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CN102557688B - 等静压铝钙硅质锡槽底砖的制备方法 - Google Patents

等静压铝钙硅质锡槽底砖的制备方法 Download PDF

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CN102557688B
CN102557688B CN2012100027185A CN201210002718A CN102557688B CN 102557688 B CN102557688 B CN 102557688B CN 2012100027185 A CN2012100027185 A CN 2012100027185A CN 201210002718 A CN201210002718 A CN 201210002718A CN 102557688 B CN102557688 B CN 102557688B
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tin bath
bottom brick
molten tin
calcium
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CN102557688A (zh
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张启山
张瑛
车建壮
李志军
孙文礼
刘杰
冯延春
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Zibo Gongtao New Materials Group Co., Ltd.
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Abstract

本发明涉及一种锡槽底砖及其制法，属于耐火材料技术领域，锡槽底砖化学组成质量百分比为Al2O3 67-76％、CaO 21-28％、SiO2为1.5-5％，余量为常见矿物杂质。经配料、等静压成型、高温烧成后制成，其配料重量百分比为：粒径为3-1mm的铝酸钙粗颗粒30-45％、粒径为1-0.1mm的铝酸钙中颗粒20-35％、＜0.088mm结合细粉25-40％。产品耐碱金属氧化物侵蚀性好、热膨胀率低、热传导率低、氢扩散率低。

Description

等静压铝钙硅质锡槽底砖的制备方法
技术领域
本发明涉及一种锡槽底砖及其制法，属于耐火材料技术领域。
技术背景
锡槽是浮法平板玻璃生产线的关键设备，熔化后的玻璃液流到锡槽中，漂浮在锡液上，前进的同时形成平滑的板状玻璃，贮存锡液所用的耐火砖称为锡槽底砖。目前市场上使用的多数为硅铝质粘土砖，在其使用过程中，由于玻璃中所含的Na2O透过锡液缓慢地渗入砖中，形成霞石并产生体积膨胀和热应力。当含有霞石的变质层增加到一定厚度时，变质层会呈片状剥落，由于其比重比锡液低，剥落的碎片浮到锡液面上时，会导致玻璃表面划伤和玻璃缺陷。
奥镁公司(RHI)研究人员采用了碱性材料铝酸钙来制作锡槽底砖，如专利US5420087所述，该公司以铝酸钙粗颗粒和细颗粒为原料，采用铝酸钙为粘结剂，经振动成型，养护后烘干、烧成。其特征是采用多孔的铝酸钙粗颗粒和细颗粒为原料，以铝酸钙的水化结合作用来形成砖体，制得1100℃烧后气孔率为43％，耐碱性氧化物侵蚀、热膨胀率低、热传导率低、气体透过率低的铝酸钙锡槽底砖。专利中指出：为防止砖在使用过程中与碱金属氧化物反应和还原气氛下的其他反应，原料中SiO2、Fe2O3的质量百分比含量应该分别低于1.5％，SiO2、Fe2O3的含量最好仅仅为少量。该砖的缺点是粗颗粒与细颗粒之间靠水化物结合，经过1100℃热处理后，铝酸钙结合相中仍包含少量结合水，在1100℃以上温度使用过程中，结合水还将溢出，制品的气孔率还会增大，会导致使用风险。
发明内容
本发明的目的在于提供一种高温烧结的铝钙硅质锡槽底砖，耐碱金属氧化物侵蚀性好、热膨胀率低、热传导率低、氢扩散率低。
本发明同时提供了其合理易行的制备方法。
本发明所述的铝钙硅质锡槽底砖，其化学组成质量百分比为Al2O3 67-76％、CaO 21-28％、SiO2为1.5-5％，余量为常见矿物杂质，如MgO、Na2O等。
产品的XRD矿物相组成为二铝酸钙占70-90％、六铝酸钙占≤10％和钙黄长石占8-25％。
产品的气孔率为18-24％。
合理易行的制备方法如下：
经配料、成型、高温烧成后制成，其特征在于配料重量百分比为：粒径为3-1mm的铝酸钙粗颗粒30-45％、粒径为1-0.1mm的铝酸钙中颗粒20-35％、＜0.088mm结合细粉25-40％。
其中，铝酸钙原料的气孔率小于3％，其化学组成质量百分比为：Al2O3 73-79％、CaO 21-27％、Fe2O3≤0.10％。
结合细粉为铝酸钙细粉、α-氧化铝细粉和硅质化合物细粉的混合物，按SiO2占混合料化学组成质量百分比的1.5-5％加入硅质化合物细粉，按混合物中SiO2质量百分比的0.8-1.4倍加入α-氧化铝粉，其余为铝酸钙细粉。
结合细粉中硅质化合物为粘土、石英、透辉石、硅灰石中至少选用一种。
将配料混合后，采用等静压成型方式成型得坯体，成型压力为50-200Mpa。
坯体干燥后烧成，一般自然干燥1-3天入窑烧成。
烧成温度为1300-1450℃，烧成保温时间为10-40小时。
烧成温度制度如下：
10℃-200℃    升温速度1-2℃/分钟
200℃-1300℃  升温速度1-3℃/分钟
1300-1450℃   保温，保温时间为10-40小时
停火降温，自然冷却。
与现有技术相比，本发明具有以下有益效果：
本发明采用致密的铝酸钙为粗颗粒和细颗粒，加入α-氧化铝粉和硅质化合物粉为结合剂，经等静压成型、烧成后形成以二铝酸钙、钙黄长石、六铝酸钙为主要矿物相的产品。产品中不含水化物，内部结构均匀，抗锡液渗透性好、耐碱金属氧化物侵蚀、热膨胀率低、热传导率低、氢扩散率低，解决了粘土质锡槽底砖易受碱金属氧化物侵蚀产生霞石，导致砖体膨胀、起皮的问题，能提高锡槽底砖的使用寿命，并且能减少由锡槽底砖产生的玻璃缺陷和锡槽底部的热量损失。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例
铝酸钙颗粒、α-氧化铝粉、硅质化合物粉等原料的理化指标如下表1中，将原料按比例加入到混炼机内，混合5-15分钟后，在50-200Mpa压力下等静压压制成型，坯体自然干燥1-3天后，在1300℃-1450℃烧成制得铝钙硅质锡槽底砖样品，检测其化学成分、矿物相组成、气孔率、体积密度、耐压强度、热传导率等理化指标见具体实施例表2。
表1原料的质量化学百分组成表
Figure BDA0000129081440000031
表2、具体实施例表
Figure BDA0000129081440000032
**铝钙硅质锡槽底砖中的MgO、Na2O等矿物成分形成少量镁铝尖晶石或玻璃相，因此主要矿物相二铝酸钙、钙黄长石、六铝酸钙的合量不足100％。

Claims (10)

1.一种等静压成型的铝钙硅质锡槽底砖，其特征在于化学组成质量百分比为Al2O3 67-76％、CaO 21-28％、SiO2为1.5-5％，余量为常见矿物杂质。
2.根据权利要求1所述的铝钙硅质锡槽底砖，其特征在于产品的XRD矿物相组成为二铝酸钙占70-90％、钙黄长石占8-25％。
3.根据权利要求2所述的铝钙硅质锡槽底砖，其特征在于产品的XRD矿物相组成中含有六铝酸钙≤10％。
4.根据权利要求1所述的铝钙硅质锡槽底砖，其特征在于产品的气孔率为18-24％。
5.一种权利要求1所述的铝钙硅质锡槽底砖的制备方法，经配料、等静压成型、高温烧成后制成，其特征在于配料重量百分比为：粒径为3-1mm的铝酸钙粗颗粒30-45％、粒径为1-0.1mm的铝酸钙中颗粒20-35％、＜0.088mm结合细粉25-40％。
6.根据权利要求5所述的铝钙硅质锡槽底砖的制备方法，其特征在于铝酸钙原料的气孔率小于3％，其化学组成质量百分比为：Al2O3 73-79％、CaO 21-27％、Fe2O3≤0.10％。
7.根据权利要求5所述的铝钙硅质锡槽底砖的制备方法，其特征在于结合细粉为铝酸钙细粉、α-氧化铝细粉和硅质化合物细粉的混合物，按SiO2占混合料化学组成质量百分比的1.5-5％加入硅质化合物细粉，按混合物中SiO2质量百分比的0.8-1.4倍加入α-氧化铝粉，其余为铝酸钙细粉。
8.根据权利要求7所述的铝钙硅质锡槽底砖的制备方法，其特征在于结合细粉中硅质化合物为粘土、石英、透辉石、硅灰石中至少选用一种。
9.根据权利要求5所述的铝钙硅质锡槽底砖的制备方法，其特征在于将配料混合后，采用等静压成型方式成型得坯体，成型压力为50-200Mpa。
10.根据权利要求5所述的铝钙硅质锡槽底砖的制备方法，其特征在于坯体干燥后烧成，烧成温度为1300-1450℃，烧成保温时间为10-40小时。
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