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Biological systems routinely regulate biomolecular transport with remarkable specificity, low energy input, and simple mechanisms. Here, the biophysical mechanisms of nuclear transport inspire the development of gels for recognition and selective permeation (GRASP). GRASP presents a new paradigm for specific transport and selective permeability, in which binding interactions between a biomolecule and a hydrogel lead to faster penetration of the gel. A molecular transport theory identifies key principles for selective transport: entropic repulsion of noninteracting molecules and affinity-mediated diffusion of multireceptor biomolecules through a walking mechanism. The ability of interacting molecules to walk through hydrogels enables enhanced permeability in polymer networks. To realize this theoretical prediction in a novel material, GRASP is engineered from a poly(ethylene glycol) network (entropic barrier) containing antibody-binding oligopeptides (affinity domains). GRASP is synthesized using simultaneous bioconjugation and polycondensation reactions. The elastic modulus, characteristic pore size, biomolecular diffusivity, and selective permeability are measured in the resulting materials, which are applied to regulate the transport of equally sized molecules by preferentially transporting a monoclonal antibody from a polyclonal mixture. Overall, this work presents rationally designed, nucleopore-inspired hydrogels that are capable of controlling biomolecular transport.

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...

© 2016 Elsevier B.V. A Schirmer tear test (STT) is commonly used to gauge human tear production, especially when dry-eye symptoms present. In an STT, the rounded tip of a standardized paper strip is inserted into the lower fornix of the eye, and the wetted length extending out from the lower lid is recorded after 5 min of eye closure. Longer wetted lengths suggest higher tear production rates. To date, however, there is no methodology to transform STT transient wetting lengths into basal tear- production rates. We develop a physical model to elucidate wetting kinetics in a Schirmer strip. Tear evaporation from the exposed portion of the strip and gravity are accounted for. Careful consideration of the initial depletion of tear in the closed-eye tear prism reveals an initial fast increase in wetted length followed by slower growth. Excellent agreement of the proposed model is achieved with experimental observation. When evaporation is negligible, the slow-growth regime exhibits a linear increase of wetted length in time. The linear-length-growth time regime permits simple calculation of quantitative tear-production rates. We suggest measuring several dynamic wetting lengths along a sheathed Schirmer strip and near the 5-min insertion duration followed by fitting to a straight line. The slope of the length-versus-time data gives the basal lacrimal-supply rate.

We measure and, for the first time, theoretically predict four prototypical aqueous-drug diffusion coefficients in five soft-contact-lens material hydrogels where solute-specific adsorption is pronounced. Two-photon fluorescence confocal microscopy and UV/Vis-absorption spectrophotometry assess transient solute concentration profiles and concentration histories, respectively. Diffusion coefficients are obtained for acetazolamide, riboflavin, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA) copolymer hydrogels as functions of composition, equilibrium water content (30-90%), and aqueous pH (2 and 7.4). At pH2, MAA chains are nonionic, whereas at pH7.4, MAA chains are anionic (pKa≈5.2). All studied prototypical drugs specifically interact with HEMA and nonionic MAA (at pH2) moieties. Conversely, none of the prototypical drugs adsorb specifically to anionic MAA (at pH7.4) chains. As expected, diffusivities of adsorbing solutes are significantly diminished by specific interactions with hydrogel strands. Despite similar solute size, relative diffusion coefficients in the hydrogels span several orders of magnitude because of varying degrees of solute interactions with hydrogel-polymer chains. To provide a theoretical framework for the new diffusion data, we apply an effective-medium model extended for solute-specific interactions with hydrogel copolymer strands. Sorptive-diffusion kinetics is successfully described by local equilibrium and Henry's law. All necessary parameters are determined independently. Predicted diffusivities are in good agreement with experiment.

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.

aLawrence Berkeley National Laboratory, Berkeley, California 94720, USA bLos Alamos National Laboratory, Los Alamos, New Mexico 87545, USA cUnited Technologies Research Center, East Hartford, Connecticut 06118, USA dSchool of Mechanical and Systems Engineering, Newcastle University, Newcastle upon Tyne NE1 7RU, United Kingdom eChemical and Biomolecular Engineering Department, University of California, Berkeley, California 94720, USA fFuel Cell Research and Development, General Motors, Pontiac, Michigan 48340, USA gBallard Power Systems, Burnaby, British Columbia V5J 5J8, Canada hFuel Cell Research Centre, Queens University, Kingston, Ontario K7L 3N6, Canada iDepartment of Mechanical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA jDepartment of Mechanical Aerospace and Biomedical Engineering, University of Tennessee at Knoxville, Knoxville, Tennessee 37996, USA kDepartment of Mechanical Engineering Technology, SUNY Alfred State College, Alfred, New York 14802, USA lDepartment of Mechanical Engineering, University of Alberta, Edmonton, Alberta T6G 2G, Canada

Two-photon confocal microscopy and back extraction with UV/Vis-absorption spectrophotometry quantify equilibrium partition coefficients, k, for six prototypical drugs in five soft-contact-lens-material hydrogels over a range of water contents from 40 to 92%. Partition coefficients were obtained for acetazolamide, caffeine, hydrocortisone, Oregon Green 488, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA, pKa≈5.2) copolymer hydrogels as functions of composition, aqueous pH (2 and 7.4), and salinity. At pH 2, the hydrogels are nonionic, whereas at pH 7.4, hydrogels are anionic due to MAA ionization. Solute adsorption on and nonspecific electrostatic interaction with the polymer matrix are pronounced. To express deviation from ideal partitioning, we define an enhancement or exclusion factor, E ≡ k/φ1, where φ1 is hydrogel water volume fraction. All solutes exhibit E > 1 in 100 wt % HEMA hydrogels owing to strong specific adsorption to HEMA strands. For all solutes, E significantly decreases upon incorporation of anionic MAA into the hydrogel due to lack of adsorption onto charged MAA moieties. For dianionic sodium fluorescein and Oregon Green 488, and partially ionized monoanionic acetazolamide at pH 7.4, however, the decrease in E is more severe than that for similar-sized nonionic solutes. Conversely, at pH 2, E generally increases with addition of the nonionic MAA copolymer due to strong preferential adsorption to the uncharged carboxylic-acid group of MAA. For all cases, we quantitatively predict enhancement factors for the six drugs using only independently obtained parameters. In dilute solution for solute i, Ei is conveniently expressed as a product of individual enhancement factors for size exclusion (Ei(ex)), electrostatic interaction (Ei(el)), and specific adsorption (Ei(ad)):Ei≡Ei(ex)Ei(el)Ei(ad). To obtain the individual enhancement factors, we employ an extended Ogston mesh-size distribution for Ei(ex); Donnan equilibrium for Ei(el); and Henry's law characterizing specific adsorption to the polymer chains for Ei(ad). Predicted enhancement factors are in excellent agreement with experiment.

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.

Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. A validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.

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.

Perfluorinated sulfonic-acid (PFSA) ionomers are widely used in polymer-electrolyte fuel cells (PEFCs) as electrolyte membranes for both separating reactant gases and transporting protons from anode to cathode. Ionomer properties like conductivity are largely affected by hydration (water uptake) and temperature. Thus, it is desirable for the membrane to operate at higher humidity and temperature. However, during practical operation, where there is high temperature and humidity, these ionomers frequently undergo hygrothermal ageing, which may, for example, result in the formation of anhydrides through a condensation reaction of the sulfonic-acid groups[1]. As a result, the properties and morphology change accordingly, which can significantly impact PEFC operation. Although there are some reports on the effects of hygrothermal ageing [2-4], much remains to be explored in terms of possible changed of the membrane’s underlying structure/property relationship. In this talk, ionomers subjected to hygrothermal ageing will be analyzed in terms of their properties to understand the role of hygrothermal ageing in membrane degradation. In this talk, the structure/property relationship of ionomers such as Nafion 212, 3M and Nafion XL will be examined both as received as well as after undergoing hygrothermal ageing at different conditions so as to correlate the separation-phased nanostructure with the membranes’ physical and transport properties. We will present the effect of pretreatment, temperature, humidity and purge flowrate on ageing and subsequent changes in mechanical, transport, uptake, and structural properties. It will be shown how the impact of ageing depends nonlinearly on humidity. We will also show how pretreatment like boiling and hot-pressing affect the impact of the ageing process. In addition, the possible effect of contamination will be discussed. Our findings provide new insight into how hygrothermal ageing affects the structure/property relationship of ionomers under different conditions. References [1] F.M. Collette, C. Lorentz, G. Gebel, F. Thominette, J. Membr. Sci., 330 (2009) 21-29. [2] S. Naudy, F. Collette, F. Thominette, G. Gebel, E. Espuche, J. Membr. Sci., 451 (2014) 293-304. [3] S. Shi, G. Chen, Z. Wang, X. Chen, J. Power Sources, 238 (2013) 318-323. [4] F.M. Collette, F. Thominette, H. Mendil-Jakani, G. Gebel, J. Membr. Sci., 435 (2013) 242-252. Acknowledgements The authors would like to thank Kyle T. Clark for his help with using some of the diagnostics equipment. AK and AZW thank C.G. Gittleman of General Motors for insightful discussions. SAXS/WAXS experiments were performed in beamline 7.3.3 at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, which is a national user facility funded by the Department of Energy, Office of Basic Energy Sciences. We thank Chenhui Zhu and Dr. Eric Schiable for their assistance during facilitating the use of equipment at ALS. Shouwen Shi greatly thanks China Scholarship Council (CSC) for financial support during his visit to Lawrence Berkeley National Laboratory. This work was funded by the Assistant Secretary for Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, of the U. S. Department of Energy under contract number DE-AC02-05CH11231 (LBNL) and program managers Donna Ho and Nancy Garland.

© 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. Partitioning of aqueous packaging, wetting, and care-solution agents into and out of soft contact lenses (SCLs) is important for improving wear comfort and also for characterizing lens physico-chemical properties. We illustrate both features of partitioning by application of fluorescent-solute partitioning into DAILIES TOTAL1® (delefilcon A) water-gradient SCLs, which exhibit a layered structure of a silicone-hydrogel (SiHy) core sandwiched between thin surface-gel layers. Two-photon fluorescence confocal laser-scanning microscopy and attenuated total-reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) characterize the lens and assess uptake profiles of six prototypical fluorescent solutes. Comparison of solute uptake in a SiHy-core prototype lens (i.e., O2OPTIXTM) validates the core SiHy structure of DAILIESTOTAL1®. To establish surface-layer charge, partition coefficients and water contents are obtained for aqueous pH values of 4 and 7.4. Solute fluorescence-intensity profiles clearly confirm a layered structure for the DAILIES TOTAL1® lenses. In all cases, aqueous solute partition coefficients are greater in the surface layers than in the SiHy core, signifying higher water in the surface gels. ATR-FTIR confirms surface-layer mass water contents of 82 ± 3%. Water uptake and hydrophilic-solute uptake at pH 4 compared with that at pH 7.4 reveal that the surface-gel layers are anionic at physiologic pH 7.4, whereas both the SiHy core and O2OPTIX™ (lotrafilcon B) are nonionic. We successfully confirm the layered structure of DAILIES TOTAL1®, consisting of an 80-μm-thick SiHy core surrounded by 10-μm-thick polyelectrolyte surface-gel layers of significantly greater water content and aqueous solute uptake compared with the core. Accordingly, fluorescent-solute partitioning in SCLs provides information on gel structure and composition, in addition to quantifying uptake and release amounts and rates.

Author(s): Liu, DE; Dursch, TJ; Taylor, NO; Chan, SY; Bregante, DT; Radke, CJ | Abstract: The authors regret that the following errors were made in the Appendix of this article. The factor of 2 on the right side of Eq. (A3) should be replaced by unity, and the right side of Eq. (A4) should be multiplied by 8/π2. Please see correct equations below - The authors would like to apologise for any inconvenience caused.

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.

In both automotive and stationary applications, proton-exchange-membrane fuel cells (PEMFCs) must permit rapid startup with minimal energy from subfreezing temperatures, known as cold-start. Under subfreezing conditions, water solidifies to form ice in the membrane-electrode assembly (MEA), severely inhibiting cell performance and often causing cell failure. By way of example1, Figure 1 displays typical evolutions of MEA cell voltage (filled symbols) during isothermal cold-start from temperatures of –6 and –20 °C at a current density of 20 mA/cm2 (open symbols). Following an initial current ramp of 0.4 mA/cm2/s, cell voltage remains constant until failure (i.e., when cell voltage rapidly declines to 0 mV). Note the short MEA cell-failure time, tfail , at –20 °C (i.e., 10 min). Clearly, elucidation of the mechanisms and kinetics of ice formation within PEMFC-porous media is critical to improving PEMFC cold-start capability. We measure and predict ice-crystallization kinetics within PEMFC gas-diffusion layers (GDLs) and catalyst layers (CLs).1-3 To validate ice-crystallization kinetics within PEMFCs, we further measure and predict cell-failure time during isothermal galvanostatic cold-start. Using a simplified PEMFC isothermal cold-start continuum model, cell-failure times are predicted using the newly obtained rate expression and compared to those using a traditional thermodynamic-based approach.1 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. As an example, Figure 2 plots isothermal tfail at a current density of 20 mA/cm2 as a function subcooling, ΔT, where ΔT is defined as the magnitude of the difference in temperature and 273 K. As ΔT increases, tfail decreases substantially. In Figure 2, tfail decreases from 15.5 and 33 h to 0.19 and 0.2 h for an increase in ΔT from 5 to 10 K, respectively. Solid lines in Figure 2 represent ice-crystallization kinetics for two cCL carbon-support materials with considerably different ice-crystallization kinetics, whereas the dashed line corresponds to a traditional thermodynamic-based approach.1 In all cases, tfail decreases substantially with increasing ΔT, in good agreement with experiment. As subcooling extends beyond 11 K, ice-nucleation times in both the cCL and cGDL are negligible, and ice-crystallization kinetics is well approximated by the thermodynamic-based approach. Therefore, we conclude that including ice-crystallization kinetics is critical in the “nucleation-limited” regime (see Figure 14 of Dursch et al.2) where ice-nucleation times are long. However, the particular ΔT that establishes the “nucleation-limited” regime relies heavily on all heat transfer and kinetic parameters.1 Consequently, these controlling parameters can be adjusted to lengthen ice-nucleation times, significantly delaying or even preventing ice formation.2,3 Acknowledgement This work was funded by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Fuel Cell Technologies, of the U. S. Department of Energy under contract number DE-AC02-05CH11231.

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