Luo Yanqi, Santos Franceska A, Wagner Taylor W, Tsoi Eric, Zhang Shanju
Department of Chemistry and Biochemistry, California Polytechnic State University , San Luis Obispo, California 93407, United States.
J Phys Chem B. 2014 Jun 5;118(22):6038-46. doi: 10.1021/jp503128v. Epub 2014 May 23.
Interfacial interactions between conjugated polymers and carbon nanotubes are pivotal in determining the device performance of nanotube-based polymer electronic devices. Here, we report on interfacial structures and crystallization kinetics of poly(3-hexylthiophene) (P3HT) in the presence of single-walled carbon nanotubes (SWNTs) in anisole by means of transmission electron microscope (TEM) and ultraviolet-visible (UV-vis) absorption spectroscopy. Confined on SWNT surfaces, the P3HT forms nanofibril crystals perpendicular to the long axis of SWNTs. The equilibrium dissolution temperature of the P3HT crystals in anisole is determined to be 381 ± 10 K according to the Hoffman-Weeks extrapolation approach. Upon cooling, the polymer solution spontaneously undergoes a time-dependent chromism. Various kinetics factors such as crystallization temperature, concentration, and SWNT loading have been investigated. It is found that the growth rate (G) of the crystals scales with concentration (C) as G ∝ C(1.70±0.16). The Avrami model is utilized to analyze the nucleation mechanism and the Avrami exponents vary between 1.0 and 1.3. The Lauritzen-Hoffman theory is applied to study the chain-folding process. The fold surface free energy is calculated to be (5.28-11.9) × 10(-2) J m(-2). It is evident that the addition of 0.30 wt % SWNTs reduces the fold surface free energy by 55.6%.
共轭聚合物与碳纳米管之间的界面相互作用对于决定基于纳米管的聚合物电子器件的性能至关重要。在此,我们借助透射电子显微镜(TEM)和紫外可见(UV-vis)吸收光谱,报道了在茴香醚中,单壁碳纳米管(SWNTs)存在下聚(3-己基噻吩)(P3HT)的界面结构和结晶动力学。受限在SWNT表面上,P3HT形成垂直于SWNTs长轴的纳米纤维晶体。根据霍夫曼-韦克斯外推法,确定P3HT晶体在茴香醚中的平衡溶解温度为381±10 K。冷却时,聚合物溶液自发地发生随时间变化的变色现象。研究了各种动力学因素,如结晶温度、浓度和SWNT负载量。发现晶体的生长速率(G)与浓度(C)成比例,即G∝C(1.70±0.16)。利用阿弗拉米模型分析成核机制,阿弗拉米指数在1.0至1.3之间变化。应用劳里岑-霍夫曼理论研究链折叠过程。计算出折叠表面自由能为(5.28 - 11.9)×10(-2) J m(-2)。显然,添加0.30 wt%的SWNTs可使折叠表面自由能降低55.6%。