CN116283256A - 一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法 - Google Patents
一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法 Download PDFInfo
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Abstract
本发明涉及一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法，属于多孔材料制备工艺领域。首先通过溶胶‑凝胶法得到(Yb0.25Y0.25Er0.25Lu0.25)2SiO5前驱体的复合溶胶，再以聚丙烯酸离子分散剂，以环氧丙烷为促凝剂，静置凝胶后加入老化液中老化，最后使用超临界干燥结合热处理工艺制备出轻质、低导热、高热稳定性的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶。本发明制得的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶具有优异的热稳定性、化学稳定性及隔热性能。
Description
技术领域
本发明涉及一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法，属于多孔材料制备工艺领域。
背景技术
气凝胶是一种具有低密度、高孔隙率、比表面积大的三维纳米骨架材料，在高温隔热和催化、生物、能源等领域均有应用。其中陶瓷气凝胶因具有低密度、熔点高、耐腐蚀、物理化学性质稳定等特点，受到学者们的广泛关注。
高熵陶瓷是近年来出现的一种的新型陶瓷，具有优异的力学、热学、电学、磁学等性能。受到高熵合金的启发衍生而来，高熵陶瓷通常是指由五种或以上陶瓷组元形成的多主元固溶体，目前高熵陶瓷已经成为陶瓷领域研究的热门。具有四个核心效应，包括热力学的高熵效应、结构的晶格畸变效应、动力学的迟滞效应和性能的“鸡尾酒”效应。2015年，几位美国的研究者Rost、Maria、Curtarolo等成功制备了一种熵稳定氧化物陶瓷，这种岩盐结构额高熵陶瓷开辟了高熵氧化物陶瓷的先河。
目前有关高熵陶瓷的研究还比较少，目前相关文章及专利仅围绕着致密化高熵陶瓷展开，有关高熵结构陶瓷的研究十分稀少，且制备温度高。专利“高熵陶瓷粉体及其制备方法和高熵陶瓷块体CN 110845237 A”采用共沉淀法制备出高熵陶瓷前驱体粉末，热处理得到高熵陶瓷粉体及块体，但其密度较大，热导率较高，且块体需要将粉末二次烧结成型。文献“Guo X,Zhang Y,Li T,et al.High-entropy rare-earth disilicate(Lu0.2Yb0.2Er0.2Tm0.2Sc0.2)2Si2O7:A potential environmental barrier coatingmaterial[J].Journal of the European Ceramic Society,2022(8):42.”采用球磨结合热处理的方法制备了一种新型稀土硅酸盐高熵陶瓷，但其为致密结构，密度大、热导率高、烧结温度高。
发明内容
本发明所要解决的技术问题在于提供一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法，该制备方法能够降低高熵陶瓷的合成温度，具有纳米级的多孔的三维骨架结构，拥有更低的密度和热导率。
本发明的技术方案为：本发明所制备的块状高熵稀土硅酸盐陶瓷气凝胶的化学式为(Yb0.25Y0.25Er0.25Lu0.25)2SiO5，采用溶胶-凝胶法结合超临界干燥法制备块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶；
其具体步骤如下：
(1)复合溶胶的制备：根据化学式(Yb0.25Y0.25Er0.25Lu0.25)2SiO5准确称取镱源、钇源、铒源和镥源，加入乙醇容器中搅拌，再加去离子水搅拌至完全水解后，然后加入硅源前驱体继续搅拌，再加入聚丙烯酸充分搅拌，最后待溶胶完全冷却后加入1,2-环氧丙烷，得到复合溶胶；
(2)湿凝胶的制备及老化：将复合溶胶倒入模具中，密封静置凝胶完全后加入老化液，老化至其脱模；
(3)高熵陶瓷气凝胶前驱体的制备：将步骤(2)得到的湿凝胶进行超临界干燥，即得到块状高熵稀土硅酸盐陶瓷气凝胶前驱体；
(4)高熵陶瓷气凝胶的制备：将步骤(3)制备的块状高熵稀土硅酸盐陶瓷气凝胶前驱体放入氧气气氛的马弗炉中进行热处理，得到块状高熵稀土硅酸盐陶瓷气凝胶。
优选步骤(1)中所述的镱源为氯化镱YbCl3或氯化镱六水合物YbCl36H2O、钇源为氯化钇YCl3或氯化钇六水合物YCl36H2O、铒源为氯化铒ErCl3或氯化铒六水合物ErCl36H2O、镥源为氯化镥LuCl3或氯化镥六水合物LuCl36H2O。
优选步骤(1)中所述的硅源前驱体为正硅酸四乙酯、正硅酸甲酯、甲基三甲氧基硅烷MTMS或甲基三乙氧基硅烷MTES的一种或几种。
优选步骤(1)中所述复合溶胶中的镱源、钇源、铒源、镥源、硅源前驱体、乙醇、水、聚丙烯酸(PAA)、1,2-环氧丙烷的摩尔比为1:1:1:1:2:(80～200):(40～200):(2～8):(16～40)。
优选步骤(2)中所述的老化时间为48～72h，每6～12h更换一次老化液。
优选步骤(2)中所述的老化液乙醇、丙酮、正己烷或异丙醇中的一种或几种。
优选步骤(3)中所述的超临界干燥为CO2超临界干燥，CO2超临界干燥的温度32～50℃，压力为9～12MPa，干燥时间为3～6h。
优选步骤(4)中所述的热处理温度为1250～1500℃，升温速率为2～20℃/min，热处理时间为1～4h。
本发明制得的块状高熵稀土硅酸盐陶瓷气凝胶的密度为0.32～0.52g/m3，1250～1500℃温度范围热处理后样品的室温热导率为0.032～0.045W/(m·K)，压缩强度为0.31～0.45MPa。
有益效果:
(1)本发明有效降低了材料的烧结温度，在1250～1500℃温度范围内制备出了具有硅酸盐结构的高熵陶瓷气凝胶，解决了块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶的制备问题，对其他体系的高熵陶瓷气凝胶材料体系具有重要的参考价值。
(2)本发明制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶晶粒细小，具有轻质、耐高温、低热导、耐腐蚀等优点，首次实现对(Yb0.25Y0.25Er0.25Lu0.25)2SiO5材料的结构化。
(3)相比与传统的气凝胶制品，本发明所制备的(Yb0.25Y0.25Er0.25Lu0.25)2SiO5可以突破传统氧化物气凝胶在1300℃烧结的瓶颈问题，并大幅提高氧化物气凝胶的耐温性。
(4)相比于传统气凝胶制品，本发明采用快速制备法减少了凝胶时间，将凝胶时间从几个小时降低至30分钟以内，并且可调可控，极大地提高了效率。
附图说明
图1为实例1制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶实物图；
图2为实例1～4制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶的XRD图；
图3为实例1制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶EDSMapping图；
图4为实例2制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶SEM图。
具体实施方式
下面结合具体实施例对本发明进行详细阐述，必须理解的是，所述的实例仅涉及本发明的优选方案，这是为了说明本发明的技术路线及特点，目的是为了便于实施，具体实例如下
实例1
将用电子天平准确称取1mol的YbCl36H2O、1mol的YCl36H2O、1mol的ErCl36H2O、1mol的LuCl36H2O)、80mol的乙醇加入容器之中搅拌，再加入40mol去离子水继续搅拌，搅拌至完全反应，再缓慢加入2mol的正硅酸四乙酯混合均匀的，搅拌至完全水解后得到混合溶胶，继续加入2mol的PAA充分搅拌，待其冷却后加入16mol的1,2-环氧丙烷，均匀搅拌后倒入模具中密封静置凝胶，加入到乙醇中老化，老化时间为48h，每6h更换一次老化液，得到老化后的湿凝胶；将样品取出进行CO2超临界干燥，干燥温度为31℃，压力为9MPa，干燥时间为3h，即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体，最后对块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体进行热处理。
所述的热处理设备：马弗炉
热处理温度：1250℃，
保温时间：1h，
升温速率：2℃/min
热处理完成后即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶。所制备的材料，密度为0.52g/m3，室温热导率为0.045W/(m·K)，压缩强度为0.45MPa。
对实例1所得的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶进行XRD表征，如图2所示，说明得到的为稀土硅酸陶瓷结构。制备的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶EDSMapping图，如图3所示说明元素在材料中分散均匀。对样品磨粉并进行SEM分析，颗粒有很明显的断裂面，无烧结现象，说明三维纳米骨架结构在超高温环境下依然存在。
实例2
将用电子天平准确称取1mol的YbCl3、1mol的YCl3、1mol的ErCl3、1mol的LuCl3、80mol的乙醇加入容器之中搅拌，再加入40mol去离子水继续搅拌，搅拌至完全反应，再缓慢加入2mol的正硅酸甲酯混合均匀的，搅拌至完全水解后得到混合溶胶，继续加入2mol的PAA充分搅拌，待其冷却后加入16mol的1,2-环氧丙烷，均匀搅拌后倒入模具中密封静置凝胶，加入到丙酮中老化，老化时间为56h，每8h更换一次老化液，得到老化后的湿凝胶；将样品取出进行CO2超临界干燥，干燥温度为40℃，压力为11MPa，干燥时间为4h，即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体，最后对块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体进行热处理。
所述的热处理设备：马弗炉
热处理温度：1350℃，
保温时间：2h，
升温速率：5℃/min
热处理完成后即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶。所制备的材料，密度为0.49g/m3，室温热导率为0.041W/(m·K)，压缩强度为0.39MPa。
对实例2所得的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶进行XRD表征，如图2所示，说明得到的为稀土硅酸陶瓷结构。对样品磨粉并进行SEM分析，如图4所示，颗粒有很明显的断裂面，无烧结现象，说明三维纳米骨架结构在超高温环境下依然存在。
实例3
将用电子天平准确称取1mol的YbCl36H2O、1mol的YCl36H2O、1mol的ErCl36H2O、1mol的LuCl36H2O)、150mol的乙醇加入容器之中搅拌，再加入150mol去离子水继续搅拌，搅拌至完全反应，再缓慢加入2mol的甲基三甲氧基硅烷(MTMS)混合均匀的，搅拌至完全水解后得到混合溶胶，继续加入6mol的PAA充分搅拌，待其冷却后加入30mol的1,2-环氧丙烷，均匀搅拌后倒入模具中密封静置凝胶，加入到正己烷中老化，老化时间为64h，每12h更换一次老化液，得到老化后的湿凝胶；将样品取出进行CO2超临界干燥，干燥温度为45℃，压力为10MPa，干燥时间为5h，即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体，最后对块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体进行热处理。
所述的热处理设备：马弗炉
热处理温度：1450℃，
保温时间：3h，
升温速率：10℃/min
热处理完成后即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶。所制备的材料，密度为0.47g/m3，室温热导率为0.035W/(m·K)，压缩强度为0.35MPa。
对实例3所得的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶进行XRD表征，如图2所示，说明得到的为稀土硅酸陶瓷结构。对样品磨粉并进行SEM分析，颗粒有很明显的断裂面，无烧结现象，说明三维纳米骨架结构在超高温环境下依然存在。
实例4
将用电子天平准确称取1mol的YbCl36H2O、1mol的YCl36H2O、1mol的ErCl36H2O、1mol的LuCl36H2O)、200mol的乙醇加入容器之中搅拌，再加入200mol去离子水继续搅拌，搅拌至完全反应，再缓慢加入2mol的甲基三乙氧基硅烷(MTES)混合均匀的，搅拌至完全水解后得到混合溶胶，继续加入8mol的PAA充分搅拌，待其冷却后加入40mol的1,2-环氧丙烷，均匀搅拌后倒入模具中密封静置凝胶，加入到异丙醇中老化，老化时间为72h，每12h更换一次老化液，得到老化后的湿凝胶；将样品取出进行CO2超临界干燥，干燥温度为50℃，压力为12MPa，干燥时间为6h，即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体，最后对块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶前驱体进行热处理。
所述的热处理设备：马弗炉
热处理温度：1500℃，
保温时间：4h，
升温速率：20℃/min
热处理完成后即得到块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶。所制备的材料，密度为0.44g/m3，室温热导率为0.032W/(m·K)，压缩强度为0.31MPa。
对实例4所得的块状(Yb0.25Y0.25Er0.25Lu0.25)2SiO5高熵陶瓷气凝胶进行XRD表征，如图2所示，说明得到的为稀土硅酸陶瓷结构。对样品磨粉并进行SEM分析，颗粒有很明显的断裂面，无烧结现象，说明三维纳米骨架结构在超高温环境下依然存在。
Claims (8)
1.一种制备块状高熵稀土硅酸盐陶瓷气凝胶的方法，其具体步骤如下：
(1)复合溶胶的制备：根据化学式(Yb0.25Y0.25Er0.25Lu0.25)2SiO5准确称取镱源、钇源、铒源和镥源，加入乙醇容器中搅拌，再加去离子水搅拌至完全水解后，然后加入硅源前驱体继续搅拌，再加入聚丙烯酸充分搅拌，最后待溶胶完全冷却后加入1,2-环氧丙烷，得到复合溶胶；
(2)湿凝胶的制备及老化：将复合溶胶倒入模具中，密封静置凝胶完全后加入老化液，老化至其脱模；
(3)高熵陶瓷气凝胶前驱体的制备：将步骤(2)得到的湿凝胶进行超临界干燥，即得到块状高熵稀土硅酸盐陶瓷气凝胶前驱体；
(4)高熵陶瓷气凝胶的制备：将步骤(3)制备的块状高熵稀土硅酸盐陶瓷气凝胶前驱体放入氧气气氛的马弗炉中进行热处理，得到块状高熵稀土硅酸盐陶瓷气凝胶。
2.根据权利要求1所述的方法，其特征在于步骤(1)中所述的镱源为氯化镱YbCl3或氯化镱六水合物YbCl36H2O、钇源为氯化钇YCl3或氯化钇六水合物YCl36H2O、铒源为氯化铒ErCl3或氯化铒六水合物ErCl36H2O、镥源为氯化镥LuCl3或氯化镥六水合物LuCl36H2O。
3.根据权利要求1所述的方法，其特征在于步骤(1)中所述的硅源前驱体为正硅酸四乙酯、正硅酸甲酯、甲基三甲氧基硅烷MTMS或甲基三乙氧基硅烷MTES的一种或几种。
4.根据权利要求1所述的方法，其特征在于步骤(1)中所述复合溶胶中的镱源、钇源、铒源、镥源、硅源前驱体、乙醇、水、聚丙烯酸(PAA)、1,2-环氧丙烷的摩尔比为1:1:1:1:2:(80～200):(40～200):(2～8):(16～40)。
5.根据权利要求1所述的方法，其特征在于步骤(2)中所述的老化时间为48～72h，每6～12h更换一次老化液。
6.根据权利要求1所述的方法，其特征在于步骤(2)中所述的老化液乙醇、丙酮、正己烷或异丙醇中的一种或几种。
7.根据权利要求1所述的方法，其特征在于步骤(3)中所述的超临界干燥为CO2超临界干燥，CO2超临界干燥的温度32～50℃，压力为9～12MPa，干燥时间为3～6h。
8.根据权利要求1所述的方法，其特征在于步骤(4)中所述的热处理温度为1250～1500℃，升温速率为2～20℃/min，热处理时间为1～4h。
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