr2O3≥98.5％。按照表1的配方称量配料，然后在搅拌机内混合搅拌均匀，并将混合料放在料罐内备用。将混合料放入电弧炉内，通电加热的方法加热熔化，电压控制在280V以上，熔化后进行吹氧，氧气压力为0.5MPa，熔炼时间为100分钟，然后倾动电弧炉将熔融料液浇注到模具内，浇铸温度为1950℃以上，浇注速度为10～20kg/s,浇铸完成后包埋在氧化铝粉的箱体中退火，待与室温一致时出箱即可。
表1采用电熔法制备的实施例高锆砖的原料组成，wt％。
| 原料 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
| ZrO2 | 86.46 | 89.81 | 88.50 | 88.20 | 87.47 | 89.88 |
| SiO2 | 10.5 | 7.5 | 9.1 | 8.6 | 9.9 | 8.1 |
| Al2O3 | 2.1 | 1.8 | 1.5 | 2.1 | 1.7 | 1.2 |
| Na2O | 0.05 | 0.08 | 0.05 | 0.03 | 0.05 | 0.10 |
| K2O | 0.18 | 0.15 | 0.15 | 0.20 | 0.20 | 0.20 |
| Cr2O3 | 0.52 | 0.46 | 0.50 | 0.68 | 0.50 | 0.32 |
| Fe2O3+TiO2 | 0.15 | 0.16 | 0.15 | 0.15 | 0.15 | 0.16 |
| P2O5 | - | - | - | - | - | - |
| B2O3 | - | - | - | - | - | - |
| CaO | - | - | - | - | - | - |
| MgO | - | - | - | - | - | - |
| SrO | - | - | - | - | - | - |
| BaO | - | - | - | - | - | - |
| 其它杂质 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
其中：“-”表示含量在0.01％以下。
表2采用电熔法制备的比较例高锆砖的原料组成，wt％。
| 原料 | 比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | 比较例6 |
| ZrO2 | 86.98 | 88.50 | 86.77 | 87.50 | 86.16 | 88.50 |
| SiO2 | 10.5 | 9.1 | 10.5 | 9.1 | 10.5 | 9.1 |
| Al2O3 | 2.1 | 1.5 | 2.1 | 1.5 | 2.1 | 1.5 |
| Na2O | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| K2O | 0.18 | 0.15 | 0.18 | 0.15 | 0.18 | 0.15 |
| Cr2O3 | - | - | 0.20 | 1.5 | 0.52 | *0.50 |
| Fe2O3+TiO2 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| P2O5 | - | - | - | - | - | - |
| B2O3 | - | - | - | - | 0.30 | - |
| CaO | - | - | - | - | - | - |
| MgO | - | - | - | - | - | - |
| SrO | - | 0.50 | - | - | - | - |
| BaO | - | - | - | - | - | - |
| 其它杂质 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
其中：“-”表示含量在0.01％以下。
比较例6中*表示以CrO3替代了Cr2O3。比较例的组成如表2所示，除原料不同外，制备方法与实施例相同。配料后在搅拌机内混合搅拌均匀，将混合料放入电弧炉内，通电加热的方法加热熔化，电压控制在280V以上，熔化后进行吹氧，氧气压力为0.5MPa，熔炼时间为100分钟，然后倾动电弧炉将熔融料液浇注到模具内，浇铸温度为1950℃以上，浇注速度为10～20kg/s,浇铸完成后包埋在氧化铝粉的箱体中退火，待与室温一致时出箱即可。
通过对实施例和比较例的样品，测量高温下的电阻率、玻璃相渗出量以及静态下的抗玻璃液侵蚀速度等物理性质。所述电阻率通过四端子法测量，并且在频率为1500℃、1650℃的条件下测定电阻率(单位为Ω·cm)。玻璃相渗出量在1500℃×4h检测条件下，依据标准JC/T493-2015测定。在1500℃的普通钠盖玻璃熔液条件下，依据标准JC/T806-2013测量静态下的抗玻璃液侵蚀速度(mm/24h)。表3示出了实施例和比较例的高锆砖的物理性质。
表3
Claims (10)
1.一种高电阻率高锆砖，其特征在于：所述高锆砖通过电熔铸造而成并且以重量百分比计包含：86.1-91.0％的ZrO2、7.5-10.5％的SiO2、1.2-2.1％的Al2O3、0.01-0.10％的Na2O、0.12-0.20％的K2O、0.30-0.70％的Cr2O3，并且其他成分的含量小于0.20％，Al2O3/Cr2O3的比值为3～4；所述高锆砖的晶相结构由斜锆石和玻璃相组成，所述玻璃相的含量为9.0～13.0％，斜锆石的含量为87.0～91.0％。
2.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述ZrO2中含有天然存在的HfO2，并且HfO2的含量为2％以下。
3.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高电阻率高锆砖中SrO的含量小于0.01％，BaO的含量小于0.01％。
4.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高电阻率高锆砖中P2O5的含量小于0.01％，B2O3的含量小于0.01％。
5.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高电阻率高锆砖中MgO的含量小于0.01％，CaO的含量小于0.01％。
6.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述其他成分中TiO2+Fe2O3的含量小于0.20％。
7.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高锆砖在1650℃和100Hz频率的条件下，电阻率≥230Ω·cm；所述高锆砖在1500℃和100Hz频率的条件下，电阻率≥500Ω·cm。
8.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高锆砖在1500℃×24h条件下抗玻璃液侵蚀速度≤0.8mm。
9.根据权利要求1所述的高电阻率高锆砖，其特征在于：所述高锆砖在1500℃×4h条件下，玻璃相渗出量≤0.4。
10.权利要求1所述的高电阻率高锆砖的制备方法，其特征在于：所述制备方法包括以下步骤：
(1)将提供ZrO2、SiO2、Al2O3、Na2CO3、K2CO3和Cr2O3起始原料混合均匀得到混合料；
(2)将所述混合料在电弧炉中加热熔化得到熔融液体；
(3)将所述熔融液体浇铸到铸型中凝固，保温退火，并加工得到所述高锆砖。
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