The annealing behaviour, including studies of recrystallisation kinetics and development of crystallographic texture, of two low carbon steels after different cold rolling reductions have been investigated using Optical Microscopy (OM), Electron Back-Scatter Diffraction (EBSD) and Transmission Electron Microscopy (TEM). The primary recrystallisation behaviour of 20, 50, 70 and 90% cold rolled Interstitial Free (IF) and High Strength Low Alloy (HSLA) steels was studied. The HSLA was initially processed to give a volume fraction of about 0.2 of fine pearlite colonies, which acted as mechanically hard particles. The presence of such particles on the HSLA steel significantly reduced the temperature needed for recrystallisation by enhancing the recrystallisation and acting as nucleation sites by the Particle Stimulated Nucleation (PSN) mechanism. The inhomogeneous deformation and the local orientation changes introduced in the neighbourhood of the carbide particles (i.e. the particle deformation zone) were observed using TEM and selected area electron diffraction. The JMAK model was used to analyse the recrystallisation kinetics of the two steels. The experimental data plotted according to the JMAK model could be represented by straight lines with a JMAK exponent n falling in the range from 1.4 to 2.0. The development of crystallographic textures after cold rolling reductions and subsequent recrystallisation has been investigated. The texture development is shown to be largely dependent on the rolling reduction. With increasing rolling reduction, the annealing texture show gradual intensification of α- and γ-fibre components. However, the intensity of both fibres is weaker in the HSLA steel. Despite the dominance of PSN in HSLA steel, the recrystallisation textures were similar to that of the rolling textures with weaker intensity of both fibres. To help clarify the reasons for that, in-situ EBSD experiments of recrystallising HSLA steel deformed to 50% and 70% have been carried out. It shows that the formation of the nucleus seems to occur within the deformation zones in regions away from the particle surface leading to recrystallisation textures similar to that of the rolling textures (i.e. both α- and γ-fibre exist). The validity of this assumption has been confirmed by the use of Monte Carlomodelling. This model was used to simulate, in general way, and study the phenomenon of PSN during the recrystallisation process. The simulation shows the discontinuous evolution of the subgrains in the deformation zone to form recrystallisation nuclei around the particle. It shows also the subsequent growth of these nuclei to consume the matrix region around the particle. The simulation results are shown to match with the experimentally observed features of the recrystallisation phenomena in low carbon steel containing coarse cementite particles.

Second phase particles play an important role in the recrystallization of aluminium alloys. They give rise to high level of local lattice misorientation around the particle, in particle deformation zone (PDZ) during processing. These can act as potent nucleation sites for new recrystallized grains in a process known as particle stimulated nucleation (PSN). This mechanism is essential to produce material with a more random texture and small grain size, which helps e.g. ductility and formability. A new HRDIC technique is used here in combination with EBSD to investigate the evolution of deformation structures by linking the local deformation (by Digital Image Correlation, DIC) to the lattice orientation before and after deformation by EBSD measurements and compared with the CPFEM predictions. The results show that strain is very heterogeneous during deformation and concentrates mainly in slip bands. The spacing between these bands is affected by several factors: applied strain, crystallographic orientation and the existence of small dispersoids. Thus, the relationship between the strain, particle size and rotation in the deformation zone is much more complex than predicted by existing models.

O encruamento e a recristalização do aço inoxidável ferrítico AISI 430 com adição de nióbio e microestrutura formada por grãos grosseiros foram investigados. Os aços inoxidáveis ferríticos podem ser utilizados na indústria automotiva, por exemplo, nas partes mais quentes do sistema de exaustão de gases. Neste trabalho, três composições distintas foram investigadas, variando-se as quantidades de nióbio e de intersticiais (carbono e nitrogênio). Com o objetivo de se obter uma microestrutura formada por grãos grosseiros útil para o estudo dos efeitos de orientação, amostras dos aços laminado a quente foram recozidas a 1250?C por 2 h. Após recozimento, o tamanho de grão foi medido usando o método padrão dos interceptos lineares. Para o estudo do encruamento, as placas foram laminadas a frio entre reduções de 20% e 80%. As amostras com 80% de redução foram recozidas em temperaturas variando entre 400 e 1000?C por 15 min para o estudo da recristalização. As curvas de encruamento e de amolecimento isócrono foram realizadas mediante a determinação da variação da microdureza Vickers. A caracterização microestrutural das amostras foi realizada com o auxílio das microscopias ótica (MO) e eletrônica de varredura (MEV) no modo de elétrons retroespalhados (BSE). A macrotextura foi determinada com o auxílio da difração de raios X (DRX). A microtextura foi determinada mediante o mapeamento de amostras representativas via difração de elétrons retroespalhados (EBSD). Os precipitados presentes na matriz ferrítica dos aços laminados a quente (FSS-B) foram extraídos utilizando duas rotas distintas: eletrolítica e química. A natureza cristalográfica dos precipitados foi determinada via DRX e a morfologia foi observada com o auxílio da MEV. As microestruturas recuperadas na condição inicial consistem de grãos alongados na DL e por partículas de Nb(C,N). A textura é caracterizada por componentes típicas de laminação no centro e de cisalhamento na superfície devido às grandes reduções por passe. Após recozimento, as macrografias revelaram que os aços FSS-A e FSS-B apresentam tamanho de grão similar, enquanto que o aço FSS-C apresentou tamanho de grãos menor. Os resultados de textura apresentaram as componentes CH (centro), Goss e Brass (superfície). A laminação a frio ocorreu de forma homogênea para as reduções inferiores a 50%. A partir desta redução, regiões bandeadas surgem na microestrutura. Notou-se que existe uma relação de orientação entre os grãos originais e as regiões bandeadas de modo que volumes regulares do grão giram na DT. Esta relação também foi observada nas regiões ao redor das partículas de Nb(C,N). A textura de laminação a frio é constituída pelas fibras ? e ?. A recristalização dos aços investigados ocorre em temperaturas entre 650 e 850ºC. A partir da microtextura, não foram observadas componentes de textura associadas ao mecanismo PSN. O aço FSS-R apresentou componentes pertencentes à fibra ?, enquanto que os aços FSS-A, FSS-B e FSS-C apresentaram além da fibra ?, componentes CH e fibra η. O recozimento em temperaturas elevadas promove o crescimento de grão e a conseqüente formação das componentes CH e fibra η. / Work hardening and recrystallization behaviors of coarse-grained Nb-containing AISI 430 ferritic stainless steels were investigated. Ferritic stainless steels can be used in automotive industry in hot parts of the gas exhaust system. In this work, three different compositions were investigated varying niobium and interstitial contents (carbon and nitrogen). Aiming to obtain a useful coarse-grained microstructure for the study of orientation effects, hot-rolled samples were annealed at 1250°C for 2 h. After annealing, grain size was determined using a standard linear intercept method. Samples were cold rolled to reductions varying from 20% up to 80%. Samples after 80% cold rolling were annealed at temperatures ranging from 400°C up to 1000°C for 15 min to investigate their recrystallization behavior. Vickers microhardness testing was performed to follow hardening and softening behaviors in the samples. Microstructural characterization of the samples was performed using both light optical and scanning electron (SEM) microscopies in the backscattered electron mode (BSE). The macrotexture was determined by X-ray diffraction. Electron backscatter diffraction (EBSD) measurements were carried out in representative samples to determine microtexture. Precipitates in hot-rolled samples (FSS-B) were both electrolytically and chemically extracted. The crystallography of precipitates was determined by X-ray diffraction and their morphology was observed using SEM. The microstructures in hot-rolled condition consist of elongated recovered grains and dispersed Nb(C,N) particles. Texture is characterized by typical rolling components in the center layer, whereas shear components appear in the surface layers. After annealing, FSS-A and FSS-B steels displayed similar grain size, whereas FSS-C displayed a finer one. The results of macrotexture show CH in the center layer and both Goss and Brass components at the surface layer. The microstructure of samples cold rolled up to reductions below 50% do not display banding. Above 50% reduction, deformation heterogeneities (bands) appear in the microstructure. The banded regions and those around coarse particles tend to rotate in TD. Cold-rolling texture displays both ? and ? fiber components. Recrystallization takes place in temperature between 650 and 850ºC. Texture due to PSN mechanism was not observed. The FSS-C steel displayed only components belonging to ? fiber, whereas FSS-A, FSS-B e FSS-C steels displayed besides ? fiber, components CH and those belonging to η fiber. Grain-growth annealing at high temperature contributes to increase CH and η fiber components.

O encruamento e a recristalização do aço inoxidável ferrítico AISI 430 com adição de nióbio e microestrutura formada por grãos grosseiros foram investigados. Os aços inoxidáveis ferríticos podem ser utilizados na indústria automotiva, por exemplo, nas partes mais quentes do sistema de exaustão de gases. Neste trabalho, três composições distintas foram investigadas, variando-se as quantidades de nióbio e de intersticiais (carbono e nitrogênio). Com o objetivo de se obter uma microestrutura formada por grãos grosseiros útil para o estudo dos efeitos de orientação, amostras dos aços laminado a quente foram recozidas a 1250?C por 2 h. Após recozimento, o tamanho de grão foi medido usando o método padrão dos interceptos lineares. Para o estudo do encruamento, as placas foram laminadas a frio entre reduções de 20% e 80%. As amostras com 80% de redução foram recozidas em temperaturas variando entre 400 e 1000?C por 15 min para o estudo da recristalização. As curvas de encruamento e de amolecimento isócrono foram realizadas mediante a determinação da variação da microdureza Vickers. A caracterização microestrutural das amostras foi realizada com o auxílio das microscopias ótica (MO) e eletrônica de varredura (MEV) no modo de elétrons retroespalhados (BSE). A macrotextura foi determinada com o auxílio da difração de raios X (DRX). A microtextura foi determinada mediante o mapeamento de amostras representativas via difração de elétrons retroespalhados (EBSD). Os precipitados presentes na matriz ferrítica dos aços laminados a quente (FSS-B) foram extraídos utilizando duas rotas distintas: eletrolítica e química. A natureza cristalográfica dos precipitados foi determinada via DRX e a morfologia foi observada com o auxílio da MEV. As microestruturas recuperadas na condição inicial consistem de grãos alongados na DL e por partículas de Nb(C,N). A textura é caracterizada por componentes típicas de laminação no centro e de cisalhamento na superfície devido às grandes reduções por passe. Após recozimento, as macrografias revelaram que os aços FSS-A e FSS-B apresentam tamanho de grão similar, enquanto que o aço FSS-C apresentou tamanho de grãos menor. Os resultados de textura apresentaram as componentes CH (centro), Goss e Brass (superfície). A laminação a frio ocorreu de forma homogênea para as reduções inferiores a 50%. A partir desta redução, regiões bandeadas surgem na microestrutura. Notou-se que existe uma relação de orientação entre os grãos originais e as regiões bandeadas de modo que volumes regulares do grão giram na DT. Esta relação também foi observada nas regiões ao redor das partículas de Nb(C,N). A textura de laminação a frio é constituída pelas fibras ? e ?. A recristalização dos aços investigados ocorre em temperaturas entre 650 e 850ºC. A partir da microtextura, não foram observadas componentes de textura associadas ao mecanismo PSN. O aço FSS-R apresentou componentes pertencentes à fibra ?, enquanto que os aços FSS-A, FSS-B e FSS-C apresentaram além da fibra ?, componentes CH e fibra η. O recozimento em temperaturas elevadas promove o crescimento de grão e a conseqüente formação das componentes CH e fibra η. / Work hardening and recrystallization behaviors of coarse-grained Nb-containing AISI 430 ferritic stainless steels were investigated. Ferritic stainless steels can be used in automotive industry in hot parts of the gas exhaust system. In this work, three different compositions were investigated varying niobium and interstitial contents (carbon and nitrogen). Aiming to obtain a useful coarse-grained microstructure for the study of orientation effects, hot-rolled samples were annealed at 1250°C for 2 h. After annealing, grain size was determined using a standard linear intercept method. Samples were cold rolled to reductions varying from 20% up to 80%. Samples after 80% cold rolling were annealed at temperatures ranging from 400°C up to 1000°C for 15 min to investigate their recrystallization behavior. Vickers microhardness testing was performed to follow hardening and softening behaviors in the samples. Microstructural characterization of the samples was performed using both light optical and scanning electron (SEM) microscopies in the backscattered electron mode (BSE). The macrotexture was determined by X-ray diffraction. Electron backscatter diffraction (EBSD) measurements were carried out in representative samples to determine microtexture. Precipitates in hot-rolled samples (FSS-B) were both electrolytically and chemically extracted. The crystallography of precipitates was determined by X-ray diffraction and their morphology was observed using SEM. The microstructures in hot-rolled condition consist of elongated recovered grains and dispersed Nb(C,N) particles. Texture is characterized by typical rolling components in the center layer, whereas shear components appear in the surface layers. After annealing, FSS-A and FSS-B steels displayed similar grain size, whereas FSS-C displayed a finer one. The results of macrotexture show CH in the center layer and both Goss and Brass components at the surface layer. The microstructure of samples cold rolled up to reductions below 50% do not display banding. Above 50% reduction, deformation heterogeneities (bands) appear in the microstructure. The banded regions and those around coarse particles tend to rotate in TD. Cold-rolling texture displays both ? and ? fiber components. Recrystallization takes place in temperature between 650 and 850ºC. Texture due to PSN mechanism was not observed. The FSS-C steel displayed only components belonging to ? fiber, whereas FSS-A, FSS-B e FSS-C steels displayed besides ? fiber, components CH and those belonging to η fiber. Grain-growth annealing at high temperature contributes to increase CH and η fiber components.

The ability to generate three dimensional (3D) microstructures in solids is of great importance in understanding their true nature, as it eliminates speculation about the spatial distribution of features associated with conventional two dimensional (2D) imaging techniques. There are several recently-developed 3D techniques for determining the spatial distribution of microstructural features, each with a given resolution. There is considerable interest in the development of a specific serial sectioning methodology, termed 3D electron backscatter diffraction (3D-EBSD), which combines a focused ion beam (FIB) with EBSD interfaced to a field emission gun scanning electron microscope. Here, FIB is used as a serial sectioning device for cutting parallel slices of single- and multi-phase materials with a site-specific accuracy of up to 50 nm. Each consecutive slice is mapped by EBSD and the complete dataset combined using advanced computer algorithms to generate a volume of a material whereby the true crystallographic features can be analyzed at submicron resolution. The aims of the thesis was to develop 3D-EBSD into a powerful materials analysis tool and use it to resolve several issues concerning the nature of the deformed state and the nucleation and the growth behaviour of recrystallizing grains. The study commenced with an investigation into the effect of material type (restricted to face centred cubic AI, Cu and Au metallic crystals), FIB milling conditions and EBSD software variables on the quality of EBSD patterns generated on ion-milled surfaces of these materials. The effect of material type on EBSD pattern quality following FIB milling was found to be significant with relatively poor quality EBSD patterns obtained for metals of low atomic number. It was demonstrated, particularly for the high atomic number metals, that moderate FIB milling currents (~1-5nA) generated good quality EBSD maps from a given ion-milled surface. This preliminary work was necessary for balancing the time required for serial sectioning during 3D-EBSD and the generation of sufficient quality EBSD maps from each ion-milled surface. The outcomes of this investigation were applied to two major 3D-EBSD investigations on the microstructural and crystallographic characteristics of: (i) deformation features generated in a cold rolled interstitial free (IF) steel, with particular emphasis on the formation of microbands; and (ii) recrystallization of a cold rolled nickel alloy containing coarse (>1 ??m) silica particles, with particular attention given to the generation of particle deformation zones and their influence on nucleation and growth of recrystallizing grains including particle stimulated nucleation (PSN), twin formation during PSN and the growth behaviour of various types of grain boundary into the deformation microstructure. The foregoing 3D-EBSD studies were significant as they revealed various microstructural and crystallographic features not usually clearly evident in conventional 2D micrographs obtained by either EBSD or optical metallography. For example, the technique demonstrated that microbands in cold rolled IF steel consist of irregular curved surfaces that reconcile findings that microbands straight and aligned parallel to slip planes when viewed in normal direction-rolling direction sections but are wavy in transverse direction-rolling direction sections. Three slip planes were found within the angular range of the curved surface of the microband, which indicates that multiple slip planes are operative during deformation. The work also showed the influence of particle diameter on the misorientations generated within particle deformation zones and clearly showed that particle stimulated nucleation (PSN) occurred at particles greater than 1.5-2 ??m. It was observed that PSN in the nickel sample also generates contiguous grains separated by both coherent and incoherent twin boundaries and, on further growth of these grains into the matrix, the coherent boundary dominates and remains parallel to the primary growth direction of the grains.

Network infrastructures often need to stage content so that it is accessible to consumers. The standard solution, deploying the content on a centralised server, can be inadequate in several situations. Our thesis is that information encoded in social networks can be used to tailor content staging decisions to the user base and thereby build better data delivery infrastructures. This claim is supported by two case studies, which apply social information in challenging situations where traditional content staging is infeasible. Our approach works by examining empirical traces to identify relevant social properties, and then exploits them. The first study looks at cost-effectively serving the ``Long Tail'' of rich-media user-generated content, which need to be staged close to viewers to control latency and jitter. Our traces show that a preference for the unpopular tail items often spreads virally and is localised to some part of the social network. Exploiting this, we propose Buzztraq, which decreases replication costs by selectively copying items to locations favoured by viral spread. We also design SpinThrift, which separates popular and unpopular content based on the relative proportion of viral accesses, and opportunistically spins down disks containing unpopular content, thereby saving energy. The second study examines whether human face-to-face contacts can efficiently create paths over time between arbitrary users. Here, content is staged by spreading it through intermediate users until the destination is reached. Flooding every node minimises delivery times but is not scalable. We show that the human contact network is resilient to individual path failures, and for unicast paths, can efficiently approximate flooding in delivery time distribution simply by randomly sampling a handful of paths found by it. Multicast by contained flooding within a community is also efficient. However, connectivity relies on rare contacts and frequent contacts are often not useful for data delivery. Also, periods of similar duration could achieve different levels of connectivity; we devise a test to identify good periods. We finish by discussing how these properties influence routing algorithms.

The fidelity of biological processes and reactions, inspite of the widespread diversity, is programmed by highly specific physico-chemical principles. This underlines our basic understanding of different interesting phenomena of biological relevance, ranging from enzyme specificity to allosteric communication, from selection of fold to structural organization / states of oligomerization, from half-sites-reactivity to reshuffling of the conformational free energy landscape, encompassing the dogma of sequence-structure dynamics-function of macromolecules. The role of striking an optimal balance between rigidity and flexibility in macromolecular 3D structural organisation is yet another concept that needs attention from the functional perspective. Needless to say that the variety of protein structures and conformations naturally leads to the diversity of their function and consequently many other biological functions in general. Classical models of allostery like the ‘MWC model’ or the ‘KNF model’ and the more recently proposed ‘population shift model’ have advanced our understanding of the underlying principles of long range signal transfer in macromolecules. Extensive studies have also reported the importance of the fold selection and 3D structural organisation in the context of macromolecular function. Also ligand induced conformational changes in macromolecules, both subtle and drastic, forms the basis for controlling several biological processes in an ordered manner by re-organizing the free energy landscape. The above mentioned biological phenomena have been observed from several different biochemical and biophysical approaches. Although these processes may often seem independent of each other and are associated with regulation of specialized functions in macromolecules, it is worthwhile to investigate if they share any commonality or interdependence at the detailed atomic level of the 3D structural organisation. So the nagging question is, do these diverse biological processes have a unifying theme, when probed at a level that takes into account even subtle re-orchestrations of the interactions and energetics at the protein/nucleic acid side-chain level. This is a complex problem to address and here we have made attempts to examine this problem using computational tools. Two methods have been extensively applied: Molecular Dynamics (MD) simulations and network theory and related parameters. Network theory has been extensively used in the past in several studies, ranging from analysis of social networks to systems level networks in biology (e.g., metabolic networks) and have also found applications in the varied fields of physics, economics, cartography and psychology. More recently, this concept has been applied to study the intricate details of the structural organisation in proteins, providing a local view of molecular interactions from a global perspective. On the other hand, MD simulations capture the dynamics of interactions and the conformational space associated with a given state (e.g., different ligand-bound states) of the macromolecule. The unison of these two methods enables the detection and investigation of the energetic and geometric re-arrangements of the 3D structural organisation of macromolecule/macromolecular complexes from a dynamical or ensemble perspective and this has been one of the thrust areas of the current study. So we not only correlate structure and functions in terms of subtle changes in interactions but also bring in conformational dynamics into the picture by studying such changes along the MD ensemble. The focus was to identify the subtle rearrangements of interactions between non-covalently interacting partners in proteins and the interacting nucleic acids. We propose that these rearrangements in interactions between residues (amino acids in proteins, nucleic acids in RNA/DNA) form the common basis for different biological phenomena which regulates several apparently unrelated processes in biology. Broadly, the major goal of this work is to elucidate the physico-chemical principles underlying some of the important biological phenomena, such as allosteric communication, ligand induced modulation of rigidity/flexibility, half-sites-reactivity and so on, in molecular details. We have investigated several proteins, protein-RNA/DNA complexes to formulate general methodologies to address these questions from a molecular perspective. In the process we have also specifically illuminated upon the mechanistic aspects of the aminoacylation reaction by aminoacyl-tRNA synthetases like tryptophanyl and pyrrolysyl tRNA synthetase, structural details related to an enzyme catalyzed reaction that influences the process of quorum sensing in bacteria. Further, we have also examined the ‘dynamic allosterism’ that manipulates the activity of MutS, a prominent component of the DNA bp ‘mismatch repair’ machinery. Additionally, our protein structure network (PSN) based studies on a dataset of Rossmann fold containing proteins have provided insights into the structural signatures that drive the adoption of a fold from a repertoire of diverse sequences. Ligand induced percolations distant from the active sites, which may be of functional relevance have also been probed, in the context of the S1A family of serine proteases. In the course of our investigation, we have borrowed several concepts of network parameters from social network analysis and have developed new concepts. The Introduction (Chapter-1) summarizes the relevant literature and lays down a suitable background for the subsequent chapters in the thesis. The major questions addressed and the main goal of this thesis are described to set an appropriate stage for the detailed discussions. The methodologies involved are discussed in Chapter-2. Chapter-3 deals with a protein, LuxS that is involved in the bacterial quorum sensing; the first part of the chapter describes the application of network analysis on the static structures of several LuxS proteins from different organisms and the second part of this chapter describes the application of a dynamic network approach to analyze the MD trajectories of H.pylori LuxS. Chapter-4 focuses on the investigation of human tryptophanyl-tRNA synthetase (hTrpRS), with an emphasis to identify ligand induced subtle conformational changes in terms of the alternation of rigidity/flexibility at different sites and the re-organisation of the free energy landscape. Chapter-5 presents a novel application of a quantum clustering (QC) technique, popular in the fields of pattern recognition, to objectively cluster the conformations, sampled by molecular dynamics simulations performed on different ligand bound structures of the protein. The protein structure network (PSN) in the earlier studies were constituted on the basis of geometric interactions. In Chapters 6 and 7, we describe the networks (proteins+nucleic acids) using interaction energy as edges, thus incorporating the detailed chemistry in terms of an energy-weighted complex network. Chapter-6 describes an application of the energy weighted network formalism to probe allosteric communication in D.hafniense pyrrolysyl-tRNA synthetase. The methodology developed for in-depth study of ligand induced changes in DhPylRS has been adopted to the protein MutS, the first ‘check-point protein’ for DNA base pair (bp) mismatch repair. In Chapter-7, we describe the network analysis and the biological insights derived from this study (the work is done in collaboration with Prof. David Beveridge and Dr. Susan Pieniazek). Chapter-8 describes the application of a network approach to capture the ligand-induced subtle global changes in protein structures, using a dataset of high resolution structures from the S1A family of serine proteases. Chapter-9 deals with probing the structural rationale behind diverse sequences adopting the same fold with the NAD(P)-binding Rossmann fold as a case study. Future directions are discussed in the final chapter of the thesis (Chapter-10).

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