Influence of electroosmotic treatment on the hydro-mechanical behaviour of clayey silts: preliminary experimental results

Preliminary results of an investigation focused on the influence of electrokinetic treatment on the mechanical and hydraulic behaviour of clayey soils are presented. The experimental programme aims at providing a contribution to the sustainability of contaminant extraction or containment via electroosmosis. Changes in the hydraulic and mechanical properties of two illitic clayey soils, subjected to a DC electric field, were investigated. Samples of the two soils were subjected to electrokinetic filtration, for different periods of time, and under different constant loads. Afterwards, they were tested under one-dimensional compression to detect changes in stiffness and hydraulic conductivity due to the electrical treatment. After the application of a DC field for a few hours, a small reversible increment in the average soil stiffness was observed, with respect to the untreated soil, while the hydraulic conductivity was not affected substantially. Dramatic changes of the mechanical and hydraulic soil properties, correlated to changes of the soil pH, were observed following non-conditioned electrokinetic treatment with duration of the order of days.     

Synthesis and aqueous solution behaviors of sodium sulfonate‐terminated dendritic poly(ester‐amine)

Sodium sulfonate‐terminated dendritic poly(ester‐amine) (SPEA) was synthesized by sulfonation of acrylic double bond‐terminated dendritic poly(ester‐amine) (APEA) with sodium hydrogen sulfite (NaHSO₃) in mixture of diglycol and 2‐butanone under normal pressure. The structure of SPEA was characterized by IR, ¹H‐NMR, and elemental analysis. SPEA was water‐soluble. 1.0–40.0% (mass) SPEA aqueous solutions appeared as dilatant fluid. When pH value varied from 1.5 to 12.0, the viscosity of 1–5% (mass) SPEA aqueous solutions changed very small, and the electric conductivity almost kept stable within pH 3.0–10.0. The relationship between the viscosity and the concentration of SPEA water solutions was similar to that of NaCl water solutions. The surface tension of SPEA water solutions was lower than that of polyethylene glycol 2000 water solutions with the same concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A disposable sensor based on immobilization of acetylcholinesterase to multiwall carbon nanotube modified screen-printed electrode for determination of carbaryl

A simple method has been devised for immobilization of acetylcholinesterase (AChE) covalent bonding to a multiwall carbon nanotube (MWNT)-cross-linked cellulose acetate composite on a screen-printed carbon electrode (SPCE) and a sensitive and disposable amperometric sensor for rapid determination of carbaryl pesticide is proposed. The immobilized enzyme was preserved on this film because of the excellent biocompatibility and non-toxicity of cellulose acetate. Based on the inherent conductive properties of the MWNT, the immobilized AChE had greater affinity for ATCl and excellent catalytic effect in the hydrolysis of ATCl. MWNT improved the interface enzymatic hydrolysis reaction and increased the amperometric response of the sensor. Under optimum conditions, the inhibition of carbaryl on AChE increased linearly with the increasing concentration of carbaryl in two ranges, from 0.01 to 0.5 μg mL⁻¹ and from 2 to 20 μg mL⁻¹, with the correlation coefficients of 0.9985 and 0.9977, respectively. The detection limit was 0.004 μg mL⁻¹ taken as the concentration equivalent to 10% decrease in signal. The sensor showed acceptable stability, accuracy and could be fabricated in batches, thus it is economic and portable. This type of disposable enzyme-based amperometric sensor has extensive application potential in environmental monitoring of pesticides.     

Influence of pencil lead hardness on voltammetric response of graphite reinforcement carbon electrodes

This work studied the voltammetric response of graphite reinforcement electrodes made of different pencil lead hardness. The studies showed that harder graphite leads, regardless of their manufacturer, are more appropriate as electrode material for voltammetric purposes due to their higher peak currents, increasing sensitivity and reproducibility, with ΔEp closer to the theoretical value for a reversible system.     

FEM model of the ohmic resistance of IP-SOFCs

In the present work, the ohmic resistance of an integrated planar-SOFC (IP-SOFC) has been evaluated by developing a model whose equations have been solved numerically through an FEM method. The model allows to estimate the distribution of voltage and current density in the cell. A comparison between simulated and experimental data of area specific resistance is reported, which shows satisfactory agreement. The mathematical model has also been used to carry out some parametric studies for optimisation purposes. Indeed, a reduction in cell pitch length and an increase in electrode thickness are predicted to lead to a reduction in ohmic losses in IP-SOFCs.     

Molecular packing and phase transitions of side-chain liquid crystalline polymethacrylates based on p-methoxyazobenzene

The phase structures and transition behaviors of a series of side-chain liquid crystalline (LC) polymethacrylates based on p-methoxyazobenzene (PMnAzs, n = 6, 8, 10, 12) were studied using differential scanning calorimetry, one- and two-dimensional (1D and 2D) wide-angle X-ray diffraction, and Fourier transform infrared spectroscopic experiments. The LC phase transition of PMnAz follows the sequence of smectic A (SmA) ? nematic (N) ? isotropic (I). For PM10Az and PM12Az, the transition of SmA-to-N is not complete upon heating. In the low-temperature SmA phase, the polymers adopt a fully interdigitated side-chain packing with the smectic layer period almost identical to the side-chain length. For all the four samples, the first-order diffraction of the SmA structure only renders when the temperature approaches the transition of SmA ? N, with the intensity much lower than that of the second-order diffraction. The absence of the first-order diffraction at low temperatures is ascribed to the possible matching of the electron densities between the center portion of the side-chain sublayer and the main-chain sublayer of the SmA structure. Since only the mesogens from the same main-chain sublayer can stack parallel together, the distribution of the azobenzene domains may cause some sort of density undulation within the smectic layer. Among the samples, PM6Az presents the strongest undulation with some additional orders. We also examined the annealing effect on the H-aggregation of PMnAzs. It is found that isothermal annealing at a temperature slightly higher than the T_g of PM8Az and PM10Az can significantly enhance the UV absorption at 326 nm, indicating a further development of H-aggregation. However, for PM6Az and PM12Az, the UV–vis spectrum of the annealed sample is nearly identical to that without annealing.     

Synthesis and characterization of novel copolymer containing pyridylazo-2-naphthoxyl group via reversible addition–fragmentation chain transfer (RAFT) polymerization

A novel monomer containing pyridylazo-2-naphthoxyl group, 1-(1-(4-vinylbenzyloxy)naphthalen-2-yl)-2-(pyridin-2-yl)diazene (VBNPA), was successfully synthesized and copolymerized with styrene (St) in N,N-dimethyl formamide (DMF) via reversible addition–fragmentation chain transfer (RAFT) polymerization using 2-cyanoprop-2-yl-1-dithionaphthalate (CPDN) as RAFT agent. The polymerization behavior exhibited “living”/controlled characters. The obtained copolymer, poly(St-co-VBNPA), with pre-determinable molecular weight and narrow molecular weight distribution can be used as a carrier in metal ion detection and analysis via pre-concentration technique. The copolymer–metal ion (copper (Cu) and europium (Eu)) complexes were prepared and characterized.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

A strategy for the electro-organic synthesis of new hydrocaffeic acid derivatives

Electrochemical treatment processes can significantly contribute to the protection of the environment through the minimization of waste and toxic materials in effluents. From a pharmaceutical point of view and due to the existing resemblance between the electrochemical and biological reactions, it can be assumed that the oxidation mechanisms on the electrode and in the body share similar principles. In this paper, the application of electrochemical studies in the design of an environmentally friendly method was delineated for the new hydrocaffeic acid (HCA, 3,4-dihydroxy hydrocinnamic acid) derivatives synthesis at carbon electrodes in an undivided cell. In this cell, the EC mechanism reaction was involved, comprising two steps alternatively; (1) electrochemical oxidation and (2) chemical reaction. In particular, the electro-organic reactions of HCA, an important biological molecule, were studied in a water–acetonitrile (90:10 v/v) mixture in the presence of benzenesulfinic acid (3) and p-toluenesulfinic acid (4). The research included the use of a variety of experimental techniques, such as cyclic voltammetry, controlled-potential electrolysis and product spectroscopic identification.     

NiCoFe/C cathode electrocatalysts for direct ethanol fuel cells

A direct ethanol fuel cell (DEFC), which is less prone to ethanol crossover, is reported. The cell consists of PtRu/C catalyst as the anode, Nafion^® 117 membrane, and Ni–Co–Fe (NCF) composite catalyst as the cathode. The NCF catalyst was synthesized by mixing Ni, Co, and Fe complexes into a polymer matrix (melamine-formaldehyde resins), followed by heating the mixture at 800 °C under inert atmosphere. TEM and EDX experiments suggest that the NCF catalyst has alloy structures of Ni, Co and Fe. The catalytic activity of the NCF catalyst for the oxygen reduction reaction (ORR) was compared with that of commercially available Pt/C (CAP) catalyst at different ethanol concentrations. The decrease in open circuit voltage (V_oc) of the DEFC equipped with the NCF catalysts was less than that of CAP catalyst at higher ethanol concentrations. The NCF catalyst was less prone to ethanol oxidation at cathode even when ethanol crossover occurred through the Nafion^®117 film, which prevents voltage drop at the cathode. However, the CAP catalyst did oxidize ethanol at the cathode and caused a decrease in voltage at higher ethanol concentrations.