Durante la última década y paralelamente al incremento de la velocidad de computación, las técnicas de simulación molecular se han erigido como una importante herramienta para la predicción de propiedades físicas de sistemas de interés industrial. Estas propiedades resultan esenciales en las industrias química y petroquímica a la hora de diseñar, optimizar, simular o controlar procesos. El actual coste moderado de computadoras potentes hace que la simulación molecular se convierta en una excelente opción para proporcionar predicciones de dichas propiedades. En particular, la capacidad predictiva de estas técnicas resulta muy importante cuando en los sistemas de interés toman parte compuestos tóxicos o condiciones extremas de temperatura o presión debido a la dificultad que entraña la experimentación a dichas condiciones. La simulación molecular proporciona una alternativa a los modelos termofísicos utilizados habitualmente en la industria como es el caso de las ecuaciones de estado, modelos de coeficientes de actividad o teorías de estados correspondientes, que resultan inadecuados al intentar reproducir propiedades complejas de fluidos como es el caso de las de fluidos que presentan enlaces de hidrógeno, polímeros, etc. En particular, los métodos de Monte Carlo (MC) constituyen, junto a la dinámica molecular, una de las técnicas de simulación molecular más adecuadas para el cálculo de propiedades termofísicas. Aunque, por contra del caso de la dinámica molecular, los métodos de Monte Carlo no proporcionan información acerca del proceso molecular o las trayectorias moleculares, éstos se centran en el estudio de propiedades de equilibrio y constituyen una herramienta, en general, más eficiente para el cálculo del equilibrio de fases o la consideración de sistemas que presenten elevados tiempos de relajación debido a su bajos coeficientes de difusión y altas viscosidades. Los objetivos de esta tesis se centran en el desarrollo y la mejora tanto de algoritmos de simulación como de potenciales intermoleculares, factor considerado clave para el desarrollo de las técnicas de simulación de Monte Carlo. En particular, en cuanto a los algoritmos de simulación, la localización de puntos críticos de una manera precisa ha constituido un problema para los métodos habitualmente utilizados en el cálculo de equlibrio de fases, como es el método del colectivo de GIBBS. La aparición de fuertes fluctuaciones de densidad en la región crítica hace imposible obtener datos de simulación en dicha región, debido al hecho de que las simulaciones son llevadas a cabo en una caja de simulación de longitud finita que es superada por la longitud de correlación. Con el fin de proporcionar una ruta adecuada para la localización de puntos críticos tanto de componentes puros como mezclas binarias, la primera parte de esta tesis está dedicada al desarrollo y aplicación de métodos adecuados que permitan superar las dificultades encontradas en el caso de los métodos convencionales. Con este fin se combinan estudios de escalado del tamaño de sitema con técnicas de "Histogram Reweighting" (HR). La aplicación de estos métodos se ha mostrado recientemente como mucho mejor fundamentada y precisa para el cálculo de puntos críticos de sistemas sencillos como es el caso del fluido de LennardJones (LJ). En esta tesis, estas técnicas han sido combinadas con el objetivo de extender su aplicación a mezclas reales de interés industrial. Previamente a su aplicación a dichas mezclas reales, el fluido de LennardJones, capaz de reproducir el comportamiento de fluidos sencillos como es el caso de argón o metano, ha sido tomado como referencia en un paso preliminar. A partir de simulaciones realizadas en el colectivo gran canónico y recombinadas mediante la mencionada técnica de "Histogram Reweighting" se han obtenido los diagramas de fases tanto de fluidos puros como de mezclas binarias. A su vez se han localizado con una gran precisión los puntos críticos de dichos sistemas mediante las técnicas de escalado del tamaño de sistema. Con el fin de extender la aplicación de dichas técnicas a sistemas multicomponente, se han introducido modificaciones a los métodos de HR evitando la construcción de histogramas y el consecuente uso de recursos de memoria. Además, se ha introducido una metodología alternativa, conocida como el cálculo del cumulante de cuarto orden o parámetro de Binder, con el fin de hacer más directa la localización del punto crítico. En particular, se proponen dos posibilidades, en primer lugar la intersección del parámetro de Binder para dos tamaños de sistema diferentes, o la intersección del parámetro de Binder con el valor conocido de la correspondiente clase de universalidad combinado con estudios de escalado. Por otro lado, y en un segundo frente, la segunda parte de esta tesis está dedicada al desarrollo de potenciales intermoleculares capaces de describir las energías inter e intramoleculares de las moléculas involucradas en las simulaciones. En la última década se han desarrolldo diferentes modelos de potenciales para una gran variedad de compuestos. Uno de los más comunmente utilizados para representar hidrocarburos y otras moléculas flexibles es el de átomos unidos, donde cada grupo químico es representado por un potencial del tipo de LennardJones. El uso de este tipo de potencial resulta en una significativa disminución del tiempo de cálculo cuando se compara con modelos que consideran la presencia explícita de la totalidad de los átomos. En particular, el trabajo realizado en esta tesis se centra en el desarrollo de potenciales de átomos unidos anisotrópicos (AUA), que se caracterizan por la inclusión de un desplazamiento de los centros de LennardJones en dirección a los hidrógenos de cada grupo, de manera que esta distancia se convierte en un tercer parámetro ajustable junto a los dos del potencial de LennardJones.En la segunda parte de esta tesis se han desarrollado potenciales del tipo AUA4 para diferentes familias de compuesto que resultan de interés industrial como son los tiofenos, alcanoles y éteres. En el caso de los tiofenos este interés es debido a las cada vez más exigentes restricciones medioambientales que obligan a eliminar los compuestos con presencia de azufre. De aquí la creciente de necesidad de propiedades termodinámicas para esta familia de compuestos para la cual solo existe una cantidad de datos termodinámicos experimentales limitada. Con el fin de hacer posible la obtención de dichos datos a través de la simulación molecular hemos extendido el potencial intermolecular AUA4 a esta familia de compuestos. En segundo lugar, el uso de los compuestos oxigenados en el campo de los biocombustibles ha despertado un importante interés en la industria petroquímica por estos compuestos. En particular, los alcoholes más utilizados en la elaboración de los biocombustibles son el metanol y el etanol. Como en el caso de los tiofenos, hemos extendido el potencial AUA4 a esta familia de compuestos mediante la parametrización del grupo hidroxil y la inclusión de un grupo de cargas electrostáticas optimizadas de manera que reproduzcan de la mejor manera posible el potencial electrostático creado por una molecula de referencia en el vacío. Finalmente, y de manera análoga al caso de los alcanoles, el último capítulo de esta tesis la atención se centra en el desarrollo de un potencial AUA4 capaz de reproducir cuantitativamente las propiedades de coexistencia de la familia de los éteres, compuestos que son ampliamente utilizados como solventes. / Parallel with the increase of computer speed, in the last decade, molecular simulation techniques have emerged as important tools to predict physical properties of systems of industrial interest. These properties are essential in the chemical and petrochemical industries in order to perform process design, optimization, simulation and process control. The actual moderate cost of powerful computers converts molecular simulation into an excellent tool to provide predictions of such properties. In particular, the predictive capability of molecular simulation techniques becomes very important when dealing with extreme conditions of temperature and pressure as well as when toxic compounds are involved in the systems to be studied due to the fact that experimentation at such extreme conditions is difficult and expensive.Consequently, alternative processes must be considered in order to obtain the required properties. Chemical and petrochemical industries have made intensive use of thermophysical models including equations of state, activity coefficients models and corresponding state theories. These predictions present the advantage of providing good approximations with minimal computational needs. However, these models are often inadequate when only a limited amount of information is available to determine the necesary parameters, or when trying to reproduce complex fluid properties such as that of molecules which exhibit hydrogen bonding, polymers, etc. In addition, there is no way for dynamical properties to be estimated in a consistent manner.In this thesis, the HR and FSS techniques are combined with the main goal of extending the application of these methodologies to the calculation of the vaporliquid equilibrium and critical point of real mixtures. Before applying the methodologies to the real mixtures of industrial interest, the LennardJones fluid has been taken as a reference model and as a preliminary step. In this case, the predictions are affected only by the omnipresent statistical errors, but not by the accuracy of the model chosen to reproduce the behavior of the real molecules or the interatomic potential used to calculate the configurational energy of the system.The simulations have been performed in the grand canonical ensemble (GCMC)using the GIBBS code. Liquidvapor coexistences curves have been obtained from HR techniques for pure fluids and binary mixtures, while critical parameters were obtained from FSS in order to close the phase envelope of the phase diagrams. In order to extend the calculations to multicomponent systems modifications to the conventional HR techniques have been introduced in order to avoid the construction of histograms and the consequent need for large memory resources. In addition an alternative methodology known as the fourth order cumulant calculation, also known as the Binder parameter, has been implemented to make the location of the critical point more straightforward. In particular, we propose the use of the fourth order cumulant calculation considering two different possibilities: either the intersection of the Binder parameter for two different system sizes or the intersection of the Binder parameter with the known value for the system universality class combined with a FSS study. The development of transferable potential models able to describe the inter and intramolecular energies of the molecules involved in the simulations constitutes an important field in the improvement of Monte Carlo techniques. In the last decade, potential models, also referred to as force fields, have been developed for a wide range of compounds. One of the most common approaches for modeling hydrocarbons and other flexible molecules is the use of the unitedatoms model, where each chemical group is represented by one LennardJones center. This scheme results in a significant reduction of the computational time as compared to allatoms models since the number of pair interactions goes as the square of the number of sites. Improvements on the standard unitedatoms model, where typically a 612 LennardJones center of force is placed on top of the most significant atom, have been proposed. For instance, the AUA model consists of a displacement of the LennardJones centers of force towards the hydrogen atoms, converting the distance of displacement into a third adjustable parameter. In this thesis we have developed AUA 4 intermolecular potentials for three different families of compounds. The family of ethers is of great importance due to their applications as solvents. The other two families, thiophenes and alkanols, play an important roles in the oil and gas industry. Thiophene due to current and future environmental restrictions and alkanols due ever higher importance and presence of biofuels in this industry.

L'étape de déliantage est une étape importante et parfois critique pour le procédé Moulage par Injection des Poudres. A cet effet, des analyses thermogravimétriques (TGA) ont été réalisées pour bien comprendre les mécanismes du déliantage thermique sous atmosphère imposée (Argon). Les méthodes de Kissinger et Ozawa ont été utilisées, en se basant sur les résultats des analyses thermogravimétriques, afin d’estimer les paramètres cinétiques nécessaires pour la simulation numérique, notre modèle se propose de décrire les phénomènes physiques liés à la dégradation du polymère, le transfert de chaleur de la déformation du composant pendant le déliantage thermique.La deuxième partie de la thèse est dédiée à la compréhension des mécanismes et du comportement du fritage des composants en tungstène sous une atmosphère d’hydrogène jusqu’à une température de 1 700°C. Des appareils expérimentaux, ont été mis en place afin de constituer une base de données physiques nécessaire pour l’identification des différents paramètres. L’identification de l’ensemble des lois de comportement a été réalisée en prenant en compte les spécificités physiques des poudres utilisées. Un modèle de comportement de type thermo élasto-viscoplastique est formulé pour représenter la loi de densification par diffusion solide, puis appliqué pour les différentes tailles de poudres de tungstène. La dernière étape consiste à valider des simulations numériques avec ABAQUS pour une meilleure détermination des densités et des retraits finaux des composants injectés. / Thermal debinding is one of the most important steps In Powder Injection Moulding process. Thermogravimetric analyses (TGA) are employed to analyze the physics and kinetics of thermal debinding behaviour under argon atmosphere. The Kissinger and Ozawa method have been used to estimate the kinetic parameters from thermogravimetric experiments. To set up the numerical simulations of thermal debinding stage using finite element method, a coupled mathematical has been developed. The basic steps of the proposed model consist to solve the following sequences of coupled problems: themal degradation of binder coupled with heat transfer and deformation phenomena by finite element method using Comsol Multiphysics software.In the second part of this thesis, sintering behaviour of tungsten powders injection moulded component, under pure hydrogen atmosphere at temperature up to 1700°C. The experimental tests are used to determine the material parameters in the parameters in the viscoplastic constitutive law, which is incorporated with the identified parameters in order to simulate the final shrinkages and densities of tungsten injection moulded components during the sintering process. Comparison between the numerical simulations results and experimental ones, in term of shrinkages and sintered densities, shows a good agreement.

A procedure to evaluate the leaching properties of radionuclides from irradiated graphite waste has been developed by combining ANSI 16.1 (USA) and NEN 7345 (Netherlands) standardised diffusion leaching techniques. The ANSI 16.1 standard has been followed to the acquire the leachates and to determine the leach rate/ diffusion coefficient and NEN 7345 standard technique has been used to determine the diffusion mechanism of radionuclides. The investigation employs simulated Drigg groundwater as a leachant using semi-dynamic technique for the production of leachate specimens. From gamma spectroscopy analysis the principal radionuclides present in terms of activity were 60Co, 137Cs, 134Cs, 155Eu, 133Ba and 46Sc. The dominant radionuclides are 60Co, 134Cs and 133Ba which together account for about 91 % of the total activity. The 91 % can be broken down into 73.4 % 60Co, 9.1 % 134Cs and 8.1 % 133Ba. Analysis of total beta and total beta without tritium activity release from Magnox graphite was measured using liquid scintillating counting. Preliminary results show that there is an initial high release of activity and decreases when the leaching period increases. This may be due to the depletion of contaminants which were absorbed by the internal pore networks and the surface. During the leaching test approximately 275.33 ± 18.20 Bq of 3H and 106.26 ± 7.01 Bq of 14C was released into the leachant within 91 days. Irradiation induced damages to the nuclear graphite crystal structure have been shown to cause disruption of the bonding across the basal planes. Moreover, the closures of Mrozowski cracks have been observed in nuclear graphite, the bulk property are governed by the porosity, in particular, at the nanometre scale. Therefore, knowledge of the crystallite structure and porosity distribution is very important; as it will assist in understand the affects of irradiated damage and location and the mechanism of the leaching of radionuclides. The work reported herein contributed several key findings to the international work on graphite leaching to offer guidance leading toward obtaining leaching data in the future: (a) the effective diffusion coefficient for 14C from graphite waste has been determined. The diffusion process for 14C has two stages resulting two different values of diffusion coefficient, i.e., for the fast and slow components; (b) the controlling leaching mechanism for 3H radionuclide from graphite is shown to be surface wash–off; and for that of 14C radionuclide the initial controlling leaching mechanism is surface wash-off following by diffusion which is the major transport mechanism ; (c) The weight loss originates from the open pore structure which has been opened up by radiolytic oxidation; at the higher weight losses much of the closed porosity in the graphite has been opened. The investigation indicates that weigh loss has a major influence on the leaching of elements from the irradiated graphite; and (d) the analysis of the pores in nuclear graphite can be categorised into three types. These three types of pores are: (1) small pores narrow which are slit-shaped pores in the binder phase or matrix, (2) gas evolution pores or gas entrapment pores within the binder phase or matrix and (3) lenticular pores which are large cracks within the filler particles. It is shown in this thesis that by using tomography to study the morphology of the different pores coupled with the distribution of impurities an understanding of the role of porosity in leaching is possible.

The diploma thesis deals with the production of warm mix asphalts, using the foam bitumen technology. The thesis is divided into theoretical and practical part. The theoretical part is focused on the basic division of roadway constructions, particularly on warm mix asphalts. The aim of the practical part was to find out whether the produced asphalt mixture retains its functional properties when the operating temperature is reduced. For this purpose, two asphalt mixtures of the ACO 11+ type at operating temperature of 150 °C and reduced operating temperature of 130 °C were made. Functional tests and empirical and functional tests were carried out on the produced asphalt mixtures and the extracted bitumen binders respectively. In the conclusion of the thesis, the results of the tests are mutually compared.

The diploma thesis is focused on the appropriate dosage of rejuvenating agents in asphalt mixtures with high content of RAP. The empirical and functional laboratory tests are described in the theoretical part. The practical part deals with the estimation of the optimal amount of rejuvenating agents by means of laboratory tests so that the rheological properties of the degraded asphalt binder can be restored by suitable dosing into the RAP. As part of the TAČR ZÉTA project, an experimental section of asphalt mixture containing 50 % of the RAP and an appropriate amount of the rejuvenating agents was created. The aim of the thesis is to find an optimal dosage of the rejuvenating agents in the samples of the RAP and laboratory aged asphalt binder of gradation 50/70, to determine the effectiveness of selected rejuvenating agents and to monitor changes in the parameters of the experimental section during the period of time.

The diploma thesis is divided into theoretical and practical part. The theoretical part is mainly focused on methods for reducing the working temperature in the production of hot mix asphalt and the main reasons for this. Most attention is paid to the warm mix asphalt, mainly foam asphalt technology. In practical part are describes working procedures of individual tests on asphalt mixtures and recovered bitumen binders. The tests were performed on 3 types of ACO 11+, one was made with working temperature 160°C without foamed bitumen and the other two with foamed bitumen,one with working temperature 160°C and the second 140°C. Then were the results compared.

The diploma thesis is focused on fire-resistant repair mortar with fine-grained filler. The aim of this work is the research and development of fine-grained Mortars resistant to high temperatures, which are characteristic at the beginning of the fire. The theoretical knowledge with subsequently realized laboratory verification was used. At-tention was paid to the masses based on the mixed binder comprising cement and blast furnace slag, respectively. high-temperature ash. Cellulose fibres were used as the dis-persed reinforcement. Two kinds of aggregate were assessed - fly ash agloporit and am-phibolite incl. combinations thereof. Laboratory tests were carried out via determination of basic material properties (density, strength, consistency, dimensional changes etc.) after exposure to extreme temperatures. A substantial part of the research was also study of different cooling conditions - slow and fast (water and air). Selected formulations were subjected to temperatures up to 1200 ° C. In the conclusion is selected several recipes that have been found to be optimal for continuing research on the basis of the results and findings.

This master's thesis describes how to use the asphalt layer called Stress Absorbing Layer (SAL) and comparises it with other types of SAL with different types of asphalt binders. In the first theoretical part is SAL generally described. In the second part is SAL practically tested and described.

The aim of bachelor thesis is to gain experience with the design mixtures of asphalt concrete for very thin layers. Familiarizing with the properties of these mixtures, as porosity, water resistance and resistance to permanent deformation. Comparing detected parameters with the requirements of standard EN 13108-2 and its National Annex.

Diploma thesis deals with the topic of using recycled material in the production of asphalt mixtures. In the theoretical part the methods of recycling flexible pavement are described and as well as ways in which recycled material is added to asphalt mixtures produced by the stationary hot mix plant. The thesis also deals with the current state of recycled material use in the Czech Republic and the reasons for its possible greater use. The practical part of the thesis studies the effect of using the amount of 20% recycled material to asphalt mixtures of asphalt concrete for wearing course ACO11+, on selected functional properties of these mixtures. It is also investigates the influence of bitumen binder contained in the recycled material, on the final properties in manufactured asphalt mixtures. An integral part of this thesis is a description of all methods that were used during the processing of the practical part. In the end of this thesis there are some results of findings about adding recycled material into asphalt mixtures.