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Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

A modified thin lens spectrometer has been used with improved geometry. The focussing properties of the instrument have been investigated for various geometries. Using this instrument the conversion electron spectra of Sn¹¹³ and Sb¹²⁵ have been taken. The intensity of the 256 kev conversion line in Sn¹¹³ spectrum showed that this transition is predominantly M1 in character and therefore the spin and parity of 648-kev level in In¹¹³ should be 1/2¯ or 3/2¯. The low energy part of the conversion spectrum of Sb¹²⁵showed the presence of the K conversion lines of 76 kev and 143 kev transitions, not observed before. The presence of these conversion lines confirmed the existence of a weak beta group feeding a level at 540 kev in the excited state of Te¹²⁵. The energy levels of Cs¹³³ have been studied through the decay of Ba¹³³. Scintillation spectra (using NaI(T1 ) crystal) together with photoelectron, conversion and e-gamma coincidence spectra have been taken. An analysis of the results indicate that the ground state and 81, 161, 383 and 437 kev levels in Cs¹³³ have spins and parities of 7/2⁺, 5/2⁺,5/2⁺,3/2⁺, 1/2⁺ respectively. The multipolarities of the connecting transitions are 383 kev (E2 ), 356 (E2 ) 302 kev (M1 with E2 admixture)} 276 kev (E2 ), 161 kev (probably M1 ) Electron capture from Ba¹³³ is limited almost entirely to the 437 and 383 kev levels in Cs¹³³, The decay energy available for capture to the 437 level is approximately 50 kev. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

We have built an imaging mass spectrometer adapted for ultrashort laser pulses as its ionization technique, as an alternative to other imaging techniques. Before my arrival, the mass spectrometer has only been subject to preliminary tests on noble gases. Since then, we’ve made some modifications to the system in order to properly analyze solids. This thesis shows how we obtain our ultrashort laser pulses, the inner workings of our homemade imaging mass spectrometer, and the results that we’ve obtained with it so far. We tested two modes of operation concerning the extraction of the ions from the system into the mass analyzer: continuous and pulsed. We discuss the advantages and disadvantages of each configuration. We also display preliminary imaging results with our imaging technique of a simple WO3 and ITO structure. We conclude by comparing the resolution of this image to the different techniques in imaging mass spectrometry, how we can further improve our mass spectrometer, and the future use of this machine. Nous avons construit un spectromètre de masse adapté pour les pulses de laser très courts comme technique d’ionisation, pour acquisition des images d’un échantillon. Avant je suis arrivé, le spectromètre de masse avait seulement été utilisé pour des tests préliminaires de gaz nobles. Depuis ce moment, nous avons modifié le système pour analyser les solides. Cette thèse démontre comment on obtient nos pulses de laser très courts, comment notre spectromètre fait maison fonctionne et les résultats nous avons obtenus jusqu’à présent. Nous avons testé deux configurations différentes au sujet de l’extraction des ions du système : constant et pulsé. Nous discutons aussi les avantages et désavantages de chaque mode d’opération. Nous démontrons aussi des images préliminaires d’un substrat mixte de WO3 et ITO. Nous concluons par comparer la résolution des images aux autres techniques de collection d’images, comment nous pouvons améliorer notre spectromètre de masse et les plans pour la machine dans le futur.

Metal oxides exhibit a wide range of chemical and electronic properties, making them an extremely interesting subject for numerous applications in modern electronics. The primary goal of this research is to develop metal-oxide-based electronic devices, including thin-film transistors (TFTs), resistance random-access memory (RRAM) and planar nano-devices. This research requires different processing techniques, novel device design concepts and optimisation of materials and devices. The first experiments were carried out to optimise the properties of zinc oxide (ZnO) semiconductors, in particular the carrier concentration, which determines the threshold voltage of the TFTs. Thermal annealing is one common method to affect carrier concentration and most work in the literature reports performing this process in a single-gas environment. In this work, however, annealing was carried out in a combination of air and nitrogen, and it was found that the threshold voltage could be tuned over a wide range of pre-determined values.Further experiments were undertaken to enhance the carrier mobility of ZnO TFTs, which is the most important material quality parameter. By optimising deposition conditions and incorporating a high-k gate dielectric layer, the devices showed saturation mobility values over 50 cm2/Vs at a low operating voltage of 4 V. This is, to our knowledge, one of the highest field-effect mobility values achieved in ZnO-based TFTs by room temperature sputtering. As an important type of metal-oxide-based novel memory devices, which have been studied intensively in the last few years, RRAM devices were also explored. New materials, such as tin oxide (SnOx), were tested, exhibiting bipolar-switching operations and a relatively large resistance ratio. As a novel process variation, anodisation was performed, which yielded less impressive results than SnOx, but with a potential for ultra-low-cost manufacturing. Finally, novel planar nano-devices were explored, which have much simpler structures than conventional multi-layered transistors and diodes. Three types of ZnO-based nano-devices (a side-gated transistor, a self-switching diode and a planar inverter) were fabricated using both e-beam lithography and chemical wet etching. After optimisation of the challenging wet etching procedure at nanometre scale, ZnO nano-devices with good reproducibility and reliability have been demonstrated.

Orientador: Marco Aurélio Zezzi Arruda / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T10:57:39Z (GMT). No. of bitstreams: 1 Galazzi_RodrigoMoretto_M.pdf: 2262907 bytes, checksum: fb6e92051f6858cd925c525071ce6540 (MD5) Previous issue date: 2013 / Resumo: Nessa dissertação, otimizou-se um método para a determinação de estanho (Sn) em amostras biológicas empregando a técnica de Espectrometria de Absorção Atômica por Geração de Hidretos e Forno Metálico (MF-HG-AAS, do inglês Metallic Furnace Hydride Generation Atomic Absorption Spectrometry). Foram avaliadas algumas variáveis químicas como o tipo e concentração do carregador/diluente da solução padrão, concentração do redutor tetraidridoborato (-1) de sódio (THB) e concentração de hidróxido de sódio, bem como variáveis físicas do sistema dentre elas a vazão de carregador, proporção de acetileno:ar na chama, volume de solução injetado, vazão de argônio como gás de arraste, vazão de água no nebulizador e área total de furos no tubo metalico Inconel600®. Foi realizado um estudo do efeito de memória observado em condições de chama oxidante nas vazões de 1,5:9; 1,4:9; 1,3:9; 1,4:10; 1,4:8 e 1,5:11 L min de acetileno:ar, respectivamente. Em todas essas proporções de chama diferentes da otimizada (1,5:10 L min acetileno:ar) há efeito de memória, o que é extremamente indesejável. Após a otimização do sistema, foram realizados testes de exatidão e precisão do mesmo com os materiais PACS-2 (sedimento) e SRM 1643e (amostra de água) em que, em ambos, foi possível recuperar o Sn adicionado obtendo limites de detecção (LD) de 7,1 mg kg e 7,6 mg L, respectivamente. Um estudo com concomitantes foi realizado para avaliar se algum dos elementos em questão poderia interferir na determinação do Sn. Foram estudados como possíveis concomitantes o cobre, chumbo e zinco em três níveis diferentes. Somente o cobre, nas razões de 1:10 e 1:20 (Sn:concomitante), interferiu na detecção de Sn. Por fim, a morfologia do atomizador foi avaliada por meio da técnica de Microscopia Eletrônica de Varredura (SEM, do inglês Scanning Electron Microscopy). Mesmo após a realização de todos os experimentos envolvendo a otimização do sistema e análise das amostras, os principais constituintes do tubo metálico Inconel600® (ferro, níquel e cromo) permaneceram homogeneamente distribuídos, indicando que esses metais podem não participar da rota de atomização do Sn. Além disso, houve formação de óxidos no atomizador que, juntamente com o uso de uma chama oxidante, sugerem uma rota de atomização do Sn via formação de óxidos. Considerando os LD, bem como a exatidão e precisão por meio da recuperação de Sn obtida nas amostras, constata-se a potencialidade da MF-HG-AAS frente a outras técnicas empregadas na determinação de Sn / Abstract: In this work, a Metallic Furnace Hydride Generation Atomic Absorption Spectrometry (MF-HG-AAS) was optimized for tin (Sn) determination in biological samples. Chemical variables, such as the type and carrier concentration, the sodium tetrahydrideborate (-1) (THB), and the sodium hydroxide concentration, as well as physical variables, such as carrier flow-rate, ratio of acetylene and air in the flame, injection volume, argon flow-rate as carrier of stannane, water flow-rate in nebulizer and total hole area of a Inconel600® metallic furnace were evaluated. A study of a memory effect observed in oxidant flame conditions such as 1.5:9; 1.4:9; 1.3:9; 1.4:10; 1.4:8 e 1.5:11 L minof acetylene:air, respectively, was realized. In any other flame flow-rate, which the optimized flame ratio (1.5:10 L min acetylene:air) was observed a memory effect, which is very undesirable. After optimizing of the system, test of accuracy and precision were realized with the PACS-2 (sediment) and SRM 1643e (water sample) materials wherein, in both, a recovery of the Sn added to the samples was possible with limits of detection (LOD) as 7,1 mg kg and 7,6 mg L, respectively. A concomitant study was carried out for checking the interferences in the Sn determination. Copper, lead and zinc at three different levels were studied as possible concomitants. Only copper, at 1:10 and 1:20 (Sn:concomitant) ratios interfered in the determination of Sn. Finally, the morphology of the atomizer employed was evaluated through Scanning Electron Microscopy (SEM) technique. Even after carrying out all experiments involved in the optimization of the system and in the sample analysis, the main constituents of Inconel600® metallic furnace (iron, nickel and chromium) remained homogeneously distributed, indicating which these elements may not participate of the Sn atomization route. Moreover, the oxide formation in the atomizer was detected, which, together with an oxidant flame used, suggests the Sn atomization route via oxides formation. Considering the LOD, as well the accuracy and precision through the Sn recovery in the samples, the MF-HG-AAS potentially is well pointed out when it is compared to other techniques employed for Sn determination / Mestrado / Quimica Analitica / Mestre em Química

Indium tin oxide (ITO) is the most widely used transparent electrode in flexible solar cells because of its high transparency and conductivity. But still, cracking of ITO on PET substrates due to tensile loading is not fully understood and it affects the functionality of the solar cell tremendously as ITO loses its conductivity. Here, we investigate the cracking evolution in ITO/PET exposed to two categories of tests. Monotonous tensile testing is done in order to trace the crack propagation in ITO coating as well as determining a loading range to focus on during our study. Five cycles test is also conducted to check the crack closure effect on the resistance variation of ITO. Analytical model for the damage in ITO layer is implemented using the homogenization concept as in laminated composites for transverse cracking. The homogenization technique is done twice on COMSOL to determine the mechanical and electrical degradation of ITO due to applied loading. Finally, this damage evolution is used for a simulation to predict the degradation of ITO as function in the applied load and correlate this degradation with the resistance variation. Experimental results showed that during unloading, crack closure results in recovery of conductivity and decrease in the overall resistance of the cracked ITO. Also, statistics about the crack spacing showed that the cracking pattern is not perfectly periodical however it has a positively skewed distribution. The higher the applied load, the less the discrepancy in the crack spacing data. It was found that the cracking mechanism of ITO starts with transverse cracking with local delamination at the crack tip unlike the mechanism proposed in the literature of having only cracking pattern without any local delamination. This is the actual mechanism that leads to the high increase in ITO resistance. The analytical code simulates the damage evolution in the ITO layer as function in the applied strain. This will be extended further to correlate the damage to the resistance variation in following studies.

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This master’s thesis deals with the issue of the release of tin in canned fruit of used packaging. The theoretical part of the thesis is described canning fruit as raw material, its composition, methods of preservation, basic technological operations fruit processing, manufacture of compote, manufacture of metal packaging, marches corrosive metal packaging, chemical behavior of tin in foods and toxicity, methods for the determination of tin in foods with a focus on optical emission spectrometry with inductively coupled plasma. I the experimental part of the thesis was first ICP-OES optimized before to analysis of the 20 different samples compote purchased in chain stores. Tin concentration was determined by a fixed proportion compote. Measured concentration of tin were compared with the maximum permissible value in canned foods, which is allowed by European legislation. The tin content in all analyzed compote did not exceed the legislative limit of 200 mg/kg. The highest concentration of tin has been measured in sample conserved apricots namely 88,6 ± 2,8 mg/kg.

This master’s thesis follows on bachelor’s thesis and deals with study of migration of aluminium and tin from metal containers. Manufactory of metal containers, corrosion of cans, chemical behaviour of aluminium and tin in food, its effects on health and possibilities of the determination in food and characterization of inductively coupled plasma optical emission spectrometry (ICP-OES) are described in theoretical part. In experimental part 30 different beverages in cans and glass and 6 tomato purees purchased at common stores were analysed. Measured concentrations of aluminium in beverages from cans and from glass containers were compared. It was found that beverages from cans didn’t contain higher concentrations of aluminium than beverages from glass containers. This could be caused by the fact that the aluminium is very stable metal, it has high corrosive endurance and therefore is very suitable for food packaging. Measured concentrations of tin in tomato purees were compared with the maximum permissible level of tin in canned food determined by European legislation. None of them exceed the 200 mg/kg level. All of the measured concentrations were very low, because all of the cans contained protective layer of lacquer, which gives protection against corrosion and also effectively protects from releasing of tin into the can content.