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.

Les verres métalliques sont des matériaux amorphes, présentant d'excellentes propriétés mécaniques à température ambiante (haute limite d'élasticité, large domaine élastique, dureté élevée, etc.) combinées à une grande capacité de mise en forme au-delà de leur transition vitreuse. Leur domaine d'application est cependant limité par leur relative fragilité à température ambiante. Dans l'optique d'élargir le champ d'application des verres métalliques, l'élaboration par co-déformation à chaud de multi-matériaux alliant verre métallique et alliage léger traditionnel s'avère prometteuse. Dans ce travail, nous nous sommes intéressés à la possibilité d'élaborer par co-pressage à chaud des stratifiés associant un verre métallique base-zirconium à un alliage de magnésium. L'étude des propriétés mécaniques des deux matériaux, et notamment de leur comportement à chaud, a permis de préciser les mécanismes de déformation associés et de sélectionner les conditions optimales de co-pressage. Une caractérisation structurale des matériaux avant et après mise en forme a été réalisée. Les interfaces verre métallique/alliage de magnésium ont été caractérisées, confirmant une bonne adhésion entre les deux matériaux et des essais mécaniques spécifiques ont été mis en œuvre pour quantifier la tenue mécanique en cisaillement des interfaces. Ces résultats ont permis de valider le procédé de co-pressage à chaud comme technique d'élaboration de multi-matériaux verre métallique / alliage léger. / Metallic glasses are amorphous materials displaying very interesting mechanical properties at room temperature (high fracture stresses, large elastic domain, etc.) together with an excellent formability above the glass transition temperature. However the use of these materials is limited by their lack of plasticity at room temperature. In order to extend their applications field, it could be of interest to associate metallic glasses with conventional light alloys. In this work, the feasibility of the elaboration of multilayered materials involving a Zr-based metallic glass and a magnesium alloy by co-pressing at high temperature has been investigated. The selected conditions for co-pressing were chosen from the knowledge of the rheological behavior of both the metallic glass and the light alloy. The structural characterization of the materials before and after the elaboration has been studied. The interfaces metallic glass/magnesium alloy has been characterized, revealing a good bonding between the two materials. In order to evaluate the mechanical strength of the bonding, specific tests have been developed. The results enabled us to valid the co-pressing process as a technique to elaborate multimaterials associating metallic glasses with light alloys.

No description available.

Os vidros metálicos baseados em Cu-Zr representam uma classe bastante promissora para a categoria de materiais estruturais, tendo em vista suas interessantes propriedades resultantes da natureza amorfa. Sabe-se que o oxigênio tem grande influência na formação da estrutura amorfa e consequentemente nas propriedades dessa classe de materiais. No presente trabalho, ligas amorfas baseadas em Cu-Zr foram analisadas termicamente a fim de se observar o comportamento das mesmas frente à contaminação com oxigênio. As análises térmicas foram realizadas em um equipamento de calorimetria exploratória diferencial (DSC), e as temperaturas características como de transição vítrea, cristalização, fusão e líquidus foram determinadas. Concluiu-se que conforme a literatura apresenta, o processo de cristalização é favorecido pela presença de oxigênio, causando uma queda na energia de ativação dos processos de cristalização das ligas trabalhadas. Através de ensaios que simularam tratamentos térmicos, cristalizou-se controladamente as amostras amorfas baseadas em Cu-Zr a fim de formar compósitos entre cristais e vidros metálicos buscando diminuir a fragilidade das ligas. / Cu-Zr-based bulk metallic glasses represent a very promising class of structural materials with interesting properties resulting from the amorphous nature. It is known that oxygen has a great influence on the formation of the amorphous structure and consequently on the properties of these materials. In the present work, Cu-Zr-based amorphous alloys were thermally analyzed in order to observe their behavior against oxygen contamination. Thermal analyzis were performed on a differential scanning calorimetry (DSC) equipment, and characteristic temperatures as glass transition, crystallization, melting and liquidus were determined. It was concluded that, according to the literature, the crystallization process is favored by the presence of oxygen, causing a decrease in the activation energy of the crystallization processes of the worked alloys. Through tests that simulated heat treatments, the amorphous samples were crystallized in order to form composites between crystals and metallic glasses in order to reduce the brittleness of the alloys.

In this study, the time-dependent deformation behavior of several model bulk metallic glasses (BMGs) was studied. The BMGs were obtained in different structural states by thermal relaxation below their glass transition temperature, cryogenic thermal cycling, and chemical rejuvenation by micro-alloying. The creep behavior of Zr52.5Ti5Cu17.9Ni14.6Al10 BMG in different structural states was investigated as a function of peak load and temperature. The creep strain rate sensitivity (SRS) indicated a transition from shear transformation zone (STZ) mediated deformation at room temperature to diffusion dominated mechanisms at high temperatures. The relaxation enthalpy of Zr47Cu46Al7 BMG was found to increase significantly with the addition of 1 at% Ti, namely for Zr47Cu45Al7Ti1. Comparison of their respective free volumes indicated that chemical rejuvenation had a more pronounced effect compared to cryogenic thermal rejuvenation. Micro-pillar compression tests supported the improved plasticity with increase in free volume from the rejuvenation effect. Effect of chemistry change on mechanical response and time-dependent deformation was investigated for topologically equivalent Pt-Pd BMGs, where the Pt atoms were systematically replaced with Pd atoms (Pt42.5-xPdx)Cu27Ni9.5P21: x=0, 7.5, 20, 22.5, 35, 42.5). The hardness and reduced modulus increased while the degree of plasticity decreased with increase in Pd-content, which was attributed to the increase in stiffer 3-atom cluster connections. STZ volume was calculated for all the BMGs using cooperative shear model (CSM) for fundamental understanding of the underlying deformation mechanisms.

Metallic glasses are amorphous alloys that do not possess long-range structural order in contrast to crystalline alloys. Ni-free Ti-based bulk metallic glasses (BMGs) have potential for biomedical applications due to their attractive properties such as high strength, good corrosion resistance and excellent micro-formability, which cannot be obtained for conventional crystalline alloys. In this PhD thesis, Ni-free Ti-based BMGs, i.e. Ti40Zr10Cu34Pd14Sn2 and Ti40Zr10Cu36-xPd14Inx (x = 0, 2, 4, 6, 8), were prepared in the shape of rods by suction casting. Both alloy classes were systematically characterized in terms of glass forming ability, thermal stability, phase formation and mechanical properties. The largest diameter obtained in the fully glassy state for Ti40Zr10Cu34Pd14Sn2 alloy is 3 mm and for Ti40Zr10Cu36-xPd14Inx (x = 2, 4, 6, 8) alloys is 2 mm. Base alloy (Ti40Zr10Cu36Pd14) contains some crystalline phase(s) in the glassy matrix for a 2 mm diameter rod. The structural transformations of Ti40Zr10Cu34Pd14Sn2 BMG upon heating were thoroughly analyzed by utilizing different combination of methods. Firstly, we used differential scanning calorimetry (DSC), X-Ray diffraction (XRD) and transmission electron microscopy (TEM) to investigate the first crystallization event. The main products of the first crystallization are possibly -(Ti, Zr) and Cu3Ti (orthorhombic) phases. Secondly, we employed in situ x-ray diffraction in transmission mode using synchrotron beam to deeply study the thermally-induced structural changes like relaxation, glass transition and crystallization. Since the first peak in the diffraction patterns reflects the structure of the glassy phase on the medium-range scale, the position, width and intensity of this peak in diffraction patterns are fitted through Voigt function below 800 K. All the peak position, width and intensity values show a nearly linear increase with increasing temperature to the onset temperature of structural relaxation, Tr = 510 K. However, these values start to deviate from the linear behavior between Tr and glass transition temperature Tg. The changes in the free volume, which was arrested during rapid quenching of the BMG, and the coefficient of volumetric thermal expansion prove that the aforementioned phenomenon is closely related to the structural relaxation. Above 800 K, three crystallization events are detected and the first exothermic event is due to the formation of metastable nanocrystals. For the Ti40Zr10Cu34Pd14Sn2 alloy, 2 mm diameter rods exhibit the best combination of mechanical properties (e.g. large plastic strain and high yield strength) among all the diameters (ø2, ø3 and ø4 mm) under the room-temperature compression tests. With the aim to improve its room-temperature mechanical properties, the processes of pre-annealing and cold rolling have been applied for the 2 mm diameter rods. Annealed and quenched specimens below Tg and in the supercooled liquid region (between Tg and onset crystallization temperature Tx) do not lead to the enhancement of the plasticity compared to as-cast alloys due to annihilation of excess free volume and crystallization. Cold rolling can effectively improve the plasticity of this BMG by inducing structural heterogeneities. Rolled samples up to a thickness reduction of 15% result in the largest plasticity of 5.7%. Low yield strength and visible work hardening ability are observed in the both 10%-rolled and 15%-rolled samples. The deformation behavior of Ti40Zr10Cu34Pd14Sn2 BMG at the elevated temperatures slightly below Tg and in the supercooled liquid region has been investigated. The stress-strain relations for this BMG over a broad range of temperatures (298 ~716 K) and strain rates (10-5 to 10-3 s-1) were established in uniaxial compression. Under compression tests at the highest test temperature of 716 K, the Ti-based BMG partially crystallizes and low strain rates can lead to the formation of larger volume fractions of crystals. In order to further improve the plasticity of Ti-Zr-Cu-Pd BMGs and simultaneously reduce the content of Cu (considering harmful element for the human body), the Ti40Zr10Cu36-xPd14Inx (x = 2, 4, 6, 8) BMGs have been newly developed with different short- or medium-range order in the structure. The compressive global strain of Ti40Zr10Cu36-xPd14Inx (x = 0, 2, 4, 6, 8) can be significantly improved from 4.5% for the In-free alloy to 10.2% for x = 4. However, a further increase of the indium content to 8 at.% results in a decrease of the plasticity. Among all the monolithic Ni-free Ti-based BMGs reported so far, the novel Ti40Zr10Cu32Pd14In4 BMG shows the largest plasticity. Inspired by the dislocation concept in crystalline materials, we propose a strategy for the design of ductile BMGs through minor substitution using relatively large atoms, which make the bonding nature become more metallic and with it less shear resistant. Such a locally modified structure results in topological heterogeneity, which appears to be crucial for achieving enhanced plasticity. This strategy is verified for Ti-Zr-Cu-Pd glassy alloys, in which Cu was replaced by In, and seems to be extendable to other BMG systems. The atomic-scale heterogeneity in BMGs is somewhat analog to defects in crystalline alloys and helps to improve the overall plasticity of BMGs.

No / A novel process chain for serial production of polymer-based devices incorporating both micro- and nano-scale features is proposed. The process chain is enabled by the use of Zr-based bulk metallic glasses (BMG) to achieve the necessary level of compatibility and complementarity between its component technologies. It integrates two different technologies, namely laser ablation and focused ion beam (FIB) milling for micro-structuring and sub-micron patterning, respectively, thus to fabricate inserts incorporating different length scale functional features. Two alternative laser sources, namely nano-second (NS) and pico-second (PS) lasers, were considered as potential candidates for the first step in this master-making process chain. The capabilities of the component technologies together with some issues associated with their integration were studied. To validate the replication performance of the produced masters, a Zr-based BMG insert was used to produce a small batch of micro-fluidic devices by micro-injection moulding. Furthermore, an experimental study was also carried out to determine whether it would be possible by NS laser ablation to structure the Zr-based BMG workpieces with a high surface integrity whilst retaining the BMG’s non-crystalline morphology. Collectively, it was demonstrated that the proposed process chain could be a viable fabrication route for mass production of polymer devices incorporating different length scale features.

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.

Pour prémunir les structures spatiales d'impacts hyper-véloces, le secteur aérospatial est continuellement à la recherche de matériaux toujours plus performants. Dans cette optique, les verres métalliques massifs se présentent comme de potentiels éléments de blindages spatiaux. De récentes études ont mis en exergue une meilleure résistance à la pénétration de ces matériaux comparativement aux blindages actuels. Les impacts par lanceurs permettent d'étudier et caractériser le comportement sous chocs des matériaux. Cependant, les vitesses des projectiles se retrouvent actuellement limitées à 10 km/s, correspondant aux niveaux d'impacts hyper-véloces les plus modérés. Pour s'affranchir de cette limitation, il est possible de se tourner vers les lasers de puissance. Ces dispositifs permettent de générer des ondes de choc dont les niveaux de pression et de vitesse de déformation sont supérieurs aux lanceurs. Les travaux menés ont permis d'étudier et de caractériser le comportement et l'endommagement de plusieurs verres métalliques ternaires ZrCuAl sous choc laser. Plusieurs campagnes expérimentales ont été réalisées sur les installations du Laboratoire pour l'Utilisation des Lasers Intenses (LULI2000 et ELFIE). Une partie de l'équation d'état des nuances étudiées a été obtenue à la fois par choc laser et compression isentropique. Les processus d'endommagement, l'influence des vitesses de déformation et de composition sur la rupture ont été étudiés. Pour des régimes de vitesse de déformation supérieurs de trois ordres de grandeur à ceux disponibles dans la littérature, il a été mis en évidence que les verres métalliques étudiés présentaient une limite à la rupture cinq à dix fois supérieure. / Space industry is always searching for efficient materials to protect space structures from high-velocity impacts. In this context, bulk metallic glasses appear as suitable elements of space debris shielding assemblies. Recent studies revealed a higher tolerance to impact of metallic glasses compared to materials currently used in shield assemblies. Gas-gun and powder launchers are usually used to study and characterize the dynamic and shock behaviour of materials. However, projectiles velocities are currently limited to 10 km/s, corresponding to the lowest high-velocity impacts levels. To overcome this limitation, one may consider shock waves induced by high-power laser facilities, whose pressure and strain rate levels can exceed those induced by canons. Hence, this work enabled to study and to characterize the dynamic and damage behaviours of several compositions of ternary ZrCuAl bulk metallic glasses subjected to shock waves induced by laser irradiation. Several experimental campaigns have been conducted on various laser facilities of the Laboratoire pour l'Utilisation des Lasers Intenses (LULI2000 and ELFIE). A part of the equation of state of the studied compositions was established using both shock waves and quasi-isentropic compressions. Damage processes and the composition and strain rate effects on fracture were also studied. For strain rate levels higher of three or more orders of magnitude than those available in the literature, it was shown that studied bulk metallic glasses displayed a five to ten times higher dynamic tensile limit.

Ce travail de thèse considère les modes de déformations des verres métalliques produits sous différentes formes (verres massifs, rubans et particules). La déformation hétérogène dans des échantillons massifs de verres métalliques à base de zirconium est étudiée par microscopie électronique à balayage. Le dégagement rapide de l'énergie élastique stockée sous forme de chaleur lors de la déformation est responsable de la fusion locale observée dans les bandes de cisaillement. Le calcul du profil de température autour d'une bande par un modèle analytique est cohérent avec les observations morphologiques et les rapports d'apparition de nano-cristaux dans la zone déformée. La mise en forme par recuit des rubans de verres métalliques a été étudiée. L'étude aboutit à la mise en forme sans fragilisation des rubans appartenant à différentes compositions de systèmes d'alliages dit métal-métal et métal-métalloïde. Un processus de traitement thermique est suggéré pour assurer la redistribution des contraintes imposées avant l'intervention de la fragilité thermique. Un brevet industriel basé sur ces résultats a été conjointement déposé avec un grand fabriquant de montres mécaniques. De nouveaux matériaux composites d'alliages légers commerciaux à base de Mg et d'Al renforcés par des dispersions de particules de verres métalliques ont été réalisés sans porosité. Une amélioration très nette des propriétés mécaniques est obtenue. / This thesis features the two modes of deformation of metallic glasses produced under different forms (bulk, ribbons and particles). Inhomogeneous deformation in bulk samples is studied by scanning electron microscopy. Heat generated by elastic energy release during deformation is responsible for the melting observed in shear bands, and calculations using an analytical model of the temperature profile around a band are consistent with morphological observations and reports of appearance of nano-crystals in or next to deformed areas. Shaping by annealing glassy ribbons was carried out. The study presents successful shaping without embrittlement of ribbons of different metal-metal and metal-metalloid compositions of glassy systems. A heat treatment process is suggested for redistribution of applied stresses before the intervention of thermal embrittlement. A joint patent for exploiting the findings has been filed with a major producer of mechanical watches. Development of new strong and light composite materials by dispersing glassy particles in aluminum and magnesium based matrices is presented and significant improvement in mechanical properties is obtained.