Influence of Phase Modifiers on the Degradation of Tri-n-octylamine/dodecane Extracting Mixture by an Acidic Solution of Vanadium (V)

The kinetics of degradation of a mixture of tri-n-octylamine (extractant) and various alcoholic phase modifiers in n-dodecane in contact with acidic aqueous sulfate solutions containing vanadium (V) has been investigated. The nature of the modifier influences the kinetics of degradation and an improvement of the resistance against the chemical degradation is obtained when secondary alcohol (2-nonanol) or tertiary alcohols such as 9-octyl-9-heptadecanol are used as phase modifiers instead of 1-tridecanol. For instance, the kinetic constant of degradation is divided by one half when 9-octyl-9-heptadecanol is used as phase modifier instead of 1-tridecanol. On the contrary, the alcohols containing aromatic substituents or fluorine atoms are responsible for an increase of the chemical degradation of the extraction solvent.     

Influence of textile treatment on mechanical and sorption properties of flax/epoxy composites

The aim of the present work is to study the effect of conventional textile treatments of woven flax on the mechanical properties and the water sorption of flax/epoxy composites. The flax fabrics are standard 2/2 twills. Various treatments are carried out on fabric such as mercerization, bleaching, and leaching for long fibers or on yarn such as leaching for short fibers. A model, based on a modified rule of mixture applied to composite reinforced with woven fabric, is developed to include the effect of fiber and porosity volume fractions on composite stiffness and strength. Most treatments improve tensile stiffness and strength of flax/epoxy composite and reduce composite water sorption. We prove by X‐ray fluorescence analysis, thermogravimetric analysis, and tensile tests of dry fabric that it is due to an improvement in the interfacial bonding between fibers and matrix. The best performances are achieved with bleaching and mercerization treatment. The weakest performances are obtained with the composites made with leached yarns. POLYM. COMPOS., 34:1761–1773, 2013. © 2013 Society of Plastics Engineers     

Infrared and ultraviolet–visible spectroscopic studies of silica, [(Cp)2ZrCl2] and trimethylaluminum interactions

Infrared and UV–vis studies of metallocene immobilization on silica are reported here. The results have indicated changes in the Zr coordination sphere of metallocene depending on the immobilization route used. The reaction of [(Cp)₂ZrCl₂] with silica formed [(Cp)₂ZrCl]⁺[SiO]⁻ species. The same metallocene, reacting with TMA modified silica, formed monomethylated and dimethylated species by the substitution of chloro for methyl ligands, stabilized on the surface by interaction with “MAO-like” species (methylaluminoxane, MAO). These monomethylated and dimethylated cationic zirconium species are the active centers for the polymerization reaction. Different order of TMA addition in the silica modification step generated surface species of a similar nature, differing in their relative quantities. The highest amount of these active species was obtained when the support was added to the TMA solution rather than adding the TMA solution to the silica support. This was the most significant parameter affecting catalytic activity in ethylene polymerization.     

Preparation of ultra‐low‐density microcellular materials

Microcellular polymeric materials can be obtained by the polymerization of a high‐internal‐phase emulsion. These materials are good candidates as targets toward inertial confinement fusion. This application requires severe specifications, including a very low density and a small cell size. In this study, we examined the influence of parameters such as emulsification conditions, surfactant nature, and the presence of a porogen on the obtainment of those requirements. It was possible to obtain microcellular polymeric foams with apparent densities as low as 0.0126 g/cm³. However, it was difficult to obtain very low material density and still maintain a small average pore size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2053–2063, 2005     

Rapid Discrimination of Neuromyelitis Optica Spectrum Disorder and Multiple Sclerosis Using Machine Learning on Infrared Spectra of Sera

Neuromyelitis optica spectrum disorder (NMOSD) and multiple sclerosis (MS) are both autoimmune inflammatory and demyelinating diseases of the central nervous system. NMOSD is a highly disabling disease and rapid introduction of the appropriate treatment at the acute phase is crucial to prevent sequelae. Specific criteria were established in 2015 and provide keys to distinguish NMOSD and MS. One of the most reliable criteria for NMOSD diagnosis is detection in patient’s serum of an antibody that attacks the water channel aquaporin-4 (AQP-4). Another target in NMOSD is myelin oligodendrocyte glycoprotein (MOG), delineating a new spectrum of diseases called MOG-associated diseases. Lastly, patients with NMOSD can be negative for both AQP-4 and MOG antibodies. At disease onset, NMOSD symptoms are very similar to MS symptoms from a clinical and radiological perspective. Thus, at first episode, given the urgency of starting the anti-inflammatory treatment, there is an unmet need to differentiate NMOSD subtypes from MS. Here, we used Fourier transform infrared spectroscopy in combination with a machine learning algorithm with the aim of distinguishing the infrared signatures of sera of a first episode of NMOSD from those of a first episode of relapsing-remitting MS, as well as from those of healthy subjects and patients with chronic inflammatory demyelinating polyneuropathy. Our results showed that NMOSD patients were distinguished from MS patients and healthy subjects with a sensitivity of 100% and a specificity of 100%. We also discuss the distinction between the different NMOSD serostatuses. The coupling of infrared spectroscopy of sera to machine learning is a promising cost-effective, rapid and reliable differential diagnosis tool capable of helping to gain valuable time in patients’ treatment.     

Alumina foam catalyst supports for industrial steam reforming processes

The manufacture and the characterisation of alumina foams as alternative catalysts supports for industrial steam reforming processes are presented here. The possibility of use of alumina foams as catalysts supports in such processes is evaluated by studying their resistance toward mechanical and chemical stresses. The alumina foams produced are characterised owing to their processing parameters (slurry infiltration, sintering temperature, template pore size). Their ability to work in hydrothermal atmosphere is assessed by characterising the evolution of microstructures and mechanical strengths upon aging. Thermodynamic studies of the stability of alumina in industrial steam reforming working conditions are performed and correlated to the experiments to demonstrate the stability of such a system.     

Anticoagulant, Antioxidant and Antitumor Activities of Heterofucans from the Seaweed Dictyopteris delicatula

In the present study, six families of sulfated polysaccharides were obtained from seaweed Dictyopteris delicatula by proteolytic digestion, followed by acetone fractionation and molecular sieving on Sephadex G-100. Chemical analyses demonstrated that all polysaccharides contain heterofucans composed mainly of fucose, xylose, glucose, galactose, uronic acid, and sulfate. The fucans F0.5v and F0.7v at 1.0 mg/mL showed high ferric chelating activity (～45%), whereas fucans F1.3v (0.5 mg/mL) showed considerable reducing power, about 53.2% of the activity of vitamin C. The fucan F1.5v presented the most prominent anticoagulant activity. The best antiproliferative activity was found with fucans F1.3v and F0.7v. However, F1.3v activity was much higher than F0.7v inhibiting almost 100% of HeLa cell proliferation. These fucans have been selected for further studies on structural characterization as well as in vivo experiments, which are already in progress.     

Electromagnetic modeling of waveguide amplifier based on Nd<Superscript>3+</Superscript> Si-rich SiO<Subscript>2</Subscript> layers by means of the ADE-FDTD method

By means of ADE-FDTD method, this paper investigates the electromagnetic modelling of a rib-loaded waveguide composed of a Nd³⁺ doped Silicon Rich Silicon Oxide active layer sandwiched between a SiO₂ bottom cladding and a SiO₂ rib. The Auxilliary Differential Equations are the rate equations which govern the levels populations. The Finite Difference Time Domain (FDTD) scheme is used to solve the space and time dependent Maxwell equations which describe the electromagnetic field in a copropagating scheme of both pumping (λ _pump = 488 nm) and signal (λ _signal = 1064 nm) waves. Such systems are characterized by extremely different specific times such as the period of electromagnetic field ~ 10^-15 s and the lifetimes of the electronic levels between ~ 10^-10s and ~ 10^-4 s. The time scaling method is used in addition to specific initial conditions in order to decrease the computational time. We show maps of the Poynting vector along the propagation direction as a function of the silicon nanograin (Si-ng) concentrations. A threshold value of 10²⁴ Si-ng m^-3 is extracted below which the pump wave can propagate so that a signal amplication is possible.     

Simulation of pH-controlled dissolution of aluminium based on a modified Scanning Electrochemical Microscope experiment to mimic localized trenching on aluminium alloys

Some constituent intermetallic (IMPs) particles at the surface of aluminium alloys are considered as preferential sites for the initiation of structural corrosion resulting in localized trenching around the particles and the surrounding Al matrix. In this work, a modified scanning electrochemical microscope (SECM) experiment was used to induce such phenomena via a local alcalinisation on 200 nm thick aluminium coatings promoting their local dissolution in an aerated 0.1 M NaCl electrolyte. The local alcalinisation was induced by the oxygen reduction reaction on the tip of a SECM which mimics the surface of an isolated IMP. From a phenomenological point of view, reproducible cylindrical damage develops in front of the platinum ultramicroelectrode (UME). Using a 2D finite element modelling to simulate the SECM experiments, the role of the local alcalinisation was validated and the calculated Al dissolution rate was found in agreement with the experimental evaluation.     

Influence of the counter-ion on the effective charge of polyacrylic acid in dilute condition

Osmotic pressure measurements were satisfactorily used to compute the effective charge of poly(acrylic) acid (PAA) at different pHs and with different monovalent and divalent counterions. This experimental method is sensitive to the osmotically active species (polymer and counterions). After correction for the polymer contribution to the total osmotic pressure (solvency and excluded volume), the remaining pressure can be attributed to the polyelectrolyte counterions and processed with Donnan and equation of state in order to compute the effective charge number per polymeric chain (Z^eff). The behavior of Z^eff against the chain concentration and pH was investigated after neutralization of PAA with LiOH, NaOH, and TMAOH. The results clearly indicate that the nature of the monovalent counterion has no effect on Z^eff leading to the conclusion that the interaction between monovalent counterions and the acrylate functionality is purely electrostatic in agreement with conductimetric and potentiometric results reported in the literature. The behavior of Z^eff against the degree of ionization of the polymer and its concentration is also in good agreement with the theoretical expectations of the theory of ionic condensation. Osmotic measurements were also used in order to understand the influence of divalent cations (Mg²⁺, Ca²⁺, Ba²⁺) on Z^eff of the sodium salt of PAA at pH 9 and at different divalent/acrylate molar ratio. All the divalent cations depress Z^eff each of one at different degrees, confirming a specific divalent/polymer interaction. The energy of hydration of cations can explain most of the observed results with divalents.