Biogeochemical reactions and vadose zone transport, in particular gas phase transport, are inherently coupled processes. To explore feedback mechanisms between these processes in a quantitative manner, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described based on the Dusty Gas Model, which provides the most generally applicable description for gas diffusion. Gas advection is described by Darcy's Law, which in the current formulation, is directly substituted into the transport equations. The model is used to investigate the interactions between geochemical reactions and transport processes with an emphasis to quantify reaction-induced gas migration in the vadose zone. Simulations of pyrite oxidation in mine tailings, gas attenuation in partially saturated landfill soil covers, and methane production and oxidation in aquifers contaminated by organic compounds demonstrate how biogeochemical reactions drive diffusive and advective transport of reactive and non-reactive gases. Pyrite oxidation in mine tailings causes a pressure reduction in the reaction zone and drives advective gas flow into the sediment column, enhancing the oxidation process. Release of carbon dioxide by carbonate mineral dissolution partly offsets pressure reduction, and illustrates the role of water-rock interaction on gas transport. Microbially mediated methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, both generation of CH4 in the methanogenic zone and oxidation of CH4 in the methanotrophic zone contribute to drive advective and diffusive fluxes. The model confirmed that non-reactive gases tend to accumulate in zones of gas consumption and become depleted in zones of gas production. In most cases, the model was able to quantify existing conceptual models, but also proved useful to identify data gaps, sensitivity, and inconsistencies in conceptual models. The formulation of the model is general and can be applied to other vadose zone systems in which reaction-induced gas transport is of importance.

Social networks have been essential throughout hominin evolution, facilitating cooperative childrearing, transmission of cultural knowledge and the sharing of information and resources. As hominins dispersed out of Africa, these networks needed to be maintained at progressively higher latitudes. The first part of this thesis explores the impact of latitude on brain organisation and the possible implications for social cognition. I hypothesise that the lower temperatures and light levels found at higher latitudes select for larger bodies and visual systems, which in turn necessitate larger somatic and visual brain areas. Using orbit size to index eye and visual cortex size, I demonstrate a robust positive relationship between absolute latitude and orbit volume in recent humans. I show that Neanderthals, who solely inhabited high latitudes, have significantly larger orbits than contemporary anatomically modern humans (AMH), who evolved in lower latitude Africa and had only relatively recently dispersed into higher latitudes. Since Neanderthals and AMH dated 27-75kya have almost identical endocranial volumes, I argue that if a greater proportion of the Neanderthal brain was required for somatic and visual processing, this would reduce the volume of neural tissue available for other functions. Since, according to the Social Brain Hypothesis, neocortex volume is positively associated with social complexity, I propose that Neanderthals might have been limited to smaller social networks than AMH. The second part of the thesis explores the challenge of maintaining social networks across greater geographic distances at higher latitudes, where high travelling costs seem to prevent whole tribes from bonding during periodic aggregations. Using a gas model I predict that at lower latitudes daily subsistence mobility allows sufficient encounters between subgroups for the tribe to maintain connectivity, whereas in (Sub)Arctic biomes additional mechanisms are required to facilitate tribal cohesion. This may explain the apparent ‘explosion’ of Upper Palaeolithic art in Europe: symbolic representations allowed social ties to be sustained in the absence of frequent face-to-face contact. Overall, this thesis demonstrates that latitude may influence both brain organisation and cultural expression and argues that both can have a substantial impact on the maintenance of hominin social networks at high latitudes.

Este trabalho tem como objetivo implementar e testar modelos de gás cinza atualizados na rotina de radiação térmica do software Fire Dynamics Simulator (FDS), além da utilização do próprio modelo de gás cinza disponível no software, para a predição do fluxo de calor radiativo. Os modelos de gás cinza estudados foram o modelo padrão do software FDS (aqui denominado como GC1), e os modelos de gás cinza mais atuais: o GC2, no qual o coeficiente de absorção do meio participante é dado por relações polinomiais, e o GC3, sendo este um modelo de gás cinza que baseia o cálculo do coeficiente de absorção no modelo WSGG. Os novos modelos de gás cinza foram implementados no código fonte do software FDS, o qual é um código aberto, e a verificação da implementação foi realizada através da solução numérica do equacionamento utilizando os valores reportados pelo software. Com os novos modelos de gás cinza já corretamente implementados, passou-se então para a simulação computacional dos casos previamente selecionados. Para todos os modelos de gás cinza, foram simulados incêndios em poças, para diferentes combustíveis (etanol, n-heptano e metanol) em diferentes cenários de incêndio, considerando ou não a presença de fuligem no sistema. Os cenários de incêndio eram: (i) totalmente fechado, (ii) totalmente aberto e (iii) com uma condição intermediária, fechado, porém com uma abertura para o meio externo. Um estudo de análise de malha e de diferentes parâmetros, como o estudo da quantidade necessária de ângulos sólidos discretos, foram realizados para correta padronização dos parâmetros. As simulações computacionais foram validadas para o modelo de gás cinza padrão do FDS através da comparação de resultados com aqueles reportados na literatura específica de cada caso. Com os modelos já validados simulou-se novamente cada cenário de incêndio com os diferentes modelos de gás cinza anteriormente implementados. A partir da análise dos resultados obtiveram-se boas concordâncias para os campos de temperatura, frações molares tanto de CO2 quanto de H2O e para as frações volumétricas de fuligem. Os fluxos de calor radiativos foram corretamente preditos para todos os modelos de gás cinza implementados. O modelo GC2 apresentou resultados com desvios médios na faixa de 15%, o modelo de gás cinza baseado no WSGG (GC3) apresentou os melhores resultados, com erros médios inferiores a 10%, enquanto que o modelo padrão do software, GC1, apresentou resultados intermediários. / This work aims to implement and test updated gray gas models in the thermal radiation routine of the Fire Dynamics Simulator (FDS) software, as well as the use of the gray gas model available in the software to the prediction of radiative heat flux. The gray gas models studied were the default model of the FDS software (determined GC1), and the most current gray gas models: the GC2, in which the absorption coefficient of the participant medium is given by a polynomial relations, and the GC3, which is a gray gas model that was based on the calculation of the absorption coefficient in the WSGG model. The most recently gray gas models were implemented in the source code, which is an open source, and the verification of the implementation was performed by the numerical solution of the equations from the reported values of the software. With the new gray gas models already implemented, the next step was the computational simulation of the previously selected cases. For all the gray gas models, pool fires were simulated different scenarios of fire for different fuels (ethanol, nheptane and methanol), with and without considering soot presence in the system. The fire scenarios were: (i) fully closed, (ii) fully open and (iii) with an intermediate condition, closed but with an opening to the external environment. A study of a mesh analysis and different parameters, such as the study of the required amount of discrete solid angles, were performed to correct the standard parameters. The computational simulations were verified for the default gray gas model of the FDS by comparing the simulations results with those reported in the specific literature of each case. With the models already verified, each fire scenario was simulated with the different gray gas models previously implemented. From the analysis of the results, good agreements were obtained for the fields of temperature, molar fraction of CO2 and H2O and soot volume fraction. The radiative heat fluxes were correctly predicted for all gray gas models early implemented. The GC2 model present results with average deviation in the range of 15%, the gray gas model based on WSGG (GC3) presented the best results, with average deviation lower than 10%, while the default software model (GC1) presented intermediate results.

The pelagic zone of lakes is defined as the water column over the area of the lake benthos that does not receive enough light from the sun to allow macrophytes to grow. The four chapters of this thesis explore the spatial ecology of predator-prey interactions between schooling fish and their fish predators in this featureless environment. We first developed novel hydroacoustics methods to study fish and fish school swimming behaviour in the pelagic zone (Chapter 1 and 2). Then we characterized our in-situ school formation and prey movement observations using an ideal gas model to better understand the mechanisms that lead to fish and school densities during the daytime (Chapter 2 and 3). With this model we estimated the functional relationship between the schooling prey densities and predator encounter rates, and verified with empirical data a counterintuitive relationship that encounter rates decreased as overall prey densities increased (Chapter 3). The encounter rates suggested that predation within the pelagic zone might be greatly influenced by external forces if they provide spatial structure which encourages greater degrees of prey aggregation in predictable locations. In this regard we examined the predator-prey dynamics under wind and found large redistributions of prey and predators under windy conditions leading to greater aggregations in downwind locations. Further, we found that our study fish were larger in lakes that were oriented into the wind, perhaps demonstrating a benefit to fish growth under windy conditions (Chapter 4).

This thesis is comprised of three independent essays. One essay is in the field of macroeconomics and the other two are in time-series econometrics. The first essay, "Productivity and Business Investment over the Business Cycle", is co-authored with my co-supervisor Hashmat Khan. This essay documents a new stylized fact: the correlation between labour productivity and real business investment in the U.S. data switching from 0.54 to -0.1 in 1990. With the assistance of a bivariate VAR, we find that the response of investment to identified technology shocks has changed signs from positive to negative across two sub-periods: ranging from the time of the post-WWII era to the end of 1980s and from 1990 onwards, whereas the response to non-technology shocks has remained relatively unchanged. Also, the volatility of technology shocks declined less relative to the non-technology shocks. This raises the question of whether relatively more volatile technology shocks and the negative response of investment can together account for the decreased correlation. To answer this question, we consider a canonical DSGE model and simulate data under a variety of assumptions about the parameters representing structural features and volatility of shocks. The second and third essays are in time series econometrics and solely authored by myself. The second essay, however, focuses on the impact of ignoring structural breaks in the conditional volatility parameters on time-varying volatility parameters. The focal point of the third essay is on empirical relevance of structural breaks in time-varying volatility models and the forecasting gains of accommodating structural breaks in the unconditional variance. There are several ways in modeling time-varying volatility. One way is to use the autoregressive conditional heteroskedasticity (ARCH)/generalized ARCH (GARCH) class first introduced by Engle (1982) and Bollerslev (1986). One prominent model is Bollerslev (1986) GARCH model in which the conditional volatility is updated by its own residuals and its lags. This class of models is popular amongst practitioners in finance because they are able to capture stylized facts about asset returns such as fat tails and volatility clustering (Engle and Patton, 2001; Zivot, 2009) and require maximum likelihood methods for estimation. They also perform well in forecasting volatility. For example, Hansen and Lunde (2005) find that it is difficult to beat a simple GARCH(1,1) model in forecasting exchange rate volatility. Another way of modeling time-varying volatility is to use the class of stochastic volatility (SV) models including Taylor's (1986) autoregressive stochastic volatility (ARSV) model. With SV models, the conditional volatility is updated only by its own lags and increasingly used in macroeconomic modeling (i.e.Justiniano and Primiceri (2010)). Fernandez-Villaverde and Rubio-Ramirez (2010) claim that the stochastic volatility model fits better than the GARCH model and is easier to incorporate into DSGE models. However, Creal et al. (2013) recently introduced a new class of models called the generalized autoregressive score (GAS) models. With the GAS volatility framework, the conditional variance is updated by the scaled score of the model's density function instead of the squared residuals. According to Creal et al. (2013), GAS models are advantageous to use because updating the conditional variance using the score of the log-density instead of the second moments can improve a model's fit to data. They are also found to be less sensitive to other forms of misspecification such as outliers. As mentioned by Maddala and Kim (1998), structural breaks are considered to be one form of outliers. This raises the question about whether GAS volatility models are less sensitive to parameter non-constancy. This issue of ignoring structural breaks in the volatility parameters is important because neglecting breaks can cause the conditional variance to exhibit unit root behaviour in which the unconditional variance is undefined, implying that any shock to the variance will not gradually decline (Lamoureux and Lastrapes, 1990). The impact of ignoring parameter non-constancy is found in GARCH literature (see Lamoureux and Lastrapes, 1990; Hillebrand, 2005) and in SV literature (Psaradakis and Tzavalis, 1999; Kramer and Messow, 2012) in which the estimated persistence parameter overestimates its true value and approaches one. However, it has never been addressed in GAS literature until now. The second essay uses a simple Monte-Carlo simulation study to examine the impact of neglecting parameter non-constancy on the estimated persistence parameter of several GAS and non-GAS models of volatility. Five different volatility models are examined. Of these models, three --the GARCH(1,1), t-GAS(1,1), and Beta-t-EGARCH(1,1) models -- are GAS models, while the other two -- the t-GARCH(1,1) and EGARCH(1,1) models -- are not. Following Hillebrand (2005) who studied only the GARCH model, this essay examines the extent of how biased the estimated persistence parameter are by assessing impact of ignoring breaks on the mean value of the estimated persistence parameter. The impact of neglecting parameter non-constancy on the empirical sampling distributions and coverage probabilities for the estimated persistence parameters are also studied in this essay. For the latter, studying the effect on the coverage probabilities is important because a decrease in coverage probabilities is associated with an increase in Type I error. This study has implications for forecasting. If the size of an ignored break in parameters is small, then there may not be any gains in using forecast methods that accommodate breaks. Empirical evidence suggests that structural breaks are present in data on macro-financial variables such as oil prices and exchange rates. The potentially serious consequences of ignoring a break in GARCH parameters motivated Rapach and Strauss (2008) and Arouri et al. (2012) to study the empirical relevance of structural breaks in the context of GARCH models. However, the literature does not address the empirical relevance of structural breaks in the context of GAS models. The third and final essay contributes to this literature by extending Rapach and Strauss (2008) to include the t-GAS model and by comparing its performance to that of two non-GAS models, the t-GARCH and SV models. The empirical relevance of structural breaks in the models of volatility is assessed using a formal test by Dufour and Torres (1998) to determine how much the estimated parameters change over sub-periods. The in-sample performance of all the models is analyzed using both the weekly USD trade-weighted index between January 1973 and October 2016 and spot oil prices based on West Texas Intermediate between January 1986 and October 2016. The full sample is split into smaller subsamples by break dates chosen based on historical events and policy changes rather than formal tests. This is because commonly-used tests such as CUSUM suffer from low power (Smith, 2008; Xu, 2013). For each sub-period, all models are estimated using either oil or USD returns. The confidence intervals are constructed for the constant of the conditional parameter and the score parameter (or ARCH parameter in GARCH and t-GARCH models). Then Dufour and Torres's union-intersection test is applied to these confidence intervals to determine how much the estimated parameter change over sub-periods. If there is a set of values that intersects the confidence intervals of all sub-periods, then one can conclude that the parameters do not change that much. The out-of-sample performance of all time-varying volatility models are also assessed in the ability to forecast the mean and variance of oil and USD returns. Through this analysis, this essay also addresses whether using models that accommodate structural breaks in the unconditional variance of both GAS and non-GAS models will improve forecasts.

The present research project is carried out at the von Karman Institute for Fluid Dynamics (Rhode-Saint-Genèse, Belgium) with the financial support of the European Space Agency. The first stage of spacecrafts (e.g. Ariane 5, Vega, Shuttle) generally consists of large solid propellant rocket motors (SRM), which often consist of segmented structure and incorporate a submerged nozzle. During the combustion, the regression of the solid propellant surrounding the nozzle integration part leads to the formation of a cavity around the nozzle lip. The propellant combustion generates liquefied alumina droplets coming from chemical reaction of the aluminum composing the propellant grain. The alumina droplets being carried away by the hot burnt gases are flowing towards the nozzle. Meanwhile the droplets may interact with the internal flow. As a consequence, some of the droplets are entrapped in the cavity forming an alumina puddle (slag) instead of being exhausted through the throat. This slag reduces the performances. The aim of the present study is to characterize the slag accumulation process in a simplified model of the MPS P230 motor using primarily optical experimental techniques. Therefore, a 2D-like cold-gas model is designed, which represents the main geometrical features of the real motor (presence of an inhibitor, nozzle and cavity) and allows to approximate non-dimensional parameters of the internal two-phase flow (e.g. Stokes number, volume fraction). The model is attached to a wind-tunnel that provides quasi-axial flow (air) injection. A water spray device in the stagnation chamber realizes the models of the alumina droplets, which are accumulating in the aft-end cavity of the motor. To be able to carry out experimental investigation, at first the the VKI Level Detection and Recording(LeDaR) and Particle Image Velocimetry (PIV) measurement techniques had to be adapted to the two-phase flow condition of the facility. A parametric liquid accumulation assessment is performed experimentally using the LeDaR technique to identify the influence of various parameters on the liquid deposition rate. The obstacle tip to nozzle tip distance (OT2NT) is identified to be the most relevant, which indicates how much a droplet passing just at the inhibitor tip should deviate transversally to leave through the nozzle and not to be entrapped in the cavity. As LeDaR gives no indication of the driving mechanisms, the flow field is analysed experimentally, which is supported by numerical simulations to understand the main driving forces of the accumulation process. A single-phase PIV measurement campaign provides detailed information about the statistical and instantaneous flow structures. The flow quantities are successfully compared to an equivalent 3D unsteady LES numerical model. Two-phase flow CFD simulations suggest the importance of the droplet diameter on the accumulation rate. This observation is confirmed by two-phase flow PIV experiments as well. Accordingly, the droplet entrapment process is described by two mechanisms. The smaller droplets (representing a short characteristic time) appear to follow closely the air-phase. Thus, they may mix with the air-phase of the recirculation region downstream the inhibitor and can be carried into the cavity. On the other hand, the large droplets (representing a long characteristic time) are not able to follow the air-phase motion. Consequently, a large mean velocity difference is found between the droplets and the air-phase using the two-phase flow measurement data. Therefore, due to the inertia of the large droplets, they may fall into the cavity in function of the OT2NT and their velocity vector at the level of the inhibitor tip. Finally, a third mechanism, dripping is identified as a contributor to the accumulation process. In the current quasi axial 2D-like set-up large drops are dripping from the inhibitor. In this configuration they are the main source of the accumulation process. Therefore, additional numerical simulations are performed to estimate the importance of dripping in more realistic configurations. The preliminary results suggest that dripping is not the main mechanism in the real slag accumulation process. However, it may still lead to a considerable contribution to the final amount of slag.

Direct Reduced Iron (DRI) is used as an alternative feedstock in electric arc furnaces, making up 50% or more of the total iron charge. DRI produced with coal based reductants (for example in rotary kilns) make up roughly 25% of DRI produced in the world. It was found that SL/RN DRI samples from a kiln cooler had high nitrogen contents (50-250ppm, depending on particle size), higher than DRI from gas-based reduction. The higher nitrogen content of SL/RN DRI would increase the levels of nitrogen of liquid steel produced in the EAFs. The problem is exacerbated by the fact that the SL/RN DRI contains virtually no carbon (which would aid in preventing nitrogen pickup). The proposed mechanism of nitrogen pick-up by the SL/RN DRI is one where nitrogen present within the atmosphere of the rotary cooler (where hot DRI, discharged at 1000°C from the rotary kiln, is cooled to approximately 100 °C in ca. two hours) penetrates the solids bed and nitrides DRI particles. Possible rate-determining steps for nitriding in the cooler have been evaluated. Nitriding of DRI particles is predicted to be rapid: the most plausible location for rapid nitrogen pickup is the first 5 meters of the rotary cooler, where the high temperature, nitrogen-rich gas atmosphere and rapid solids bed mixing are conducive to nitriding; solid-state and pore diffusion of nitrogen into DRI particles are predicted to be rapid too. The most plausible rate determining step for nitriding of DRI particles is that of nitrogen dissociation on the DRI surface, which can be further retarded by the presence of sulphur. A strong correlation was found between the amount of “melt-in” carbon in the liquid steel and the final tap nitrogen content, with 0.3% C resulting in nitrogen levels as low as 50 ppm (80 ppm or less is desired on the plant in question) at tap, even with DRI material that is high in nitrogen and contains virtually no carbon. Proposals to increase the melt-in carbon are included. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted

The phenomenon of energy loss that occurs when an ion interacts with matter, also called stopping power, has been investigated for more than a century, and has provided findings of interest. However, reliable procedures for obtaining accurate experimental measurements and a fully theoretical comprehension of the process are tasks still in high demand by the scientific community. Moreover, stopping power data are prerequisites in several applications in modern science, such as engineering, ion implantation and modification of materials, damage to electronics devices (e.g. space radiation), medical physics (e.g. proton therapy), among others. In this thesis we i) develop a rigorous experimental protocol to measure stopping power with high precision, and ii) investigate the collapse of the free electron gas (FEG) model in energy loss of light ions (protons) at a low energy range in transition and rare-earth metals. In the first part, we present an approach to obtain, with high accuracy, the stopping cross sections in the pure materials Al and Mo for protons in the energy range of [0.9 - 3.6] MeV by means of the transmission method. The traceability of the sources of uncertainties are fully evaluated and the final accuracy of the results is 0.63% (0.32% rand. and 0.54% syst.) for Al, and 1.5 % (0.44 % rand. and 1.4% syst.) for Mo, with both results primarily limited by the quality and homogeneity of the stopping foils. For Al, this high accuracy represents an improvement compared to the results obtained in previous studies and serves as a benchmark for our procedure. The most important sources of uncertainties were random - the uncertainty in the peak positions and in the Gaussian fits; and systematic - the non-uniformity thickness of the foils (a special procedure was developed to correct this). Even though the final uncertainty for Mo is higher than for Al, our results improve on the amount of data currently available for the energy range considered. Both data sets are compared with the most commonly employed theoretical models and Monte Carlo codes in the literature. In the second part, electronic stopping cross sections of nontrivial solids, that is, transition and rare earth metals (Ta and Gd) for slow protons are experimentally investigated, and the data were compared with the results for Pt and Au, to understand how energy losses in these metals are correlated with electronic band structures, and to understand the failure of the FEG model predictions. The higher stopping powers found for Ta and Gd cannot be explained by means of the FEG model; however, these effects are successfully correlated with the high density of states (DOS) of both the occupied and unoccupied electronic levels in these metals. For the case of Gd, the experimental data are extended in the energy range until the Bragg\'s peak is reached. The two parts of this thesis were published in Physical Review A 93 022704 (2016), and in Physical Review Letters 18 103401 (2017), respectively. / O fenômeno de perda de energia quando um íon interage com a matéria, também conhecido como poder de freamento, vem sendo investigado por mais de um século, gerando grandes descobertas. Entretanto, conseguir obter medidas experimentais com alta precisão, ou elaborar um completo entendimento teórico dos processos de perda de energia são tarefas extremamente difíceis e ainda muito requeridas pela comunidade científica. Além disso, dados de perda de energia são pré-requisitos em várias aplicações e ramos da ciência moderna, tais como: engenharia, implantação e modificação de materiais, danos em dispositivos eletrônicos (radiação espacial), física médica (próton terapia), etc. Esta tese tem dois focos: i) desenvolver um rigoroso protocolo experimental para medir stopping power com alta precisão e ii) investigar a quebra de validade do modelo de Gás de Elétrons Livres (FEG) para a perda de energia de prótons lentos em metais de transição e terra raras. Na primeira parte apresentamos uma abordagem experimental para obter com alta precisão o poder de freamento em materiais puros (Al e Mo) para prótons no intervalo de energia de [0,9 - 3,6] MeV pelo método de transmissão. A rastreabilidade das fontes de incerteza foi determinada e as incertezas finais encontradas foram: 0,63 % (0,32 % aleat. e 0,54 % sist.) para Al e 1,5 % (0,44 % aleat. e 1,4 % sist.) para Mo, ambas devido a qualidade e homogeneidade das folhas freadoras. Para Al, esta acurácia representa um avanço comparado com publicações anteriores e, assim, serviu como uma referência de nosso procedimento. As mais importantes fontes de incerteza foram: aleatória incerteza das posições dos picos e dos ajustes Gaussianos e sistemática não-uniformidade das folhas-alvo (um procedimento foi desenvolvido para corrigir isso). Embora a incerteza final do Mo é um pouco maior do que do Al, nossos resultados ajudaram a complementar a baixa quantidade de dados disponíveis para o intervalo de energia considerado. Ambos conjuntos de dados foram comparados com os mais comuns modelos teóricos e códigos de Monte Carlo na literatura. Para a segunda parte, poder de freamento em metais não tão comuns tais como transição (Ta) e terras-raras (Gd) para prótons com baixas velocidades foram experimentalmente investigados, e os dados comparados com resultados de Pt e Au, a fim de entender como o stopping power destes metais está correlacionado com as estruturas de bandas eletrônicas, e assim tentar explicar a falha do modelo de FEG. Os altos valores das perdas de energias encontradas para Ta e Gd não puderam ser explicadas pelo modelo de FEG, e portanto foram correlacionados com a densidade de estados (DOS) em ambos os níveis ocupados e não ocupados destes metais. Para o caso do Gd, os dados experimentais foram estendidos em um intervalo de energia até alcançarem o pico de Bragg. A primeira parte desta tese foi publicada na Physical Review A 93 022704 (2016), e a segunda parte na Physical Review Letters 18 103401 (2017).

Simulações acopladas do escoamento reativo e dos processos de transferência de calor para o estudo de chamas são problemas dispendiosos computacionalmente. A transferência de calor por radiação em processos de combustão, devido às elevadas temperaturas, é o processo de troca energética dominante. Ainda, o comportamento altamente irregular do coeficiente de absorção com o comprimento de onda se constitui em uma dificuldade adicional na modelagem da transferência radiativa em meios participantes. Para contornar essa dificuldade modelos espectrais foram desenvolvidos com o objetivo de simular o comportamento de um gás real. Dentre esses modelos destacam-se o gás cinza (GG: Gray Gas), o mais simples, que negligencia o comportamento espectral do coeficiente de absorção, e o modelo da soma-ponderada-de-gases-cinza (WSGG: Weighted-Sum-of-Gray-Gases) onde a integração sobre todo o espectro é substituída por um número finito de gases cinza. Com o avanço de ferramentas computacionais, principalmente códigos CFD (Computational Fluid Dynamics), abordagens computacionais se tornaram atrativas frente ou em complemento às abordagens experimentais. Desse modo, o presente trabalho tem por objetivo a aplicação dos modelos WSGG e GG com novas correlações na simulação detalhada de chamas difusivas laminares de metano diluído com dióxido de carbono e nitrogênio com o código CFD comercial ANSYS/Fluent. Foram desenvolvidas rotinas de usuário (UDF: User-Defined Functions) para o acoplamento dos modelos espectrais ao código CFD. A verificação das rotinas de usuário foi realizada comparando os resultados obtidos via simulação Fluent com dados obtidos pelo modelo WSGG com um código FORTRAN próprio desenvolvido pelo grupo de pesquisa do Laboratório de Radiação Térmica (LRT/UFRGS) para o problema unidimensional de superfícies negras e infinitas preenchidas por um meio não-isotérmico e não-homogêneo. Os erros encontrados para o fluxo de calor radiativo nas superfícies e para o termo fonte radiativo ao longo do meio foram da ordem de 1% indicando o funcionamento correto das rotinas UDF acopladas ao Fluent. Por fim, as rotinas foram aplicadas na simulação numérica para chamas de potência constante com diluição dos reagentes e os dados obtidos com a solução numérica foram comparados com dados experimentais para a fração radiante e fluxo de calor radiativo. Os desvios médios encontrados para o fluxo de calor radiativo ficaram em torno de 10% para todas as chamas, excetuando as chamas com diluição de CO2 de 30%, 40% e 50%, em volume, para as quais os desvios médios ficaram em torno de 15%. O termo fonte para as chamas apontou para a predominância da emissão do meio em relação à absorção. Todas as chamas estudadas se encontram no regime opticamente fino (optically thin) para o qual, segundo apontam estudos da literatura, a escolha do modelo espectral possui impacto pequeno em resultados globais da chama como a temperatura e a concentração das espécies na mistura. Nesse aspecto os resultados encontrados concordaram com a previsão da literatura, entretanto para a transferência radiativa, o modelo GG se mostrou sensivelmente menos preciso em comparação ao modelo WSGG, principalmente para a fração radiante e para o fluxo radiativo na região da pluma aquecida, indicando a dependência do modelo espectral adotado. / Coupled simulations of the reactive flow with the heat transfer processes for flame studying are computationally demanding problems. The radiative transfer in combustion processes is the main heat transfer mechanism due to the high temperatures involved. However, the highly irregular behavior o f the absorption coefficient with the wavenumber composes in an additional difficulty on modeling the radiative transfer in participating media. In order to overcome this issue, spectral models were developed with the objective of simulate the behavior of real gases. Some of the most known models are the gray gas (GG) for which the spectral behavior of the radiative properties of the medium is neglected and the weighted-sum-of-gray-gases (WSGG) for which the integration over the entire spectrum is replaced by a summation over a finite number of gray gases with constant absorption coefficients. With the development of computational tools, mainly Computational Fluid Dynamics (CFD) codes, numerical approaches became attractive instead or in complement of experimental set ups. In this way, the present work aims to couple the WSGG and the GG models with new correlations in a detailed simulation of diffusive laminar flames of methane diluted with carbon dioxide and nitrogen with the commercial CFD code ANSYS/Fluent. User-defined functions (UDF) were developed to the coupling of the spectral models. The verification was carried out through the WSGG model by comparing the Fluent solution with a solution obtained with a FORTRAN code developed by the Thermal Radiation Laboratory (LRT/UFRGS) research group for the one-dimensional system of black surfaces filled with a non-homogeneous and non-isothermal medium. The deviations for the radiative heat flux for the walls and the radiative heat source along the domain were of 1% or less, indicating the correct coupling between the UDF routines and the CFD code. Finally, the UDF were applied in the solution of constant power flames with fuel diluted with carbon dioxide and nitrogen. The obtained data was then compared with experimental measurements for the radiant fraction and the radiative heat flux along the flame axis. The average deviations found were in order of 10% for all flames, except for the flames with 30%, 40% and 50% of CO2 dilution, in volume, for which the deviatioms found were in order of 15%. The radiative heat source was plotted and indicated for the medium emission predominance in comparison with the medium absorption. All flames studied were optically thin flames for which, studies pointed, the spectral model have minor impact over global results as flame temperature and mixture concentration. For this aspect the results found showed agreement with the literature studies predictions, however the GG model showed itself less accurate in comparison with the WSGG model for the radiant fraction and the radiative heat flux computations. So the spectral models have influence on the radiative transfer even if its effect on flame structure can be negligible.

Des gaz vont être générés par corrosion des conteneurs de déchets radioactifs au niveau d'un stockage en couche géologique profonde. Une bulle de gaz se crée et monte en pression. Si le gaz pénètre difficilement la formation géologique, l'augmentation de pression pourra la fissurer et créer des chemins préférentiels à la migration de radionucléides. Les argilites du Callovo-Oxfordien sont ici caractérisées. Un dispositif permettant de mesurer de très faibles perméabilités à l'hydrogène/hélium a été utilisé couplé au Dusty Gas Model. Les argilites proches de la saturation ont une porosité accessible au gaz inférieure à 1% voire 0,1% de la porosité totale. A partir de l'étude de l'effet Knudsen cette porosité pourrait être due à des pores de 50 à 200 nm de diamètre mis en évidence lors de la caractérisation des réseaux. En intégrant ces résultats dans un modèle opérationnel de l'ANDRA, la pression maximale atteinte au sein d'une alvéole de stockage serait de 83 bar.