CN106810293B - 一种低热膨胀和高气孔率堇青石陶瓷及制备方法 - Google Patents
一种低热膨胀和高气孔率堇青石陶瓷及制备方法 Download PDFInfo
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Abstract
本发明为一种低热膨胀和高气孔率堇青石陶瓷及制备方法。本发明充分利用原料自身结构,包括硅藻土自身具有网孔结构,滑石、高岭土具有的层状结构,埃洛石具有的管状结构,这些网状、片状和管状结构在陶瓷烧结过程中保留,以其为模板原位合成堇青石,形成纯相堇青石陶瓷。这些结构交叉组合,可以提高陶瓷的气孔率,同时可避免堇青石在陶瓷中定向排列,可以有效降低陶瓷的热膨胀性。在陶瓷混合料中加入合适的添加剂,可以有效减小堇青石的热膨胀异向性,进一步降低陶瓷的热膨胀系数。最终获得气孔率大于65%,热膨胀系数小于0.1×10‑6/℃的堇青石多孔陶瓷。
Description
技术领域
本发明涉及一种低热膨胀和高气孔率的绿色环保材料及制备方法。充分利用原料结构,以其为模板原位合成纯相堇青石,并添加能够减小堇青石热膨胀异向性的添加剂,最终获得低热胀、高气孔率的堇青石陶瓷的制备方法。
背景技术
堇青石陶瓷具有热稳定性好,结构疏松,低热膨胀性能良好的特点,并且具有一定的力学强度。可以制备多孔壁薄,升温速率快的蜂窝陶瓷,在其表面喷涂催化剂,作为催化剂的载体。同时蜂窝堇青石陶瓷比表面积大,具有较强的吸附能力,可以吸附有害物质,较大的比表面积可以使催化剂和有害物质充分接触,使催化剂被活化从而讲解有害物质。因此堇青石常被用来净化汽车尾气和各种工业废气。
2010,朱凯在“低膨胀堇青石材料的制备与性能研究”一文中研究表明:以高岭土、滑石和矾土为原料,以(TiO2,Al2O3)为添加剂,添加15wt%后,材料中生成低膨胀钛酸铝相,膨胀系数降低为2.1×10-6℃-1。《中国陶瓷》2012,48(1):18-20,罗民华在“锂辉石对堇青石多孔陶瓷的影响”一文中,添加5.0wt%的锂辉石为添加剂,获得了热膨胀系数为1.73×10-6℃-1的堇青石多孔陶瓷。《非金属矿》2011,34(3):35-37刘振英在“Bi2O3对合成堇青石性能的影响”一文中,添加6wt%的Bi2O3可使堇青石的热膨胀系数从2.37×10-6℃-1降低到2.08×10-6℃-1。《非金属矿》2007,30(1):17-19,赵军在“煤系高岭土合成堇青石工艺研究”一文中,添加2wt%BaCO3,合成堇青石的热膨胀系数最小,为1.84×10-6℃-1。201610341915.8,康宁公司在“堇青石多孔陶瓷蜂窝体制品”专利中,最低可使堇青石蜂窝陶瓷热膨胀系数降低到0.1×10-6℃-1。
《硅酸盐通报》2016,35(12):4267-4271,张浩在“纤维素基对多孔陶瓷微结构和力学性能的影响”一文中,添加经3-氨丙基三乙氧基硅烷(APTES)改性的微晶纤维素(MCC)为造孔剂,添加含量为20wt%时,可获得54.1%的显气孔比例。《山东陶瓷》2005,28(1):3-5,陈艳林“以淀粉为造孔剂制备多孔陶瓷”一文中,添加一定含量的淀粉为造孔剂,制备出了表观密度为1.15-1.52g/cm3,显气孔率为30.9%-47.7%的多孔陶瓷。《人工晶体学报》2013,42(4):737-741,李月丽在“成孔剂对堇青石蜂窝陶瓷结构和性能的影响”一文中,添加中空丙烯酸发泡树脂小球为造孔剂,可使堇青石蜂窝陶瓷的孔容增加到0.33cm3/g。200480003007.3,康宁公司在“堇青石陶瓷体和方法”专利中添加造孔剂可使气孔率达到65%。目前,美国Corning公司和日本NJK公司可获得热膨胀系数仅为0.1-0.5×10-6℃-1的堇青石陶瓷制备方法。当前国内市场仍然销售热膨胀系数为1.6-2.0×10-6℃-1的堇青石陶瓷,与国际水平仍有一定的差距。
如何进一步提高堇青石陶瓷的气孔率,降低其热膨胀系数的研究依然是目前本领域的研究重点,对应的产品开发也在进行。
发明内容
本发明将针对上述问题,提出一种低热膨胀和高气孔率堇青石陶瓷和制备方法。本发明将以滑石、硅藻土、高岭土、埃洛石和γ-氧化铝为原料并加入添加剂,在一定的配比下混合、成型、烧结,原位合成堇青石,制备堇青石多孔陶瓷。其中引入硅藻土为硅源利用硅藻的高比表面积和网孔状结构为模板,引入高岭土和滑石为铝、硅、镁源利用其片状结构为模板,引入埃洛石为铝、硅源利用其管状结构为模板,γ-氧化铝为补充铝源并利用其活性,原位合成堇青石。形成网状、管状、片状、粒状形貌复合,孔径大小和粒径级配合理的多孔堇青石陶瓷。同时,加入可以有效抑制堇青石热膨胀异向性的添加剂,可以获得气孔率大于65%,热膨胀系数小于0.1×10-6/℃的高性能多孔陶瓷。
本发明的目的是通过以下技术方案实现的:
按重量百分比:滑石(粒径小于800目)39%-42%,提纯高岭土15%-25%,提纯埃洛石25%-15%,γ-氧化铝(粒径小于800目)5%-15%,提纯硅藻土15%-5%,添加剂1%-4%。
按如下顺序和步骤制备堇青石陶瓷(见附图):
a.硅藻土提纯和煅烧;选用直连硅藻土进行提纯,条件:液固比10:1,擦洗次数3-5次,沉降分离、过滤、干燥,之后500℃煅烧去除硅藻孔中有机物。
b.高岭土埃洛石酸洗和煅烧;选用层状高岭石和管状埃洛石,利用5%-10%的盐酸进行洗涤处理,经过滤、干燥。埃洛石提纯后550℃煅烧,部分脱水,清除结构管中充填物。
c.按照配方设计中各种原料的比例,将滑石(粒径小于800目)、提纯高岭土、提纯埃洛石、γ-氧化铝(粒径小于800目)、提纯硅藻土采用高速搅拌机进行混合处理;
d.将混合均匀的原料加入添加剂、适量水和油采用练泥机进行混炼;
e.将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
f.将成型的坯体微波干燥后入窑,采用梯度升温,控制高温焙烧温度为1350℃~1380℃,保温120min;
g.随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷;
有益效果:与高纯度氧化物高温合成制备堇青石陶瓷相比,本发明充分利用原料自身结构,如硅藻土自身具有网状结构,高岭土具有层状结构,埃洛石具有管状结构原位合成堇青石,这些原料的网状结构、片状结构和管状结构在堇青石陶瓷中相互交错复合可以有效增大堇青石陶瓷的气孔率。同时,可以防止堇青石晶体定向排列,从而降低陶瓷的热膨胀系数。同时添加剂的引入可以有效降低堇青石晶体的热膨胀异向性,进一步降低陶瓷的热膨胀系数。
低热胀高气孔率陶瓷的制备可以进一步扩大其应用领域,用于环保要求跟高的场所,具有广阔的引用前景。
附图说明
图1为堇青石陶瓷制备工艺流程图。
具体实施方式
下面结合实施例作进一步详细说明:
按如下顺序和步骤制备堇青石陶瓷:
a.滑石(粒径小于800目)39%-42%,提纯高岭土15%-25%,提纯埃洛石25%-15%,γ氧化铝(粒径小于800目)5%-15%,提纯硅藻土15-5%,添加剂1%-4%,分别按照百分比称量;
b.将各种原料采用高速搅拌机进行混合搅拌5-10min;
c.将混合好的原料加入添加剂和适量的水和油进行混炼1-2h;
d.将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
e.将成型的坯体采用微波干燥;
f.干燥后的坯体入窑烧结,采用梯度升温,控制高温焙烧温度为1350℃~1380℃,保温2-4h;
g.随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷;
实施例1
a.滑石(粒径小于800目)39%,提纯高岭土20%,提纯埃洛石20%,γ氧化铝(粒径小于800目)10%,提纯硅藻土10%,添加剂1%,分别按照百分比称量;
b.将各种原料采用高速搅拌机进行混合搅拌10min;
c.将混合好的原料加入添加剂和适量的水和油进行混炼1h;
d.将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
e.将成型的坯体采用微波干燥;
f.干燥后的坯体入窑烧结,采用梯度升温,控制高温焙烧温度为1360℃,保温4h;
g随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷。
实施例2
a.滑石(粒径小于800目)40%,提纯高岭土18%,提纯埃洛石23%,γ氧化铝(粒径小于800目)8%,提纯硅藻土9%,添加剂2%,分别按照百分比称量;
b.将各种原料采用高速搅拌机进行混合搅拌8min;
c.将混合好的原料加入添加剂和适量的水和油进行混炼1h;
d.将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
e.将成型的坯体采用微波干燥;
f.干燥后的坯体入窑烧结,采用梯度升温,控制高温焙烧温度为1370℃,保温3h;
g.随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷。
实施例3
a.滑石(粒径小于800目)41%,提纯高岭土20%,提纯埃洛石22%,γ氧化铝(粒径小于800目)7%,提纯硅藻土7%,添加剂3%,分别按照百分比称量;
b.将各种原料采用高速搅拌机进行混合搅拌10min;
c.将混合好的原料加入添加剂和适量的水和油进行混炼1h;
d.将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
e.将成型的坯体采用微波干燥;
f.干燥后的坯体入窑烧结,采用梯度升温,控制高温焙烧温度为1380℃,保温2h;
g.随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷。
Claims (2)
1.一种低热膨胀和高气孔率堇青石陶瓷的制备方法,其特征在于:陶瓷原料重量百分比为:滑石39%-42%,提纯高岭土15%-25%,提纯埃洛石25%-15%,γ氧化铝5%-15%,提纯硅藻土15%-5%,添加剂1%-4%;所述滑石粒径小于800目;所述γ氧化铝粒径小于800目;陶瓷的制备工艺过程,包括如下步骤:
a滑石、提纯高岭土、提纯埃洛石、γ氧化铝、提纯硅藻土、添加剂,分别按照百分比称量;
b 将各种原料采用高速搅拌机进行混合搅拌5-10min;
c 将混合好的原料加入添加剂和适量的水和油进行混炼1-2h;
d. 将混炼均匀的陶瓷坯料采用挤出成型机挤压成型;
e. 将成型的坯体采用微波干燥;
f. 干燥后的坯体入窑烧结,采用梯度升温,控制高温焙烧温度为1350℃~1380℃,保温2-4h;
g随炉冷却,制得样品即为低热膨胀高气孔率堇青石陶瓷。
2.根据权利要求1所述的一种低热膨胀和高气孔率堇青石陶瓷的制备方法,其特征在于:所述的堇青石陶瓷气孔率大于65%,热膨胀系数小于1.0*10-7/℃。
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