CN107721428A - 一种Si/Zr/C复相陶瓷材料的制备方法 - Google Patents

一种Si/Zr/C复相陶瓷材料的制备方法 Download PDF

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CN107721428A
CN107721428A CN201710913241.9A CN201710913241A CN107721428A CN 107721428 A CN107721428 A CN 107721428A CN 201710913241 A CN201710913241 A CN 201710913241A CN 107721428 A CN107721428 A CN 107721428A
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zirconium
diphase ceramic
silicon
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周权
倪礼忠
刘帅帅
彭峥强
卢丹
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East China University of Science and Technology
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Abstract

本发明公开了一类Si/Zr/C复相陶瓷材料的制备方法。本方法采用一种在固化过程中可以发生Diels‑Alder反应和Si‑H加成反应的硅炔树脂PTSA，以及一种溶解性良好、锆含量较高的含锆前驱体ZNP，由共混法得到锆硅均相溶液ZPS。该制备方法工艺简单、操作方便，并且改善了共混法的不均一性以及直接合成法的难控制性，制备得到的陶瓷前驱体具备良好的储存稳定性，有助于实现Si/Zr/C复相陶瓷材料在耐烧蚀领域的广泛应用。

Description

一种Si/Zr/C复相陶瓷材料的制备方法
技术领域
本发明属于高性能树脂基陶瓷前驱体制备技术领域，特别涉及一种Si/Zr/C复相陶瓷材料的制备及前驱体的合成方法。
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、高硬度、高温稳定性、高导电率和抗腐蚀等优异的性能，成为高温结构应用的潜在候选材料。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。
SiC作为基体具有耐高温、硬度大、强度高、高温性能优异的优点，同时其高温氧化后在材料表面形成一层SiO2薄膜，能够避免氧化性气体与复合材料直接接触，从而达到提高复合材料抗氧化性能的目的。而研究表明，含有硅锆的复相陶瓷材料，能够发挥ZrC、SiC、以及ZrO2的性能优势，在耐高温材料领域可望得到广泛应用。
本发明采用直接共混法将一种在固化过程中可以发生Diels-Alder反应和Si-H加成反应的硅炔树脂PTSA，以及一种溶解性良好、锆含量较高的含锆前驱体ZNP，利用两者在有机溶剂中优异的溶解性，制备锆硅均相前驱体，经过热处理后得到Si/Zr/C复相陶瓷材料，其较高的陶瓷转化率和锆含量，有望在耐烧蚀材料的研究领域得到进一步发展。
发明内容
将锆元素引入含硅聚合物中制备Si/Zr/C复相陶瓷材料，可以很大程度提高材料的耐烧蚀性能。本发明利用实验室已合成的硅炔树脂PTSA作为硅源，以溶解性良好的含锆聚合物ZNP作为锆源，利用两者的良好溶解性，以质量比1:2、1:1、2:1共混得到锆硅均相前驱体ZPS。将其置于高纯氩气氛下1600~1800℃热处理3~5h，即得到Si/Zr/C复相陶瓷材料。
本发明采用了一种含锆聚合物ZNP，其具有良好的溶解性和较高的锆含量，其结构见说明书附图图1。
本发明所述硅炔树脂PTSA为一类分子主链结构中含有C≡C和Si-H基团的杂化聚合物，其固化发生交联可以变为三维网状结构，其结构式见说明书附图图2。
本发明另一目的是制备Si/Zr/C复相陶瓷材料，其特征如下:
（1）将ZNP与PTSA分别溶解于甲苯中，将两者以不同的质量比共混，得到澄清透明溶液，旋蒸除溶剂后即得ZPS。
（2）氩气保护下，1600~1800℃保温3~5h，得到Si/Zr/C复相陶瓷。
（3）该锆硅前驱体具有较高的陶瓷转化率，且复相陶瓷中锆硅含量较高。
本发明通过将锆元素引入到主链含有大量C≡C和Si-H基团的硅炔树脂中，利用它们的良好溶解性，通过物理共混即可得到均一体系，操作方便，比例易于控制；另外该前驱体在很好保留了硅炔树脂性能的基础上，又能发挥锆元素的耐烧蚀优势，具备良好的陶瓷化性能，有助于实现Si/Zr/C复相陶瓷材料在耐高温烧蚀领域的广泛应用。
具体实施方式：
结合实施例对该复相陶瓷的制备方法进行进一步说明，但其并不限制本发明的保护范围：
实施例1：
取1gZNP和1gPTSA分别溶解于甲苯中，共混得到淡黄色澄清溶液，60℃下旋蒸除溶剂，得蜡状固体ZPS。将其置于高纯氩气氛保护下的管式炉内，按照5℃/min的升温速率升至1600℃，保温3h。即得复相陶瓷。陶瓷转化率为75.98%，锆、硅质量含量分别为39.81%和42.05%。
实施例2：
取2gZNP和1gPTSA分别溶解于甲苯中，共混得到淡黄色澄清溶液，60℃下旋蒸除溶剂，得蜡状固体ZPS。将其置于高纯氩气氛保护下的管式炉内，按照5℃/min的升温速率升至1800℃，保温3h。即得复相陶瓷。陶瓷转化率为74.60%，锆、硅质量含量分别为52.01%和28.65%。
实施例3：
取1gZNP和2gPTSA分别溶解于甲苯中，共混得到淡黄色澄清溶液，60℃下旋蒸除溶剂，得蜡状固体ZPS。将其置于高纯氩气氛保护下的管式炉内，按照5℃/min的升温速率升至1800℃，保温5h。即得复相陶瓷。陶瓷转化率为74.83%，锆、硅质量含量分别为28.39%和48.68%。
综上所述可见，本发明提供的Si/Zr/C复相陶瓷材料的制备方法，操作简单况且锆硅比例可调，其良好的互溶性有助于该复相陶瓷材料在耐烧蚀领域的应用。
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为硅炔树脂PTSA的结构。

Claims (5)

1.一类Si/Zr/C复相陶瓷材料的制备方法，其特征在于：采用一种在固化过程中可以发生Diels-Alder反应和Si-H加成反应的硅炔树脂PTSA，以及一种溶解性良好、锆含量较高的含锆前驱体ZNP，将两者按不同的质量比共混得到锆硅均相溶液ZPS。
2.权利要求1所述的Si/Zr/C复相陶瓷材料的制备方法，其特征在于：所述的硅炔树脂PTSA为一类分子主链结构中含有C≡C和Si-H基团的杂化聚合物，其结构式见说明书附图的图2。
3.权利要求1所述的Si/Zr/C复相陶瓷材料的制备方法，其特征在于：所述的含锆前驱体ZNP，其结构式见说明书附图的图1。
4.权利要求1所述的Si/Zr/C复相陶瓷材料的制备方法，其特征在于：将ZNP与PTSA分别溶解于甲苯中，按质量比2:1、1:1、1:2共混，得到澄清透明溶液，旋蒸除去溶剂，即得ZPS。
5.权利要求1所述的Si/Zr/C复相陶瓷材料的制备方法，其特征在于：氩气保护下，1600~1800°C管式炉内保温3~5h，得到Si/Zr/C复相陶瓷。
CN201710913241.9A 2017-09-30 2017-09-30 一种Si/Zr/C复相陶瓷材料的制备方法 Pending CN107721428A (zh)

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CN111057244A (zh) * 2019-12-06 2020-04-24 中国科学院化学研究所 一种ZrC/SiC/C复相陶瓷前驱体材料及其制备方法

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WD01 Invention patent application deemed withdrawn after publication