Crystallizability of Free and Tethered Chains in Nanometer‐Sized Droplets

Confining polymers to nanometric sizes often interferes with the characteristic length scales of structure formation and thus significantly alters crystallization or nucleation behavior at nanoscale. To investigate such effects in samples, past studies relied either on heavily constraining environments like block copolymer mesophases deposited droplets that exhibit significant variation size, requiring extensive analysis assign size classes. This studypresents a novel method create nanometer-sized polymer narrow volume distribution study their dynamic thermodynamic using change orientational polarization. A combination gold-nanoparticle deposition grafting-to reaction nanostructured electrode setup enabled measurement poly-ε-caprolactone (PCL) consisting ten chains average for relatively small molecular weight. Distinct melting signatures spin-cast demonstrate sensitivity this approach. In contrast, grafted aggregates no signs crystallization, which is attributed considerable constraints configuration, limited chain motion too wide spacing. Nevertheless, presented capable studying ensembles individualized (macro-) molecules.