Made available in DSpace on 2014-12-17T14:07:16Z (GMT). No. of bitstreams: 1 CesarRMS_TESE.pdf: 4847104 bytes, checksum: d7b76254ab621fe30c0fe75fd8680501 (MD5) Previous issue date: 2013-06-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / For the chemical method of synthesis of co-precipitation were produced ferrite powders manganese-cobalt equal stoichiometric formula Mn (1-x) Co (x) Fe2O4, for 0 < x < 1, first reagent element using as the hydroxide ammonium and second time using sodium hydroxide. The obtained powders were calcined at 400 ? C, 650 ? C, 900 ? C and 1150 ? C in a conventional oven type furnace with an air atmosphere for a period of 240 minutes. Other samples were calcined at a temperature of 900 ? C in a controlled atmosphere of argon, to evaluate the possible influence of the atmosphere on the final results the structure and morphology. The samples were also calcined in a microwave oven at 400 ? C and 650 ? C for a period of 45 minutes possible to evaluate the performance of this type of heat treatment furnace. It was successfully tested the ability of this group include isomorphic ferrite with the inclusion of nickel cations in order to evaluate the occurrence of disorder in the crystalline structures and their changes in magnetic characteristics.To identify the structural, morphological, chemical composition and proportions, as well as their magnetic characteristics were performed characterization tests of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDX), thermogravimetric (TG), vibrating sample magnetometry (MAV) and M?ssbauer spectroscopy. These tests revealed the occurrence of distortion in the crystal lattice, changes in magnetic response, occurrence of nanosized particles and superparamagnetism / Pelo m?todo qu?mico da s?ntese da coprecipita??o foram produzidos p?s de ferritas de mangan?s-cobalto com f?rmula estequiom?trica igual a Mn(1-x)Co(x)Fe2O4, para 0 < x <1, primeiramente utilizando como elemento reagente o hidr?xido de am?nio e, em segundo momento, utilizando hidr?xido de s?dio. Os p?s obtidos foram calcinados nas temperaturas de 400?C, 650?C, 900?C e 1150?C, em forno convencional tipo mufla com atmosfera de ar pelo per?odo de 240 minutos. Outras amostras foram calcinadas na temperatura de 900?C, em atmosfera controlada de arg?nio, para possibilitar avaliar a influ?ncia da atmosfera nos resultados finais de estrutura e morfologia. As amostras foram tamb?m calcinadas em forno de microondas nas temperaturas de 400?C e 650?C, durante per?odo de 45 minutos, possibilitando avaliar o desempenho do tratamento t?rmico neste tipo de forno. Foi testada com ?xito a capacidade de inclus?o isom?rfica deste grupo de ferrita com a inclus?o de c?tions de n?quel, permitindo avaliar ocorr?ncia de dist?rbio nas estruturas cristalinas e respectivas altera??es das caracter?sticas magn?ticas. Para identificar as caracter?sticas estruturais, morfol?gicas, de composi??o qu?mica e propor??es, bem como suas caracter?sticas magn?ticas, foram realizados ensaios de caracteriza??o de difra??o de raios X (DRX), microscopia eletr?nica de varredura (MEV), microscopia eletr?nica de transmiss?o (MET), espectroscopia de energia dispersiva (EDX), termogravimetria (TG), magnetometria de amostra vibrante (MAV) e espectroscopia M?ssbauer. Estes ensaios revelaram ocorr?ncia de distor??es na rede cristalina, altera??es de resposta magn?tica, ocorr?ncia de part?culas nanom?tricas e superparamagnetismo

Abstract: Isobutylene is a high demand chemical that contributes to the production of fuel, plastic, and rubbers. It is produced industrially by different processes, as a byproduct of steam cracking of naphtha or a fluidized catalytic cracking or by isobutane dehydrogenation. Catalytic dehydrogenation of isobutane is in increasing importance because of the growing demand for isobutylene and the better economic advantage compared to other isobutylene production processes. Isobutane dehydrogenation is an endothermic reaction and to achieve good yields; it is preferred to work at higher temperatures. At these temperatures, carbon deposition leads to catalyst deactivation, which requires the catalyst to be regenerated on a frequent basis. Most of the current processes to produce isobutylene use either expensive platinum-based metal or toxic chromium-based catalysis. Hence, there is a demand to search for alternative catalysts that are a relatively cheap and non-toxic. To achieve this goal, Zirconia-supported Iron catalysts were prepared. To study the effect of active phase distribution, different iron loadings were tested for impregnation (3% to 10%) and co-precipitation (10%-20%). The catalysts show promising results that can achieve an isobutylene selectivity and yield of 91% and 31%, respectively, with isobutane conversion of 35%.

This thesis focuses on developing an appropriate cathode material throughnanotechnology as a key component for a promising alternative of renewable energygenerating systems, Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFC).Aiming at a working cathode material for IT-SOFC, a recently reported capable oxideperovskite material has been synthesized through two different chemical methods.BaxSr1-xCoyFe1-yO3−δ (BSCF) with y =0.8 and x =0.2 was fabricated in nanocrystallineform by a novel chemical alloying approach, co-precipitation- as well as conventionalsol-gel method to produce oxide perovskites. The thermal properties, phase constituents,microstructure and elemental analysis of the samples were characterized by TG-DSC,XRD, SEM and EDS techniques respectively. Thermodynamic modeling has beenperformed using a KTH-developed software (Medusa) and Spark Plasma Sintering (SPS)has been used to obtain pellets of BSCF, preserving the nanostructure and generatingquite dense pellets for electrical conductivity measurements.The results show that the powders synthesized by solution co-precipitation have cubicperovskite-type structure with a high homogeneity and uniform distribution and meanparticle size of 50-90 nm range, while sol-gel powders are not easy to form a pure phaseand mostly the process ends up with large particle containing two or three phases.Finer resultant powder compared to sol-gel technique and earlier research works onBSCF has been achieved in this project using oxalate co-precipitation method. Topreserve nanoscaled features of BSCF powder which possess a significant increase ofelectrical conductivity due to decrease the electrical resistivity of grain boundaries, forthe sample synthesized through co-precipitation, ~92% dense pellet sintered by SPS atV1080 °C and under 50 MPa pressure and its electrical conductivity has been measuredfrom room temperature to 900 °C.Specific conductivity values were precisely measured and the maximum of 63 S.cm-1 at430 °C in air and 25 S.cm-1 at 375°C in N2 correspondingly are two times higher thanconventional BSCF implying a high pledge for nano-BSCF as a strong candidate ascathode material in IT-SOFC.

Nowadays, nanomedicine is one of the most important application areas fornanoparticles (NPs), where the design and synthesis of new hybrid nanostructures have attracted much interest, when combining properties and functionalities from different constituents. For example, they have been extensivelyused for dual-mode imaging. In this work, a water-based synthesis of hybridNPs with co-precipitation method was studied. To obtain superparamagnetichybrid NPs for X-ray fluorescence computed tomography (XFCT), severalhybridization mechanisms were followed, combining the superparamagneticbehavior of iron oxide NPs with active X-ray fluorescence (XRF) elements –Rh or Ru. The NP surface had to be engineered to improve the NP stabilityand dispersion in water, and to grant high biocompatibility. The resulting hybrid nanostructures exhibit promising characteristics for dual-mode imagingand hyperthermia treatments. We present on the details of the synthetic process, as well as the characterization of the synthesized nanomaterials / Nanomedicin är för närvarande ett av de viktigaste tillämningsområdena för nanopartiklar. Design och syntes av nya nanostrukturer som kombinerar egenskaper från olika beståndsdelar, såsom hybridnanopartiklar, harväckt stort intresse. Nanopartiklarna används exempelvis i hög utsträckningvid dual-mode imaging. I föreliggande arbete undersöktes en vattenbaseradsyntes av hybridnanopartiklar genom samfällning. För att erhålla superparamagnetiska hybridnanopartiklar för Röntgenfluorescenstomografi (RFT) genomfördes olika hybridiseringsmetoder som kombinerade det superparamagnetiska beteendet hos nanopartiklarna med aktiva element av röntgenfluorescens (XRF) - antingen Rh eller Ru. Ytan på nanopartiklarna konstrueradesför att förbättra stabiliteten och spridningen hos dessa samt för att säkerställahög biokompabilitet. De framtagna hybridnanostrukturerna uppvisar lovande egenskaper för dual-mode imaging och hypotermibehandling. Detaljernakring syntesprocessen presenteras tillsammans med egenskaperna hos de syntetiserade nanomaterialen.

A green synthesis method for the synthesis of hydrotalcite has been previously developed but this process has not yet been optimised. The main focus of this dissertation was on aluminium-based LDHs. The purpose of this investigation were; to determine optimum synthesis conditions for the formation of hydrotalcite using the dissolution-precipitation method and to determine the possibility of partial substituting the divalent metal species in hydrotalcite and hydrocalumite with other metal species. During the optimisation process for the formation of hydrotalcite using the dissolution precipitation method, the formation of hydromagnesite was proved to be dominant reaction at lower reaction temperatures. With the increase in reaction time and temperature the decomposition of hydromagnesite occurred to form magnesite. At low temperatures the formation of Mg-Al-CO3 LDH is limited due to the low solubility of gibbsite. Mg-Al-CO3 LDH formation of 80 % was achieved at 140 oC after 2 hours reaction time, but crystallinity was low. To achieve an Mg-Al-CO3 LDH conversion higher than 96 % a reaction temperature of 160 oC for a minimum of 4 hours is required, but is achieved within 1 hour at 180 oC. A 99.37 % conversion was achieved at 180 oC for 5 hours with a high crystallinity and homogeneity. The surface area for Mg-Al-CO3 LDH at 180 oC after 5 hours reaction time proved to be 9.19 m2/g. The average particle size obtained for a high crystalline LDH was in the range of approx. 3 μm and 6.8 μm at temperatures of 160 oC and above for a minimum of 3 hours reaction time. The following are recommended for future work:  Determine the effect of mixing speed on the shape of the platelets.  Determine the difference between freshly precipitated metal oxides/hydroxides as reagents compared to aged metal oxides/hydroxides. The presence of Mg(OH)2 and Ca(OH)2 in solution (respectively) did increase the pH enough for the dissolution of gibbsite and most of the Mx+ metal species. A reaction time and temperature of 5 hours at 180 oC in a carbonate environment proved to be close to the ideal conditions for the formation of Mg/Mo-Al-CO3 LDH and Mg/Zn-Al-CO3 LDH. The results for the formation of Mg/Ti-Al-CO3 LDH were inconclusive. Isolation of the possible Mg/Ti-Al-CO3 LDH is recommended to determine the degree of substitution. The conditions for the dissolution of the metal species for the following experiments were proven to be successful:  Ca/Mn(lV)-Al  Ca/Mo-Al  Ca/Ni-Al  Ca/Ti-Al The following recommendations are made for the improvement on the formation of an Mx+-impregnated LDH/precursor:  Determine the effect of different reaction time and temperature.  Determine the effect of adding the carbonate source at temperatures above 100 oC under pressure.  Determine the effect of synthesising at different pH conditions. Cobalt and tin showed no/negligible amount of possible solubility. / Dissertation (MSc)--University of Pretoria, 2014. / Chemical Engineering / MSc / Unrestricted

No description available.

The superior properties of carbon nanotubes (CNTs) are best manifest in bulk materials when the CNTs are organized in tandem and embedded in a continuous matrix. Decorating the CNTs with magnetic nanoparticles (MNPs) facilitates their expedient organization with a magnetic field. One of the most convenient methods for their decoration is to first treat the CNTs with oxidative acids, and then coprecipitated MNPs in situ. This method results magnetized CNTs that are covalently functionalized with the MNPs. The associated destruction in the CNTs required running a comparative study of this protocol to identify the influence of the acid treatment on the decoration of multiwalled CNTs (MWNTs). Further, we explore means to tune the physical properties of these magnetized CNTs (mMWNTs) by varying the (1) MNP material composition, and (2) MNP:MWNT (w/w) magnetization weight ratio (γ). The resulted composite materials (mMWNTs) are utilized to synthesize a novel and hitherto unreported class of colloidal suspensions (MCCs) for which the dispersed phase, which consists of MWNTs decorated with MNPs, is both magnetoresponsive and electrically conductive. Synthesis of the dispersed phase merges processes for producing ferrofluids and mMWNTs. Later, these MCCs are adapted and engineered to produce a biological ink containing MWNTs that are twice functionalized, first with MNPs and thereafter with the anti-c-Myc monoclonal antibodies (Abs). The ink is pipetted and dynamically self-organized by an external magnetic field into a dense electrically conducting sensor strip that measures the decrease in current when a sample containing c-Myc antigens (Ags) is deposited on it. On the other side, a nondestructive methods to magnetize MWNTs and provide a means to remotely manipulate them is through the electroless deposition of magnetic nickel nanoparticles on their surfaces. The noncovalent bonds between Ni nanoparticles and MWNTs produce a Ni-MWNT hybrid material (NiCH) that is electrically conductive and has an enhanced magnetic susceptibility and elastic modulus. Raising γ (Ni:MWNT weight ratios) increases the coating layer thickness, which influences the NiCH magnetic properties and tunes its elastic modulus. The NiCH was used to fabricate Ni-MWNT macrostructures and tune their morphologies by changing the direction of an applied magnetic field. Leveraging the hydrophilic Ni-MWNT outer surface, a water-based conductive ink was created and used to print a conductive path that had an electrical resistivity of 5.9 Ωm, illustrating the potential of this material for printing electronic circuits. Further, the NiCHs are introduced into an epoxy matrix at low 0.25-1% volume fractions and aligned along the direction of an applied magnetic field, which produces anisotropic bulk properties. However, nanoparticles aligned in perpendicular directions in sequential layers result in an effectively isotropic composite material. Furthermore, the subsequent annealing of the NiCH in the presence of air oxidizes nickel to nickel oxide whereas carbon is released as gaseous carbon dioxide, which leads to a novel approach for the fabrication of nickel oxide nanotubes (NiONTs) based on MWNTs as a sacrificial template. New chelating polyelectrolytes are used as dispersing agents to achieve high colloidal stability both for NiCH and NiONTs. A gravimetric specific capacitance of 245.3 F g-1 and areal capacitance of 3.28 F cm-2 at a scan rate of 2 mV s-1 is achieved with an electrode fabricated using nickel oxide nanotubes as the active element with a mass loading of 24.1 mg/cm2. / Thesis / Doctor of Philosophy (PhD) / The superior properties of carbon nanotubes (CNTs) are best manifested in bulk materials when the CNTs are organized axially and in tandem, and embedded in a continuous matrix. Decorating the CNTs with magnetic nanoparticles (MNPs) facilitates their organization through “action from a distance” with a magnetic field. The attachment of MNPs to the surfaces of CNTs can be realized through covalent or non-covalent (i.e. physical) bonding. This work develops both methodologies to investigate how the physical properties of magnetized CNT (mCNT) can be tuned and produce new CNT-based nanostructures for particular applications. First, mCNTs are utilized to synthesize a hitherto unreported class of colloidal suspensions based on which a magnetic bio-ink is fabricated to print a fast-response biological sensor. Next, nickel-coated CNTs prepared using electroless deposition are used in the form of a filler at low volume fractions in an epoxy matrix, where they are aligned along multiple-direction using a magnetic field, producing either anisotropic or isotropic bulk properties on demand. Finally, subsequent annealing of nickel-coated CNTs in air oxidizes nickel to nickel oxide while carbon is released in the form of gaseous carbon dioxide. This leads to another novel approach for the fabrication of nickel oxide nanotubes, which are demonstrated to be an alternate viable material to fabricate electrodes for use in supercapacitors.

Este trabalho trata da obtenção e caracterização de cerâmicas do sistema supercondutor Bi:Pb:Sr:Ca:Cu:O. O pó cerâmico foi feito por dois processos, mistura de óxidos/carbonatos e co-precipitação de oxalatos, com o objetivo de se estabelecer o procedimento mais favorável ao aparecimento da fase de temperatura critica de 110K. A caracterização do pó precursor foi feita através das técnicas de Plasma Indutivamente Acoplado (ICP), Picnometria, Sedigrafia, Difração de Raios X e Microscopia Eletrônica de Varredura. Na etapa de sinterização do pó estudamos, paralelamente a sinterização convencional, uma técnica alternativa de aplicação de corrente elétrica simultaneamente à ação da temperatura com o objetivo de acelerar a reação de formação e promover, possivelmente, uma maior fração da fase de mais alta temperatura critica. Ao final do processamento as amostras foram caracterizadas estruturalmente, por difração de raios X, e quanto às propriedades elétrica (resistividade elétrica) e magnética (susceptibilidade magnética). Na análise comparativa das características elétricas e estruturais das pastilhas obtidas convencional e quimicamente não observamos diferenças significativas entre elas. No entanto as medidas de susceptibilidade magnética mostraram uma grande diversificação de fases com temperaturas criticas abaixo de 110K, para a pastilha obtida por co-precipitação de oxalatos. Também verificamos que a fase 2223 encontra-se, nessa amostra, em maior proporção do que na pastilha proveniente de pó convencional. O processo alternativo de sinterização promoveu algumas alterações no comportamento da resistividade elétrica do material / This work is about the obtaining and characterizing pellets of the Bi:Pb:Sr:Ca:Cu:O system. The powder was prepared by two processes: oxide/carbonate mixture and oxalate co-precipitation. These two processes were used in order to establish the most favorable process to the 110 K phase formation. The characterization techniques were Inductively Coupled Plasma, Picnometry, Sedigraphy, X Ray Diffraction and SEM. The sinterization was made by conventional and an alternative techniques. The alternative one consists in applying electrical current simultaneously to the temperature action. The expectation was that this technique would accelerate the reactions and consequently, to promote higher volume fraction of the 110K phase. The pellets were structural, electrical and magnetically characterized by X Ray Diffraction, SEM, electrical resistivity and magnetic susceptibility. In the analysis of the electrical and structural characterization of the pellets made by both processing methods, we could not find any difference between them. But, the magnetization measurements indicated that there are numerous phases with critical temperature below 110 K, in addition a higher fraction of 2223 phase, in the pellet made by co-precipitation of oxalates. The alternative sintering process promoted a few alterations in the behavior of the electrical resistivity as a function of the applied temperature

The objectives of this project were to synthesise semi-conducting ceramic nanoparticles including zinc oxide (ZnO) and aluminium doped zinc oxide (AZO) through a wet chemistry route to obtain nanoparticles with a controlled size and morphology. Wet chemistry methods (co-precipitation method and hydrothermal method) were used to synthesise ZnO and AZO particles. In the synthesis, various compounds and morphologies were synthesised. ZnO, Zn(OH)2 and unknown phases were co-precipitated, with only ZnO obtained following hydrothermal treatment. Morphologies ranging from platelets, flower-like, nanorods and microflowers were obtained. Particle sizes as small as 11 nm were characterised. Nanorod and nanosphere AZO particles were also synthesised with the results indicated the average grain size decreasing with increasing Al atomic content. Three orthogonal arrays were carried out to investigate the effects of the reaction parameters on the size and morphology of ZnO particles. The applicability of the orthogonal array was successful, with the optimum parameters of both hydrothermal experiments showing an increase in aspect ratio. The L/D ratio of ZnO nanorods obtained in the confirmation experiment increased to 9.4 which was larger than the ZnO synthesised using other reaction conditions (1.0 8.0). Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterise the properties of the obtained particles. Morphology, crystallinity and particle size were all characterised.

Este trabalho trata da obtenção e caracterização de cerâmicas do sistema supercondutor Bi:Pb:Sr:Ca:Cu:O. O pó cerâmico foi feito por dois processos, mistura de óxidos/carbonatos e co-precipitação de oxalatos, com o objetivo de se estabelecer o procedimento mais favorável ao aparecimento da fase de temperatura critica de 110K. A caracterização do pó precursor foi feita através das técnicas de Plasma Indutivamente Acoplado (ICP), Picnometria, Sedigrafia, Difração de Raios X e Microscopia Eletrônica de Varredura. Na etapa de sinterização do pó estudamos, paralelamente a sinterização convencional, uma técnica alternativa de aplicação de corrente elétrica simultaneamente à ação da temperatura com o objetivo de acelerar a reação de formação e promover, possivelmente, uma maior fração da fase de mais alta temperatura critica. Ao final do processamento as amostras foram caracterizadas estruturalmente, por difração de raios X, e quanto às propriedades elétrica (resistividade elétrica) e magnética (susceptibilidade magnética). Na análise comparativa das características elétricas e estruturais das pastilhas obtidas convencional e quimicamente não observamos diferenças significativas entre elas. No entanto as medidas de susceptibilidade magnética mostraram uma grande diversificação de fases com temperaturas criticas abaixo de 110K, para a pastilha obtida por co-precipitação de oxalatos. Também verificamos que a fase 2223 encontra-se, nessa amostra, em maior proporção do que na pastilha proveniente de pó convencional. O processo alternativo de sinterização promoveu algumas alterações no comportamento da resistividade elétrica do material / This work is about the obtaining and characterizing pellets of the Bi:Pb:Sr:Ca:Cu:O system. The powder was prepared by two processes: oxide/carbonate mixture and oxalate co-precipitation. These two processes were used in order to establish the most favorable process to the 110 K phase formation. The characterization techniques were Inductively Coupled Plasma, Picnometry, Sedigraphy, X Ray Diffraction and SEM. The sinterization was made by conventional and an alternative techniques. The alternative one consists in applying electrical current simultaneously to the temperature action. The expectation was that this technique would accelerate the reactions and consequently, to promote higher volume fraction of the 110K phase. The pellets were structural, electrical and magnetically characterized by X Ray Diffraction, SEM, electrical resistivity and magnetic susceptibility. In the analysis of the electrical and structural characterization of the pellets made by both processing methods, we could not find any difference between them. But, the magnetization measurements indicated that there are numerous phases with critical temperature below 110 K, in addition a higher fraction of 2223 phase, in the pellet made by co-precipitation of oxalates. The alternative sintering process promoted a few alterations in the behavior of the electrical resistivity as a function of the applied temperature