Omar Hassan, Ahamadi Shayan, Hülagü Deniz, Hidde Gundula, Hertwig Andreas, Szymoniak Paulina, Schönhals Andreas
Bundesanstalt für Materialforschung und -prüfung (BAM) (Fachbereich 6.6), Unter den Eichen 87, 12205 Berlin, Germany.
Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
J Chem Phys. 2024 Aug 7;161(5). doi: 10.1063/5.0223415.
This work studies the influence of the adsorbed layer on the glass transition of thin films of polysulfone. Therefore, the growth kinetics of the irreversibly adsorbed layer of polysulfone on silicon substrates was first investigated using the solvent leaching approach, and the thickness of the remaining layer was measured with atomic force microscopy. Annealing conditions before leaching were varied in temperature and time (0-336 h). The growth kinetics showed three distinct regions: a pre-growth step where it was assumed that phenyl rings align parallel to the substrate at the shortest annealing times, a linear growth region, and a crossover from linear to logarithmic growth observed at higher temperatures for the longest annealing times. No signs of desorption were observed, pointing to the formation of a strongly adsorbed layer. Second, the glass transition of thin polysulfone films was studied in dependence on the film thickness using spectroscopic ellipsometry. Three annealing conditions were compared: two with only a tightly bound layer formed in the linear growth regime and one with both tightly bound and loosely adsorbed layers formed in the logarithmic growth regime. The onset thickness and increase in the glass transition temperature increases with annealing time and temperature. These differences were attributed to the distinct conformations of the formed adsorbed layers.
本研究探讨了吸附层对聚砜薄膜玻璃化转变的影响。因此,首先采用溶剂浸出法研究了聚砜在硅衬底上不可逆吸附层的生长动力学,并用原子力显微镜测量了剩余层的厚度。浸出前的退火条件在温度和时间(0 - 336小时)上有所变化。生长动力学表现出三个不同的区域:一个预生长阶段,在最短退火时间下,假定苯环与衬底平行排列;一个线性生长区域;以及在最长退火时间和较高温度下观察到的从线性生长到对数生长的转变。未观察到解吸迹象,表明形成了强吸附层。其次,使用光谱椭偏仪研究了聚砜薄膜的玻璃化转变与薄膜厚度的关系。比较了三种退火条件:两种仅在线性生长区域形成紧密结合层,一种在对数生长区域同时形成紧密结合层和松散吸附层。玻璃化转变温度的起始厚度和增加量随退火时间和温度的增加而增加。这些差异归因于所形成吸附层的不同构象。