L'objectif de ce travail a été d'apporter une meilleure compréhension des mécanismes réactionnels de l'hydratation de ciments appartenant à la famille de ciment BCSAF afin de développer des schémas réactionnels simplifiés permettant d'optimiser les ciments à base d'un clinker BCSAF et d'autres constituants pour des applications spécifiques. Les ciments étudiés ont été réalisés à partir d'un clinker contenant 52% de belite, 33% de ye'elimite and 14% de ferrite et diverses quantités d'anhydrite et de calcaire. A partir de l'étude détaillée de l'hydratation d'un ciment contenant 95% de clinker et 5% d'anhydrite, il a été démontré que le mécanisme de l'hydratation est constitué de deux périodes successives : le début de l'hydratation est contrôlé par l'hydratation de la ye'elimite réagissant avec l'anhydrite, tandis que la suite de l'hydratation est contrôlée par les hydratations de la belite et de la ferrite qui réagissent avec certains des hydrates formés lors de la première période. La vitesse de nucléation de la strätlingite contrôle le début de l'hydratation de la belite. Le principal paramètre qui contrôle cette dernière est la concentration en sulfate de la phase aqueuse qui doit être très faible. Ainsi C-S-H n'est pas formé au début de l'hydratation de la belite parce qu'elle n'est pas saturé à cause de faible concentration de calcium et silicon et sa formation est retardé plus tard à cause de l'inhibition de sa nucléation par de trop fortes quantités d'aluminate en solution. Par conséquence, c'est indirectement la concentration en sulfate de la solution qui contrôle le début de l'hydratation de la belite and ainsi les réactions conduisant à sa réduction à travers la précipitation de phase notamment lors de l'hydratation de la ye'elimite pour former de l'ettringite. Ainsi d'une façon générale, la strätlingite commence à nucléer quand la ye'elimite a complètement réagi. D'autre part, une synergie entre les hydratations de la belite et de la ferrite permet de former des hydrogrenats et des C-S-H à des temps longs au détriment de la strätlingite formée auparavant. Un mécanisme d'hydratation similaire a été trouvé pour les ciments contenant des quantités plus importantes d'anhydrite à l'exception de ceux qui contiennent une quantité d'anhydrite supérieure que la quantité théorique permettant de faire réagir toute la ye'elimite en ettringite. Toutefois pour le premier type de ciments, une augmentation de la quantité d'anhydrite allonge à la fois le temps d'apparition de la seconde période et la durée des différentes étapes de cette dernière. Donc l'hydratation est globalement plus lente. Pour le second type de ciment, contenant de fortes quantités d'anhydrite, le mécanisme d'hydratation est assez différent car l'hydratation de la belite commence dès le début de l'hydratation et conduit à la formation, soit d'ettringite contenant Si, soit de C-S-H. L'effet de 15% de calcaire a également été étudié pour le ciment contenant 95% de clinker et 5% d'anhydrite. Les résultats ont montré que le calcaire ne change pas la première période de l'hydratation mettant en jeu principalement la ye'elimite et l'anhydrite. Par contre la seconde période, durant laquelle la belite et la ferrite s'hydratent, est fortement retardée à son début. Ceci peut être dû à un retard de la nucléation de la strätlingite à cause de concentrations en sulfate de la solution restant plus longtemps élevées par le fait que l'ettringite est stabilisée en présence de carbonate par la formation de phases AFm carbonatées qui inhibent la formation de monosulfoaluminate de calcium hydraté. Pour finir, des perspectives sont données notamment afin de réduire la durée de la première période de l'hydratation et ainsi permettre un démarrage plus rapide de l'hydratation de la belite et de la ferrite.

Printed Circuit Board (PCB) industry is one of the two major Integrated Circuit (IC) part manufacturing industries in Taiwan, but it derives many environmental problems because large amount of chemicals and special materials are used in its process, especially copper sludge generated from wastewater treatment. Although the heavy metal sludge can be treated by solidification, heavy metals contained in the sludge may still be leached out due to longtime exposure to acid rain. Therefore, there are urgent needs of research and development of technologies regarding how to reduce both quantity and volume of the hazardous heavy metal sludge and how to recycle the valuable heavy metals. Acid leaching method, chemical exchange method and ferrite process are applied to study how to recycle and stabilize copper sludge of PCB industry. The ultimate goal is to achieve cleaning production and sustainable development by transforming the hazardous waste into valuable byproducts, reducing the amount of the waste and lowering the treatment costs. Experimental results show that a method is successfully developed to recycle copper from the sludge generated by PCB industry by using the combination of acid leaching, chemical exchange and ferrite process. Via this method, not only is pure copper powder recycled, but highly valuable nano-scaled catalyst-CuFe2O4 is also produced. Hence, the problem that copper sludge has nowhere to go is solved, as well as the high cost of catalyst in catalytic incineration is reduced to nearly zero. The achievements of this study are summarized as follow: (1) Characteristic analysis of industrial sludge Water content and pH of the sludge is 60% and 7.05, respectively. The drop in quantity of ignition is 23%. The screening test results show that particle size of the sludge varies from 0.4 £gm to 200 £gm, with D50 of 25.0 £gm. Cu, Pb, Cd, Zn, Ni and Cr are found in the sludge, and the biggest part of heavy metals is Cu, with a concentration of 158,000 mg/kg (dry basis), whereas the other heavy metals are all below 105 mg/kg (dry basis). (2) Study of recycling of pure copper powder The optimal operational condition of acid leaching method is that concentration of sulfuric acid is 2.0 N, temperature is 50¢J and treatment time is 60 minutes. Under this operational condition, more than 99% of heavy metals can be extracted to liquid phase and the sediment of treated sludge meet Toxicity Characteristic Leaching Procedure (TCLP) standards and therefore is considered as general industrial waste. The optimal operational condition of chemical exchange method is that molar ratio of Fe/Cu is 5.0, pH is 2.0 and treatment temperature is 50¢J. Under this operational condition, more than 95.0% of Cu can be recovered. The optimal operational condition of ferrite process is that Fe/Cu=10.0, pH=9.0, treatment temperature=80¢J, aeration rate=3 L/min/per liter waste liquid and reaction time = 30 min. Under this operational condition, TCLP concentrations of all heavy metals of both supernatant and sludge are well below regulatory standards, which proves that ferrite process is very effective. (3) Resourcing of spinel sludge In the potential of catalytic incineration of volatile organic compounds test, the sludge generated from ferrite process is used to catalyze the isopropyl alcohol (IPA). The catalyst is replaced by the same volume of glass wool on a reactive bed as a blank. Experimental result shows that the conversion of IPA is only 10% at 200¢J and 75% at 500¢J in the absence of catalyst under the conditions that IPA inlet concentration=1,700 ppm, space velocity=24,000 hr-1, O2 concentration=21%, and relative humidity=19%, which indicates that the destruction of IPA is associated with the consumption of much energy when no catalyst was used. But when ferrite catalyst is applied, IPA is decomposed completely at 200¢J, showing that the sludge has great potential of catalyst. (4) Synthesizing five VOCs catalyzing ferrite catalysts via ferrite process As to the synthesis of five ferrite catalysts in the laboratory, IPA conversion rate is higher than 58% at 200¢J. The sequence of IPA conversion from good to bad is Cu-ferrite catalyst > Mn-ferrite catalyst > Ni-ferrite catalyst > Zn-ferrite catalyst > Cr-ferrite catalyst, where Cu/Fe is most efficiency, with IPA conversion rate of 75% at 150¢J and 100% at 200¢J.

The aim of this thesis work was to develop magnetoelectric (ME) composites consisting of piezoelectric and magnetostrictive components. The piezoelectric constituent was selected as a PZT ceramic modified by strontium, bismuth and manganese. The magnetostrictive phase was nickel ferrite (NF) ceramic doped by cobalt, copper and manganese. The properties of component phases were optimized in order to enhance the ME effect in the composite. In the first part of the thesis, effects of sintering temperature on the dielectric and piezoelectric properties of PZT and on the electrical and magnetic properties of NF ceramics were investigated in the temperature range covered from 1150 to 1250 &deg / C. The best piezoelectric properties in PZT were attained at 1250 &deg / C. At this sintering temperature, values of piezoelectric strain coefficient, dielectric constant, and electromechanical coupling coefficient were 434 pC/N, 1320 and 0.48, respectively. NF ceramics showed poor densification / 80 %TD was attained at 1250 &deg / C. In order to obtain higher densities in ferrites, Bi2O3 was used as a sintering aid. Addition of Bi2O3 enhanced densification up to 97 %TD, and improved electrical and magnetic properties of ferrites. Highest DC-resistivity of 1.15*10^8 ohm-cm and highest magnetostriction of ~26 ppm were attained in NF ceramics doped with 1 wt% Bi2O3. In the second part of the thesis, ME composites were manufactured either as bulk composites or as laminated composites. The efficiency of different composite types was evaluated in terms of voltage output in response to the applied magnetic field. Higher outputs were observed in laminated composites.

The magnetic separation approach has several advantages compared with conventional separation methods / it can be performed directly in crude samples containing suspended solid materials without pretreatment, and can easily isolate some biomolecules from aqueous systems in the presence of magnetic gradient fields. This thesis focused on the development of new class of magnetic separation material particularly useful for the separation of histidine-tagged proteins from the complex matrixes through the use of imidazole side chains of histidine molecules. For that reason surface modified cobalt ferrite nanoparticles which contain Ni-NTA affinity group were synthesized. Firstly, cobalt ferrite nanoparticles with a narrow size distribution were prepared in aqueous solution using the controlled coprecipitation method. In order to obtain small size of agglomerates two different dispersants, oleic acid and sodium chloride, were tried. After obtaining the best dispersant and optimum experimental conditions, ultrasonic bath was used in order to decrease the size of agglomerates. Then, they were coated with silica and this was followed by surface modification of these nanoparticles by amine in order to add functional groups on silica shell. Next, &ndash / COOH functional groups were added to silica coated cobalt ferrite magnetic nanoparticles through the NH2 groups. After that N&alpha / ,N&alpha / -Bis(carboxymethyl)-L-lysine hydrate, NTA, was attached to carboxyl side of the structure. Finally, nanoparticles were labeled with Ni (II) ions. The size of the magnetic nanoparticles and their agglomerates were determined by FE-SEM images, particle size analyzer, and zeta potential analyzer (zeta-sizer). Vibrational sample magnetometer (VSM) was used to measure the magnetic behavior of cobalt ferrite and silica coated cobalt ferrite magnetic nanoparticles. Surface modifications of magnetic nanoparticles were followed by FT-IR measurements. ICP-OES was used to find the amount of Ni (II) ion concentration that was attached to the magnetic nanoparticle.

Ferrite process (denoted by FP) has been used for treating the waste-liquid containing heavy metal for many years. Related researches have shown that this method could catch the heavy metal regulated by environmental law into the structure of spinel, and sludge from FP also conformed the standards of toxicity characteristic leaching procedure in EPA of Taiwan. On comparing with neutral precipitation of conventional method, spinel¡¦s sludge produced in FP had an ease separation of solid-liquid and no need of solidification in further treatment. These spinel, belonged to the magnetic material, could be used for applications such as brick of blinder guide, magnetic symbol, absorber of electric wave and adsorbent. Therefore, this method has a great potential for treating the waste containing heavy metal in laboratory. This study was to investigate the optima conditions in removal of heavy metal in waste liquid in laboratory by using the FP of conventional, two and three stage. All experiments, including one ion and ten ions heavy metal mixed in a solution, were conducted in a batch- type reactor for total concentration of 2000 mg/L heavy metals. The major parameters included temperature, ferric ion dosage, aeration intensity and pH. The performance of treatment in FP was judging by that the concentration of all heavy metals in filtered solution and the heavy metal containing in sediment sludge should be below the regulations of effluent standards and TCLP standards. In conventional one stage of FP experiments performed at constant temperature and pH, the residual concentration of heavy metals in filtered solution was below the effluent standards except of Cd and of Hg; in results of TCLP showed that higher dissolvion of Cd, Cu and Pb leached from sediment and the rest ions of heavy metal passed the regulations. Thus, we conducted individually for Cd, Cu and Pb to find the optimal conditions. The optimal pH of 7 and temperature above 70 ¢J for Cd and Pb and the optimal pH of 10 and temperature above 80 ¢J for Cu were obtained. They were be used for combination of process in various stage to achieve the goal of treatment performance. After the combination of two and three stage reactions, three stage reactions in series was the only selection in removal of ten heavy metals performed by FP. As a result, the sequences were in the following: (1) 70¢J, pH=9 (2) 90¢J, pH=9 (3) 80¢J, pH =10 , and the reaction period was 40 min for each stage.

In industrial wastewater, there are usually many kinds of organics and heavy metals and can cause damage on human health and environment without well treatment. Printed Circuit Board (PCB) industrial wastewater is a typical example due to the complicated manufacture processes and the use of specific chemicals. In this study, the PCB industrial wastewater is collected and then treated by the combination of Fenton method and Ferrite Process (or called Fenton-Ferrite Process, FFP). Moreover, the recycling possibility of sludge generated from FFP is also studied. Through this study, the treatment procedure of wastewater containing organics heavy metals is established and the direction of sludge reuse is also provided. To realize the characteristic of PCB industrial wastewater, the wastewater from some PCB factory in southern Taiwan was firstly collected and analyzed to identify the pollution concentrations and then treated by FFP. The experimental results showed that the optimum parameters of Fenton method in FFP were pH = 2, [Fe2+]= 500 mg/L, [H2O2]= 3000 mg/L, reaction time= 60 min and batch dosing, and the residual COD and TOC were 84.9 mg/L and 58.3 mg/L under the COD regulation standard 120 mg/L. Meanwhile, the proper conditions of Ferrite Process in FFP were pH= 10, reaction temperature= 80¢J, reaction time= 40 min, aeration rate= 3 L/min/L wastewater, Fe/Cu molar ratio= 10 and three-stage reaction. Under that circumstance, the residual [Cu2+] in wastewater was 0.18 mg/L and the Toxicity Characteristic Leaching Procedure (TCLP) test of sludge from FFP was 4.58 far below the effluent standard 3 mg/L and TCLP standard 15 mg/L. The properties of sludge were further investigated by X-Ray Diffractometer (XRD), Scanning Electron Microscope (SEM) and Superconducting Quantum Interference Device (SQUID). The pattern of XRD indicated that the major structures were Fe3O4 and CuFe2O4; the figure of SEM showed that the surface of sludge was composed of many round particles and the distribution of particle size was from 50 nm-100 nm; the magnetic property analyzed by SQUID showed that the saturation moment was 62.85 emu/g. In the research of sludge applied in catalytic incineration, the o-xylene conversion was 97 % by sludge but only 31 % by quartz sand at 400 ¢J. Moreover, in the 72 hr-decay test of catalyst, the results clearly indicated that the performance did not obviously decline and there were no any byproducts but CO2. Therefore, the investigation revealed that the sludge had great potential in catalytic reaction. The catalytic performance of various ferrospinels generated from different manufactured conditions was also studied. Through the screening of catalysts, the order of various ferrospinels activity was Cu-ferrite > Mn-ferrite > ferrite ¡Ü Zn-ferrite and the most effective Cu-ferrite was manufactured at pH= 9 and T= 90 ¢J. After 72 hr test, the decay of catalyst was not also found. In the examination of Cu-ferrite physical property, the XRD pattern showed that the structure was CuFe2O4; the figure of SEM illustrated that there was no difference between the surface of fresh and used catalyst; the magnetic property measured by SQUID showed that the saturation moment was 30.89 emu/g.

In this thesis, the commercial viability of the aminolytic synthesis method is explored through robustness, versatility, and waste reduction studies. We report the preparation of metal precursors and the development of a synthetic approach using an aminolytic reaction of metal carboxylates in oleylamine and non-coordinating solvent. Manganese doping in the cobalt ferrites allows for the investigation of the couplings. All the compositions in the series Co1-xMnxFe2O4, 0.0  x  1.0 were synthesized via the aminolytic reaction. The coercivity decreases with increasing Mn2+ concentration due to reducing of high magnetic anisotropy ion (Co2+) content. To our knowledge, this work is the first completed series of Co1-xMnxFe2O4. The method is used to synthesize manganese ferrites dope with chromium. This allows for the investigation of the effects of orbital momentum quantum coupling. All the compositions of MnFe2-xCrxO4, x= 0.0, 0.05, 0.13, 0.25, 0.43, 0.62, and 0.85, were synthesized via the In-situ aminolytic method. Chromium concentration weakens the couplings resulting in the decrease in overall magnetic moment. All by-products can be recycled for re-utilization. The "mother" solution can be used for multiple batches without treatment. Our trials have shown that the reaction could undergo ten reactions using the same solution without scarifying the quality or yield of the product. Finally, an environmental application is explored through the use of iron oxides. Samples of goethite, maghemite, magnetite, and hematite were synthesized and characterized. These nanoparticles were exposed to arsenic and chromium solutions to measure the percent uptake of contaminant by each phase. Adsorption isotherms were plotted to obtain Freundlich parameters. The adsorption constant (K) averages over a 400% increase on literature values. We synthesized hematite and maghemite core-shell particles and exposed them to arsenite and maghemite core-shell particles have the higher removal affinity due to their smaller size.

Des céramiques ferrites à couches d'ârret de type spinelle et hautement densifiées ont été élaborées. Si les propriétés diélectriques varient fortement selon les conditions d' élaboration, les propriétés magnétiques sont au contraire peu altérées. Des relaxations diélectrique et d'impedance ont été mises en évidence, elles ont été modélisées; leurs caractéristiques ont été déterminées en fonction de la composition des grains et des paramètres de préparation des échantillons.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18987号 / 工博第4029号 / 新制||工||1620 / 31938 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 白井 泰治, 教授 松原 英一郎 / 学位規則第4条第1項該当

Le travail présenté dans cette thèse s'inscrit dans la thématique " intégration de puissance ". Il porte sur l'étude des propriétés du matériau ferrite NiZnCu nanostructuré produit par SPS (frittage simple et réactif) et la réalisation de composants électromagnétiques monolithiques intégrés et leurs caractéristiques électriques. Les objectifs fixés au début de la thèse ont été atteints. Nous avons montré que des ferrites nanostructurés ayant des bonnes propriétés peuvent être obtenues par SPS. Pour un frittage simple, les principales caractéristiques structurales, diélectriques et magnétiques ont été déterminées pour différentes températures et temps de densification. Ces échantillons frittés montrent qu'après une décarburation et des valeurs élevées de résistivité électrique, des faibles valeurs de la permittivité diélectrique, et des valeurs élevées de permabilité magnétique initiale et du facteur de mérite peuvent être obtenues et controlées par le temps et la température de frittage. La synthèse in-situ par SPS montrent aussi des propriétés similaires à celles obtenues par frittage simple. Nous avons aussi montré, pour des oxydes de départ de taille nanométrique, que les conditions de broyage et la synthèse in-situ par SPS permettent de concevoir des ferrites ayant des propriétès intéressantes avec des pertes constantes jusqu'à 3 MHz à 15 mT et jusqu'à une température voisine à 60 °C. Les derniers obectifs ont été aussi atteints, l'ensemble des cofrittages du ferrites avec des matériaux conducteurs et diélectriques montrent qu'il est possible de réaliser des composants électromagnétiques monolithiques intégrés. Ces cofrittages montrent que le ferrite est compatible avec le cuivre, le titanate de barrium et des bandes coulées de diélectriques. Des composants inductifs et des transformateurs intégrés ont été réalisées. Les caractéristiques fréquentielles des composants inductifs montrent que l'insertion du diélectrique augmente les performances du composant en reduisant les pertes et l'impact des courants de polarisation. Pour les transformateurs réalisés avec diélectriques les résultats n'ont pas été satisfaisants. Seul un transformateur sans matériau diélectrique a pu être réalisé et testé et comme attendu, le coefficient de couplage entre le primaire et secondaire s'est avéré faible.