Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.

On the electrical conductivity of Ti-implanted alumina

Ion implantation of metal species into insulators provides a tool for the formation of thin, electrically conducting, surface layers with experimenter-controlled resistivity. High energy implantation of Pt and Ti into alumina accelerator components has been successfully employed to control high voltage surface breakdown in a number of cases. In the work described here we have carried out some basic investigations related to the origin of this phenomenon. By comparison of the results of alumina implanted with Ti at 75 keV with the results of prior investigations of polymers implanted with Pt at 49 eV and Au at 67 eV, we describe a physical model of the effect based on percolation theory and estimate the percolation parameters for the Ti-alumina composite. We estimate that the percolation dose threshold is about 4 x 10(16) cm(-2) and the maximum dose for which the system remains an insulator-conductor composite is about 10 x 10(16) cm(-2). The saturation electrical conductivity is estimated to be about 50 S/m. We conclude that the observed electrical conductivity properties of Ti-implanted alumina can be satisfactorily described by percolation theory. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3697900]

From Sample Processing to Quantification: A Full Electrochemical Approach for Neutral Analyte Derivatization, Capillary Electrophoresis Separation, and Contactless Conductivity Detection

A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-(CD)-D-4) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 x 10(-5) mol As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-(CD)-D-4 and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

Quantification of terbinafine in pharmaceutical tablets using capillary electrophoresis with contactless conductivity detection and batch injection analysis with amperometric detection

Terbinafine hydrochloride (TerbHCl) is an allylamine derivative with fungicidal action, especially against dermatophytes. Different analytical methods have been reported for quantifying TerbHCl in different samples. These procedures require time-consuming sample preparation or expensive instrumentation. In this paper, electrochemical methods involving capillary electrophoresis with contactless conductivity detection, and amperometry associated with batch injection analysis, are described for the determination of TerbHCl in pharmaceutical products. In the capillary electrophoresis experiments, terbinafine was protonated and analyzed in the cationic form in less than 1 min. A linear range from 1.46 to 36.4 mu g mL(-1) in acetate buffer solution and a detection limit of 0.11 mu g mL(-1) were achieved. In the amperometric studies, terbinafine was oxidized at +0.85 V with high throughput (225 injection h(-1)) and good linear range (10-100 mu mol L-1). It was also possible to determine the antifungal agent using simultaneous conductometric and potentiometric titrations in the presence of 5% ethanol. The electrochemical methods were applied to the quantification of TerbHCl in different tablet samples; the results were comparable with values indicated by the manufacturer and those found using titrimetry according to the Pharmacopoeia. The electrochemical methods are simple, rapid and an appropriate alternative for quantifying this drug in real samples. (C) 2012 Elsevier B.V. All rights reserved.

Additional scaled solutions to Richards' equation for infiltration and drainage

Warrick and Hussen developed in the nineties of the last century a method to scale Richards' equation (RE) for similar soils. In this paper, new scaled solutions are added to the method of Warrick and Hussen considering a wider range of soils regardless of their dissimilarity. Gardner-Kozeny hydraulic functions are adopted instead of Brooks-Corey functions used originally by Warrick and Hussen. These functions allow to reduce the dependence of the scaled RE on the soil properties. To evaluate the proposed method (PM), the scaled RE was solved numerically using a finite difference method with a fully implicit scheme. Three cases were considered: constant-head infiltration, constant-flux infiltration, and drainage of an initially uniform wet soil. The results for five texturally different soils ranging from sand to clay (adopted from the literature) showed that the scaled solutions were invariant to a satisfactory degree. However, slight deviations were observed mainly for the sandy soil. Moreover, the scaled solutions deviated when the soil profile was initially wet in the infiltration case or when deeply wet in the drainage condition. Based on the PM, a Philip-type model was also developed to approximate RE solutions for the constant-head infiltration. The model showed a good agreement with the scaled RE for the same range of soils and conditions, however only for Gardner-Kozeny soils. Such a procedure reduces numerical calculations and provides additional opportunities for solving the highly nonlinear RE for unsaturated water flow in soils. (C) 2011 Elsevier B.V. All rights reserved.

A direct D-bar reconstruction algorithm for recovering a complex conductivity in 2D

A direct reconstruction algorithm for complex conductivities in W-2,W-infinity(Omega), where Omega is a bounded, simply connected Lipschitz domain in R-2, is presented. The framework is based on the uniqueness proof by Francini (2000 Inverse Problems 6 107-19), but equations relating the Dirichlet-to-Neumann to the scattering transform and the exponentially growing solutions are not present in that work, and are derived here. The algorithm constitutes the first D-bar method for the reconstruction of conductivities and permittivities in two dimensions. Reconstructions of numerically simulated chest phantoms with discontinuities at the organ boundaries are included.

Invariant Solutions of Richards' Equation for Water Movement in Dissimilar Soils

Scaling methods allow a single solution to Richards' equation (RE) to suffice for numerous specific cases of water flow in unsaturated soils. During the past half-century, many such methods were developed for similar soils. In this paper, a new method is proposed for scaling RE for a wide range of dissimilar soils. Exponential-power (EP) functions are used to reduce the dependence of the scaled RE on the soil hydraulic properties. To evaluate the proposed method, the scaled RE was solved numerically considering two test cases: infiltration into relatively dry soils having initially uniform water content distributions, and gravity-dominant drainage occurring from initially wet soil profiles. Although the results for four texturally different soils ranging from sand to heavy clay (adopted from the UNSODA database) showed that the scaled solution were invariant for a wide range of flow conditions, slight deviations were observed when the soil profile was initially wet in the infiltration case or deeply wet in the drainage case. The invariance of the scaled RE makes it possible to generalize a single solution of RE to many dissimilar soils and conditions. Such a procedure reduces the numerical calculations and provides additional opportunities for solving the highly nonlinear RE for unsaturated water flow in soils.

Electrical conductivity of silicate glasses with tetravalent cations substituting Si

The effects of substituting Si by M4+ cations in soda-lime silica glasses were analyzed by impedance spectroscopy in the frequency range of 1 Hz-1 MHz. The glass composition was (mol%) 22Na(2)O center dot 8CaO center dot 65SiO(2)center dot 5MO(2), M = Si, Ti, Ge, Zr, Sn, and Ce. Although the Na+ concentration in the glasses is constant, the Zr-containing glass exhibits the highest dc conductivity and the lowest activation energy, while the Ce-containing glass exhibits the lowest conductivity. The activation energies obtained experimentally agree with those obtained by a theoretical equation proposed by Anderson and Stuart. The differences in electrical conductivity presented by the several M-containing glasses are attributed to the effect that the M4+ ion has on the mobility of the diffusing Na+ ion. (C) 2012 Elsevier B.V. All rights reserved.

Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3)

Glasses in the system [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3) (0.0 <= x <= 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and B-11, P-31, and Na-23 high resolution solid state magic-angle spinning (MAS) NMR techniques. P-31 MAS NMR peak assignments were made by the presence or absence of homonuclear indirect P-31-P-31 spin-spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B-S-P connectivity in the glassy network was quantified by P-31{B-11} and B-11{P-31} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74-, pyrothiophosphate, Na/P = 2:1, units into PS43-, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B S B. Detailed inspection of the B-11 MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2 groups all the way to the fully depolymerized orthothioborate (BS33-) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (T-g) and ionic conductivities can be rationalized. Up to x = 0.4, the dominant process can be described in a simplified way by the net reaction equation P-1 + B-1 reversible arrow P-0 + B-4, where the superscripts denote the number of BS atoms for the respective network former species. Above x = 0.4, all of the thiophosphate units are of the P-0 type and both pyro-(B-1) and orthothioborate (B-0) species make increasing contributions to the network structure with increasing x. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B-S-P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.

Validation and comparison of two soil-vegetation-atmosphere transfer models for tropical Africa

This study aims to compare and validate two soil-vegetation-atmosphere-transfer (SVAT) schemes: TERRA-ML and the Community Land Model (CLM). Both SVAT schemes are run in standalone mode (decoupled from an atmospheric model) and forced with meteorological in-situ measurements obtained at several tropical African sites. Model performance is quantified by comparing simulated sensible and latent heat fluxes with eddy-covariance measurements. Our analysis indicates that the Community Land Model corresponds more closely to the micrometeorological observations, reflecting the advantages of the higher model complexity and physical realism. Deficiencies in TERRA-ML are addressed and its performance is improved: (1) adjusting input data (root depth) to region-specific values (tropical evergreen forest) resolves dry-season underestimation of evapotranspiration; (2) adjusting the leaf area index and albedo (depending on hard-coded model constants) resolves overestimations of both latent and sensible heat fluxes; and (3) an unrealistic flux partitioning caused by overestimated superficial water contents is reduced by adjusting the hydraulic conductivity parameterization. CLM is by default more versatile in its global application on different vegetation types and climates. On the other hand, with its lower degree of complexity, TERRA-ML is much less computationally demanding, which leads to faster calculation times in a coupled climate simulation.

Enhancement of Electrical Conductivity in Plasticized Chitosan Based Membranes

Plasticized natural macromolecules-based polymer electrolyte samples were prepared and characterized. The plasticization of chitosonium acetate with glycerol increased the ionic conductivity value from 3.0 x 10(-7) S/cm to 1.1 x 10(-5) S/cm. The conductivity temperature relationship of the samples exhibits either VTF or Arrhenius type depending on the glycerol concentration in the sample. The dielectric studies evidencing the relaxation process in the plasticized sample at low frequency region are due to the electric polarization effect. Moreover, the samples were transparent in the Vis region, showed thermal stability up to 160 degrees C and good surface uniformity.

Densification and enhancement of the grain boundary conductivity of gadolinium-doped barium cerate by ultra fast flash grain welding

Doped barium cerate is a promising solid electrolyte for intermediate temperature fuel cells as a protonic conductor. However, it is difficult to sinter it to high density at a reasonable temperature. Moreover, it presents a high grain boundary resistivity at intermediate temperatures. Flash grain welding was applied to compacted samples, starting from a temperature of 910 degrees C and applying, for a short time, an ac electric polarization of 40 V, 1000 Hz. At that frequency, the resulting current flows through the grain boundaries promoting a welding via a local Joule heating. A large decrease of the grain boundary resistivity was observed by impedance spectroscopy. Scanning electron microscopy observations of polished and etched surfaces revealed highly sintered regions. Attempts were also made to combine flash grain welding with conventional sintering. (C) 2012 Elsevier Ltd. All rights reserved.

Soil properties in a sugarcane plantation after the application of treated sewage effluent and phosphogypsum in Brazil

In a field experiment performed in Lins County (Sao Paulo State, Brazil), treated sewage effluent (TSE) irrigation increased sugarcane yield but caused an excessive increase in the exchangeable sodium percentage (ESP) and clay dispersion after 16 months due to an intense irrigation regime (2500 mm/16 months) with sodium rich effluents. After two additional complete cycles with lower TSE irrigation rates (1200 mm year(-1)), 1700 kg ha(-1) of phosphogypsum was added to a section of the irrigated plots to evaluate its residence time and its implications on Na+ dynamics and other soil properties. Undisturbed soil cores were taken 2 years after phosphogypsum application to verify soil physical properties up to 0.2 m depth, and disturbed soil samples were taken every year up to 1 m depth for chemical analyses. After 5 years of consecutive TSE irrigation (2005-2010), soil acidity (pH approximate to 5) and basic cations (Ca approximate to 12, Mg approximate to 6 and K approximate to 2 mmol(c) kg(-1)) were maintained in adequate conditions for plant development without the necessity of liming, while acidity was increased (pH approximate to 4.5) and Ca (approximate to 9 mmol(c) kg(-1)), and the Mg (approximate to 4.5 mmol(c) kg(-1)) concentration decreased in the rainfed without phosphogypsum treatment. An increase in water retention capacity at -30 (from 0.14 to 0.17 m(3) m(-3)) and -1500 kPa (from 0.08 to 0.12 m(3) m(-3)) potentials was also observed in all TSE irrigated treatments. The plots with a phosphogypsum treatment showed average increases of 2 mmol(c) kg(-1) of Ca2+ and 7 mg kg(-1) of S-SO42- in all soil profiles and an average reduction of 2 mmol(c) kg(-1) of Na+ up to 0.4 m from 2008 to 2009. However, the extent of the chemical effects was greater after the first year compared to the second year. The high concentration of Na+ found in previous studies performed in the same area returned to low concentrations after continued TSE irrigation at lower rates, even without the phosphogypsum application. An unusual phosphorus migration was observed to the 0.4-0.8 m soil layer as a result of TSE irrigation, most likely due to a high pH and a Na carbonate-dominated TSE. (C) 2012 Elsevier B.V. All rights reserved.

Automated system of seedling image analysis (SVIS) and electrical conductivity to assess sun hemp seed vigor

The development of new procedures for quickly obtaining accurate information on the physiological potential of seed lots is essential for developing quality control programs for the seed industry. In this study, the effectiveness of an automated system of seedling image analysis (Seed Vigor Imaging System - SVIS) in determining the physiological potential of sun hemp seeds and its relationship with electrical conductivity tests, were evaluated. SVIS evaluations were performed three and four days after sowing and data on the vigor index and the length and uniformity of seedling growth were collected. The electrical conductivity test was made on 50 seed replicates placed in containers with 75 mL of deionised water at 25 ºC and readings were taken after 1, 2, 4, 8 and 16 hours of imbibition. Electrical conductivity measurements at 4 or 8 hours and the use of the SVIS on 3-day old seedlings can effectively detect differences in vigor between different sun hemp seed lots.

Hydro-physical characterization of soils under tropical semi-deciduous forest

The study of the hydro-physical behavior in soils using toposequences is of great importance for better understanding the soil, water and vegetation relationships. This study aims to assess the hydro-physical and morphological characterization of soil from a toposequence in Galia, state of São Paulo, Brazil). The plot covers an area of 10.24 ha (320 × 320 m), located in a semi-deciduous seasonal forest. Based on ultra-detailed soil and topographic maps of the area, a representative transect from the soil in the plot was chosen. Five profiles were opened for the morphological description of the soil horizons, and hydro-physical and micromorphological analyses were performed to characterize the soil. Arenic Haplustult, Arenic Haplustalf and Aquertic Haplustalf were the soil types observed in the plot. The superficial horizons had lower density and greater hydraulic conductivity, porosity and water retention in lower tensions than the deeper horizons. In the sub-superficial horizons, greater water retention at higher tensions and lower hydraulic conductivity were observed, due to structure type and greater clay content. The differences observed in the water retention curves between the sandy E and the clay B horizons were mainly due to the size distribution, shape and type of soil pores.