Search for: All records

We elucidate a previously unknown synthesis pathway that leads to polymeric nanospheres, orientation-controlled microgels, or microspheroids via single-step polymerization of divinylbenzene (DVB) using initiated chemical vapor deposition (iCVD) in liquid crystals (LC). iCVD supplies vapor-phase reactants continuously, avoiding the critical limitation of reactant-induced disruption of LC structure that has plagued past LC-templated polymerization processes. LC is leveraged as a real-time display of the polymerization conditions and particle emergence, captured using an in situ long–focal range microscope. Detailed image analysis unravels key LC-guided mechanisms during polymerization. pDVB forms nanospheres due to poor solubilization by nematic LC. The nanospheres partition to the LC-solid interface and further assemble into microgel clusters whose orientation is guided by the LC molecular alignment. On further polymerization, microgel clusters transition to microspheroids that resemble liquid drops. We identify key energetic factors that guide trajectories along the synthesis pathway, providing the fundamental basis of a framework for engineering particle synthesis with shape control. 

Abstract Over the past few decades, chemical vapor deposition (CVD) of [2.2]paracyclophanes has captured significant attention as an emergent technology, producing conformal, chemically pure, and pinhole‐free coatings for biomedical and industrial applications. Compelling examples range from functional CVD polymers to tailored nanostructures. In this work, the unique functional properties of polymers derived from [2.2]paracyclophanes are connected with emergent applications. Special attention is given to the function‐property relationships in the areas of electronic materials, biomaterials, and separation materials. A particular focus is to highlight the versatility of CVD polymerization to process these polymers.