Polyacrylonitrile Interactions with Carbon Nanotubes in Solution: Conformations and Binding as a Function of Solvent, Temperature, and Concentration

Polyacrylonitrile (PAN) is among the most promising precursor polymers to produce strong and lightweight carbon fiber. Conformations in solution and the extent of binding to carbon nanotubes (CNTs) are critical during gel spinning and for alignment of graphitic layers upon carbonization. Here, quantitative insights into these processes are reported using molecular dynamics simulations at the atomic scale including virtual π electrons and comparisons to experimental data. Common solvents for fiber spinning induce significant differences in PAN conformation in dilute solutions at 25 °C with persistence lengths between 0.5 and 2 nm. Variations in conformation become smaller at 75 °C, in the presence of CNTs, and at higher PAN concentration. “Aging” of PAN conformations in dimethylformamide and dimethylsulfoxide at higher temperature is explained and a correlation between extended polymer conformations and increased binding to CNTs is identified in dilute solutions. PAN is overall barely attracted to CNTs under common solution conditions and enters significant surface contact only at higher concentration as solvent is physically removed. The impact of temperature is small, whereby binding increases at lower temperatures. The results provide guidance to control interactions of polymers with CNTs to induce distinct conformations and specific binding at the early stages of assembly. Polyacrylonitrile solution properties, conformations, and interactions with carbon nanotubes are quantified in N,N‐dimethyl formamide, N,N‐dimethyl acetamide, and dimethyl sulfoxide using molecular dynamics simulations in comparison to experimental data. Binding is weak across a range of temperatures and concentrations, and solvent evaporation is necessary for ordered alignment on the carbon nanotube surface.