N.m.r. study of the ferroelectric phase transition in a 7030mol% copolymer of vinylidene fluoride (VF2) and trifluoroethylene (TrFE)

Nuclear magnetic resonance (n.m.r.) studies of ¹⁹F nuclei in a $\text{70}\text{30}\text{mol}\text{\%}$ random copolymer of vinylidene fluoride and trifluoroethylene were performed at 9.14 MHz and 20.0 MHz. The free induction decays (FIDs) were analysed in terms of two T₂ components attributed to the amorphous and crystalline portions of the polymer. The changes in crystallinity as well as the effects of the ferroelectric transition were observed during cycles of heating and cooling between 20°C and 140°C. The crystalline component of the FID lengthens by a factor of 2 at 100°C on heating and decreases by this factor at 60°C on cooling, thus exhibiting the thermal hysteresis of this ferroelectric transition. The spin-lattice relaxation was also investigated. From measurements at 9.14 MHz the observed longitudinal relaxation time T₁ appears to be dominated by the dynamics of the amorphous phase and exhibits no anomaly through the phase transition. However, from measurements at 20 MHz, well defined minima of T₁ were observed, which are associated with the ferroelectric transition (especially after repeated annealing of the samples). Results are discussed in terms of the crystalline phase structure, which appears dynamically disordered above the ferroelectric phase transition. An analogy is considered with the plastic phase transitions encountered in molecular crystals.     

Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.     

Analysis of Caching and Replication Strategies for Web Applications

Developers often use replication and caching mechanisms to enhance Web application performance. The authors present a qualitative and quantitative analysis of state-of-the art replication and caching techniques used to host Web applications. Their analysis shows that selecting the best mechanism depends heavily on data workload and requires a careful review of the application's characteristics. They also propose a technique for Web practitioners to compare different mechanisms' performance on their own     

Determination of structural parameters of metallic foams from permeametry measurements

An experimental technique, permeametry, is carried out in order to determine the dynamic specific surface area and the tortuosity of three nickel foams. A capillary-type model allows calculation of these structural parameters from pressure-drop measurements. Studying pressure drops of two different flow configurations also allows quantification of a third parameter due to the anisotropy of the material structure. The values of the parameters determined throughout this work are compared with those obtained in previous works using different experimental methods.Nomenclature A experimental coefficient defined by Equation 3 (Pa sm^–2) - A _vd dynamic specific surface area, related to volume of solid (m^–1) - A _ve specific surface area, related to volume of porous medium (m^–1) - B experimental coefficient defined by Equation 4 (Pas²m^–3) - Cr precision criterion - D hydraulic diameter of the cell (m) - d equivalent pore diameter (m) - f friction factor - H bed height or thickness of porous material (m) - J coefficient defined by Equation 8 (m^–1) - K coefficient defined by Equation 9 (m^–2) - l pore length (m) - mre mean relative error - n+1 number of pressure taps - P pressure drop (Pa) - R anisotropy factor or shape anisotropy ratio - Re superficial Reynolds number, Re = U _o d/u - Re_i interstitial Reynolds number, Re _i = U _o d/() - T tortuosity - U _o superficial velocity (m s^–1) - porosity - dynamic viscosity (Pa s) - fluid density (kg m^–3)     

Mass transfer at the electrodes of the ‘falling-film cell’

In the falling-film cell the electrolyte flows as a thin film in the channel between an inclined plane plate and a sheet of expanded metal which work as electrodes. The present work gives the mass transfer coefficients at both electrodes; the experimental variables are the electrolyte flow-rate, the angle of inclination of the channel and the interelectrode distance. The results allow three different flow regimes to be characterized. At low flow rates, there exists a particular regime where capillary effects are present; in this regime the mass transfer coefficient decreases with increasing flow rate, which is interesting from the point of view of possible industrial electrolytic applications.Nomenclature b width of the inclined channel - D diffusion coefficient - d interelectrode distance - e _m mean film thickness - Grashof number, based ond - Grashof number, based onL - ¯k overall mass transfer coefficient, defined by Equation 9 - L electrode length - Q _v volumetric flow rate - volumetric flow rate per unitQ _vl width of channel - Reynolds number - Schmidt number - Sherwood number, based ond - Sherwood number, based onL - mean velocity of the liquid film - inclination angle of the channel with respect to the horizontal - kinematic viscosity of them electrolyte     

Shear rates investigation in a scraped surface heat exchanger

The electrodiffusion technique was performed in order to investigate the shear rate on a scraped surface heat exchanger. Microelectrodes were placed inside: the walls of the outer cylinder; the inlet and outlet bowls; the rotor and the blades. Highly viscous Newtonian fluid (Emkarox HV45 solutions) and non-Newtonian model fluid (aqueous solutions of CMC) were used. The electrodiffusion method allowed us to measure wall shear rates. Maximum shear rate was observed at the scraping surface and caused by blades scraping, high shear rate was also measured on the leading edge of the blades. In the other parts of the exchanger, shear rate remained low but the development of Taylor vortices completely modified the scraped surface heat exchangers behaviour inside the surface of the bowls. A dimensionless representation of the friction factor was established for the inner and outer wall surface of the exchanger.     

Development of the Acidity of Zirconia-Supported Niobia Catalysts

A series of NbO _x /ZrO₂ catalysts containing up to 2.67wt Nb (ca. 80 nominal surface coverage) was prepared by incipient wetness impregnation from niobium oxalate and oxalic acid solution. The structure of the catalysts was monitored by X-ray diffraction and Raman spectroscopy. The results indicated the presence of a surface Nb phase. No evidence for the formation of crystalline Nb₂O₅ species was found. The development of the acidity as a function of Nb loading was monitored by adsorption of a basic probe molecule followed by infrared spectroscopy. The results indicated the appearance of Brnsted acid sites for a threshold of Nb loading. The abundance of Brnsted acid sites correlated well with the isopropanol dehydration activity. The overall behavior was very similar to that reported earlier for the WO _x /ZrO₂ system.     

Boolean factors as a means of clustering of interestingness measures of association rules

Measures of interestingness play a crucial role in association rule mining. An important methodological problem, on which several papers appeared in the literature, is to provide a reasonable classification of the measures. In this paper, we explore Boolean factor analysis, which uses formal concepts corresponding to classes of measures as factors, for the purpose of clustering of the measures. Unlike the existing studies, our method reveals overlapping clusters of interestingness measures. We argue that the overlap between clusters is a desired feature of natural groupings of measures and that because formal concepts are used as factors in Boolean factor analysis, the resulting clusters have a clear meaning and are easy to interpret. We conduct three case studies on clustering of measures, provide interpretations of the resulting clusters and compare the results to those of the previous approaches reported in the literature.     

Experimental comparison of electrochemical and dot-paint methods for the study of decaying swirling flow

Swirling decaying flow in an annular cell fitted with a tangential inlet equal in diameter to the gap width was experimentally investigated. The attention was focused on the local flow field on both cylinders, the structure of which was determined using two experimental techniques: wall shear stress measurements achieved by means of the limiting electrodiffusional current on microelectrodes and a wall visualization method, the so-called dot-paint method which was used in order to determine he flow direction. This study showed the complex structure of the flow field just downstream of the tangential inlet, where a recirculation zone is set up, the effects of which are more sensitive on the inner cylinder, and the flow structure can be considered as three-dimensional in the whole entrance section. This paper was presented at the International Workshop on Electrodiffusion Diagnostics of Flows held in Dourdan, France, May 1993.