<p>For many applications within the defense, aerospace, and electricity-producing industries, available material choices for high-performance devices that fulfill necessary requirements are limited. Choosing a metallic material or a ceramic material may be optimal for only some of the required properties. For instance, choosing a metal may optimize ductility but compromise oxidation resistance, yield strength, or creep resistance. Of potential interest, ceramic-metal (cermet) composites can address several fundamental concerns such as high temperature mechanical toughness and stiffness and oxidation/corrosion resistance. However, cost-effective, scalable manufacturing of complex-shaped, high-temperature cermets can be challenging.</p> <p>A cermet of interest is niobium and yttrium oxide, Y2O3. Both materials exhibit high melting points with similar coefficients of thermal expansion. Basic thermodynamic calculations suggest that these materials are chemically compatible, and that Y2O3/Nb cermets may be generated by reactive melt infiltration using the patented Displacive Compensation of Porosity (DCP) process. With the DCP process, a liquid fills a porous perform, and a displacement reaction occurs to produce products of larger solid volume. This reaction yields the cermet of interest, formed in a reduced-stress condition, while maintaining a generally near net shape and high relative density.</p> <p>In order to get to the point of designing cermet components for various applications, a focus of this work has been to create a Y2O3/Nb composite by hot pressing powders at high temperatures at the predicted stoichiometric ratios, and then characterizing the thermal and mechanical properties. The reduction reaction between liquid yttrium and solid niobium (IV) oxide (NbO2) was then characterized to evaluate kinetic mechanisms affecting the reaction rate which is necessary for future DCP-based cermet component manufacturing.</p> <p>Lastly, the mechanical behavior of this cermet was modeled and compared to another cermet processed using liquid metal infiltration using a temperature-dependent elasto-visco-plastic self-consistent model. The effects of cooling from processing temperatures, as well as thermally cycling of these cermets, were quantified. As high temperature experiments can be time intensive with high costs, it is advantageous to have a computationally efficient, desktop design tool to quantify the impacts of changing processing and use conditions on material performance.</p>

Zr-2.5Nb is currently used for pressure tubes in the CANDU (CANada Deuterium Uranium) reactor. A complete understanding of the deformation mechanism of Zr-2.5Nb is important if we are to accurately predict the in-reactor performance of pressure tubes and guarantee normal operation of the reactors. This thesis is a first step in gaining such an understanding; the deformation mechanism of ZrNb alloys at room temperature has been evaluated through studying the effect of texture and microstructure on deformation. In-situ neutron diffraction was used to monitor the evolution of the lattice strain of individual grain families along both the loading and Poisson’s directions and to track the development of interphase and intergranular strains during deformation. The following experiments were carried out with data interpreted using elasto-plastic modeling techniques: 1) Compression tests of a 100%Zr material at room temperature. 2) Tension and compression tests of hot rolled Zr-2.5Nb plate material. 3) Compression of annealed Zr-2.5Nb. 4) Cyclic loading of the hot rolled Zr-2.5Nb. 5) Compression tests of ZrNb alloys with different Nb and oxygen contents. The experimental results were interpreted using a combination of finite element (FE) and elasto-plastic self-consistent (EPSC) models. The phase properties and phase interactions well represented by the FE model, the EPSC model successfully captured the evolution of intergranular constraint during deformation and provided reasonable estimates of the critical resolved shear stress and hardening parameters of different slip systems under different conditions. The consistency of the material parameters obtained by the EPSC model allows the deformation mechanism at room temperature and the effect of textures and microstructures of ZrNb alloys to be understood. This work provides useful information towards manufacturing of Zr-2.5Nb components and helps in producing ideal microstructures and material properties for pressure tubes. Also it is helpful in guiding the development of new materials for the next generation of nuclear reactors. Furthermore, the large data set obtained from this study can be used in evaluation and improving current and future polycrystalline deformation models. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2008-09-05 13:51:30.42

The currently operating Generation II Advanced Gas-Cooled Reactors (AGR) in the nuclear power stations in the UK, mainly built in the 1960s and 1970s, are approaching their designed life. Besides the development of the new generation of reactors, the government is also seeking to extend the life of some AGRs. Creep and failure properties of Type 316H austenitic stainless steels used in some components of AGR at elevated temperature are under investigation in EDF Energy Ltd. However, the current empirical creep models used and examined in EDF Energy have deficiency and demonstrate poor agreement with the experimental data in the operational complex thermal/mechanical conditions. The overall objective of the present research is to improve our general understanding of the creep behaviour of Type 316H stainless steels under various conditions by undertaking theoretical studies and developing a physically based multiscale state variable model taking into account the evolution of different microstructural elements and a range of different internal mechanisms in order to make realistic life prediction. A detailed review shows that different microstructural elements are responsible for the internal deformation mechanisms for engineering alloys such as 316H stainless steels. These include the strengthening effects, associated with forest dislocation junctions, solute atoms and precipitates, and softening effects, associated with recovery of dislocation structure and coarsening of precipitates. All the mechanisms involve interactions between dislocations and different types of obstacles. Thus change in the microstructural state will lead to the change in materials' internal state and influence the mechanical/creep property. Based on these understandings, a multiscale self-consistent model for a polycrystalline material is established, consisting of continuum, crystal plasticity framework and dislocation link length model that allows the detailed dislocation distribution structure and its evolution during deformation to be incorporated. The model captures the interaction between individual slip planes (self- and latent hardening) and between individual grains and the surrounding matrix (plastic mismatch, leading to the residual stress). The state variables associated with all the microstructure elements are identified as the mean spacing between each type of obstacles. The evolution of these state variables are described in a number of physical processes, including the dislocation multiplication and climb-controlled network coarsening and the phase transformation (nucleation, growth and coarsening of different phases). The enhancements to the deformation kinetics at elevated temperature are also presented. Further, several simulations are carried out to validate the established model and further evaluate and interpret various available data measured for 316H stainless steels. Specimens are divided into two groups, respectively ex-service plus laboratory aged (EXLA) with a considerable population of precipitates and solution treated (ST) where precipitates are not present. For the EXLA specimens, the model is used to evaluate the microscopic lattice response, either parallel or perpendicular to the loading direction, subjected to uniaxial tensile and/or compressive loading at ambient temperature, and macroscopic Bauschinger effect, taking into account the effect of pre-loading and pre-crept history. For the ST specimens, the model is used to evaluate the phase transformation in the specimen head volume subjected to pure thermal ageing, and multiple secondary stages observed during uniaxial tensile creep in the specimen gauge volume at various temperatures and stresses. The results and analysis in this thesis improve the fundamental understanding of the relationship between the evolution of microstructure and the creep behaviour of the material. They are also beneficial to the assessment of materials' internal state and further investigation of deformation mechanism for a broader range of temperature and stress.

Worldwide interest in gas production from shale formations has rapidly increased in recent years, mostly by the successful development of gas shales in North America. The Haynesville Shale is a productive gas shale resource play located in Texas and Louisiana. It produces primarily through enhanced exposure to the reservoir and improved permeability resulting from horizontal drilling and hydraulic fracturing. Accordingly, it is important to estimate the reservoir properties that influence the elastic and geomechanical properties from seismic data. This thesis estimates pore shapes, which affect the transport, elastic, and geomechancial properties, from wellbore seismic velocity in the Haynesville Shale. The approach for this work is to compare computed velocities from an appropriate rock physics model to measured velocities from well log data. In particular, the self-consistent approximation was used to calculate the model-based velocities. The Backus average was used to upscale the high-frequency well log data to the low-frequency seismic scale. Comparisons of calculated velocities from the self-consistent model to upscaled Backus-averaged velocities (at 20 Hz and 50 Hz) with a convergence of 0.5% made it possible to estimate pore aspect ratios as a function of depth. The first of two primary foci of this approach was to estimate pore shapes when a single fluid was emplaced in all the pores. This allowed for understanding pore shapes while minimizing the effects of pore fluids. Secondly, the effects of pore fluid properties were studied by comparing velocities for both patchy and uniform fluid saturation. These correspond to heterogeneous and homogeneous fluid mixing, respectively. Implementation of these fluid mixtures was to model them directly within the self-consistent approximation and by modeling dry-rock velocities, followed by standard Gassmann fluid substitution. P-wave velocities calculated by the self-consistent model for patchy saturation cases had larger values than those from Gassmann fluid substitution, but S-wave velocities were very similar. Pore aspect ratios for variable fluid properties were also calculated by both the self-consistent model and Gassmann fluid substitution. Pore aspect ratios determined for the patchy saturation cases were the smallest, and those for the uniform saturation cases were the largest. Pore aspect ratios calculated by Gassmann fluid substitution were larger because the velocity is inversely related to the aspect ratio in this particular modeling procedure. Estimates of pore aspect ratios for uniform saturation were 0.051 to 0.319 with the average of 0.171 from the velocity modeling using the self-consistent model. For patchy saturation, the aspect ratios were 0.035 to 0.296 with a mean of 0.145. These estimated pore aspect ratios from the patchy saturation case within the self-consistent model are considered the most reasonable set of values I determined. This is because the most likely in-situ fluid distribution is heterogeneous due to the extremely low permeability of the Haynesville Shale. Estimated pore aspect ratios using this modeling help us to understand elastic properties of the Haynesville Shale. In addition, this may help to find zones that correspond to optimal locations for fracturing the shale while considering brittleness and in-situ stress of the formation. / text

Thermal oxidation of silicon belongs to the most decisive steps in microelectronic fabrication because it allows creating electrically insulating areas which enclose electrically conductive devices and device areas, respectively. Deal and Grove developed the first model (DG-model) for the thermal oxidation of silicon describing the oxide thickness versus oxidation time relationship with very good agreement for oxide thicknesses of more than 23 nm. Their approach named as general relationship is the basis of many similar investigations. However, measurement results show that the DG-model does not apply to very thin oxides in the range of a few nm. Additionally, it is inherently not self-consistent. The aim of this paper is to develop a self-consistent model that is based on the continuity equation instead of Fick’s law as the DG-model is. As literature data show, the relationship between silicon oxide thickness and oxidation time is governed—down to oxide thicknesses of just a few nm—by a power-of-time law. Given by the time-independent surface concentration of oxidants at the oxide surface, Fickian diffusion seems to be neglectable for oxidant migration. The oxidant flux has been revealed to be carried by non-Fickian flux processes depending on sites being able to lodge dopants (oxidants), the so-called DOCC-sites, as well as on the dopant jump rate.

Thermal oxidation of silicon belongs to the most decisive steps in microelectronic fabrication because it allows creating electrically insulating areas which enclose electrically conductive devices and device areas, respectively. Deal and Grove developed the first model (DG-model) for the thermal oxidation of silicon describing the oxide thickness versus oxidation time relationship with very good agreement for oxide thicknesses of more than 23 nm. Their approach named as general relationship is the basis of many similar investigations. However, measurement results show that the DG-model does not apply to very thin oxides in the range of a few nm. Additionally, it is inherently not self-consistent. The aim of this paper is to develop a self-consistent model that is based on the continuity equation instead of Fick’s law as the DG-model is. As literature data show, the relationship between silicon oxide thickness and oxidation time is governed—down to oxide thicknesses of just a few nm—by a power-of-time law. Given by the time-independent surface concentration of oxidants at the oxide surface, Fickian diffusion seems to be neglectable for oxidant migration. The oxidant flux has been revealed to be carried by non-Fickian flux processes depending on sites being able to lodge dopants (oxidants), the so-called DOCC-sites, as well as on the dopant jump rate.

Οι πηγές πλάσματος επαγωγικής ζεύξης (Inductively Coupled Plasma Sources – ICP’s), παρέχουν πλάσμα υψηλής πυκνότητας ηλεκτρονίων σε χαμηλή πίεση και έχουν ευρεία εφαρμογή στη σύγχρονη βιομηχανία ημιαγωγών και την κατεργασία επιφανειών. Σε πολύ χαμηλές πιέσεις, (~mTorr), οι εκκενώσεις πλάσματος παρουσιάζουν ιδιαίτερη συμπεριφορά όσον αφορά τη διείσδυση του ηλεκτρομαγνητικού πεδίου και την αλληλεπίδραση κύματος-σωματιδίου: Η ανώμαλη επιδερμική διείσδυση (anomalous skin effect) και η συντονισμένη αλληλεπίδραση κύματος-σωματιδίου όταν υπερτίθεται στατικό μαγνητικό πεδίο (resonant wave-particle interaction) είναι δύο φαινόμενα τυπικά σε αυτές τις εκκενώσεις. Η κατανόηση και μαθηματική ανάλυση αυτών των ιδιαίτερα περίπλοκων φαινομένων, ώστε να προσομοιωθούν με ακρίβεια αλλά και χωρίς χρονοβόρες υπολογιστικά διαδικασίες οι πηγές πλάσματος επαγωγικής ζεύξης, αποτελεί μια σύγχρονη επιστημονική και υπολογιστική πρόκληση. Στα πλαίσια αυτά, στην παρούσα διατριβή τέθηκε ως στόχος η αξιοποίηση της υπάρχουσας επιστημονικής γνώσης στον τομέα της υπολογιστικής προσομοίωσης πλάσματος, για την ανάπτυξη ταχύτατων προσομοιώσεων των πηγών πλάσματος επαγωγικής ζεύξης, διασφαλίζοντας ταυτόχρονα την εξαγωγή έγκυρων συμπερασμάτων: Η προσέγγιση αυτή συνίσταται στη διατύπωση υπόθεσης (μοντέλου), τον έλεγχό της σε σχέση με υπάρχοντα δεδομένα και την επαναδιατύπωσή της μέχρις ότου το μοντέλο να κριθεί επαρκές. Αρχικά αναπτύχθηκε ένα ρευστοδυναμικό μοντέλο πλάσματος βασισμένο στην υπόθεση ψευδουδετερότητας και αμφιπολικής διάχυσης των φορέων φορτίου, προκειμένου να προσομοιωθεί η ενισχυμένης μαγνητικής διαπερατότητας πηγή επαγωγικής ζεύξης MaPE–ICP. Τα αποτελέσματα της προσομοίωσης συγκρίνονται με τα πειραματικά στοιχεία προηγούμενων ερευνητών για εκκενώσεις Αργού και εξετάζεται η ικανότητα του ρευστοδυναμικού μοντέλου να παρέχει μια στοιχειώδη ποσοτική περιγραφή πλάσματος επαγωγικής ζεύξης σε χαμηλή πίεση. Η αξιοπιστία του ρευστοδυναμικού μοντέλου εξελίσσεται περεταίρω, με την ενσωμάτωση μιας αποτελεσματικής αριθμητικής επίλυσης της κινητικής εξίσωσης Boltzmann για τα ηλεκτρόνια. Τα αποτελέσματα της υβριδικής προσομοίωσης για εκκένωση Αργού πίεσης 30 mTorr στον αντιδραστήρα MaPE–ICP συγκρίνονται τόσο με αντίστοιχα πειραματικά δεδομένα όσο και με τα προηγούμενα αποτελέσματα της ρευστοδυναμικής προσομοίωσης και εξετάζεται η βελτίωση της ποιοτικής συμφωνίας όσον αφορά την επίδραση των παραμέτρων με ιδιαίτερο ενδιαφέρον. Στη συνέχεια αναπτύχθηκε ένα ρευστοδυναμικό μοντέλο εκκενώσεων αίγλης τύπου ECWR (Electron Cyclotron Wave Resonance) βασισμένο σε προκαθορισμένες οριακές συνθήκες για το ηλεκτρομαγνητικό πεδίο. Προσομοιώθηκε ένα διάκενο με πλάσμα Αργού σε πίεση 15 mTorr (μονοδιάστατο μοντέλο) και τα αποτελέσματα ελέγχθηκαν έναντι αναλυτικής θεωρίας, πειραματικών δεδομένων και αποτελεσμάτων προσομοίωσης Particle In Cell/Monte Carlo (PIC/MC). Επιπρόσθετα, τα αποτελέσματα προσομοίωσης για μια εκκένωση Αργού σε πίεση 1 mTorr εντός κυλινδρικού αντιδραστήρα τύπου ECWR (δισδιάστατο μοντέλο), συγκρίνονται με τα αποτελέσματα προσομοίωσης και πειραματικά στοιχεία. Τέλος, το μοντέλο έχει επεκταθεί για να περιλάβει την διάδοση του πλάσματος που παράγεται από μια τυπική πηγή πλάσματος τύπου ECWR σε μια περιοχή διάχυσης. Τα αποτελέσματα για εκκένωση Αργού πίεσης 5 mTorr συγκρίνονται με τα αντίστοιχα αποτελέσματα ενός μοντέλου σφαιρικής διάχυσης πλάσματος και εν προκειμένω εξετάζεται η πλήρης επεκτασιμότητα του εισαχθέντος ρευστοδυναμικού μοντέλου ECWR σε διεργασίες πλάσματος. / Inductively Coupled Plasma Sources (ICP’s) are capable of producing high density-low pressure plasmas in a variety of applications for the semiconductor and material processing industry. In the mTorr range, ICP discharges exhibit an extraordinary behaviour concerning the electromagnetic field propagation and wave-particle interaction: Anomalous skin effect and resonant wave-particle interaction within a superimposed static magnetic field consist two of the most typical phenomena. The efficient comprehension and mathematical description of such a complex gas discharge in order to fast and accurately simulate ICP sources, is still a challenging task. Within this context, the thesis focuses on evaluating the existing scientific knowledge in plasma computational modeling in order to develop not only rapidly converging but reliable ICP simulations: The implementation methodology consists on formulating an hypothesis (model) and repetitively inquiring its accuracy by checking the simulation results against existing experimental and/or other simulation data. The continuation of the model re-formulation process depends on the accuracy of the simulation results. Initally a simulation of a Magnetic Pole Enhanced (MaPE)-ICP plasma source was developed, under the assumptions of plasma quasineutrality and ambipolar diffusion. The simulation results were checked against the experimental data of previous workers for Argon discharges and the ability of the model to provide an elementary quantitative description of low pressure ICP sources was scrutinized. The validity of the fluid model was enhanced with the incorporation of a time effective numerical solution of the Boltzmann transport equation for electrons. Simulation results of the hybrid model were compared to the previous fluid simulation results and existing experimental data, for a 30 mTorr Argon discharge in the MaPE–ICP reactor. The major improvements of the qualitative agreement in regard to the effect of parameters with particular interest are discussed. Moreover, a fluid model of ECWR (Electron Cyclotron Wave Resonance) discharges, based on predefined boundary conditions for the electromagnetic field, was developed: The simulation results for a 15 mTorr Argon plasma within a slab (1-dimensional model) were checked against the particle in cell/Monte Carlo (PIC/MC) simulation results that can be found in the literature and also compared to the analytical theory and experimental data. In addition, the model was further developed to simulate realistic geometries as a cylindrical ECWR reactor (2-D) and the data were also compared to both simulation results and experimental data of other researchers. Finally, the model was extended in order to simulate plasma propagation from a typical ECWR plasma source to a diffusion region. The simulation results for an Argon plasma generated from a cylindrical ECWR source in a processing chamber at 5 mTorr were presented in order to verify the feasibility of model application in ECWR plasma processes.