CN107805307A - 一种含锆陶瓷前驱体的制备方法 - Google Patents
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Abstract
本发明公开了一类以Zr‑O‑Zr为主链的含锆陶瓷前驱体的制备方法。该聚合物ZNP以正丙醇锆、乙酰丙酮和乙二醇为原料,在惰性气体保护下,分三步反应制得:正丙醇锆与乙酰丙酮配位鳌合反应;乙二醇对鳌合产物的取代反应;离心、除溶剂制得产物ZNP。该聚合物在有机溶剂中具有良好的溶解性,解决了以往前驱体合成法产物难溶解的问题,另外反应条件易于控制,且减少了以ZrCl4为原料需除盐的麻烦。本发明阐述的含锆聚合物在管式炉高纯氩气氛中1600℃保温3h后,所得的ZrC‑ZrO2陶瓷含锆量为36.34%(At%),陶瓷转化率达32.66%。因其良好的溶解性能,可以进一步通过共混制备SiC‑ZrC‑ZrO2复相陶瓷前驱体,在耐高温材料方面得到进一步应用。
Description
技术领域
本发明属于高性能陶瓷前驱体制备技术领域,特别涉及一种以Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法。
背景技术
含Zr有机前驱体树脂在高温下可以陶瓷化形成ZrO2、ZrC覆盖在材料表面,因ZrO2、ZrC具有高强度、高熔点、高温稳定性、高导电率和抗腐蚀等优异的性能,因而可以保护内部的材料不被高温破坏,在高温情况下还能保持较好的力学性能。目前,含Zr、C等元素的有机前驱体树脂已成为研究热点,可以适用于制备耐高温聚合物的基体、陶瓷化前驱体、耐烧蚀材料等。
传统的在材料中引入ZrO2、ZrC的方法是将ZrO2、ZrC等直接添加到沥青或树脂浸渍剂中。这种方法虽然操作简单,但是掺杂进去的添加物分散较难,分布不均,容易产生团聚现象,影响耐烧蚀性能。随着化学合成技术的发展,另外一种引入ZrO2、ZrC的方法是先驱体合成法,通过在分子结构中引入Zr元素得到含锆有机先驱体,其在高温下会发生陶瓷化形成ZrO2、ZrC。石岳等以ZrOC12·8H2O为锆源、C3H6OH 为溶剂、乙酰丙酮为配位剂,通过真空浸渍的方法合成得到了含锆有机液相,将其置1 000°C和1 600°C下会分别转化为纳米级的二氧化锆和纳米碳化锆。曹溯伟等采用聚硅碳硅烷(PSCS)和乙酰丙酮锆为基本原料制备出了一种聚锆碳硅烷。先驱体合成法得到的含锆有机先驱体分子设计性好,可以溶于一般的有机溶剂、较易成型,在高温下烧结形成的ZrO2、ZrC分散均匀,不易发生团聚,材料的耐高温和耐烧蚀性能明显提高,为超耐高温抗烧蚀材料的制备提供了方法。但是上述含锆有机先驱体中的Zr元素均以配位键引入到结构中,结合力较小,化学稳定性较差,不易长时间存储,从而限制了其使用场合。
本发明通过采用直接合成法制备得到主链为Zr-O-Zr的陶瓷前驱体ZNP,其具有良好的溶解性和储存稳定性,且制备方法简单易于操作。对ZNP进一步进行陶瓷化处理,得到的ZrC-ZrO2陶瓷含锆量达36.34%(At%),陶瓷转化率达32.66%。因此利用其良好的溶解性能,可以进一步共混制备SiC-ZrC-ZrO2复相陶瓷前驱体,实现工业应用价值。
发明内容
要解决的技术问题
将锆元素引入含硅聚合物中制备SiC-ZrC-ZrO2复相陶瓷材料,可以很大程度提高材料的耐热性能。但含锆聚合物的合成困难,且产物不易溶于有机溶剂、储存稳定性差,从而限制了其在耐高温材料方面的应用。本发明针对存在的问题,提出一种以Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,得到溶解性能良好的含锆聚合物,并且进一步研究各原料配比与产物陶瓷化之间的关系,也为进一步制备SiC-ZrC-ZrO2复相陶瓷材料提供了依据。
技术方案
本发明合成了一种含锆聚合物ZNP,其结构见说明书附图。
本反应以Zr(OPr)4、Hacac和乙二醇为原料,THF为溶剂,合成溶解性能良好的含锆聚合物,其反应流程见说明书附图。
具体实施方式:
结合实施例进一步说明本发明的技术解决方案,但其并不限制本发明的保护范围:
实施例1:
惰性气体保护下,将40mlTHF加入三口瓶中,再加入1mol Zr(OPr)4,搅拌,水浴冷却。向体系内缓慢滴加入1mol Hacac,控制温度在30℃。滴加完毕,恒温反应30min。将0.2mol乙二醇和12mlTHF混合后置于恒压漏斗中,缓慢滴加入体系内。滴加完毕,调节水浴至60℃并反应2h。将反应产物放于离心管内,离心后取上层淡黄色澄清溶液,60℃下旋蒸除溶剂。所得产物ZNP为淡黄色不透明粘性物,冷却后为蜡状固体ZNP。
将ZNP置于高纯氩气氛保护下,1600℃管式炉内保温3h得到ZrC-ZrO2陶瓷:锆含量为32.16%(At%),陶瓷化产率为29.45%。
实施例2:
惰性气体保护下,将40mlTHF加入三口瓶中,再加入1mol Zr(OPr)4,搅拌,水浴冷却。向体系内缓慢滴加入2mol Hacac,控制温度在30℃。滴加完毕,恒温反应30min。将0.2mol乙二醇和12mlTHF混合后置于恒压漏斗中,缓慢滴加入体系内。滴加完毕,调节水浴至60℃并反应2h。将反应产物放于离心管内,离心后取上层淡黄色澄清溶液,60℃下旋蒸除溶剂。所得产物ZNP为淡黄色不透明粘性物,冷却后为蜡状固体ZNP。
将ZNP置于高纯氩气氛保护下,1600℃管式炉内保温3h得到ZrC-ZrO2陶瓷:锆含量为36.29%(At%),陶瓷化产率为30.22%。
实施例3:
惰性气体保护下,将40mlTHF加入三口瓶中,再加入1mol Zr(OPr)4,搅拌,水浴冷却。向体系内缓慢滴加入2mol Hacac,控制温度在50℃。滴加完毕,恒温反应50min。将0.2mol乙二醇和12mlTHF混合后置于恒压漏斗中,缓慢滴加入体系内。滴加完毕,调节水浴至60℃并反应2h。将反应产物放于离心管内,离心后取上层淡黄色澄清溶液,60℃下旋蒸除溶剂。所得产物ZNP为淡黄色不透明粘性物,冷却后为蜡状固体ZNP。
将ZNP置于高纯氩气氛保护下,1600℃管式炉内保温3h得到ZrC-ZrO2陶瓷:锆含量为36.34%(At%),陶瓷化产率为32.66%。
实施例4:
惰性气体保护下,将40mlTHF加入三口瓶中,再加入1mol Zr(OPr)4,搅拌,水浴冷却。向体系内缓慢滴加入2mol Hacac,控制温度在50℃。滴加完毕,恒温反应50min。将0.4mol乙二醇和12mlTHF混合后置于恒压漏斗中,缓慢滴加入体系内。滴加完毕,调节水浴至60℃并反应2h。将反应产物放于离心管内,离心后取上层淡黄色澄清溶液,60℃下旋蒸除溶剂。所得产物ZNP为淡黄色不透明粘性物,冷却后为蜡状固体ZNP。
将ZNP置于高纯氩气氛保护下,1600℃管式炉内保温3h得到ZrC-ZrO2陶瓷:锆含量为35.38%(At%),陶瓷化产率为22.79%。
以上所述仅是本发明的实施方式的具体举例,应当指出,对于本领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。
附图说明
说明书附图中图1为含锆聚合物ZNP的结构,图2为含锆聚合物的反应流程。
Claims (5)
1.一种以Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,其特征在于:对正丙醇锆和乙酰丙酮的配位鳌合反应产物,用乙二醇进行取代,制备以Zr-O-Zr为主链的含锆陶瓷前驱体ZNP,并对该前驱体进行热处理,研究其陶瓷化性能。
2.权利要求1所述的Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,其特征在于:所述的含锆陶瓷前驱体ZNP的结构,见说明书附图。
3.权利要求1所述的Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,其特征在于:反应的流程见说明书附图。
4.权利要求1 所述的Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,其特征在于:聚合物ZNP在THF、甲苯、二甲苯等有机溶剂中均具有良好的溶解性。
5.权利要求1 所述的Zr-O-Zr为主链的含锆陶瓷前驱体的制备方法,其特征在于:高纯氩保护下,1600℃管式炉内保温3h后得到ZrC-ZrO2陶瓷。
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