Department of Polymer Engineering, University of Akron, Akron, Ohio 44325, USA.
J Phys Chem B. 2010 Jun 17;114(23):7791-6. doi: 10.1021/jp1033454.
Self-motion of a growing single crystal of azobenzene chromophore in triacrylate solution (TA) is investigated in relation to the solid-liquid phase diagram bound by the solidus and liquidus lines. Upon thermal quenching from the isotropic melt to the crystal + liquid gap, various single crystals develop in a manner dependent on concentration and supercooling depth. During the crystal growth, TA solvent is rejected from the growing faceted fronts, enriching with TA in close proximity to the crystal-solution interface. The concentration gradient that formed as the result of TA expulsion induces convective flows in the solution and generates spatial variability of surface tension usually responsible for Marangoni effect. Either or both of these phenomena may have contributed to the observed self-motion including swimming, sinking, and floating of the azobenzene rhomboidal crystal in TA solution. A stationary rhomboidal crystal is also shown to swim upon irradiation with the UV light because of a mechanical torque generated by the trans-cis isomerization. Judging from the sinking or floating behavior of the azobenzene crystal, it may be inferred that the nucleation occurs at the solution-air interface.
在固体相线和液体相线所界定的固-液相图的范围内,研究了偶氮苯发色团在三丙烯酸酯溶液(TA)中生长单晶的自运动。在从各向同性熔体热淬火到晶体+液体间隙时,各种单晶以依赖于浓度和过冷深度的方式生长。在晶体生长过程中,TA 溶剂从生长的有面晶体前沿被排斥,在靠近晶体-溶液界面处 TA 富集。由于 TA 排出形成的浓度梯度在溶液中诱导对流流动,并产生通常负责 Marangoni 效应的表面张力空间变化。这些现象中的一个或两个都可能导致观察到的自运动,包括偶氮苯菱形晶体在 TA 溶液中的游动、下沉和漂浮。由于 trans-cis 异构化产生的机械扭矩,静止的菱形晶体在受到紫外光照射时也会游动。根据偶氮苯晶体的下沉或漂浮行为,可以推断出成核发生在溶液-空气界面。