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arXiv 2008.00241cond-mat.soft
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浓缩PNIPAM微凝胶体积相变的原子尺度研究

Atomic scale investigation of the volume phase transition in concentrated PNIPAM microgels

M. Zanatta, L. Tavagnacco, E. Buratti, E. Chiessi, F. Natali, M. Bertoldo, A. Orecchini, E. Zaccarelli

摘要:

结合弹性非相干中子散射和差示扫描量热法,我们调查的体积相变(VPT)的发生在非常集中的PNIPAM微凝胶悬浮液,从聚合物的重量分数为30~wt\%的干燥条件。虽然样品在宏观尺度上被捕获,但原子自由度是平衡的,并且可以以可再现的方式进行探测。通过中子散射得到的PNIPAM氢原子的均方位移的急剧下降是VPT的明显特征。作为浓度的函数,随着接近干燥条件,VPT变得更平滑,而VPT温度在约43重量%处显示出最小值。量热法测量定性地证实了这种行为。分子动力学模拟是用来补充实验结果,并获得进一步的洞察VPT的性质,确认它涉及到一个有吸引力的凝胶状态之间的微凝胶的形成。总体而言,这些结果提供的证据表明,在PNIPAM为基础的系统中的VPT可以在不同的时间和长度尺度,以及在过度拥挤的条件下检测。

英文摘要:

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.

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