Ballistic thermal phonons traversing nanocrystalline domains in oriented polyethylene

Thermally conductive polymer crystals are of both fundamental and practical interest for their high thermal conductivity that exceeds that of many metals. In particular, polyethylene fibers and oriented films with uniaxial thermal conductivity exceeding 50 [Formula: see text] have been reported recently, stimulating interest into the underlying microscopic thermal transport processes. While ab initio calculations have provided insight into microscopic phonon properties for perfect crystals, such properties of actual samples have remained experimentally inaccessible. Here, we report the direct observation of thermal phonons with mean free paths up to 200 nm in semicrystalline polyethylene films using transient grating spectroscopy. Many of the mean free paths substantially exceed the crystalline domain sizes measured using small-angle X-ray scattering, indicating that thermal phonons propagate ballistically within and across the nanocrystalline domains; those transmitting across domain boundaries contribute nearly one-third of the thermal conductivity. Our work provides a direct determination of thermal phonon propagation lengths in molecular solids, yielding insights into the microscopic origins of their high thermal conductivity.