The Effect of Nanotube Content and Orientation on the Mechanical Properties of Polymer–Nanotube Composite Fibers: Separating Intrinsic Reinforcement from Orientational Effects

We have measured the mechanical properties of coagulation‐spun polymer–nanotube composite fibers. Both the fiber modulus, Y, and strength, σ_B, scale linearly with volume fraction, V_f, up to V_f ～10%, after which these properties remain constant. We measured dY/dV_f = 254 GPa and dσ_B/dV_f = 2.8 GPa in the linear region. By drawing fibers with V_f < 10% to a draw ratio of ～60%, we can increase these values to dY/dV_f = 600 GPa and dσ_B/dV_f = 7 GPa. Raman measurements show the Herman's orientation parameter, S, to increase with drawing, indicating that significant nanotube alignment occurs. Raman spectroscopy also shows that the nanotube effective modulus, Y_Eff, also increases with drawing. We have calculated an empirical relationship between the nanotube orientation efficiency factor, η_o, and S. This allows us to fit the data for Y_Eff versus η_o, showing that the fiber modulus scales linearly with η_o, as predicted theoretically by Krenchel. From the fit, we estimate the nanotube modulus to be; Y_NT = 480 GPa. Finally, we show that the fiber strength also scales linearly with η_o, giving an effective interfacial stress transfer of τ = 40 MPa and a nanotube critical length of l_c=1250 nm. This work demonstrates the validity of the Cox‐Krenchel rule of mixtures and shows that continuum theory still applies at the near‐molecular level.