This doctoral thesis gives background to the field of electrochemical energy storage in supercapacitors. It attempts to place the supercapacitor device in context of available and future technologies for alternative energy systems for transportation. Limitations of cells and electrodes and key challenges in the supercapacitor development are introduced. One objective of the thesis is to investigate and describe ionic transport in active carbon and possible restrictions in nanostructured porous systems with focus on small (micro and meso) pores. Another is to develop a model suitable for investigations of concentration and potential profiles from a single particle perspective. The results from the studies are presented in this thesis together with the scientific papers this thesis is based on. Studying electrochemical gradients (concentration and potential) of large electrodes and single particles may give important information of the limitations of the material. In larger three-electrode experimental set-ups, these gradients can be studied for electrodes but single particles are not available for experimental studies to the same extent since the matrix of an electrode consist of many particles, all adding to the total gradient of the electrode. The experimental part of this thesis is based on different experimental techniques: Three-electrode experiments for larger electrodes, microelectrode experiments for single particles, numerical simulations using Multiphysics (software) of large electrodes consisting of single particles. Four Papers are appended to the thesis. They present results and discussions regarding ionic transport, surface functionalities and modeling of a particle based supercapacitor electrode. Estimated effective diffusivities for an active carbon containing micro, meso and macropores are presented. Surface functionalities in the form of oxygen-containing groups were present in a carbon studied using two experimental set-ups. Faradaic peaks, previously not reported in activated carbon were seen. The occurrence of Faradaic phenomena in one experimental set-up but not the other is further analyzed and the origin of these peaks discussed. The particle based mathematical model, where galvanostatic and cyclic voltammetry is simulated, is presented. Concentration profiles both in the particles and electrodes are discussed and some of the numerical results are compared with experimental data. / QC 20100809

Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction. In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements. The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu2MeS)I:I2 (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu2MeS)I:I2-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation. Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems. Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized / QC 20101013

<p>This thesis presents an analysis of the material properties and phase behavior of divalent ionic surfactant salts, and protein and polymer glasses. There has been extensive interest in understanding the phase behavior of divalent ionic surfactants due to the many applications of ionic surfactants in which they come into contact with divalent ions, such as detergency, oil recovery, and surfactant separation processes. One goal of determining the phase boundaries was to explore the option of incorporating a hydrophobic molecule into the solid phase through the micelle-to-crystal bilayer transition, either for drug delivery applications (with a biologically compatible surfactant) or for the purpose of studying the hydrophobic molecule itself. The liquid micellar and solid crystal phases of the alkaline earth metal dodecyl sulfates were investigated using calorimetry, visual inspection, solubilization of a fluorescent probe, and x-ray diffraction. The Krafft temperature and dissolution enthalpy were determined for each surfactant, and partial composition-temperature phase diagrams of magnesium dodecyl sulfate-water, calcium dodecyl sulfate-water, as well as sodium dodecyl sulfate with MgCl₂ and CaCl₂ are presented. As a proof of concept, fluorescence microscopy images showed that it is, in fact, possible to incorporate a small hydrophobic molecule, diphenylhexatriene, into the solid phase.</p><p>The second, and main, part of this thesis expands on work done previously in the lab by using the micropipette technique to study two-phase microsystems. These microsystems consist of a liquid droplet suspended in a second, immiscible liquid medium, and can serve as direct single-particle studies of drug delivery systems that are formed using solvent extraction (e.g., protein encapsulated in a biodegradable polymer), and as model systems with which to study the materials and principles that govern particle formation. The assumptions of the Epstein-Plesset model, which predicts the rate of droplet dissolution, are examined in the context of the micropipette technique. A modification to the model is presented that accounts for the effect a solute has on the dissolution rate. The modification is based on the assumption that the droplet interface is in local thermodynamic equilibrium, and that the water activity in a solution droplet can be used to determine its dissolution (or dehydration) rate. The model successfully predicts the dissolution rates of NaCl solutions into octanol and butyl acetate up to the point of NaCl crystallization. The dehydration of protein solutions (lysozyme or bovine serum albumin) results in glassified microbeads with less than a monolayer of water coverage per protein molecule, which can be controlled by the water activity of the surrounding organic medium. The kinetics of dehydration match the prediction of the activity-based model, and it is shown how the micropipette technique can be used to study the effect of dissolution rate on final particle morphology. By using a stable protein with a simple geometry (lyosyzme), this technique was be used to determine the distance dependence of protein-protein interactions in the range of 2-25 &Aring;, providing the first calculation of the hydration pressure decay length for globular proteins. The distance-dependence of the interaction potential at distances less than 9 &Aring; was found to have a decay length of 1.7 &Aring;, which is consistent with the known decay length of hydration pressure between other biological materials. Biodegradable polyesters, such as poly(lactide-co-glycolide) (PLGA), are some of the most common materials used for the encapsulation of therapeutics in microspheres for long-term drug release. Since they degrade by hydrolysis, release rates depend on water uptake, which can be affected by processing parameters and the material properties of the encapsulated drug. The micropipette technique allows observations not possible on any bulk preparation method. Single-particle observations of microsphere formation (organic solvent extraction into a surrounding aqueous phase) show that as solvent leaves the microsphere and the water concentration in the polymer matrix becomes supersaturated, water phase separates and inclusions initially grow quickly. Once the concentration in the polymer matrix equilibrates with the surrounding aqueous medium, the water inclusions continue to grow due to dissolved impurities, solvent, and/or water-soluble polymer fragments resulting from hydrolysis, all of which locally lower the water activity in the inclusion. Experiments are also presented in which glassified protein microbeads were suspended in PLGA solution prior to forming the single microspheres. This technique allowed the concentration of protein in a single microbead/inclusion to be determined as a function of time.</p> / Dissertation

Tissue-engineering (TE) is one of the most innovative approaches for tackling many diseases and body parts that need to be replaced, by developing artificial tissues and organs. For this, tissue scaffolds play an important role in various TE applications. A tissue scaffold is a 3D (3D) structure with interconnected pore networks and used to facilitate cell growth and transport of nutrients and wastes while degrading gradually itself. Many fabrication techniques have been developed recently for incorporating living cells into the scaffold fabrication process and among them; dispensing-based rapid prototyping techniques have been drawn considerable attention due to its fast and efficient material processing. This research is aimed at conducting a preliminary study on the dispensing-based biofabrication of 3D cell-encapsulated alginate hydrogel scaffolds. Dispensing-based polymer deposition system was used to fabricate 3D porous hydrogel scaffolds. Sodium alginate was chosen and used as a scaffolding biomaterial. The influences of fabrication process parameters were studied. With knowledge and information gained from this study, 3D hydrogel scaffolds were successfully fabricated. Calcium chloride was employed as crosslinker in order to form hydrogels from alginate solution. The mechanical properties of formed hydrogels were characterized and examined by means of compressive tests. The influences of reagent concentrations, gelation time, and gelation type were studied. A post-fabrication treatment was used and characterized in terms of strengthening the hydrogels formed. In addition, the influence of calcium ions used as crosslinker on cell viability and proliferation during and after the dispensing fabrication process was examined and so was the influence of concentration of calcium solutions and exposing time in both media and alginate hydrogel. The study also showed that the density of encapsulated cells could affect the viscosity of alginate solution. In summary, this thesis presents a preliminary study on the dispensing-based biofabrication of 3D cell-encapsulated alginate hydrogel scaffolds. The results obtained regarding the influence of various factors on the cell viability and scaffold fabrication would form the basis and rational to continue research on fabricating 3D cell-encapsulated scaffolds for specific applications.

Tissue-engineering (TE) is one of the most innovative approaches for tackling many diseases and body parts that need to be replaced, by developing artificial tissues and organs. For this, tissue scaffolds play an important role in various TE applications. A tissue scaffold is a 3D (3D) structure with interconnected pore networks and used to facilitate cell growth and transport of nutrients and wastes while degrading gradually itself. Many fabrication techniques have been developed recently for incorporating living cells into the scaffold fabrication process and among them; dispensing-based rapid prototyping techniques have been drawn considerable attention due to its fast and efficient material processing. This research is aimed at conducting a preliminary study on the dispensing-based biofabrication of 3D cell-encapsulated alginate hydrogel scaffolds. Dispensing-based polymer deposition system was used to fabricate 3D porous hydrogel scaffolds. Sodium alginate was chosen and used as a scaffolding biomaterial. The influences of fabrication process parameters were studied. With knowledge and information gained from this study, 3D hydrogel scaffolds were successfully fabricated. Calcium chloride was employed as crosslinker in order to form hydrogels from alginate solution. The mechanical properties of formed hydrogels were characterized and examined by means of compressive tests. The influences of reagent concentrations, gelation time, and gelation type were studied. A post-fabrication treatment was used and characterized in terms of strengthening the hydrogels formed. In addition, the influence of calcium ions used as crosslinker on cell viability and proliferation during and after the dispensing fabrication process was examined and so was the influence of concentration of calcium solutions and exposing time in both media and alginate hydrogel. The study also showed that the density of encapsulated cells could affect the viscosity of alginate solution. In summary, this thesis presents a preliminary study on the dispensing-based biofabrication of 3D cell-encapsulated alginate hydrogel scaffolds. The results obtained regarding the influence of various factors on the cell viability and scaffold fabrication would form the basis and rational to continue research on fabricating 3D cell-encapsulated scaffolds for specific applications.

Electron-impact ionization of low-temperature water ice leads to H+, H2+, and H+(H2O)n=1-8 desorption. The threshold energy for ESD of H2+ from CI and H3O+ from PASW and ASW is 22 ± 3 eV. There is also a H2+ yield increase at 40 ± 3 eV and a 70 ± 3 eV threshold for ESD of H+(H2O)n=2-8 from PASW and ASW. H2+ production and desorption involves direct molecular elimination and reactive scattering of an energetic proton. Both of these channels likely involve localized two-hole one-electron and/or two-hole final states containing 4a1, 3a1 and/or 2a1 character. The 70 eV cluster ion threshold implicates either an initial (2a1-2) state localized on a monomer or the presence of at least two neighboring water molecules each containing a single hole. The resulting correlated two-hole or two-hole, one-electron configurations are localized within a complex and result in an intermolecular Coulomb repulsion and cluster ion ejection. The changes in the yields with phase and temperature are associated with structural and physical changes in the adsorbed water and longer lifetimes of excited state configurations containing a1 character. The dependence of the ESD cation yields on the local potential has been utilized to examine the details of HCl interactions on low temperature ice surfaces. The addition of HCl increases cluster ion yields from pure ice while decreasing H+ and H2+ yields. These changes reflect the changes in the local electronic potential due to the changing bond lengths at the surface of the ice as HCl ionizes and the surrounding water molecules reorient to solvate the ions. This work has been extended to ionic solutions at higher temperatures using a liquid jet and ultraviolet photoionization to interrogate the surface of aqueous ionic interfaces. Desorption of protonated water clusters and solvated sodium ion clusters were measured over a range of concentrations from NaCl, NaBr, and NaI solutions. The flux dependence indicated a multiple photon process and the proposed mechanism involves a Coulomb explosion resulting from the repulsion of nearby ions. The surface is investigated with regard to its importance in heterogeneous atmospheric chemistry.

Soybean oil, palm oil and waste cooking oil as feedstock were used to measure the effects of different heating methods, reaction time, molar ratio of methanol to oil, temperature, power, catalyst type and catalyst concentration on the biodiesel yield in this study. Additionally, reducing reaction time for the transesterification reaction used microwave heating to make more complete. The optimized operating conditions of conventional heating used palm oil, concentration for 0.75 wt% sodium methoxide, molar ratio of methanol to oil for 6:1, reaction time for 90 min and reaction temperature for 60 ¢J offered the best yield of 98.1%. the microwave heating used palm oil, concentration for 0.75 wt% sodium methoxide, molar ratio of methanol to oil for 6:1, reaction time for 3 min and power for 750 W offered the best yield of 99.5% Used soybean oil and palm oil as biodiesel feedstock production, its yield was higher than the waste cooking oil. This reason is caused by composition complex and high viscosity of waste cooking oil compare with pure vegetable oil. The catalyst of sodium methoxide is higher effective than sodium oxide used in transesterification reaction, because the reaction process will not formation of water and saponification. Use ionic liquid [Pyr12CN][Cl], [MorEtH][HSO4], [MorMeMe][MeSO4], [PyrMeH][HSO4] and [MorMeEt][EtSO4] as biodiesel catalyst, the optimized operating conditions of concentration for 2.00 wt% [Pyr12CN][Cl], molar ratio of methanol to oil for 6:1, reaction time for 6 min and power for 750 W offered the best yield of 98.1%.

Articulated rigid-rod polymers asPBI were synthesized via polycondensation reaction. Using 2-sulfoterephthalic acid and 5-sulfoisophthalic acid in different ratios for copolycondensation reaction making the fully conjugated rigid-rod backbone became articulated. Both rigid-rod and articulated rigid-rod were further derivatized using alkane sulfonated pendants and became water-soluble rigid-rod and articulated rigid-rod polyelectrolytes. Lithium salt doped cast films of the polyelectrolytes showed a root-temperature DC conductivity parallel to film surface (

In this study, we measured the binding constant, KCOC, between several humic acids and benzo(h)quinoline, a nitrogen contained PAHs via using fluorescence quenching method. KCOC of humic acids and phenanthrene, a parent PAHs, is also studied in comparison. Moreover, pH and ionic strength effect on the KCOC were investigated. According to our results, the phenanthrene¡¦s KCOC decreases as the pH increases due to the lower hydrophobicity of humic acid in higher pH values. The variation of benzo(h)quinoline¡¦s KCOC with pH exhibits a more complicated trend, with a maximum value at pH close to the pKb of benzo(h)quinoline. For pH lower than pKb, benzo(h)quinoline is protonated to be benzo(h)quinolinium, a cation, so that the ionic exchange is the dominant prosess in sorption mechanism. Therefore, the binding sites of humic acid increase with pH such that the KCOC increases with pH. In contrast, different mechanism involved in the binding for pH higher than pKb, neutral benzo(h)qunoline becomes dominant and hydrophobic interaction controls the binding prosess in sorption mechanism. At last, the composition of different functional groups of humic acid is also found significant in the binding affinity of benzo(h)qunoline or phenanthrene. Moreover, the benzo(h)qunoline¡¦s KCOC exhibits decreasing trend with increasing magnesium ionic strength because of the reduction of molecular size as well as the benzo(h)qunoline binding sites of humic acid. Findings from this study could provide valuable information for numerical simulation of transport and fates of HOPs in aquatic environment.

ABSTRACT Hydrophobic organic pollutants (HOPs) are in general characterized by high toxicity, long environmental half-life and high bio-accumulation factors. Due to their hydrophobicity, HOPs tend to sorb onto particles in environment. The influence of the dissolved organic matters (DOMs) on the sorption partition coefficient is observed because of their interactions with HOPs. This binding between DOM and HOPs increases apparent solubility and mobility of the HOPs in natural aquatic system. On the purpose of obtaining data closer to the real world, many aquatic factors, such as the concentration and types of DOM, pH value and ionic strength, are studied intensively recently. There are many studies about the mechanisms in the association of DOM and HOPs. Most of them assume achievement of equilibrium in their measurement. Recently, it was reported (Engebretson and von Wandruszka, 1998) that slow, revering, and even oscillating kinetics are observed. It is great concern and interest to those related studies in literatures. Complicated kinetic may in fact be a cause of the reproducibility problems for measurements of HOPs associated with both humic acid and metals. As such, by monitoring fluorescence intensity, we investigate the equilibrium kinetic of pyrene in HA solutions. In this study, results show that there are two stages of the fluorescence intensity after pyrene spiked into HA solutions: First, the fluorescence intensity decreases steeply due to the first dispersion of pyrene and the reaction of pyrene and HA (the front is dominance). Secound, fluorescence intensity decreases gently because of wall-effect. The dispersion rate of pyrene in HA solutions is difference with HA molecular size and quantity. As the ionic strength rising, cations reacting with specific binding sites on HA, the molecules¡¦ configuration of HA is changed, and less obstruct for dispersing of pyrene. It works as well as little molecular quantity. For second stage when ionic strength rising, wall- associations is less because of the hydrophobic-binding of pyrene and LHA is more stronger. Furthermore, it is not observed the ¡§migration¡¨ of Mg2+ within the LHA molecular structure as described by Engebretson and von Wandruszka .The reasons that make different results may depend on the species of humic acid. Therefore, the observations of Engebretson and von Wandruszka could not be used directly questioning those results in literatures. In addition, the effects of various cations (Mg2+, Ca2+and Sr2+) on Kdom are studied. It is believed different cation reacts with different specific binding sites on HA. As such, both charge density and affinity of cation with specific binding sites on HA should be considered in discussing the effects of metal ionic on the binding constants between PAHs and DOM.