论文标题

电荷对局限于油水界面的聚电解质微凝胶行为的影响

Influence of charges on the behavior of polyelectrolyte microgels confined to oil-water interfaces

论文作者

Schmidt, Maximilian M., Bochenek, Steffen, Gavrilov, Alexey A., Potemkin, Igor I., Richtering, Walter

论文摘要

在文献中,已经有争议地讨论了静电剂对聚电解质微凝胶的界面特性的作用。目前尚不清楚库仑相互作用是在界面限制下的行为。在这项工作中,我们结合了压缩等温线,原子力显微镜成像和计算机模拟,以进一步研究pH响应微凝胶在油水界面上的行为。在低压下,带电的微凝胶比未充电的微凝胶可以压缩更多。与未充电的微凝胶相比,被带电的微凝胶的平面内有效区域较小。因此,可压缩性由微凝胶与界面的平面相互作用控制。然而,在高压下,带电的微凝胶不如未充电的微凝胶可压缩。位于水相中的微凝胶馏分与未充电的微凝胶相比,由于其垂直于界面的肿胀不同。因此,高压下的可压缩性由平面外相互作用控制。另外,研究的微凝胶的大小起着关键作用。仅观察到小微凝胶但没有观察到低压下的压缩性的电荷依赖性差异,而高压下的行为不取决于大小。我们的结果强调了与刚性胶体颗粒相比,软聚合物微凝胶的复杂性质。我们清楚地表明,静电相互作用会影响聚电解质微凝胶的界面特性。

The role of electrostatics on the interfacial properties of polyelectrolyte microgels has been discussed controversially in the literature. It is not yet clear if, or how, Coulomb interactions affect their behavior under interfacial confinement. In this work, we combine compression isotherms, atomic force microscopy imaging, and computer simulations to further investigate the behavior of pH-responsive microgels at oil-water interfaces. At low compression, charged microgels can be compressed more than uncharged microgels. The in-plane effective area of charged microgels is found to be smaller in comparison to uncharged ones. Thus, the compressibility is governed by in-plane interactions of the microgels with the interface. At high compression, however, charged microgels are less compressible than uncharged microgels. Microgel fractions located in the aqueous phase interact earlier for charged than for uncharged microgels because of their different swelling perpendicular to the interface. Therefore, the compressibility at high compression is controlled by out-of-plane interactions. In addition, the size of the investigated microgels plays a pivotal role. The charge-dependent difference in compressibility at low compression is only observed for small but not for large microgels, while the behavior at high compression does not depend on the size. Our results highlight the complex nature of soft polymer microgels as compared to rigid colloidal particles. We clearly demonstrate that electrostatic interactions affect the interfacial properties of polyelectrolyte microgels.

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