Orientador: Kleber Roberto Pirota / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-20T23:05:11Z (GMT). No. of bitstreams: 1 Macedo_GleyguestoneLopesde_M.pdf: 4864713 bytes, checksum: a6eff7f69f1d64274cacac58dc118e5c (MD5) Previous issue date: 2012 / Resumo: Neste trabalho, seguindo uma nova rota de síntese, foram produzidas três amostras de nanopartículas do tipo dímero de prata com magnetita (Ag-Fe3O4), onde a única diferença entre elas é no valor da concentração de partículas de prata utilizadas na síntese. As amostras de tipo dímero possuem concentrações de prata iguais a 0,003 g/mL, 0,007 g/mL e 0,01 g/mL e foram chamadas, respectivamente, de AgFeO_1, AgFeO_2 e AgFeO_3. Sobre estes sistemas realizaram-se medidas da magnetização do tipo Zero Field cooling/Field cooling (ZFC-FC) onde se observou nos três sistemas um aumentou brusco da temperatura de irreversibilidade (Tirr) da magnetita quando unida a prata. Também se observou que somente na amostra com menor concentração de prata sofre um grande aumento em sua temperatura de bloqueio (T B), aproximadamente 130K, que pode ser devido a fatores como aumento do tamanho da partícula de magnetita contida no dímero, aglomerações e interações entre particulas. Porém, através de medidas de dicroísmo circular magnético de raios-X (XMCD) observou-se que com a união da prata a magnetita provoca nesta um aumento de seu momento orbital sendo mais intenso para a amostra com menor concentração de prata (AgFeO_1). Tal resultado pode explicar o aumento em Tirr e TB, já que o momento orbital é diretamente proporcional à anisotropia magnética. Por fim, gostaria de salientar que, em conjunto com meu orientador (Prof. Kleber Roberto Pirota) foi decidido optar por uma estrutura na qual inicio com descrição das bases teóricas de interesse, logo comento rapidamente sobre as técnicas experimentais utilizadas e, finalmente, anexo os trabalhos publicados. Porém, como alguns resultados obtidos neste trabalho ainda não foram publicados, decidi resumir-los no final da tese (capítulo 4) / Abstract: In this work, following a new synthesis route, three samples were produced nanoparticle type silver dimer with magnetite (Ag-Fe3O4), where the only difference between them is the value of the concentration of silver particles used in the synthesis. Samples of dimer type silver concentrations have equal 0,003 g/mL, 0,007 g/mL e 0,01 g/mL and were named, respectively AgFeO_1, and AgFeO_2 AgFeO_3. On these systems were expressed as the magnetization of the type Zero Field cooling/Field cooling (ZFC-FC) where it was observed in all three systems a sudden increase in temperature of irreversibility (T IRR) of magnetite attached to silver. It was also observed that the sample with only low silver concentration undergoes a sharp increase in its temperature block (TB), to approximately 130K, which may be due to factors such as increasing the particle size of magnetite contained in the dimer interactions and agglomerations. However, through measures of magnetic circular dichroism X-ray (XMCD) observed that with the union of silver magnetite causes this increased their orbital momentum being more intense for the sample with lower concentration of silver (AgFeO_1). This result may explain the increase in TB and TIRR, since the orbital momentum is directly proportional to the magnetic anisotropy. Finally, let me emphasize that, together with my advisor (Prof. Kleber Roberto Pirota) it was decided to opt for a structure in which beginning with a description of the theoretical bases of interest, just comment quickly on the experimental techniques used and eventually annex published works. However, as some results of this work have not yet been published, I decided to summarize them at the end of the thesis (Chapter 4) / Mestrado / Física / Mestre em Física

>Magister Scientiae - MSc / The global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately, it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe₃O₄/SiO₂/TiO₂ photocatalyst. Magnetically separable Fe₃O₄/SiO₂/TiO₂ composite with core–shell structure were synthesized by the deposition of uniform anatase TiO₂ NPs on Fe₃O₄/SiO₂ by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on TiO₂ layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO₂ catalyst, increase of the surface area and adsorption properties. Lastly and most importantly magnetic nanoparticles upsurge the production of hydroxyl groups or reduced charge recombination. The a synthesized catalysts were characterized using Transmission Electron Microscopy, X-ray Diffraction; Infra-red Spectroscopy, Scanning Electron Microscope and Energy Dispersive Spectroscopy. Other characterization techniques includeVibrating Sample Magnetometry, Brunauer Emmett Teller analysis and Thermogravimetric analysis. The average size of the particles size is 72 nm. Furthermore the photocatalytic performances of the magnetic catalysts were assessed in comparison with that commercial titanium dioxide for the degradation of methylene blue using photochemical reactor under ultra violet light. The results showed that the photocatalytic activity was enhanced using Fe₃O₄/SiO₂/TiO₂ and Ag-Fe₃O₄/SiO₂/TiO₂ compared with that for Fe₃O₄, commercial titanium dioxide powder.

Please read he abstract in the section 00front of this document / Dissertation (M Eng (Chemical Engineering))--University of Pretoria, 2007. / Chemical Engineering / unrestricted

Iron ore sinter is produced from fine-grained ore in order to provide a direct charge to the blast furnace. During the sinter production process fine sinter is produced that is not acceptable as feedstock for the blast furnace. This fine material is screened off and returned to the sinter plant to be recycled. The production of these recirculating fines therefore results in loss of revenue for the sinter producing facility. The aim of this study is to compare the composition and phase chemistry of the fine and normal sinter to determine if chemical or operational changes can be made to reduce the amount of fine sinter formed. This will be achieved through the analyses of real industrial sinter samples, synthetically produced lab-based samples and sinter test pot samples. Iron ore sinter was collected from the Vanderbijl Park sinter plant in South Africa. The samples were prepared for X-ray diffraction (XRD) and X-ray fluorescence (XRF) analysis to test the reproducibility of the equipment used as well as the reproducibility of the sample preparation method. The results obtained showed that the methods applied produced accurate results and the preparation method was then applied on all samples that were analyzed. The XRD analyses show that the sinter contains spinel (mainly magnetite with variable Mg), hematite, dicalcium silicate (C2S) and silico ferrite of calcium and aluminum (SFCA) and that there are distinct differences between the fine and normal sinter. Fine sinter contains more hematite and less SFCA than normal sinter. The presence of the SFCA is considered to be essential for the production of strong sinter. The XRF analyses show that there are no distinctive differences in the chemistry of fine and normal sinter. The samples were then analyzed with an electron microprobe. It was found that the compositions of some of the SFCA phases present in the samples do not correspond to those described in the literature. Optical microscopy combined with point counting was conducted on the fine and normal sinter in order to determine differences and to compare the point counting data to the XRD results. The point counting results showed that the hematite present in the fine sinter is largely relict or unreacted hematite. Sinter pot test samples were analyzed with XRD and XRF. It was found that the pot test samples exhibited similar trends as the samples taken at the sinter plant. This shows that it is not only plant parameters such as sample transport that result in the formation of fines, but that carbon addition, flame temperature and reaction time may also play a role in the formation of fine sinter material. It has been concluded that the production of fine sinter is a direct function of the amount of hematite present in the sinter. The proposed hypothesis for this phenomenon involves the incomplete reaction of the sinter material during processing. Suggestions to decrease the amount of fine sinter formed include: uniform heat distribution during ignition, pO2 alteration by reductant addition, lower ignition temperature, regulating the cooling regime and decreasing the grain size of lime. / Dissertation (MSc(Applied Science))--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted

Magnetic nanoparticles are used in nanotechnologies and biomedical applications, such as drug targeting, hyperthermia, MRI contrasting agents, and bio-separation of compound solutions. Magnetite (Fe3O4) nanoparticles stand to be effective in these roles due to the non-toxic nature of magnetite and its ease of manufacture. To this end, a greater understanding of the magnetic behavior of the individual magnetite nanoparticles is needed when a collection of them is used. This research seeks to discover the local magnetic ordering of ensembles of magnetite nanoparticles at various stages of the magnetization process, temperatures above and below their blocking temperature, and for various particle sizes. We use x-ray circular dichroism and x-ray resonant magnetic scattering (XRMS), which provides information about the magnetic orders in the samples. Here we discuss the modeling of the magnetic scattering data using a one-dimensional chain of nanoparticles in real space as well as an empirical Gaussian packet model in reciprocal space. We find that at low temperature, and field values close to the coercive point, magnetite nanoparticles experience a significant amount of antiferromagnetic ordering that increases with particle size.

The aim of this work was to study the possibilities of using magnetite for phosphorus removal and recovery from wastewater. It was also aimed to investigate how the structure of magnetite influences the efficiency of adsorption and desorption of phosphorus. Methodology used in this study is literature review and laboratory experiments. The study is mainly focused on the influence of Fe(II)/Fe(III) ratio in magnetite (coefficient K) on the P removal and recovery rate. Several sets of experiments were also done to study the influence of some factors (e.g. contact time, starting concentrations, amount of base needed, etc.) on the efficiency of the processes. Study results showed that magnetite has a great potential for phosphorus removal because of its high efficiency, especially at low concentrations of input phosphorus. It was also found that the contact time and sedimentation time of the method is relatively small. Recovering of magnetite is also possible, but for its reuse additional renovation stage is needed. It was concluded that magnetite purification could be preferably used as the polishing method. It can be introduced in already existing wastewater treatment facilities and substitute some older technologies. The method seems to be easy in starting and operation; it has relatively low operational and investment costs.

Two types of (polymer-imaging agent-drug) complexes were prepared and characterized. These included block and graft copolymer complexes with magnetite nanoparticles and manganese ions. Magnetite block ionomer complexes (MBICs) were formed through binding of a portion of the anionic segment of poly(ethylene oxide)-b-poly(acrylic acid) (PEO-b-PAA) block copolymers with the magnetite nanoparticle surfaces. The remainder of the carboxylic acids were utilized to bind with high concentrations of the cationic antibiotic gentamicin (31 wt%). A near zero-order release of gentamicin (pH 7.4 in PBS) that reached ~35 wt% of the initial gentamicin within 10 hours was observed, and this was followed by slower release of another 7 % by 18 hours. These nanoparticles were efficiently taken up by macrophages and appeared to enhance intracellular antimicrobial activities of gentamicin. To increase the complex sizes and NMR T2 relaxivities, amine functional MBICs (MBICs-NH2) were first assembled by adsorbing the polyacrylate block of an aminofunctional poly(ethylene oxide)-b-poly(acrylic acid)) (H2N-PEO-b-PAA) copolymer onto magnetite nanoparticles. Amines at the tips of the H2N-PEO corona were then linked through reaction with a PEO diacrylate oligomer to yield MBIClusters where the metal oxides in the precursor nanoparticles were distinctly separated by the hydrophilic polymer. These MBIClusters with hydrophilic intra-cluster space had transverse relaxivities (r2's) that increased from 190 to 604 s-1 mM Fe-1 measured at 1.4 T and 37°C as their average sizes increased. The clusters were loaded with up to ~38 wt% of the multi-cationic drug gentamicin. MRI scans focused on the livers of mice demonstrated that these MBIClusters are very sensitive contrast agents. These results indicate that these complexes could be potential theranostic agents for dual imaging and drug delivery. Manganese graft ionomer complexes (MaGICs) comprised of Mn ions and a novel polyaminobisphosphonate-g-PEO copolymer were developed for use as T1 weighted MRI positive contrast agents. The graft copolymers were prepared by free radical copolymerization of ammonium bisphosphonate methacrylate monomers with PEO-acrylate macromonomers. The complexes exhibited good colloidal stability without release of free manganese and did not show any in vitro toxicity against mouse hepatocytes. The T1 relaxivities of the MaGICs were 2-10 times higher than that of a commercial manganese based contrast agent MnDPDP. These MaGICs with encapsulated anticancer drugs including doxorubicin, cisplatin and carboplatin have encapsulation efficiencies of 80-100 %. Drug release was sustained and depended on environmental pH, drug structure and drug concentration in the MaGICs. Moreover, these drug-loaded complexes exhibited high anticancer efficacy against MCF-7 breast cancer cells. The prominent MRI relaxivities and high anticancer efficacy suggest that these MaGICs have potential as effective dual imaging and chemotherapeutic agents. / Ph. D.

Within this thesis, a comprehensive study of the initial growth process of pure Fe3O4 films and Fe3O4/NiO bilayers on Nb:SrTiO3(001) substrates including the thermal interdiffusion behavior of these bilayers is presented. The sensitive interplay between magnetic, electronic and structural properties of these materials has been investigated in detail. In the first study, the initial growth behavior of high-quality ultrathin magnetite films on SrTiO3(001) deposited by reactive molecular beam epitaxy depending on the deposition temperature has been analyzed. For this purpose, the growth process has been monitored in situ and during the deposition by grazing incidence x-ray diffraction (GIXRD). The second part provides a comparative study of Fe3O4/NiO bilayers grown on both MgO(001) and Nb:SrTiO3(001) substrates exploring morphological, structural and magnetic properties. These structures have been investigated by means of x-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), x-ray reflectivity (XRR) and diffraction (XRD), as well as vibrating sample magnetometry (VSM). Subsequently, thermal stability of these bilayers and the thermally induced interdiffusion process have been studied successively accompanied by a comprehensive characterization of the fundamental electronic, structural and magnetic properties using additional techniques such as angle resolved hard x-ray photoelectron spectroscopy (AR-HAXPES) and x-ray magnetic circular dichroism (XMCD). Finally, an alternative pathway for the preparation of ultrathin nickel ferrite films through interdiffusion is provided.

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