Propriétés magnétiques des multicouches Tb/Fe amorphes recuites

The magnetic properties in the iron layers of Tb/Fe amorphous multilayers are investigated using ⁵⁷Fe Mössbauer spectrometry as a function of the nominal iron thickness and adequate heat treatment. We show that the perpendicular magnetic anisotropy is improved after homogenisation of the terbium-iron interface when the initial multilayer is of modulated composition Tb/Tb-Fe/Tb.     

Propriétés optiques et thermophysiques de composites polyméres-cristaux liquides (PDLC)

Polymer dispersed liquid crystal (PDLC) films can be switched electrically from a light scattering off-state to a highly transparent on-state. Thin films were prepared via a polymerization-induced phase separation process using electron beam radiation. The liquid crystal (LC)/polymer materials were obtained from blends of a eutectic nematic mixture E7 and a polyester acrylate based polymer precursor. The optical and electrooptical properties of the obtained PDLC films strongly depend on the LC concentration. The LC solubility limit in the polymer matrix and the fractional amount of LC contained in the droplets were determined by calorimetric measurements.     

Propriétés physico-chimiques de composés à caractère aromatique IX

Résumé Le spectre U.V. de solutions contenant un dérivé N-méthylé aza-aromatique en présence d'un hydrocarbure polycyclique présente une bande supplémentaire, qui est attribuée à un complexe de transfert de charge. Cette hypothèse est étayée par la comparaison des énergies de transition avec celles observées pour les transferts de charge entre les ions I^– et ces mêmes dérivés N-méthylés.Les positions des bandes de transfert de charge de l'iodure de pyridinium sont interprétées sur la base de considérations théoriques.

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The U.V. spectra of solutions of N-methylated monoaza-aromatic compounds show new absorption bands when polycyclic aromatic hydrocarbons are added. This is attributed to the formation of charge transfer complexes. This hypothesis is supported by the comparison of these spectra with those obtained from the interaction of I^– with the same methylated monoazaaromatic compounds.An attempt to interpret the positions of the charge transfer bands in the spectra of pyridinium iodide and N-methylpyridinium iodide, based on theoretical data, is given.

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Zusammenfassung Die UV-Spektren von Lösungen eines N-Methyl-aza-aromaten in Gegenwart eines polycyclischen Kohlenwasserstoffes zeigen eine zusätzliche Bande, die einem Elektronenacceptordonator-Komplex zuzuordnen ist. Diese Hypothese wird durch den Vergleich des Spektrums mit demjenigen des analogen Jod-Komplexes gestützt.Außerdem wird die Lage der Charge-Transfer-Bande des Pyridiniumjodids durch theoretische Überlegungen erklärt.

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Pour I et VIII voir respectivement: a) Coppens, G., et J. Nasielski: Bull. Soc. Chim. Beige 70, 136 (1961); b) Anthoine, G., J. Nasielski et E. Vander Donckt: Bull. Soc. Chim. Beige (sous presse).

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Associé du F.N.R.S.

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Aspirant du F.N.R.S.

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Nous exprimons notre gratitude à Monsieur le professeur R. H. Martin qui a suivi ces recherches avec le plus vif intérêt.Que le Ponds National de la Recherche Scientifique (F.N.R.S.) trouve ici l'expression de notre gratitude pour l'aide morale et financière dont nous avons bénéficié.Nos remerciements vont également au Fonds de la Recherche Scientifique Fondamentale Collective pour le subside octroyé au laboratoire.Nous tenons aussi à remercier très sincèrement Monsieur V. Bellevitch, Directeur du Comité d'Etude et d'exploitation des Calculateurs Electroniques, qui a mis au point le programme de résolution des équations séculaires et qui nous a fourni les vecteurs et valeurs propres utilisées dans ce travail.     

Propriétés rhéologiques à l'état fondu de polyesters thermoplastiques chargés de fibres de verre

A study of rheological properties in the molten state of two short glass fibre reinforced polyesters (polyethylene terephthalate and polybutylene terephthalate) was carried out, both in steady and dynamic flow. The results lead to information on the flow behaviour of these composite materials. Moreover, this study confirms the presence of fibre tied entanglements and shows the influence of the matrix.     

Propriétés catalytiques de la montmorillonite intercalée au titane dans l'oxydation de l'alcool allylique (E)-hex-2-én-1-ol

Catalytic properties of Ti-pillared montmorillonite for the epoxidation of (E)-hex-2-en-1-ol allylic alcohol. The present work is relative to the epoxidation of allylic alcohols by a well-characterised Ti-pillared montmorillonite (Ti-PILC) prepared by intercalating polymeric Ti cations formed by partial hydrolysis of TiCl₄ with HCl. The interlayer distance, the specific surface area and thermal stabilities of the resulting pillared clays depend mainly on the pH of the pillaring solution. For a ratio H⁺/Ti = 0.24, the Ti-PILC shows a basal spacing of 2,6 nm and a specific surface area of 316 m²·g^–1, stable up to 773 K. In the conversion of isopropanol, this Ti-PILC shows a Lewis type acidity and a low redox activity. It catalyses the oxidation of allylic alcohol (E)-hex-2-en-1-ol with tert-butyl hydroperoxide in the presence of diethyl tartrate. The yield and nature of the final products depend on the reaction temperature and catalyst activation: no epoxidation could be obtained with non calcined samples. With a solid calcined in air at 773 K and then converted to a Ti-PILC, the main product is hexenoic acid for a reaction below 273 K, while the epoxide of the allylic alcohol is formed with 50 % yield at 298 K. This yield is comparable to that reported for the same substrate for polymer supported Ti(IV) catalysts.     

Propriétés thermoélectriques du sélénium liquide pur et dopé à i'lode

Abstract

On a étudié le pouvoir thermoélectrique du sélénium en fonction de la température pour des échantillons de puretés diverses et dopés ayantn subi divers cyles thermiques. II varie beaucoup, passant d'un signe à l'autre; le dopage à l'iode tend à donner une conductibilité de type p.

Thermoelectric power of selenium vs temperature has been studies for samples of variable purity or doped having undergone various thermal treatments. Large variations appear, with either sign; doping with iodine favours p-type conduction.     

Une famille d’aimants bimétalliques CuIIMnII à précurseurs moléculaires et contre-cations chiraux : synthèse et propriétés magnétiques

A family of three compounds of general formula Mn₂〚Cu(opba)〛₃(cat)_x(solv)_y has been synthesised, where opba stands for ortho-phenylenebis(oxamato), (solv) are solvent molecules and (cat) are the chiral counter-cations N,N’-dimethyl-nicotinium (nicot), dimethyl-hydroxymethyl-2-éthyl-hydroxymethyl-1-propyl-ammonium (ambutol) and N,N-dimethyl-ephedrinium (dmeph). The magnetic properties of the three compounds show characteristic ferrimagnetic behaviour with a minimum in the χ_M T versus T plot and a magnetic phase transition around 20 K. The use of high temperature expansion of the partition function and molecular mean field approach allow us to show that these compounds adopt a two–dimensional structure.     

Propriétés antitumorales cytostatiques et cytotoxiques des cellules péritonéales de souris conventionnelles et axéniques stimulées ou non par corynebacterium parvum

The treatment by Corynebacterium parvum induced an increase of peritoneal cell number in conventional mice but no modifications in germ-free mice. Against YC8 tumoral target cells, cytostatic properties of peritoneal cells were of the same intensity in conventional and germ-free after C. parvum treatment. Against K.BALB cells, C. parvum treatment induced an increase of cytostatic properties from 9 to 93% in conventional mice and from 51 to 84% in germ-free mice. Cytotoxic properties were increased by C. parvum in conventional mice but were inchanged in germ-free mice. The bacterial flore could play a role in the cytotoxic and cytostatic properties of peritoneal cells in conventional mice.     

Propriétés rhéologiques à l'état fondu du polypropène renforcé de fibres de verre

Steady state flow properties of molten polypropene reinforced with short glass fibres confirm the existence of an interphase less mobile than the matrix. Moreover, knowledge of the flow behaviour of these reinforced materials lead to the prediction that their processing by injection molding must be achieved under the same conditions as the matrix itself.     

Sur les propriétés électroniques de la phénothiazine et de son radical

Résumé La phénothiazine et son radical sont probablement pliées le long de l'axe passant par les deux hétéroatomes centraux. Des calculs sont effectués par la méthode des orbitales moléculaires sur la modification des caractéristiques électroniques de la phénothiazine en fonction du pliage. On montre, que les densités de spin calculées pour les différentes configurations spatiales possibles du radical phénothiazinique permettent, par comparaison avec les densités expérimentales, de choisir la configuration la plus probable. C'est la configuration pliée dans laquelle le proton attaché à l'azote se trouve placé entre les deux cycles latéraux. L'étude des potentiels d'oxydation polarographique montre qu'au contraire dans les dérivés 10-substitués de la phénothiazine, le substituant aliphatique trop volumineux est placé hors des cycles latéraux.

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Phenothiazine and its free radical are probably folded along the axis passing through the two central heteroatoms. Calculations are carried out by the molecular orbital method on the modification of the electronic characteristics of the phenothiazine ring as a result of folding. It is shown, in particular, that the spin densities calculated for the different possible geometrical configurations of the phenothiazine free radical permit, by comparison with experimental spin densities, to deduce which configuration is the most probable. In the present case, this is the folded configuration in which the proton attached to the nitrogen atom is placed between the two lateral rings. The energy of the highest filled molecular orbital is also a sensitive function of the geometrical configuration of the molecule. The study of the polarographic oxidation potential of substituted phenothiazines shows that, in contrast to the parent molecule, in the N-alkyl substituted derivatives the voluminous alkyl substituent is probably pushed out to an external position with respect to the lateral rings.

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Zusammenfassung Phenothiazin und sein Radikal sind wahrscheinlich längs der N-S-Verbindungslinie geknickt. Wir berechneten nach der MO-Methode die Änderungen der elektronischen Eigenschaften des Moleküls mit dem Knickwinkel. Der Vergleich der für die verschiedenen denkbaren Konfigurationen des Radikals berechneten Spindichten mit Meßwerten erlaubt, eine von ihnen als am wahrscheinlichsten auszuwählen. Es ist die geknickte Form, in der das H-Atom am Stickstoff zwischen den aromatischen Ringen liegt. Die Untersuchung der polarographischen Oxydationspotentiale zeigt dagegen, daß in den N-alkyl-substituierten Phenothiazinderivaten die aliphatische Gruppe von den Seiten-Ringen wegsteht.

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Ce travail a bénéficié de la subvention CY-3073 du Public Health Service des Etats-Unis (National Cancer Institute).     

Etude,par thermogravimétrie et spectrographie d'absorption infrarouge,de quelques sulfates doubles de la série magnésienne

Résumé Les spectres d'absorption infrarouge de sulfates doubles hexahydratés de la série magnésienne permettent de confirmer l'existence de fortes liaisons hydrogéne entre les molécules d'eau et le reste de la molécule.

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Summary The infrared absorption spectra of the hexahydrates of the double sulfates of the magnesium series provided evidence confirming the existence of strong hydrogen bonds between the water molecules and the rest of the molecule.

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Zusammenfassung Die IR-Absorptionsspektren der Doppelsulfathexahydrate des Nickels, Kobalts, Magnesiums, Zinks und Eisens bestätigen die Existenz starker Wasserstoffbindungen zwischen den Wassermolekülen und dem übrigen Anteil des Moleküls.

     

Adsorption d'acides aminés sur des phosphates de calcium carbonatés analogues aux tissus calcifiés

The adsorption of alanine and phenylalanine onto apatites, containing simultaneously HPO₄²⁻ and CO₃²⁻ ions in various amount, was studied. These apatites are similar to the mineral part of calcified tissues at different stages of its maturation. The adsorption isotherms are Langmuirian in all cases whatever the amounts of HPO₄² or CO₃²⁻. However, these amounts play a role in the adsorption properties of these apatites. The largest amounts of aminoacids were adsorbed by the compounds with the highest HPO₄²⁻ content. The influence of the presence of PO₄³⁻ ions in the incubation media was studied. These ions hinder the adsorption process by competing with the aminoacid carboxylate groups for the calcium ions at the surface of the solid. The nature of the aminoacid lateral chain, especially its size, plays a role in the adsorption. The amount of aminoacid bound at saturation decreases as the size of the side chain increases.     

Synthèse et propriétés de composés de neptunium(V) formés avec le ligand polyazoté Tptz

Synthesis and properties of Np(V) compounds formed with nitrogen planar ligand Tptz. Under special conditions, Np(V) compounds are formed with N-donor aromatic ligands. In this work, synthesis as well as optical properties and thermal stability of solids [NpO₂Cl(Tptz)H₂O]·H₂O (I) and NpO₂Br(Tptz)·n H₂O (II) are investigated. To cite this article: N.A. Budantseva et al., C. R. Chimie 8 (2005).     

Utilisation des Plans d'Expériences Pour la Modélisation de l'Élaboration d'un Phosphate de Calcium de Propriétés Antiseptiques à Usage Biomédical

La synthèse d'une apatite oxygénée phosphocalcique de rapport molaire Ca/P égal à 1.575 a été étudiée par un plan composite centré orthogonal. Cette étude nous a permis d'établir un modèle mathématique qui décrit l'influence des variables: pH, concentration de la solution du chlorure de calcium ([Ca ²⁺ ]), durée de maturation (D) et température (T), sur la réponse: rapport molaire Ca/P. L'exploitation de ce modèle permet de définir des conditions d'obtention d'un solide de rapport molaire Ca/P égal à 1.575.

The synthesis of phosphocalcic oxygenated apatite of Ca/P ratio equal to 1.575 was studied by an orthogonal central composite design. This study checks the effect of certain variables on the reaction, pH, concentration of the calcium chloride solution ([Ca ²⁺ ]), ripening time (D) and temperature (T) on the response, and Ca/P ratio with a mathematical model. The exploitation of this model allowed us to define conditions for obtaining a solid of Ca/P ratio equal to 1.575.     

Radicaux imidazoline-nitroxyde,briques moléculaires paramagnétiques pour la construction d’édifices magnétiques

The synthesis, characterization and magnetic properties of new series of metal complexes based on spin-labelled pyridine, bipyridine, terpyridine, polyaza-macrocycles and calix[4]arene scaffolds have been described. Magneto-structural correlations revealed that the nature and the amplitude of the magnetic interactions strongly depend on the torsion angles between the radical and the metallic centre. In the 6,6’-bis-NIT-2,2’-bipyridine/Cu²⁺ case, the interaction is antiferromagnetic, with J ≈ –167 cm^–1, while with Ni²⁺ a large range of ferromagnetic interactions is found, depending on the geometry of the first coordination sphere [from 40 to 7 cm^–1], NIT for a nitronyle-nitroxyde radical. The presence of a pyridine spacer between the NIT radical and the metallic centre (4’-NIT-2,2’:6’,6’’-terpyridine case) notably mitigates the interaction, which remains antiferromagnetic in all cases (J ≈ –7 cm^–1 with Ni²⁺). In the podand bipyridine-ligand, one nitroxide arm is bound equatorially and the second arm is axially coordinated to Cu²⁺. With the Ni²⁺ and Zn²⁺ cations, both radicals are axially bounded. In all complexes, the bipyridine/aminomethyl fragment is meridionally complexed to the metal centre.     

Dépôt de revêtements peu rugueux de diamant sur un alliage de titane

Deposition of smooth diamond coatings on titanium alloy. A new process has been perfected to deposit smooth diamond coatings, at 600 °C, on titanium alloys. Scanning electron microscopy, X-ray diffraction, visible and UV Raman spectroscopy show that these coatings are smooth and mainly composed of crystalline diamond with a fine-grained morphology. The results are compared here to those obtained with classical rough polycrystalline coatings. Optical emission spectroscopy reveals important differences between the plasma species produced for the deposition of these smooth coatings and the plasma species produced for the deposition of both polycrystalline diamond and nanocrystalline films. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASdiamond / coating / titanium alloy / plasma / roughness / Raman spectroscopy / emission spectroscopy     

Détermination des cinétiques de croissance et de dissolution du perborate de sodium tetrahydrate en lit fluidisé

The authors present the results of an experimental study on the crystallization of tetrahydrate sodium perborate in a fluidized bed. The influences of supersaturation, seed crystal size, temperature and solution velocity on the overall growth rate were examined. The overall dissolution rate determined under comparable hydrodynamical conditions for various seed crystal sizes and temperatures is also reported.The growth rate is not very sensitive to the variations in crystal size, the temperature and the hydrodynamical conditions, but it depends on the supersaturation and the presence of some soluble impurities.The comparison between growth and dissolution rates shows that under actual working conditions the diffusional mass transfer step is not the limiting step of the growth mechanism.     

Étude de la phényl-2 oxine et de ses chélates: Préparation et propr1étés de la phényl-2 oxine

The authors prepared phenyloxin by three different methods. They obtained a product whose melting point was 59° C and then another form melting at 72° C. Ultraviolet absorption spectra were determined in cyclohexan and in alcohol-watermixtures; from these determiaations, the solubilities of phenyloxin in water and in alcohol-water mixtures of different concentrations were obtained. If ultraviolet absorption spectra are plotted for different pH values (from 1.1 to 13.7) several isobestic points are noted.