Caroline R. Szczepanski

Spontaneous, Phase-Separation Induced Surface Roughness: A New Method to Design Parahydrophobic Polymer Coatings with Rose Petal-like Morphology

While the development of polymer coatings with controlled surface topography is a growing research topic, a fabrication method that does not rely on lengthy processing times, bulk solvent solution, or secondary functionalization has yet to be identified. This study presents a facile, rapid, in situ method to develop parahydrophobic coatings based on phase separation during photopolymerization. A comonomer resin of ethylene glycol diacrylate (EGDA) and 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) is modified with a thermoplastic additive (PVDF) to induce phase separation during polymerization. If applied to a glass substrate and photopolymerized, the EGDA/PFDA copolymer forms a homogeneous network with a single glass transition temperature (T(g)) and slight hydrophobicity (θ(w) ∼ 114°). When the resin is modified with PVDF, phase separation occurs during photopolymerization producing a heterogeneous network with two T(g) values. The phase separation causes differences in composition and cross-link density within the network, which leads to local variations in polymerization shrinkage across the nonconstrained material interface. Domains with higher cross-link densities shrink and contract toward the bulk material more dramatically, permitting the formation of rough surfaces with submicron sized spheres enriched in PVDF dispersed in a continuous matrix of EGDA/PFDA copolymer. Both the surface roughness and hydrophobic components in the resin render these surfaces parahydrophobic with θ(w) ∼ 150°, high water adhesion, and a similar morphology to rose petals observed in nature.

A template-free approach to nanotube-decorated polymer surfaces using 3,4-phenylenedioxythiophene (PhEDOT) monomers

In this work, novel 3,4-phenylenedioxythiophene (PhEDOT) monomers with alkyl, branched, and aromatic substituents were synthesized and tested for their efficacy at forming surfaces with unique wetting properties and surface morphology without the aid of surfactants. Monomers with a naphthalene substituent clearly showed the highest capacity to stabilize gas bubbles (O2 or H2) formed in solution during electrodeposition from trace water, resulting in the formation of nanotubes. Variation in the resulting density, diameter, and height of nanotubes was demonstrated by varying the electropolymerization protocol, conditions, or electrolyte used. The wetting induced by the nanotube formation results in the surfaces formed having both high contact angles with water (θW) and strong adhesion, despite all polymers being intrinsically hydrophilic. This one-step and easily tunable approach to nanotube formation has potential to advance applications in membrane design, water transport and harvesting, as well as sensor design.

Recent advances in the study and design of parahydrophobic surfaces: From natural examples to synthetic approaches

Parahydrophobic surfaces are an interesting class of materials that combines both high contact angles and very strong adhesion with wetting fluids, most commonly water. This unique set of properties makes parahydrophobic surfaces attractive for a variety of applications, including water harvesting and collection, guided fluid transport, and membrane development, amongst many others. Taking inspiration from natural surfaces that display this same behavior such as rose petals and gecko feet, synthetic approaches aim to incorporate the nano- and micro-scale topography as well as the low surface energy chemistry found on these interfaces. Here, we discuss the chemical and physical factors that contribute to parahydrophobic behavior and provide a comprehensive overview on the current technologies and procedures used towards constructing surfaces that mimic this behavior already observed in nature. This includes etching processes, colloidal assemblies, deposition methods, and in situ growth of surface features. Furthermore, issues such as ease of scale-up, efficiency of technical procedures, and other current challenges associated with these methods will be discussed to provide insight as to the future directions for this growing area of research.

Stress reduction in phase-separated, cross-linked networks: Influence of phase structure and kinetics of reaction

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10-20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15-25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains.

Using poly(3,4-ethylenedioxythiophene) containing a carbamate linker as a platform to develop electrodeposited surfaces with tunable wettability and adhesion

To control the wettability of polymer interfaces with water without using perfluorinated chains, the 3,4-ethylenedioxythiophene (EDOT) monomer and its derivatives have been good candidates for surfaces formed by electrodeposition. In this work, a series of original EDOT-based monomers were studied. A carbamate linker was used to introduce alkyl and aromatic substituents onto the EDOT-monomer, and the side groups were found to significantly influence the resulting surface structuration and wettability. As the chain length of the alkyl substituent increases, rougher, more hydrophobic surfaces form. With significantly long alkyl side groups (C6), superhydrophobic properties including water contact angles (θwater) up to 158° were observed despite the intrinsic hydrophilicity of the polymers. In general the monomers with aromatic substituents formed smoother surfaces. Oleophobicity was tested using diiodomethane, and it was found that the wetting state varied with the side group: longer alkyl (C8) and aromatic substituents were completely penetrated by diiodomethane (Wenzel state of wetting), while shorter alkyl substituents followed the Cassie Baxter state. With a relatively facile synthetic route to develop the monomers, these polymers are very attractive for anti-bioadhesion, anti-icing, and anti-fog applications.

Variation of Goliathus orientalis (Moser, 1909) Elytra Nanostructurations and Their Impact on Wettability

Among the different species of flower beetles, there is one of particular notoriety: the Goliath beetle. This large insect can grow up to 11 cm long and is well-known for its distinctive black and white shield. In this paper, we focus on a particular Goliathus species: G. orientalis (Moser, 1909). We investigated the variations in properties of both the black and white parts of the upper face of G. orientalis; more precisely, the variation in surface properties with respect to the wettability of these two parts. This work reveals that the white parts of the shield have a higher hydrophobic character when compared to the black regions. While the black parts are slightly hydrophobic (θ = 91 ± 5°) and relatively smooth, the white parts are highly hydrophobic (θ = 130 ± 3°) with strong water adhesion (parahydrophobic); similar to the behavior observed for rose petals. Roughness and morphology analyses revealed significant differences between the two parts, and, hence, may explain the change in wettability. The white surfaces are covered with horizontally aligned nanohairs. Interestingly, vertically aligned microhairs are also present on the white surface. Furthermore, the surfaces of the microhairs are not smooth, they contain nanogrooves that are qualitatively similar to those observed in cactus spines. The nanogrooves may have an extremely important function regarding water harvesting, as they preferentially direct the migration of water droplets; this process could be mimicked in the future to capture and guide a large volume of water.