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Synthesis and Liquid Crystal Phase Transitions of Zirconium Phosphate Disks
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Solvent-mediated self-assembly of nanoparticles is an effective and efficient way for the bottom-up organization of functional structures. The primary object of this work is to build up a model system for the study of suspensions of disk-shaped nanoparticles, and use it for the study of self-assembly and discotic liquid crystal phase transitions of discotic particles. The work was introduced by the control over the size and polydispersity of zirconium phosphate (ZrP) disks through synthesis. Systematic experiments revealed that regular-shaped α-zirconium phosphate crystalline disks with a size-to-thickness ratio from 1 to 50 and size polydispersity as low as 0.2 can be obtained through hydrothermal treatment in 3 M to 15 M phosphoric acid solutions. Transmission and scanning electron micrographs revealed that the growth of the disks is mediated by oriented attachment, which happened continuously throughout the hydrothermal treatment between various sized disks. Ostwald ripening is effective in improving the regularity of the shape of the disks, especially under prolonged hydrothermal treatment. Under the microwave assisted hydrothermal conditions, the rate of attachment on the flat surfaces of the disks is accelerated, which leads to the formation of the column-shaped crystals. With the ability to adjust the size, aspect ratio, and polydispersity of ZrP disks, the study on self-assembly behavior and the discotic liquid crystal phases was enabled. Firstly, liquid crystal phases of aqueous suspensions of ZrP disks were investigated. Iridescent smectic phase and the critical points of phase transitions were found. Moreover, monolayer ZrP nanosheets with extremely high aspect ratio, which were achieved by exfoliating the ZrP crystals, were also used in this study. The high aspect ratio of nanosheets produces a laminar phase at low nanosheet concentration. Chiral liquid crystal phases were demonstrated when increased the concentration of the nanosheets. The competition between the chirality and layering leads to twisted and layered structures. For the final part, solvent-mediated self-assembly of disks and nanosheets via undulation of liquid crystal phases showed an interesting approach for bottom-up design of functional nano-structures.
Shuai, Min (2013). Synthesis and Liquid Crystal Phase Transitions of Zirconium Phosphate Disks. Doctoral dissertation, Texas A&M University. Available electronically from