The densification and sintering of ceramics using microwaves is first reported in the mid‐1960s. Today, the reduced carbon footprint of this process has renewed interest as it uses less energy overall compared to conventional process heating/furnaces. However, scaling up and commercializing the microwave sintering process of ceramics remains a formidable challenge. As a contactless method, microwave sintering offers geometric flexibility over other field‐assisted sintering processes. Yet, the inability to address multiscale, multiphysics‐driven heterogeneities arising during microwave coupling limits discussions about a future scale‐up process. Herein, the case is made that unlike 60 years ago, new advances in multiscale computational modeling, materials characterization, control systems, and software open up new avenues for addressing these challenges. More importantly, the rise of additive manufacturing techniques demands the innovation of sintering processes in the ceramics community for realizing near‐net‐shaped and complex parts for applications ranging from medical implants to automotive and aerospace parts.

Oxidative chemical vapor deposition (oCVD) is a versatile technique that can simultaneously tailor properties (e.g., electrical, thermal conductivity) and morphology of polymer films at the nanoscale. In this work, we report the thermal conductivity of nanoscale oCVD grown poly(3,4-ethylenedioxythiophene) (PEDOT) films for the first time. Measurements as low as 0.16 W m⁻¹ K⁻¹ are obtained at room temperature for PEDOT films with thicknesses ranging from 50–100 nm. These values are lower than those for solution processed PEDOT films doped with the solubilizing agent PSS (polystyrene sulfonate). The thermal conductivity of oCVD grown PEDOT films show no clear dependence on electrical conductivity, which ranges from 1 S cm⁻¹ to 30 S cm⁻¹. It is suspected that at these electrical conductivities, the electronic contribution to the thermal conductivity is extremely small and that phonon transport is dominant. Our findings suggest that CVD polymerization is a promising route towards engineering polymer films that combine low thermal conductivity with relatively high electrical conductivity values.