CN110436941A - 一种锆修饰膨胀石墨的改性方法 - Google Patents

一种锆修饰膨胀石墨的改性方法 Download PDF

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CN110436941A
CN110436941A CN201910840389.3A CN201910840389A CN110436941A CN 110436941 A CN110436941 A CN 110436941A CN 201910840389 A CN201910840389 A CN 201910840389A CN 110436941 A CN110436941 A CN 110436941A
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expanded graphite
zirconium
modifying
carbon
vacuum
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涂军波
魏军从
王梓祎
王子琦
郑晓艺
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North China University of Science and Technology
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Abstract

本发明涉及一种锆修饰膨胀石墨的改性方法，其技术方案是：将膨胀石墨与锆源按照一定比例混合，经真空浸渍后埋碳热处理制备得到改性膨胀石墨。按本发明制得的膨胀石墨抗氧化性及结构完整性得到提高，可应用于耐火材料行业。本方法操作简单，环境友好。

Description

一种锆修饰膨胀石墨的改性方法
技术领域
本发明属于耐火材料原料改性领域，具体涉及一种锆修饰膨胀石墨的改性方法。
背景技术
因为石墨本身优良的热导性和低膨胀性以及对炉渣不润湿，使得碳复合耐火材料具有优异的抗热震稳定性、抗渣侵蚀性而被广泛的用于转炉、电炉及精炼炉的内衬材料。但是由于石墨容易氧化成温室气体，一方面破坏环境；另一方面冶炼低碳钢时增加了钢水的含碳量，因此碳复合耐火材料的低碳化成为了趋势，但是研究发现耐火材料的碳含量降低后，材料的抗渣性和抗剥落性降低，所以需要采取复合碳素原料来对其性能进行改进，大多数采用石墨烯、膨胀石墨和碳纳米管线等作为碳素原料。而膨胀石墨本身存在一定的结构缺陷，虽然膨胀石墨能缓冲碳复合材料的热应力，但在抗氧化性和结构完整上却不如鳞片石墨。在之前的研究中，多数采用硅、氮、硼修饰膨胀石墨，但其在1200℃以上结构发生蚀变严重强度下降不利于改善耐火材料性能。而碳化锆是一种超硬材料且其化学稳定性好,比如高熔点、高强度、高硬度以及良好的耐腐蚀、耐高温性能,是一种优良的表面保护材料和高温结构材料，本发明申请用锆源进行膨胀石墨的修饰，旨在膨胀石墨端面断键处形成含锆的饱和键，改善膨胀石墨的结构完整性，并提高其抗氧化性，让膨胀石墨更好的应用于碳复合耐火材料中，提高产品性能。
发明内容
为了解决膨胀石墨作为碳素原料在使用过程中易发生的结构蚀变和抗氧化性较差的问题，本发明旨在提供一种提高膨胀石墨的抗氧化性和结构稳定性的改性方法。具体实施方法是用锆源作为修饰剂，对膨胀石墨真空浸渍法并埋碳热处理的方法来实现。
为了达到上述目的，本发明采用的技术方案是：取适量膨胀石墨按照碳源和锆源质量为1：4至1：8的比例将其与氧氯化锆混合均匀采用真空浸渍法，即得到改性膨胀石墨。
采用上述方案所得的改性膨胀石墨干燥后，进行高温处理。在温度较低的时候，掺杂离子首先会与膨胀石墨表面的点缺陷处的碳原子形成共价结合，而此时的掺杂离子可以作为电子受体。因此可以在一定程度上减少结构的无序性。在温度升高时，膨胀石墨结构中原有的含氧官能团相互之间会发生缩聚反应，生成水和ZnO2，从而降低膨胀石墨中的氧含量，从而降低膨胀石墨的反应活性。当温度更高时，会转化为ZnC ,进一步降低了膨胀石墨的氧含量，降低反应活性，从而提高了膨胀石墨的热氧化分解温度。
具体实施例1
取0.8g膨胀石墨，加入6.4g氧氯化锆，将混合物放入100mL的乙醇溶液中进行磁力搅拌与超声混合使二者分散均匀，将样品放入真空箱中真空浸渍60min，真空度为5000Pa，然后经过过滤干燥得到改性膨胀石墨，于1550℃埋碳处理1h。
经检测发现，经过锆修饰后的改性膨胀石墨晶型完整度提高；改性膨胀石墨的石墨化度得到改善，石墨化度提高了59%，氧化温度提高53℃。
具体实施例2
取0.8g膨胀石墨，加入6.4g氧氯化锆，将混合物放入100mL的乙醇溶液中进行磁力搅拌与超声混合使二者分散均匀，将样品放入真空箱中真空浸渍60min，真空度为5000Pa，然后经过过滤干燥得到改性膨胀石墨，于1600℃埋碳处理1h。
经检测发现，经过锆修饰后的改性膨胀石墨晶型完整度提高；改性膨胀石墨的石墨化度得到改善，石墨化度提高了69%。，氧化温度提高65℃。

Claims (4)

1.一种锆修饰膨胀石墨的改性方法，其特征是向膨胀石墨中加入锆源，碳源与其比例为1：4至1：8，加入锆源后的膨胀石墨与无水乙醇混合均匀后，将混合物放入真空泵中真空浸渍，过滤干燥之后混合物经高温埋碳处理得到锆修饰改性膨胀石墨，其具有较为完整的结构和较好的抗氧化性。
2.权利1所述的制备原料，其特征在于锆源为氧氯化锆，纯度为分析纯度。
3.权利1所述的制备方法，其特征在于真空浸渍时间为60至90min，真空度为6000Pa以下。
4.权利1所述的较佳制备方法，其特征在于碳化热处理温度为1500℃至1600℃之间，1000℃以下时升温速率为5℃/min，1000℃以上为2℃/min，保温时间为1至3个小时。
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Application publication date: 20191112

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