A study on the diffusion of quinhydrone in polymer electrolyte

The diffusion coefficients (D) of quinhydrone were estimated in polymer electrolytes by using non-steady-state chronoamperometry and steady-state current voltammetry. The D values have been estimated in polyethylene glycol (PEG) containing different concentrations, and cations of supporting electrolytes, and in different solvents over a range of temperatures. The dependencies of electroactive probe diffusion coefficients on temperature, supporting electrolyte concentration and polymer chain length are discussed. The results show that D increases with increasing temperature and decreasing concentration of supporting electrolyte. The diffusion coefficient depends strongly on the length of polymer chain and decreases sharply with increasing polymer chain length. The contribution of electron self-exchange has been explored and it seems to be negligible here. (C) 1998 Elsevier Science S.A.

THE APPLICATION OF THE MPB4 THEORY TO THE INTERFACE BETWEEN 2 IMMISCIBLE ELECTROLYTE-SOLUTIONS .2. THE DIFFERENTIAL CAPACITANCE OF THE WATER 1,2-DICHLOROETHANE INTERFACE

The MPB4 theory is used to calculate the differential capacitance of the interface between LiCl in water and TBATPB in 1,2-dichloroethane at electrolyte concentrations of 0.005, 0.01 and 0.02 M. The effects of the ion size and the image force, and the influence of the electrolyte concentration, the surface charge density and the solvent effect on the inner layer potential drop are considered simultaneously. These effects can be ascribed to the ionic penetration into the opposite solution and ion-ion correlations across the interface. Our results are in better agreement with experimental data than those obtained using Gouy-Chapman theory. This indicates that the MPB4 theory may also describe the structure of the water \1,2-dichloroethane interface provided that the influence of the electrolyte concentration, the surface charge density and the solvent effect on the inner layer potential distribution are included in the calculation. Comparison of the theoretical results with those of the water \nitrobenzene interface shows that the structure of the water \1,2-dichloroethane interface is similar to that of the water \nitrobenzene interface, except that in the former case the inner-layer potential drop is much higher and the effects of the image force and the ion size are more pronounced.

On-line concentration of proteins in pressurized capillary electrochromatography coupled with electrospray ionization-mass spectrometry

Pressurized capillary electrochromatography (pCEC) and electrospray ionization-mass spectrometry (ESI-MS) have been hyphenated for protein analysis. Taken cytochrome c, lysozyme, and insulin as samples, the limits of detection (LODs) for absolute concentrations are 10(-11) mol (signal-to-noise ratio S/N = 3) with relative standard deviations (RSDs) of retention time and peak area, respectively, of less than 1.7% and 4.8%. In order to improve the detection sensitivity, on-line concentration by field-enhanced sample-stacking effect and chromatographic zone-sharpening effect has been developed, and parameters affecting separation and detection, such as pH and electrolyte concentration in the mobile phase, separation voltage, as well as enrichment voltage and time, have been studied systematically. Under the optimized conditions, the LODs of the three proteins could be decreased up to 100-fold. In addition, the feasibility of such techniques has been further demonstrated by the analysis of modified insulins at a concentration of 20 mu g/mL.

Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.

Application of Microelectrode Voltammetry to Study the Properties of Surfactant Solutions: Alkyltrimethylammonium Bromides

Microelectrode cyclic voltammetry (MV) has been employed to investigate the micellar properties of solutions of homologous alkyltrimethylammonium bromides, RMe(3)ABr, R = C(10), C(12), and C(14), in water and in the presence of added NaBr. The micellar self-diffusion coefficient was calculated from the limiting current for the reversible electron transfer of micelle-bound ferrocene. From the values of this property, other parameters were calculated, including the micellar hydrodynamic radius, RH, and aggregation number, N(agg); the latter was also theoretically calculated. We determined the values of the diffusion coefficient as a function of various experimental variables and observed the following trends: The diffusion coefficient decreases as a function of increasing surfactant concentration (no additional electrolyte added); it decreases as a function of increasing surfactant concentration at fixed NaBr concentration; and it shows a complex dependence (increase then decrease) on the NaBr concentration at a fixed RMe(3)ABr concentration. The value of the intermicellar interaction parameter decreases and then increases as a function of increasing NaBr concentration. These results are discussed in terms of intermicellar,interactions and the effect of NaBr on the micellar surface charge density and sphere-to-rod geometry change. The NaBr concentration required to induce the latter change increases rapidly as a function of decreasing the length of R: no geometry change was detected for C(10)Me(3)ABr. Values of N(agg) increase as I function of increasing the length of R and are in good agreement with both literature values and values that were calculated theoretically. Thus, MV is a convenient and simple technique for obtaining fundamental properties of surfactant solutions, including additive-induced changes of micellar parameters (N(agg)) and morphology changes.

Forces measured between latex spheres in aqueous electrolyte : Non-DLVO behavior and sensitivity to dissolved gas

An atomic force microscope was used to measure the forces acting between two polystyrene latex spheres in aqueous media. The results show an electrostatic repulsion at large separations which is overtaken by an attractive “hook” that pulls the two spheres into contact from a considerable range (20−400 nm), much larger than could be expected for a van der Waals attraction. The range of operation of this attraction varies from one experiment to another and is not correlated with electrolyte concentration. However, the range is found to decrease significantly when the level of dissolved gas in the water is reduced.

Stability of aqueous films between bubbles. Part 1. The effect of speed on bubble coalescence in purified water and simple electrolyte solutions

Film thinning experiments have been conducted with aqueous films between two air phases in a thin film pressure balance. The films are free of added surfactant but simple NaCl electrolyte is added in some experiments. Initially the experiments begin with a comparatively large volume of water in a cylindrical capillary tube a few millimeters in diameter, and by withdrawing water from the center of the tube the two bounding menisci are drawn together at a prescribed rate. Thismodels two air bubbles approaching at a controlled speed. In pure water, the results show three regimes of behavior depending on the approach speed; at slow speed (<1 μm/s) it is possible to form a flat film of pure water, ∼100 nm thick, that is stabilized indefinitely by disjoining pressure due to repulsive double-layer interactions between naturally charged air/water interfaces. The data are consistent with a surface potential of -57mV on the bubble surfaces. At intermediate approach speed (∼1-150 μm/s), the films are transiently stable due to hydrodynamic drainage effects, and bubble coalescence is delayed by ∼10-100 s. At approach speeds greater than ∼150 μm/s, the hydrodynamic resistance appears to become negligible, and the bubbles coalesce without any measurable delay. Explanations for these observations are presented that take into account Derjaguin-Landau-Verwey-Overbeek and Marangoni effects entering through disjoining pressure, surface mobility, and hydrodynamic flow regimes in thin film drainage. In particular, it is argued that the dramatic reduction in hydrodynamic resistance is a transition from viscosity-controlled drainage to inertia-controlled drainage associated with a change from immobile to mobile air/water interfaces on increasing the speed of approach of two bubbles. A simple model is developed that accounts for the boundaries between different film stability or coalescence regimes. Predictions of the model are consistent with the data, and the effects of adding electrolyte can be explained. In particular, addition of electrolyte at high concentration inhibits the near-instantaneous coalescence phenomenon, thereby contributing to increased foam film stability at high approach speeds, as reported in previous literature. This work highlights the significance of bubble approach speed as well as electrolyte concentration in affecting bubble coalescence.

Preparação e caracterização de coacervatos e vidros a base de fosfato, dopados com európio

Pós-graduação em Química - IQ

Eutectic grain size and strontium concentration in hypoeutectic aluminium-silicon alloys

Recently it has been shown that modification with strontium causes an increase in the size of eutectic grains. The eutectic grain size increases because there are fewer nucleation events, possibly due to the poisoning of phosphorus-based nuclei that are active in the unmodified alloy. The current paper investigates the effect of strontium concentration on the eutectic grain size. In the aluminium-10 wt.% silicon alloy used in this research, for fixed casting conditions, the eutectic grain size increases as the strontium concentration increases up to approximately 150ppm, beyond which the grain size is relatively stable. This critical strontium concentration is likely to differ depending on the composition of the base alloy, including the concentration of minor elements and impurities. It is concluded that processing and in-service properties of strontium modified aluminium-silicon castings are likely to be more stable if a minimum critical strontium concentration is exceeded. If operating below this critical strontium concentration exceptional control over composition and casting conditions is required. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis of discrete allyl-functional polyethylene glycol for efficient hydrophilization of dihydr (polydimethylsiloxane)

Amphiphilic poly(ethylene glycol)-block-pol (dimethylsiloxane)-block-poly(ethylene glycol)(PEG-block-PDMS block-PEG) triblock copolymers have been successfully prepared via hydrosilylation using discrete and polydisperse PEG of various chain lengths. Facile synthesis of discrete PEG (dPEG) is achieved via systematic tosylation and etherification of lower glycols. Amphiphilicity of the dPEG block-PDMS-block-dPEG triblock copolymer is illustrated by dynamic light scattering (DLS) and measurement of the critical micelle concentration (CMC).

Morphology changes and mechanistic aspects of the electrochemically-induced reversible solid-solid transformation of microcrystalline TCNQ into Co TCNQ 2-based materials (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane)

The chemically reversible solid−solid phase transformation of a TCNQ-modified glassy carbon, indium tin oxide, or metal electrode into Co\[TCNQ]2(H2O)2 material in the presence of Co2+(aq) containing electrolytes has been induced and monitored electrochemically. Voltammetric data reveal that the TCNQ/Co\[TCNQ]2(H2O)2 interconversion process is independent of electrode material and identity of cobalt electrolyte anion. However, a marked dependence on electrolyte concentration, scan rate, and method of electrode modification (drop casting or mechanical attachment) is found. Cyclic voltammetric and double potential step chronoamperometric measurements confirm that formation of Co\[TCNQ]2(H2O)2 occurs through a rate-determining nucleation and growth process that initially involves incorporation of Co2+(aq) ions into the reduced TCNQ crystal lattice at the TCNQ|electrode|electrolyte interface. Similarly, the reverse (oxidation) process, which involves transformation of solid Co\[TCNQ]2(H2O)2 back to parent TCNQ crystals, also is controlled by nucleation−growth kinetics. The overall chemically reversible process that represents this transformation is described by the reaction:  2TCNQ0(s) + 2e- + Co2+(aq) + 2H2O \[Co(TCNQ)2(H2O)2](s). Ex situ SEM images illustrated that this reversible TCNQ/Co\[TCNQ]2(H2O)2 conversion process is accompanied by drastic size and morphology changes in the parent solid TCNQ. In addition, different sizes of needle-shaped nanorod/nanowire crystals of Co\[TCNQ]2(H2O)2 are formed depending on the method of surface immobilization.

Plasmonic Ag nanoparticles via environment-benign atmospheric microplasma electrochemistry

Atmospheric-pressure microplasma-assisted electrochemistry was used to synthesize Ag nanoparticles (NPs) for plasmonic applications. It is shown that the size and dispersion of the nanoparticles can be controlled by variation of the microplasma-assisted electrochemical process parameters such as electrolyte concentration and temperature. Moreover, Ag NP synthesis is also achieved in the absence of a stabilizer, with additional control over the dispersion and NP formation possible. As the microplasma directly reduces Ag ions in solution, the incorporation of toxic reducing agents into the electrolytic solution is unnecessary, making this an environmentally friendly fabrication technique with strong potential for the design and growth of plasmonic nanostructures for a variety of applications. These experiments therefore link microplasma-assisted electrochemical synthesis parameters with plasmonic characteristics.

Growth responses of sugarcane to mycorrhizal spore density and phosphorus rate

Arbuscular mycorrhizal (AM) fungi, commonly found in long-term cane-growing fields in northern Queensland, are linked with both negative and positive growth responses by sugarcane (Saccharum spp.), depending on P supply. A glasshouse trial was established to examine whether AM density might also have an important influence on these growth responses. Mycorrhizal spores (Glomus clarum), isolated from a long-term cane block in northern Queensland, were introduced into a pasteurised low-P cane soil at 5 densities (0, 0.06, 0.25, 1, 4 spores/g soil) and with 4 P treatments (0, 8.2, 25, and 47 mg/kg). At 83 days after planting, sugarcane tops responded positively to P fertilizer, although responses attributable to spore density were rarely observed. In one case, addition of 4 spores/g led to a 53% yield response over those without AM at 8 mgP/kg, or a relative benefit of 17 mg P/kg. Root colonisation was reduced for plants with nil or 74 mg P/kg. For those without AM, P concentration in the topmost visible dewlap (TVD) leaf increased significantly with fertiliser P (0.07 v. 0.15%). However, P concentration increased further with the presence of AM spores. Irrespective of AM, the critical P concentration in the TVD leaf was 0.18%. This study confirms earlier reports that sugarcane is poorly responsive to AM. Spore density, up to 4 spores/g soil, appears unable to influence this responsiveness, either positively or negatively. Attempts to gain P benefits by increasing AM density through rotation seem unlikely to lead to yield increases by sugarcane. Conversely, sugarcane grown in fields with high spore densities and high plant-available P, such as long-term cane-growing soils, is unlikely to suffer a yield reduction from mycorrhizal fungi.

Soil phosphorus–crop response calibration relationships and criteria for winter cereal crops grown in Australia

Soil testing is the most widely used tool to predict the need for fertiliser phosphorus (P) application to crops. This study examined factors affecting critical soil P concentrations and confidence intervals for wheat and barley grown in Australian soils by interrogating validated data from 1777 wheat and 150 barley field treatment series now held in the BFDC National Database. To narrow confidence intervals associated with estimated critical P concentrations, filters for yield, crop stress, or low pH were applied. Once treatment series with low yield (<1 t/ha), severe crop stress, or pHCaCl2 <4.3 were screened out, critical concentrations were relatively insensitive to wheat yield (>1 t/ha). There was a clear increase in critical P concentration from early trials when full tillage was common compared with those conducted in 1995–2011, which corresponds to a period of rapid shift towards adoption of minimum tillage. For wheat, critical Colwell-P concentrations associated with 90 or 95% of maximum yield varied among Australian Soil Classification (ASC) Orders and Sub-orders: Calcarosol, Chromosol, Kandosol, Sodosol, Tenosol and Vertosol. Soil type, based on ASC Orders and Sub-orders, produced critical Colwell-P concentrations at 90% of maximum relative yield from 15 mg/kg (Grey Vertosol) to 47 mg/kg (Supracalcic Calcarosols), with other soils having values in the range 19–27 mg/kg. Distinctive differences in critical P concentrations were evident among Sub-orders of Calcarosols, Chromosols, Sodosols, Tenosols, and Vertosols, possibly due to differences in soil properties related to P sorption. However, insufficient data were available to develop a relationship between P buffering index (PBI) and critical P concentration. In general, there was no evidence that critical concentrations for barley would be different from those for wheat on the same soils. Significant knowledge gaps to fill to improve the relevance and reliability of soil P testing for winter cereals were: lack of data for oats; the paucity of treatment series reflecting current cropping practices, especially minimum tillage; and inadequate metadata on soil texture, pH, growing season rainfall, gravel content, and PBI. The critical concentrations determined illustrate the importance of recent experimental data and of soil type, but also provide examples of interrogation pathways into the BFDC National Database to extract locally relevant critical P concentrations for guiding P fertiliser decision-making in wheat and barley.