School of Materials Science and Engineering, Georgia Institute of Technology , Atlanta, Georgia 30332-0245, United States.
Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University , 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
Langmuir. 2017 Apr 4;33(13):3187-3199. doi: 10.1021/acs.langmuir.6b04622. Epub 2017 Mar 21.
The surface morphology and organization of poly(ionic liquid)s (PILs), poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] are explored in conjunction with their molecular architecture, adsorption conditions, and postassembly treatments. The formation of stable PIL Langmuir and Langmuir-Blodgett (LB) monolayers at the air-water and air-solid interfaces is demonstrated. The hydrophobic bis(trifluoromethylsulfonyl)imide (TfN) is shown to be a critical agent governing the assembly morphology, as observed in the reversible condensation of LB monolayers into dense nanodroplets. The PIL is then incorporated as an unconventional polyelectrolyte component in the layer-by-layer (LbL) films of hydrophobic character. We demonstrate that the interplay of capillary forces, macromolecular mobility, and structural relaxation of the polymer chains influence the dewetting mechanisms in the PIL multilayers, thereby enabling access to a diverse set of highly textured, porous, and interconnected network morphologies for PIL LbL films that would otherwise be absent in conventional LbL films. Their compartmentalized internal structure is relevant to molecular separation membranes, ultrathin hydrophobic coatings, targeted cargo delivery, and highly conductive films.
聚离子液体（PILs）的表面形态和组织，聚[1-(4-乙烯基苄基)-3-丁基咪唑双（三氟甲烷磺酰基）亚胺]，与它们的分子结构、吸附条件和后组装处理一起进行了探索。证明了在气-水和气-固界面处稳定的 PIL 朗缪尔（Langmuir）和朗缪尔-布洛杰特（Langmuir-Blodgett，LB）单层的形成。发现疏水性双（三氟甲烷磺酰基）亚胺（TfN）是控制组装形态的关键因素，如 LB 单层可逆凝聚成致密纳米液滴中所观察到的那样。然后，PIL 被用作具有疏水性特征的层层（LbL）膜中的非常规聚电解质组分。我们证明了毛细力、高分子链的迁移性和结构松弛之间的相互作用影响了 PIL 多层膜的去湿机制，从而能够获得各种高度纹理化、多孔和相互连接的网络形态的 PIL LbL 膜，否则在传统的 LbL 膜中是不存在的。它们的分区内部结构与分子分离膜、超薄疏水性涂层、靶向货物输送和高导电性薄膜有关。
