Department of Chemical Engineering, The University of Western Australia, Perth 6009, Australia.
Centre for Microscopy, Characterization and Analysis, The University of Western Australia, Perth 6009, Australia.
Phys Chem Chem Phys. 2018 Jul 18;20(28):19221-19233. doi: 10.1039/c8cp01382a.
Natural (N-) and synthetic (S-) hectorite suspensions were found to display significant time-dependent rheology or ageing behaviour and shear thinning flow behaviour. The ageing behaviour was characterised by an increasing yield stress with rest time. The yield stress continued to increase even after a week of rest, a reflection of a long process. An open sponge-like cellular microstructure formed by platelet particles interacting attractively in the overlapping edge-face configuration was captured by cryo-SEM of gel samples prepared at high pressure (∼2000 bar) and subjected to rapid cryo-freezing, for both N- and S-hectorite gels. Even nano-discotic S-hectorite particles formed platelet particles hundreds of nanometres in length in the overlapping coin configuration. This structure, displaying a cell size ranging from tens to several hundred nanometres, is formed by strong attractive and repulsive forces. The platelets showed deformations such as bending and curling of the edges in response to these forces. The S-hectorite platelets are smaller and more rigid. During ageing the particles in the structure experience a net force. These particles will move in response causing force imbalance to be experienced by neighbouring particles and they will move in response. This action and reaction percolate through the network structure causing a high concentration of particles to respond. As a consequence the ageing process takes a long time to reach equilibrium. Various ageing models were used to fit the ageing data. The N-hectorite gels displayed a maximum yield stress at pH ∼ 8 and a particle zeta potential of -35 mV. This suggests the presence of critical positive and negative charge density is needed to form a structure with maximum strength. The zeta potential is negative and quite insensitive to pH from pH 4 to 12.
天然(N-)和合成(S-)羟乙基纤维素悬浮液表现出显著的时变流变学或老化行为和剪切变稀流动行为。老化行为的特点是随着静置时间的增加屈服应力增加。即使在一周的休息后,屈服应力仍继续增加,反映出一个漫长的过程。通过对在高压(约 2000 巴)下制备的凝胶样品进行快速冷冻的冷冻扫描电子显微镜(Cryo-SEM)观察,发现由带板颗粒在重叠的边缘-面构型中相互吸引形成的开放式海绵状细胞微结构,无论是 N-和 S-羟乙基纤维素凝胶。即使是纳米盘状 S-羟乙基纤维素颗粒也在重叠的硬币构型中形成了数百纳米长的带板颗粒。这种结构显示出的细胞尺寸范围从几十到几百纳米,是由强烈的吸引力和排斥力形成的。由于这些力的作用,带板会发生变形,如边缘的弯曲和卷曲。S-羟乙基纤维素带板较小且刚性较大。在老化过程中,结构中的颗粒会经历净力。这些颗粒会移动以响应,导致相邻颗粒受力不平衡,它们会随之移动。这种作用和反作用在网络结构中渗透,导致高浓度的颗粒做出响应。因此,老化过程需要很长时间才能达到平衡。使用了各种老化模型来拟合老化数据。N-羟乙基纤维素凝胶在 pH ∼ 8 和颗粒 ζ 电位为-35 mV 时显示出最大屈服应力。这表明需要存在临界正电荷和负电荷密度才能形成具有最大强度的结构。ζ 电位为负,并且对 pH 从 4 到 12 相当不敏感。