Synthetic growth by self-lubricated photopolymerization and extrusion inspired by plants and fungi.

Many natural organisms, such as fungal hyphae and plant roots, grow at their tips, enabling the generation of complex bodies composed of natural materials as well as dexterous movement and exploration. Tip growth presents an exemplary process by which materials synthesis and actuation are coupled, providing a blueprint for how growth could be realized in a synthetic system. Herein, we identify three underlying principles essential to tip-based growth of biological organisms: a fluid pressure driving force, localized polymerization for generating structure, and fluid-mediated transport of constituent materials. In this work, these evolved features inspire a synthetic materials growth process called extrusion by self-lubricated interface photopolymerization (E-SLIP), which can continuously fabricate solid profiled polymer parts with tunable mechanical properties from liquid precursors. To demonstrate the utility of E-SLIP, we create a tip-growing soft robot, outline its fundamental governing principles, and highlight its capabilities for growth at speeds up to 12 cm/min and lengths up to 1.5 m. This growing soft robot is capable of executing a range of tasks, including exploration, burrowing, and traversing tortuous paths, which highlight the potential for synthetic growth as a platform for on-demand manufacturing of infrastructure, exploration, and sensing in a variety of environments.

Volumetric Additive Manufacturing of Dicyclopentadiene by Solid-State Photopolymerization.

Polymerization in the solid state is generally infeasible due to restrictions on mobility. However, in this work, the solid-state photopolymerization of crystalline dicyclopentadiene is demonstrated via photoinitiated ring-opening metathesis polymerization. The source of mobility in the solid state is attributed to the plastic crystal nature of dicyclopentadiene, which yields local short-range mobility due to orientational degrees of freedom. Polymerization in the solid state enables photopatterning, volumetric additive manufacturing of free-standing structures, and fabrication with embedded components. Solid-state photopolymerization of dicyclopentadiene offers a new paradigm for advanced and freeform fabrication of high-performance thermosets.

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.