Anisotropic pressure response of thermal conductivity in crystalline polytetrafluoroethylene
Compression can change thermal conductivity differently along polymer chains and across them by altering phonon velocities and lifetimes. We examine this directional response in orthorhombic Form III polytetrafluoroethylene (PTFE) at calculated pressures of 1.503, 3.452, and 5.056 GPa, using first-principles harmonic and cubic force constants within the single-mode relaxation-time approximation (SMRTA). At 100, 200, and 300 K, the chain-axis conductivity decreases at every pressure step. Between 3.452 and 5.056 GPa, both transverse components recover: at 300 K they increase by 23.7% and 13.7%, while the longitudinal conductivity decreases by 14.5%. An exact factorization separates the conductivity into a heat-capacity--velocity factor and a weighted effective lifetime. The transverse recovery follows from larger heat-capacity-weighted squared velocities, consistent with stiffer interchain restoring forces. Along the chains, shorter effective lifetimes dominate, and both conductivity-weighted Normal and Umklapp rates increase at 300 K. Comparing the same cubic force-constant blocks at all three pressures, we find that interchain coupling is already substantial at 1.503 GPa and increases under compression.