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arXiv 2404.04032cond-mat.soft
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中性与带电微凝胶悬浮液的数值研究:从单粒子到集体行为

Numerical study of neutral and charged microgel suspensions: from single-particle to collective behavior

Giovanni Del Monte, Emanuela Zaccarelli

AI总结:

本文通过分子动力学模拟对比中性与带电微凝胶悬浮液,揭示收缩和变形导致的结构重入现象及其与动力学减速的差异,并提出多Hertzian模型解释核心刚度增强效应,为理解微凝胶物理机制建立了新框架。

摘要:

我们对溶胀条件下真实微凝胶粒子系综在宽范围堆积分数 $ζ$ 内进行了大规模分子动力学模拟。我们比较了中性与带电微凝胶,其中考虑了符合实验条件的电荷分布。通过对单粒子行为的详细分析,我们能够识别随浓度增加而出现的不同状态:从收缩到变形和互穿,并始终将我们的发现与可获得的实验观测相联系。随后,我们将这些单粒子特征与悬浮液的集体行为联系起来,发现了结构重入现象的证据,而这种重入在动力学中没有对应表现。因此,虽然径向分布函数的最大值随 $ζ$ 增加表现出非单调行为,但由微凝胶均方位移量化的动力学却始终减慢。这种行为与简单 Hertzian 模型不一致,可以用唯象的多 Hertzian 模型来描述,该模型考虑了核心增强的内部刚度。然而,当变形开始起作用时,该模型也会失效,此时需要更真实的多体模型。我们能够揭示导致结构重入的关键物理机制,即收缩和变形,该重入现象一直持续到非常大的堆积分数。我们进一步确定了中性与带电微凝胶之间的关键相似性和差异性,对于后者,我们在足够高的 $ζ$ 下检测到带电壳层的融合,这一现象此前被用来解释关键实验发现,并且是结构重入的原因。总体而言,我们的研究建立了一个强有力的框架来揭示微凝胶悬浮液的物理机制,为处理实验证据仍然有限的不同状态和内部结构架构铺平了道路。

英文摘要:

We perform extensive Molecular Dynamics simulations of an ensemble of realistic microgel particles in swollen conditions in a wide range of packing fractions $ζ$. We compare neutral and charged microgels, where we consider charges distribution adherent to experimental conditions. Through a detailed analysis of single-particle behavior, we are able to identify the different regimes occurring upon increasing concentration: from shrinking to deformation and interpenetration, always connecting our findings to available experimental observations. We then link these single-particle features to the collective behavior of the suspension, finding evidence of a structural reentrance, that has no counterpart in the dynamics. Hence, while the maximum of the radial distribution function displays a non-monotonic behavior with increasing $ζ$, the dynamics, quantified by the microgels' mean-squared displacement, always slows down. This behavior, at odds with simple Hertzian model, can be described by a phenomenological multi-Hertzian, which takes into account the enhanced internal stiffness of the core. However, also this model fails when deformation enters into play, whereby more realistic many-body models are required. We are able to unveil the key physical mechanisms, shrinking and deformation, giving rise to the structural reentrance that holds up to very large packing fractions. We further identify key similarities and differences between neutral and charged microgels, for which we detect at high enough $ζ$ the fusion of charged shells, previously invoked to explain key experimental findings, and responsible for the structural reentrance. Overall, our study establishes a powerful framework to uncover the physics of microgel suspensions, paving the way to tackle different regimes and internal structural architectures, where experimental evidence is still limited.

机构、总结、中文摘要均由AI分析而来,可能存在错误,请以论文正文为准。

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