Nanocząstki tlenków żelaza w hipertermii magnetycznej

Wydział Fizyki

A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

Síntese e impregnação de peneiras moleculares Fe MCM-41 derivada de sílica da casca do arroz

The mesoporous molecular sieves of the MCM-41 and FeMCM-41 type are considered promissory as support for metals used as catalysts in oil-based materials refine processes and as adsorbents for environmental protection proposes. In this work MCM-41 and FeMCM41 were synthesized using rice husk ash - RHA as alternative to the conventional silica source. Hydrothermal synthesis was the method chosen to prepare the materials. Pre-defined synthesis parameters were 100°C for 168 hours, later the precursor was calcinated at 550°C for 2 hours under nitrogen and air flow. The sieves containing different proportions of iron were produced by two routes: introduction of iron salt direct synthesis; and a modification post synthesis consisting in iron salt 1 % and 5% impregnation in the material followed by thermal decomposition. The molecular sieves were characterized by X ray diffraction XRD, Fourier transform infrared spectroscopy FT-IR, X ray fluorescence spectroscopy XFR, scanning electronic microscopy SEM, specific surface area using the BET method, Termogravimetry TG. The kinetic model of Flynn Wall was used with the aim of determining the apparent activation energy of the surfactant remove (CTMABr) in the MCM- 41 porous. The analysis made possible the morphology characterization, identifying the presence of hexagonal structure typical for mesoporous materials, as well as observation of the MCM41 and iron of characteristic bands.

EFFECT OF INTERMITTENT FRYING ON FATTY ACIDS, VITAMIN E, LIPID OXIDATION AND ACRYLAMIDE IN OILS AND PLANTAIN CHIPS COLLECTED FROM SMALL- SCALE PRODUCERS IN CAMEROON

Deep-fat frying is susceptible to induce the formation of undesirable products as lipid oxidation products and acrylamide in fried foods. Plantain chips produced by small-scale producers are sold to consumers without any control. The objective of this study was to evaluate the quality of plantain chips from local producers in relation to production process parameters and oils, and to identify the limiting factors for the production of acrylamide in plantain chips. Samples of frying oils and plantain chips prepared with either palm olein or soybean oil were collected from 10 producers in Yaoundé. Quality parameters determined in this study were: fatty acid composition of the oils, determined by gas chromatography (GC) of free acid methyl ester; trans fatty acids, determined by Fourier transform infra-red spectroscopy; Tocopherols and tocotrienols as markers of nutritional quality were analyzed by High Performance Liquid Chromatography in isocratic mode. Free fatty acids and acylglycerols as markers of lipid hydrolysis were analyzed by GC of trimethylsilyl derivatives of glycerides. Conjugated dienes, Anisidine value and viscosity as markers of lipid oxidation and thermal decomposition of the oils; acrylamide which is formed through Maillard reaction and identified as a toxic compound in various fried products. Asparagine content of the raw fresh plantain powder was also determined. Fatty acid composition of palm oleins was stable within a day of intermittent frying. In soybean oils, about 57% and 62.5% of linoleic and linolenic acids were lost but trans fatty acids were not detected. Soybean oils were partly hydrolysed leading to the formation of free fatty acids, monoacylglycerols and diacylglycerols. In both oils, tocopherols and tocotrienols contents decreased significantly by about 50%. Anisidine value (AV) and polymers contents increased slightly in fried palm oleins while conjugated hydroperoxides, AV and polymers greatly increased in soybean oils. Acrylamide was not detected in the chips. This is explained by the absence of asparagine in the raw plantains, the other acrylamide precursors being present. This study shows that the plantain chips prepared at the small-scale level in Yaounde with palm olein are of good quality regarding oxidation and hydrolysis parameters and the absence of acrylamide. In contrast, oxidation developed with soybean oil whose usage for frying should be questioned. Considering that asparagine is the limiting factor for the formation of acrylamide in plantain chips, its content depending on several factors such as production parameters and maturity stage should be explored.

Síntese, estudo cinético e análise microestrutural do sistema cério-níquel obtido pelo método pechini

The cerium oxide has a high potential for use in removing pollutants after combustion, removal of organic matter in waste water and the fuel-cell technology. The nickel oxide is an attractive material due to its excellent chemical stability and their optical properties, electrical and magnetic. In this work, CeO2-NiO- systems on molars reasons 1:1(I), 1:2(II) e 1:3(III) metal-citric acid were synthesized using the Pechini method. We used techniques of TG / DTG and ATD to monitor the degradation process of organic matter to the formation of the oxide. By thermogravimetric analysis and applying the dynamic method proposed by Coats-Redfern, it was possible to study the reactions of thermal decomposition in order to propose the possible mechanism by which the reaction takes place, as well as the determination of kinetic parameters as activation energy, Ea, pre-exponential factor and parameters of activation. It was observed that both variables exert a significant influence on the formation of complex polymeric precursor. The model that best fitted the experimental data in the dynamic mode was R3, which consists of nuclear growth, which formed the nuclei grow to a continuous reaction interface, it proposes a spherical symmetry (order 2 / 3). The values of enthalpy of activation of the system showed that the reaction in the state of transition is exothermic. The variables of composition, together with the variable temperature of calcination were studied by different techniques such as XRD, IV and SEM. Also a study was conducted microstructure by the Rietveld method, the calculation routine was developed to run the package program FullProf Suite, and analyzed by pseudo-Voigt function. It was found that the molar ratio of variable metal-citric acid in the system CeO2-NiO (I), (II), (III) has strong influence on the microstructural properties, size of crystallites and microstrain network, and can be used to control these properties

Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Síntese de nanopartículas de magnetita via decomposição térmica em meio não-aquoso

This work aims at obtaining nanoparticles of iron oxide, the magnetite one (Fe3O4), via synthesis by thermal decomposition through polyol. Thus, two routes were evaluated: a simple decomposition route assisted by reflux and a hydrothermal route both without synthetic air atmosphere using a synthesis temperature of 260ºC. In this work observed the influence of the observe of surfactants which are generally applied in the synthesis of iron oxide nanoparticles decreasing cluster areas. Further, was observed pure magnetite phase without secondary phases generally found in the iron oxide synthesis, a better control of crystallite size, morphology, crystal structure and magnetic behavior. Finally, the introduction of hydroxyl groups on the nanoparticles surface was analyzed besides its employment in the polymer production with OH radicals. The obtained materials were characterized by XRD, DLS, VSM, TEM, TG and DSC analyses. The results for the magnetite obtainment with a particle size greater than 5 nm and smaller than 11 nm, well defined morphology and good magnetic properties with superparamagnetic behavior. The reflux synthesis was more efficient in the deposition of the hydroxyl groups on the nanoparticles surface

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

Synthesis of Anisotropic Magnetic Nanoobjects Designed for Locomotion in External Magnetic Fields

The subject of the present work is the synthesis of novel nanoscale objects, designed for self-propulsion under external actuation. The synthesized objects present asymmetric hybrid particles, consisting of a magnetic core and polymer flagella and their hydrodynamic properties under the actuation by external magnetic fields are investigated. The single-domain ferromagnetic cobalt ferrite nanoparticles are prepared by thermal decomposition of a mixture of metalorganic complexes based on iron (III) cobalt (II) in non-polar solvents. Further modification of the particles includes the growth of the silver particle on the surface of the cobalt ferrite particle to form a dumbbell-shaped heterodimer. Different possible mechanisms of dumbbell formation are discussed. A polyelectrolyte tail with ability to adjust the persistence length of the polymer, and thus the stiffness of the tail, by variation of pH is attached to the particles. A polymer tail consisting of a polyacrylic acid chain is synthesized by hydrolysis of poly(tert-butyl acrylate) obtained by atom transfer radical polymerization (ATRP). A functional thiol end-group enables selective attachment of the tail to the silver part of the dumbbell, resulting in an asymmetric functionalization of the dumbbells. The calculations on the propulsion force and the sperm number for the resulting particles reveal a theoretical possibility for the propelled motion. Under the actuation of the particles with flagella by alternating magnetic field an increase in the diffusion coefficient compared to non-actuated or non-functionalized particles is observed. Further development of such systems for application as nanomotors or in drug delivery is promising.

Homoleptic and Heteroleptic Metal Carbonyl Clusters and Nanoclusters

This Thesis aims at presenting the general results achieved during my PhD, that was focused on the study and characterisation of new homoleptic and heteroleptic metal carbonyl clusters. From a dimensional point of view, the nuclearity of such species ranges from 2 to 44 metal atoms. Lower nuclearity compounds may be viewed as polymetallic complexes, whereas higher nuclearity species can reach the nanocluster size, by resembling to ultrasmall nanoparticles (USNPs). Initially, my research was focused on the investigation of small MCCs stabilised by N-Heterocyclic carbene (NHCs) ligands. At this regard, a general strategy for the synthesis of mono-anionic [Fe(CO)4(MNHC)]− and neutral Fe(CO)4(MNHC)2, Co(CO)4(MNHC) (M = Cu, Ag, Au; NHC = IMes, IPr) species has been developed. Furthermore, during this investigation, neutral trimetallic Fe(CO)4(MNHC)(M’NHC) (M, M’ = Cu, Ag, Au; M ≠ M'; NHC = IPr) and neutral heteroleptic Fe(CO)4(MNHC)(MNHC’) (M = Au; NHC = IMes, IPr) compounds have been isolated. Thermal treatment turned out to be an efficient method for the growth of the dimension of MCCs. Indeed, species of the type [M3Fe3(CO)12]3– and [M4Fe4(CO)16]4– (M = Ag, Au) as well as larger clusters were formed during the thermal treatment of the new Fe-M (M = Ag, Cu, Au) carbonyl compounds. These species inspired the investigation of promising reaction paths for the synthesis of Fe-M (M = Ag, Cu, Au) carbonyl compounds devoid of ancillary ligands and alloy MCCs, such as the heterometallic [MxM’5-xFe4(CO)16]3− (M, M' = Cu, Ag, Au; M ≠ M'; x = 0-5) carbonyl clusters. The second part of this Thesis regards high nuclearity MCCs. In particular, new strategies for the growth of platinum carbonyl clusters involving, for instance, the employment of bidentate phosphines are described, as well as the syntheses and the thermal decomposition of new Ni-M (Pd, Pt) carbonyl clusters.