Made available in DSpace on 2017-07-21T20:43:47Z (GMT). No. of bitstreams: 1 Mauricio Castro.pdf: 5841824 bytes, checksum: 35f8699394396800943abee89ca868ba (MD5) Previous issue date: 2015-01-30 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / This study aims to compare the supply capacity of power each of the three main types of high-energy mills: The "SPEX", Planetary and "Attritor" mills. The system used was chromium oxide with metallic aluminum, both are powders. The reduction reaction of chromium oxide with aluminum in the milling does not occur instantaneously, but is stimulated with mechanical activation of the reagents. The mechanical activation in milling, together with the subsequent heat treatment is that makes a reaction. The energy comparison was made between the mill in two steps: In the first step the milling power was varied for the three mills to be able to identify the milling resulted in the highest exotermic energy peak in the reaction, whereas in the second stage ranged -if the time for milling time find themselves exhibited higher energy released in the reaction. This comparison between the reaction energy peaks confirmed the SPEX as the mill with greater power supply capacity, ie: The mill with the largest peak energy released, followed by the Planetary mill and finally by Attritor mill. In the energy comparison, we studied the influence of the presence of a process control agent in the reaction energy peaks at different milling powers. The milled samples had their power surges reaction determined by thermal analysis of the post. This energy released in the process varied, tending to exhibit a higher peak energy for each of the evaluated parameters (milling power and milling time). There was the use of x-ray diffraction to show the reduction of ground and treated material. Some samples of the powders were pressed only ground and heat treated in an oven. In order to observe the structures formed in the scanning electron microscope, and correlate the structures formed by reactive process studied. Obtained structures consisting of chromium beads dispersed among a substrate of aluminum oxide, both products of the reduction reaction. / Este trabalho tem como objetivo comparar a capacidade de fornecimento de energia de cada um dos três principais tipos de moinhos de alta energia: Os moinhos “SPEX”, Planetário e “Attritor”. O sistema usado foi o óxido de cromo com alumínio metálico, ambos na forma de pós. A reação de redução do óxido de cromo pelo alumínio não ocorre instantaneamente na moagem, mas é estimulada com a ativação mecânica dos reagentes. A ativação mecânica na moagem, aliada ao tratamento térmico posterior é que faz a reação ocorrer. A comparação energética entre os moinhos foi feita em duas etapas: Na primeira etapa variou-se o poder de moagem para os três moinhos a fim de identificar o poder de moagem que proporcionou o maior pico de energia na reação, enquanto que na segunda etapa variou-se o tempo para encontrar-se o tempo de moagem que exibiu maior energia liberada na reação. Esta comparação entre os picos de energia de reação confirmou o SPEX como o moinho com maior capacidade de fornecimento de energia, ou seja: O moinho com o maior pico energia liberada, seguido pelo moinho Planetário e por fim pelo moinho Attritor. Além da comparação energética, estudou-se a influência da presença de um agente controlador de processo nos picos de energia de reação em diferentes poderes de moagem. As amostras moídas tiveram seus picos de energia da reação determinados por análises térmicas dos pós. Essa energia liberada no processo variou, tendendo a exibir um maior pico de energia para cada um dos parâmetros avaliados (poder e tempo de moagem). Fez-se o uso da difração de raios x para evidenciar a redução do material moído e tratado. Algumas amostras dos pós apenas moídos foram prensadas e tratadas termicamente em forno. A fim de se observar as estruturas formadas em microscópio eletrônico de varredura, bem como correlacionar as estruturas formadas ao processo reativo estudado. Obteve-se estruturas constituídas por esferas de cromo dispersas em meio a um substrato de óxido de alumínio, ambos produtos da reação de redução.

Submitted by admin tede (tede@pucgoias.edu.br) on 2018-08-23T17:16:34Z No. of bitstreams: 1 SILVIO MAGRI FILHO.pdf: 583881 bytes, checksum: 8163d00e54a8b712b124036c73fdf2fb (MD5) / Made available in DSpace on 2018-08-23T17:16:34Z (GMT). No. of bitstreams: 1 SILVIO MAGRI FILHO.pdf: 583881 bytes, checksum: 8163d00e54a8b712b124036c73fdf2fb (MD5) Previous issue date: 2013-02-22 / This work was produced and determined the activity of an enzyme complex extracted from the fungus Aspergillus awamori and evaluated the apparent digestibility coefficients (CDAs) of crude protein, gross energy and dry matter ration reference tambaqui with 3 increasing levels of enzyme solution obtained from the fungus. The experiment was a completely randomized design with four treatments (100ml water solution without enzyme/kg of ration, 100 ml of enzyme/kg feed, 150 ml of enzyme/kg of ration and 200 mL of enzymatic solution/Kg ration) and three replications in time. It was installed on Aquaculture Research Laboratory in the Department of Animal Science LAPOA - PUC Goiás. A total of 96 tambaqui, Colossoma macropomum, with an average weight of 55.69 (± 2.55) g, distributed in twelve tanks of 100 liters, system in closed recirculating water containing 8 fish per experimental unit. Fish were fed every hour in the morning, at 8:00 h, 9:00 h, 10:00 h, 11:00 h and 12:00 h. Thirty minutes after the last meal the fish were transferred to units collect feces for up to 300 L. To determine digestibility was added will feed the chromic oxide-III marked as inert. The addition of the enzyme solution improved the digestibility of the ration, increasing the utilization of dry matter, crude protein and gross energy in the inclusion level of 0.05% (P <0.05%). / Neste trabalho foi produzido e determinado a atividade de um complexo enzimático extraído do fungo Aspergillus awamori e avaliou-se os coeficiente de digestibilidade aparente (CDa) da proteína bruta, energia bruta e matéria seca de ração referência para juvenis de tambaqui com 3 níveis crescentes de solução enzimática obtida do fungo. O experimento foi montado em delineamento inteiramente casualizado com quatro tratamentos (100ml de água sem solução enzimática/Kg de ração; 100 ml de solução enzimática/Kg da ração; 150 ml de solução enzimática/Kg da ração e 200 mL de solução enzimática/Kg da ração) e três repetições no tempo. Foi instalado no Laboratório de Pesquisas em Aquicultura LAPOA do Departamento de Zootecnia da PUC Goiás. Foram utilizados 96 juvenis de tambaqui, Colossoma macropomum, com peso médio de 55,69 (±2,55) g, distribuídos em doze aquários de 100 litros, em sistema de fechado de recirculação de água, contendo 8 peixes por unidade experimental. Os peixes foram alimentados de hora em hora no período matutino, as 8:00h, 9:00h, 10:00h, 11:00h e 12:00h. Trinta minutos após a última refeição os peixes foram transferidos para as unidades de coleta de fezes, com capacidade para 300 L. Para determinação da digestibilidade foi adicionado á ração o óxido de crômio-III como marcado inerte. A adição da solução enzimática melhorou a digestibilidade aparente da ração, aumentando o aproveitamento da matéria seca, da proteína bruta e da energia bruta no nível de inclusão de 0,05% (P<0,05%).

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The experiment was carried out to evaluate the ingestive behavior and forage intake by lambs on ryegrass pasture under different forage allowance (FA): 6, 9 and 12% of body weight (BW). The grazing method was intermittent and the experimental animals were Suffolk lambs. The experimental design was completely randomized with a split-plot structure, being the forage allowance the main plots and the phenological stages the subplots, and the methods for the determination of intake were the sub-subplots. The intake, in the vegetative stage of ryegrass, is independent of forage allowance. The lower allowances limit the forage intake from pre-flowering, while in the reproductive stage of ryegrass the intake is lower, intermediate and higher in FA 6, 9 and 12% of BW, respectively. The grazing time and bite mass were similar between forage allowances. Lambs remained more time ruminating and less time doing other activities in FA 9 and 12% of BW. The number of stations visited per minute and the time at each station were related to the forage allowance in the vegetative 2 and flowering stages. The bite rate was higher in FA 6 and 9% of the BW and is associated with the canopy height. The number of meals was higher, intermediate and lower in FA 12, 9 and 6% of BW, respectively, and similar at all phenological stages and is associated with the leaf blades participation in the canopy. The duration of the meals was higher in FA 6, intermediate in 9 and lower in 12% and is associated with changes in lambs' bite rate, the leaf blades allowance and leaf blade: stem ratio. In the phenological stages of ryegrass the bite rate is adjusted to compensate for changes in bite mass. The grazing time at the phenological stages of ryegrass is associated with the forage mass and the leaf blades allowance. The duration of the interval between meals is similar between forage allowances and in different phenological stages of ryegrass it is correlated with the activities of rumination and other activities. The estimate of herbage intake on ryegrass pasture is similar when using chromium oxide and fecal nitrogen as markers. The forage intake on the basis of forage allowance is dependent on the canopy structure and is limited in the pre-flowering and flowering, due to the high mass of stems. The phenological stages of ryegrass were more important in changes in pasture structure and ingestive behavior of lambs than the forage allowances used. The bite mass is unchanged by forage allowances ranging from 6 to 12% of BW and any of them can be used in ryegrass pasture. / O trabalho foi conduzido com o objetivo de avaliar o comportamento ingestivo e consumo de forragem por cordeiras em pastagem de azevém sob diferentes ofertas de forragem (OF): 6, 9 e 12% do peso corporal (PC). O método de pastejo foi intermitente e os animais experimentais foram cordeiras da raça Suffolk. O delineamento experimental foi inteiramente casualizado, com estrutura de parcelas sub-subdivididas, sendo as ofertas de forragem as parcelas principais, os estádios fenológicos as subparcelas, e os métodos de determinação do consumo as sub-subparcelas. O consumo, no estádio vegetativo do azevém, independe da oferta de forragem. As menores ofertas limitam o consumo de forragem a partir do pré-florescimento enquanto no estádio reprodutivo do azevém o consumo é menor, intermediário e maior nas OF 6, 9 e 12% do PC, respectivamente. O tempo de pastejo e a massa de bocado foram semelhantes entre as ofertas de forragem. As cordeiras permaneceram mais tempo ruminando e menor tempo realizando outras atividades nas OF 9 e 12% do PC. O número de estações visitadas por minuto e o tempo em cada estação variou em função das ofertas de forragem nos estádios vegetativo 2 e florescimento. O número de bocados foi maior nas OF 6 e 9% do PC. O número de refeições foi maior, intermediário e menor nas OF 12, 9 e 6% PC, respectivamente e similar em todos os estádios. A duração das refeições foi maior na OF 6, intermediária na 9 e menor na 12%. A estimativa de consumo de matéria orgânica por cordeiras em pastagem de azevém é similar quando são utilizados o óxido de cromo e o nitrogênio fecal como marcadores. O consumo de forragem em função das ofertas de forragem é dependente da estrutura do dossel e é limitado no pré-florescimento e florescimento, em função da elevada massa de colmos. A taxa de bocado é dependente da altura do dossel e varia nos estádios fenológicos do azevém para compensar alterações na massa de bocado. O tempo de pastejo é similar com ofertas de forragem variando de 6 a 12% do PC, mas durante os estádios fenológicos do azevém é dependente da massa de forragem e da oferta de lâminas foliares. A duração da refeição varia com alterações na taxa de bocado de cordeiras, oferta de lâminas foliares e relação lâmina: colmo. O número de refeições não se altera com o avanço no ciclo do azevém, mas é influenciado pela participação de lâminas foliares no dossel. A duração do intervalo entre refeições é similar entre as ofertas de forragem e nos diferentes estádios fenológicos do azevém está correlacionada com as atividades de ruminação e outras atividades. A estimativa de consumo de matéria orgânica por cordeiras em pastagem de azevém é similar quando são utilizados o óxido de cromo e o nitrogênio fecal como marcadores. O consumo de forragem em função das ofertas de forragem é dependente da estrutura do dossel e é limitado no final do ciclo do pasto em função da elevada massa de colmos. Os estádios fenológicos do azevém tiveram maior importância nas mudanças ocorridas na estrutura do pasto e no comportamento ingestivo de cordeiras do que as ofertas de forragem utilizadas. A massa de bocado é inalterada por ofertas de forragem que variam entre 6 a 12 % do PC e qualquer uma delas pode ser utilizada em pastagem de azevém.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Feeding behavior, forage intake by beef heifers, the pasture structure in two phenological stages of annual ryegrass (Lolium multiflorum): pre-flowering and flowering with heifers subjected to different feed systems: heifers exclusively on pasture or receiving corn grain (0.78% of body weight) or extruded fat (0.2% of body weight) as a supplement was studied. The experimental design was completely randomized in a factorial arrangement 3 x 2 (three supplements x two phenological stages of Italian ryegrass). The behavioral assessments were made by visual observation in four continuous 14 hour periods. Total DM and pastures intake were similar in both phenological stages. DM intake from pasture was higher for heifers consuming only ryegrass, intermediate for heifers that received fat, and lower when the supplement used was corn grain. Average daily gain of heifers was similar, regardless of the supplement received and the phenological stage of the ryegrass. The body condition score of heifers was similar in evaluations at pre-flowering and flowering stage of ryegrass. The heifers receiving corn grain had higher body condition score. The supply of corn grain caused a stocking rate 18% above other supplements tested. Grazing and ruminating time did not differ with the advance of the ryegrass cycle. Idle time was reduced from 312.22 to 228.68 minutes / day in the pre-flowering and flowering stage. The diurnal grazing, rumination and idle time were similar among heifers receiving different treatments. / Foram estudados o comportamento ingestivo, o consumo de forragem por novilhas de corte e a estrutura da pastagem em dois estádios de desenvolvimento do azevém (Lolium multiflorum Lam.): pré-florescimento e florescimento com bezerras submetidas à diferentes sistemas alimentares : novilhas exclusivamente em pastejo ou recebendo grão de milho (0,78% de peso corporal de grão de milho) ou gordura extrusada como suplemento (0,2% de peso corporal de gordura extrusada. O delineamento experimental foi o inteiramente casualizado, com arranjo fatorial 3 x 2 (três suplementos x dois estádios fenológicos do azevém). As avaliações de comportamento foram feitas por meio de observação visual, em quatro períodos contínuos de 14 horas. As ingestões de MS total e do pasto foram semelhantes nos dois estádios fenológicos. A ingestão de MS do pasto foi maior para as novilhas exclusivamente em pastagem de azevém, intermediária para as novilhas que recebiam gordura, e inferior quando o suplemento utilizado foi o milho. O ganho médio diário das novilhas foi semelhante, independente do suplemento recebido e do estádio fenológico do azevém. O escore de condição corporal das novilhas foi semelhante nas avaliações no estádio pré-florescimento e florescimento do azevém. As novilhas que receberam milho apresentaram escore de condição corporal superior. O fornecimento de milho ocasionou taxa de lotação 18% superior aos demais suplementos testados. Os tempos de pastejo e ruminação não diferiram com o avanço do ciclo do azevém. O tempo de ócio foi reduzido de 312,22 para 228,68 minutos/dia do pré-florescimento para o florescimento. O tempo diurno de pastejo, ruminação e de ócio foi semelhante entre as novilhas que recebiam os diferentes suplementos.

Dans cette thèse, nous montrons dans des amas d’oxyde de chrome épitaxiés, la contrainte conduit à l'apparition d'une phase multiferroïques, ainsi qu'un effet magnéto-électrique géant tel que le coefficient ME est de plusieurs ordres de grandeur supérieur que le terme linéaire dans Cr2O3 massif. Cela illustre que des contraintes épitaxiales dans des amas manométriques de taille réduite, crée un nouveau matériau magnéto-électrique ouvrant la possibilité d'utiliser un champ électrique pour orienter l'aimantation du matériau. Le coefficient magnéto-électrique linéaire calculé (6.7ns.m-1) est de trois ordres de grandeur plus élevé que dans l’oxyde de chrome massif (4.17ps.m-1) . Nous avons alors exalter ce coefficient sur des amas d’oxyde de chrome fortement contraintes. Nous avons aussi déclarés une assemblée d’amas n’ont pas seulement super-paramagnétique mais aussi super-paraélectrique.Dans la deuxième partie de notre travail nous avons donc utilisé une méthode d’optique non-linéaire afin d’observer cette polarisation spontanée à la température ambiante.Les mesures du magnéto-transport à température ambiante ne permettent pas d’étudier la polarisation électrique dans le Cr2O3, puisque la magnétorésistance tunnel mesurée à RT est nulle. Nous avons donc cherché une autre méthode la génération de la seconde harmonique qui est une méthode d’optique non linéaire, qui peut donner des informations sur l’état de la polarisation électrique dans un matériau non centrosymétriques. Elle a été utilisée dans notre cas pour déterminer la polarisation d’amas d’oxyde de chrome Cr2O3 super-paraélectriques à température ambiante> / In this thesis, it was shown the strained nanometre size chromium oxide particles embedded in a single crystallise dielectric matrix exhibit magneto-electric coefficients several orders of magnitude larger than the linear terms in bulk Cr2O3 . These clusters are studied in a double tunnel junction Fe/MgO-Cr-MgO/Fe and their magnetization varies under bias voltage, opening the possibility of efficient use of electric field for controlling the magnetization of the material. It also provides evidence for the occurrence of a significant spontaneous electric polarization on the chromium oxide particles which not only behave as super-paramagnetic but also as super-paraelectric material. The electric polarization is of order of 0,22 μC cm-2 at low temperature. In order to study the electric and magnetic proprieties of these clusters with different transport conditions compared to the double tunnel junction in reference, we reproduced smaller clusters in dielectric matrix MgO as the upper magnetic layer of iron is replaced by a non magnetic layer Pd.In the second part of our work, we used a non- linear optical method to observe the spontaneous polarization at room temperature.The magneto-transport measurements at room temperature do not allow to study the electrical polarization in the Cr2O3, since the tunnel magnetoresistance measured RT is zero. We therefore sought an alternative method of generating the second harmonic which is a nonlinear optical method, which can provide information on the state of the electric polarization in a non- centrosymmetric material. It has been used in our case to determine the super- cluster Cr2O3 paraelectric at room temperature of chromium oxide polarization .Under application of a positive voltage , the variation of the SHG intensity gradually changing to 7 V with 40 % of the reports . We eliminated two major phenomena may induce this change as the influence of capacitive loads or a plasmonic effect , to suggest that this variation is due to the spontaneous polarization is aligned along the applied electric field. The variation of the SHG is observed for an electric field applied in the plane , but it shows instability . We attribute this change in this case an electro- migration in the MgO . we show the SHG variation in function of the voltage for several junctions studied an electric field perpendicular . It can be adjusted by a Langevin function of applied electric field.

Le contexte industriel de cette étude est la modification de surface de l’alliage 690(60%Ni, 30%Cr, 10%Fe) utilisé dans la fabrication de tubes de générateurs de vapeur.L’objectif de ce travail de thèse est donc de former, par traitement de fusion par laser nanopulsé, une couche de Cr2O3 étanche au relâchement du nickel. Pour maîtriser la formation decette couche, il est primordial de déterminer les paramètres opératoires influant sur lespropriétés de cette couche. L’objectif scientifique est alors d’expliquer les phénomènesintervenant pendant et après l’impulsion laser au niveau de l’extrême surface.Suite à une étude paramétrique détaillée, un traitement de fusion superficielle par laser nanopulsé a permis d’obtenir un fort rapport Cr/Ni en surface et une couche d’oxyde dense etcontinue. Afin de vérifier l’efficacité du traitement, des coupons traités ont été introduits dansune boucle simulant le milieu primaire.Des expériences et des calculs ont été mis en oeuvre pour tenter d’expliquer l’enrichissementen chrome de la surface à l’aide de ce procédé. Les résultats expliquent l’enrichissement enchrome jusqu’à la solidification du bain liquide en surface qui précède la formation du Cr2O3favorisée par la forte affinité du chrome avec l’oxygène et la grande stabilité de l’oxyde Cr2O3. / Alloy 690 (60%Ni, 30%Cr, 10%Fe) is mainly used in primary circuit pipes fornuclear power plants.The aim of this thesis is to form a Cr2O3 layer, using laser surface melting, with the objective ofcreating a chromium-rich oxide layer. In order to optimize the treatment, it was first important todetermine parameters influence on the layer oxide properties then, with the objective of adeeper understanding of mechanisms involved, to address thermo-physical phenomenaoccurring during and after the laser pulse striking the upper surface.A deep parametric study first enabled to find an optimized laser surface treatment whichproduces chromium enrichment of the upper surface and a dense and continuous oxide layer.This treatment has been applied on samples, set in a primary medium simulation loop.Experiments and calculations were carried out to provide understanding of surface chromiumenrichment by laser process. The results were shown to explain chromium enrichment until meltpool solidification occurred on the upper surface, assumingly just before chromium oxideformation. This was also promoted by a high affinity with oxygen and a higher stability of Cr2O3oxide compared with other potential oxide formation.

The constant pursuit in the automotive industry to increase the engines performance, new solutions are always developed and tested to reduce the friction and increase the efficiency in the engine. One component that contributes to friction losses is the piston ring pack where the top compression stands for up to 40 %. This master thesis collaborated with Scania’s material science department Basic engine and covers the friction and wear of four different materials on the cylinder liner surface against the top compression ring.The four tested materials were grey cast iron with different honing quality and three atmospheric plasma sprayed coatings with titanium oxide, chromium oxide and Metco’s mixture F2071 which is a stainless steel mixed with a ceramic. A martensitic steel piston ring with a chromium coated sliding surface was used for all the testing in the Cameron-Plint TE77 test-rig. This is a pin-on-disc test method and the parameters used for testing is set to replicate the environment the ring is exposed to at the top dead centre.The test-rig has been in Scania’s possession for a long time and has not always given a satisfying result. An uneven contact between the ring and liner has been a problem resulting in only worn edges of the liner specimen. The piston ring holder was therefore redesigned to be able to adjust the radius of the ring. This allowed a good conformability between the ring and liner to be obtained.The tested materials were evaluated according to friction and wear. Friction was measured with the test-rig and the wear was calculated with surface profiles that were measured before and after testing. Worn surfaces were studied in a SEM to verify which wear mechanism that was active. The changes of the surfaces was studied with the use of following surface parameters Ra, Rk, Rpk, Rvk and if there was a connection between these parameters and friction and wear coefficient.Independent of honing quality showed the grey cast iron lowest friction coefficient just under 0.13, the F2071 liner showed a friction coefficient just above 0.13. Both oxide layers showed similar friction where the chromium oxide had a friction just below 0.15 and the titanium oxide lay just above 0.15. Lowest wear coefficient had the chromium oxide followed by F2071, titanium oxide and the bad honed grey cast iron. These three liners showed almost the exact same wear coefficient. Worst wear coefficient had the grey cast iron with a good honing quality. A mild abrasive wear mechanism was active during the wear test and vague wear marks was found on the surface. There is no connection between wear coefficient and friction and the change in surface roughness during the test does not affect the friction.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18607号 / エネ博第303号 / 新制||エネ||62(附属図書館) / 31507 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 平藤 哲司 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Acid/Base characterizations of metal oxide surfaces are often used to explain their catalytic behavior. However, the vast majority of these studies have been performed on powders or supported oxides, and there is very little information available in the literature on the interaction of acid/base probe molecules with well-defined oxide surfaces of known coordination geometry and oxidation state. The well-defined, single crystal surfaces of Cu₂O (111), SnO₂ (110), and Cr₂O₃ (101̲2) were investigated for their acid/base properties by the interactions between the probe molecules and the well-defined surface features. The adsorption of NH₃ at cation sites was used to characterize the Lewis acidity of SnO₂ (110) and Cu₂O (111) surfaces. The adsorption of CO₂, a standard acidic probe molecule, was used to characterize the Lewis basicity of the oxygen anions on SnO₂ (110), Cu₂O (111) , and Cr₂O₃ (101̲2) surfaces. BF₃, while not a standard probe molecule, has been tested as a probe of the Lewis basicity of the oxygen anions on SnO₂ (110) and Cr₂O₃ (101̲2). By studying probe molecules on well-defined metal oxide surfaces with known coordination geometry and oxidation state, an overall evaluation of NH₃, CO₂, and BF₃ as probe molecules can be made using the surfaces studied. NH₃ probed differences in Lewis acidity of Sn cations on SnO₂ (110), which had differences in coordination environments and oxidation states. But, NH₃ adsorption failed to provide any direct information on differences in Lewis acidity of Cu cations in different local coordination geometries on Cu₂O (111). CO₂ is a poor probe of the Lewis basicity of oxygen anions on the metal oxide surfaces studied here. CO₂ does not strongly adsorb to either SnO₂ (110) or Cu₂O (111). On Cr₂O₃ (101̲2), CO₂ does interact with oxygen sites but in two different coordinations, which vary with surface condition, making a comparison of basicity difficult. In the cases studied here, CO₂ either does not adsorb, or it does not provide a clear set of results that can be related simply to Lewis basicity. BF₃ seems to be a much better probe of the Lewis basicity than CO₂ for the well-defined metal oxide surfaces studied here. On SnO₂ (110) and Cr₂O₃ (101̲2), the boron atom of BF₃ directly interacts with oxygen sites by accepting their electrons. BF₃ thermal desorption seems to provide a direct measure of the Lewis basicity of different surface oxygen species as long as they are thermally-stable in vacuum. / Ph. D.

Metal Oxide (MO)semiconductors are one of the most widely used materials in commercial gas sensor devices. The basic principle of chemoresistive gas sensor operation stems on the high sensitivity of electrical resistance to ambient gaseous conditions. Depending on whether the oxide is "p type" or "n type", the resistance increases (or decrease), when placed in atmosphere containing reducing (or oxidizing) gases. The study of conductometric metal oxide semiconductor gas sensors has dual importance in view of their technological device applications and understanding fundamental MO-gas interactions. Metal oxides based sensors offer high thermal, mechanical and chemical stability. A large number of MOs show good sensitivities to various gases like CO, NOX, SOX, NH3, alcohols and other Volatile Organic Compounds (VOCs). VOCs are very common hazardous pollutants in the environment. Gas sensors are in great demand for their various applications such as food quality control, fermentation industries, road safety, defence, environmental monitoring and other chemical industries. The aim of the study is to explore the possibility of advancements in semiconducting MO based gas sensor devices through tuning microstructural parameters along with chemical dopants or additives. And further to investigate the underlying mechanism of conductometric MO gas sensors. The novel synthesis method employed is based on the solution combustion method coupled with ultrasonically nebulized spray pyrolysis technique. The well studied SnO2 and relatively unexplored Cr2O3 oxide systems are selected for the study. The non-equilibrium processing conditions result in unique microstructure and defect chemistry. In addition, using this technique MO - Reduced Graphene Oxide (RGO) nanocomposite films has also been fabricated and its application to room temperature gas sensor devices is demonstrated. The thesis comprises of seven chapters. the following section describe the summery of individual chapters. The Chapter 1 describes the introduction and background literature of this technology. A brief review of developments in gas sensor technology so far has been enlisted. This chapter also gives a glimpse of applications of MO semiconductors based sensors. The underlying mechanism involved in the sensing reaction and the primary factors influencing the response of a gas sensor device are enlisted. Further in the later part of the chapter focused the material selection criteria, effect of additives/dopants and future prospects of the technology. The end of this chapter highlights the objective and scope of the work in this dissertation. In the Chapter 2 the the materials selection, characterization techniques and particularly the experimental setups used are elaborated. This includes the deposition method used, which is developed in our group and the the in house built gas sensing system including its working principles and various issues have been addressed. The Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) is a novel deposition method devised, which is a combination of conventional spray pyrolysis and solution combustion technique. Spray pyrolysis is versatile, economic and simple technique, which can be used for large area deposition of porous films. The intention is to exploit the exothermicity of combustion reaction in order to have high crystallinity, smaller crystallite size with high surface area, which are extremely important in gas sensor design and its efficiency. Further the gas sensing system and its operation are discussed in detail including the advantages of vertical sensing chamber geometry, wider analyte concentration range (ppm to percentage) obtained through vapor pressure data and simultaneous multi sensor characterization allowing better comparison. Here in this work, Chromium oxide (Cr2O3) and Tin oxide (SnO2) are selected as gas sensing materials for this work as a p-type and n-type metal oxide semiconductors respectively. Nevertheless Cr2O3 is a less explored gas sensing material as compared to SnO2, which is also being used in many commercially available gas sensor devices. Thus, studying and comparing gas sensing properties of a relatively novel and a well established material would justify the potential of the novel deposition technique developed. In Chapter 3, the effect of exothermic reaction between oxidizer and fuel, on the morphology, surface stoichiometry and observed gas sensing properties of Cr2O3 thin films deposited by UNSPACM, is studied. An elaborative study on the structural, morphological and surface stoichiometry of chromium oxide films is undertaken. Various deposition parameters have been optimized. An extensive and systematic gas sensing study is carried out on Cr2O3 films deposited, to achieve unique microstructure. The crystallinity and microstructure are investigated by varying the deposition conditions. Further, the effect of annealing in oxygen gas atmospheres on the films was also investigated. The gas sensing properties are studied for various VOCs, in temperature range 200 - 375 oC. The possible sensing mechanism and surface chemical processes involved in ethanol sensing, based on empirical results, are discussed. In chapter 4, the effect of 1% Pt doping on gas sensing properties of Cr2O3 thin films prepared by UNSPACM, is investigated. The chemical analysis is done using x-ray photoelectron spectroscopy to find the chemical state of Pt and quantification is done. The gas sensing is done towards gases like NO2, Methane and Ethanol. The enhancement in sensitivity and remarkable reduction in response as well as recovery times have been modeled with kinetic response analysis to study the variation with temperature as well as concentration. Further the analysis of observations and model fittings is discussed. The Chapter 5 deals with the defects induced ferromagnetism and gas sensing studies SnO2 nanoparticles prepared by solution combustion method. The structural, chemical analysis of as-synthesized and annealed SnO2 nanoparticles reveal gradual reduction in defect concentration of as-prepared SnO2. The findings of various characterization techniques along with optical absorption and magnetic studies to investigate the defect structure of the material are presented. As defects play crucial role in gas sensing properties of the metal oxide material, the defect induced room temperature ferromagnetism in undoped SnO2 has been used as a potential tool to probe the evidence of the defects. Finally a correlation is established between observed room temperature ferromagnetism and gas sensing studies and primary role of defects in gas sensing mechanism over microstructure is realized . The Chapter 6 presents the deposition of SnO2 thin films by UNSPACM method on glass substrates for gas sensing application. The readiness of UNSPACM in making sensor materials with unform dopant distribution is demonstrated in order to improve the sensor performance in terms of response and selectivity. The chemical composition, film morphology and gas sensing studies are reported. The SnO2 is doped with Cr and Pt to enhance the sensing properties of the material. The doped Oxide films are found to show enhancement in sensitivity and improve the selectivity of the films towards specific gases like NO2 and CO. Further in Chapter 7 an effort has been made to overcome the problem of high operating temperature of metal oxide gas sensors through use of Reduced Graphene Oxide (RGO) and metal oxide nanocomposite films. Although RGO shows room temperature response towards many toxic and hazardous gases but it exhibits poor sensor signal recovery. This has been successfully solved by making nanohybrids of RGO and SnO2. It not only improves the sensor signal kinetics but it enhances the sensitivity also. Thus this chapter endeavors towards low power consumption gas sensing devices. The key findings and future aspects are summarized in the Chapter 8.