Controllable Frontal Polymerization and Spontaneous Patterning Enabled by Phase-Changing Particles.

Frontal polymerization provides a rapid, economic, and environmentally friendly methodology to manufacture thermoset polymers and composites. Despite its efficiency and reduced environmental impact, the manufacturing method is underutilized due to the limited fundamental understanding of its dynamic control. This work reports the control and patterning of the front propagation in a dicyclopentadiene resin by immersion of phase-changing polycaprolactone particles. Predictive and designed patterning is enabled by multiphysical numerical analyses, which reveal that the interplay between endothermic phase transition, exothermic chemical reaction, and heat exchange govern the temperature, velocity, and propagation path of the front via two different interaction regimes. To pattern the front, one can vary the size and spacing between the particles and increase the number of propagating fronts, resulting in tunable physical patterns formed due to front separation and merging near the particles. Both single- and double-frontal polymerization experiments in an open mold are performed. The results confirm the front-particle interaction mechanisms and the shapes of the patterns explored numerically. The present study offers a fundamental understanding of frontal polymerization in the presence of heat-absorbing second-phase materials and proposes a potential one-step manufacturing method for precisely patterned polymeric and composite materials without masks, molds, or printers.

Direct Patterning of Colloidal Nanocrystals via Thermally Activated Ligand Chemistry.

Precise patterning with microscale lateral resolution and widely tunable heights is critical for integrating colloidal nanocrystals into advanced optoelectronic and photonic platforms. However, patterning nanocrystal layers with thickness above 100 nm remains challenging for both conventional and emerging direct photopatterning methods, due to limited light penetration depths, complex mechanical and chemical incompatibilities, and others. Here, we introduce a direct patterning method based on a thermal mechanism, namely, the thermally activated ligand chemistry (or TALC) of nanocrystals. The ligand cross-linking or decomposition reactions readily occur under local thermal stimuli triggered by near-infrared lasers, affording high-resolution and nondestructive patterning of various nanocrystals under mild conditions. Patterned quantum dots fully preserve their structural and photoluminescent quantum yields. The thermal nature allows for TALC to pattern over 10 µm thick nanocrystal layers in a single step, far beyond those achievable in other direct patterning techniques, and also supports the concept of 2.5D patterning. The thermal chemistry-mediated TALC creates more possibilities in integrating nanocrystal layers in uniform arrays or complex hierarchical formats for advanced capabilities in light emission, conversion, and modulation.