Goracci G, Arbe A, Alegría A, Lohstroh W, Su Y, Colmenero J
Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizabal 5, 20018 San Sebastián, Spain.
Heinz Maier-Leibnitz Zentrum, Technische Universität München, Lichtenbergstraße 1, D-85748 Garching, Germany.
J Chem Phys. 2015 Sep 7;143(9):094505. doi: 10.1063/1.4929906.
We have investigated a mixture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and tetrahydrofuran (THF) (70 wt. % PDMAEMA/30 wt. % THF) by combining dielectric spectroscopy and quasielastic neutron scattering (QENS) on a labelled sample, focusing on the dynamics of the THF molecules. Two independent processes have been identified. The "fast" one has been qualified as due to an internal motion of the THF ring leading to hydrogen displacements of about 3 Å with rather broadly distributed activation energies. The "slow" process is characterized by an Arrhenius-like temperature dependence of the characteristic time which persists over more than 9 orders of magnitude in time. The QENS results evidence the confined nature of this process, determining a size of about 8 Å for the volume within which THF hydrogens' motions are restricted. In a complementary way, we have also investigated the structural features of the sample. This study suggests that THF molecules are well dispersed among side-groups nano-domains in the polymer matrix, ruling out a significant presence of clusters of solvent. Such a good dispersion, together with a rich mobility of the local environment, would prevent cooperativity effects to develop for the structural relaxation of solvent molecules, frustrating thereby the emergence of Vogel-Fulcher-like behavior, at least in the whole temperature interval investigated.
我们通过对一个标记样品进行介电谱和准弹性中子散射(QENS)相结合的方法,研究了聚(甲基丙烯酸2-(二甲氨基)乙酯)(PDMAEMA)和四氢呋喃(THF)的混合物(70 wt.% PDMAEMA/30 wt.% THF),重点关注THF分子的动力学。已识别出两个独立的过程。“快速”过程被认为是由于THF环的内部运动导致氢位移约3 Å,且活化能分布相当广泛。“缓慢”过程的特征是特征时间具有类似阿仑尼乌斯的温度依赖性,这种依赖性在时间上持续超过9个数量级。QENS结果证明了该过程的受限性质,确定了THF氢运动受限的体积大小约为8 Å。作为补充,我们还研究了样品的结构特征。该研究表明,THF分子在聚合物基体的侧基纳米域中分散良好,排除了溶剂团簇的大量存在。这种良好的分散性,加上局部环境丰富的流动性,将阻止溶剂分子结构弛豫的协同效应发展,从而至少在所研究的整个温度区间内抑制类似Vogel-Fulcher行为的出现。