High-thermal-conductivity polymers are very sought after for applications in various thermal management systems. Although improving crystallinity is a common way for increasing the thermal conductivity (k) of polymers, it has very limited capacity when the crystallinity is already high. In this work, by heat-stretching a highly crystalline microfiber, a significant k enhancement is observed. More interestingly, it coincides with a reduction in crystallinity. The sample is a Spectra S-900 ultrahigh-molecular-weight polyethylene (UHMW-PE) microfiber of 92% crystallinity and high degree of orientation. The optimum stretching condition is 131.5 °C, with a strain rate of 0.0129 s^–1 to a low strain ratio (∼6.6) followed by air quenching. The k enhancement is from 21 to 51 W/(m·K), the highest value for UHMW-PE microfibers reported to date. X-ray diffraction study finds that the crystallinity reduces to 83% after stretching, whereas the crystallite size and crystallite orientation are not changed. Cryogenic thermal characterization shows a reduced level of phonon-defect scattering near 30 K. Polarization Raman spectroscopy finds enhanced alignment of amorphous chains, which could be the main reason for the k enhancement. A possible relocation of amorphous phase is also discussed and indirectly supported by a bending test.

The photothermal phenomenon involves material photon heating in the form of continuous waves, modulated waves, or pulses. The resulting temperature rise carries very rich information about the material's structures and thermophysical properties. This review is constructed to cover some of the extended ideas of the photothermal phenomenon for measuring a material's thermophysical properties and interface thermal conductance/resistance. For frequency-domain photothermal phenomena, the photoacoustic (PA) and photothermal radiation (PT) techniques provide great ways to measure coatings and suspended samples, which can also be measured using the laser flash and time-domain thermoreflectance (TDTR) techniques. Thermal probing based on electrical thermal sensing is successfully implemented in the transient photo-electro-thermal (TPET) and pulsed laser-assisted thermal relaxation (PLTR) techniques, which significantly extend the capability of laser flash technique to micro/nanoscale 1D structures. The energy transport state-resolved Raman (ET-Raman) is distinct from traditional techniques in its material-specific thermal sensing capability and integral way of ultrafast thermal sensing. Detailed physics discussions are provided for all these techniques, including their advantages and limitations. Still, large development rooms exist for the relatively new techniques, including TPET, PLTR, and ET-Raman. These include measurements under extreme situations, sensitivity improvement, and distinguishing conjugated physical processes.

A novel transient thermal characterization technology is developed based on the principles of transient optical heating and Raman probing: time-domain differential Raman. It employs a square-wave modulated laser of varying duty cycle to realize controlled heating and transient thermal probing. Very well defined extension of the heating time in each measurement changes the temperature evolution profile and the probed temperature field at μs resolution. Using this new technique, the transient thermal response of a tipless Si cantilever is investigated along the length direction. A physical model is developed to reconstruct the Raman spectrum considering the temperature evolution, while taking into account the temperature dependence of the Raman emission. By fitting the variation of the normalized Raman peak intensity, wavenumber, and peak area against the heating time, the thermal diffusivity is determined as 9.17 × 10⁻⁵, 8.14 × 10⁻⁵, and 9.51 × 10⁻⁵ m²/s. These results agree well with the reference value of 8.66 × 10⁻⁵ m²/s considering the 10% fitting uncertainty. The time-domain differential Raman provides a novel way to introduce transient thermal excitation of materials, probe the thermal response, and measure the thermal diffusivity, all with high accuracy.