Functionalization of PVC by grafting of plasticizing group in a twin screw extruder

Substitution reactions are an appropriate way to attach chemical functions to polymer chains for improving properties and to diversify the application of polymer materials. The stereoselective substitution of chlorine atoms affords a useful way to plasticize polyvinychloride (PVC) by attaching appropriate plasticizing functions (ester group) such as isooctylthiosalicylate. Thus, the substitution of chlorine atoms of PVC by reactant bearing plasticizing groups was carried out in a continuous mixing apparatus such as a twin screw extruder. This continuous chemical engineering process taking place in the extruder is studied as the function of the residence time distribution (RTD) measured by a UV method. This function combined with the kinetics of the chemical reaction allows to define a new function G as the distribution of the extent of conversion by analogy with the RTD function.     

The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites

V-silicalite catalysts (VS-1 and VS-2) prepared by hydrothermal synthesis have been studied by ESR, XAFS (XANES and EXAFS) and photoluminescence spectroscopy. The in situ characterization of these V-silicalites shows that vanadium is present within the zeolitic framework as a highly dispersed tetrahedrally coordinated V-oxides, VO₄ unit, having a short V=O bond length. Photoluminescence spectroscopy in static and dynamic mode, as well as XAFS studies allow to detect in the V-silicalites different V species than that present in V-HMS or V/SiO₂, in terms of V=O bond length, vibrational energy, bond angle and lifetime of the excited triplet state. It is suggested that the combined contribution of the neighboring Si---OH group attached to the VO₄ unit and the zeolitic rigid framework structure of V-silicalites cause a more significant and pronounced effect on the chemical properties of the VO₄ unit than the flexible structure of V-HMS or V/SiO₂. Moreover, the dynamic quenching of the phosphorescence by the addition of reactant molecules such as NO or propane indicates that the V species in the excited triplet state can be expected to be the active sites for the photocatalytic reactions.     

The Future of the Refractory Industry, with a Chinese Perspective

Globalization is a reality resulting in many changes in the refractory industry. In this paper some of the threats and opportunities, which are influencing the future prosperity of the refractory industry on a worldwide basis, are being evoked. Some key technical and management issues are underlined, in terms of adjusting the productivity-quality-cost to the customers requirements ; producing unshapes versus shapes; innovations supported by research; international profile for the import-export game; training and education. Consequences for China, who does play a dominant role due to the size of its internal market （ customers demand） and the magnitude of its production capability （including raw materials availability）, are being drawn.     

Experimental and theoretical analysis of the operation of a natural gas cogeneration system using a polymer exchange membrane fuel cell

This paper reports experimental and numerical results of an investigation of five identical cogeneration systems using PEM (Polymer Exchange Membrane) fuel cells and running on natural gas. The natural gas is reformed locally to produce hydrogen. The accuracy of numerical results is validated by comparison with experimental data and the system performances are analysed in terms of electrical, thermal and total efficiencies. It appears that the energetic performances are low, particularly at low current. Simple solutions for enhancing the system electrical performances by modifying control laws are proposed.     

Powerful Parallel and Symmetric 3D Thinning Schemes Based on Critical Kernels

The main contribution of the present article consists of new 3D parallel and symmetric thinning schemes which have the following qualities:

They are effective and sound, in the sense that they are guaranteed to preserve topology. This guarantee is obtained thanks to a theorem on critical kernels;

They are powerful, in the sense that they remove more points, in one iteration, than any other symmetric parallel thinning scheme;

They are versatile, as conditions for the preservation of geometrical features (e.g., curve extremities or surface borders) are independent of those accounting for topology preservation;

They are efficient: we provide in this article a small set of masks, acting in the grid ?³, that is sufficient, in addition to the classical simple point test, to straightforwardly implement them.

     

In situ visualization of drop deformation,erosion, and breakup in high viscosity ratio polymeric systems under high shearing stress conditions

In this paper, deformation and breakup under simple shear of single molten polymer drops in a polymer matrix were investigated. Flow visualization was carried out in a Couette‐Flow apparatus under relatively high shear rates and temperatures up to 230°C. Drop/Matrix combinations were composed of polystyrene drops of 0.5–0.6 mm in diameter in polyethylene matrix, and ethylene–propylene copolymer drops of approximately the same size in polypropylene matrix. The deformation and breakup processes were studied under steady state and time‐dependent shearing conditions. Either for steady state or time‐dependant shearing conditions, drop elasticity generated at relatively high shear rates helped the drops to align perpendicular to the flow direction, i.e., parallel to vorticity axis. Also, the most striking non‐Newtonian effects for the high viscosity ratio systems were the surface erosion and the drop splitting mechanisms. The particles eroded off the main droplet surface were very fine, in the range of 10–50 μm, and led to a significant reduction in main drop size before its final breakup. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2582–2591, 2006     

Impedance of a porous electrode with an axial gradient of concentration

When the impedance is measured on a battery, an inductive impedance is often observed in a high frequency range. This inductance is frequently related to the cell geometry and electrical leads. However, certain authors claimed that this inductance is due to the concentration distribution of reacting species through the pores of battery electrodes. Their argument is based on a paper in which a fundamental error was committed. Hence, the impedance is re-calculated on the basis of the same principle. The model shows that though the diffusion process plays an outstanding role, the overall reaction rate is never completely limited by this process. The faradaic impedance due to the concentration distribution is capacitive. Therefore, the inductive impedance observed on battery systems cannot be, by any means, attributed to the concentration distribution inside the pores. Little frequency distribution is found and the impedance is close to a semi-circle. Therefore depressed impedance diagrams in porous electrodes without forced convection cannot be ascribed to either a Warburg nor a Warburg-de Levie behaviour.Nomenclature A D¦C¦ (mole cm s^–1) - B j+K¦C¦ (mole cm s^–1) - b Tafel coefficient (V^–1) - C(x) Concentration ofS in a pore at depthx (mole cm^–3) - C ₀ Concentration ofS in the solution bulk (mole cm^–3) - C C(x) change under a voltage perturbation (mole cm^–3) - ¦C¦ Amplitude of C (mole cm^–3) - D Diffusion coefficient (cm² s^–1) - E Electrode potential (V) - E Small perturbation inE namely a sine-wave signal (V) - ¦E¦ Amplitude of E(V) - F Faraday constant (96500 A s mol^–1) - F(x) Space separate variable forC - f Frequency in Hz (s^–1) - g(x) KC(x)¦E¦(mole cm s^–1) - I Apparent current density (A cm^–2) - I _st Steady-state current per unit surface of pore aperture (A cm^–2) - j Imaginary unit [(–1)^1/2] - K Pseudo-homogeneous rate constant (s^–1) - K Potential derivative ofK, dK/dE (s^–1 V^–1) - K ^* Heterogeneous reaction rate constant (cm s^–1) - L Pore depth (cm) - n Reaction order - P Reaction product - p Parameter forF(x), see Equation 13 - q Parameter forF(x), see Equation 13 - R _e Electrolyte resistance (ohm cm) - R _p Polarization resistance per unit surface of pore aperture (ohm cm²) - R _t Charge transfer resistance per unit surface of pore aperture (ohm cm²) - S Reacting species - S _a Total surface of pore apertures (cm²) - S ₀ Geometrical surface area - S _p Developed surface area of porous electrode per unit volume (cm² cm^–3) - s Concentration gradient (mole cm^–3 cm^–1) - t Time - U Ohmic drop - x Distance from pore aperture (cm) - Z Faradaic impedance per unit surface of pore aperture (ohm cm²) - Z _x Local impedance per unit pore length (ohm cm³) - z Charge transfer number - Porosity - Thickness of Nernst diffusion layer - Penetration depth of reacting species (cm) - Penetration depth of a.c. signal determined by the potential distribution (cm) - Electrolyte (solution) resistivity (ohm cm) - ₀ Flow of S at the pore aperture (mole cm² s^–1) - Angular freqeuncy of a.c. signal, 2f(s^–1) - Integration constant     

Electrochemistry at capped platinum nanoparticle Langmuir Blodgett films: A study of the influence of platinum amount and of number of LB layers

Platinum nanoparticles (n-Pt), over-grafted with 2-thiophenecarbonyl chloride are assembled on gold electrodes, by the Langmuir Blodgett (LB) technique using behenic acid (BHA) as promoting agent. These layers are electrochemically active without any preliminary activation. The [Fe(CN)₆]^3−/4− redox couple was used as electrochemical probe. This paper reports on the influence of the number of deposited LB layers, and the n-Pt density on the electrochemical response. n-Pt density was modified by the change of the “BHA/n-Pt” ratio. Cyclic voltammograms of “[Fe(CN)₆]^3−/4−” were observed whatever the coating conditions. As soon as the first layer was deposited the electrochemical response was associated to the n-Pt coverage, its response slightly increased up to a steady state for five or seven layers. As expected, the increase of the Pt density favored the increase of the current density. XPS analysis performed before and after electrochemical cycling showed that 4-mercaptoaniline capped platinum nanoparticles, and their over grafting were chemically and electrochemically stable. Analysis of influence of the number or the n-Pt density of the layers showed that the electrochemically active part of LB electrodes was provided by the last layer plus a part of the underlying one.     

Flow Characterization of a Three‐Phase Circulating Fluidized Bed Using an Ultrasonic Technique

The axial and radial distributions of solid and gas holdups were investigated in an air‐water‐glass bead circulating fluidized bed (GLSCFB) using a new ultrasonic technique, with a new method based on signal fluctuations. The cross‐sectional averaged gas and solid holdups measured at two axial positions appear to be similar at all studied operating conditions. The radial non‐uniformity decreases with increasing liquid velocity but does not change with an increasing solid circulating rate. The radial distribution of gas holdup was more uniform for 1.3 mm beads than for 433 µm glass beads.     

Ice sheet survey over Antarctica using satellite altimetry: ERS-2, Envisat,SARAL/AltiKa,the key importance of continuous observations along the same repeat orbit

From September 2002 to October 2010, the Envisat radar altimeter surveyed Greenland and Antarctica ice sheets on a 35 day repeat orbit, providing a unique data set for ice sheet mass balance studies. Up to 85 repeat cycles are available and the whole Envisat data set may be along-track processed in order to provide height variability and trend with a good spatial resolution for the objectives of ice sheet survey.

Soon, a joint Centre National d’Etudes Spatiales/Indian Space Research Organisation mission, SARAL (Satellite with Argos and AltiKa), with the AltiKa payload on board, will be launched on exactly the same orbit (less than 1 km of the nomimal orbit in the across-track direction). This will allow an extension of previous European Remote Sensing (ERS) satellite, ERS-1 and ERS-2, and Envisat missions of the European Space Agency (ESA), in particular from the point of view of ice altimetry. However, AltiKa operates in the Ka band (36.8 GHz), a higher frequency than the classical Ku band (13.6 GHz), leading to important modifications and potential improvements in the interactions between radar wave and snow-pack.

In this paper, a synthesis is presented of all available information relevant to ice altimetry scientific purposes as derived from the Envisat mission: mean and temporal derivatives of the height ? but also of the backscatter and of the two waveform parameters ? snow-pack change corrections, across-track surface slope at 1 km scale, etc. The spatial and temporal variability of ice sheet surface elevation is investigated with the help of the high-resolution Envisat along-track observations. We show that at least 50 repeat cycles are needed to reach the required accuracy for the elevation trend. It is thus advocated as potentially highly beneficial for SARAL/AltiKa as a follow-on mission. Moreover, the novel characteristics of SARAL/AltiKa are promising in improving our understanding of snow penetration impact.