Investigating the adsorption of anisotropic diblock copolymer worms onto planar silica and nanocellulose surfaces using a quartz crystal microbalance,Polymer Chemistry

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Investigating the adsorption of anisotropic diblock copolymer worms onto planar silica and nanocellulose surfaces using a quartz crystal microbalance
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-09-06 , DOI: 10.1039/d1py00644d
Joakim Engström ₁ , Michael S. Reid ₂ , Emma E. Brotherton ₃ , Eva Malmström ₁ , Steven P. Armes ₃ , Fiona L. Hatton ₃

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Electrostatic adsorption of cationic polyelectrolytes onto anionic cellulosic substrates is an attractive route for facile surface modification of biorenewable materials. Recently, attention has focused on adsorbing cationic spherical diblock copolymer nanoparticles onto model cellulose and/or nanocellulosic substrates. Herein, we investigate physical adsorption of highly anisotropic copolymer worms bearing either anionic or cationic charge onto planar silica, cellulose nanocrystal (CNC) or cellulose nanofibril (CNF) surfaces using quartz crystal microbalance with dissipation monitoring. Electrostatic interactions dominate in the case of anionic silica and CNC surfaces because the adsorbed mass of cationic worms was greater than that of anionic worms. However, either anionic or cationic worms could be adsorbed onto in situ generated CNF substrates, suggesting that additional interactions were involved: hydrogen bonding, van der Waals forces, and possibly covalent bond formation. Scanning electron and atomic force microscopy studies of the dried planar substrates after adsorption experiments confirmed the presence of adsorbed copolymer worms. Finally, composite worm/CNF films exhibited restricted swelling behavior when immersed in water compared to reference CNF films, suggesting that the worms reinforce CNF films by acting as a physical crosslinker. This study is the first investigation of the physical adsorption of highly anisotropic diblock copolymer worms onto cellulosic surfaces.

中文翻译：

使用石英晶体微天平研究各向异性二嵌段共聚物蠕虫在平面二氧化硅和纳米纤维素表面上的吸附

阳离子聚电解质在阴离子纤维素基材上的静电吸附是一种对生物可再生材料进行简便表面改性的有吸引力的途径。最近，注意力集中在将阳离子球形二嵌段共聚物纳米颗粒吸附到模型纤维素和/或纳米纤维素基材上。在此，我们使用带有耗散监测的石英晶体微天平研究了带有阴离子或阳离子电荷的高度各向异性共聚物蠕虫在平面二氧化硅、纤维素纳米晶体 (CNC) 或纤维素纳米纤维 (CNF) 表面上的物理吸附。在阴离子二氧化硅和 CNC 表面的情况下，静电相互作用占主导地位，因为阳离子蠕虫的吸附质量大于阴离子蠕虫的吸附质量。然而，阴离子或阳离子蠕虫都可以原位吸附到生成了 CNF 底物，表明还涉及其他相互作用：氢键、范德华力和可能的共价键形成。吸附实验后干燥平面基材的扫描电子和原子力显微镜研究证实了吸附的共聚物蠕虫的存在。最后，与参考 CNF 薄膜相比，复合蠕虫/CNF 薄膜在浸入水中时表现出有限的溶胀行为，这表明蠕虫通过充当物理交联剂增强了 CNF 薄膜。这项研究是对高度各向异性的二嵌段共聚物蠕虫在纤维素表面上的物理吸附的首次研究。

更新日期：2021-09-13

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