论文标题
浓缩PNIPAM微凝胶中体积相变的原子量表研究
Atomic scale investigation of the volume phase transition in concentrated PNIPAM microgels
论文作者
论文摘要
结合了弹性不连贯的中子散射和差异扫描量热法,我们研究了体积相变(VPT)以非常浓度的PNIPAM Microgel悬浮液的发生,从30〜wt \%的聚合物重量分数到干燥条件。尽管样品以宏观尺度停滞,但原子自由度是平衡的,可以以可重复的方式进行探测。 VPT的明确特征是通过中子散射获得的PNIPAM氢原子的均方根位移的急剧下降。作为浓度的函数,随着干燥条件接近,VPT变得更加光滑,而VPT温度在约43 〜wt \%处显示最低。通过量热测量定性地证实了这种行为。分子动力学模拟用于补充实验结果并获得对VPT性质的进一步见解,证实了它涉及微凝胶之间有吸引力的凝胶状态的形成。总体而言,这些结果提供了证据表明,可以在不同的时间和长度尺度以及在人满为患的情况下检测到基于PNIPAM的系统中的VPT。
Combining elastic incoherent neutron scattering and differential scanning calorimetry, we investigate the occurrence of the volume phase transition (VPT) in very concentrated PNIPAM microgel suspensions, from a polymer weight fraction of 30~wt\% up to dry conditions. Although samples are arrested at the macroscopic scale, atomic degrees of freedom are equilibrated and can be probed in a reproducible way. A clear signature of the VPT is present as a sharp drop of the mean square displacement of PNIPAM hydrogen atoms obtained by neutron scattering. As a function of concentration, the VPT gets smoother as dry conditions are approached whereas the VPT temperature shows a minimum at about 43~wt\%. This behavior is qualitatively confirmed by calorimetry measurements. Molecular dynamics simulations are employed to complement experimental results and gain further insights into the nature of the VPT, confirming that it involves the formation of an attractive gel state between the microgels. Overall, these results provide evidence that the VPT in PNIPAM-based systems can be detected at different time- and length-scales as well as in overcrowded conditions.