论文标题

纤维素纳米晶体的凝胶中缓慢的动力学和时间组装叠加

Slow dynamics and time-composition superposition in gels of cellulose nanocrystals

论文作者

Morlet-Decarnin, Lise, Divoux, Thibaut, Manneville, Sebastien

论文摘要

纤维素纳米晶体(CNC)是类似棒状的生物包配的胶体颗粒,用作越来越多的具有创新的机械或光学特性材料的关键构件。尽管CNC在纯净水中的低体积分数下形成稳定的悬浮液,但它们在存在盐的存在下聚集,并与时间相关的特性形成胶体凝胶。在这里,我们研究了盐浓度对CNC凝胶缓慢老化动力学的影响,因为高剪切流量完全使样品充满了流动。我们表明,盐含量越高,流动停止时的弹性恢复越快。最值得注意的是,弹性模量$ g'$ obeys一个时间组合叠加原则:$ g'$的时间演变可以重新缩放到通用的sigmoidaser曲线上,跨越了13个数量级,以达到较广泛的盐浓度。这种重新恢复是通过较陡峭的幂律随着盐浓度升高的陡峭幂律衰减而获得的,直到它在较大的盐含量下饱和为止。这些发现对盐类型和CNC含量的变化是可靠的。我们进一步表明,可以根据沿普通主曲线的样本年龄重新缩放各种组合物的CNC凝胶的线性和非线性流变特性。我们的结果为CNC凝胶衰老动力学的普遍性提供了有力的证据,并呼吁在恢复过程中进行微结构研究,以及在棒状胶体中时间组合叠加的理论建模。

Cellulose nanocrystals (CNCs) are rodlike biosourced colloidal particles used as key building blocks in a growing number of materials with innovative mechanical or optical properties. While CNCs form stable suspensions at low volume fractions in pure water, they aggregate in the presence of salt and form colloidal gels with time-dependent properties. Here, we study the impact of salt concentration on the slow aging dynamics of CNC gels following the cessation of a high-shear flow that fully fluidizes the sample. We show that the higher the salt content, the faster the recovery of elasticity upon flow cessation. Most remarkably, the elastic modulus $G'$ obeys a time-composition superposition principle: the temporal evolution of $G'$ can be rescaled onto a universal sigmoidal master curve spanning 13 orders of magnitude in time for a wide range of salt concentrations. Such a rescaling is obtained through a time-shift factor that follows a steep power-law decay with increasing salt concentration, until it saturates at large salt content. These findings are robust to changes in the type of salt and in the CNC content. We further show that both linear and nonlinear rheological properties of CNC gels of various compositions, including, e.g., the frequency-dependence of viscoelastic spectra and the yield strain, can be rescaled based on the sample age along the general master curve. Our results provide strong evidence for universality in the aging dynamics of CNC gels, and call for microstructural investigations during recovery as well as theoretical modelling of time-composition superposition in rodlike colloids.

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