Utilization of amorphous metallic alloy has received much attention for use in numerous microelectronic and electrochemical devices since they provide unique electrical, thermal conductivity, and magnetic properties. To develop these functional properties, it is essential to understand the amorphous structure and the property relationships. First principles calculations provide insight into the structure, thermodynamic stability, electronic and magnetic properties of amorphous alloys. For Ru- and Co-based alloys, the thermodynamic stability was examined by calculating the mixing energy along with those of crystalline counterparts. The amorphous RuP, CoP, RuB, and CoB alloys, become energetically more favorable than their crystalline counterparts at moderate P(B) content. The atomistic structures have well-defined local structures depending on the atomic size ratio and electronic interactions between constituent elements. Their local ordering is attributed to strong p-d hybridization, which contributes to stabilizing the Ru(Co)-P(B) alloys. Surface segregation of P(B) and interfacial adhesion with copper were also studied. Li-X (X: Si, Ge, and Sn) were examined when 1 or 2 Li atoms are inserted into the interstitial sites. Li insertion in the tetrahedral site, which is the most preferable site in the diamond matrix, causes outward displacement and charge localization around the X neighbors, thereby weakening of the covalent bonds leading to destabilization of the host matrix. We present the energetics, structure, electronic and mechanical properties of crystalline and amorphous Li-X (X: Si, Ge, Sn, and Si+Sn) alloys. Our calculations show that the incorporation of Li leads to disintegration of the tetrahedrally-bonded X network into small clusters of various shapes. Electronic structure analysis highlights that the charge transfer leads to weakening or breaking of X bonds with the growing splitting between s and p states, and consequently the Li-X alloys softens with increasing Li content. / text

We investigated dynamic response of Cu46Zr54 metallic glass under adiabatic planar shock wave loading (one-dimensional strain) with molecular dynamics simulations, including Hugoniot (shock) states, shock-induced plasticity, and spallation. The Hugoniot states are obtained up to 60 GPa along with the von Mises shear flow strengths, and the dynamic spall strengths, at different strain rates and temperatures. For the steady shock states, a clear elastic-plastic transition is identified. The local von Mises shear strain analysis is used to characterize local deformation, and the Voronoi tessellation analysis, the corresponding local structures at various stages of shock, release, tension and spallation. The plasticity in this glass, manifested as localized shear transformation zones, is of local structure rather than thermal origin, and void nucleation occurs preferentially at the highly shear-deformed regions. The Voronoi and shear strain analyses show that the atoms with different local structures are of different shear resistances that lead to shear localization. Additionally, we performed large-scale molecular dynamics simulations to investigate plasticity in Cu/Cu46Zr54 glass nanolaminates under uniaxial compression. Partial and full dislocations are observed in the Cu layers, and screw dislocations, near the amorphous−crystalline interfaces (ACIs). Shear bands are directly induced by the dislocations in the crystalline Cu layer through ACIs, and grow from the ACIs into the glass layers and absorb ambient shear transformation zones. Plasticity in the glass layers is realized via pronounced, stable shear banding. As the last part of the dissertation, we investigated with nonreactive molecular dynamics simulations, the dynamic response of phenolic resin and its carbon-nanotube (CNT) composites to shock wave compression. For phenolic resin, our simulations yielded shock states in agreement with experiments on similar polymers, except the "phase change" observed in experiments, indicating that such phase change is chemical in nature. The elastic–plastic transition is characterized by shear stress relaxation and atomic-level slip, and phenolic resin shows strong strain hardening. Shock loading of the CNT-resin composites was applied parallel or perpendicular to the CNT axis, and the composites demonstrated anisotropy in wave propagation, yield and CNT deformation. Our simulations suggested that the bulk shock response of the composites depends on the volume fraction, length ratio, impact cross-section, and geometry of the CNT components; the short CNTs in current simulations had insignificant effect on the bulk response of resin polymer.

Apresentaremos uma série de estudos realizados sobre o tema anisotropias magnéticas induzidas (Kind) em 1igas amorfas. Foram usados vários tipos de tratamentos térmico, com o objetivo de obtermos uma visão amp1a do assunto. A análise teórica dos dados de Kind e de \"after-effect\" magnético (MAE) foi feita com um modelo baseado em sistemas de dois níveis (TLS). A partir da análise dos dados experimentais obtém-se um largo espectro de energias de ativação. Estas energias estão relacionadas aos tempos de re1axação, através da equação de Arrhenius: = 0 exp (E/kT), onde o pré-fator 0 é da ordem do inverso da frequência de Debye. Construiu-se um forno para tratamentos térmicos em ligas amorfas, que opera em um eletroimã de 6 kOe e desenvolveu-se os programas para análise de dados experimentais. Essas facilidades, associadas ao traçador de curvas de histerese, permitiram os seguintes estudos de anisotropias induzidas em ligas amorfas ferromagnéticas: 1. Estudo da cinética de indução de anisotropia por tratamentos térmicos na faixa de temperatura de 190 a 250 °C, para fitas amorfas \"as cast\" de composição C070.4Fe4.6 Si15B10. Com o modelo TLS pode-se obter o espectro de energias de ativação, que se apresentou na faixa de energia de 1.50 a 1.85eV, com 0 = 1.6 x 10-13s. 2. Realizou-se também o estudo da indução de anisotropia na presença de um campo magnético de 5 kOe, para amostras pré-tratadas a 400 °C por 10 minutos. Estas são de composição Co77-X Mnx Si14 B9, com X = 2 e 6 e foram submetidas a tratamentos isotérmicos a temperaturas entre 240 e 325 °C. Neste caso pode-se verificar que para as duas composiQ6es 0 pré-fator é maior ( 10-8S). Quanto ao espectro de energias de ativação, em ambos os casos, apresenta-se na faixa de energias de 1.10 a 1.55 eV. 3.Outro experimento, neste caso com amostras de composição Co67Fe4Mo1Si12B16 consistiu na aplicação, à temperatura ambiente, de tensão mecânica ( 800 MPa) na fita, enquanto se monitorava a energia de anisotropia magnética. Pudemos então observar uma variação continua dessa propriedade e posteriormente uma recuperação completa da condição inicial, com a remoção da tensão aplicada, mostrando um processo de caráter anelástico. Procuramos estudar os efeitos de tensões mecânicas sobre as propriedades magnéticas de amostras com composição Co67Fe4Mo1Si12B16. Duas linhas de trabalho foram adotadas: 4) Numa olhou-se para a isotropia induzida em amostras pré-tratadas, quando submetidas a tratamentos térmicos na faixa de temperatura de 200 a 400 °C, sob tensão mecânica de 500 MPa e posteriormente na ausência de tensão. A partir desses ensaios foi possível se separar uma componente plástica e outra anelástica na anisotropia induzida. 5) Noutra, obteve-se o comportamento do MAE, para amostras com e sem tensão mecânica aplicada, no intervalo de 300 a 500 K. Os resultados obtidos demonstram a não existência de efeitos plásticos ou anelásticos nas energias de ativação dos processos envolvidos no \"after-effect\". Por outro lado verificamos uma grande alteração na intensidade do MAE, devido à tensão. / In this thesis we will present a series of studies related to induced magnetic anisotropies (Kind) in amorphous alloys. In order to get a more general view of this theme, we used several different kinds of annealings. The theoretical analysis of the data of Kind and magnetic after-effect (MAE) was performed using a model based on two-level systems (TLS). From the analysis of the experimental data we get a large actiyation energy spectrum. These energies are related to the relaxation times, through the Arrheniu \'s expression: = 0 exp(E/kT), where the pre-factor 0 is of the order of the inverse of the Debye frequency . We constructed a furnace for thermal annealing of the amorphous alloys, which operates within an electromagnet producing 6 kOe. We also wrote, the computer programs for the analysis of the experimental data. These facilities, together with the hysteresis loop tracer permitted the followings studies of the induced anisotropies in amorphous alloys: 1) A study of the kinetics of the induced anisotropy by annealing in the temperature range from 190 to 250 °C, in as cast amorphous ribbons of composition Co70.4Fe4.6Si15B10. Using the TLS model we obtained the activation energy spectrum. It presents two peaks in the energy range from 1.50 to 1.85eV and a pre-factor 0= 1.6x10-13 s. 2) Using a 5 KOe magnetic field we studied the effects of a Field annealing treatment in samples pre-annealed at 400 °C for 10 minutes. The isothermal annealings were made in Co70-XMnXSi14B9 with x = 2 and 6, in the temperature range from 240 to 325 °C. In this case we observed for these two compositions a larger pre-factor ( 10-8s) than before. The activation-energy spectra, for the both composition, are found in the energy range from 1.10 to 1.55eV. 3) Another experiment was done using samples of Co67Fe4Mo1Si12B16. We applied a tensile stress (800MPa) to the ribbon and measured the magnetic anisotropy energy. We observed a continuous variation of this energy and, after removal of the stress, the sample recuperated its initial condition, showing a process characteristically anelastic. We studied the effects of mechanic stress on the magnetic properties of samples of composition Co67Fe4Mo1Si12B16. We worked in two directions: 4) We studied the induced anisotropy in pre-annealed samples, submitted to annealing in the range from 200 to 400 °C, under a tensile stress of 500MPa and without applied stress. From these resul ts we can separate a plastic and an anelastic component in the induced anisotropy. 5) In other, we studied the behavior of the MAE, for samples with and with and without applied tensile stress, in the range from 300 to 500 K. The results obtained show neither plastic nor anelastic effects on the activation energies of the processes involved in the MAE. On the other h~nd we can see a strong alteration in the intensity of the MAE, due the stress.

In this dissertation, nano-manufacturing of amorphous alloys for electro-catalytic applications is reported and the role of chemistry and active surface area on catalytic behavior is discussed. The catalytic activity of recently developed platinum and palladium-based metallic glasses was studied using cyclic voltammetry and localized electrochemical techniques. The synergistic effect between platinum and palladium was shown for amorphous alloys containing both these elements. The mechanism for superior catalytic behavior was investigated through electronic structure and surface chemical state of the alloys. A correlation between the work function and catalytic performance of the amorphous alloys with widely varying chemistries was established. To address the high cost associated with the noble-metal containing catalysts, the performance of non-noble Ni-P amorphous catalyst was evaluated for electro-catalysis. A facile pulsed electrodeposition approach was used for the nano-manufacturing of these amorphous catalysts. This nano-manufacturing route allowed the synthesis of fully amorphous nano-wires at room temperature for alloys with little or no noble-metal content. A wide range of nano-wires with varying aspect ratios from 25 to 120 was synthesized using commercially obtained anodic aluminum oxide (AAO) nano-molds. Cyclic voltammetry and chrono-amperometry demonstrated superior performance in terms of electrocatalytic activity and stability of the metallic glass nano-wires towards electro-oxidation of methanol. The mechanism for amorphization during pulsed electrodeposition is discussed and compared with the conventional approach of rapid quenching of the liquid melt.

L'objectiu de la tesi és estudiar la cinètica de les cristal·litzacions primàries en vidres metàl·lics mitjançant simulacions de tipus phase field. Una cristal·lització primària és una transició de fase sòlid-sòlid on la fase que cristal·litza (fase transformada o fase secundaria) té una composició química diferent de la fase precursora (fase no transformada o fase primària).Les dades experimentals obtingudes a partir de l'estudi calorimètric de cristal·litzacions primàries s'analitzen generalment en el marc del model KJMA (Kolmogorov, Johnson & Mehl, Avrami). Aquest model proporciona l'evolució temporal de la fracció transformada basant-se en tres hipòtesis: - Els nuclis de la fase secundaria estan distribuïts aleatòriament en tot l'espai.- El creixement d'aquests nuclis és isotròpic.- El creixement s'atura únicament per xoc directe (hard impingement).En la cristal·lizació de vidres metàl·lics s'ha observat experimentalment un alentiment de la cinètica respecte del comportament calculat emprant la citada cinètica KJMA. Aquest alentiment s'explica a la literatura en base a que en aquest tipus de transformacions, controlades per difusió, la interacció entre els cristalls no és directa sinó que es produeix a través dels perfils de concentració (soft impingement) i, a més, l'evolució d'aquests perfils de concentració causa canvis en la concentració de la matriu amorfa, estabilitzant la i per tant fent que la nucleació de nous cristalls esdevingui no aleatòria. Diversos autors han proposat modificacions del model KJMA per tal d'intentar superar aquestes limitacions, basats bé en consideracions geomètriques, bé en aproximacions de camp mitjà. A pesar de tot, cap d'aquests models és capaç d'explicar satisfactòriament la cinètica observada en cristal·litzacions primàries. L'objectiu d'aquest treball ha estat la simulació realista de la cinètica de les transformacions primàries per trobar una explicació consistent a les diferències observades entre les dades experimentals i els models teòrics disponibles.Per tal de poder descriure de forma realista el procés de cristal·lització primària s'ha d'estudiar el procés de nucleació i creixement de la fase secundaria alhora que es resol l'equació de difusió en la fase primària. En aquest treball s'ha emprat un model de simulació phase field que permet estudiar aquest sistema introduint una nova variable lligada al camp de concentració que pren dos valors diferents segons es tracti de fase transformada o no transformada. Amb aquest tipus de models també es poden introduir diferents protocols de nucleació i per tant estudiar independentment els efectes de la nucleació en la cinètica. D'aquesta manera s'han realitzat simulacions en 2 i 3 dimensions de cristal·litzacions primàries amb diferents graus de fracció transformada final). Els resultats de les simulacions s'ha comparat amb el model KJMA i, contra el que es preveia, s'ha obtingut un bon acord entre les fraccions transformades del model KJMA i de les simulacions. Donat que el model KJMA no reprodueix satisfactòriament el comportament experimental d'aquest resultat es dedueix que ni el soft impingement ni la nucleació no aleatòria son les responsables de l'alentiment de la cinètica obtingut en cristal·litzacions primàries. Per tal de trobar una explicació físicament convincent del comportament observat experimentalment s'ha aprofundit en l'estudi teòric de les cristali·litzaciones primàries, incloent-hi l'efecte dels canvis composicionals que tenen lloc en la matriu a mesura que la transformació es produeix. Aquest fet, tot i ser conegut a la bibliografia, ha estat sistemàticament ignorat en l'elaboració de models cinètics. En concret, s'ha fet palès que canvis en la composició química de la fase primària han d'afectar de forma radical a la viscositat, que varia fortament a prop de la transició vitrea, i han de produir canvis en les propietats de transport atòmic. Això s'ha modelat a través de l'assumpció d'un coeficient de difusió depenent de la concentració, en base a la relació modificada d'Stokes-Einstein entre la viscositat i el coeficient de difusió. Les simulacions phase-field amb un coeficient de difusió d'aquest tipus donen lloc a una cinètica més lenta i que mostra un acord excel·lent amb la cinètica experimentalment observada en cristal·litzacions primàries de vidres metàl·lics. Per tant, les simulacions phase field confirmen que la cinètica de les cristal·litzacions primàries està controlada fonamentalment pel canvi en les propietats de transport atòmic, mentre que els efectes de soft impingement i nucleació no aleatoria, tot i estar presents, son secundaris. / El objetivo de la tesi es estudiar la cinética de las cristalizaciones primarias en vidrios metálicos mediante simulaciones de tipo phase field. Una cristalización primaria es una transición de fase sólido-sólido donde la fase que cristaliza (fase transformada o fase secundaria) tiene una composición química diferente a la fase precursora (fase no transformada o fase primaria).Los datos experimentales obtenidos a partir del estudio calorimétrico de cristalizaciones primarias se analizan generalmente en el marco del modelo KJMA (Kolmogorov, Johnson & Mehl, Avrami). Este modelo proporciona la evolución temporal de la fracción transformada basándose en tres hipótesis: - Los núcleos de la fase secundaria están distribuidos aleatoriamente en todo el espacio- El crecimiento de estos núcleos es isotrópico- El crecimiento se detiene únicamente por choque directo (hard impingement).En la cristalización de vidrios metálicos se ha observado experimentalmente un retardo de la cinética respecto del comportamiento calculado usando la cinética KJMA. Este retardo se explica en la literatura en base a que en este tipo de transformaciones, controladas por difusión, la interacción entre los cristales no es directa sino que se produce a través de los perfiles de concentración (soft impingement) y, además, la evolución de estos perfiles de concentración causa cambios en la concentración de la matriz amorfa, estabilizándola y por tanto haciendo que la nucleación de nuevos cristales sea no aleatoria. Varios autores han propuesto modificaciones del modelo KJMA para intentar superar estas limitaciones, basados bien en consideraciones geométricas, bien en aproximaciones de campo medio. A pesar de todo, ninguno de estos modelos es capaz de explicar satisfactoriamente la cinética observada en cristalizaciones primarias. El objetivo de este trabajo ha sido la simulación realista de la cinética de las transformaciones primarias para hallar una explicación consistente a las diferencias entre los datos experimentales y los modelos teóricos disponibles.Para describir de manera realista el proceso de cristalización primaria se tiene que estudiar el proceso de nucleación y crecimiento de la fase secundaria a la vez que se resuelve la ecuación de difusión en la fase primaria. En este trabajo se ha usado un modelo de simulación phase-field que permite estudiar este sistema introduciendo una nueva variable ligada al campo de concentración que toma dos valores diferentes según se trate de fase transformada o no transformada. Con este tipo de modelos también se pueden introducir diferentes protocolos de nucleación y por tanto estudiar independientemente los efectos de la nucleación en la cinética. De esta manera se han realizado simulaciones en 2 y 3 dimensiones de cristalizaciones primarias con diferentes grados de fracción transformada final. Los resultados de la simulaciones se han comparado con el modelo KJMA y, en contra de lo que se preveía, se ha obtenido un buen acuerdo entre las fracciones transformadas del modelo KJMA y de las simulaciones. Dado que el modelo KJMA no reproduce satisfactoriamente el comportamiento experimental, de este resultado se deduce que ni el soft impingement ni la nucleación no aleatoria son las responsables del retardo en la cinética obtenido en cristalizaciones primarias.Para encontrar una explicación físicamente convincente del comportamiento observado experimentalmente se ha profundizado en el estudio teórico de las cristalizaciones primarias, incluyendo el efecto de los cambios composicionales que tienen lugar en la matriz a medida que la transformación se produce. Este hecho, aún y ser conocido en la bibliografía, ha sido sistemáticamente ignorado en la elaboración de modelos cinéticos. En concreto, se ha hecho patente que cambios en la composición química de la fase primaria tienen que afectar de forma radical a la viscosidad, que varía fuertemente cerca de la transición vítrea, y tienen que producirse cambios en las propiedades de transporte atómico. Esto se ha modelado a través de la asunción de un coeficiente de difusión dependiente de la concentración, en base a la relación de Stokes-Einstein modificada entre la viscosidad y el coeficiente de difusión. Las simulaciones phsae-field con un coeficiente de difusión de este tipo dan lugar a una cinética más lenta y que muestra un acuerdo excelente con la cinética experimentalmente observada en cristalizaciones primarias de vidrios metálicos. Por tanto, las simulaciones phase-field confirman que la cinética de las cristalizaciones primarias está controlada fundamentalmente por los cambios en las propiedades de transporte atómico, mientras que los efectos de soft-impingement y nucleación no aleatoria, aún y estar presentes, son secundarios. / The aim of this thesis is to study the kinetics of primary crystallization in metallic glasses by means of phase-field simulations. A primary crystallization is a solid-solid phase transformation where the crystallized phase (transformed phase or secondary phase) has a chemical composition different than the precursor phase (untransformed phase or primary phase).Experimental data from calorimetric studies of primary crystallization are usually studied in the framework of the KJMA model (Kolmogorov, Johnson & Mehl, Avrami). This model yields the temporal evolution of the transformed fraction on the basis of three main assumptions: - A random distribution of particle nuclei of the secondary phase- The growth of these nuclei is isotropic- The growth is only halted by direct collisions (hard impingement).In the crystallization of metallic glasses, a slowing down of the kinetics respect the behavior calculated with the KJMA kinetics has been observed. This delay is explained in the literature by the fact that in this kind of transformations, that are diffusion controlled, the interaction between the crystals is not direct but through the concentration profiles (soft impingement) and moreover, the evolution of these profiles causes changes in the concentration of the amorphous matrix, stabilizing it and thus, the nucleation of new nuclei become non random. Several authors had proposed modifications to the KJMA model to try to overcome these limitations, based either on geometrical considerations or in mean field approaches. However, none of these models is able to explain the observed kinetics in primary crystallizations. The aim of this work has been the realistic simulation of the kinetics of primary crystallization to find a explanation to the differences between the experimental data and the available theoretical models.In order to describe in a realistic way the process of a primary crystallization, the nucleation and growth process of the secondary phase has to be studied at the same time that the diffusion equation is solved in the primary phase. In this work, it has been used a phase field model for the simulations that allows to study this system introducing a new variable, coupled to the concentration field, that takes two different values in each of the existing phases. With these kinds of models, different nucleation protocols can also be introduced and thus, independently study the effects of the nucleation in the kinetics. Therefore, 2 and 3 dimensional simulations of primary crystallization have been performed with several degrees of final transformed fraction. The simulation results have been compared with the KJMA model and, unexpectedly, a good agreement between the simulations and the KJMA model has been obtained. As the KJMA model does not reproduce satisfactorily the experimental behavior, from this result can be deduced that neither the soft impingement nor the non random nucleation are the responsible of the slowing down observed in the kinetics of primary crystallization.In order to find a physical convincing explanation of the observed experimental behavior, the theoretical study of primary crystallization has been extended, including the effects of the compositional changes that take place in the matrix as the transformation proceed. This fact, notwithstanding being known in the literature, has been systematically ignored in the development of the kinetics models. In particular, it has become clear that changes in the chemical composition of the primary phase have to radically affect the viscosity, that strongly varies near the glass transition, and some changes in the atomic transport properties must occur. This has been modeled through the assumption of a compositional dependent diffusion coefficient, on the basis of a modified Stokes-Einstein relation between viscosity and diffusion coefficient. Phase field simulations with a diffusion coefficient of this type yield a slower kinetics and show an excellent agreement with the kinetics experimentally observed in primary crystallization of metallic glasses. Thus, phase field simulations confirm that the kinetics of primary crystallization is fundamentally controlled by the changes in the atomic transport properties, while the soft impingement and non random effects, although being present, are secondary.

Το θέμα αυτής της διπλωματικής είναι παρασκευή άμορφων μεταλλικών συμπαγών κραμάτων με τήξη σε βολταϊκό τόξο και ο χαρακτηρισμός της δομής τους και των μηχανικών ιδιοτήτων τους. Στο πρώτο κεφάλαιο γίνεται εισαγωγή στη δομή των υλικών και επεξηγούνται βασικές έννοιες των άμορφων υλικών και επίσης παρουσιάζονται οι κυριότερες εφαρμογές των άμορφων μεταλλικών συμπαγών κραμάτων. Στο δεύτερο κεφάλαιο περιγράφονται οι τεχνικές που χρησιμοποιούνται για την παρασκευή άμορφων συμπαγών μεταλλικών κραμάτων και στο τρίτο κεφάλαιο αναφέρονται οι κυριότερες φυσικές ιδιότητες των άμορφων μεταλλικών συμπαγών κραμάτων. Στο τέταρτο κεφάλαιο παρουσιάζεται η βαθμονόμηση της συσκευής περίθλασης ακτίνων Χ και της συσκευής παραγωγής και μέτρησης υπερήχων που χρησιμοποιήθηκαν για την μέτρηση των δειγμάτων που παρασκευάστηκαν στο εργαστήριο. Στο πέμπτο κεφάλαιο περιγράφεται ο τρόπος παρασκευής των άμορφων κραμάτων ζιρκονίου (Zr) και σιδήρου (Fe) και επίσης παρουσιάζονται και αναλύονται τα XRD διαγράμματα τους και τα μέτρα ελαστικότητας Young (E), διάτμησης (G) και όγκου (B). Τέλος στο έκτο κεφάλαιο αναφέρονται άλλες μετρήσεις που θα μπορούσαν να γίνουν για να χαρακτηριστούν τα παραπάνω δείγματα και περιγράφονται οι προοπτικές των άμορφων κραμάτων σιδήρου ως αντικείμενο έρευνας για το μέλλον. / The subject of this diploma thesis is the preparation of bulk amorphous metallic alloys with arc-melting technique and the characterization of their structure and their mechanical properties. The first chapter is an introduction to the structure of materials and it is explaine the basic concepts of amorphous materials. It is also present the main applications of bulk amorphous metallic alloys. The second chapter describes the techniques that used in the preparation of bulk amorphous metallic alloys and the third chapter refers the main physical properties of bulk amorphous metallic alloys. The fourth chapter describes the calibration of X-ray diffractοmeter and ultrasound measurement system that used for measuring the samples that have been prepared in the laboratory. In the fifth chapter is described the preparation of amorphous zirconium based (Zr) and iron based (Fe) alloys and also is presented and isanalyzed their XRD patterns and also their elastic moduli, like Young modulus(E), shear modulus (G) and bulk modulue (B). Finally the sixth chapter refers to other measurements that could be used to charactirize the samples that prepared and describes the prospects of amorphous iron based alloys as a research subject for the future.

Made available in DSpace on 2016-06-02T19:10:27Z (GMT). No. of bitstreams: 1 6459.pdf: 4283564 bytes, checksum: 527069b2b33732466b82a6f78943d62f (MD5) Previous issue date: 2014-02-21 / Financiadora de Estudos e Projetos / This thesis presents the development of a new criterion which can indicate new compositions for amorphous metallic alloys. This new criterion was based on dense packing of spheres combined with the lambda criterion through the coordination number. The mathematical development is presented and a software was developed with the purpose of indicating alloys with best glass forming ability (GFA). This software includes and concatenates several other criteria. For this purpose, we performed a mathematical analysis of the criteria, which included: (i) (λmin) criterion which uses the minimum topological instability parameter and it is used as an indication of phase competition during the solidification. (ii) the γ parameter, which reflects the relative GFA between bulky metallic glasses (BMG) and it is based on characteristic temperatures, such as: the glass transition temperature - Tg, the crystallization onset temperature - Tx and the liquidus temperature - Tl. (iii) the parameter Zc that is the critical thickness for bulky glass formation, which corresponds to the maximum dimension in which the molten can be formed without any crystals precipitation and (iv) the parameter Rc that is the critical cooling rate for glass formation, which decreases inversely to the Zc values. Through a mathematical formalism combining all the parameters, the software can decide the most suitable composition range to produce a new alloy. The results are presented and compared with the ones available on the literature. Also, for comparison, new alloys were developed by using the new criterion. These results indicate good agreement with the literature and with the experimental data since it is not a general theory, but intends to meet some specific cases with a reasonable convergence and which still need to be better studied. / Esta tese apresenta o desenvolvimento de um novo critério para indicar novas composições de ligas metálicas amorfas. Este novo critério foi baseado no empacotamento denso de esferas combinado com o critério lambda através do número de coordenação. O desenvolvimento matemático é apresentado e um software que engloba e concatena diversos outros critérios foi desenvolvido com o propósito de indicar as melhores ligas metálicas com alta tendência à formação de vidros (GFA). Para tal, houve uma análise matemática dos critérios, entre eles: (i) o critério λmin, que usa o parâmetro de mínima instabilidade topológica, usado como indicativo da competição de fases durante a solidificação; (ii) o parâmetro γ, que reflete a GFA relativa entre vidros metálicos volumosos (BMG) com base nas temperaturas características como a temperatura de transição vítrea - Tg; temperatura de início de cristalização - Tx e a temperatura liquidus - Tl; (iii) o parâmetro Zc, que é a espessura crítica para a formação do vidro volumoso e que corresponde à máxima dimensão com que o fundido pode ser formado sem que haja precipitação de cristais e (iv) o parâmetro Rc, que é a taxa de resfriamento crítico para a formação de vidro a qual decresce inversamente aos valores de Zc. Através de formalismo matemático para combinar todos os parâmetros, o software pode decidir qual a faixa de composição mais adequada para a produção de uma nova liga. Os resultados são apresentados e comparados com a bibliografia existente, além de terem sido desenvolvidas ligas experimentais para comparação. Estes resultados indicam uma boa concordância com a literatura e com os dados experimentais, uma vez que não se trata de uma teoria geral, mas que pretende atender a alguns casos específicos com razoável convergência e que ainda precisam ser melhor estudados.

Influence of transformer lamination from amorphous steel on permeability disturbance by transformer This diploma work is about difference between current materials and amorphous plates which are used as pivots of transformers. Samples are tested by frequence 50-2500 Hz. By using more suitable materials we avoid the unallowable electromagnetic interruption better and we get more positive continuance of the retroactivity on the net.

Gegenstand dieser Arbeit ist die Entwicklung, Herstellung und Charakterisierung verschiedener glasbildender Eisenbasislegierungen, mit dem Ziel: 1. durch umfangreiche Charakterisierung der Startlegierung Fe44,63Cr4,93Co4,93Mo12,61Mn11,03C15,56B5,81Y1,5 (at.%) Möglichkeiten zu evaluieren mit dieser Legierung Komposite aus amorpher Matrix und kristalliner Zweitphase herzustellen, 2. den Einfluss der Legierungselemente Kobalt, Chrom und Molybdän auf die strukturellen, thermischen und mechanischen Eigenschaften des Startlegierungstyps zu bestimmen und 3. auf Grundlage der Startlegierung Glasmatrixkomposite mit Zusatzelementen herzustellen. Die Erkenntnisse sollen als Grundlage für die Verbesserung der plastischen Eigenschaften der hochfesten aber auch außerordentlich spröden amorphen Eisenbasislegierungen dienen. Für den Beginn der Forschungsarbeiten wurde die von Lu et al. publizierte Legierung mit der Zusammensetzung Fe44,63Cr4,93Co4,93Mo12,61Mn11,03C15,56B5,81Y1,5 at. % und einem kritischen Gießdurchmesser von 12 mm gewählt [Lu04], da aufgrund der hohen Anzahl von Legierungselementen, stark unterschiedlichen Atomgrößen und dem internen Sauerstoffgetter Yttrium zu erwarten ist, dass die Glasbildungsfähigkeit auch nach Legierungsmodifikationen hoch bleibt. Dadurch ist es möglich, die Auswirkungen von Zusammensetzungsveränderungen auf die Eigenschaften der amorphen Legierungen und Glasmatrixkomposite zu studieren. Als erstes wurde die Startlegierung umfangreich strukturell, thermisch und mechanisch charakterisiert (Kapitel 5). Daran schließt sich die Untersuchung des Einflusses der Elemente Kobalt, Chrom und Molybdän auf die thermischen, strukturellen und mechanischen Eigenschaften an (Kapitel 6). Das Kapitel 7 hat zum Ziel zu zeigen, welche Arten von Glasmatrixkompositen auf der Basis der Startlegierung herstellbar sind. Es wurden Komposite mit Zirkoniumkarbid, Titankarbid, Niobkarbid, Silber und Kupfer hergestellt und charakterisiert.

Multicomponent high-entropy and amorphous alloys represent relatively new classes of structural materials with complex atomic configurations and exceptional mechanical properties. However, there are several knowledge gaps in the relationships between their atomic structure and mechanical properties. Understanding these critical relationships will enable novel alloy design and tailoring of their mechanical properties for desired engineering applications. In this dissertation, first-principles calculations and molecular dynamics simulations are applied to investigate the local atomic configurations and ordering in high-entropy and amorphous alloys. Our findings suggest that fluctuations in local atomic configurations for high- entropy alloys result in significant changes in stacking fault energy, twin energy, dislocation behavior, dislocation-twin interactions, and critical shear stress. For amorphous alloys or metallic glasses, the short-range order (SRO) and medium-range order (MRO) were found to play decisive roles in determination of their mechanical properties. Structural relaxation was found to lead to shear localization, which was attributed to free volume change and evolution of SRO and MRO to more brittle nature. In contrast, rejuvenated metallic glasses had relatively large and uniform free volume distribution giving rise to homogeneous flow and increased plasticity.