Centre for Liquid Crystal Research, Jalahalli, Bangalore 560 013, India.
J Phys Chem B. 2010 Jan 21;114(2):697-704. doi: 10.1021/jp9071394.
Thermal and extensive rheological characterization of a nematic liquid crystal gelated with a novel monodisperse dipeptide, also a liquid crystal, has been carried out. For certain concentrations, the calorimetric scans display a two-peak profile across the chiral nematic-isotropic (N*-I) transition, a feature reminiscent of the random-dilution to random-field crossover observed in liquid crystal gels formed with aerosil particles. All samples show shear thinning behavior without a Newtonian plateau region at lower shear rates. Small deformation oscillatory data at lower frequencies exhibit a frequency dependence of the storage (G') and loss (G'') moduli that can be described by a weak power-law, characteristic of soft glassy rheological systems. At higher frequencies, while lower concentration composites have a strong frequency dependence with a trend for possible crossover from viscoelastic solid to viscoelastic liquid behavior, the higher-concentration gels show frequency-independent rheograms of entirely elastic nature G' > G''. The plateau modulus of G' is described by a power-law with an exponent again common to soft materials, such as foams, slurries, etc. Other features which are a hallmark of such materials observed in the present study are: (i) above a critical strain, a strain softening of the moduli with a peak in the loss modulus, (ii) power-law variation of the storage modulus in the nonlinear viscoelastic regime, and (iii) absence of Cox-Merz superposition for the complex viscosity. An attractive feature of these gels is the fast recovery upon removal of large strain and qualitatively different temporal behavior of the recovery between the low and high concentration composites, with the latter indicating the presence of two characteristic time scales.
新型单分散二肽凝胶化向列液晶的热学和广泛流变特性研究。在一定浓度下,量热扫描显示在手性向列-各向同性(N*-I)转变过程中存在双峰轮廓,这一特征类似于在气溶胶粒子形成的液晶凝胶中观察到的随机稀释到随机场交叉。所有样品在较低剪切速率下均表现出剪切稀化行为,不存在牛顿平台区。较低频率下的小变形振荡数据表现出储能模量(G')和损耗模量(G")的频率依赖性,可以用弱幂律来描述,这是软玻璃态流变体系的特征。在较高频率下,虽然低浓度复合材料具有较强的频率依赖性,并且可能从粘弹性固体转变为粘弹性液体行为,但高浓度凝胶表现出完全弹性性质的频率无关流型,即 G' > G"。G'的平台模量可以用幂律来描述,其指数与泡沫、浆料等软材料相同。在本研究中观察到的此类材料的其他特征是:(i)在临界应变以上,模量出现应变软化,并伴有损耗模量峰值;(ii)在非线性粘弹性区,储能模量呈幂律变化;(iii)复粘度的 Cox-Merz 叠加不成立。这些凝胶的一个吸引人的特点是在去除大应变后能够快速恢复,并且在低浓度和高浓度复合材料之间,恢复的时间行为存在质的不同,后者表明存在两个特征时间尺度。