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Recent experiments have revealed that a variety of associative polymers with different architecture (linear and branched) and different nature of the associating interaction (associative protein domains and metal–ligand bonds) exhibit unexplained superdiffusive behavior. Here, Brownian dynamics simulations of unentangled coarse-grained associating star-shaped polymers are used to establish a molecular picture of chain dynamics that explains this behavior. Polymers are conceptualized as particles with effective Rouse diffusivities that interact with a mean field background through attachments by stickers at the end of massless springs that represent the arms of the polymer. The simulations reveal three mechanisms of molecular diffusion at length scales much larger than the radius of gyration: hindered diffusion, walking diffusion, and molecular hopping, all of which depend strongly on polymer concentration, arm length, and the association/dissociation rate constants. The molecular model establishes that su...

Perfluorinated sulfonic acid (PFSA) ionomers are the most widely used solid electrolyte in electrochemical technologies due to their remarkable ionic conductivity with simultanous mechanical stability, imparted by their phase-separated morphology. In this work, the morphology and swelling of PFSA ionomers (Nafion and 3M) as bulk membranes (>10 μm) and dispersion-cast thin films (

Perfluorosulfonic-acid (PFSA) membranes are frequently subjected to high humidity and temperature cycles during fuel-cell operation. It is of great interest to understand how the properties of the membrane change with ageing conditions and time. In this study, we investigate how the properties of as-received and pretreated Nafion membranes change after exposure to hygrothermal ageing, including the chemical structure, mechanical properties, water uptake, ionic conductivity, and morphology. Our findings demonstrate that anhydrides form during ageing via a condensation reaction, which results in chemical crosslinks that impair the membrane functionalities by reducing water uptake and conductivity and increasing the storage modulus and α relaxation temperature. In addition, a membrane aged in a 75% relative humidity environment exhibits more dramatic changes compared to that aged in 100% conditions. It is also shown that the impact of ageing can be recovered through a post-treatment by boiling the membrane in strong acid.

Copyright © 2017 American Academy of Optometry. SIGNIFICANCE A corneal heat-transfer model is presented to quantify simultaneous measurements of fluorescein tear-breakup area (TBA) and ocular-surface temperature (OST). By accounting for disruption of the tear-film lipid layer (TFLL), we report evaporation rates through lipid-covered tear. The modified heat-transfer model provides new insights into evaporative dry eye. PURPOSE A quantitative analysis is presented to assess human aqueous tear evaporation rate (TER) through intact TFLLs from simultaneous in vivo measurement of time-dependent infrared OST and fluorescein TBA. METHODS We interpret simultaneous OST and TBA measurements using an extended heat-transfer model. We hypothesize that TBAs are ineffectively insulated by the TFLL and therefore exhibit higher TER than does that for a well-insulting TFLL-covered tear. As time proceeds, TBAs increase in number and size, thereby increasing the cornea area-averaged TER and decreasing OST. Tear-breakup areas were assessed from image analysis of fluorescein tear-film-breakup video recordings and are included in the heat-transfer description of OST. RESULTS Model-predicted OSTs agree well with clinical experiments. Percent reductions in TER of lipid-covered tear range from 50 to 95% of that for pure water, in good agreement with literature. The physical picture of noninsulating or ruptured TFLL spots followed by enhanced evaporation from underlying cooler tear-film ruptures is consistent with the evaporative-driven mechanism for local tear rupture. CONCLUSIONS A quantitative analysis is presented of in vivo TER from simultaneous clinical measurement of transient OST and TBA. The new heat-transfer model accounts for increased TER through expanding TBAs. Tear evaporation rate varies strongly across the cornea because lipid is effectively missing over tear-rupture troughs. The result is local faster evaporation compared with nonruptured, thick lipid-covered tear. Evaporative-driven tear-film ruptures deepen to a thickness where fluorescein quenching commences and local salinity rises to uncomfortable levels. Mitigation of tear-film rupture may therefore reduce dry eye-related symptoms.

Author(s): Dursch, TJ; Trigu, GJ; Lujan, R; Liu, JF; Mukundan, R; Radkead, CJ; Weberb, AZ | Abstract: Nucleation and growth of ice in the catalyst layer of a proton-exchange-membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry and isothermal galvanostatic cold-starts. Isothermal ice-crystallization rates and ice-nucleation rates are obtained from heat-flow and induction-time measurements at temperatures between 240 and 273 K for four commercial carbon-support materials with varying ionomer fraction and platinum loading. Measured induction times follow expected trends from classical nucleation theory and reveal that the carbon-support material and ionomer fraction strongly impact the onset of ice crystallization. Conversely, dispersed platinum particles play little role in ice crystallization. Following our previous approach, a nonlinear ice-crystallization rate expression is obtained from Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory. A validated rate expression is now available for predicting ice crystallization within water-saturated catalyst layers. Using a simplified PEMFC isothermal cold-start continuum model, we compare cell-failure time predicted using the newly obtained rate expression to that predicted using a traditional thermodynamic-based approach. From this comparison, we identify conditions under which including ice-crystallization kinetics is critical and elucidate the impact of freezing kinetics on low-temperature PEMFC operation. The numerical model illustrates that cell-failure time increases with increasing temperature due to a longer required time for ice nucleation. Hence, ice-crystallization kinetics is critical when induction times are long (i.e., in the "nucleation-limited" regime for T g 263 K). Cell-failure times predicted using ice-freezing kinetics are in good agreement with the isothermal cold-starts, which also exhibit long and distributed cell-failure times for T g 263 K. These findings demonstrate a significant departure from cell-failure times predicted using the thermodynamic-based approach. © 2013 The Electrochemical Society. All rights reserved.

Non-isothermal ice melting in the fibrous gas-diffusion layer (GDL) of a proton-exchange-membrane fuel cell (PEMFC) is investigated using differential scanning calorimetry (DSC). Non-isothermal ice-melting rates and ice-melting times are obtained from heat-flow measurements in water-saturated Toray GDLs at heating rates of 1, 2.5, 5, 10, and 25 K/min. In all cases, ice-melting times decrease nonlinearly with increasing heating rate. Nevertheless, melting temperatures remain at 272.9 ± 0.5 and 272.7 ± 0.4 K for bulk ice and ice within the GDL, respectively, reiterating that melting is thermodynamic-based at a rate limited by heat transfer. The slight GDL ice melting-point depression is consistent with the Gibbs–Thomson equation for equilibrium melting using an average pore diameter of 30 μm. Ice-melting endotherms are predicted from overall DSC energy balances coupled with a moving-boundary Stefan problem, where an ice-melting front within a GDL propagates with volume-averaged properties through an effective medium. Agreement between DSC experiment and theory is excellent. The proposed model accurately predicts ice-melting endotherms for Toray GDLs with two ice saturations and for bulk ice. Further, a pseudo-steady-state analysis obtains an analytical expression for ice-melting time, which is controlled by the time for heat addition to the propagating solid/liquid interface. Significantly, the new expression elucidates parameters controlling ice melting and allows for better design of both GDL materials and heating strategies to enhance the success of PEMFC cold-start.

Author(s): Dursch, TJ; Liu, JF; Trigub, GJ; Radke, CJ; Weber, AZ | Abstract: Under subfreezing conditions, ice forms in the gas-diffusion (GDL) and catalyst layers (CL) of proton-exchange-membrane fuel cells (PEMFCs), drastically reducing cell performance. Although a number of strategies exist to prevent ice formation, there is little fundamental understanding of ice-crystallization mechanisms and kinetics within PEMFC components. We incorporate recently developed ice-crystallization kinetic expressions (1-3) within the CL and GDL of a simplified 1-D transient PEMFC cold-start model. To investigate the importance of ice-crystallization kinetics, we compare liquid-water and ice saturations, and cell-failure time predicted using our kinetic rate expression relative to that predicted using a thermodynamic-based approach. We identify conditions under which ice-crystallization kinetics is critical and elucidate the impact of freezing kinetics on low-temperature PEMFC operation. © The Electrochemical Society.

Non-isothermal ice-crystallization kinetics in the fibrous gas-diffusion layer (GDL) of a proton-exchange-membrane fuel cell is investigated using differential scanning calorimetry (DSC). Non-isothermal ice-crystallization rates and ice-crystallization temperatures are obtained from heat-flow measurements in a water-saturated commercial GDL at cooling rates of 2.5, 5, 10, and 25 K/min. Our previously developed isothermal ice-crystallization rate expression is extended to non-isothermal crystallization to predict ice-crystallization kinetics in a GDL at various cooling rates. Agreement between DSC experimental results and theory is good. Both show that as the cooling rate increases, ice-crystallization rates increase and crystallization temperatures decrease monotonically. Importantly, we find that the cooling rate during crystallization has a negligible effect on the crystallization rate when crystallization times are much faster than the time to decrease the sample temperature by the subcooling. Based on this finding, we propose a pseudo-isothermal method for obtaining non-isothermal crystallization kinetics using isothermal crystallization kinetics evaluated at the non-isothermal crystallization temperature.

Under subfreezing conditions, ice forms in the gas-diffusion (GDL) and catalyst layers (CL) of proton-exchange-membrane fuel cells (PEMFCs), drastically reducing cell performance. Although a number of strategies exist to prevent ice formation, there is little fundamental understanding of ice-crystallization mechanisms and kinetics within PEMFC components. We use differential scanning calorimetry (DSC) to measure ice-crystallization kinetics in both the GDL and CL. Nonlinear ice-crystallization rate expressions are developed from a convolution integral over nucleation and growth rates, following Johnson-Mehl-Avrami-Kolmogorov theory. Quantitative agreement is found with the DSC data. Validated rate expressions are now available for predicting ice-crystallization kinetics within both GDL and CL components of PEMFCs.

Author(s): Shi, S; Dursch, TJ; Blake, C; Mukundan, R; Borup, RL; Weber, AZ; Kusoglu, A | Abstract: Perfluorosulfonic-acid (PFSA) membranes are widely used as the solid electrolyte in electrochemical devices where their main functionalities are ion (proton) conduction and gas separation in a thermomechanically stable matrix. Due to prolonged operational requirements in these devices, PFSA membranes' properties change with time due to hygrothermal aging. This paper studies the evolution of PFSA structure/property relationship changes during hygrothermal aging, including chemical changes leading to changes in ion-exchange capacity (IEC), nanostructure, water-uptake behavior, conductivity, and mechanical properties. Our findings demonstrate that with hygrothermal aging, the storage modulus increases, while IEC and water content decrease, consistent with the changes in nanostructure, that is, water- and crystalline-domain spacings inferred from small- and wide-angle X-ray scattering (SAXS/WAXS) experiments. In addition, the impact of aging is found to depend on the membrane's thermal prehistory and post-treatments, although universal correlations exist between nanostructural changes and water uptake. The findings have impact on understanding lifetime, durability, and use of these and related polymers in various technologies.

Under sub-freezing conditions, ice forms in the gas-diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC) drastically reducing cell performance. Although a number of strategies exist to prevent ice formation, there is little fundamental understanding of the mechanisms of freezing within PEMFC components. Differential scanning calorimetry (DSC) is used to elucidate the effects of hydrophobicity (Teflon® loading) and water saturation on the rate of ice formation within three commercial GDLs. We find that as the Teflon® loading increases, the crystallization temperature decreases due to a change in internal ice/substrate contact angle, as well as the attainable level of water saturation. Classical nucleation theory predicts the correct trend in freezing temperature with Teflon® loading.

Equilibrium water content of and solute partitioning in silicone hydrogels (SiHys) are investigated using gravimetric analysis, fluorescence confocal laser-scanning microscopy (FCLSM), and back extraction with UV/Vis-absorption spectrophotometry. Synthesized silicone hydrogels consist of silicone monomer, hydrophilic monomer, cross-linking agent, and triblock-copolymer macromer used as an amphiphilic compatibilizer to prevent macrophase separation. In all cases, immiscibility of the silicone and hydrophilic polymers results in microphase-separated morphologies. To investigate solute uptake in each of the SiHy microphases, equilibrium partition coefficients are obtained for two hydrophilic solutes (i.e., theophylline and caffeine dissolved in aqueous phosphate-buffered saline) and two oleophilic solutes (i.e., Nile Red and Bodipy Green dissolved in silicone oil), respectively. Measured water contents and aqueous-solute partition coefficients increase linearly with increasing solvent-free hydrophilic-polymer volume fraction. Conversely, oleophilic-solute partition coefficients decrease linearly with rising solvent-free hydrophilic-polymer volume fraction (i.e., decreasing hydrophobic silicone-polymer fraction). We quantitatively predict equilibrium SiHy water and solute uptake assuming that water and aqueous solutes reside only in hydrophilic microdomains, whereas oleophilic solutes partition predominately into silicone microdomains. Predicted water contents and solute partition coefficients are in excellent agreement with experiment. Our new procedure permits a priori estimation of SiHy water contents and solute partition coefficients based solely on properties of silicone and hydrophilic homopolymer hydrogels, eliminating the need for further mixed-polymer-hydrogel experiments.