Driven by the surface activity of graphene, electrically conductive elastomeric foams have been synthesized by the controlled reassembly of graphene sheets; from their initial stacked morphology, as found in graphite, to a percolating network of exfoliated sheets, defining hollow spheres. This network creates a template for the formation of composite foams, whose swelling behavior is sensitive to the composition of the solvent, and whose electrical resistance is sensitive to physical deformation. The self‐assembly of graphene sheets is driven thermodynamically, as graphite is found to act as a 2D surfactant and is spread at high‐energy interfaces. This spreading, or exfoliation, of graphite at an oil/water interface stabilizes water‐in‐oil emulsions, without the need for added surfactants or chemical modification of the graphene. Using a monomer such as butyl acrylate for the emulsion's oil phase, elastomeric foams are created by polymerizing the continuous oil phase. Removal of the aqueous phase then results in robust, conductive, porous, and inexpensive composites, with potential applications in energy storage, filtration, and sensing.
- Award ID(s):
- 1653676
- NSF-PAR ID:
- 10175829
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 15
- Issue:
- 47
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 9665 to 9675
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Porous MXene-polymer composites have gained attention due to their low density, large surface area, and high electrical conductivity, which can be used in applications such as electromagnetic interference shielding, sensing, energy storage, and catalysis. High internal phase emulsions (HIPEs) can be used to template the synthesis of porous polymer structures, and when solid particles are used as the interfacial agent, composites with pores lined with the particles can be realized. Here, we report a simple and scalable method to prepare conductive porous MXene/polyacrylamide structures via polymerization of the continuous phase in oil/water HIPEs. The HIPEs are stabilized by salt flocculated Ti 3 C 2 T x nanosheets, without the use of a co-surfactant. After polymerization, the polyHIPE structure consists of porous polymer struts and pores lined with Ti 3 C 2 T x nanosheets, as confirmed by scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. The pore size can be tuned by varying the Ti 3 C 2 T x concentration, and the interconnected Ti 3 C 2 T x network allows for electrical percolation at low Ti 3 C 2 T x loading; further, the electrical conductivity is stable for months indicating that in these composites, the nanosheets are stable to oxidation at ambient conditions. The polyHIPEs also exhibit rapid radio frequency heating at low power (10 °C s −1 at 1 W). This work demonstrates a simple approach to accessing electrically conductive porous MXene/polymer composites with tunable pore morphology and good oxidation stability of the nanosheets.more » « less
-
2D particle surfactants are attractive for the formation of highly stable emulsions and use as templates to prepare composite structures with performance properties dependent on the composition. Cobalt oxide nanosheets (CONs) are a relatively understudied class of 2D particle surfactants that can be produced by the chemical exfoliation of lithium cobalt oxide, a transition metal oxide known for excellent gas-sensing, catalytic, and electrochemical properties. Here, we report a simple method to access CONs stabilized oil-in-water Pickering emulsions and use these as templates to prepare particles with a core of polymer and shell of CONs. Salt-flocculated CONs produce emulsions with droplets of hydrophobic monomer ( e.g. , styrene) in water that are stable for at least 24 hours, and suspension free radical polymerization is used to produce CON-armored particles. Characterization by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) confirmed the presence of CONs on the surface of the polymer core. We then demonstrated the CON-armored polymer particles can activate the oxidant peroxymonosulfate (PMS) for the degradation of bisphenol A (BPA). Freshly prepared and artificially aged CON-armored particles showed full degradation of BPA in less than an hour and no decrease in activity was observed after two uses. CON-armored particles combine high surface area of the nanosheets with the ease of recoverability of the particles.more » « less
-
Abstract Waterborne pressure sensitive adhesives (PSAs) consisting of polymer microparticle emulsions (i.e. latex) are more commonly used in commercial applications than solvent‐borne alternatives, as the use of water as a suspension medium provides better consumer safety and reduces environmental impact. However, the lower mechanical performance of waterborne PSAs prevents their use in applications requiring permanent adhesion or strong bonding between substrates. This reduction in mechanical strength is often attributed to void spaces that form during water evaporation and coalescence of the latex particles, and thus a potential strategy to improve PSA strength would be to add filler materials to occupy these voids. Fundamental studies investigating how interfacial interactions between the latex and fillers affect the collective strength of the films would enable better design of adhesive compositions to tailor PSA mechanical properties. Here we report the use of polymer brush‐grafted nanoparticles (PGNPs) as a means of mechanically reinforcing the PSAs, and determine how different aspects of the particle and polymer brush designs enable this improvement in adhesive performance. The PGNPs investigated here are intentionally designed to phase segregate into the aqueous phase of the initial latex suspension, which allows them to both fill free pore volume and also form multivalent supramolecular interactions with the latex particles to form polymer bridges that improve the interconnectivity of the final film. These studies provide insight into potential design strategies for tuning PSA properties with PGNPs, and enable up to 32% improvements to the cohesive strength of the PSAs without the typical deterioration of adhesive strength observed in PSAs using non‐brush‐coated particle fillers.
-
For decades, explorations with ground state, thermal reactions combined with pseudophase kinetic models and methods for interpreting the results have provided insights into the properties of the different regions of homogeneous association colloids. More recent successful determination of antioxidant (AO) distributions by this approach is providing new insights into AO efficiency in opaque, well‐mixed two‐phase intact emulsions and eliminating the need to separate the phases. The chemical probe reacts with AOs exclusively in the interfacial region of the emulsion, permitting simplification of the kinetic treatment, and determining its distribution between the oil, interfacial, and aqueous regions. AO distributions are obtained from the two partition constants,
and , of the AOs between the oil‐interfacial and aqueous‐interfacial regions, respectively. and values are obtained by fitting the observed rate constant, k obs, versus surfactant concentration profiles with an overall kinetic approach or model we call the “pseudophase chemical kinetic method.” However, because emulsions break up and reform, and reactants and other components diffuse at various time scales within and between the oil, interfacial, and water regions,k obscould also depend on reactant diffusion coefficients. Here we demonstrate that reactant diffusion is generally orders of magnitude faster than most thermal reactions and reactant distributions between the multiple oil, aqueous, and interfacial droplets and regions of emulsions are in dynamic equilibrium throughout the multiphase systems during the time course of the reaction. Thus, kinetic probes are powerful tools for determining structure‐reactivity, for example, the HLB, relationships governing AO distributions and efficiencies in emulsions.Practical applications: The analysis presented here demonstrates that one of the basic assumptions of the pseudophase chemical kinetic model that we have developed has a solid foundation in the properties of emulsions. That is, we can determine the distributions of reactants between oil (O), interfacial (I), and aqueous (W) regions of the emulsions because the diffusivity coefficients of reactants within emulsions are orders of magnitude greater than the rate of the reaction between the antioxidant and the 4‐hexadecylbenzenediazonium probe. Consequently, we can use the same kinetic model in emulsions as we have used in homogeneous microemulsions. The method permits determination of the partition constants of many antioxidants between the O‐I and W‐I regions of the emulsions and from them their distributions. The method provides new insights into the relationships between antioxidant hydrophobic‐lipophilic balance (HLB) and its efficiency in emulsions and a natural explanation for the cut‐off effect observed with increasing antioxidant HLB.Interpreting chemical reactivity in emulsions requires that reactive components
A andB be in dynamic equilibrium, that separate second order rate constants,k defined for the oil, interfacial, and aqueous regions, subscripts O, I, and W, and for simplicity, the volume of each region depends on the added volumes of oil, surfactant, and water.