Vollmer Doris, Hinze Gerald, Ullrich Beate, Poon Wilson C K, Cates Michael E, Schofield Andrew B
MPI for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Langmuir. 2005 May 24;21(11):4921-30. doi: 10.1021/la047090w.
In mixtures of thermotropic liquid crystals with spherical poly (methyl methacrylate) particles, self-supporting networklike structures are formed during slow cooling past the isotropic-to-nematic phase transformation. To characterize the process of network formation in terms of morphology, phase transformation kinetics, and mechanical properties, we have combined data from polarization and laser scanning confocal microscopy with calorimetric, NMR, and rheological results. Our data suggest that the mechanism of network formation is dominated by a broadened temperature and time interval of phase transformation rather than by particle size or concentration. The observation that the width of the transformation interval strongly depends on sample preparation supports the hypothesis that a third component, most likely alkane remnants slowly liberated from the particles, plays a crucial role. In addition, calorimetric findings for liquid crystal/colloid mixtures, heated and cooled up to 13 times, point to separation of the liquid crystal into two compartments with different phase transformation kinetics. This could be explained by redistribution and enrichment of alkane in the particle-composed network walls. A further increase of the storage modulus, G', and incomplete dissolution of the networks in the isotropic state indicate that the formation of two compartments during repeated temperature cycles stabilizes the network and confers strong memory effects.
在热致液晶与球形聚甲基丙烯酸甲酯颗粒的混合物中,在缓慢冷却经过各向同性向向列相转变的过程中会形成自支撑的网络状结构。为了从形态学、相变动力学和力学性能方面表征网络形成过程,我们将偏振和激光扫描共聚焦显微镜的数据与量热、核磁共振和流变学结果相结合。我们的数据表明,网络形成的机制主要由相变的温度和时间间隔变宽主导,而非颗粒大小或浓度。转变间隔宽度强烈依赖于样品制备这一观察结果支持了如下假设:第三种成分,很可能是从颗粒中缓慢释放出的烷烃残余物,起着关键作用。此外,对液晶/胶体混合物进行多达13次加热和冷却的量热结果表明,液晶分离成了具有不同相变动力学的两个部分。这可以通过烷烃在由颗粒组成的网络壁中的重新分布和富集来解释。储能模量G'的进一步增加以及网络在各向同性状态下的不完全溶解表明,在重复温度循环过程中两个部分的形成使网络稳定并赋予了强烈的记忆效应。