A thermogravimetric technique for continuous quantitative sulphur analysis at elevated temperatures

The problems of conventional methods for determining sulphur content at elevated temperatures are discussed and a thermogravimetric technique for a direct continuous analysis is described. The technique is illustrated by employing the Cu-S system at 1200 and with a discussion of the necessary correction factors for buoyancy and volatilization being included.

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Zusammenfassung Es werden die Probleme der üblichen Methoden der Schwefelbestimmung bei hohen Temperaturen erörtert und eine thermogravimetrische Methode zur direkten kontinuierlichen Analyse vorgeschlagen. Das Verfahren wird an dem Beispiel des Systems Cu-S bei 1200 gezeigt mit Hinweis auf die infolge Auftrieb und Verflüchtigung nötige Korrektur.

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Résumé On discute les problèmes posés par les méthodes conventionnelles pour doser le soufre aux températures élevées et l'on décrit une méthode thermogravimétrique pour l'analyse directe en continu. La technique est illustrée sur l'exemple du système Cu-S à 1200; on discute les facteurs correctifs que l'on doit appliquer pour tenir compte de la poussée et de la volatilisation.

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. Cu-S 1200 .

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One of the authors, C. W. B., is grateful to the Noranda Research Centre for a graduate fellowship. We are also grateful to the Canadian National Research Council for financial assistance.     

Model for heat conduction in nanofluids

A comprehensive model has been proposed to account for the large enhancement of thermal conductivity in nanofluids and its strong temperature dependence, which the classical Maxwellian theory has been unable to explain. The dependence of thermal conductivity on particle size, concentration, and temperature has been taken care of simultaneously in our treatment. While the geometrical effect of an increase in surface area with a decrease in particle size, rationalized using a stationary particle model, accounts for the conductivity enhancement, a moving particle model developed from the Stokes-Einstein formula explains the temperature effect. Predictions from the combined model agree with the experimentally observed values of conductivity enhancement of nanofluids.     

Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO₂) and iodine monoxide (IO) radicals using a violet laser diode at λ=404.278 nm. A noise-equivalent (1σ≡ root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5×10^-8 was demonstrated with a mirror reflectivity of ∼0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8×10¹⁰ molecule cm^-3 and towards the IO radical of 3.3×10⁹ molecule cm^-3 were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO₂+NO→RO+NO₂). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO₂ in the reaction NO₂+O→NO+O₂. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3×10¹⁰ molecule cm^-3 in the discharge-flow-tube experiments. Received: 4 February 2003 / Revised version: 10 March 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +44-1865/275-410, E-mail: vlk@physchem.ox.ac.uk     

Understanding Behavior of Polycaprolactone–Gelatin Blends under High Pressure CO<Subscript>2</Subscript>

Polycaprolactone (PCL) is widely used in biomedical applications as electrospun fibers or porous foams. As PCL is synthetic polymer, many researchers have explored blends of PCL–gelatin to combine mechanical and bioactive properties of individual components. High pressure carbon dioxide (CO2) has been studied to foam and impregnate many biocompatible polymers. In case of PCL–gelatin blends, certain compositions can be swelled reversibly under high pressure CO₂ without permanent deformation. This allows successful impregnation of PCL–gelatin blends under CO₂. This study summarizes effect of different treatments adopted during impregnation process including high pressure CO2 on several blend compositions of PCL–gelatin blends. Stress relaxation, polymer melting and dissolution were observed during several treatments which affects porosity and scaffold structure significantly. Results summarized in this study will aid in optimum selection of PCL–gelatin blend composition for biomedical applications. Furthermore, CO₂ solubility in polymers is restricted due to thermodynamic limitations but can be altered in the presence of a co-solvent to produce better foams. PCL can be foamed using supercritical CO₂. However, CO₂ foaming of PCL–gelatin blend becomes challenging to simultaneous swelling of PCL and compression of gelatin providing blend structural stability. This study has demonstrated ability of supercritical CO₂ to foam PCL–gelatin blends in presence of water to create porous structure. These foams were subjected post-fabrication crosslinking and supercritical CO₂ without losing porosity of foams. Thus, creating a strategy to use environmentally benign processes to fabricate, crosslink and impregnate porous scaffolds for biomedical applications.     

A micro-convection model for thermal conductivity of nanofluids

Increase in the specific surface area as well as Brownian motion are supposed to be the most significant reasons for the anomalous enhancement in thermal conductivity of nanofluids. This work presents a semi-empirical approach for the same by emphasizing the above two effects through micro-convection. A new way of modeling thermal conductivity of nanofluids has been explored which is found to agree excellently with a wide range of experimental data obtained by the present authors as well as the data published in literature     

Regeneration of surface roughness by the Langevin equation using stochastic analysis on AFM image of a carbon fiber

A new method was developed using AFM images of a fiber surface to regenerate the surface roughness in 3D geometry, such as the cylindrical shape of a “model” fiber. The Langevin equation was used to derive the fluctuations of a carbon fiber surface image. The equation contains two quantities, D⁽¹⁾ (h) and D⁽²⁾ (h) which in physics represent drift and diffusion coefficients. Knowing this coefficient and adding a proper noise function, a similar surface of larger dimension with the same statistical properties of the initial data was created. The generated surface was mapped into cylindrical coordinates, then a mesh generated. The resulting reconstructed surface, input over the geometry of a cylindrical shape, can be implemented for finite element analysis of a single fiber surrounded by matrix and generalized to a many fiber model.     

Characteristic parameters of drift vortices coupled to Alfvén waves in an inhomogeneous space plasma

We present detailed measurements of ion scale vortices of drift type coupled to Alfvén waves in an inhomogeneous and collisionless space magnetoplasma. The two free parameters of a dipolar vortex, intensity and spatial radius, are measured. The vortices are driven by a strong density gradient on a boundary layer with scale size of the same order as the vortex diameter. Observations of vortices off the gradient show that symmetry-breaking conditions in a real inhomogeneous plasma can lead not only to cross-field but also to cross-boundary anomalous transport of particles and energy.     

Calix Receptor Edifice; Scrupulous Turn Off Fluorescent Sensor for Fe(III), Co(II) and Cu(II)

Novel Supramolecular fluorescence receptor derived from calix-system i.e. calix[4]resorcinarene bearing dansylchloride as fluorophore was designed and synthesized. The compound was purified by column chromatography and characterized by elemental analysis, NMR and Mass spectroscopy. Tetradansylated calix[4] resorcinarene (TDCR) shows a boat conformation with C₂v symmetry. The complexation behaviour of metal cations [Ag(I), Cd(II), Co(II), Fe(III), Hg(II), Cu(II), Pb(II), Zn(II), U(VI) (1?×?10^-4?M)] with tetra dansylated calix[4]resorcinarene (1?×?10^-6?M) was studied by spectophotometry and spectrofluorometry. Red shift in the absorption spectra led us to conclude that there is strong complexation Fe(III), Co(II) and Cu(II) with TDCR. These metal cations also produce quenching with red shifts in the emission spectra. The maximum quenching in emission intensity was observed in the case of Fe(III) and its binding constant was also found to be significantly higher than that of Co(II) and Cu(II). Quantum yield of metal complexes of Fe(III) was found to be lower in comparison with Co(II) and Cu(II) complexes. Stern Volmer analysis indicates that the mechanism of fluorescence quenching is either purely dynamic, or purely static.