Impedance characteristics of the diamond/carbon fiber electrodes for electrical double-layer capacitor

The electrochemical performance of carbon fibers (CF) and boron-doped diamond electrodes grown on carbon fiber substrate (BDD/CF) was studied. CF substrates were obtained from polyacrylonitrile precursor heat treated at two different temperatures of 1000 and 2000 degrees C to produce the desirable CF carbon graphitization index. This graphitization process influenced the CF conductivity and its chemical surface, also analyzed from X-ray photoelectron spectroscopy measurements. These three-dimensional CF structures allowed a high incorporation of diamond films compared to other carbon substrates such as glass carbon or HOPG. The electrochemical responses, from these four classes of electrodes, were evaluated focusing their application as electrical double-layer capacitors using cyclic voltammetry and impedance measurements. Cyclic voltammetry results revealed that the electrode formed from BDD grown on CF-2000 presented a typical capacitor behavior with the best rectangular shape, compared to those electrodes of CF or BDD/CF-1000. Furthermore, the BDD/CF-2000 electrode presented the lowest impedance, associated to its significant capacitance value of 1940 mu F/cm(2) taking into account the BDD films. This behavior was attributed to the strong dependence between diamond coating texture and the CF graphitization temperature. The largest surface area of BDD/CF-2000 was promoted by its singular film growth mechanism associated to the substrate chemical surface. (c) 2008 Elsevier B.V. All rights reserved.

Molecular dynamics simulation of the spherical electrical double layer of a soft nanoparticle. Effect of the surface and counterion valence

Molecular dynamics simulations were performed to study the ion and water distribution around a spherical charged nanoparticle. A soft nanoparticle model was designed using a set of hydrophobic interaction sites distributed in six concentric spherical layers. In order to simulate the effect of charged functionalyzed groups on the nanoparticle surface, a set of charged sites were distributed in the outer layer. Four charged nanoparticle models, from a surface charge value of −0.035 Cm−2 to − 0.28 Cm−2, were studied in NaCl and CaCl2 salt solutions at 1 M and 0.1 M concentrations to evaluate the effect of the surface charge, counterion valence, and concentration of added salt. We obtain that Na + and Ca2 + ions enter inside the soft nanoparticle. Monovalent ions are more accumulated inside the nanoparticle surface, whereas divalent ions are more accumulated just in the plane of the nanoparticle surface sites. The increasing of the the salt concentration has little effect on the internalization of counterions, but significantly reduces the number of water molecules that enter inside the nanoparticle. The manner of distributing the surface charge in the nanoparticle (uniformly over all surface sites or discretely over a limited set of randomly selected sites) considerably affects the distribution of counterions in the proximities of the nanoparticle surface.

Comparing the concentration of calcium hydroxide in the diffuse double layer by modeling and experiment

The leaching of elements from the surface of charged fly ash particles is known to be an unsteady process. The mass transfer resistance provided by the diffuse double layer has been quantified as one of the reasons for this delayed leaching. In this work, a model based on mass transfer principles for predicting the concentration of calcium hydroxide in the diffuse double layer is presented. The significant difference between predicted calcium hydroxide concentration and the experimentally measured is explained.

A double layer model of the gas bubble/water interface

Zeta potential is a physico-chemical parameter of particular importance to describe sorption of contaminants at the surface of gas bubbles. Nevertheless, the interpretation of electrophoretic mobilities of gas bubbles is complex. This is due to the specific behavior of the gas at interface and to the excess of electrical charge at interface, which is responsible for surface conductivity. We developed a surface complexation model based on the presence of negative surface sites because the balance of accepting and donating hydrogen bonds is broken at interface. By considering protons adsorbed on these sites followed by a diffuse layer, the electrical potential at the head-end of the diffuse layer is computed and considered to be equal to the zeta potential. The predicted zeta potential values are in very good agreement with the experimental data of H-2 bubbles for a broad range of pH and NaCl concentrations. This implies that the shear plane is located at the head-end of the diffuse layer, contradicting the assumption of the presence of a stagnant diffuse layer at the gas/water interface. Our model also successfully predicts the surface tension of air bubbles in a KCl solution. (c) 2012 Elsevier Inc. All rights reserved.

Role of the surface state and structural feature in the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The sols produced by admixture of ZrOCl2 acidified solutions to hot H2SO4 aqueous solutions were studied to clarify the effects of Cl- and SO42- ions on the kinetic stability of nanoparticles and to obtain some new evidence concerning the mechanism of a thermoreversible sol-gel transition observed in this system. The study of suspensions prepared with different molar ratios R-S = [Zr]/[SO42-] and R-Cl = [Zr]/[Cl-] revealed domains of composition of formation of thermoreversible gels, thermostable sols, and powder precipitation. The effects of R-S and R-Cl on the structural features of nanoparticles and on the particle solution interface were systematically analyzed for samples of thermoreversible and thermostable sol domains. Small-angle X-ray scattering measurements revealed the presence of small fractal aggregates in all samples of thermoreversible domains, while compact packing aggregates of primary particles are present in the thermostable sol. Extended X-ray absorption fine structure and elemental chemical analysis revealed that irrespective of the nominal value of R-S and R-Cl all studied samples of the thermoreversible domain are constituted by a well-defined compound possessing an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded on the surface by complexing sulfate ligands. zeta potentials of powders extracted by freeze-drying from the thermoreversible gel revealed a point of surface charge inversion attributed to the specific adsorption of SO42- ion. Thermoreversible gel formation is rationalized by considering the effect of the specific adsorption on the electrical double-layer repulsion together with the temperature dependency of the physical chemical properties of ions in solution.

STYREENI-BUTADIEENILATEKSIN VALMISTUS EMULSIOPOLYMEROIN-NILLA JA LATEKSIN VISKOSITEETTIIN VAIKUTTAVAT TEKIJÄT.

Työn tavoitteina oli kirjallisuusosassa selvittää emulsiopolymeroinnin perusperiaatteet ja lateksien viskositeettiin vaikuttavat tekijät. Kokeellisessa osassa selvitettiin eräiden kaupallisten lateksien viskositeettiin vaikuttavia tekijöitä. Tutkittujen kaupallisten lateksien viskositeettien riippuvuudelle kuiva-ainepitoisuudesta saatiin tulokset, jotka ovat melko hyvin yhtäpitäviä kirjallisuudesta saatujen tulosten kanssa. Tutkitut lateksit erosivat lähinnä maksimaalisen polymeeripartikkelin tilavuusosuuden kohdalla kirjallisuudesta saaduista arvoista. Tämän todettiin johtuvan sähköisen kaksoiskerroksen ja partikkelin pintaan kiinnittyneiden ryhmien vaikutuksesta. Tämä tulos varmentui elektrolyyttipitoisuuden vaikutusta selvitettäessä. Elektrolyyttilisäys laski lateksien viskositeetteja ja pienensi lateksien välisiä viskositeettieroja. Lateksin pH:n nostolla oli selvästi viskositeettia kasvattava vaikutus. Tämä johtuu osaltaan myös sähköisen kaksoiskerroksen kasvamisesta happoryhmien ionisoituessa. Latekseja toisiinsa verrattaessa havaittiin selkeästi karboksyylihapon ja initiaattorista peräisin olevien happoryhmien määrän vaikutus lateksin viskositeetin muutokselle. Paljon karboksyylihappoa ja initiaattoria sisältävien lateksien viskositeetti muuttui selvästi voimakkaammin pH:n muuttuessa. Latekseissa havaittiin myös ero heikkojen karboksyylihapporyhmien ja vahvojen initiaattorista peräisin olevien happoryhmien ionisoitumisen välillä. Vahvat happoryhmät ionisoituivat matalammassa pH:ssa kuin vahvat ja nostavat näin myös viskositeettia matalammassa pH:ssa kuin karboksyylihapporyhmät. Anionisen emulgaattorin lisäyksellä ei havaittu olevan kovinkaan suurta vaikutusta viskositeettiin. Partikkelikoon vaikutusta voitiin tutkia ainoastaan prosessista saadun mittausaineiston avulla. Partikkelikoon vaikutukset peittyivät suurelta osin muiden tekijöiden alle. Ainoastaan yhdelle lateksityypille saatiin selkeä riippuvuus partikkelikoon ja viskositeetin välille. Riippuvuus noudattaa kirjallisuudesta saatuja tietoja eli partikkelikoon kasvaessa viskositeetti laskee. Myös lateksin viskositeetin riippuvuus käytetystä leikkaus-nopeudesta noudattaa hyvin kirjallisuudesta saatuja tuloksia. Lateksin viskositeetti laskee leikkausnopeuden kasvaessa.

Development of Electrochemical and Fluorescent Sensors

Chemical sensors have growing interest in the determination of food additives, which are creating toxicity and may cause serious health concern, drugs and metal ions. A chemical sensor can be defined as a device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. The chemical information may be generated from a chemical reaction of the analyte or from a physical property of the system investigated. Two main steps involved in the functioning of a chemical sensor are recognition and transduction. Chemical sensors employ specific transduction techniques to yield analyte information. The most widely used techniques employed in chemical sensors are optical absorption, luminescence, redox potential etc. According to the operating principle of the transducer, chemical sensors may be classified as electrochemical sensors, optical sensors, mass sensitive sensors, heat sensitive sensors etc. Electrochemical sensors are devices that transform the effect of the electrochemical interaction between analyte and electrode into a useful signal. They are very widespread as they use simple instrumentation, very good sensitivity with wide linear concentration ranges, rapid analysis time and simultaneous determination of several analytes. These include voltammetric, potentiometric and amperometric sensors. Fluorescence sensing of chemical and biochemical analytes is an active area of research. Any phenomenon that results in a change of fluorescence intensity, anisotropy or lifetime can be used for sensing. The fluorophores are mixed with the analyte solution and excited at its corresponding wavelength. The change in fluorescence intensity (enhancement or quenching) is directly related to the concentration of the analyte. Fluorescence quenching refers to any process that decreases the fluorescence intensity of a sample. A variety of molecular rearrangements, energy transfer, ground-state complex formation and collisional quenching. Generally, fluorescence quenching can occur by two different mechanisms, dynamic quenching and static quenching. The thesis presents the development of voltammetric and fluorescent sensors for the analysis of pharmaceuticals, food additives metal ions. The developed sensors were successfully applied for the determination of analytes in real samples. Chemical sensors have multidisciplinary applications. The development and application of voltammetric and optical sensors continue to be an exciting and expanding area of research in analytical chemistry. The synthesis of biocompatible fluorophores and their use in clinical analysis, and the development of disposable sensors for clinical analysis is still a challenging task. The ability to make sensitive and selective measurements and the requirement of less expensive equipment make electrochemical and fluorescence based sensors attractive.

Numerical Simulation of Electroosmotic Flow with Step Change in Zeta Potential

Electroosmotic flow is a convenient mechanism for transporting polar fluid in a microfluidic device. The flow is generated through the application of an external electric field that acts on the free charges that exists in a thin Debye layer at the channel walls. The charge on the wall is due to the chemistry of the solid-fluid interface, and it can vary along the channel, e.g. due to modification of the wall. This investigation focuses on the simulation of the electroosmotic flow (EOF) profile in a cylindrical microchannel with step change in zeta potential. The modified Navier-Stoke equation governing the velocity field and a non-linear two-dimensional Poisson-Boltzmann equation governing the electrical double-layer (EDL) field distribution are solved numerically using finite control-volume method. Continuities of flow rate and electric current are enforced resulting in a non-uniform electrical field and pressure gradient distribution along the channel. The resulting parabolic velocity distribution at the junction of the step change in zeta potential, which is more typical of a pressure-driven velocity flow profile, is obtained.

Interaction of polysaccharide-protein complex from Agaricus blazei with Langmuir and Langmuir-Blodgett films of phospholipids

The use of natural substances in health applications may be hampered by the difficulties in establishing the mechanisms of action, especially at molecular-level. The protein-polysaccharide complex extracted from the mushroom Agaricus blazei Murill, referred to as CAb, has been considered for treating various diseases with probable interaction with cell membranes. In this study, we investigate the interaction between CAb and a cell membrane model represented by a Langmuir monolayer of dimyristoyl phosphatidic acid (DMPA). CAb affects the structural properties of DMPA monolayers causing expansion and increasing compressibility. In addition, interaction with DMPA polar heads led to neutralization of the electrical double layer, yielding a zero surface potential at large areas per molecule. CAb remained at the interface even at high surface pressures, which allowed transfer of Langmuir-Blodgett (LB) films onto solid supports with the CAb-DMPA mixture. The mass transferred, according to quartz crystal microbalance (QCM) measurements, increased linearly with the number of deposited layers. With UV-vis absorption, fluorescence and FTIR spectroscopies, we confirmed that the LB films contain polysaccharides, proteins and DMPA. Therefore, the CAb biological action must be attributed not only to polysaccharides but also to proteins in the complex. (C) 2008 Elsevier Inc. All rights reserved.

Modelagem Matemática e Computacional de fenômenos eletrocinéticos em meios porosos carregados eletricamente

In this work we present a mathematical and computational modeling of electrokinetic phenomena in electrically charged porous medium. We consider the porous medium composed of three different scales (nanoscopic, microscopic and macroscopic). On the microscopic scale the domain is composed by a porous matrix and a solid phase. The pores are filled with an aqueous phase consisting of ionic solutes fully diluted, and the solid matrix consists of electrically charged particles. Initially we present the mathematical model that governs the electrical double layer in order to quantify the electric potential, electric charge density, ion adsorption and chemical adsorption in nanoscopic scale. Then, we derive the microscopic model, where the adsorption of ions due to the electric double layer and the reactions of protonation/ deprotanaç~ao and zeta potential obtained in modeling nanoscopic arise in microscopic scale through interface conditions in the problem of Stokes and Nerst-Planck equations respectively governing the movement of the aqueous solution and transport of ions. We developed the process of upscaling the problem nano/microscopic using the homogenization technique of periodic structures by deducing the macroscopic model with their respectives cell problems for effective parameters of the macroscopic equations. Considering a clayey porous medium consisting of kaolinite clay plates distributed parallel, we rewrite the macroscopic model in a one-dimensional version. Finally, using a sequential algorithm, we discretize the macroscopic model via the finite element method, along with the interactive method of Picard for the nonlinear terms. Numerical simulations on transient regime with variable pH in one-dimensional case are obtained, aiming computational modeling of the electroremediation process of clay soils contaminated

Structure and dynamics of ionic liquid,electrode interfaces

In the early 20th century, Gouy, Chapman, and Stern developed a theory to describe the capacitance and the spatial ion distribution of diluted electrolytes near an electrode. After a century of research, considerable progress has been made in the understanding of the electrolyte/electrode interface. However, its molecular-scale structure and its variation with an applied potential is still under debate. In particular for room-temperature ionic liquids, a new class of solventless electrolytes, the classical theories for the electrical double layer are not applicable. Recently, molecular dynamics simulations and phenomenological theories have attempted to explain the capacitance of the ionic liquid/electrode interface with the molecular-scale structure and dynamics of the ionic liquid near the electrode. rnHowever, experimental evidence is very limited. rnrnIn the presented study, the ion distribution of an ionic liquid near an electrode and its response to applied potentials was examined with sub-molecular resolution. For this purpose, a new sample chamber was constructed, allowing in situ high energy X-ray reflectivity experiments under potential control, as well as impedance spectroscopy measurements. The combination of structural information and electrochmical data provided a comprehensive picture of the electric double layer in ionic liquids. Oscillatory charge density profiles were found, consisting of alternating anion- and cation-enriched layers at both, cathodic and anodic, potentials. This structure was shown to arise from the same ion-ion correlations dominating the liquid bulk structure that were observed as a distinct X-ray diffraction peak. Therefore, existing physically motivated models were refined and verified by comparison with independent measurements. rnrnThe relaxation dynamics of the interfacial structure upon potential variation were studied by time resolved X-ray reflectivity experiments with sub-millisecond resolution. The observed relaxation times during charging/discharging are consistent with the impedance spectroscopy data revealing three processes of vastly different characteristic time-scales. Initially, the ion transport normal to the interface happens on a millisecond-scale. Another 100-millisecond-scale process is associated with molecular reorientation of electrode-adsorbed cations. Further, a minute-scale relaxation was observed, which is tentatively assigned to lateral ordering within the first layer.

Modelling, simulation and characterization of epithelial cell culture biochip

A microfluidic Organ-on-Chip has been developed for monitoring the epithelial cells monolayer. Equivalent circuit Model was used to determine the electrical properties from the impedance spectra of the epithelial cells monolayer. Black platinum on platinum electrodes was electrochemically deposited onto the surface of electrodes to reduce the influence of the electrical double layer on the impedance measurements. Measurements of impedance with an Impedance Analyzer were done to validate the equivalent circuit model and the decrease of the double layer effect. A Lock-in Amplifier was designed to measure the impedance.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.