This work presents the synthesis and characterization of a pearylated polysiloxane material (PAP) from a polycondensation reaction, followed by functionalization with HClSO3 by an electrophilic substitution reaction. According to the characterization techniques applied, a sulfonated pearylated polysiloxane was also obtained, (SPAP). The purpose of this sulfonated material is to obtain an ionomer able to be applied in hydrogen fuel cells of the proton exchange membrane kind (PEMFC). The reaction to produce the polysiloxane precursor was carried out with the commercial reagents: PhSiCl3, Ph2SiCl2 and Ph3SiCl in anhydrous THF at 75 °C and the SPAP material was obtained by sulfonation of the precursor with chlorosulfonic acid. PAP and SPAP were characterized by 1H, NMR for liquids, 29Si NMR for solids, IR-ATR, SEM, and cyclic voltammetry. The NMR 29Si spectra show that PAP and PAPS contain crosslinking regions due to PhSiCl3, growing chain zones due to Ph2SiCl2 and polymer termination zones due to Ph3SiCl, obtaining a mixture of siloxanes. The analysis by cyclic voltammetry indicates that by integrating the area under the curve of the adsorption peaks of H2, a value of 0.062 mC/cm2 is obtained, a value close to the commercial ionomer of Nafion®.

In this study, we report developments towards the application of large zeolite particles, with diameter ca. 40 μm, as tracers in Positron Emission Particle Tracking (PEPT) imaging using 68Ga. The influence of intrapore Na+ and TEA+ (tetraethylammonium) cation concentrations and framework Si/Al ratio on the morphology of mordenite particles has been investigated, advancing understanding of the relationship between these factors. Moreover, the influence of ethanol concentration in the gel during aging on intrapore cation concentration, Si/Al ratio and particle morphology has also been investigated. Additionally, facile ion-exchange between aqueous Ga3+ and intrapore H+ in mordenite has been demonstrated. The influence of pH and gallium speciation on ion-exchange has been investigated to determine favourable conditions for 68Ga3+ uptake by the zeolite.

Phosphonated graphene oxide (pGO) has been incorporated to sulfonated poly(styrene-isobutylene-styrene) (SO3H SIBS) to prepare polymer nanocomposite membranes (PNMs) for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The performance of the membranes was evaluated per SIBS sulfonation level (i.e. 38, 61, and 90 mole %), filler type (i.e. GO and pGO) and filler loading (i.e. 0.1, 0.5 and 1.0 wt.%). The transport properties (i.e. proton conductivity and methanol and vapor permeability) were determined to assess the performance of the PNMs per each application. The ionic interactions between the phosphonic and sulfonic groups (i.e. PO3H2 and SO3H, respectively) altered the pathways of SO3H SIBS, influencing the transport of permeants through the membranes. SIBS 61 pGO 0.1 presented the highest separation efficiency and a DMFC performance comparable to the state-of-the-art Nafion®, indicating that this membrane could potentially be implemented as protective fabric as well as functioning for fuel cell applications.

The formation mechanism and chemical form of insoluble C-14 found in PWR need to be examined in order to predict its environmental behavior after disposal. This study investigates the alteration of ion-exchange resin by heating and irradiation, because past studies indicated the ion-exchange resin may be the origin of insoluble C-14.

Resin was heated at 300 °C in solution with low oxygen content to simulate the environment of PWR coolant. The sulfo group was found to detach within 8 h, and structures similar to polystyrene were remained. This is followed by detachment of H from the alkyl group, condensation reaction, and the formation of amorphous carbon-like structure. After heating for 24 and 96 h, the resin was irradiated by 60Co γ-rays in the solution. The FT-IR and TG measurements after irradiation suggested that OH and COOH groups were formed on the surface of the resin. These functional groups may be involved in reactions that finally form the amorphous carbon.

In addition, the characteristics of heated and irradiated resin were compared to real insoluble-C (CRUD) sample in PWR (in Appendix).

Pure and Nb-doped zirconium germanate materials of composition K2-xZr1-xNbxGe3O9.H2O where x = 0, 0.1, 0.2 and 0.3 with the structure of the natural mineral umbite have been prepared in high yield using hydrothermal synthesis methods. The parent material displays virtually no ion exchange of the K+ for Cs+ but the doped materials show rapidly enhanced exchange with replacement of ca. 70% of the K+ by Cs+ for the 30% doped material. Rietveld analysis of the powder X-ray diffraction data is consistent with no change in the unit cell parameters or K+ bonding prior to the exchange, hence we propose the improved property is due to the creation of cation defect sites within the pores of the material that facilities greater cation mobility and leads to exchange.

Salinity gradient is an enormous source of clean energy. A process for potential generation from an ionic concentration gradient produced in single and multicell assembly is presented. The ionic gradient is created using a fuel cell type cell with a micro-porous ion exchange membrane, both anionic (AEM) and cationic (CEM). Various salinity gradients, Salt : Fresh, from 100 : 0 to 16000 : 0 was established using NaCl solution, in the electrode chambers. A potential of 20 mV/cm to 25 mV/cm can be realized at ambient temperatures and pressures for a bipolar AEM/CEM cell. The performance was optimized for various static and dynamic flow rates of the saline and fresh water. The cell performance can further be optimized for Membrane Electrode System (MES) morphology. A multicell unit was assembled and the results presented for various conditions like concentration gradients, flow rates and pressure. The thermodynamic and electrical efficiency needs to be evaluated for various gradients and flow rates. The relation with number of valance electrons/ ion and the potential generated changes for various dynamic condition of salinity. The higher the salinity gradient the larger is the potential generated. This is limited by the membrane characteristics. There exists a monotonic relation between the number of valence electron/ion/unit time and the potential generated up to about 16000 concentration. The membrane characteristics have been studied for optimal ion crossover for various gradients and flow. The graph between ln (gradient) versus Voltage provides insights into this process. This presents a very cost effective and clean process of energy conversion.

Researchers have investigated hydrogels as potential materials for biological monitoring. Hydrogel compositions have been designed to respond to changes in temperature, pH, glucose concentration and ionic strength concentration. Hydrogels designed to respond to changes in environmental conditions have demonstrated their ability to respond via a swelling or shrinking action. This swelling behavior can be exploited using a variety of signal transduction methods. While this technology shows promise, the degradation of hydrogel materials has not yet been characterized with respect to the shelf life of hydrogel samples or to their use in continuous testing. A series of experiments were performed to test hydrogels stored for extended periods of time then subjected to oscillatory testing, and the results have been analyzed to determine whether hydrogels can be used for extended periods of time for biological sensing applications.

A novel method for introducing quaternary ammonium-bearing side chains has been developed and applied to a polybenzimidazole backbone to generate new anionic-exchange polymers, TMHA-m-FPBI where m = the degree of substitution of available sites (values ranging from 74 to 100%). These polymers have been shown to exhibit hydroxide ion conductivities up to 34 mS cm-1 in hydrated membranes at ambient temperature and 13 mS cm-1 at 60 °C, RH = 95%. Immersion of these polymers in 2 M KOH at 60 °C has shown they remain stable with no sign of chemical structure degradation to a period of at least 15 days.

Adsorption of charged biomolecules onto atomically flat mica substrates is facilitated by the deposition of metal ions. Despite successfully acting as preferential anchoring sites, the presence of ions on the mica surface also changes its physicochemical characteristics something that is rarely quantified from a nanoscale point of view. In this study the nanoscale physicochemical properties of nickel-functionalized Muscovite mica are investigated by reconstructing the conservative force profile between an atomic force microscopy (AFM) tip and the surface. Various nickel ion concentrations (i.e. 1.0 mM to 20.0 mM) along with different incubation times (30 seconds and 5 minutes) are directly analyzed. Details in the spatial and temporal variations in surface properties due to the ion mediated adsorption of water are presented in details and in light of the binding efficiency of the metal ions. This insight benefits our understanding in the behavior of ion distribution that plays a crucial role in biomolecule imaging using AFM.

Hot Isostatic Pressing of Cs-exchanged IONSIV IE-911 samples is shown to produce a mixture of ceramic phases, the nature and mass fractions of these have been determined by Rietveld analysis of powder X-ray diffraction data. The main Cs phase that forms is Cs2TiNb6O18, after this reaches approximately 30% of the total crystalline content the remaining Cs is partitioned into Cs2ZrSi6O15. Durability tests using the PCT-B method for 7 days at 90 °C with deionised water lead to Cs leach rates of 0.032 and 0.038 g∙m−2∙day−1 for samples exchanged to 6 and 12 wt% Cs, respectively, indicating a durable wasteform is produced.

Phosphonated polysulfones in the acid form (PPSU-As) with degree of phosphonation (DP) = 0.4, 0.75, and 0.96 were successfully synthesized and utilized for the preparation of polymer blend with sulfonated poly(ether ether ketone) (SPEEK) having a degree of sulfonation (DS) = 75. The resulted blend membranes were characterized and investigated as new polyelectrolyte membrane for fuel cells applications. SPEEK/PPSU-A blend membranes formed ionic networks through hydrogen bonding bridges between the strong sulfonic acid groups and the amphoteric phosphonic acid groups. These ionic interactions resulted in enhanced membrane properties in terms of water swelling, methanol uptake, methanol permeability, mechanical strength, and thermal stability, without significant loss of proton conductivity. All the blend membranes were transparent to visible light with presence of microphases in the order of 10–20 nm. When compared to parent SPEEK membranes, the new SPEEK/PPSU-A blend membranes showed slightly lower methanol permeability compared to neat SPEEK membrane. Membranes with 30 wt% phosphonic acid content with DP = 0.75 and 0.96, exhibited slightly higher proton conductivities at temperatures above 50 °C in comparison with Nafion membrane.

A clickable surface was prepared using nanoporous SBA-15 support. Methylimidazolium, an ionic liquid, was immobilized on this surface through the click reaction. Detailed characterization using nitrogen adsorption, elemental analysis, x-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis showed that the ionic system was fixed inside the channels and the ordered porous structure remained stationary. Influence of this material on photoluminescence emission of 5-amino-4-hydroxy-7-sulfonaphthalene-2-sulfonate anion (H-acid) in aqueous solutions was evaluated. This click reaction product can be used effectively for H-acid removal from wastewater.

Thermal stability, hydration and mechanical properties of thermally cross-linked Sulfonated Aromatic Polymers (SAP) with high ionic exchange capacity (IEC) were measured and compared to untreated samples. The formation of cross-linking greatly stabilizes SAP in terms of thermal, mechanical, and hydrolytic degradation: they can resist in water even at a temperature of 145 °C with improved mechanical properties. Acid-base titration and FTIR spectra consistently indicate that SAP microstructure stabilization is related to cross-linking of the polymer chains by SO2 bridges, which is promoted by temperature.

In this work the effect on the adsorption of Cr (VI) by thermally treated Hydrotalcite-like Material (HTM) synthesized by the sol-gel method with a Mg/Al = 2 was studied. The characterization of the HTM before and after Cr (VI) removal, as well as the kinetic studies were carried out. When the HTM are thermally treated at 350ºC the hydrotalcite crystalline structure remains and the textural properties improve. The Cr (VI) adsorption capacity of HTM was 125 mg of Cr (VI) / g of HTM. This capacity augments at 132 mg of Cr (VI) / g of HTM after heating HTM at 300°C. The crystallinity as well the porosity of the HTM diminished after adsorption of Cr (VI), due to the obstruction of both the pores and the interlayer space. The adsorption of Cr (VI) occurred before 4 minutes contact time. It can be concluded that HTM exhibits a high Cr (VI) adsorption capacity in a short time.

Experimental results are presented to demonstrate feasibility of small scale power generation using static reverse electrodialysis (RED) of CuSO4 solutions. In contrast to conventional macro scale reverse electrodialysis, the concentrated and diluate compartments were not refreshed, resulting in limited power delivery times. This is important in energy harvesting applications from limited supply of ionic concentrations. Maximum output power density of 0.17 μW·cm−2 was recorded using microfiltration membranes. The evolution of the open circuit output voltage with time is accurately modeled at various concentration ratios.

Neutron imaging as a method to perform in situ studies of hydrogen fuel cells, hydrogen storage devices, heat pipes, and batteries has made tremendous progress in recent years. Neutrons are useful to study light elements mixed with heavy Z elements where penetration by other forms of radiation is either impossible or incapable of contrasting the light elements. Useful spatial resolution available at neutron imaging facilities is now approaching 10 micrometers. Complimentary time resolution of 30 fps or greater is also possible with a spatial resolution approaching 300 micrometers. Here we will provide an overview of the technique of neutron imaging and experimental studies with neutrons at the National Institute of Standards and Technology. Examples of in situ studies of fuel cells, hydrogen storage devices, heat pipes and batteries will be discussed.

The lithium titanate Li2Ti6O13 has been prepared from Na2Ti6O13 by Li ion exchange in molten LiNO3 at 325ºC. Chemical analysis and powder X-ray diffraction study of the reaction product, respectively, indicate that total Na/Li exchange takes place and the Ti-O framework of the Na2Ti6O13 parent structure is kept under those experimental conditions. The electrochemical characterization shows that Li2Ti6O13 is able to insert ca. 5 Li per formula unit under equilibrium conditions in the voltage range 1.5-1.0 V vs. Li+/Li. This corresponds to a specific discharge capacity of 250 mAh g-1. Lithium insertion occurs at an average equilibrium voltage of 1.5 V which is typical for oxides and titanates where Ti(IV)/Ti(III) is the active redox couple. After the first redox cycle a high reversible capacity is obtained (ca. 160 mAh g-1 at C/12, with a 70% capacity retention related to a phase transformation upon cycling). On the basis of these results, we are proposing Li2Ti6O13 as new lithium battery anode material to be further investigated.

The configurations of proton channel network on the surface of Nafion® membranes were studied using current sensing atomic force microscopy after the membranes were annealed at elevated temperatures, aimed at understanding the effect of aging process in the membranes. The results reveal that proton conductance of the membranes becomes more uniform and the proton channels become chain-like aligning in parallel to the membrane surface. Accompanied to the configuration changes, the proton conductivity of the membrane shows an increase. As the annealing continues, the chain-like configuration for the proton channels persists but the conductance of the membranes decreases. The time constant of the conductivity decay decreases with increase of the annealing temperature. The observed changes can be attributed to reorientation of proton channels near the membrane surface from perpendicular to parallel to the surface as the annealing temperature approaches the glass transition of the membranes.

A small-angle neutron scattering (SANS) investigation of saturated aqueous proton exchange membranes is presented. Our membranes were synthesized by radiation-induced grafting of poly(ethylene-alt-tetrafluoroethylene) (ETFE) with styrene in the presence of crosslinker (divinylbenzene, DVB) and the polystyrene was sulfonated subsequently. The contrast variation method was used to understand the relationship between morphology, water uptake, and proton conductivity. We find that the membranes are separated into two phases, mostly following the morphology already defined in the semi-crystalline ETFE base film. The amorphous phase hosts the water and swells upon hydration, swelling being inversely proportional to the degree of crosslinking. Proton conductivity and volumetric fraction of water are related by a power law, indicating a percolated and most likely random network of finely dispersed aqueous pores in the hydrophilic domains.

The suitability of Portland cement blends for encapsulation of Cs-Ionsiv in a monolithic wasteform was investigated. No evidence of reaction or dissolution of the Cs-Ionsiv in the cementitious environment was found by scanning electron microscopy and X-ray diffraction. However, a small fraction (≤1.6 wt%) of the Cs inventory was released from the encapsulated Ionsiv during leaching experiments carried out on hydrated samples. Cs release was enhanced by exchange of K and Na present in the cementitious pore water. Cement systems lower in K and Na, such as slag based blends, showed lower Cs release than the fly ash based analogues.