Lim Jacob Song Kiat, Gan Chee Lip, Hu Xiao Matthew
School of Material Science and Engineering, Nanyang Technological University, Nanyang Avenue, 639798 Singapore, Singapore.
Temasek Laboratories, Nanyang Technological University, 50 Nanyang Drive, 637553 Singapore.
ACS Omega. 2019 Jun 20;4(6):10799-10808. doi: 10.1021/acsomega.9b00859. eCollection 2019 Jun 30.
Water diffusion into polymers like thermosetting epoxies is well-studied; however, comparably little has been reported thus far on the related but very different mechanism of acid diffusion and the corresponding influence on material degradation. The diffusion of hydrochloric acid into an amine-cured epoxy system was studied in this work using gravimetric analysis and dielectric monitoring concurrently, and the mass uptake behavior was observed to differ significantly compared with water diffusion, faster by an order of magnitude. A unique 3-stage diffusion of acid into epoxy was observed due to the influence of Coulombic interactions between oppositely charged ionic species diffusing at different rates. Material characterization studies have revealed that the dominant degradation mechanism is physical in nature, with the formation of surface cracks driven by the swelling stresses due to the core-shell swelling behavior in highly concentrated hydrochloric acid, leading to an erosion-type degradation phenomenon. The insights gained from understanding acid electrolyte diffusion could serve to design a more effective and efficient process to enable thermoset recycling by facilitating rapid material breakdown or the design of acid-resistant materials for various applications in chemical storage tanks, batteries, and protective coatings in a corrosive environment.
水扩散到热固性环氧树脂等聚合物中的现象已得到充分研究;然而,迄今为止,关于相关但截然不同的酸扩散机制及其对材料降解的相应影响的报道相对较少。在这项工作中,同时使用重量分析和介电监测研究了盐酸在胺固化环氧体系中的扩散,观察到质量吸收行为与水扩散相比有显著差异,速度快了一个数量级。由于不同扩散速率的带相反电荷离子物种之间的库仑相互作用的影响,观察到酸在环氧树脂中呈现独特的三阶段扩散。材料表征研究表明,主要的降解机制本质上是物理性的,在高浓度盐酸中由于核壳膨胀行为产生的溶胀应力导致表面裂纹的形成,从而导致侵蚀型降解现象。从理解酸性电解质扩散中获得的见解有助于设计更有效和高效的工艺,通过促进材料快速分解来实现热固性材料的回收利用,或者设计耐酸材料,用于化学储存罐、电池以及腐蚀性环境中的防护涂层等各种应用。