Department of Physics, Adam Mickiewicz University, Poznań, Poland.
J Phys Chem B. 2010 Feb 4;114(4):1614-20. doi: 10.1021/jp9052456.
The structural relaxation behavior of aqueous solution of poly(ethylene glycol) and methoxy-capped poly(ethylene glycol), both of mean molecular mass 400 g/mol, is investigated by Brillouin scattering experiments. In both cases non-Debye relaxation processes have been detected, proceeding on the picosecond time scale. The average values of the detected relaxation time distributions fail to follow the simple Arrhenius behavior. The temperature evolution of the relaxation time is adequately fitted using the phenomenological Vogel-Fulcher-Tamman (VFT) model. In spite of the different temperature and concentration dependences observed for the two kinds of systems, with the exception of the highest samples concentrations, a unique scaling behavior has been found for the real and imaginary parts of the loss modulus plotted as a function of the reduced inverse temperature, T(0)/T, T(0) being the VFT arrest temperature. The presence of a unique scaling law in aqueous solutions of polymers characterized by different end groups suggests the establishment of similar hydrogen-bonded local structures. Within this scenario, water acts as a stabilizer and plays the main role bridging neighboring polymer chains. The possible physical interpretation of the obtained fit parameters is discussed, and the results are compared with other literature findings.
通过布里渊散射实验研究了平均分子量均为 400g/mol 的聚乙二醇(PEG)和甲氧基封端聚乙二醇(mPEG)水溶液的结构弛豫行为。在这两种情况下,都检测到了非德拜弛豫过程,弛豫时间在皮秒范围内。检测到的弛豫时间分布的平均值不符合简单的阿仑尼乌斯行为。使用经验的 Vogel-Fulcher-Tamman(VFT)模型对弛豫时间的温度演化进行了适当拟合。尽管两种系统观察到的温度和浓度依赖性不同,但除了最高的样品浓度外,还发现损耗模量的实部和虚部作为降低的逆温度 T(0)/T 的函数绘制时具有独特的标度行为,其中 T(0)是 VFT 停止温度。具有不同末端基团的聚合物在水溶液中存在独特的标度定律表明建立了类似的氢键局部结构。在这种情况下,水作为稳定剂发挥作用,将相邻的聚合物链桥接起来。讨论了获得的拟合参数的可能物理解释,并将结果与其他文献结果进行了比较。