论文标题
一系列基于Triphenylene的柱状液晶的多个玻璃动力学 - 宽带介电光谱和高级量热法的研究
Multiple glassy dynamics of a homologous series of triphenylene-based columnar liquid crystals -- A study by broadband dielectric spectroscopy and advanced calorimetry
论文作者
论文摘要
由芳族三苯基核心和烷基侧链组成的六烷基(N-烷基氧基)(HATN)是构成柱状中间体的模型盘状液体晶体(DLC)系统。在中间相中,HATN的分子在色谱柱中自组装,该分子沿列具有一维的高电荷载体迁移率。在这里,使用差异扫描量热法(DSC),宽带介电光谱(BDS)和先进的量热量学技术,研究了一系列具有不同长度的烷基链(n = 5,6,8,10,12)的同源系列HATN(n = 5,6,8,10,12)。利用DSC实验进行了对相行为的研究,并揭示了烷基链长度对相行为的影响。通过探测分子迁移率的介电研究,在塑料晶体相的温度范围内观察到了$γ$ - 递延以及两个玻璃状动力学引起的$γ$ - 递归。此外,使用高级量热法进一步研究了观察到的玻璃动力学。所有观察到的松弛过程归因于可能的特定分子波动,并详细讨论。从结果中,n = 8的过渡从刚性约束(n = 5,6)到较软的系统(n = 10,12)的过渡显示,烷基链长度的增加。在阻碍的玻璃跃迁的背景下,讨论了聚乙烯类似烷基链的两种竞争效应和烷基链的行为和自组织的限制。
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n=5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations probing the molecular mobility, a $γ$-relaxation due to localized fluctuations as well as two glassy dynamics the $α$ core and $α$ alkyl relaxation were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n=8 from a rigid constrained (n=5,6) to a softer system (n=10,12) was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition.