Diclofenac and mefenamic acid are structurally similar non steroidal anti-inflammatory compounds that are challenging to detect simultaneously. Repeated voltammetric cycling conducted on screen printed carbon electrodes under alkaline conditions confirms the emergence of a secondary oxidation peak for both compounds following prior oxidation suggestive of adsorbed oxidation product formation. Tafel analysis and peak width evaluation are consistent with the initial oxidation proceeding through an irreversible one electron transfer pathway followed by a chemical reaction. Dimer formation then occurs on the electrode surface. Electrochemical impedance spectroscopy conducted with a ferri/ferrocyanide redox probe suggests electroactive film formation with comparable interfacial double-layer capacitance and similar reduced charge transfer resistance values for both compounds. Under alkaline conditions the mefenamate film however showed substantially higher pseudocapacitive contributions within the bulk, approximately five times greater than the diclofenac film. Lower deep-film resistance values for the mefenamate film, indicated more efficient ionic transport through the matrix and a more ion-permeable and electrochemically homogeneous structure. Enhanced charge storage and reduced transport limitations for the mefenamate film are consistent with a more hydrated and less sterically constrained film morphology, facilitating ion mobility and redox reactivity. Diclofenac appears to form a more transport-limited film. Differential pulse voltammetry successfully separated the oxidation peaks of the two electroactive films (by almost 80 mV) suggesting that an in-situ electroactive film-based approach is adventitious in discriminating between the two compounds in samples containing both compounds.

The hydrolytic stability of thin poly(ethyl 2-cyanoacrylate), PECA, adhesive films on grit-blasted mild steel substrates was investigated using electrochemical impedance spectroscopy (EIS). Using this novel approach for such adhesive films, the effects of two additives, salicylic acid (SA) and phthalic anhydride (PA), were studied, specifically measuring their influence on polymer film/surface impedance and capacitance changes over a period of 14 days. Results indicate that SA decreased the polymer film hydrolytic stability rapidly, resulting in a substantial drop in impedance modulus from ~10 kΩcm2 to ~10 Ωcm2 at 100 Hz due to electrolyte ingress, whilst the PA-containing film modulus also diminished from ~4 MΩcm2 to ~1 kΩcm2 at 100 Hz. Furthermore, the capacitance values of the SA-containing films rose (up to ~100 µFcm−2), demonstrating the onset of a charge transfer (corrosion) process within the first 12 h exposure to a saline electrolyte. In contrast, the PA-containing film’s transition from a film-dominated capacitance (~0.01 µFcm−2) to a larger double-layer capacitance took (~1 µFcm−2) took several days and was accounted for by differences in the additive’s chemistry, demonstrating the ability of EIS to detect changes in both bulk film (e.g., moisture ingress and bond scission) and metal-film interfacial processes (e.g., onset of corrosion) in real time. Comparison was also made with a standard industry combined tensile test/hydrolytic accelerated ageing regime. Unlike, EIS this did not, however, give useful time-dependent information, although after 6 weeks a decrease in bond strength occurred in the order PA-containing film < PECA< SA-containing film in agreement with the EIS results, thus demonstrating the effectiveness of EIS for monitoring the degradation of such thin film adhesives.

The voltammetric behaviour of diclofenac and mefenamic acid at a screen printed carbon electrode is very similar and both compounds share a similar molecular structure to that of diphenylamine. In each case on repeated scanning, an electroactive film is deposited due to the polymerisation of either of the molecules. The resultant film adheres to the electrode and is stable in aqueous solution for both diclofenac and mefenamic acid. This film formation is unique to a carbon electrode as no layers were found to form on Pt or Au. The formal potential of the confined layer shifts with pH, with a slope of about -59mV/pH unit. Such layers will prevent the multiple use of the electrode in quantitative analysis unless it is cleaned between runs. A model based on the polymer formation from a diphenylamine backbone is proposed.

Electrochemical impedance spectroscopy (EIS) was employed in an attempt to gain insight into the mechanisms of ethyl 2-cyanoacrylate (ECA) curing (polymerisation) and bonding on aluminium alloy 2024 metal. EIS can detect ionic movement, adsorption processes, charge transfer and storage occurring at an adhesive/substrate interface and/or in a bulk bond line during curing. Low-frequency capacitance measurements demonstrated sensitivity to surface polymerisation reactions and were modelled using an equivalent circuit model with two time constants in series. At a frequency of 1 kHz, changes in the dielectric polymer could be readily followed with time, confirmed by employing a crown ether to accelerate the polymerisation process. Hydrolytic degradation of poly-ECA bonds at a stainless steel interface was also investigated. An equivalent circuit model containing a number of circuit components comprising pore, charge transfer and diffusional impedances, along with polymer film, double layer and diffusional capacitances (represented by constant phase elements), was developed. Three regions were identified in the frequency domain and ascribed to processes taking place at the polymer/electrolyte and polymer/metal oxide interfaces. In short, EIS can be employed to follow the rate of polymerisation of ethyl-2-cyanoacrylate and also the degradation of the resulting polymer in saline solution.

Salts of hexacyanoferrate II/III anions have been widely used as redox couple probe molecules to determine the characteristics of electrode surfaces. Examples include the assessment of electrocatalysts for energy applications and electrocatalysts for the detection of biological or chemical species, as well as the determination of electrochemically active surface areas. An examination of the electrochemical literature, based largely on cyclic voltammetric investigations, reveals a wide range of peak separation and/or heterogeneous electron transfer rate constants, classified sometimes as inner or outer sphere electron transfer processes. Originally developed for the mechanistic interpretation of inorganic transition metal compounds in solution, this terminology has since been extended to account for heterogeneous electron transfer occurring at electrodes. In the case of the hexacyanoferrate II/III anions, there can be a number of reasons why it sometimes behaves as an outer sphere probe and at other times displays inner sphere electron transfer characteristics. After examining some of the structural and chemical properties of the hexacyanoferrate II/III species, the methods used to determine such classifications are described. The most common method involves measuring peak-to-peak separation in a cyclic voltammogram to ascertain a heterogeneous rate constant, but it has inherent flaws. This paper reviews the reasons for the classification disparity, including the effects of various oxygen surface species, the influence of organic surface films, the nature of the cation counter-ion, surface adsorption and surface hydrophilicity/hydrophobicity. Other surface interactions may also take place, such as those occurring with Au corrosion or pH effects. These can impact the electrical double layer and thus may affect the electron transfer process. Consequently, it is recommended that hexacyanoferrate II/III should be considered a multi-sphere or alternatively a surface-sensitive electron transfer species.

This work presents the use of a simple microcalorimetry cyanoacrylate (CA) polymerisation system for investigating aspects of CA adhesive cure through gap and adsorption of adhesive acid stabiliser by a range of metal and glass substrates. It is well established that strong acid induced inhibition periods (IPs) are almost directly proportional to the acid concentration in weak base initiated polymerisations of alkyl CAs in tetrahydrofuran (THF). Ethyl cyanoacrylate (ECA) polymerisation IP measurements were used to determine the adsorption of methanesulfonic acid (MSA) in THF or ECA solutions by a range of metal, glass and polypropylene (PP) lap shears surfaces. The extent of substrate acid sorption was found to decrease in the order: Copper-zinc alloy (C23000) > grit blasted mild steel > aluminium alloy 2024T3 > mild steel > glass > aluminium > stainless steel alloy 304 > PP. Differences in the extent of acid adsorption were accounted for in terms of two effects: surface acidity/basicity and surface area (roughness). The decrease in MSA concentration following lap shear immersion in an MSA solution was related to the reactivity of the substrates for catalysing bond line polymerisations as described in a recently reported confocal Raman spectroscopic study of ECA/substrate reactivity.

In deionised water, ascorbic acid (AH−), through oxidation by oxygen in the presence of copper(ii), was found to degrade with zero-order kinetics. The magnitude of the reaction rate varied directly with the copper(ii) concentration. At a higher pH (7.4), the same reaction was found to be pseudo-first order. Once again, the magnitude of the rate increased linearly with copper(ii) concentration at a micromolar level. Dissolved oxygen levels, in excess AH− and trace copper(ii), displayed similar kinetics under both conditions. Monitoring of either AH− levels or dissolved oxygen concentration was found to be a useful novel undergraduate practical laboratory for trace copper(ii) determination. Students can measure the kinetics for standards and their unknown copper solution and quantitate the unknown copper.

ABSTRACT Bromocresol Purple,(BCP) cast onto an acetate sheet, was used to sense ammonia. This simple layer responded reversibly to a low concentration (15 ppm) of ammonia in the presence of water vapour. The BCP solution was spincoated on an acetate sheet from a solution in dichloromethane. This layer was exposed to nitrogen and NH3/H2O vapour in quick succession. The colour change occurred from yellow to purple rapidly in the solid state. The λmax for the neutral (acid) form of the BCP was found to be 435 nm and the λmax for the dianion (base form) of the BCP was found to be 610 nm A mechanism previously predicted theoretically was confirmed using FTIR identifying the presence of a peak associated with a carbonyl in the dianion form.

Compared with traditional methods for preparing dielectric elastomer (DE) films, electrohydrodynamic (EHD) 3D printing displays many advantages, notably full automation, computer control and flexible design. It also confers high printing resolution, high preparation efficiency with minimal probability of nozzle clogging. In this article, EHD 3D printing was employed to fabricate silicone rubber (SR) based DE films. In order to increase their dielectric constant, high dielectric copper phthalocyanine (CuPc) particles were added into the SR ink. Optimal printing conditions were determined by analyzing the effects of printing voltage and ink properties on the formation of liquid cone and the printed line width. The SR/CuPc composite film with 3 wt% CuPc particles (SR/CuPc-3) exhibits a high dielectric constant of 5.52, with a large actuated area strain of 23.7% under an electric field of 39.4 V μm−1. Furthermore, under 100 cycles of electric field loading, SR/CuPc-3 demonstrate excellent electromechanical stability, indicating that EHD 3D printing holds a considerable potential for fabricating high-performance DE films in an efficacious manner.

Optical lenses driven by dielectric elastomer (DE) actuators with tunable focal lengths are presented here. They are inspired by the architecture of the crystalline lens and the ciliary muscle of the human eye and have prompted a growing interest. The most commonly used DEs in tunable lenses have often required highly transparent films and also the need to encapsulate clear liquid silicone to act as the lens. There is a restriction on the properties of the tunable lens imposed by materials limitations. Here, the fabrication of a fully 3D printed tunable lens with an inhomogeneous structure is described. It exhibited a 29% change in focal length from 33.6 mm to 26.1 mm under a dynamic driving voltage signal control. Furthermore, it displayed excellent stability when the focal length was tuned from far to near (30.1 mm to 25.3 mm) for 200 cycles. The tunable lens obtained mimics the working principle of the human eye in auto adjusting the focal length and has evident potential applications in imaging, information storage, beam steering and bifocal technology.

In this work, a recently developed 3D additive processing technology termed electrohydrodynamic (EHD) printing was employed to fabricate dielectric elastomer (DE) films by using styrene-ethylene-butylene-styrene (SEBS) inks with the addition of high dielectric titanium dioxide (TiO2) nanoparticles. In order to improve the dispersibility of TiO2 in the SEBS matrix, extracted walnut polyphenols were utilized for surface modification of TiO2 nanoparticles labelled wp-TiO2. The effect of the applied voltage on the ink jet morphology of the obtained SEBS based inks during EHD printing was analyzed. The prepared films had precision patterned shapes and their morphology was studied. It revealed that the dispersibility of TiO2 nanoparticles in the SEBS matrix and their compatibility were greatly improved using this procedure. Furthermore, the printed DE films were found to have excellent mechanical, dielectric and electromechanical properties. For the range of DEs fabricated, the SEBS/10%wp-TiO2 composite exhibited the maximum actuated area strain of 21.5% at an electric field of about 34.0 V/mu m without degradation of other properties.

A macro-scale metal-semiconductor-metal device comprising CeO2 nanoparticles cast from a suspension of cerium dioxide formed by a novel synthetic method was fabricated. Thin CeO2 films of 40 nm thickness placed between panels of aluminium and/or copper displayed memristive-like resistive switching behaviour upon the application of potential sweeps ranging between -0.6 V and 0.6 V. A mechanism is proposed based on the notion that an electrolytic cell operates under such conditions with the initial formation of p and n-type regions within the central semiconductive thin film. Evidence is presented for the existence of numerous point defects in these nanosized CeO2 films, which are also likely to play a role in the device's operation acting as internal dopants. Steady currents were observed upon the imposition of constant potentials, most notably at higher potential values (both anodic and cathodic). It is suggested that electrons and holes act as charge carriers in these devices rather than ionic species as proposed in some other mechanisms.

In situ spatial temporal measurement of monomer conversion during adhesive bondline curing remains a challenging area. The aim of this work was to demonstrate the effectiveness of using confocal Raman microscopy in a specially configured experimental set-up, as a versatile tool for measuring monomer concentration changes as a function of both time and adhesive bond depth during ethyl cyanoacrylate polymerisation. This also allowed monitoring of the extent of polymerisation at the adhesive substrate interface independently of the bulk bondline polymerisation region. Key kinetic parameters such as inhibition time tlag, rate of reaction Rmax and extent of reaction [αt]max were obtained by fitting the experimental data to sigmoidal growth curves using simple piecewise regression models. A systematic characterisation of a polymerisation reaction was conducted using different sample substrate types (copper alloy (red brass), aluminium, aluminium alloy, stainless steel and borosilicate glass) and at various reaction temperatures. Reaction rates were found to decrease further away from the substrate interface in the bulk volume region. The fastest kinetics occurred in the vicinity of nucleophilic hydroxyl rich surfaces such as at the copper alloy (red brass). In addition to substrate surface chemistry, surface roughness was also a factor, with the highest reaction rates occurring with a grit blasted (roughened) aluminium alloy (2024 T3) surface. An approximately linear dependence of the ln Rmax vs. 1/T (Arrhenius) plot was recorded within the temperature range of 291-328 K. A better fit was obtained however through the use of two separate linear slopes, possibly indicative of a change of polymerisation reaction mechanism taking place at elevated temperatures with two distinct activation energies. Further work conducted using a larger number of temperatures would be useful to verify this finding. This work confirmed that differences in the rates of interfacial and bulk polymerisation processes could be readily measured in situ using confocal Raman microscopy which is a powerful technique for investigating such surface-confined and bulk polymerisation reactions.

The detection of low levels of drugs including Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) in natural waters and wastewaters is becoming increasingly important. Electrochemical methods offer an attractive means of detection, as they overcome many disadvantages associated with the currently available analytical methods. Cerium dioxide nanoparticles were synthesised and then incorporated onto the working electrodes of commercial graphite-based Screen Printed Carbon Electrodes (SPCE) then used to determine diclofenac levels. Following initial Cyclic Voltammetry studies, Square Wave Voltammetry (SWV) investigations were conducted over a range of conditions to optimise the peak potential separation and sensitivity of the method. The use of background correction as signal processing is highlighted since it constitutes a mandatory pre-treatment of data before the analysis of results. SWV study was carried out on diclofenac over a concentration range from 0.4 mu M up to 26 mu M which indicated that the response was linear with a limit of detection of 0.4 mu M and a sensitivity of 0.058 mu A/mu M. The SWV method provides a rapid means of diclofenac detection where cerium dioxide nanoparticles combined with electrode vacuum heat treatment and use of background correction all play an important role.

The original version of this article contained a mistake.

In this work, one compartment Photoelectrochemical Cell (PEC) fabricated with inexpensive materials photodegraded selected organic compounds present in model waste waters, with the advantage of producing electrical current. Degradation of pollutants in waste waters by photoeletrocatalysis is well known. The photoelectrocatalytic degradation behaviour of the anti-inflammatory Sodium Diclofenac and others organic contaminants in aqueous solution was studied. TiO2 was utilized as the catalyst under different sources of UV and solar radiance. The catalyst was immobilized in a carbon cloth and in a variety of conductive supports as the photoanode and an air-cathode was utilized to allow an increase in oxygen concentration during the reduction process. By utilizing this photocatalytic process in a Photo Fuel Cell (PFC) device, the rate of organic pollutants destruction may be greatly enhanced, at the same time producing useful electrical energy. A range of environmental conditions will be explored such as fuel/pollutant concentration level, electrolyte composition and pH variation, in order to determine the best performing catalyst/support/environment combination. A transition metal oxide-based air cathode will also be used (replacing expensive platinum) in conjunction with a modified PFC design, thus characteristics and mechanistic insights will be ascertained as a result.

ABSTRACTElectromechanical instability (EMI) is regarded as a significant factor in preventing dielectric elastomers (DEs) from achieving large voltage‐induced deformations. In this study, the strain‐stiffening effect was used to control the occurrence of EMI in DEs. The results show that the stretching ratio required to provide a feasible strain‐stiffening effect in silicone rubber (SR) was smaller than that needed for a commercial DE material, VHB 4910. The experimental data were compared with currently used models for the simulation of EMI in DEs. We found that EMI could be eliminated in the deformation of these elastomers when prestretching was used. Through the application of a prestretching ratio of above 2.0, EMI was suppressed in both the VHB 4910 and SR samples. The findings of this research are of great significance in the maximization of the electromechanical performance of DE materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45733.

A square wave voltammetric waveform ( SWV) was applied to an inlaid microdisk electrode in a solution of K4[Fe(CN)6]. A simple model relying on the assumption of steady state current throughout the scan was used to model the current potential behaviour. However, experimental peak current magnitudes were between 30% and 50% greater than those predicted by the model. The model predicts an increase of peak current and peak width at half height with pulse height Esw and no effect of the parameters frequency, f and step height, ∆Es. Experimental peak current magnitudes and peak current magnitudes predicted by the model both increased with increasing Esw but were not affected by f or ∆Es.

Fatigue life prediction is of great significance in ensuring magnetorheological elastomer (MRE) based rubber components exhibit reliability and do not compromise safety under complex loading, and this necessitates the development of plausible fatigue life predictors for MREs. In this research, silicone rubber based MREs were fabricated by incorporating soft carbonyl iron magnetic particles. Equi-biaxial fatigue behaviour of the fabricated MREs was investigated by using the bubble inflation method. The relationship between fatigue life and maximum engineering stress, maximum strain and strain energy density were studied. The results showed that maximum engineering stress and stored energy density can be used as reliable fatigue life predictors for SR based MREs when they are subjected to dynamic equi-biaxial loading. General equations based on maximum engineering stress and strain energy density were developed for fatigue life prediction of MREs.

Electromechanical instability (EMI) is one of most common failure modes for dielectric elastomers (DEs). It has been reported that pre-stretching a DE sample can suppress EMI due to strain stiffening taking place for larger strains and a higher elastic modulus are achieved at high stretch ratios when a voltage is applied to the material. In this work, the influence of equi-biaxial stretch on DE secant modulus was studied using VHB 4910 and silicone rubber (SR) composites containing barium titanate (BaTiO3, BT) particles and also dopamine coated BT (DP-BT) particles. The investigation of equi-biaxial deformation and EMI failure for VHB 4910 was undertaken by introducing a voltage-stretch function. The results showed that EMI was suppressed by equi-biaxial pre-stretch for all the DEs fabricated and tested. The stiffening properties of the DE materials were also studied with respect to the secant modulus. Furthermore, a voltage-induced strain of above 200% was achieved for the polyacrylate film by applying a pre-stretch ratio of 2.0 without EMI occurring. However, a maximum voltage-induced strain in the polyacrylate film of 78% was obtained by the SR/20 wt% DP-BT composite for a lower applied pre-stretch ratio of 1.6 and again EMI was eliminated.