Yossef A. Elabd

Super Proton Conductive High-Purity Nafion Nanofibers

In this paper, we report the high proton conductivity of a single high-purity Nafion nanofiber (1.5 S/cm), which is an order of magnitude higher than the bulk Nafion film ( approximately 0.1 S/cm). We also observe a nanosize effect, where proton conductivity increases sharply with decreasing fiber diameter. X-ray scattering provides a rationale for these findings, where an oriented ionic morphology was observed in the nanofiber in contrast to the isotropic morphology in the bulk film. This work also demonstrates the successful fabrication of high-purity Nafion nanofibers ( approximately 99.9 wt %) via electrospinning and higher humidity sensitivity for nanofibers compared to the bulk. These results should have a significant impact on fuel cells and sensors.

Chemical Bath Deposition of ZnO Nanowires at Near-Neutral pH Conditions without Hexamethylenetetramine (HMTA): Understanding the Role of HMTA in ZnO Nanowire Growth

Chemical bath deposition (CBD) is an inexpensive and reproducible method for depositing ZnO nanowire arrays over large areas. The aqueous Zn(NO(3))(2)-hexamethylenetetramine (HMTA) chemistry is one of the most common CBD chemistries for ZnO nanowire synthesis, but some details of the reaction mechanism are still not well-understood. Here, we report the use of in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to study HMTA adsorption from aqueous solutions onto ZnO nanoparticle films and show that HMTA does not adsorb on ZnO. This result refutes earlier claims that the anisotropic morphology arises from HMTA adsorbing onto and capping the ZnO {10 1 0} faces. We conclude that the role of HMTA in the CBD of ZnO nanowires is only to control the saturation index of ZnO. Furthermore, we demonstrate the first deposition of ZnO nanowire arrays at 90 °C and near-neutral pH conditions without HMTA. Nanowires were grown using the pH buffer 2-(N-morpholino)ethanesulfonic acid (MES) and continuous titratation with KOH to maintain the same pH conditions where growth with HMTA occurs. This semi-batch synthetic method opens many new opportunities to tailor the ZnO morphology and properties by independently controlling temperature and pH.

Diffusion of water in Nafion using time-resolved Fourier transform infrared-attenuated total reflectance spectroscopy.

Hydrogen fuel cells are attractive alternative power sources for applications such as transportation; however, fuel cell performance is a strong function of water equilibrium content and water sorption and desorption kinetics in polymer electrolyte membranes (e.g., Nafion). Although similar water sorption isotherms for Nafion have been reproduced in many laboratories, reported diffusion coefficients of water in Nafion vary by 4 orders of magnitude. In this study, sorption and desorption dynamics of water vapor in Nafion were measured as a function of water vapor activity and flow rate using time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Both integral and differential experiments were performed, where integral experiments consisted of increasing the vapor activity from 0% RH to one of five values (22, 43, 56, 80, or 100% RH), while in differential experiments the activity was sequentially increased in smaller steps from 0 to 22 to 43 to 56 to 80 to 100% RH. For integral experiments, non-Fickian behavior was observed at both low and high vapor activities, while Fickian behavior was observed at moderate vapor activities. For differential experiments, Fickian behavior was observed at all vapor activities except at low vapor activities (0-22% RH). Sorption kinetics was found to be a function of flow rate, where mass transfer resistance at the vapor/polymer interface was significant at low flow rates but was insignificant at high flow rates. Accurate sorption and desorption diffusion coefficients were calculated in this study (measured at high flow rates with no mass transfer resistance) and were similar, on the order of 10(-7) cm(2)/s, and weak functions of water vapor activity.

Single-wall carbon nanotube latexes.

A nanolatex copolymer (25−30 nm) of an imidalozium bromide acrylate is reported that provides stable waterborne dispersions of single-walled carbon nanotubes (SWCNT) and thermally and electrically conducting coatings that adhere to plastics. This approach to dispersing SWCNT leaps past previous reports by providing stabilization and binder functions simultaneously. Resulting films exhibit 10-fold anisotropy in both thermal and electrical conductivity and appear free of interfacial phonon scattering problems. The electrically conducting networks assembled upon film formation provide a new route to priming plastics for electrodeposition in addition to providing simple antistatic layer formulations. The efficacy of these nanolatexes is assigned to the imidazolium and bromide components shown in other studies to have an affinity for graphene surfaces.

Water Clustering in Glassy Polymers

In this study, water solubility and water clustering in several glassy polymers, including poly(methyl methacrylate) (PMMA), poly(styrene) (PS), and poly(vinylpyrrolidone) (PVP), were measured using both quartz spring microbalance (QSM) and Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Specifically, QSM was used to determine water solubility, while FTIR-ATR spectroscopy provided a direct, molecular-level measurement of water clustering. The Flory-Huggins theory was employed to obtain a measure of water-polymer interaction and water solubility, through both prediction and regression, where the theory failed to predict water solubility in both PMMA and PVP. Furthermore, a comparison of water clustering between direct FTIR-ATR spectroscopy measurements and predictions from the Zimm-Lundberg clustering analysis produced contradictory results. The failure of the Flory-Huggins theory and Zimm-Lundberg clustering analysis to describe water solubility and water clustering, respectively, in these glassy polymers is in part due to the equilibrium constraints under which these models are derived in contrast to the nonequilibrium state of glassy polymers. Additionally, FTIR-ATR spectroscopy results were compared to temperature-dependent diffusivity data, where a correlation between the activation energy for diffusion and the measured water clustering was observed.

Tuning Ion Conducting Pathways Using Holographic Polymerization

Polymer electrolyte membranes (PEMs) with high and controlled ionic conductivity are important for energy-related applications, such as solid-state batteries and fuel cells. Herein we disclose a new strategy to fabricate long-range ordered PEMs with tunable ion conducting pathways using a holographic polymerization (HP) method. By incorporating polymer electrolyte into the carefully selected HP system, electrolyte layers/channels with length scales of a few tens of nanometers to micrometers can be formed with controlled orientation and anisotropy; ionic conductivity anisotropy as high as 37 has been achieved.

Polymerized ionic liquid block copolymers for electrochemical energy

Polymerized ionic liquid (PIL) block copolymers are an emerging class of polymers that synergistically combine the benefits of both ionic liquids (ILs) and block copolymers into one, where the former possesses a unique set of physiochemical properties and the latter self assembles into a range of nanostructures. The potential to synthesize a vast array of new block copolymers is almost limitless with numerous IL cations and anions available. In this paper, we highlight the very recent work on PIL block copolymers, specifically, synthesis and unique solid-state properties for electrochemical energy.

Liquid water transport in polylactide homo and graft copolymers

The successful design of new biodegradable, renewable resource plastics as replacements to commodity barrier plastics would benefit from an accurate measurement of sorption and diffusion of liquids. In this study, the diffusion of liquid water in amorphous polylactide [PLA] and a PLA graft copolymer, poly(1,5-cyclooctadiene-co-5-norbornene-2-methanol-graft-dl-lactide) [PCNL], was examined with time-resolved Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian behavior was observed for all experiments, indicated by a slow approach to steady state due to diffusion and polymer relaxation occurring on similar time scales. This non-Fickian behavior highlights the variability of the sorption isotherms reported in the literature, where others have collected nonequilibrium sorption behavior (instead of true steady-state equilibrium sorption) at different time points and film thicknesses. The dynamic infrared data provided direct evidence for both water diffusion and water-induced polymer relaxation, where both were quantified and regressed to a diffusion-relaxation model to determine the diffusion coefficient and the polymer relaxation time constant. In addition to the successful measurement and modeling of the diffusion-relaxation phenomena for diffusion of a liquid in a nonequilibrium state glassy polymer, this study also determined that the diffusivity of water in the PLA graft copolymer (with only 5 wt % rubber) was 3-fold lower than in the PLA homopolymer.

Plasma-aided template synthesis of inorganic nanotubes and nanorods

This work presents a new sol–gel deposition method to synthesize high purity SiO2 and ZrO2 nanotubes and nanorods using track-etched membrane templates. Oxygen plasma pretreatment ensures pore-filling of the precursor solution and covalent bonding between template and precursor, while pyrolysis of the template–nanostructure composite completely removes organics and produces inorganic nanostructures. The nanotube/nanorod aspect ratio was tunable by the pore size and thickness of the template, while the wall thickness (from tube to rod) was controlled by the precursor concentration. The solvent-free plasma treatment and pyrolysis provide an efficient synthetic route to produce high purity inorganic nanostructures.

Sulfonated Polymerized Ionic Liquid Block Copolymers.

The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions.