Fujimori Atsuhiro, Araki Tohru, Nakahara Hiroo
Department of Chemistry, Faculty of Science, Saitama University, Shimo-okubo 2 5 5, Saitama, 338-8570, Japan.
J Colloid Interface Sci. 2002 Mar 15;247(2):351-60. doi: 10.1006/jcis.2001.8107.
The monolayer behavior of long-chain esters of acrylic and methacrylic acids containing perfluoro or partially fluorinated carbon chains at the air/water interface was studied by surface pressure-area isotherm measurements and Brewster angle microscopy. It has been found that a minor change in the chemical structures of these fluorinated amphiphiles, such as a hydrogen substituted at the omega-position of the hydrophobic fluorocarbon tails instead of a fluorine as well as hydrophilic vinyl ester groups inserted between acrylates and methacrylates, induces a drastic change in the isotherms for the monolayers, suggesting different molecular orientation and packing in the films. The monolayers were transferred by horizontal lifting, Langmuir-Blodgett, and surface-lowering methods to give the X-, Y-, and Z-type films, respectively. These films were characterized by scanning probe microscopy, to clarify the mesoscopic surface structures of the molecular films exposed with the hydrophilic or hydrophobic moieties in air, depending upon the dipping methods. The Z-type films with the outermost surface of the fluorinated substituents were examined in relation to the frictional properties that strongly depend upon the fluorine and the hydrogen atoms at the end of the hydrophobic fluorocarbon chains, which is controllable at the atomic level.
通过表面压力-面积等温线测量和布儒斯特角显微镜研究了含全氟或部分氟化碳链的丙烯酸和甲基丙烯酸长链酯在空气/水界面的单分子层行为。已发现这些氟化两亲物化学结构的微小变化,如疏水氟碳链的ω位上的氢取代氟以及在丙烯酸酯和甲基丙烯酸酯之间插入亲水乙烯基酯基团,会导致单分子层等温线发生剧烈变化,这表明薄膜中分子的取向和堆积不同。通过水平提拉、朗缪尔-布洛杰特法和表面降低法分别转移单分子层以得到X型、Y型和Z型薄膜。通过扫描探针显微镜对这些薄膜进行表征,以阐明根据浸渍方法在空气中暴露有亲水或疏水部分的分子薄膜的介观表面结构。研究了具有氟化取代基最外表面的Z型薄膜与摩擦性能的关系,摩擦性能强烈依赖于疏水氟碳链末端的氟和氢原子,这在原子水平上是可控的。