Tailored deposition of coloured coatings: on the widening of the available colour range

Dissertação de mestrado integrado em Engenharia de Materiais

Flexible thin-film lithium battery

Tese de Doutoramento Programa Doutoral em Engenharia Electrónica e Computadores.

Comportamiento tribomecánico de sistemas de sustrato: recubrimiento duros

En aplicaciones como la conformación en frío, donde los metales duros recubiertos con películas de naturaleza cerámica son ampliamente empleados, la existencia de un contacto mecánico repetitivo induce tensiones Hertzianas y origina el fallo por fatiga. En este trabajo, se investigan diversos recubrimientos cerámicos depositados por deposición física desde fase vapor sobre calidades diferentes de metal duro y un acero rápido pulvimetalúrgico para evaluar sus respectivas respuesta al contacto y comportamiento a fatiga. El trabajo experimental incluye la caracterización de los sistemas mediante ensayos de rayado y nanoindentación y la evaluación de las curvas tensión-deformación de indentación esférica de los sustratos, tanto desnudos como recubiertos, poniendo especial atención en determinar las tensiones de contacto críticas asociadas a la deformación plástica y a la aparición de grietas circulares en la superficie recubierta. A este estudio, le siguen numerosos ensayos a fatiga a cargas inferiores a aquéllas identificadas como críticas bajo carga monotónica y para un número de ciclos comprendido entre 1.000 y 1.000.000 de ciclos. Los resultados experimentales indican que las películas cerámicas no parecen desempeñar un papel relevante en la aparición de la cedencia plástica, siendo la deformación plástica global controlada por la deformación del sustrato. No obstante, para tensiones elevadas de indentación durante el régimen plástico, existe la aparición de grietas circulares en los recubrimientos cerámicos. Además, la aparición de las mismas es sensible a la fatiga por contacto. Este análisis mecánico se complementa con una inspección detallada del daño generado en profundidad y superficie.

Crystal growth, Raman scattering and optical properties of the superconductor Cd2Re2O7(16O, 18O)/

Using the Physical Vapor Transport method, single crystals of Cd2Re207 have been grown, and crystals of dimensions up to 8x6x2 mm have been achieved. X-ray diffraction from a single crystal of Cd2Re207 has showed the crystal growth in the (111) plane. Powder X-ray diffraction measurements were performed on ^^O and ^^O samples, however no difference was observed. Assigning the space group Fd3m to Cd2Re207 at room temperature and using structure factor analysis, the powder X-ray diffraction pattern of the sample was explained through systematic reflection absences. The temperatiure dependence of the resistivity measurement of ^^O has revealed two structural phase transitions at 120 and 200 K, and the superconducting transition at 1.0 K. Using Factor Group Analysis on three different structiures of Cd2Re207, the number of IR and Raman active phonon modes close to the Brillouin zone centre have been determined and the results have been compared to the temperature-dependence of the Raman shifts of ^^O and ^*0 samples. After scaling (via removing Bose-Einstein and Rayleigh scattering factors from the scattered light) all spectra, each spectrum was fitted with a number of Lorentzian peaks. The temperature-dependence of the FWHM and Raman shift of mode Eg, shows the effects of the two structurjil phase transitions above Tc. The absolute reflectance of Cd2Re207 - '^O single crystals in the far-infrared spectral region (7-700 cm~^) has been measured in the superconducting state (0.5 K), right above the superconducting state (1.5 K), and in the normal state (4.2 K). Thermal reflectance of the sample at 0.5 K and 1.5 K indicates a strong absorption feature close to 10 cm~^ in the superconducting state with a reference temperature of 4.2 K. By means of Kramers-Kronig analysis, the absolute reflectance was used to calculate the optical conductivity and dielectric function. The real part of optical conductivity shows five distinct active phonon modes at 44, 200, 300, 375, and 575 cm~' at all temperatures including a Drude-like behavior at low frequencies. The imaginary part of the calculated dielectric function indicates a mode softening of the mode 44 cm~' below Tc.

Future changes in atmospheric rivers and their implications for winter flooding in Britain

Within the warm conveyor belt of extra-tropical cyclones, atmospheric rivers (ARs) are the key synoptic features which deliver the majority of poleward water vapour transport, and are associated with episodes of heavy and prolonged rainfall. ARs are responsible for many of the largest winter floods in the mid-latitudes resulting in major socioeconomic losses; for example, the loss from United Kingdom (UK) flooding in summer/winter 2012 is estimated to be about $1.6 billion in damages. Given the well-established link between ARs and peak river flows for the present day, assessing how ARs could respond under future climate projections is of importance in gauging future impacts from flooding. We show that North Atlantic ARs are projected to become stronger and more numerous in the future scenarios of multiple simulations from five state-of-the-art global climate models (GCMs) in the fifth Climate Model Intercomparison Project (CMIP5). The increased water vapour transport in projected ARs implies a greater risk of higher rainfall totals and therefore larger winter floods in Britain, with increased AR frequency leading to more flood episodes. In the high emissions scenario (RCP8.5) for 2074–2099 there is an approximate doubling of AR frequency in the five GCMs. Our results suggest that the projected change in ARs is predominantly a thermodynamic response to warming resulting from anthropogenic radiative forcing.

Diagnosing links between atmospheric moisture and extreme daily precipitation over the UK

Atmospheric moisture characteristics associated with the heaviest 1% of daily rainfall events affecting regions of the British Isles are analysed over the period 1997–2008. A blended satellite/rain-gauge data set (GPCP-1DD) and regionally averaged daily rain-gauge observations (HadUKP) are combined with the ERA Interim reanalysis. These are compared with simulations from the HadGEM2-A climate model which applied observed sea surface temperature and realistic radiative forcings. Median extreme daily rainfall across the identified events and locations is larger for GPCP (32 mm day−1) than HadUKP and the simulations (∼25 mm day−1). The heaviest observed and simulated daily rainfall events are associated with increased specific humidity and horizontal transport of moisture (median 850 hPa specific humidity of ∼6 g kg−1 and vapour transport of ∼150 g kg−1 m s−1 for both observed and simulated events). Extreme daily rainfall events are less common during spring and summer across much of the British Isles, but in the south east region, they contribute up to 60% of the total number of distinct extreme daily rainfall events during these months. Compared to winter events, the summer events over south east Britain are associated with a greater magnitude and more southerly location of moisture maxima and less spatially extensive regions of enhanced moisture transport. This contrasting dependence of extreme daily rainfall on moisture characteristics implies a range of driving mechanisms that depend upon location and season. Higher spatial and temporal resolution data are required to explore these processes further, which is vital in assessing future projected changes in rainfall and associated flooding.

Los grandes ejes de comercio y transporte en Sudamérica: realidades y potenciales de los corredores transcontinentales

En las dos ediciones siguientes del Boletín se destacan partes de dos estudios recientes preparados por esta Comisión acerca de las realidades y potenciales de los corredores transcontinentales de Sudamérica. En esta edición se entregan pormenores sobre las relaciones que unen los tráficos con las infraestructuras, sobre la estructuración del mercado de servicios de transporte terrestre y sobre el marco institucional, tales como se describen en el documento "Una primera aproximación al estudio de los servicios de transporte en los espacios de integración: El caso de Argentina y Chile" (LC/R.1633) CEPAL, abríl de 1996.

Filmes nanoestruturados aplicados ao sistema de língua eletrônica: um estudo de interfaces

Pós-graduação em Ciência e Tecnologia de Materiais - FC

CoO doping effects on the ZnO films through EBPDV technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Advanced aspects of radiation protection in the use of particle accelerators in the medical field

In this work, the well-known MC code FLUKA was used to simulate the GE PETrace cyclotron (16.5 MeV) installed at “S. Orsola-Malpighi” University Hospital (Bologna, IT) and routinely used in the production of positron emitting radionuclides. Simulations yielded estimates of various quantities of interest, including: the effective dose distribution around the equipment; the effective number of neutron produced per incident proton and their spectral distribution; the activation of the structure of the cyclotron and the vault walls; the activation of the ambient air, in particular the production of 41Ar, the assessment of the saturation yield of radionuclides used in nuclear medicine. The simulations were validated against experimental measurements in terms of physical and transport parameters to be used at the energy range of interest in the medical field. The validated model was also extensively used in several practical applications uncluding the direct cyclotron production of non-standard radionuclides such as 99mTc, the production of medical radionuclides at TRIUMF (Vancouver, CA) TR13 cyclotron (13 MeV), the complete design of the new PET facility of “Sacro Cuore – Don Calabria” Hospital (Negrar, IT), including the ACSI TR19 (19 MeV) cyclotron, the dose field around the energy selection system (degrader) of a proton therapy cyclotron, the design of plug-doors for a new cyclotron facility, in which a 70 MeV cyclotron will be installed, and the partial decommissioning of a PET facility, including the replacement of a Scanditronix MC17 cyclotron with a new TR19 cyclotron.

Electrical, photoelectrical and morphological properties of ZnO nanowire networks grown on SiO2 and on Si

ZnO nanofibre networks (NFNs) were grown by vapour transport method on Si-based substrates. One type of substrate was SiO2 thermally grown on Si and another consisted of a Si wafer onto which Si nanowires (NWs) had been grown having Au nanoparticles catalysts. The ZnO-NFN morphology was observed by scanning electron microscopy on samples grown at 600 °C and 720 °C substrate temperature, while an focused ion beam was used to study the ZnO NFN/Si NWs/Si and ZnO NFN/SiO2 interfaces. Photoluminescence, electrical conductance and photoconductance of ZnO-NFN was studied for the sample grown on SiO2. The photoluminescence spectra show strong peaks due to exciton recombination and lattice defects. The ZnO-NFN presents quasi-persistent photoconductivity effects and ohmic I-V characteristics which become nonlinear and hysteretic as the applied voltage is increased. The electrical conductance as a function of temperature can be described by a modified three dimensional variable hopping model with nanometer-ranged typical hopping distances.

Experimental and numerical study of cw green laser crystallization of a-Si:H thin films

Crystallization and grain growth technique of thin film silicon are among the most promising methods for improving efficiency and lowering cost of solar cells. A major advantage of laser crystallization and annealing over conventional heating methods is its ability to limit rapid heating and cooling to thin surface layers. Laser energy is used to heat the amorphous silicon thin film, melting it and changing the microstructure to polycrystalline silicon (poly-Si) as it cools. Depending on the laser density, the vaporization temperature can be reached at the center of the irradiated area. In these cases ablation effects are expected and the annealing process becomes ineffective. The heating process in the a-Si thin film is governed by the general heat transfer equation. The two dimensional non-linear heat transfer equation with a moving heat source is solve numerically using the finite element method (FEM), particularly COMSOL Multiphysics. The numerical model help to establish the density and the process speed range needed to assure the melting and crystallization without damage or ablation of the silicon surface. The samples of a-Si obtained by physical vapour deposition were irradiated with a cw-green laser source (Millennia Prime from Newport-Spectra) that delivers up to 15 W of average power. The morphology of the irradiated area was characterized by confocal laser scanning microscopy (Leica DCM3D) and Scanning Electron Microscopy (SEM Hitachi 3000N). The structural properties were studied by micro-Raman spectroscopy (Renishaw, inVia Raman microscope).

Synthesis and Thermophysical Properties of Ether Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis(trifluoromethyl)sulfonylimide, [NTf2]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.

The Performance Characteristics of a Surface-Modified Cutting Tool

In the past, many papers have been presented which show that the coating of cutting tools often yields decreased wear rates and reduced coefficients of friction. Although different theories are proposed, covering areas such as hardness theory, diffusion barrier theory, thermal barrier theory, and reduced friction theory, most have not dealt with the question of how and why the coating of tool substrates with hard materials such as Titanium Nitride (TiN), Titanium Carbide (TiC) and Aluminium Oxide (Al203) transforms the performance and life of cutting tools. This project discusses the complex interrelationship that encompasses the thermal barrier function and the relatively low sliding friction coefficient of TiN on an undulating tool surface, and presents the result of an investigation into the cutting characteristics and performance of EDMed surface-modified carbide cutting tool inserts. The tool inserts were coated with TiN by the physical vapour deposition (PVD) method. PVD coating is also known as Ion-plating which is the general term of the coating method in which the film is created by attracting ionized metal vapour in this the metal was Titanium and ionized gas onto negatively biased substrate surface. Coating by PVD was chosen because it is done at a temperature of not more than 5000C whereas chemical Vapour Deposition CVD process is done at very high temperature of about 8500C and in two stages of heating up the substrates. The high temperatures involved in CVD affects the strength of the (tool) substrates. In this study, comparative cutting tests using TiN-coated control specimens with no EDM surface structures and TiN-coated EDMed tools with a crater-like surface topography were carried out on mild steel grade EN-3. Various cutting speeds were investigated, up to an increase of 40% of the tool manufacturer’s recommended speed. Fifteen minutes of cutting were carried out for each insert at the speeds investigated. Conventional tool inserts normally have a tool life of approximately 15 minutes of cutting. After every five cuts (passes) microscopic pictures of the tool wear profiles were taken, in order to monitor the progressive wear on the rake face and on the flank of the insert. The power load was monitored for each cut taken using an on-board meter on the CNC machine to establish the amount of power needed for each stage of operation. The spindle drive for the machine is an 11 KW/hr motor. Results obtained confirmed the advantages of cutting at all speeds investigated using EDMed coated inserts, in terms of reduced tool wear and low power loads. Moreover, the surface finish on the workpiece was consistently better for the EDMed inserts. The thesis discusses the relevance of the finite element method in the analysis of metal cutting processes, so that metal machinists can design, manufacture and deliver goods (tools) to the market quickly and on time without going through the hassle of trial and error approach for new products. Improvements in manufacturing technologies require better knowledge of modelling metal cutting processes. Technically the use of computational models has a great value in reducing or even eliminating the number of experiments traditionally used for tool design, process selection, machinability evaluation, and chip breakage investigations. In this work, much interest in theoretical and experimental investigations of metal machining were given special attention. Finite element analysis (FEA) was given priority in this study to predict tool wear and coating deformations during machining. Particular attention was devoted to the complicated mechanisms usually associated with metal cutting, such as interfacial friction; heat generated due to friction and severe strain in the cutting region, and high strain rates. It is therefore concluded that Roughened contact surface comprising of peaks and valleys coated with hard materials (TiN) provide wear-resisting properties as the coatings get entrapped in the valleys and help reduce friction at chip-tool interface. The contributions to knowledge: a. Relates to a wear-resisting surface structure for application in contact surfaces and structures in metal cutting and forming tools with ability to give wear-resisting surface profile. b. Provide technique for designing tool with roughened surface comprising of peaks and valleys covered in conformal coating with a material such as TiN, TiC etc which is wear-resisting structure with surface roughness profile compose of valleys which entrap residual coating material during wear thereby enabling the entrapped coating material to give improved wear resistance. c. Provide knowledge for increased tool life through wear resistance, hardness and chemical stability at high temperatures because of reduced friction at the tool-chip and work-tool interfaces due to tool coating, which leads to reduced heat generation at the cutting zones. d. Establishes that Undulating surface topographies on cutting tips tend to hold coating materials longer in the valleys, thus giving enhanced protection to the tool and the tool can cut faster by 40% and last 60% longer than conventional tools on the markets today.