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La cristallisation assistée par ultrasons permet de diminuer le temps d'induction et la largeur de la zone métastable, de modifier la distribution de tailles, de modifier le faciès des cristaux et d'augmenter le nombre des cristaux formés. L'origine microscopique de cet effet reste à ce jour non élucidée. Les ultrasons de puissance engendrent dans un liquide la naissance et l'oscillation très violente de milliards de petites bulles de gaz, phénomène appelé cavitation. Le cycle d'une de ces bulles sur une période acoustique consiste en une phase explosive suivie d'une implosion violente. A la fin de l'implosion, la pression peut atteindre 1 GPa. Plusieurs hypothèses sur les mécanismes mis en jeu sont proposées dans la littérature : refroidissement de la solution et augmentation de la pression au voisinage de l'interface, évaporation du solvant dans la bulle, et ségrégation des molécules ou des ions du soluté au voisinage de la bulle lors de la phase implosive. Afin d'examiner l'influence de la pression, des expériences de cristallisation du sulfate de zinc heptahydraté ont été menées (mesure de temps d'induction). Ce sel présente une solubilité indépendante de la pression entre 0 et 10 000 bars. Nos expériences ont montré que le temps d'induction est fortement diminué en présence d'ultrasons. Ce résultat nous permet d'affirmer que la pression au voisinage de la bulle n'entre pas en jeu dans le mécanisme de la nucléation primaire du ZnSO4,7H2O en présence d'ultrasons. Après l'étude de l'effet de la sursaturation, nous avons essayé d'exploré l'effet de la puissance ultrasonore, du gaz dissous et de la hauteur du liquide dans la cuve sur le temps d'induction. Il a été constaté que les ultrasons permettent de diminuer le temps d'induction. Il a été observé que la courbe du temps d'induction en fonction de la hauteur de la solution présente un minimum. Un autre volet de cette thèse réservé à la modélisation et la simulation. Dans un premier temps, la concentration en clusters ou agrégats moléculaires au voisinage de la bulle été calculée dans le cas du ZnSO4,7H2O grâce à la théorie de la ségrégation en fonction de la pression acoustique. La simulation montre qu'il y a une sur-concentration des clusters (jusqu'à 25 fois supérieure à la concentration stationnaire) augmentant ainsi la probabilité de contact des clusters, durant un temps très court, pouvant ainsi modifier le processus global de nucléation. Dans un deuxième temps, la modélisation/simulation de l'acoustique par COMSOL est réalisée en vue de déterminer les résonances de notre système (liquide + parois de la cuve). Les résonances observées sont cohérentes avec les mesures de temps d'induction. / Power ultrasound is known to enhance crystals nucleation, and nucleation times can be reduced by oneup to three orders of magnitude for several organic or inorganic crystals. The precise physics involved in this phenomenon still remains unclear, and various mechanisms involving the action of inertial cavitation bubbles have been proposed. In this paper, two of these mechanisms, pressure and ségrégation effects, are examined. The first one concerns the variations of supersaturation induced by the high pressures appearing in the neighbourhood of a collapsing bubble, and the second one results from the modification of clusters distribution in the vicinity of bubble. Crystallisation experiments were performed on zinc sulphate heptahydrate ZnSO4. 7H2O, which has been chosen for its pressure-independent solubility, so that pressure variations have no effect on supersaturation. As observed in past studies on other species, induction times were found lower under insonification than under silent conditions at low supersaturations, which casts some doubts on a pure pressure effect. The interfacial energy between the solid and the solution was estimated from induction times obtained in silent conditions, and, using classical nucléation theory, the steady-state distribution of the clusters was calculated. Segregation theory was then applied to calculate the over-concentrations of n-sized clusters at the end of the collapse of a 4 lmbubble driven at 20 kHz by different acoustic pressures. The over-concentration of clusters close to the critical size near a collapsing bubble was found to reach more than one order of magnitude, which may favour the direct attachment process between such clusters, and enhance the global nucleation kinetics. The effects of acoustic cavitation on crystallization of ZnSO4. 7H2O was observed in a sono-reactor build-up from a large emitting area transducer located at the bottom of the vessel. The experimental results have shown that the dissipated acoustic power passes through a maximum at about 15±1 cm, and that the induction-time passes through a minimum for the same liquid-level. The dissipated-power and the induction-time are found to be well correlated as the liquid height was varied. The acoustics of the sono-reactor was studied with linear acoustics, accounting for the wall vibrations by using the COMSOL software. Theoretical dissipated acoustic powers were compared to the experimental ones.

L’objectif de cette étude est de réaliser la synthèse d’un ciment riche en phases réactives, obtenu par cuisson à une température inférieure ou égale à 1300°C d’un cru constitué de vase de barrage et d’un complément de chaux et utilisant du sulfate de zinc comme minéralisateur. Cette étude donne les caractéristiques minéralogiques et les propriétés physico- mécaniques du ciment synthétisé. L’analyse qualitative et quantitative par diffraction des rayons X a été utilisée pour caractériser les matériaux bruts et les minéraux du ciment. L’évolution du durcissement des pâtes de ce ciment a été suivie et quantifiée par calorimétrie isotherme, DTG, diffraction des rayons X et au moyen d’essais mécaniques en compression sur éprouvettes de pâte pure. Les résistances obtenues à 7 et 28 jours permettent de viser une classification CEM II 32,5 N. / The objective of this study is the synthesis of a cement rich in reactive phases, obtained by burning, at a temperature lower than or equal to 1300 °C, a raw material composed of sludge from a dam with a complement of lime, and using zinc sulphate as a mineralizer. This study gives the mineralogical, physical and mechanical characteristics and properties of the synthesized cement. Qualitative and quantitative X-ray diffraction analysis was used to characterize the raw materials and the minerals of the cement. The evolution of its hardening was monitored and quantified by isothermal calorimetry, DTG, X-ray diffraction and mechanical compression tests on pure paste samples. The strengths obtained at 7 and 28 days make it possible to aim at a CEM II 32.5 N classification.

Studies in the USA have reported that species of meiobenthic copepods can be used as bioindicators of sediment-associated contaminants. The main objective of this research project was to develop and validate methods to assess the effects of estuarine pollution, using the marine benthic copepod Robertsonia propinqua as a bioindicator of environmental health in New Zealand intertidal / estuarine areas. Cultures of R. propinqua were set up and maintained in the laboratory and individuals used in 96h acute and full life-cycle chronic bioassays using the pre-selected contaminants atrazine and zinc sulphate. From the 96h acute experiments it was found that the lethal doses at which 50% mortality occurred (LC50) for exposed nauplii and adult individuals were 7.5 mg/L and 31.8 mg/L, respectively for atrazine and 1.7 mg/L and 2.7 mg/L, respectively for zinc sulphate. This indicated that the nauplii life stage was more sensitive than were the adult life stages for exposure to both contaminants. Based on the 'trigger' values reported (atrazine = 0.013 mg/L, zinc = 0.015 mg/L) in the Australian and New Zealand guidelines for fresh and marine water quality, which provide values at which concentrations of contaminants can occur in the environment before they begin causing effects on aquatic fauna, it is unlikely that the calculated LC50s in the current research will induce biological effects in exposed copepods in the short-term. The calculated LC50 results were then used to further investigate the effects of chronic exposure of sediment-associated contaminants on the complete life-cycle (egg-reproductive adult) of R. propinqua. In a laboratory-based full life-cycle toxicity test, field-collected sediments from polluted sites in the Auckland and Bay of Plenty regions reduced reproductive output (nauplii and copepodite production) of R. propinqua individuals, but the number of males and females, gravid females, clutch size per female and the number of eggs produced were not affected by either the polluted or non-polluted (reference) sediment samples from both field regions. Field investigations of meiofauna community composition in polluted and non-polluted field sites were carried out in 2004 in the Auckland and Bay of Plenty field regions in New Zealand. Greater sediment organic content and a correspondingly deeper redox potential discontinuity layer occurred in all polluted field sites compared with the non-polluted sites. However, species composition could not be used to characterise polluted and non-polluted sites, as there were no dominant taxa which were representative of these sites. The results presented in this thesis indicate that R. propinqua has strong potential to be a good candidate species as a bioindicator of environmental contamination. Furthermore, the full life-cycle toxicity test could be used as a rapid test to detect immediate changes in individual reproduction and development as well as long-term population effects. The technologies developed as part of this research may eventually provide additional tools for commercial environmental consultancies and may compliment existing standard operating procedures for environmental assessments involving pollution of estuarine ecosystems.