Insight into β-Carotene Thermal Degradation in Oils with Multiresponse Modeling

The aim of this study was to gain further insight into β-carotene thermal degradation in oils. Multiresponse modeling was applied to experimental high-performance liquid chromatography–diode array detection (HPLC–DAD) data (trans-, 13-cis-, and 9-cis-β-carotene concentrations) during the heat treatments (120–180 °C) of two β-carotene-enriched oils, i.e., palm olein and copra. The test of different reaction schemes showed that β-carotene isomerization reactions were dominant and reversible. The resulting cis isomers and trans-β-carotene simultaneously underwent oxidation and cleavage reactions at the same rate constant. From the kinetic analysis, it appeared that—contrary to oxidation and cleavage reactions—isomerization rate constants did not follow the Arrhenius law. However, the isomerization equilibrium constant increased with temperature, favoring isomer production, particularly 9-cis-β-carotene. Its production was shown to be concomitant with oxidation and cleavage reactions, indicating that 9-cis-β-carotene could be a good degradation indicator during oil storage or processing.     

Mechanism of formation of urchin-like ZnO

Thin films composed of ZnO nanowires (NWs) hierarchically organized with an urchin-like 3D morphology were obtained by combining the electrochemical deposition and sphere lithography methods. Deposited on a transparent conductive oxide substrate (TCO), a monolayer of carboxylate modified polystyrene spheres organized with a hexagonal closed-packed structure played the role of a template. The spheres were activated in a solution of zinc chloride by the formation of bonds between the carboxylate terminals and the Zn²⁺ ions and were used as a template for the electrodeposition of vertically aligned ZnO NWs around them. Without this treatment, ZnO NWs were deposited only on the TCO substrate between the PS spheres. To reach a density of nanowires high enough to obtain the urchin morphology, the concentration of ZnCl₂ had to be at least equal to 2 M. It was also found, as soon as small grains of ZnO started to be electrodeposited on the polystyrene spheres that the spheres were no longer close packed. The space created between them increased with the increase in the number of small ZnO grains and the increase in their length, allowing the further growth of the nanowires between the spheres. As a result the initial round shape of the spheres was modified and the urchin-like ZnO exhibited an ellipsoidal shape.     

Carbon/PbO2 asymmetric electrochemical capacitor based on methanesulfonic acid electrolyte

A new hybrid electrochemical capacitor based on an activated carbon negative electrode, lead dioxide thin film and nanowire array positive electrode with an electrolyte made of a lead salt dissolved in methanesulfonic acid was investigated. It is shown that the maximum energy density and specific capacity of the C/PbO₂ nanowire system increase during the first 50 cycles before reaching their maximum values, which are 29 Wh kg⁻¹ and 34 F g⁻¹, respectively, at a current density of 10 mA cm⁻² and a depth of discharge (positive active electrode material) of 3.8%, that corresponds to a 22C rate. This is 7–8 times higher than the corresponding maximum values reached with a C/PbO₂ thin film cell operated in the same conditions. After an initial activation period, the performances of the C/PbO₂ nanowire system stay constant and do not show any sign of degradation during more than 5000 cycles. For comparison, the C/PbO₂ thin film system exhibits a 50% decrease of its performances in similar conditions.     

Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

Mechanism of anodic oxidation of molybdenum in nearly-neutral electrolytes studied by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy

Anodic oxidation of molybdenum in weakly acidic, nearly neutral and weakly alkaline electrolytes was studied by voltammetric and electrochemical impedance spectroscopic measurements in a wide potential and pH range. Current vs. potential curves were found to exhibit two pseudo-Tafel regions suggesting two parallel pathways of the dissolution process. Electrochemical impedance spectra indicated the presence of at least two reaction intermediates. X-ray photoelectron spectroscopic (XPS) results pointed to the formation of an oxide containing Mo(IV), Mo(V) and Mo(VI), the exact ratio between different valence states depending on potential and pH of the solution. A physico-chemical model of the processes is proposed and a set of kinetic equations for the steady-state current vs. potential curve and the impedance response are derived. The model is found to reproduce quantitatively the current vs. potential curves and impedance spectra at a range of potentials and pH and to agree qualitatively with the XPS results. Subject to further improvement, the model could serve as a starting point for the optimization of the electrochemical fabrication of functional molybdenum oxide coatings.     

Gas sensors based on thick films of semi-conducting single walled carbon nanotubes

A comparative study was made of sorted semi-conducting single walled carbon nanotube (SWCNT) films and unsorted SWCNT films for gas sensing applications. The transmission line method is used to monitor separately the SWCNTs film resistance and the contact resistance between electrodes and the SWCNTs, thus revealing that the sensing mechanism mainly relies on a modification of the tube conductivity during gas exposure. The fabricated sensors demonstrate a detection limit of 20 ppb NO₂ and 600 ppb NH₃ mainly attributed to experimental setup limitations. Moreover, semi-conducting nanotubes happened to be 2.5 times more sensitive to NH₃ than unsorted ones, thus proving that selectivity can be improved by sorting the SWCNTs. The temperature dependence of the sensor sensitivity was studied, and a good agreement was found between experimental results and the Langmuir adsorption model.     

Flow behavior in a corotating twin‐screw extruder of pure polymers and blends: Characterization by fluorescence monitoring technique

The objective of this work was to investigate the flow behavior of pure polymers and blends, especially miscible polymer/polymer systems, in a corotating twin‐screw extruder (TSE) using an online fluorescence monitoring device. An immiscible blend was also studied for the sake of comparison. The fluorescence signal was obtained by using synthesized fluorescence tracers added to the melt at very low concentrations. These tracers consisted of two styrene‐maleic anhydride copolymers (SMA) labeled with anthracene. The investigated blends were SMA8 (8 wt % of MA in SMA)/polystyrene (PS), SMA14 (14 wt % of MA in SMA)/styrene acrylonitrile copolymer (SAN), and poly(methyl methacrylate) (PMMA)/ethyl acrylate‐methyl methacrylate copolymer (PMMAEA). The residence time distribution (RTD), the mean residence time (t ), the dimensionless variance (σ_θ²), the Peclet number (Pe) and the fluorescence peak intensity distribution of pure polymers and binary polymer systems were investigated and interpreted in terms of polymers rheological properties. It was observed that polymers presenting higher viscosity or higher pressure showed longer residence time. A difference in behavior was also observed for the RTD of miscible and immiscible blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toward a continuous synthesis of porous carbon xerogel beads

A continuous process for producing porous carbon xerogel beads has been developed. It consists in injecting a pre‐cured aqueous solution of resorcinol and formaldehyde on top of a column filled with hot oleic acid. The latter is pumped on the top of the column and fed at the bottom, generating an upward flow that can be adjusted to match the terminal velocity of the settling beads. Thus, the bead residence time in the column can be adjusted to match the gelation time, allowing the beads to solidify before reaching the bottom of the vessel. The obtained beads are subsequently dried and pyrolyzed. The developed experimental setup proved the continuous synthesis of porous carbon beads is possible. Nevertheless, the shaping process caused various texture changes of the porous carbon, which mainly yields macropores instead of micro and mesopores. This process also leads to the build‐up of a denser skin around the beads. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1049–1058, 2018     

Metal‐Free,Radical Addition to Alkenes via Desulfitative Chlorine Atom Transfer

An efficient method for radical additions to unactivated alkenes via desulfitative chlorine‐atom transfer is described. The reaction is based on the use of readily available sulfonyl chlorides as starting materials and cheap radical initiators such as azobisisobutyronitrile (AIBN), di‐tert‐butyldiazene (DTBD), and dilauroyl peroxide (DLP). No transition metal catalyst is required and the reaction takes place under mild conditions at temperatures ≤85 °C.