Liu Benxue, Gao Min, Liu Xiaochan, Xie Yongshuai, Yi Xibin, Zhu Luyi, Wang Xinqiang, Shen Xiaodong
Qilu University of Technology (Shandong Academy of Science), Advanced Materials Institute, Shandong Provincial Key Laboratory for Special Silicone-Containing Materials Jinan 250014 P. R. China
State Key Laboratory of Crystal Materials, Institute of Crystal Materials, Shandong University Jinan 250100 P. R. China.
RSC Adv. 2018 Dec 12;8(72):41603-41611. doi: 10.1039/c8ra08263d. eCollection 2018 Dec 7.
Zirconia (ZrO) aerogels are potential candidates for use at temperatures higher than those attainable with silica aerogels. However, fabricating a robust ZrO aerogel with a high thermal stability is still a challenge. The extreme electronegativity of Zr makes the hydrolysis and polycondensation of zirconium precursors difficult to control, leading to poor structural integrity and unsatisfactory physical properties. In the present research, we prepared a ZrO aerogel by using a synthetic zirconium precursor, namely polyacetylacetonatozirconium (PAZ), and ammonia hydroxide as the gel initiator. The ammonia hydroxide catalyzes the cross-linking of PAZ promotion of the dehydration between hydroxyls in PAZ and the acetylacetonate group in PAZ binds the zirconium ion firmly upon the addition of ammonia hydroxide to avoid a gel precipitate. A monolithic ZrO aerogel with a large diameter size of 4.4 cm and high optical transmittance was achieved after drying. The surface area and pore volume of the as-dried ZrO aerogel were as high as 630.72 m g and 5.12 cm g, respectively. They decreased to 188.62 m g and 0.93 cm g after being heat-treated at 1000 °C for 2 h. The best mechanical performances of the ZrO aerogels showed a compressive strength of 0.21 ± 0.05 MPa and a modulus of 1.9 ± 0.3 MPa with a density of 0.161 ± 0.008 g cm. Both pore structures and mechanical performances varied according to the ammonia hydroxide gel initiator used. The thermal insulating properties of the ZrO aerogel performed better than a silica aerogel blanket with a thermal conductivity of 0.020 W (m K).
氧化锆(ZrO)气凝胶是在高于二氧化硅气凝胶所能达到的温度下使用的潜在候选材料。然而,制备具有高热稳定性的坚固氧化锆气凝胶仍然是一项挑战。Zr的极高电负性使得锆前驱体的水解和缩聚难以控制,导致结构完整性差和物理性能不理想。在本研究中,我们使用一种合成锆前驱体,即聚乙酰丙酮锆(PAZ),以及氢氧化铵作为凝胶引发剂制备了氧化锆气凝胶。氢氧化铵催化PAZ的交联,促进PAZ中羟基之间的脱水,并且在加入氢氧化铵后,PAZ中的乙酰丙酮基团将锆离子牢固地结合,以避免凝胶沉淀。干燥后获得了直径尺寸为4.4 cm的大尺寸整体式氧化锆气凝胶,其具有高透光率。干燥后的氧化锆气凝胶的比表面积和孔体积分别高达630.72 m²/g和5.12 cm³/g。在1000℃下热处理2小时后,它们分别降至188.62 m²/g和0.93 cm³/g。氧化锆气凝胶的最佳机械性能表现为抗压强度为0.21±0.05 MPa,模量为1.9±0.3 MPa,密度为0.161±0.008 g/cm³。孔结构和机械性能都根据所使用的氢氧化铵凝胶引发剂而变化。氧化锆气凝胶的隔热性能优于导热率为0.020 W/(m·K)的二氧化硅气凝胶毡。