Conformational Relaxation of Poly(styrene-co-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films,Macromolecules

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Conformational Relaxation of Poly(styrene-co-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films
Macromolecules ( IF 5.1 ) Pub Date : 2018-03-06 00:00:00 , DOI: 10.1021/acs.macromol.7b02756
Biao Zuo ₁ , Manabu Inutsuka , Daisuke Kawaguchi , Xinping Wang ₁ , Keiji Tanaka

Affiliation

The local conformation of poly(styrene-co-butadiene) rubber (SBR) chains in direct contact with a quartz substrate was examined by interface-sensitive sum-frequency generation (SFG) spectroscopy. SFG signals, which could be obtained from functional groups only oriented at the interface, were clearly observed for SBR in a film at room temperature which was much higher than the bulk glass transition temperature (T_g). When the film was thermally annealed, SBR chains at the quartz interface changed their conformation to one with a lower energy state, accompanied by the randomization of both the main and side chain parts. The characteristic temperature, at which interfacial chains started to lose their orientations, was much higher than the bulk T_g. Also, the extent found to be more remarkable for the spin-coated film than for the solvent-cast one. This implies that the stress accumulated at the interface, which resulted from the centrifugal force during the spin-coating process, accelerates the mobility of chains there. Finally, the kinetics experiment well supports the slower orientation relaxation at the interface.

中文翻译：

旋涂和溶剂流延薄膜中基体界面处的聚（苯乙烯-共-丁二烯）链的构象弛豫

通过界面敏感的和频生成（SFG）光谱检查了与石英衬底直接接触的聚（苯乙烯-共-丁二烯）橡胶（SBR）链的局部构象。在室温下，薄膜中的SBR明显高于整体玻璃化转变温度（T _g），因此可以清楚地观察到SFG信号，该信号可以从仅位于界面处的官能团获得。当薄膜进行热退火时，石英界面处的SBR链将其构象变为具有较低能态的构象，并伴有主链和侧链部分的随机化。界面链开始失去取向的特征温度比整体温度T _g高得多。。另外，发现旋涂膜的程度比溶剂浇铸膜的程度更显着。这意味着在旋涂过程中，由于离心力而在界面处累积的应力会加速链的迁移。最后，动力学实验很好地支持了界面处较慢的取向松弛。

更新日期：2018-03-06

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