Recent research demonstrated that polymer based nanocomposites (PNCs) have been engineered in order to improve the arc interruption capability of the circuit breakers. PNCs are the combination of nano-sized inorganic nanoparticles (NPs) and polymers, opened up new developments in materials science and engineering applications. Inorganic NPs are selected based on their physical and chemical properties which could make multifunctional PNCs in order to interrupt the electrical arcs effectively. In particular, we presented the PNCs fabricated by using CuO, Fe3O4, ZnO and Au NPs in a poly (methyl methacrylate) (PMMA) matrix via in-situ polymerization method, recently developed method to avoid NPs agglomeration, leading to good spatial distribution in the polymer matrix. Thus, several samples with various wt% of NPs in PMMA matrix have been fabricated. These PNCs have been characterized in detail for the morphology of NPs, interaction between NPs and polymer matrix, and radiative/thermal energy absorption properties. In the next stage, PNCs are tested to determine their arc interruption performance and impact on the electrical arcs of current 1.6 kA generated using a specially designed test set-up. When PNCs interact with the electrical arcs, they generate ablation of chemical species towards core of the electrical arc, resulting in cooling-down the arc due to strong temperature and pressure gradient in the arc quenching domain. This thesis demonstrates for the first time that these engineered PNCs are easily processed, reproducible, and can be used to improve the arc interruption process in electrical switching applications. / Ny forskning har visat att polymerbaserade nanokompositer (PNCs) har utformats för att förbättra strömbrytares förmåga att undvika ljusbågar vid överslag. PNCs är en kombination av nanostora oorganiska nanopartiklar (NP) och polymerer, som har öppnat upp för ny utveckling inom materialvetenskap och tekniska tillämpningar. Oorganiska NP väljs baserat på deras fysikaliska och kemiska egenskaper som kan hjälpa PNCs att motverka elektriska ljusbågar effektivt. I synnerhet, presenterade vi PNCs tillverkade genom användning av CuO, Fe3O4, ZnO och Au NP i en poly (metylmetakrylat) (PMMA)-matris via in situ-polymerisationsmetod, nyligen utvecklad för att undvika NP-agglomerering, vilket leder till god rumslig fördelning i polymermatrisen. Därför har flera prover med olika vikt% av NP i PMMA-matris tillverkats. Dessa PNCs har utvärderats i detalj för NP-morfologi, interaktion mellan NP och polymermatris, och strålnings- och värmeenergiabsorption. I nästa skede testas PNCs för att bestämma deras förmåga att undvika ljusbågar och påverkan på de elektriska ljusbågarna av 1,6 kA strömstyrka, genererade med hjälp av en specialdesignad test-set-up. När PNCs interagerar med de elektriska ljusbågarna, genererar de ablation av kemiska ämnen mot kärnan i den elektriska ljusbågen, vilket resulterar i nedkylning av ljusbågen på grund av starka temperatur- och tryckgradienter i området. Denna avhandling visar för första gången att dessa konstruerade PNCs är lätta att framställa, reproducerbara, och kan användas för att förbättra avbrottsprocessen för ljusbågen i elektriska kopplingstillämpningar. / <p>QC 20170303</p>

No description available.

Nanostructured materials especially, one-dimensional (1D) nanostructures have unique physical, chemical, mechanical properties and are the building blocks for a range of nanoscale devices. The procedure employed for the synthesis of nanostructures involves the use of sophisticated instruments or rigorous chemical reactions. The motivation of our work is to develop a strategy that is simple, cost effective and applicable to a host of oxide materials. Nanostructures of various oxides have been grown from the metal as the source material. 1D ZnO nanostructures have been obtained by simply heating Zn metal in ambient air at temperatures below 600 °C. The nanostructures grow on the surface of the source material and the morphology is controlled by monitoring the curvature of the source material. This technique has an added advantage that neither any catalyst nor any gas flow is required. Tetrapods of ZnO are obtained when Zn is heated above 700 °C in ambient air. It has been shown that the morphology and the aspect ratio (length-to-diameter ratio) of the tetrapods depend on the temperature and the temperature gradient. Photoluminescence studies reveal good optical quality ZnO nanostructures. The technique employed to synthesize 1D ZnO nanostructures has been checked for other oxides. The temperature required for the synthesis of Ga2O3 nanostructures is 1200 °C. Many researchers have shown that Ga2O3 emits in the blue-green region. A red emission is required to get the impression of white light which has been seen for nitrogen doped Ga2O3. As the temperature is very high and Ga is heated in ambient air, unintentional nitrogen doping of 1D Ga2O3 nanostructures is obtained which is the reason for white light emission. The morphology of Ga2O3 nanostructures has been controlled by monitoring the curvature of the starting material as is the case of ZnO. Similar technique has also been employed for the synthesis of CuO nanostructures. The morphology is temperature dependent and 1D CuO nanostructures are obtained when the synthesis temperature is between 400 and 600 C. Possible growth mechanisms have been proposed for all these oxide materials. The entire thesis is based on the results discussed above. It has been organized as follows: Chapter 1 deals with the introduction to nanostructures, importance of 1D nanostructures, the specific applications of different morphologies, materials that are widely explored in the synthesis of nanostructures and different approaches to the synthesis of nanostructures. Growth mechanisms like VLS, VS and SLS are briefly discussed. A brief review on the basic physical properties, applications and different morphologies of ZnO, Ga2O3 and CuO is outlined with emphasis to the various synthesis techniques. Finally the aim and scope of the present work is discussed. Chapter 2 describes the experimental setup used for the synthesis and the basic principles of characterization techniques like x-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectrum (EDS), electron energy loss spectroscopy (EELS), photoluminescence (PL), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), UV-Visible spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Chapter 3 deals with the synthesis of 1D ZnO nanostructures with different morphologies such as nanoneedles, nanorods, nanobelts from Zn powder/granule. The growth process is found to be different from the conventional VS mechanism. The advantage and the versatility of the method is emphasized. In this method, neither a catalyst nor any gas flow is required for the synthesis of oxide nanostructures. Depending upon the Zn powder or Zn granules as the starting material different nanostructures of ZnO have been synthesized. The as-synthesized materials are characterized by XRD, SEM, HRTEM, EDS, TGA and Raman spectroscopy and the results are discussed. Chapter 4 describes the controlled growth of ZnO tetrapods and the influence of temperature and temperature gradient on the growth process. Though there are several methods to synthesize ZnO tetrapods and it has been established that ZnO tetrapods can be synthesized by heating Zn in air, it is advantageous to grow tetrapods of different morphologies with different lengths. The large scale synthesis of ZnO tetrapods by heating Zn in air ambient is discussed in this chapter. The key parameters that control the diameter, length, and morphology of tetrapods are identified. It is shown that the morphology and dimensions of the tetrapods depend not only on the vaporization temperature but also on the temperature gradient of the furnace. The influence of vaporization temperature and growth temperature on the morphology of the tetrapods is discussed elaborately. Chapter 5 explains the one-step synthesis of nitrogen doped Ga2O3 nanostructures of different morphologies and the different growth mechanisms. The experimental method employed for the synthesis of nanostructures is simple and is different from the other reported methods. Neither any catalyst/substrate preparation nor any gas flow is required for the synthesis of Ga2O3 nanostructures. The synthesis involves the heating of molten Ga at high temperatures. Single crystalline monoclinic phase of nitrogen-doped Ga2O3 nanorods, nanobelts and nanoneedles are obtained by this method. The morphology is controlled by monitoring the curvature of the Ga droplet which is achieved by using different substrates. Possible growth processes of different morphology have been proposed. Chapter 6 includes some surprising results on the white light emission of Ga2O3 nanorods. High synthesis temperature generates a high vapor pressure suitable for the growth of Ga2O3 nanorods, creates oxygen vacancy and incorporates nitrogen from the ambient. The oxygen vacancy is responsible for the bluish-green emission, while nitrogen is responsible for the red emission. As a consequence, white light emission is observed from Ga2O3 nanorods when irradiated with UV light. The interesting point is that neither post-treatment of the nanorods nor size control is required for white light emission. Chapter 7 describes the synthesis of CuO nanostructures by heating Cu foil in air ambient. This is an attempt to check whether the synthesis technique employed for ZnO and Ga2O3 is applicable to other oxides. The as-synthesized CuO nanostructures are characterized by XRD, SEM, HRTEM, EDS, TGA, UV-visible, FTIR and the results are discussed. Chapter 8 gives the conclusions and the overall summary of the thesis.

The availability of high quality thermodynamic data on solid solutions and compounds present in multicomponent systems assists in optimizing processing parameters for synthesis, and in evaluating stability domains and materials compatibility under different conditions. Several oxide systems of technological interest, for which thermodynamic data was either not available or is inconsistent were selected for study. Thermodynamic properties of phases present in the binary systems Nb-O and Ta-O were measured in the temperature range from 1000 to 1300 K using solid state electrochemical cells based on (Y2O3) ThO2 as the electrolyte. Based on these measurements and more recent data on heat capacity and phase transitions reported in the literature, Gibbs energy of formation for NbO, NbO2, NbO2.422, Nb2O5-x and Ta2O5 were reassessed. Significant improvements in the data for NbO2, Nb2O5 and Ta2O5 are suggested. The pseudo binary system MoO2-TiO2 was investigated because of the inconsistency between the phase diagram and thermodynamic properties of the solid solution reported in the literature. Based on new electrochemical measurements, a new improved phase diagram for the system MoO2-TiO2, incorporating recently discovered monoclinic to tetragonal phase transition in MoO2 at 1533 K, is presented. Isothermal section of the phase diagram for the ternary systems Cr-Rh-O and Ta-Rh-O and thermodynamic properties of ternary oxides CrRhO3 and TaRhO4 were measured for the first time in the temperature range from 900 to 1300 K. Phase relations for these systems have been computed as a function of oxygen potential at fixed temperature and as a function of temperature at selected oxygen partial pressures. Metal-spinel-corundum three-phase equilibrium in the Ni-Al-Cr-O system at 1373 K has been explored because of its relevance to high temperature corrosion of super alloys. The Gibbs energy of mixing of spinel solid solution was derived from the tie-line data and is compared with the values calculated from cation distribution models. An oxygen potential diagram is developed for the decomposition of spinel solid solution to nickel and corundum solid solution at 1373 K under reducing conditions. The high temperature thermodynamic properties of the phases present in quaternary systems Ca-Co-Al-O and Ca-Cu-Ti-O have been measured by solid state electrochemical cells based on stabilized zirconia. Gibbs energies of formation of the quaternary oxides Ca3CoAl4O10 in the temperature range from 1150 to1500 K and CaCu3Ti4O12 in the range from 900 to 1350 K are presented. Chemical potential diagrams have been computed for the system Al2O3-CaO-CoO at 1500 K. The oxygen potential corresponding to the decomposition of the complex perovskite CaCu3Ti4O12 (CCTO) has been calculated as a function of temperature from the emf of the cell. The effect of the oxygen partial pressure on the phase relations in the pseudo-ternary system CaO-(CuO/Cu2O)-TiO2 at 1273 K has been evaluated. The phase diagrams are useful for the control of the secondary phases that form during synthesis of CCTO, a material exhibiting colossal dielectric response.

Οι υψηλές θερμοκρασίες λειτουργίας των κελιών καυσίμου στερεού ηλεκτρολύτη (Solid Oxide Fuel Cells - SOFCs), οδηγούν σε σημαντική επιβάρυνση των σημείων συνένωσης και στεγανότητας των στοιχείων των επί μέρους εξαρτημάτων των κελιών, που διατάσσονται σε στοιβάδες. Στα σημεία συνένωσης και εναλλακτικά στα μέχρι σήμερα χρησιμοποιούμενα συγκολλητικά, με βάση ενώσεις υαλοκεραμικών, εξετάζεται η χρήση ενός συνδυασμού υλικών αποτελούμενων από κεραμικό οξείδιο ως μονωτικό (isolation layer), καθώς κι ένα μεταλλικής βάσης υλικό ως συγκολλητικό. Κατά τη συγκόλληση στον αέρα, χωρίς χρήση κενού ή προστατευτικού αερίου, το μεταλλικής βάσης συγκολλητικό έρχεται σε επαφή με την επίστρωση μονωτικού (MgO, MgAl2O4 ή ένα μίγμα MgO + MgAl2O4) και με τα μεταλλικά στοιχεία των κελιών (φερριτικοί χάλυβες, Cr ≈ 22%, Mn ≈ 0.6%). Οι κύριες απαιτήσεις που πρέπει να ικανοποιεί το συγκολλητικό είναι η καλή προσαρμογή των διαφορετικών συντελεστών θερμικής διαστολής, μακροχρόνια αντοχή στις οξειδωτικές συνθήκες λειτουργίας των κελιών, ισχυρό δεσμό και απουσία χημικής φύσης αλληλεπιδράσεων στη σχηματιζόμενη διεπιφάνεια, για τη διατήρηση της μηχανικής ευστάθειας και της χαμηλής αεριοδιαπερατότητας της συγκόλλησης. Οι φυσικοχημικές και μηχανικές ιδιότητες του καθαρού αργύρου (Ag) ως συγκολλητικό, ικανοποιούν εν γένει τις παραπάνω απαιτήσεις, μειονεκτώντας όμως, ως προς τη δημιουργία ισχυρού δεσμού στις σχηματιζόμενες διεπιφάνειες. Προσθέτοντας στον Ag το διεπιφανειακά ενεργό οξείδιο του χαλκού (CuO), βελτιώνεται σημαντικά η διαβρεξιμότητα του κεραμικού (μονωτικό) και του μετάλλου (φερριτικός χάλυβας), από το τήγμα του κράματος Ag+CuO (γωνία επαφής θ < 90ο) και συνεπώς η ισχύς του δεσμού στις διεπιφάνειες.. Στόχος της παρούσας εργασίας είναι η επιλογή του κατάλληλου τρόπου προσθήκης του CuO στον Ag, ώστε να επιτευχθεί ένας ισχυρός δεσμός μεταξύ του συγκολλητικού και των υλικών προς συγκόλληση, αποφεύγοντας τον εκτεταμένο σχηματισμό προϊόντων αντίδρασης στις διεπιφάνειες. Πραγματοποιήθηκαν δύο τρόποι προσδιορισμού της γωνίας επαφής, της κεραμικής και μεταλλικής φάσης, με πειράματα διαβροχής. Στη συνέχεια, για τον έλεγχο της μακροχρόνιας ευστάθειας των συγκολλήσεων, μέρος των δοκιμίων υποβλήθηκαν σε θερμική ανόπτηση στους Τ=1073 Κ για χρονικό διάστημα t=1000 h, στον αέρα. Μετά το πέρας των πειραμάτων πραγματοποιήθηκε έλεγχος της διεπιφάνειας με μεθόδους ηλεκτρονικής μικροσκοπίας και μικροανάλυσης. / For mobile applications, the rapid heating rates and the high operating temperatures of solid oxide fuel cells (SOFCs) lead to increased stress on the joining and sealing points of the material components used for the development of planar SOFC stacks. At the junctions of the metallic components and alternatively to the currently used glass-ceramic solders the possible use of oxide ceramic as an insulation layer in combination with air braze filler metal was examined. The joining of the components in air, without the use of vacuum or inert gases, requires that the filler metal forms strong interfacial bonds with both the ceramic (insulating layer) and the additional sheet (ferritic steel). In addition, it should be resistant to oxidation at the high operating temperatures and its thermal expansion coefficient should match those of the materials to be joined. When ceramic and metal are joined, the presence of a ductile interfacial phase compensates the differences in the thermal expansion coefficients of the phases involved. Also, it is necessary for the mechanical stability of the bond, that the binding partners are well wetted by the interfacial phase. Both Ag and Cu provide high mechanical strength, ductility, and thermal, as well as electrical conductivity. Although Ag is more expensive than Cu, it is preferred as a basis metal due to the lower process temperature and the lower oxygen affinity. A problem in using pure Ag is the poor wetting properties, at the liquid state, when in contact with oxide ceramic and steel. The high values of the contact angle (θ>120o) measured in oxide ceramic/Ag systems at oxygen concentrations of 0-3 ppm is reduced in air, but overall, the systems remain non-wetting (θ>90°). Good wetting (θ<<90o) is crucial for a strong interfacial bond between the phases in contact and simultaneously ensures the mechanical stability and gas tightness of the joints. Wetting can be improved by adding an interfacial active compound that is soluble in the noble metal solvent. A suitable material is CuO, which forms a pseudo-binary alloy with Ag in the solid state, as they present mutual solubility in the liquid state [11]. Depending on the percentage of CuO in the mixture, small contact angles (θ<20o) can be achieved in oxide ceramics/Ag + CuO systems. Requirements on the ceramic insulation layer include a high electrical and thermal resistance, a high thermal expansion coefficient, stability under mechanical pressure, structural stability and oxidation resistance at high operating temperatures. The most suitable ceramics for these requirements are MgO, MgAl2O4 or a mixture of MgO and MgAl2O4. The proposed Ag + CuO brazes come in contact with the ferritic steel of the interconnect part and with the additional sheet, as well as with the SOFC's electrolyte, 8 mol% Yttria-stabilized Zirconia (8YSZ), in the cell periphery. Ferritic steels, which have a Cr content above 20 wt% and a Mn content below 1 wt%, form a double outer layer in air that consists of Cr2O3 on the inside, towards the steel side, and a MnCr2O4 spinel phase on the outside. During the wetting experiment, the active CuO contained in the liquid Ag migrates towards the interface and a mixed oxide interface layer can be formed by reaction with the diffused cations Fe, Cr and Mn from the steel. The formation of the reaction zone improves the wetting behaviour (θ<90ο), but due to its higher brittleness, the mechanical interface stability of the composite can be reduced. In the present work, the amount of CuO additive in Ag filler metal and the way in which this additive is applied, varied to achieve good wetting properties, and stable braze’s joints. The aim was to achieve a strong interfacial bond between the contacting phases and to prevent extensive interface reactions. Reaction products that form during the early stages of the brazing process must remain constant at the operating conditions. For this reason, the long-term stability after heat treatment in air, of the material combination oxide / brazes/ steel was examined after wetting experiments.

Made available in DSpace on 2016-06-02T19:56:52Z (GMT). No. of bitstreams: 1 5331.pdf: 11740082 bytes, checksum: e8f5288e8c937187089b53d5c0ebd1c9 (MD5) Previous issue date: 2013-04-26 / Financiadora de Estudos e Projetos / The combustion of petroleum fuels produces large emissions of NOX, SOX and other strong atmospheric pollutants. The abatement of NOX can be achieved by the nonselective catalytic reduction of NO with CO, for that, supported noble metals have been the most commonly used, with high cost as disadvantage. Transition metal oxides show good activity for this reaction, however, they have poor performance in the presence of SO2, O2 and water steam. Thus, this study aimed to prepare, characterize and evaluate catalysts based on CuO, Fe2O3 and CuO-Fe2O3 supported on TiO2, ZrO2 and their mixtures, in the reduction of NO to N2 with CO in the presence or absence of water steam. XRD data, N2 adsorption and H2-TPR showed that mixed oxides and their catalysts, prepared by sol-gel in-situ, presented specific surface areas between 30 to 60 m2/g, with Cu or Fe species highly distributed, having the last greater interaction with titanium. Rietveld refinement showed preferential formation of zirconium titanate, then showing a close interaction of these species in the mixed supports. All catalysts were highly active in the reduction of NO to N2. At temperatures below 500 °C a CuO catalysts were more active and selective for the formation of N2 than Fe2O3, with the formation of N2O being favored with the increase of zirconium in the support. At 600 °C, the high conversion of NO to N2 on CuO was not influenced by the content of TiO2 in the support. Also at 600 °C, an increasing in the content of titanium in the Fe2O3 catalysts resulted in a significant drop in the conversion of NO to N2. The presence of water steam during the reduction of NO with CO at 600 °C caused a significant decrease in the conversion of NO to N2 and CO to CO2 on the CuO catalyst on the support with higher titanium content. The water steam completely eliminates the activity for the reduction of NO to N2 on Fe2O3 catalysts, but keeping a high conversion of CO to CO2. The CuO and CuO-Fe2O3 catalysts on zirconium-rich supports showed high potential for the abatement of NOX in the presence of water steam at temperatures above 500 ºC. / A combustão de derivados do petróleo gera grandes emissões de NOX, SOX e outros fortes poluentes da atmosfera. O abatimento de NOX pode ser realizado por meio da redução catalítica não seletiva com CO, onde os metais nobres suportados têm sido os mais empregados, com a desvantagem de seu elevado custo. Óxidos de metais de transição apresentam boa atividade nessa reação, no entanto, têm baixo desempenho na presença de SO2, O2 e vapor de água. Assim, este trabalho teve como objetivo preparar, caracterizar e avaliar catalisadores a base de CuO, Fe2O3 e CuO-Fe2O3 suportados em TiO2, ZrO2 ou suas misturas, na redução de NO a N2 com CO na presença ou ausência de vapor de água. Dados de DRX, adsorção de N2 e RTP-H2 mostraram que os suportes mistos e seus catalisadores, que foram preparados via síntese sol-gel in-situ, apresentaram áreas superficiais específicas entre 30 e 60 m2/g, com as espécies de Cu ou Fe altamente distribuídas, tendo essas últimas maior interação com a titânia. Refinamento de Rietveld mostrou formação preferencial de titanato de zircônia, evidenciando a estreita interação dessas espécies nos suportes mistos. Todos os catalisadores foram altamente ativos na redução de NO a N2. Em temperaturas inferiores 500 ºC os catalisadores de CuO foram mais ativos e seletivos à formação de N2 que o Fe2O3, com a formação de N2O sendo favorecida com o aumento de zircônia no suporte. A 600 ºC, a alta conversão de NO a N2 sobre CuO não foi influenciada pelo conteúdo de TiO2 no suporte. Nessa temperatura, o aumento do teor de titânia provocou nos catalisadores de Fe2O3 uma queda significativa na conversão de NO a N2. A presença de vapor de água durante a redução de NO com CO a 600 ºC provocou sobre CuO queda significativa da conversão de NO a N2 e de CO a CO2 sobre o suporte com maior conteúdo de titânia. Nos catalisadores de Fe2O3 puro, o vapor de água anulou completamente a atividade para a redução de NO a N2, mas manteve-se a conversão de CO a CO2. Os catalisadores de CuO e CuO-Fe2O3 sobre suporte contendo alto teor de zircônia apresentaram alto potencial para o abatimento de NOx na presença de vapor de água em temperaturas superiores a 500 ºC.

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-07-19T18:00:38Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) ronan_peixoto_gontijo.pdf: 1104745 bytes, checksum: 61495fad179d3458b9a10be7203acb6e (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-08-22T12:55:16Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) ronan_peixoto_gontijo.pdf: 1104745 bytes, checksum: 61495fad179d3458b9a10be7203acb6e (MD5) / Made available in DSpace on 2018-08-22T12:55:16Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) ronan_peixoto_gontijo.pdf: 1104745 bytes, checksum: 61495fad179d3458b9a10be7203acb6e (MD5) Previous issue date: 2017 / Objetivou-se avaliar os efeitos das t?cnicas de matura??o a v?cuo (wet ageing) e a seco (dry-ageing) nas caracter?sticas de qualidade da carne bovina proveniente do m?sculo dianteiro semispinales thoracis de animais Nelore. Foram processados 40 cortes, com peso ap?s toalete de aproximadente 2000g. Estes cortes foram maturados pelas duas t?cnicas de matura??o (embalados em polietileno para t?cnica a v?cuo e sem embalagem para t?cnica a seco) em c?mara fria padr?o comercial, com temperatura m?dia de 3?C e umidade relativa do ar m?dia de 69% durante 5 tempos, a saber: 0, 7, 14, 21 e 28 dias. Os cortes maturados pela t?cnica a seco foram diariamente virados e aspergidos com solu??o de 2% (v/v) de ?cido ac?tico. Os cortes da t?cnica a v?cuo foram aspergidos com a mesma solu??o e imediatamente embalados a v?cuo. Em cada tempo de matura??o foram avaliados rendimentos, for?a de cisalhamento, cor (L a* b* C and H ?), capacidade de reten??o de ?gua, perda de peso por coc??o, pH, quantifica??o superificial de coliformes totais e termotolerantes, assim como os teores de prote?na, gordura, massa seca e res?duo mineral fixo. N?o foram verificadas diferen?as (P>0,05) para a for?a de cisalhamento, perda de peso por coc??o, pH, par?metros microbiol?gicos e bromatol?gicos, com o decorrer dos 28 dias de matura??o, para ambas as t?cnicas. Na carne maturada ? v?cuo foram observados (P<0,05) aumento no croma e diminui??o na capacidade de reten??o de ?gua. A carne maturada a v?cuo apresentou os maiores rendimentos totais (P<0,05) comparada com a carne maturada a seco. A carne maturada ? seco apresentou maior capacidade de reten??o de ?gua e menor perda de peso por coc??o, em compara??o a carne maturada a v?cuo. A matura??o a seco por 21 dias proporcinou estabilidade da cor sem altera??es nos par?metros f?sico-qu?micos e redu??o na for?a de cisalhamento da carne proveniente do m?sculo semispinalis thoracis. A matura??o a v?cuo por 28 dias proporcionou redu??o da for?a de cisalhamento da carne proveniente do m?sculo semispinalis thoracis. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Zootecnia, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The objective of this study was to evaluate the effects of vacuum (wet-ageing) and dry-ageing techniques on the quality characteristics of bovine meat from the semispinales thoracis muscle of Nellore animals. 40 cuts were processed, with weight after trim of approximately 2000g. These cuts were matured by the two maturation techniques (packed in polyethylene for vacuum technique and without packaging for dry technique) in a commercial standard cold chamber, with a mean temperature of 3?C and a relative humidity of 69% for 5 times , namely: 0, 7, 14, 21 and 28 days. The sections matured by the dry-ageing technique were tacked daily and sprayed with a 2% (v / v) solution of acetic acid. The vacuum technique cuts were sprayed with the same solution and immediately vacuum packed. At each maturation time, yields, shear force, color (L a* b* C and H ?), water retention capacity, weight loss by cooking, pH, superificial quantification of total and thermotolerant coliforms, the levels of protein, fat, dry matter and fixed mineral residue were evaluated. No differences (P> 0.05) were observed for the shear force, weight loss per cooking, pH, microbiological and bromatological parameters, during the 28 days of maturation, for both techniques. In the vacuum packed meat (P <0.05), chroma increase and decrease in water retention capacity were observed. The vacuum packed meat had the highest total yields (P <0.05) compared to dry-aged meat. Dry-aged meat had a higher water retention capacity and less weight loss per cooking compared to vacuum packed meat. Dry maturation for 21 days provided color stability without changes in the physical-chemical parameters and reduction in the shear force of the meat from the semispinalis thoracis muscle. The 28-day vacuum maturation provided a reduction in the shear force of meat from the semispinalis thoracis muscle.

Four cluster models for a copper(I)oxide (111) surface have been designed, of which three were studied with respect to their applicability in density functional calculations in the general gradient approximation. Formic acid adsorption on these systems was modelled and yielded four different adsorption structures, of which two were found to have a high adsorption energy. The energetically most favourable adsorption structure was further investigated with respect to its decomposition and a few reactions with adsorbed H and OH species using synchronous transit methods to estimate reaction barriers and single point energy calculations for the reaction energy.

Four cluster models for a copper(I)oxide (111) surface have been designed, of which three were studied with respect to their applicability in density functional calculations in the general gradient approximation. Formic acid adsorption on these systems was modelled and yielded four different adsorption structures, of which two were found to have a high adsorption energy. The energetically most favourable adsorption structure was further investigated with respect to its decomposition and a few reactions with adsorbed H and OH species using synchronous transit methods to estimate reaction barriers and single point energy calculations for the reaction energy.:1 Introduction 1.1 Preliminary Work 1.2 Known Reactions and Issues 1.3 Overview of Reactions and Species involved in Formic Acid Decomposition 2 Theoretical Background 2.1 The Schrödinger-Equation 2.2 Density Functional Theory 2.3 Exchange-Correlation Functionals 2.4 The Self-Consistent-Field Procedure 2.5 Geometry Optimization and Transition State Searches 2.6 Kinetics 3 Computational Details 3.1 Synchronous Transit Schemes 3.2 Transition State Searches using Eigenvector Following 4 Model System 5 Results and Discussion 5.1 Geometry of the Cu2O cluster structures 5.2 Adsorption of formic acid 5.3 Decomposition and Reaction Paths 5.3.1 Vibrational Analysis of the adsorbed Formic Acid Molecule 5.3.2 Reaction Modelling using Linear Synchronous Transit 5.3.3 Transition State Searches using Eigenvector Following 6 Summary and Outlook

Des monocristaux de YBa2Cu3O7 ont été préparés par une méhode de flux en creuset d'or. Une analyse des spirales de croissance et des domaines ferroélastiques révélés par une étude en microscopie optique en lumière polarisée et en microscopie électronique a balayage sur la face principale (001) à été effectuée. Un ensemble de caractérisations physico-chimiques (diffraction X, EPMA, détermination de la température critique par mesures électriques, spectroscopie micro-Raman, mesures des susceptibilités alternatives en champ faible) réalisé sur des cristaux bruts de croissance et recuits sous oxygène à permis de relier l'évolution des propriétés supraconductrices à la non stoechiométrie en oxygène. Enfin le phénomène de dégradation atmosphérique de YBa2Cu3O7 à été confirmé par une étude sur monocristal, à l'aide des techniques spectroscopiques (micro-Raman, Auger, XPS)