Interfacial Photopolymerization: A Method for Light-Based Printing of Thermoplastics.

Ultraviolet (UV) printing of photopolymers is a widely adopted manufacturing method because of its high resolution and throughput. However, available printable photopolymers are typically thermosets, resulting in challenges in postprocessing and recycling of printed structures. Here, we present a new process called interfacial photopolymerization (IPP) which enables photopolymerization printing of linear chain polymers. In IPP, a polymer film is formed at the interface between two immiscible liquids, one containing a chain-growth monomer and the other containing a photoinitiator. We demonstrate the integration of IPP in a proof-of-concept projection system for printing of polyacrylonitrile (PAN) films and rudimentary multi-layer shapes . IPP shows in-plane and out-of-plane resolutions comparable to conventional photoprinting methods. Cohesive PAN films with number-average molecular weights greater than 15 kg mol-1 are obtained, and to our knowledge this is the first report of photopolymerization printing of PAN. A macrokinetics model of IPP is developed to elucidate the transport and reaction rates involved and evaluate how reaction parameters affect film thickness and print speed. Last, demonstration of IPP in a multilayer scheme suggests its suitabiliy for three-dimensional printing of linear-chain polymers.

Oxidation of Gallium-based Liquid Metal Alloys by Water.

Gallium alloys with other low melting point metals, such as indium or tin, to form room-temperature liquid eutectic systems. The gallium in the alloys rapidly forms a thin surface oxide when exposed to ambient oxygen. This surface oxide has been previously exploited for self-stabilization of liquid metal nanoparticles, retention of metastable shapes, and imparting stimuli-responsive behavior to the alloy surface. In this work, we study the effect of water as an oxidant and its role in defining the alloy surface chemistry. We identify several pathways that can lead to the formation of gallium oxide hydroxide (GaOOH) crystallites, which may be undesirable in many applications. Furthermore, we find that some crystallite formation pathways can be reinforced by typical top-down particle synthesis techniques like sonication. This improved understanding of interfacial interactions provides critical insight for process design and implementation of advanced devices that utilize the unique coupling of flexibility and conductivity offered by these gallium-based liquid metal alloys.

Graphene-based encapsulation of liquid metal particles.

Liquid metals are a promising functional material due to their unique combination of metallic properties and fluidity at room temperature. They are of interest in wide-ranging fields including stretchable and flexible electronics, reconfigurable devices, microfluidics, biomedicine, material synthesis, and catalysis. Transformation of bulk liquid metal into particles has enabled further advances by allowing access to a broader palette of fabrication techniques for device manufacture or by increasing area available for surface-based applications. For gallium-based liquid metal alloys, particle stabilization is typically achieved by the oxide that forms spontaneously on the surface, even when only trace amounts of oxygen are present. The utility of the particles formed is governed by the chemical, electrical, and mechanical properties of this oxide. To overcome some of the intrinsic limitations of the native oxide, it is demonstrated here for the first time that 2D graphene-based materials can encapsulate liquid metal particles during fabrication and imbue them with previously unattainable properties. This outer encapsulation layer is used to physically stabilize particles in a broad range of pH environments, modify the particles' mechanical behavior, and control the electrical behavior of resulting films. This demonstration of graphene-based encapsulation of liquid metal particles represents a first foray into the creation of a suite of hybridized 2D material coated liquid metal particles.

Three-Dimensional Graphene-Based Microbarriers for Controlling Release and Reactivity in Colloidal Liquid Phases.

Two-dimensional materials are of great interest as high-performance molecular barriers. Graphene in particular is atomically thin, is impermeable to all molecules, and in some forms can be easily deposited over large areas into planar multilayer films that have been shown to suppress molecular transport. Graphene and graphene oxide sheets are also known to spontaneously self-assemble at liquid-liquid interfaces on the surfaces of dispersed droplets, but much less is known about the barrier properties of these ultrathin films in 3D curved microgeometries. This article demonstrates that 3D films self-assembled from graphene oxide or reduced graphene oxide sheets can be exploited to control the release of small molecules from dispersed liquid phase droplets by evaporation. The release rate and containment time can be tuned by addition of multivalent cations that recruit additional sheets from the bulk liquid to the interface, which is shown by molecular dynamics to occur by an electrostatic bridging mechanism. 3D graphene-based films on droplet surfaces can also be used to control the release and transport of soluble molecules from the droplet to surrounding bulk solvent phases. In some cases, the release can be effectively stopped to produce unique kinetically trapped emulsion phases consisting of two fully miscible but segregated liquids. Finally, interfacial graphene-based films are also shown to control interfacial chemical reaction processes by serving as transport barriers between the phases or by intercepting reactive cross-phase molecular collisions. This reaction control is demonstrated by using 3D graphene-based microbarriers to protect oxidation-sensitive oils from attack by aqueous-phase reactive oxygen species, which is an undesirable pathway implicated in many chemical product degradation and spoilage processes.

Effects of surface-engineered nanoparticle-based dispersants for marine oil spills on the model organism Artemia franciscana.

Fine particles are under active consideration as alternatives to chemical dispersants for large-scale petroleum spills. Fine carbon particles with engineered surface chemistry have been shown to stabilize oil-in-water emulsions, but the environmental impacts of large-scale particle introduction to the marine environment are unknown. Here we study the impact of surface-engineered carbon-black materials on brine shrimp (Artemia franciscana) as a model marine microcrustacean. Mortality was characterized at 50-1000 mg/L, and levels of heat shock protein 70 (hsp70) were characterized at sublethal particle concentrations (25-50 mg/L). Functionalized carbon black (CB) nanoparticles were found to be nontoxic at all concentrations, while hydrophobic (annealed) and as-produced CB induced adverse effects at high concentrations. CB was also shown to adsorb benzene, a model hydrocarbon representing the more soluble and toxic low-molecular weight aromatic fraction of petroleum, but the extent of adsorption was insufficient to mitigate benzene toxicity to Artemia in coexposure experiments. At lower benzene concentrations (25-75 mg/L), coexposure with annealed and as-produced CB increased hsp70 protein levels. This study suggests that surface functionalization for increased hydrophilicity can not only improve the performance of CB-based dispersants but also reduce their adverse environmental impacts on marine organisms.

Two-dimensional materials as emulsion stabilizers: interfacial thermodynamics and molecular barrier properties.

A new application for two-dimensional (2D) materials is emulsification, where they can serve as ultrathin platelike interfacial stabilizers in two-liquid systems. We present a first detailed thermodynamic analysis of atomically thin 2D materials at organic-aqueous liquid-liquid interfaces and derive expressions for the transfer free energies of emulsion stabilization that account for material geometry, van der Waals transparency or opacity, and variable hydrophobicity. High mass potency is shown to be an intrinsic property of the 2D geometry, which at the atomically thin limit places every atom in contact with both liquid phases, resulting in unit atom efficiency. The thermodynamic model successfully predicts that graphene oxide but not pristine graphene has a favorable hydrophobic-hydrophilic balance for oil-water emulsion stabilization. Multilayer tiling is predicted to occur by the passivation of droplet surface patches left uncovered by packing inefficiencies in the first monolayer, and complete multilayer coverage is confirmed by cryogenic scanning electron microscopy. The molecular barrier function of graphene interfacial films causes a significant suppression of dispersed-phase evaporation rates with potential applications in controlled release. Finally, these emulsions can be used as templates for creating solid graphene foams or graphene microsacks filled with lipophilic cargos. Emerging 2D materials are promising as dispersants or emulsifiers where high mass potency and multifunctional properties are desired.