Les différentes voies de modélisation macroscopique du procédé de dépôt de SiC par voie gazeuse

The different macroscopic modelling routes and chemical databases are reviewed for the growth of silicon carbide from the vapour phase in the Si-C-H-Ar system. Theses databases have been built up by experts over many years through the critical assessment of primary experimental data and ab-initio calculations. The thermodynamic modelling route addresses several important issues with respect to vapour deposition techniques. This approach is a useful tool in understanding the complex chemistry involved during the growth, but should be used with careful attention to the assumptions underlying the application. The transport modelling approach extends the previous analysis to dynamical systems. It is based on the conservation equations for momentum and heat transfer combined with mass transfer including thermodiffusion and chemical reactions based on thermodynamic and kinetic data. In addition to empirical, lumped chemical kinetic models, we propose a new modelling route linking transfers models with local thermochemical equilibrium (LTCE) computations. The modelling results have been validated with the help of the SiC sublimation technique for the transfer-LTCE concept, and of the chemical vapour deposition technique for lumped chemistry models. The simulated results allow the quantification of the different modelling proposals.     

Simulation numérique déterministe de la turbulence

We first present techniques of large-eddy simulation (LES) in physical und Fourier spaces. We show how LES allows vortex control in mixing layers, and good prediction of velocity statistics in a turbulent channel. We study also in a developed boundary layer the dynamics of high- and low-speed streaks at the wall, and the associated pressure fluctuations. Following this, we show in rotating shear flows a universal behaviour ol the mean velocity in regions whosw local Rossby number is sirictly inferior to — 1. Finally, we present for LES of compressible flows a formalism based on Favre averages.     

Méthode de détermination des épaisseurs de films conducteurs par mesures de résistance de surface

To evaluate the thickness of the layers of a Ti/TiAl₃/Al system, experiments based on surface resistance measurements have been performed. The thickness of each layer is deduced from a comparison among calculated and measured values of resistance. We present here a solution for the simulation of surface resistance and the results obtained with this method on Ti/TiAl₃/Al systems.     

Géométrie de l'intermittence en turbulence développée

A geometrical interpretation of intermittency in fully developed turbulence is realized through an hierarchy of fractal structures Ω_p of dimensions Δ_p linked each other by the relations Ω_{p + 1} − Ω_p (i.e. Δ_{p + 1} < Δ_p) and γ = (Δ_{p + 1} − Δ_∞)/(Δ_p − Δ_∞) with γ = ((1 + 3/√8)^1/3 + (1 − 3/√8)^1/3)³ and Δ_∞ = 1 and Δ_∞ = 1. This is obtained by the introduction of an entropy jump, defined at the scale r, ΔS_p(r) = (Δ_{p + 1} − Δ_p) ln (r/r₀) characterizing the order level of each sub-structure Ω_p and verifying a linear relation ΔS_p(r) = γ ΔS_{p − 1}(r).     

Nouvelle méthode de synthèse d’acides et d’esters arylboroniques par électroréduction de dérivés aromatiques halogénés en présence d’agents boratants

Novel synthesis of arylboronic acids and esters by electroreduction of aromatic halides in the presence of borating agents. A novel strategy for the one-step synthesis of arylboronic acids and esters by an electrochemical coupling reaction is described. It is based on the reductive coupling between the aromatic halides and a borating agent (trialkyl borate or pinacolborane). The reactions are carried out in DMF or THF with the use of sacrificial magnesium or aluminium anodes in a single-compartment cell. Arylboronic acids and esters are obtained with moderate-to-good isolated yields. To cite this article: C. Laza, E. Duñach, C. R. Chimie 6 (2003).     

Détermination de la composition énantiomérique dˈesters dˈacides aminés par spectroscopie de RMN à lˈaide dˈune chiroporphyrine de cobalt(III) comme agent chiral de déplacement chimique

We wish to propose a novel chiral shift reagent for the determination of enantiomer composition of amino acid derivatives. This reagent, chlorocobalt(III) tetramethylchiroporphyrin CoCl(TMCP), effects quantitative in situ derivatization of amino compounds in the NMR tube, without any detectable kinetic resolution. The influences of the chiral cavity and of the porphyrin ring current on the signals of the coordinated amino acid methyl ester L* can be seen in the high-field region of the ¹H NMR spectrum of the bis-adduct [Co(L*)₂(TMCP)]⁺Cl^–. The signatures of the (R) and (S) ligands are well resolved at 200 MHz, and their relative intensities can be readily determined by peak integration. To cite this article: M. Claeys-Bruno et al., C. R. Chimie 5 (2002) 21–25     

Etude des réactions de l'acétylformazyle et de ses dérivés avec les ions minéraux

Résumé L'étude systématique de l'acétylformazyle et de ses dérivés pour l'analyse à la touche à fourni des réactions sensibles permettant la recherche du mercure avec la thiosemicarbazone, du cuivre et du palladium avec l'oxime.

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Summary The systematic study of acetylformazyl and its derivatives for spot test analysis has yielded sensitive reactions which permit the detection of mercury by means of the thiosemicarbazone, and of copper and palladium with the oxime.

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Zusammenfassung Die systematische Untersuchung von Acetylformazyl und seinen Derivaten für die Zwecke der Tüpfelanalyse führte zu empfindlichen Reaktionen zur Prüfung auf Quecksilber mit dem Thiosemicarbazon, auf Kupfer und Palladium mit dem Oxim.

     

Interprétation de l'isoréflectance des dépôts périodiques

From the two envelopes of reflectance obtained in the passband of a periodic optical filter, the concept of monochromatic isoreflectance already defined for a single wavelength is generalised to an exended spectral range. A method is proposed to obtain coatings with this property. These coatings are interesting for the design and the manufacture.     

Méthodes de concentration préalable dans la détermination spectrochimique d'éléments à l'état de trace

Résumé La concentration préalable est très intéressante en vue des déterminations analytiques des traces d'éléments qui, en très petite concentration, se trouvent dans les sols de culture, les engrais chimiques, et commes des impuretés, ou des petites quantités des éléments, dans des alliages ou d'autres divers matériaux. Pour cette sorte de microdosage, nous avons spécialement choisi les méthodes spectrochimiques, comme celles les plus convenables pour la détermination simultanée de plusieurs éléments dans les échantillons étudiés. Avec cette concentration préalable des traces d'éléments on obtient dans des méthodes spectrochimiques, l'élimination la plus grande possible des éléments principales qui peuvent troubler ou bien déguiser les lignes appropriées pour le dosage des traces d'éléments. Des divers techniques utilisées pour la concentration préalable nous avons poursuivi spécialement celles qui basent sur l'emploi des réactifs chimiques appropriés, aussi bien qu'à cause de leur spécificité de la précipitation, aussi bien qu'à cause des procès de coprécipitation ou trainage qu'elles provoquent. Parmi les méthodes qui employent des réactifs organiques on a étudié, entre autres, la détermination spectrographique quantitative de petites quantités de bismuth comprises dans des alliages ternaires en base de plomb. On a employé le cupferron comme un réactif sélectif qui précipite le bismuth en présence de plomb et de cadmium, après avoir étudié la zone optime deph (0,5–1,5) dans laquelle ceci est possible. On a aussi étudié la détermination spectrochimique des traces de baryum à l'égard des diverses problèmes, en concentrant préalablement le baryum moyennant un procès de trainage ou coprécipitation provoqué par le ion sulfate en présence de plomb, qui s'ajoute excessivement, et que nous employons comme étalon interne spectral. Cette méthode a été employée pour le dosage de baryum dans certains procès d'adsorption, étudiés dans nos laboratoires.

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Summary The preliminary concentration is of great interest with regard to analytical determinations of traces of elements which occur at very low concentrations in agricultural soils, chemical fertilizers, and as impurities, or of minute quantities of elements in alloys or other divers materials. For this kind of microdetermination, we have especially chosen spectrochemical methods as being the most convenient for the simultaneous determination of several elements in the samples studied. With this preliminary concentration of traces of elements, there is obtained in the spectrochemical methods, the greatest possible elimination of the principal elements which may interfere with or entirely disguise the appropriate lines to be followed for determining the traces of elements. Among the various techniques employed for the preliminary concentration, we have followed especially those which are based on the use of appropriate chemical reagents, both because of there specific precipitating action, or because of the process of coprecipitation or entrainment which they provoke. Among the methods, which utilize organic reagents, there have been studied, for instance, the spectrographic quantitative determination of small quantities of bismuth contained in ternary alloys containing principally lead. Cupferron has been used as a selective reagent, which precipitates bismuth in the presence of lead and cadmium, after establishing the optimalph zone (0,5–1,5) in which this separation is possible. A study has also been made of the spectrochemical determination of barium by means of an entrainment of coprecipitation process brought about by sulfate ion in the presence of lead, added in excess, and which we have used as an internal spectral standard. This method has been used for the determination of barium in certain adsorption processes studied on our laboratories.

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Zusammenfassung Die vorhergehende Anreicherung hat für die analytische Bestimmung von Spurenelementen in Ackerböden und im Kunstdünger oder von geringsten Beimengungen und Verunreinigungen in Legierungen oder sonstigem Material große Bedeutung. Wir verwenden für solche Mikrobestimmungen vor allem spektralanalytische Methoden, da sie sich für die gleichzeitige Bestimmung mehrerer Elemente in einer Probe am besten eignen. Mit einer solchen der Spektralanalyse vorangehenden Anreicherung erzielt man die größtmögliche Entfernung der Hauptbestandteile, die die zur spektralanalytischen Bestimmung der Spuren geeigneten Linien stören oder sogar überdecken können. Von den verschiedenen zur Anreicherung geeigneten Verfahren verwenden wir vor allem die mit Hilfe von chemischen Reagenzien, sei es daß sich diese zufolge ihrer Spezifität hierzu besonders eignen, sei es weil sie bei der Niederschlagsbildung die gesuchten Elemente mit ausfällen oder mitschleppen. Unter Zuhilfenahme organischer Reagenzien studierten wir unter anderem die spektralanalytische Bestimmung kleiner Mengen Wismuth, wie sie sich in Legierungen auf Bleibasis finden. Wir verwendeten hierfür als selektives Reagens Cupferron, welches Wismuth in Gegenwart von Blei und Cadmium ausfällt. Als geeignetstesph-Bereich hierfür wurde 0,5 bis 1,5 bestimmt. Weiters untersuchten wir die spektralanalytische Bestimmung von Bariumspuren mit Rücksicht auf gewisse Problemstellungen, indem wir das Barium vorher mit Sulfationen gleichzeitig mit Blei ausfällten, welches im Überschuß zugefügt und von uns als Vergleichssubstanz verwendet wurde. Diese Methode wurde zur Bariumbestimmung bei gewissen Adsorptionsversuchen verwendet, die in unserem Laboratorium durchgeführt werden.

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Avec 4 figures.     

Critère d'initiation de délaminage dans les stratifiés

A criterion is proposed to predict delamination initiation in angle-ply laminates. An analytical model permits to calculate interface stresses between two layers in any laminate. The criterion is based on the maximum value of these stresses and takes into account the scale effects (number of layers). The numerical results are validated by a comparison with experimental data.     

Amorçage de la décohésion dans l'essai d'arrachement

By revisiting the classical formulation of fracture mechanics, the study of debonding in composite materials can be modelised by a principle of least energy. We are interested in the study of the fibre pull-out problem. Considering a cylindric reinforced beam characterised by the ε ratio of its radius to its length, an energy study shows, by taking into account free-edge effects near the interface, that debonding happens suddenly when the length is of order √ε.     

Etude du phénomène de dépiégeage des ondes de densité de charge dans les systèmes de basse dimensionnalité

Numerical results of the behaviour of a low dimensional system show that the electric resistivity depends on the friction coefficient generated by the defects. We also show that the electric field dependence of the response time at different friction coefficients follows a power law. The divergence of the charge density wave response time near the threshold field indicates that depinning may be viewed as a dynamical critical phenomenon.     

Activité dénitrifiante et temps de génération chez 4 espèces de Rhizobium

Denitrifying capacity and doubling time were measured among 44 strains of Rhizobium belonging to 4 species: B. japonicum, R. lupini, R. meliloti et R. leguminosarum. There was no correlation between doubling time and the rate of production of N₂O in the presence of C₂H₂ in B. japonicum and R. lupini. In 38 other strains, only denitrifying capacity was measured. The percentage of strains showing denitrification capacity varied according to the species: 70 % in B. japonicum, 90 % in R. lupini, 37 % in R. meliloti and 14 % R. leguminosarum. The strains of the latter species showed a very low level of denitrifying activity in comparison with the strains of the 3 other species.     

Un bicristal mince déformé sous l'effet d'un réseau bipériodique de dislocations de misfit

The elastic field of a planar two-period network of misfit dislocations parallel to the two free surfaces of a thin bimaterial is explicitly determined from the assumption of an isotropic elasticity for each crystal. A few calculations of normal stresses enable the elastic field relaxation to be illustrated for CoSi₂/Si(111).     

Méthode de détermination de l'exclusion d'un electrolyte fort par une membrane échangeuse d'ions

We have developed a new method to evaluate the strong electrolyte exclusion of ion exchange membranes. This method is based on the continuous measurement by conductivity of the amount of imbibed electrolyte released into a large excess of permuted water. Its principal advantage is to distinguish between the co-ions in the exchanger and those in the adhering liquid film. The method is tested on two sulfonic membranes: CRP (Rhone-Poulenc) and Nafion (Du Pont De Nemours). The results indicate that the exclusion rate is related to the external concentration and to the molarity of fixed ionic groups.     

Description eulerienne de la mécanique d'un front de discontinuité avec apparition d'une localisation de la déformation

We study the exchanges occurring through a discontinuity front in a continuum. We focus in particular on the jump condition corresponding to the Clausius-Duhem inequality. We analyse the possibility of a localised glide on a discontinuity surface, emphasizing two different terms in the dissipation on the surface: one resulting from a possible movement of the front, the other ensuing from localisation.     

Préparation d'une argile activée pour la décoloration de l'huile d'olive

The optimum conditions for acid activation of a clay were determined in order to bleach olive oil. The methodology of experimental research, with an orthogonal central composite design, has been used in this study and the selected variables were temperature, reaction time, initial acid concentration and liquid/solid weight ratio. The last is the most significant factor in the activation process followed in decreasing order of importance, by time, temperature and initial acid concentration. Good agreement between theoretical analysis and experimental results was obtained. The quality of the bleached oil is similar to that of commercial oil. Finally, the low cost of the activated clay makes it economically very attractive.     

Étude d'un procédé de brassage électromagnétique en écoulement de Stokes

This note deals with a process allowing electromagnetic mixing of a conductor fluid in Stokes flow. The flow, which is generated by two inductor wires (arranged around a cylindrical vat), undergoes a rotation. In order to solve analytically this electromagnetic flow, we use a magnetostatic pattern and we replace the dynamics in the electromagnetic layer by a tangential velocity. We superimpose then a periodic rotation on the flow (triangular signal). The investigated parameters are an a dimensional number (τ), which compares the velocities of the rotation and the flow, the inversion's periodicity of the rotation (k) and the distance of the wires from the vat (d). In studying the stretching and scattering of a drop of the fluid, an optimal choice of these parameters is subsequently suggested. Finally, prospects are considered of the possibilities of stationary three-dimensional and mixing.