Camphene as a Mild, Bio-Derived Porogen for Near-Ambient Processing and 3D Printing of Porous Thermoplastics.

Porous structures are ubiquitous in nature due to their advantageous mechanical and transport properties. These structures have inspired various synthetic porous polymer technologies, including lightweight structural materials and membranes. While many manufacturing processes have been developed to generate porous thermoplastics, these usually include hazardous processes, such as high pressures and temperatures, or chemical components. Furthermore, few are compatible with additive manufacturing methods, such as 3D printing. Herein, we introduce bio-derived terpene camphene as a solvent and porogen for the freeze-casting of thermoplastic parts under mild conditions. Enabled by a low melting point (50 °C), camphene is used as a solvent for melt processing camphene-polymer solutions at moderate temperatures that later undergo room-temperature crystallization to template polymer-rich domains. Due to its high vapor pressure, camphene can be sublimed directly from these biphasic structures, resulting in an interconnected microporous polymer structure. Various polymers are demonstrated to be soluble in camphene, including polystyrene, an olefinic elastomer, a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene elastomer, a cyclic olefin copolymer, and poly(ethyl methacrylate). Porous samples of each polymer were generated from camphene mixtures via compression molding, cooling, and subsequent vacuum annealing at room temperature to remove camphene. The porosity and pore structures were dependent on solution composition, including both the polymer type and polymer loading. Across the compositions investigated, porosity decreased monotonically from 93 to 65% with increasing polymer content. In the case of polystyrene, samples with pore diameters varying from ∼20 to <5 µm were generated. Rheological measurements were conducted on a series of polystyrene-camphene solutions to understand and optimize the formulation and conditions for direct ink write 3D printing. Porous parts with complex structures were successfully printed under mild conditions. These results underscore the advantages of camphene as a sustainable, nontoxic porogen and will inform future development of porous polymer systems derived from these methods.

Controlling Surface Deformation and Feature Aspect Ratio in Photochemically Induced Marangoni Patterning of Polymer Films.

Thin liquid polymer films can be topographically patterned when polymer/air interfaces are deformed by surface-tension gradients. Toward this end, a recently developed method first photochemically patterns surface-tension gradients along a solid, flat polymer film. On heating to the liquid state, the film initially develops topography reflecting the patterned surface-tension gradients. But capillary leveling and diffusion of the photoproduct oppose this causing the features to eventually decay back to a flat film upon extended thermal annealing. Intuitively, this interplay between competing mechanisms sets a limit on the maximum film deformation during the process. Prior studies show that the initial film thickness, photomask periodicity, and amount of photochemical conversion significantly affect the maximum film deformation. Here, we use a model based on lubrication theory to develop additional insights into this observation. We identify two regimes, capillary-leveling-dominated and photoproduct-diffusion-dominated, wherein the respective dominant mechanism determines the maximum film deformation that can be additionally related to various experimental parameters. Scaling laws for the variation of maximum film deformation and aspect ratio with film thickness and surface-tension pattern periodicity are also developed. Complementary experiments show good agreement with model predictions. Insights into the effect of surface-tension pattern asymmetry on the maximum film deformation are also provided. These findings reveal mechanistic detail and fundamental principles that are useful for controlling the process to form target patterns of interest.

Achieving Stable Patterns in Multicomponent Polymer Thin Films Using Marangoni and van der Waals Forces.

Liquid-air interfaces can be deformed by surface-tension gradients to create topography, a phenomenon useful for polymer film patterning. A recently developed method creates these gradients by photochemically patterning a solid polymer film. Heating the film to the liquid state leads to flow driven by the patterned surface-tension gradients, but capillary leveling and diffusion of surface-active species facilitate eventual dissipation of the topography. However, experiments demonstrate that using blends of high- and low-molar-mass polymers can considerably delay the decay in topography. To gain insight into this observation, we develop a model based on lubrication theory that yields coupled nonlinear partial differential equations describing how the film height and species concentrations evolve with time and space. Incorporation of a nonmonotonic disjoining pressure is found to significantly increase the lifetime of topographical features, making the model predictions qualitatively consistent with experiments. A parametric study reveals the key variables controlling the kinetics of film deformation and provides guidelines for photochemically induced Marangoni patterning of polymer films.