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© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cosmetics 5 (2018): 34, doi:10.3390/cosmetics5020034., The move toward green, sustainable, natural products has been growing in the cosmetic and personal care industry. Ingredients derived from marine organisms and algae are present in many cosmetic products. In this study, a new green ingredient, a wax (i.e., long-chain alkenones) derived from Isochyrsis sp., was evaluated as an alternative for cosmetic waxes. First, the melting point was determined (71.1–77.4 °C), then the alkenones’ thickening capability in five emollients was evaluated and compared to microcrystalline wax and ozokerite. Alkenones were compatible with three emollients and thickened the emollients similarly to the other waxes. Then, lipsticks and lip balms were formulated with and without alkenones. All products remained stable at room temperature for 10 weeks. Lipstick formulated with alkenones was the most resistant to high temperature. Finally, alkenones were compared to three cosmetic thickening waxes in creams. Viscosity, rheology, and stability of the creams were evaluated. All creams had a gel-like behavior. Both viscosity and storage modulus increased in the same order: cream with alkenones < cetyl alcohol < stearic acid < glyceryl monostearate. Overall, alkenones’ performance was comparable to the other three waxes. Alkenones can thus offer a potential green choice as a new cosmetic structuring agent., This research was funded by the Washington Research Foundation and a private donor from friends of the Woods Hole Oceanographic Institution, grant number N-126478.

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cosmetics 5 (2018): 34, doi:10.3390/cosmetics5020034., The move toward green, sustainable, natural products has been growing in the cosmetic and personal care industry. Ingredients derived from marine organisms and algae are present in many cosmetic products. In this study, a new green ingredient, a wax (i.e., long-chain alkenones) derived from Isochyrsis sp., was evaluated as an alternative for cosmetic waxes. First, the melting point was determined (71.1–77.4 °C), then the alkenones’ thickening capability in five emollients was evaluated and compared to microcrystalline wax and ozokerite. Alkenones were compatible with three emollients and thickened the emollients similarly to the other waxes. Then, lipsticks and lip balms were formulated with and without alkenones. All products remained stable at room temperature for 10 weeks. Lipstick formulated with alkenones was the most resistant to high temperature. Finally, alkenones were compared to three cosmetic thickening waxes in creams. Viscosity, rheology, and stability of the creams were evaluated. All creams had a gel-like behavior. Both viscosity and storage modulus increased in the same order: cream with alkenones < cetyl alcohol < stearic acid < glyceryl monostearate. Overall, alkenones’ performance was comparable to the other three waxes. Alkenones can thus offer a potential green choice as a new cosmetic structuring agent., This research was funded by the Washington Research Foundation and a private donor from friends of the Woods Hole Oceanographic Institution, grant number N-126478.

The morphology and anion transport of an alpha-C modified imidazolium functionalized anion exchange membrane, 1,4,5-trimethyl-2-(2,4,6-trimethoxyphenyl)imidazolium functionalized polyphenylene oxide (with ion exchange capacity {IEC} = 1.53 or 1.82 mequiv/g), were studied in detail. The novel cation is less susceptible to OH attack (0% degradation) compared to unsubstituted imidazolium functionalized polyphenylene oxide (25% degradation) after 24 h at 80 deg C in 1 M KOH. The two different IEC materials (with the same protected cation) show interesting differences in membrane performance. From AFM and SAXS under humid conditions, the domain sizes of the membrane change, which impact the transport properties. The lower IEC sample showed a smaller tortuosity and, thus, needs a longer diffusion time for the water molecules to be fully hindered inside the hydrophobic clusters, which is confirmed by water self-diffusion measurements from pulsed field gradient NMR. From conductivity and diffusion measurements, the higher IEC sample exhibited Vogel Tammann Fulcher behavior, thus indicating that the polymer chain s movement dominates the transport. However, the lower IEC sample exhibited the linear Arrhenius behavior signifying water-mediated transport. The maximum Cl conductivity observed was 23 mS/cm at 95% RH and 90 deg C., Published in the Journal of Physical Chemistry C, v118 n28 p15136-15145, 2014.

Structure I methane hydrates are formed in situ from water-in-mineral oil emulsions in a high pressure rheometer cell. Viscosity is measured as hydrates form, grow, change under flow, and dissociate. Experiments are performed at varying water volume fraction in the original emulsion (0–0.40), temperature (0–6 °C), and initial pressure of methane (750–1500 psig). Hydrate slurries exhibit a sharp increase in viscosity upon hydrate formation, followed by complex behavior dictated by factors including continued hydrate formation, shear alignment, methane depletion/dissolution, aggregate formation, and capillary bridging. Hydrate slurries possess a yield stress and are shear-thinning fluids, which are described by the Cross model. Hydrate slurry viscosity and yield stress increased with increasing water volume fraction. As driving force for hydrate formation decreases (increasing temperature, decreasing pressure), hydrate slurry viscosity increases, suggesting that slower hydrate formation leads to larger and more porous aggregates. In total, addition of water to a methane saturated oil can cause more than a fifty-fold increase in viscosity if hydrates form.

Structure I methane hydrates are formed in situ from water-in-mineral oil emulsions in a high pressure rheometer cell. Viscosity is measured as hydrates form, grow, change under flow, and dissociate. Experiments are performed at varying water volume fraction in the original emulsion (0–0.40), temperature (0–6 °C), and initial pressure of methane (750–1500 psig). Hydrate slurries exhibit a sharp increase in viscosity upon hydrate formation, followed by complex behavior dictated by factors including continued hydrate formation, shear alignment, methane depletion/dissolution, aggregate formation, and capillary bridging. Hydrate slurries possess a yield stress and are shear-thinning fluids, which are described by the Cross model. Hydrate slurry viscosity and yield stress increased with increasing water volume fraction. As driving force for hydrate formation decreases (increasing temperature, decreasing pressure), hydrate slurry viscosity increases, suggesting that slower hydrate formation leads to larger and more porous aggregates. In total, addition of water to a methane saturated oil can cause more than a fifty-fold increase in viscosity if hydrates form.

A new randomly crosslinked polymer is investigated for use as an ion-exchange membrane. The polymer was produced through amination of chlorinated poly(propylene) (PP) with poly(ethyleneimine) (PEI) and quaternized with iodoethane. The synthesis of the new polymer is confirmed by FTIR 1H and 13C NMR. The microstructure of the polymer consists of aggregates on the order of 1 micrometer. Environmentally controlled small and wide angle X-ray analysis showed a relatively featureless amorphous morphology over length scales less than 105 nm through a full range of humidity environments. Little physical swelling of the films were observed, but very high internal water uptake was observed with lamba = 50. The highest in-plane ionic conductivity with chloride as the counter ion observed was 0.29 mS cm 1 at 90 deg C and 95% relative humidity. Infrared spectroscopy was used to monitor the relatively rapid rate of counter-ion reaction of hydroxide with ambient CO2 to form a mixture of carbonate and bicarbonate when exposed to air., The original document contains color images. Published in Electrochimica Acta, 2013.

Block copolymers of polystyrene-b-poly(vinyl benzyl trimethylammonium tetrafluoroborate) (PS-b-[PVBTMA][BF4]) were synthesized by sequential monomer addition using atom transfer radical polymerization. Membranes of the block copolymers were prepared by drop casting from dimethylformamide. Initial evaluation of the microphase separation in these PS-b-[PVBTMA][BF4] materials via SAXS revealed the formation of spherical, cylindrical, and lamellar morphologies. Block copolymers of polystyrene-b-poly(vinyl benzyl trimethylammonium hydroxide) (PS-b-[PVBTMA][OH]) were prepared as polymeric alkaline anion exchange membranes materials by ion exchange from PS-b-[PVBTMA][BF(sub 4)] with hydroxide in order to investigate the relationship between morphology and ionic conductivity. Studies of humidity [relative humidity (RH)]- dependent conductivity at 80 deg C showed that the conductivity increases with increasing humidity. Moreover, the investigation of the temperature-dependent conductivity at RH = 50, 70, and 90% showed a significant effect of grain boundaries in the membranes against the formation of continuous conductive channels, which is an important requirement for achieving high ion conductivity., The original document contains color images. Published in Journal of Polymer Science Part B: Polymer Physics, 2012. Sponsored in part by DoE. Prepared in cooperation with the Departments of Polymer Science and Engineering and Physics, University of Massachusetts, Amherst, and the Department of Chemical and Biological Engineering, Colorado School of Mines, Golden.

In this study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer with various quaternary ammonium cations attached with sulfonamide linkage. The degree of functionalization varied depending on the cation species, resulting in different ion exchange capacities (IECs), 0.33 0.72 meq g(expn -1). There was evidence of polymer degradation when the films were exposed to hydroxide, and hence all membrane characterization was performed in the chloride form. Conductivity was dependent on cation species and IEC, E(sub a) = 36 59 kJ mol(expn -1). Diffusion of water through the membrane was relatively high 1.6 x 10(expn -5) cm(expn 2) s(expn -1) and indicated restriction over a range of diffusion times, 6 700 ms. Water uptake (WU) in the membranes was generally low and the hydration level varied based on cation species, k =6 11. Small-angle scattering experiments suggested ionic aggregation, 37 42 A , independent of cation species but slight differences in long-range order with cation species., The original document contains color images. Published in Journal of Polymer Science Part B: Polymer Physics, 2012. Prepared in cooperation with the Departments of Chemical and Biological Engineering and Chemistry and Geochemistry, Colorado School of Mines, Golden. Sponsored in part by DoE.

An alkaline exchange membrane (AEM) based on an aminated trimethyl poly(phenylene) is studied in detail. This article reports hydroxide ion conductivity through an in situ method that allows for a more accurate measurement. The ionic conductivities of the membrane in bromide and carbonate forms at 90 deg C and 95% RH are found to be 13 and 17 mS cm(expn -1) respectively. When exchanged with hydroxide, conductivity improved to 86 mS cm(expn -1) under the same experimental conditions. The effect of relative humidity on water uptake and the SAXS patterns of the AEM membranes were investigated. SAXS analysis revealed a rigid aromatic structure of the AEM membrane with no microphase separation. The synthesized AEM is shown to be mechanically stable as seen from the water uptake and SAXS studies. Diffusion NMR studies demonstrated a steady state long-range diffusion constant, D1 of 9.8 x 10(expn -6) cm(expn 2) s(expn -1) after 50 100 ms., The original document contains color images. Published in Journal of Polymer Science Part B: Polymer Physics, 2012. Sponsored in part by DoE. Prepared in collaboration with the Department of Materials, Devices, and Energy Technologies, Sandia National Laboratories, Albuquerque, NM. Prepared in cooperation with the Departments of Chemical and Biological Engineering and Chemistry and Geochemistry, Colorado School of Mines, Golden.

There is increasing interest in the alkaline exchange membrane (AEM) fuel cells as this device, if realized, could allow the use of inexpensive metal catalysts and the oxidation of a variety of convenient liquid fuels. While there have been some dramatic early achievements, there is still a need for a fundamental study of anion transport, cation stability and the formation of robust thin films in this area. We have undertaken a comprehensive study of AEMs where theory is linked to well-defined model systems, both in solution and in the solid state, which are characterized using very careful environmental control such that the models can be validated and used predictively. We are also fabricating a number of random copolymer AEMs that can be produced readily in large quantities, allowing us to understand film formation coupled with transport and stability. Those based on perfluorinated backbones invite interesting comparisons with the analogous proton exchange membranes., Presented at the Electrochemical Society Meeting (220th) held in Boston, MA on 9-11 October 2011. Published in ECS Transactions, v41 n1 p1761-1774, 2011. The original document contains color images.