Marqueurs atmosphériques d'exposition aux particules Diesel

L'évolution du parc français d'automobiles particulières a pris depuis une vingtaine d'années un essor formidable. De près de 12 millions de voitures en 1970, il est passé à 23,5 millions en 1991, soit un doublement. Une telle augmentation entraîne bien évidemment un accroissement de la pollution atmosphérique d'origine automobile et a conduit la Communauté Européenne à réglementer les émissions dès 1970. La pollution automobile était alors traitée comme un problème global, tous types de véhicules confondus. Depuis, deux événements sont venus modifier les règle

A reaction-diffusion model for the hydration/setting of cement

We propose a heterogeneous reaction-diffusion model for the hydration and setting of cement. The model is based on diffusional ion transport and on cement specific chemical dissolution/precipitation reactions under spatial heterogeneous solid/liquid conditions. We simulate the spatial and temporal evolution of precipitated micro structures starting from initial random configurations of anhydrous cement particles. Though the simulations have been performed for two dimensional systems, we are able to reproduce qualitatively basic features of the cement hydration problem. The proposed model is also applicable to general water/mineral systems.Comment: REVTeX (12 pages), 4 postscript figures, tarred, gzipped, uuencoded using `uufiles', coming with separate file(s). Figure 1 consists of 6 color plates; if you have no color printer try to send it to a black&white postscript-plotte

Composition, silicate anion structure and morphology of calcium silicate hydrates (C-S-H) synthesized by silica-lime reaction and by the controlled hydration of tricalcium silicate (C3S)

The main product of Portland cement hydration is C-S-H. Despite constituting more than half of the volume of hydrated pastes and having an important role in strength development, very little is known about the factors that determine its morphology. To investigate the relationship between the chemical composition, silicate anion structure and morphology of C-S-H, samples were synthesized via silica-lime reactions and by the hydration of C3S under controlled lime concentrations and with/ without accelerators. The silicate anion structure of the samples was studied by 29Si MAS NMR and the morphology and chemical composition by TEM and SEM. All samples prepared via silica-lime reactions with bulk Ca/Si up to 1.5 were foil-like. The hydration of C3S at fixed lime concentration yielded foil-like C-S-H for [CaO]22mmol/L. A relationship between the silicate anion structure and the morphology of C-S-H was found for the samples fabricated with accelerators

Importance of outer-sphere and aggregation phenomena in the relaxation properties of phosphonated gadolinium complexes with potential applications as MRI contrast agents

[Abstract] A series composed of a tetra-, a tris- and a bisphosphonated ligand based on a pyridine scaffold (L4, L3 and L2, respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous solutions (25.0 °C, 0.1 M NaClO4), showing that the tetraphosphonated complexes are among the most stable LnIII complexes reported in the literature. The complexation of L4 was further studied by different titration experiments using mass spectrometry and various spectroscopic techniques including UV/Vis absorption, and steady state and time-resolved luminescence (Ln=Eu and Tb). Titration experiments confirmed the formation of highly stable [LnL4] complexes. 31P NMR experiments of the LuL4 complex revealed an intramolecular interconversion process which was studied at different temperatures and was rationalized by DFT modelling. The relaxivity properties of the GdIII complexes were studied by recording their 1H NMRD profiles at various temperatures, by temperature dependent 17O NMR experiments (GdL4) and by pH dependent relaxivity measurements at 0.47 T (GdL3 and GdL2). In addition to the high relaxivity values observed for all complexes, the results showed an important second-sphere contribution to relaxivity and pH dependent variations associated with the formation of aggregates for GdL2 and GdL3. Finally, intravenous injection of GdL4 to a mouse was followed by dynamic MRI imaging at 1.5 T, which showed that the complex can be immediately found in the blood stream and rapidly eliminated through the liver and in large part through the kidneys.Torino. Compagnia di San Paolo; CSP-2012 NANOPROGL

Self‐aggregated dinuclear lanthanide(III) complexes as potential bimodal probes for magnetic resonance and optical imaging

[Abstract] Homodinuclear lanthanide complexes (Ln=La, Eu, Gd, Tb, Yb and Lu) derived from a bis‐macrocyclic ligand featuring two 2,2′,2′′‐(1,4,7,10‐tetraazacyclododecane‐1,4,7 triyl)triacetic acid chelating sites linked by a 2,6‐bis(pyrazol‐1‐yl)pyridine spacer (H2L3) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the EuIII and TbIII complexes indicate the presence of one inner‐sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (∅H2O=0.01 for [Eu2(L3)] and 0.50 for [Tb2(L3)] in 0.01 MTRIS/HCl, pH 7.4; TRIS=tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd2(L3)] are characteristic of slowly tumbling systems, showing a low‐field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous GdIII complex containing a 4,4′ dimethyl‐2,2′‐bipyridyl spacer ([Gd2(L1)]). The relaxivity of [Gd2(L3)] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM−1 s−1. The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd2(L1)] and [Gd2(L3)], respectively. TEM images of [Gd2(L3)] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.Ministerio de Educación y Ciencia; CTQ2009‐10721Xunta de Galicia; IN845B‐2010/06

A base-free synthetic route to anti-bimetallic lanthanide pentalene complexes

We report the synthesis and structural characterisation of three homobimetallic complexes featuring divalent lanthanide metals (Ln = Yb, Eu and Sm) bridged by the silylated pentalene ligand [1,4-{SiiPr3}2C8H4]2− (= Pn†). Magnetic measurements and cyclic voltammetry have been used to investigate the extent of intermetallic communication in these systems, in the context of molecular models for organolanthanide based conducting materials

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Etude expérimentale et modélisation thermodynamique du système CaO-SiO2-(Al2O3)-H2O

L objectif de ce travail est de proposer un modèle thermodynamique à 25C qui permette de décrire les principaux produits d hydratation d un ciment Portland ordinaire avec et sans matériaux cimentaires secondaires : les hydrosilicates de calcium. La composition riche en aluminium de ces produits de substitution modifie la nature et la composition des hydrates de la pâte de ciment.Nous avons donc étudié le système simplifié CaO-SiO2-H2O, pour lequel nous avons réalisé différentes synthèses de C-S-H dans des conditions de synthèse et d analyse identiques. Nous avons distingué le cas où la solution d hydratation est sous-saturée de celui où elle est sursaturée par rapport à la Portlandite.Nous avons ensuite étendu le système simplifié précédent au système CaO-Al2O3-SiO2-H2O, pour lequel nous avons réalisé différentes synthèses de C-A-S-H et déterminé le protocole le plus adéquat pour obtenir des hydrates purs.La nature nanoparticulaire et la surface spécifique importante des C-S-H nous ont conduit à développer un modèle thermodynamique qui tiennent compte de réactions de surface. Ainsi, le modèle thermodynamique proposé dans ce travail, inspiré de différents travaux antérieurs du laboratoire, permet de décrire la composition de la solution, la stoechiométrie, et les propriétés de surface des C-S-H à l équilibre. Ce premier modèle a été étendu aux C-A-S-H, en implémentant dans le modèle précédent des réactions de surface qui permettent de décrire l incorporation de l aluminium dans les différents sites possibles.Ce modèle a été appliqué à des cas simples tels que l étude de la rétention d alcalins par les C-S-H, et l évaluation de l impact de l incorporation d aluminium dans les C-S-H sur la répartition minéralogique des hydrates à l équilibre pour un mélange cimentaire avec une forte teneur en aluminiumThe aim of this work is to build a thermodynamic model at 25C to describe the main hydrates of ordinary Portland cement with or without supplementary cementitious materials (SCM) : calcium hydrosilicates. With high aluminium content, SCM in blended cements modify the nature and the composition of the hydrates of cement paste.The simplified model system CaO-SiO2-H2O was studied by synthesising of C-S-H with identical protocol and analysis. We distinguished, hydration solutions undersaturated and supersaturated from Portlandite.This last system has been extended to CaO-Al2O3-SiO2-H2O system. Then, we determined the most suitable protocol to synthesize pure C-A-S-H.The nanoparticular nature and high specific surface of C-S-H lead us to build a surface dependant thermodynamic model. The modelling described in this work, which is inspired from previous works of our laboratory, enables to describe chemistry of solution, solid composition but also surface properties of C-S-H at equilibrium. This first model has been extended to C-A-S-H. Incorporation of aluminium in C-S-H has been taken into account through surface reactions on different titrable sites.Our models were applied to some simple cases such as the study of alkali retention by C-S-H, the evaluation of the impact of aluminium incorporation in C-S-H on hydrates nature and distribution for highly substituted blended cements, i.e. with high aluminium contentDIJON-BU Doc.électronique (212319901) / SudocSudocFranceF

Etude de paramètres endogènes et exogènes au ciment Portland ordinaire influençant l'hydratation de sa phase principale (le silicate tricalcique)

Ce travail consacré à l étude des différents paramètres influençant l hydratation de la phase silicate principale du Ciment Portland Ordinaire (OPC) a été réalisé au Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB). Cette étude s inscrit dans le cadre du projet Crystal Growth Control initié par BASF dans le but de contrôler et de prévoir le mieux possible l hydratation du Ciment Portland Ordinaire. La dissolution de l alite, comme celle du C3S pur, est rapide dans l eau pure. La vitesse diminue avec l écart à l équilibre et la concentration en ions aluminates en solution. On observe également une adsorption sur la surface de l alite de l aluminium libéré par la dissolution. La germination et la croissance des C-S-H a été étudié d une part, en présence d aluminates en solution et d autre part en présence de sels inorganiques connus pour être des accélérateurs de l hydratation du ciment Portland Ordinaire. La présence d aluminium ne modifie pas la germination initiale des C-S-H mais semble participer directement à l origine de la période dormante du ciment. L hydratation du C3S dans des solutions salines conduit à former pendant la germination initiale d autant plus de C-S-H que la solution est concentrée. De plus la morphologie des germes est modifiée. Chaque germe doit contenir plus de matière en occupant moins de surface. La simulation de l ensemble de la courbe d avancement de l hydratation observée dans les solutions de sels de nitrates et d halogénures de calcium, sodium et potassium à l aide du modèle de croissance par agrégation de particules cubiques confirme l anisotropie au cours de la croissance des germes. La vitesse de croissance des C-S-H perpendiculairement à la surface des grains augmente avec la concentration et l effet est très dépendant de la nature de l anion. Ce comportement est à rapprocher des séries d HofmeisterThis work devoted to study various parameters influencing hydration of silicate phase main Ordinary Portland Cement (OPC) was performed at the Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB). This study is part of the project "Crystal Growth Control" initiated by BASF in order to monitor and provide the best as possible the hydration of Ordinary Portland Cement. The dissolution of alite, like the pure C3S one, is fast in pure water. Speed decreases with deviation from equilibrium and the concentration of aluminates ions in solution. There is also an adsorption on the surface of the aluminum which is into the alite and released by dissolution. Germination and growth of C-S-H has been studied on the one hand, in the presence of aluminates ions within the solution and the other, in the presence of inorganic salts known to be accelerators of Ordinary Portland cement hydration. The presence of aluminum does not alter the initial germination of C-S-H but seems directly involved in the origin of the dormant period of cement. The hydration of C3S in salt solutions leads to the formation during the initial germination even more C-S-H that the solution is concentrated. In addition, the morphology of seeds is modified. Each seed must contain more material occupying less space. Simulation of the entire hydration progress curve observed in solutions of salts of nitrates and halides of calcium, sodium and potassium with the growth model based on the cubic particles aggregation confirms the anisotropy in the growth of seeds. The C-S-H perpendicular growth rate to the surface of the grains increases with the salt concentration and the effect is very dependent on the nature of the anion. This behavior is closer to the Hofmeister seriesDIJON-BU Doc.électronique (212319901) / SudocSudocFranceF