Probing the Dynamic Structural Evolution of End-Functionalized Polybutadiene/Organo-Clay Nanocomposite Gels before and after Yielding by Nonlinear Rheology and <sup>1</sup>H Double-Quantum NMR
Wansu Peng,
Chengdong Feng,
Jiawen Hou,
Rongchun Zhang,
Pingchuan Sun,
Yun Gao,
Xiaoliang Wang
Affiliations
Wansu Peng
Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Chengdong Feng
Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Jiawen Hou
Key Laboratory of Functional Polymer Materials of Ministry of Education and College of Chemistry and School of Physics, Nankai University, Tianjin 300071, China
Rongchun Zhang
South China Advanced Institute for Soft Matter Science and Technology (AISMST), School of Emergent Soft Matter, Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou 510640, China
Pingchuan Sun
Key Laboratory of Functional Polymer Materials of Ministry of Education and College of Chemistry and School of Physics, Nankai University, Tianjin 300071, China
Yun Gao
Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Xiaoliang Wang
Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Understanding the structural evolution process after the yielding of networks in polymer nanocomposites can provide significant insights into the design and fabrication of high-performance nanocomposites. In this work, using hydroxyl-terminated 1,4-polybutadiene (HTPB)/organo-clay nanocomposite gel as a model, we explored the yielding and recovery process of a polymer network. Linear rheology results revealed the formation of a nanocomposite gel with a house-of-cards structure due to the fully exfoliated 6 to 8 wt% organo-clays. Within this range, nonlinear rheologic experiments were introduced to yield the gel network, and the corresponding recovery processes were monitored. It was found that the main driving force of network reconstruction was the polymer–clay interaction, and the rotation of clay sheets played an important role in arousing stress overshoots. By proton double-quantum (1H DQ) NMR spectroscopy, residual dipolar coupling and its distribution contributed by HTPB segments anchored on clay sheets were extracted to unveil the physical network information. During the yielding process of a house-of-cards network, e.g., 8 wt% organo-clay, nearly one-fourth of physical cross-linking was broken. Based on the rheology and 1H DQ NMR results, a tentative model was proposed to illustrate the yielding and recovery of the network in HTPB/organo-clay nanocomposite gel.
