论文标题
聚合物刷中的压力各向异性及其对润湿的影响
Pressure anisotropy in polymer brushes and its effects on wetting
论文作者
论文摘要
聚合物刷,由密集移植的大分子组成的涂层,经历了固有的侧向压缩压力,源自链条弹性和排除体积相互作用。这种横向压力使对界面的适当定义变得复杂,从而确定和解释界面张力及其与刷子润湿行为的关系。在这里,我们研究了使用粗粒分子动力学模拟的聚合物刷中接枝诱导的压缩侧压,界面张力和刷润湿性之间的联系。我们专注于嫁接密度和聚合物 - 液体亲和力,以使聚合物和液体不倾向于混合。对于这些系统,核心结果是液体接触角与嫁接密度无关,这意味着接枝诱导的刷子中的横向压缩压力不会影响其润湿性。尽管刷界面紧张的定义因接枝引起的压力而变得复杂,但湿刷和干刷之间的界面张力差异非常明确。我们从Young定律中明确确认,这种差异提供了对刷子润湿性的准确描述。然后,我们探索一种方法,即假设界面张力与嫁接密度无关,将接枝诱导的对侧压的贡献分离出来。这种情况确实允许除了靠近混合点外,还可以为广泛参数解散界面和嫁接效果。我们根据自噬脱水分别讨论后一种情况。
Polymer brushes, coatings consisting of densely grafted macromolecules, experience an intrinsic lateral compressive pressure, originating from chain elasticity and excluded volume interactions. This lateral pressure complicates a proper definition of the interface and, thereby, the determination and interpretation of the interfacial tension and its relation to the wetting behavior of brushes. Here, we study the link between grafting-induced compressive lateral pressure in polymer brushes, interfacial tension, and brush wettability using coarse-grained molecular dynamics simulations. We focus on grafting densities and polymer-liquid affinities such that the polymer and liquid do not tend to mix. For these systems, a central result is that the liquid contact angle is independent of the grafting density, which implies that the grafting-induced lateral compressive pressure in the brush does not influence its wettability. Although the definition of brush interfacial tensions is complicated by the grafting-induced pressure, the difference in interfacial tension between wet and dry brushes is perfectly well-defined. We confirm explicitly from Young's law that this difference offers an accurate description of the brush wettability. We then explore a method to isolate the grafting-induced contribution to the lateral pressure, assuming the interfacial tension to be independent of grafting density. This scenario indeed allows to disentangle interfacial and grafting effects for a broad range of parameters, except close to the mixing point. We separately discuss the latter case in the light of autophobic dewetting.