Olanya Geoffrey, Iruthayaraj Joseph, Poptoshev Evgeni, Makuska Ricardas, Vareikis Ausvydas, Claesson Per M
Department of Chemistry, Surface Chemistry, Royal Institute of Technology, SE-100 44 Stockholm, Sweden.
Langmuir. 2008 May 20;24(10):5341-9. doi: 10.1021/la703739v. Epub 2008 Apr 19.
The adsorption behavior of bottle-brush polymers with different charge/PEO ratio on silica was studied using optical reflectometry and QCM-D. The results obtained under different solution conditions clearly demonstrate the existence of two distinct adsorption mechanisms depending on the ratio of charge/PEO. In the case of low-charge density brush polymers (0-10 mol %), the adsorption occurs predominantly through the PEO side chains. However, the presence of a small amount of charge along the backbone (as low as 2 mol %) increases the adsorption significantly above that of the uncharged bottle-brush polymer in pure water. As the charge density of the brush polymers is increased to 25 mol % or larger the adsorption occurs predominantly through electrostatic interactions. The adsorbed layer structure was studied by measuring the layer dissipation using QCM-D. The adsorbed layer formed by the uncharged brush polymer dissipates only a small amount of energy that indicates that the brush lie along the surface, the scenario in which the maximum number of PEO side chains interact with the surface. The adsorbed layers formed by the low-charge density brush polymers (2-10 mol %) in water are more extended, which results in large energy dissipation, whereas those formed by the high-charge density brush polymers (50-100 mol %) have their backbone relatively flat on the surface and the energy dissipation is again low.
利用光学反射法和石英晶体微天平耗散技术(QCM-D)研究了不同电荷/聚环氧乙烷(PEO)比例的刷状聚合物在二氧化硅上的吸附行为。在不同溶液条件下获得的结果清楚地表明,根据电荷/PEO的比例存在两种不同的吸附机制。对于低电荷密度的刷状聚合物(0-10摩尔%),吸附主要通过PEO侧链发生。然而,主链上存在少量电荷(低至2摩尔%)会使吸附量比纯水中不带电荷的刷状聚合物显著增加。当刷状聚合物的电荷密度增加到25摩尔%或更高时,吸附主要通过静电相互作用发生。通过使用QCM-D测量层耗散来研究吸附层结构。由不带电荷的刷状聚合物形成的吸附层仅耗散少量能量,这表明刷状聚合物沿表面排列,即PEO侧链与表面相互作用数量最多的情况。低电荷密度的刷状聚合物(2-10摩尔%)在水中形成的吸附层更伸展,这导致大量能量耗散,而高电荷密度的刷状聚合物(50-100摩尔%)形成的吸附层其主链在表面相对平坦,能量耗散再次降低。