http://www.pharmacol.usyd.edu.au/thesis This thesis is primarily concerned with a class of chemical compounds known as pyridazinediones, being 6-membered aromatic rings containing two adjacent nitrogen atoms (pyridazine), doubly substituted with oxygen. In particular, the work focuses on pyridazine-3,6-diones, derivatives of maleic hydrazide (1). Understanding of the chemistry of these compounds is extended, using theoretical and synthetic techniques. This thesis is also concerned with two very important classes of receptors which bind amino acids in the brain: firstly, the inhibitory GABA receptor, which binds g-aminobutyric acid (GABA) (2) in vivo, and for which muscimol (3) is an agonist of the GABAA subclass; secondly, Excitatory Amino Acid (EAA) receptors, which bind glutamate (4) in vivo, and in particular the AMPA subclass, for which (S)-2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl)propionic acid (AMPA) (5) is an agonist. The connection between pyridazinediones and amino acid receptors is the design, synthesis, and evaluation of structures based on pyridazinediones as potential GABA and EAA receptor ligands. Techniques of theoretical chemistry, molecular modelling, synthetic chemistry, and in vitro pharmacology are used to explore pyridazine-3,6-dione derivatives as ligands.

La stratégie la plus utilisée aujourd'hui pour la conception de nouveaux matériaux luminescents est basée sur des méthodes d'essais-erreurs. Cependant, ces méthodes peuvent souvent entraîner une consommation d'argent et de temps. En ce sens, un modèle théorique agissant comme un outil prédictif peut servir comme une stratégie alternative. De tels modèles sont également étudiés et utilisés par des scientifiques du monde entier, mais ils sont pour la plupart difficiles à utiliser. Dans ce travail, deux modèles semi-empiriques conviviaux et faciles à utiliser ont été proposés pour la conception de luminophores intégrés dans le développement de technologies importantes, en particulier dans les éclairages à base de LED et les cellules solaires. Ces modèles sont: 1) le modèle de facteur environnemental (EF) basé sur la théorie diélectrique de la liaison chimique proposée par Philips et 2) le modèle de transfert de charge métal-métal (MMCT) utilisées pour trouver des relations entre les propriétés structurelles d'un matériau et sa luminescence. Le modèle EF a été appliqué à la famille des composés AIBIIPO4 (AI = cation monovalent, BII = cation divalent) dopés à Eu2+. Il était capable d'estimer l'énergie du bord d'excitation et d'identifier les sites de dopage à ± 1000 cm-1. Il peut donc être utilisé pour la conception de nouveaux luminophores appartenant à cette famille. Dans la deuxième partie, les deux modèles ont été utilisés pour identifier la nature de la luminescence dans les oxydes dopés à Bi3+. A cet effet, une méthode combinant les modèles motionnés avec les valeurs de Stokes shift a été trouvé fiable. En outre, la a été jugée utile pour expliquer la modification des propriétés luminescentes de YVO4:Bi3+ sous haute pression. Dans la troisième partie, les deux modèles ont été utilisés pour explorer la luminescence des oxydes dopés à Sb3+ par analogie avec Bi3+. Cependant, les résultats n'étaient pas assez bons pour identifier la nature de la luminescence dans ces matériaux. La raison pourrait être liée à la position décentrée du dopant (Sb3+). / The most used strategy for the design of new luminescent materials today is based on trial-error methods. However, these methods may often result in consummation of money and time. In this sense, a theoretical model acting as a predictive tool can serve as an alternative strategy. Such models are also studied and used by scientists around the world but they are mostly difficult to use. In this work, two friendly and easy to use semi-empirical theoretical models were proposed as a criterion for designing phosphors integrated in the development of important technologies especially in LED-based lightings and solar cells. These models are: 1) the environmental factor model (EF) based on the dielectric theory of chemical bonding proposed by Philips and 2) the metal to metal charge transfer (MMCT) model by Boutinaud that were both used for the purpose of finding relationships between the structural properties of a material and its luminescence. The EF model was applied on the family of AIBIIPO4 (AI= monovalent cation, BII= divalent cation) compounds doped with Eu2+. It was able to estimate the excitation edge energy and to identify the doping sites within uncertainty of ± 1000 cm-1. It can therefore, be used for the design of new phosphors belonging to this family. In a second part, both models were used to identify the nature of luminescence in Bi3+-doped oxides. For this purpose, a method combining the mentioned models along with the values of the Stokes shift was found reliable. In addition, the method was found useful to explain the change in luminescent properties of YVO4:Bi3+ under high pressure. In the third part, the two models were used to explore the luminescence of Sb3+-doped oxides by analogy with Bi3+. However, the results were not good enough to identify the nature of luminescence in these materials. The reason could be related to the off-centered position of the dopant (Sb3+).

The major aim of this work is to develop a framework for the estimation of Evapotranspiration (ET) over the Indian landmass using remote sensing (RS) datasets in a repeated and consistent manner with improved spatial resolution. Different RS based ET models exist in the literature, out of which, the triangle, the S-SEBI and the Sim-ReSET models were compared for the estimation of daytime integrated latent heat flux (λEday). These three models were chosen as they can be driven only with RS based inputs without the need for any ground measurements. The results showed that the application of simpler contextual models may yield better results than physically based models when ground data is limited or not available. To improve the spatial resolution of one of the key surface variable, Land Surface Temperature (LST), the performance of five different vegetation indices Normalised Difference Vegetation Index (NDVI), Fraction Vegetation Cover (FVC), Normalised Difference Water Index (NDWI), Soil Adjusted Vegetation Index (SAVI) and Modified SAVI (MSAVI) were tested in the existing DisTrad disaggregation model. Results suggested that the most commonly used vegetation indices NDVI and FVC yielded better results only under wet conditions. Under drier surface conditions, using NDWI for disaggregation resulted in relatively higher accurate LST. A model for spatial disaggregation of Evaporative Fraction (EF) called DEFrac (Disaggregation of Evaporative Fraction) was developed based on the relationship between EF and NDVI to obtain finer spatial resolution EF from coarser resolution estimates. The experimental results suggested that the DEFrac model developed in this study, yielded more accurate disaggregated EF. The disaggregated EF was further used to get disaggregated λEday. Finally, The issue of lack of proper ET dataset over India was addressed by developing two data products one over entire India at 0.05° spatial resolution and the second product over the Kabini basin at 1 km spatial resolution. Both the products were developed with a temporal resolution of 8-day and for the period 2001–2014. The developed ET products were validated against ground observed data at seven sites across India and against ET simulated by a hydrological model over a forested watershed. Further the developed ET products were compared with some other global ET products such as MOD16, LandFlux Eval synthesis ET and GLEAM ET. Analyses revealed that only in regions where ET is predominantly driven by rainfall and where irrigation is not applied at very large scales, the global ET products tend to capture the ET patterns satisfactorily. On the other hand, the ET products developed in this work captured the spatial and temporal patterns of ET quite realistically all across India.

Concrete has proven to be, by far, one of the most reliable materials for the construction of critical infrastructure. However, despite its structural capacity, concrete members are susceptible to damage mechanisms that may decrease its performance and durability throughout its service life. One such mechanism is alkali-silica reaction (ASR), which takes place when unstable siliceous phases present in coarse or fine aggregates react with the alkali hydroxides from the concrete pore solution, generating a secondary product (i.e., ASR gel); this product swells upon moisture uptake from the surrounding environment, leading to cracking and expansion of the affected concrete. In severe cases of ASR-affected infrastructure, structural safety could become a problem, and thus requiring the demolition of affected members. It is, therefore, necessary to adopt effective protocols for the diagnosis and prognosis of aging infrastructure, to ensure its performance over time along with properly planning for rehabilitation strategies, whether required. This work presents a two-stage case study of the S.I.T.E. building at the University of Ottawa for the diagnosis and prognosis of ASR-affected members (i.e., columns) after nearly 20 years in service. The diagnosis phase was conducted with the aim of evaluating the cause and extent of distress and interpreting its impact on the performance of the affected structure. First, a visual inspection was conducted to evaluate potentially damaged members, in order to select the best location for core-drilling. Once ASR was confirmed through petrographic examination, specimens were evaluated through the multi-level assessment (i.e., coupling of microscopic and mechanical assessment). A range of damage was discovered among the examined columns (i.e., 0.03%, 0.05%, and 0.08% expansion). Moreover, evidence of developing freeze and thaw (FT) damage was discovered in columns with greater levels of expansion, raising future concerns regarding the durability and serviceability of members affected by this coupling of damage (i.e., ASR+FT). For the second stage of this project (i.e., prognosis), a novel ASR semi-empirical model was developed with the aim of predicting future ASR-induced expansion and damage in the S.I.T.E. building. The above model was developed and validated (using ASR exposure site data) through the coupling of existing chemo-mechanical macro-models, which were used to predict material behaviour on the structural scale, and novel mathematical relationships for the prediction of anisotropy in the columns. Moreover, the use of the multi-level assessment to predict the mechanical implications of predicted distress was found to enhance the model’s capacity for prognosis and demonstrated important potential for the accurate prediction of multi-level damage in the S.I.T.E. columns.

Maritime transportation emits about 3% of global greenhouse gas, International Maritime Organization (IMO) aims to reduce shipping’s emissions by 50% with respect to 2008 levels. Proton exchange membrane fuel cells (PEMFCs) are considered among the most promising clean technologies for decarbonizing the maritime sector. One of the challenges for commercial application of PEMFCs is their limited durability. The purpose of this thesis was to assess the most significant degradation mechanisms and operating conditions of the PEMFC in marine applications, including membrane and catalyst layer degradation during idle, start-stop cycles, and dynamic load cycles, and to build a model to forecast the lifetime.A semi-empirical approach was developed to evaluate the PEMFC lifetime through a 2D COMSOL model. The model takes into account the empirical relationships for membrane conductivity loss and electrochemical surface area (ECSA) decay as functions of cycling numbers, aging process, and idling time. The 2D model has been validated with the experimental data in the literature and are also compared with a previous 1D model. The polarization curves show the voltage output against current density, lifetime is evaluated using a 10% voltage reduction criterion at the current density 0.6 A/cm2.An improved ECSA degradation model with variable load levels increases the lifetime of the ferry in Case 5 from 5500 hours to 7500 hours. Load cycling and idling cause the most severe degradation, but the impact can be reduced by a hybrid system with battery supplement and onshore charging. The lifetime of the ferry in Case 5 has been significantly further improved from 7500 hours to 22500 hours, which is comparable to the 20000-hour lifetime of commercial products for marine applications. Furthermore, membrane thickness effect analysis showed that fuel cells with thinner membranes (such as NR211) have better performance before degradation due to higher proton conductivity, but degrade faster during load cycling due to hydrogen crossover. The results of this research can be extended to help optimize fuel cell, stack and power system designs to avoid worst-case operating conditions and thereby limit fuel cell degradation. / Sjötransporter släpper ut cirka 3% av de globala växthusgaserna, International Maritime Organization (IMO) har som mål att minska sjöfartens utsläpp med 50 % jämfört med 2008 års nivåer. PEM-bränsleceller anses vara bland de mest lovande rena teknikerna för att minska koldioxidutsläppen i den maritima sektorn. En av utmaningarna för kommersiell användning av PEM-bränsleceller är deras begränsade hållbarhet. Syftet med denna avhandling var att bedöma de viktigaste nedbrytningsmekanismerna och driftsförhållandena för PEM-bränsleceller i marina applikationer, inklusive nedbrytning av membran och katalysatorskikt under tomgång, start-stopp-cykler och dynamiska belastningscykler, och att bygga en modell för att förutsäga livslängd.En semi-empirisk metod utvecklades för att utvärdera PEMFC:s livslängd genom en 2D COMSOL-modell. Modellen tar hänsyn till de empiriska sambanden för membrankonduktivitetsförlust och den elektrokemisk ytareans (ECSA) sönderfall som funktioner av cyklingstal, åldrandeprocess och tomgångstid. 2D-modellen har validerats med experimentella data i litteraturen och jämförs även med en tidigare 1D-modell. Polarisationskurvorna visar utspänningen mot strömtätheten, livslängden utvärderas med ett 10 % spänningsreduktionskriterium vid strömtätheten 0.6 A/cm2.En förbättrad modell för nedbrytning av elektrokemisk yta med varierande lastnivåer ökar färjans livslängd i fall 5 från 5500 timmar till 7500 timmar. Lastcykling och tomgång orsakar den allvarligaste försämringen, men påverkan kan minskas genom ett hybridsystem med batteritillägg och landladdning. Färjans livslängd i fall 5 har förbättrats avsevärt ytterligare från 7500 timmar till 22500 timmar, vilket är jämförbart med 20000 timmars livslängd för kommersiella produkter för marina applikationer. Vidare visade membrantjocklekseffektanalys att bränsleceller med tunnare membran (som NR211) har bättre prestanda före nedbrytning på grund av högre protonledningsförmåga, men bryts ned snabbare under belastningscykler på grund av väteövergång. Resultaten av denna forskning kan utökas för att hjälpa till att optimera designen av bränsleceller, stack och kraftsystem för att undvika värsta driftsförhållanden och därigenom begränsa nedbrytningen av bränsleceller.

A vessel operating in the real world has to overcome wind, waves and ocean currents. The result of all the above is a motion of 6 degrees of freedom (DOF). Typically, for the maneuvering phase, the Newton-Euler equations are used to derive the equation of motion of the rigid body and the maneuvering theory to model the external forces and moments acting on a vessel. The main topic in this Master Thesis is to assess the maneuvering behavior of a specific container vessel through a 4DOF model. The purpose behind this study is to investigate the differences between the expected maneuvering behavior of the vessel and the operational one. To accomplish that, raw data from the vessel’s sea trials were used and a time domain simulation model created with the sway-roll yaw movements coupled and surge decoupled. The Son and No moto maneuvering model served as the base for the motion equations. The maneuvering coefficients (MC) were firstly estimated by semi-empirical formulas using the vessel particulars. The model was validated using the Esso Osaka sea trials data. The validation was limited to maneuvering parameters such as advance, tactical diameter, yaw overshoot angle etc. The final model was used on the sea trials data of the container vessel taking into consideration the wind forces through the Blender mann wind model. Moreover, correction factors for swallow water effects were used on the MC in order to provide a better accuracy and also to allow comparison between the operational data and the simulated ones since the sea trials depth could not be considered as deep waters. Finally, a system identification procedure was perfomed in order to investigate the possibility of identifying the exact MC values of a vessel. The results were encouraging. The simulation follows the patterns of the raw data relative accurately. In addition, the swallow water corrections provided enough evidence of the different behavior of the vessel depending on the depth under keel. From the SI side, a list of issues were encountered like parameter drift, multicollinearity and cost function prone to local minimum. A series of different procedures and algorithm proposed to overcome those difficulties and the results were promising.

Lubricated friction issues are central to all hydraulic actuation systems undergoing motion and any in-depth understanding of the nature of lubricated friction will advance future component design. The classic friction models of hydraulic actuation systems under steady state conditions and their dependency on velocity and temperature have been studied extensively over the past years. A model which is commonly employed to represent the characteristics of friction is that of Stribeck in which the dependency of the friction force is based on velocity alone. However, experimentally, it has been found that lubricated friction is dependent on acceleration. Thus, the Stribeck model can be considered as a subset of a dynamic friction model in which acceleration is zero. Thus, it can be concluded that the Stribeck model is best applied to cases when the change rate of the velocities is very small. This thesis considers the dependency of lubricated friction on acceleration when pressure and temperature changes are relatively constant. As such, the basic hypothesis for this study was proposed as follows: “Lubricated friction in hydraulic actuation systems is not only a function of velocity, but is also a function of both velocity and acceleration”. In this thesis several terms are defined which facilitate the description under which friction models are developed. For example, the term non-steady state friction is used to account for the effect of acceleration on lubricated friction force while in motion. Further, the lubricated friction models are divided into two groups: steady state friction models and non-steady state friction models. Nonlinear friction modeling and measuring methods are reviewed in this dissertation. This review also includes nonlinear lubricated friction modeling in hydraulic actuation systems. A conclusion from this review was that limited research has been done in documenting and explicitly demonstrating the role of acceleration on lubricated friction. The research first introduced a methodology to experimentally measure friction as a function of acceleration and to demonstrate this dependency in the form of a three dimensional graph. A novel technique to experimentally obtain data for the lubricated friction model was introduced. This allowed the lubricated friction forces to be measured as a function of velocity in a continuous manner, but with acceleration being held constant as a family parameter. Two different valve controlled hydraulic actuation systems (VCHAS) were studied under a wide variety of accelerations at constant temperature and pressure. To enable repeatable data collection for the different friction conditions and to accommodate for the effect of hysteresis, a periodic parabolic displacement waveform was chosen which enabled the acceleration to be a family parameter. The second phase of the research introduced a method of representing the data (lubricated friction model) in a lookup table form. The relationship of lubricated friction (in this work, pressure differential, ΔP across the actuator) as a function of velocity and acceleration was presented in a unique semi-empirical 2D lookup table (2D LUT). Limitations of this experimental approach were identified, but the dependency on acceleration was clearly established. The last phase of the study implemented this 2D LUT model into a practical software model of an actuator and demonstrated its accuracy when compared to its experimental counterpart. The semi-empirical model (2D LUT) was experimentally verified by implementing the semi-empirical and Stribeck models into a real time simulation of an actuator and by comparing the experimental outputs against simulated outputs for a common sinusoidal input. A sinusoidal actuator displacement input was chosen to test the simulations as it was not used in the collection of the original data. The output of the simulation was compared to the experimental results and it was evident that for the range in which data could be collected in developing the model, the proposed 2D LUT model predicted an output that was superior to a model which used a standard Stribeck model. It was concluded that the semi-empirical model could be integrated into a simulation environment and predict outputs in a superior fashion when compared to the Stribeck friction model. Thus it was concluded that the stated hypothesis is consistent with the experimental evidence shown by all hydraulic actuators considered. Further, it was also observed that the traditional Stribeck form (steady state dynamic friction) does change with increasing acceleration to the point that the standard breakaway friction almost disappears. It is evident that the 2D LUT is a viable tool for modeling the non-steady state friction of hydraulic actuation systems. The semi-empirical 2D LUT model so developed is a more global representation of hydraulic actuator lubricated friction. In this research, only linear hydraulic actuators were considered; however, the novel nonlinear semi-empirical 2D LUT lubricated friction model can be applied to any actuator (linear and rotary) and provides a new way in which the dynamic friction can be viewed and modeled.

Le boulonnage et le câblage à ancrage réparti sont deux techniques de renforcement du terrain couramment utilisées dans l'industrie minière et dans le génie civil. Au fil de cette recherche, on s'intéresse à la réponse de ces éléments sous des sollicitations axiales de traction, en régime statique. Dans ces conditions, l'expérience montre que la rupture se produit le plus fréquemment à l'interface barre-scellement via un processus de décohésion qui commence dès que la force sur la barre atteint une valeur limite. L'objectif est de mieux comprendre le comportement de cette interface, avant et après rupture. Premièrement, on revoit l'état de l'art afin de comprendre le travail effectué et les aspects non maîtrisés à ce jour. Deuxièmement, on décrit des outils analytiques qui permettent de comprendre la réponse d'un boulon ou d'un câble à ancrage réparti soumis à une force de traction. Ensuite, on présente les études expérimentales menées en laboratoire et in situ. Des essais d'arrachement ont été effectués pour déterminer les principaux facteurs qui régissent la réponse de l'interface. Finalement, on analyse les résultats des essais effectués en laboratoire sur les boulons. Après l'obtention des variables nécessaires, on propose un modèle semi-empirique d'interface, qui devra être validé par des essais complémentaires. Cette perspective et d'autres améliorations sont également présentées. / Rockbolting and cablebolting are two ground reinforcement techniques broadly used in civil and mining engineering. This research focuses on the behaviour of fully grouted bolts subjected to tensile axial loads, in static conditions. Under these circumstances, experience throughout the world proves that failure usually takes place at the bolt-grout interface via a decoupling process that starts if the load on the bolt exceeds a critical value. The objective is to gain more insight into the behaviour of this interface, before and after failure. First, the state-of-the-art is presented to understand the existing advances and to identify the lacking aspects. Secondly, analytical tools that help understand the response of a fully grouted bolt subjected to a tensile load are described. Then, the field and laboratory experimental campaigns are exposed. Pull-out tests have been conducted to determine the most influencing parameters on the interface behaviour. Finally, the laboratory results on rockbolts are analyzed. Once the necessary variables are obtained, a semi-empirical interface behaviour model is proposed. The further evaluation of this model and other improvements are suggested as perspectives of evolution.

Le dioxyde d’uranium UO2 est le combustible standard dans les réacteurs nucléaires à eau pressurisée (REP). Durant le fonctionnement du réacteur les pastilles combustibles subissent des contraintes thermiques et mécaniques. Pour cette raison il est très important de bien connaître les propriétés de ce système à la fois dans les conditions de fonctionnement normales et accidentelles (300 à 2000K). Lors des réactions de fission de l’uranium, des gaz rares comme le xénon sont produits à l’intérieur du combustible. En raison de leur faible solubilité, ces gaz vont former des bulles intra- et inter- granulaires dans l’UO2. La présence de ces bulles dans le combustible a un impact sur les propriétés macroscopiques de ce dernier. A l'échelle nanométrique, les bulles intragranulaires prennent la forme d’un octaèdre facetté, essentiellement suivant les directions (111) et (100). Devant la complexité de l’étude de la stabilité de cet octaèdre, nous avons décomposé le problème afin de pouvoir l’étudier de façon plus systématique et de découpler les différents effets. Dans un premier temps, nous avons déterminé la stabilité des surfaces planes (111) et (100) de l’UO2 et les modifications de microstructure engendrées par leur relaxation. Dans un deuxième temps, nous avons caractérisé les isothermes d’adsorption du xénon sur ces surfaces relaxées, en les comparant à ceux de l’incorporation dans une boîte vide pour identifier les effets de surface. Une attention particulière a été portée sur la microstructure du xénon dans ces systèmes. Finalement, nous avons effectué une analyse des propriétés mécaniques (profils de pression et de contrainte au voisinage des surfaces). / Uranium dioxide UO2 is the standard fuel in nuclear pressurized water reactors (PWR). During the operation of the reactor the fuel pellets undergo thermal and mechanical stresses. For this reason it is very important to understand these thermomechanical properties of this system both in normal operation conditions and accidental situations (300 to 2000K). During fission reactions of uranium, rare gases such as xenon are produced within the fuel. Due to their low solubility, these gases will either be released or form intra- and inter-granular bubbles inside the UO2. The presence of these bubbles in the fuel has an impact on the thermomechanical properties of the latter. We focus in this thesis on the study of intragranularbubbles and their impact on the thermomechanical properties of UO2 , through modeling at the atomic scale. At this scale, intragranular bubbles take the shape of an octahedron, presenting mainly (111) and (100) facets. Given the complexity of the study of the stability of this octahedron, we have simplified the problem in order to study it in a more systematic way and to decouple the various effects. First, the stability of (100) and (111) extended surfaces of UO2 and microscructural modifications generated by their relaxation were studied. In a second step, we dermined adsorption isotherms of xenon on these relaxed surfaces, and compared them to the incorporation ones inside an empty box in order to isolate surface effects. A specific attention has been given to the microstructure of xenon in these systems. Finally, an analysis of the mechanical properties (pressure and stress profiles near by the surface).

The presence of the ordered $\gamma^{\prime}$ phase ($\text{Ni}_{3}\text{Al}$) in Ni-base superalloys is fundamental to the performance of engineering components such as turbine disks and blades which operate at high temperatures and loads. Hence for these alloys it is important to optimize their microstructure and phase composition. This is typically done by varying their chemistry and heat treatment to achieve an appropriate balance between $\gamma^{\prime}$ content and other constituents such as carbides, borides, oxides and topologically close packed phases. In this work we have set out to investigate the onset of $\gamma^{\prime}$ ordering in Ni-Al single crystals and in Ni-Al bicrystals containing coincidence site lattice grain boundaries (GBs) and we do this at high temperatures, which are representative of typical heat treatment schedules including quenching and annealing. For this we use the atomistic simulation methods of molecular dynamics (MD) and density functional theory (DFT). In the first part of this work we develop robust Bayesian classifiers to identify the $\gamma^{\prime}$ phase in large scale simulation boxes at high temperatures around 1500 K. We observe significant \gamma^{\prime} ordering in the simulations in the form of clusters of $\gamma^{\prime}$-like ordered atoms embedded in a $\gamma$ host solid solution and this happens within 100 ns. Single crystals are found to exhibit the expected homogeneous ordering with slight indications of chemical composition change and a positive correlation between the Al concentration and the concentration of $\gamma^{\prime}$ phase. In general, the ordering is found to take place faster in systems with GBs and preferentially adjacent to the GBs. The sole exception to this is the $\Sigma3 \left(111\right)$ tilt GB, which is a coherent twin. An analysis of the ensemble and time lag average displacements of the GBs reveals mostly `anomalous diffusion' behaviour. Increasing the Al content from pure Ni to Ni 20 at.% Al was found to either consistently increase or decrease the mobility of the GB as seen from the changing slope of the time lag displacement average. The movement of the GB can then be characterized as either `super' or `sub-diffusive' and is interpreted in terms of diffusion induced grain boundary migration, which is posited as a possible precursor to the appearance of serrated edge grain boundaries. In the second part of this work we develop a method for the training of empirical interatomic potentials to capture more elements in the alloy system. We focus on the embedded atom method (EAM) and use the Ni-Al system as a test case. Recently, empirical potentials have been developed based on results from DFT which utilize energies and forces, but neglect the electron densities, which are also available. Noting the importance of electron densities, we propose a route to include them into the training of EAM-type potentials via Bayesian linear regression. Electron density models obtained for structures with a range of bonding types are shown to accurately reproduce the electron densities from DFT. Also, the resulting empirical potentials accurately reproduce DFT energies and forces of all the phases considered within the Ni-Al system. Properties not included in the training process, such as stacking fault energies, are sometimes not reproduced with the desired accuracy and the reasons for this are discussed. General regression issues, known to the machine learning community, are identified as the main difficulty facing further development of empirical potentials using this approach.