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Étude des mécanismes de la plasticité dans les verres métalliques massifs. Ce travail a porté sur une approche des mécanismes de la plasticité à la transition vitreuse dans les verres métalliques massifs base zirconium. Une étude bibliographique des verres métalliques, ses caractéristiques essentielles a été tout d'abord introduite, particulièrement orientée vers leurs propriétés de stabilité structurale, ainsi que vers leurs propriétés mécaniques à haute température. Le modèle de volume libre (selon l'approche de Spaepen) a été utilisé dans une modélisation par éléments finis de la plasticité du verre. Le verre métallique de composition Zr_{52,5}Cu_{22}Al_{10}Ni_{13}Ti_{2,5}, étudié dans cette thèse, est élaboré par différentes méthodes d'hypertrempe sous forme de barreaux et de rubans. Les caractérisations physico-chimiques ont été menées par DSC, DRX et MEB. Les résultats de DSC ont montré que les verres élaborés possèdent un large intervalle de transition vitreuse et une bonne stabilité thermique. L'étude couplant DSC et DRX à haute température a permis d'établir la nature des phases et leur ordre d'apparition en cours de cristallisation. La transition vitreuse et la cristallisation ont été étudiées en détail par DSC modulée (MDSC) par la suite. La cinétique de cristallisation du verre a été généralement analysée par DSC isotherme.La caractérisation de la relaxation du verre métallique à partir de traitements thermiques successifs, par DSC et DRX à température proche de la température de transition vitreuse T_g pendant des temps différents, est rapportée dans le quatrième chapitre. Ce phénomène de relaxation peut être observé directement par les études structurales en utilisant la DSC et la diffraction des rayons X. Ensuite, l'évolution de la relaxation du verre est étudiée par mesure de dureté et de densité. La variation de la dureté H_v par rapport à la profondeur de pénétrateur h, après les traitements thermiques, a été menée par micro-dureté. La mesure de volumique du verre Zr_{52,5}Cu_{22}Al_{10}Ni_{13}Ti_{2,5} a été menée après les différents temps de relaxation thermique, nous donnent une densité d'environ de 6,769g/cm^3. Les traitements thermiques isothermes sur ce verre ont montré une augmentation de sa densité au cours du temps. Afin d'observer l'apparition puis l'évolution des mécanismes de déformation dans le verre métallique à l'échelle locale, une nouvelle technique - lithographie électronique - avec un dispositif d'essai mécanique in situ, permettant de déposer des microgrilles à la surface d'une éprouvette et de réaliser un essai de compression dans un MEB, est présentée dans le cinquième chapitre. Puis, les résultats sont analysés par corrélation d'images. La démarche expérimentale des essais MEB in situ est détaillée dans ce chapitre.Des essais à vitesse de déformation constante sont présentées dans le chapitre suivant. Ils ont été conduits dans l'intervalle de transition vitreuse (entre 673K et 713K). Enfin, les études de champs de déformation par corrélation d'image ont montré une limite de détection de la localisation supérieure à 2 micromètre sur les cartes de déformation. S'il y a des bandes de cisaillement, soit leurs déformation en inférieure à celles due à l'oxydation, soit elles sont plus fines que 2 micromètre (échelle de mesure). Le dernier chapitre présente une modélisation pour décrire le comportement élastique et plastique des verres métalliques. Dans le cadre de cette thèse, une approche de la modélisation des essais mécanique en se basant sur le modèle du volume libre a été conduite à l'aide du logiciel ZéBulon. Des travaux préliminaires pour étudier la localisation dans le cadre du volume libre ont été conduits et vont nécessiter une étude plus poussée.Mots clef : verre métallique, transition vitreuse, relaxation structurale, volume libre, caractérisation, micro-dureté, lithographie, compression, MEB in situ, modélisation / Study of the mechanisms of the plasticity in the massive metallic glasses. This work concerned an approach of the mechanisms of the plasticity in the glassy transition in the massive metallic glasses base zirconium. A bibliographical study of the metallic glasses, its essential characteristics was introduced first of all, particularly directed to their properties of structural stability, as well as to their high-temperature mechanical properties. The model of free volume (according to the approach of Spaepen) was used in a modelling by elements finished by the plasticity of the glass. The metallic glass of composition Zr _ (52,5) Cu _ (22) Al _ {10} Nor _ (13) Ti _ {2,5}, studied in this thesis(theory), is developed by various methods of hypertempering in the form of bars and of ribbons.

Depuis leur découverte, un travail de recherche important a été développé sur la production, la structure, la microstructure, les propriétés et les applications des alliages métalliques amorphes. Cependant, la question de ce qui est entendu exactement par le terme « amorphe » n’est pas considérée dans la majorité des études publiées. Or, il n’existe pas de verres réels représentant un désordre parfait comme il n’existe pas de cristaux réels avec une structure parfaitement ordonnée. Il est difficile de donner une définition précise sans donner les limites d’échelle et la technique de détection de cette non-cristallinité. L’étude est une interrogation, pour un alliage particulier, sur le terme « amorphe » en fonction de l’échelle et de la technique. Cette étude comporte une analyse des conditions de préparation d’échantillons amorphes de mêmes compositions. Des techniques complémentaires de détection de leurs différences, en particulier à l’échelle de la structure et de la microstructure ont été utilisées. Des échantillons Pd82Si18 d’épaisseurs différentes ont été produits par solidification ultra rapide sur roue, avec différents paramètres, tels que la vitesse de rotation de la roue, la pression du gaz d’éjection, les dimensions de l’orifice d’éjection, la température de trempe et l’existence ou non d’un traitement thermique du liquide avant la trempe, etc. Les échantillons ont été ensuite analysés avec plusieurs techniques, telles que la diffraction des rayons X et des neutrons, la diffusion des neutrons aux petits angles, la microscopie électronique à transmission, la calorimétrie, les essais mécaniques, la fractographie par microscopie électronique à balayage / Since their discovery, an important research work has been developed on the production, the structure, the microstructure, the properties and the applications of amorphous metallic alloys. However, the question of what is exactly meant by the term “amorphous” is not considered in most of the reported studies. As a matter of fact, there exist no real glasses representing a perfect disorder, as there exist no real crystals with a perfectly ordered structure. It is thus difficult to give a precise definition without giving the limitations in scale and in detection of this non-crystallinity. The aim the study is an interrogation, in the case of a specific alloy, on the term “amorphous” as a function of the two directions of reference given above (the scale and the technique). This study thus contains an analysis of the conditions of synthesis of amorphous samples of similar compositions. Furthermore, complementary detection techniques of their differences at the scale of the structure and microstructure have been used. Samples of Pd82Si18 of different thickness have been produced by melt-spinning with different parameters, such as the rotation speed of the wheel, the pressure of the gas, the dimensions of the nozzle, the quenching temperature and the existence or not of a heat treatment of the melt before quench. The samples have been analysed by various techniques such as diffraction of standard X rays and of neutrons, small angle neutrons scattering, transmission electron microscopy, calorimetry, mechanical tests and fractography by scanning electron microscopy

The glass-forming Ti75Zr10Si15 alloy is regarded as a potential new material for implant applications due to its composition of non-toxic, biocompatible elements and many interesting mechanical properties. The effects of partial substitution of 15 at.-% Ti by Nb on the microstructure and mechanical behavior of the alloy have been investigated. The limited glass-forming ability (GFA) of the Ti75Zr10Si15 alloy results for melt-spun ribbons mainly in nanocomposite structures with β-type nanocrystals being embedded in a glassy matrix. Addition of Nb increases the glass-forming ability. Raising the overheating temperature of the melt prior to melt-spinning from 1923 K to 2053 K yields a higher amorphous phase fraction for both alloys. A decrease of hardness (H), ultimate stress and reduced Young’s modulus (Er) is observed for Ti60Zr10Nb15Si15 rods as compared to Ti75Zr10Si15 ones. This is attributed to an increase of the fraction of the β-type phase. The melt-spun ribbons show an interesting combination of very high hardness values (H) and moderate reduced elastic modulus values (Er). This results in comparatively very high H/Er ratios of >0.075 which suggests these new materials for applications demanding high wear resistance. The corrosion and passivation behavior of these alloys in their homogenized melt-spun states have been investigated in Ringer solution at 37°C in comparison to their cast multiphase crystalline counterparts and to cp-Ti and β-type Ti-40Nb. All tested materials showed very low corrosion rates. Electrochemical and surface analytical studies revealed a high stability of their passive states in a wide potential range. The addition of Nb does not only improve the glass-forming ability and the mechanical properties but also supports a high pitting resistance even at extreme anodic polarization. With regard to the corrosion properties, the Nb-containing nearly single-phase glassy alloy can compete with the β-type Ti-40Nb alloy. In addition, it has been demonstrated that thermal oxidation could be well applied to Ti75Zr10Si15 and Ti60Zr10Nb15Si15 melt-spun ribbons. Thermal oxidation treatment is one of the simple and cost-effective surface modification methods to improve the surface characteristics of these alloys. In the first tests, ribbon samples of the ternary and the quaternary alloy which were oxidized at 550°C in synthetic air showed suitable fundamental properties for implant applications, i.e. high hardness, good wettability and hydroxyapatite-forming ability after 10 days. All these properties recommend the new glass-forming alloys for application as wear- and corrosion-resistant coating materials for implants. / Die glasbildende Legierung Ti75Zr10Si15 wird wegen ihrer biokompatiblen Zusammensetzung ohne toxische Elemente und auf Grund interessanter mechanischer Eigenschaften als potentielles neues Implantatmaterial betrachtet. Es wurden 15 at.-% Ti durch Nb partiell substituiert und die Effekte auf die Mikrostruktur und die mechanischen Eigenschaften der Legierung untersucht. Auf Grund der eingeschränkten Glasbildungsfähigkeit von Ti75Zr10Si15 bestehen die schmelzgeschleuderten Bänder dieser Legierung hauptsächlich aus Nanokomposit-Strukturen mit β-phasigen Nanokristallen in einer glasartigen Matrix. Die Zugabe von Nb steigert die Glasbildungsfähigkeit. Das Anheben der Überhitzungstemperatur der Schmelze vor dem Schmelzschleudern von 1923 auf 2053 K führt für beide Legierungen zu einem höheren Anteil amorpher Phase. Es wird bei der Legierung Ti60Zr10Nb15Si15 im Vergleich zur Ti75Zr10Si15-Legierung eine Abnahme der Härte (H), Bruchfestigkeit und ein reduzierter E-Modul (Er) beobachtet. Dies wird mit dem Anstieg des beta-Phasenanteils erklärt. Die schmelzgeschleuderten Bänder zeigen eine interessante Kombination aus sehr hoher Härte und moderaten E-Modul Werten (Er). Dies führt zu vergleichsweise sehr hohen H/Er-Verhältnissen von >0,075, wodurch diese Materialien für Anwendungen mit hohen Verschleißanforderungen geeignet sind. Das Korrosions- und Passivierungsverhalten dieser Legierungen in ihrem homogenisierten schmelzgeschleuderten Zustand wurde in Ringer-Lösung bei 37°C untersucht und mit dem gegossenen vielphasigen kristallinen Zustand dieser Legierungen sowie mit cpTi und beta-Typ Ti-40Nb verglichen. Alle untersuchten Materialien zeigten sehr niedrige Korrosionsraten. Elektrochemische Studien und Oberflächenanalysen belegen eine hohe Stabilität der Passivfilme in einem weiten Potentialbereich. Die Zugabe von Niob verbessert nicht nur die Glasbildungsfähigkeit und die mechanischen Eigenschaften, sondern erhöht weiterhin die Lochfraßbeständigkeit, selbst bei stark anodischer Polarisation. Bezüglich der Korrosionseigenschaften konkurriert die Nb-haltige fast einphasige glasartige Legierung mit β-phasigem Ti-40Nb. Weiterhin wurde gezeigt, dass an schmelzgeschleuderten Bändern der Legierung Ti75Zr10Si15 und Ti60Zr10Nb15Si15 eine thermische Oxidation erfolgreich durchgeführt werden konnte. Die thermische Oxidation ist eine der einfachsten und kosteneffektivsten Möglichkeiten der Oberflächenmodifikation um die Eigenschaften der Oberflächen dieser Legierungen zu verbessern. In den ersten Tests zeigten die Bänder-Proben der ternären und der quaternären Legierung, die bei 550°C in synthetischer Luft oxidiert wurden, entsprechende Eigenschaften für Implantat-Anwendungen, d.h. hohe Härte, gute Benetzbarkeit und die Fähigkeit nach 10 Tagen Hydroxylapatit auf der Oberfläche zu bilden. Alle zuvor genannten Eigenschaften machen diese neuen glasbildenden Legierungen zu geeigneten Materialien für die Anwendung als verschleiß- und korrosionsbeständige Beschichtung für Implantate.

Fe-based amorphous powders are fabricated through gas and water atomization using industrial grade raw materials. The atomic structure of the powder is examined by X-Ray Diffraction (XRD). Eight of totally thirteen different compositions are proved completely amorphous or amorphous with traces of crystalline phase in the desired powder particle size (d > 75 μm) and five are crystalline. It reveals that the Glass Forming Ability (GFA) of atomized powders is well correlated to the GFA of as-casted rods or melt-span ribbons. In the present study at least 1.5-2 mm critical size of GFA for a target composition is necessary for the formation of amorphous powders in the desired particle size. The thermal stability of the amorphous powder is examined by Differential Scanning Calorimetry (DSC). Applying the conventional powder metallurgy process the amorphous powders are mixed with the crystalline Somaloy® 110i, a commercial Soft Magnetic Composite (SMC) material from Höganäs AB in Sweden, and made into toroid-shaped components. The components are annealed aiming for improved soft-magnetic properties. The magnetic measurements are taken on copper-wire double coiled toroids. As a result, the total magnetic flux (B), coercivity (HC) and permeability (μmax) is reduced due to the addition of amorphous powders to Somaloy® 110i powder but the core losses (P) is at the same level despite reduced density. An improved soft magnetic property and core loss is revealed by the comparison to recent literature reports on SMC mixing of crystalline and amorphous powders.

Additive manufacturing (AM), also known as 3D-printing, has made it possible to produce components made of bulk metallic glass (BMG) which have remarkable properties compared to parts made of conventional alloys. A metallic glass is a metastable noncrystalline alloy that form if a melt is quenched with a sufficient cooling rate. Research on systems with low critical cooling rates have made the maximum dimensions of these alloys to grow to what is called BMG's. The high local cooling rate obtained during AM makes it in principle possible to bypass the dimension restrictions that otherwise have been present when creating these alloys but the procedure is complex. It is believed that oxygen impurities in the powder feedstock material used during AM of Zr-based alloys makes it favourable for nucleation of stable crystalline phases at lower activation energies which hinders fully glass features to develop. The purpose of this thesis is to investigate how the limiting solute concentration in the bulk of the AM produced alloy AMZ4 (Zr59.3Cu28.8Al10.4Nb1.5(at\%)) impact the nucleation. Using a numerical model based on classical nucleation theory (CNT) that couples the interfacial and long range fluxes makes it possible to study how impurities impact the nucleation event. However, missing oxygen dependent data makes this a study on how limiting solute impact the nucleation in AMZ4. The numerical model is validated against earlier work and the results obtained from the simulations on AMZ4 shows a strong connection between the nucleation event and the limiting solute concentration. Further investigations on phase separation energies and the production of concentration dependent time-temperature-transformation (TTT) diagrams are needed to fully describe the connection to oxygen concentration. Nevertheless, the implemented model captures important features that the classical model cannot describe which needs to be taken into account when describing the nucleation in AMZ4. / Friformsframställning (eng. additive manufacturing (AM)), också känt som 3D-printing, har gjort det möjligt att producera komponenter gjorda av bulkmetallglas (eng. bulk metallic glass (BMG)) vilka har anmärkningsvärda egenskaper jämfört med delar gjord av konventionella legeringar. Ett metalliskt glas är en metastabil icke kristallin legering som skapas om en smälta släcks med en tillräcklig kylhastighet. Forsking på system med låga kritiska kylhastigheter har gjort att de maximala dimensionerna av dessa legeringar har ökat till vad som kallas BMG's. Den höga lokala kylhastigheten som erhålls under AM gör att  dimensionsrestriktionerna principiellt kan kringgås vilka annars är närvarande vid skapandet dessa legeringar men proceduren är komplex. Det är trott att orenheter av syre i pulver-råvarumaterialet som används vid AM av Zr-baserade legeringar gör det fördelaktigt för kärnbildning av stabila kristallina faser vid lägre aktiveringsenergier vilket hindrar fulla glas egenskaper från att utvecklas. Syftet med denna uppsats är att undersöka hur den begränsande lösningen påverkar kärnbildningsförloppet i den AM producerade legeringen AMZ4 (Zr59.3Cu28.8Al10.4Nb1.5(at\%)). En numerisk modell baserad  på klassisk kärnbildningsteori (eng. classical nucleation theory (CNT)) som kopplar gränsskikt- och långdistans-flödet gör det möjligt att studera hur orenheter påverkar kärnbildningsförloppet. Syreberoende data gör dock detta till en studie om hur den begränsande lösningen påverkar kärnbildningen i AMZ4. Den numeriska modellen valideras mot tidigare arbeten och resultaten från simuleringarna av AMZ4 visar ett starkt samband mellan kärnbildningsförloppet och den begränsade lösningskoncentrationen. Vidare studier rörande fas-separeringsenergier och framställningen av koncentrationsberoende tid-temperature-transformation (eng. time-temperature-transformation (TTT)) diagram behövs för att till fullo beskriva kopplingen till syrekoncentrationen. Den implementerade modellen fångar dock viktiga egenskaper som den klassiska modellen inte kan beskriva vilka måste tas hänsyn till när kärnbildning i AMZ4 ska beskrivas.

Yes / 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.

In this study, the surface degradation behavior was studied for typical examples from bulk metallic glasses (BMGs), metallic glass composites (MGCs) and high entropy alloys (HEAs) alloy systems that are of scientific and commercial interest. The corrosion and wear behavior of two Zr-based bulk metallic glasses, Zr41.2Cu12.5Ni10Ti13.8Be22.5 and Zr57Cu15.4Ni12.6Al10Nb5, were evaluated in as-cast and thermally relaxed states. Significant improvement in corrosion rate, wear behavior, and friction coefficient was seen for both the alloys after thermal relaxation. Fully amorphous structure was retained with thermal relaxation below the glass transition temperature. This improvement in surface properties was explained by annihilation of free volume, the atomic scale defects in amorphous metals resulting from kinetic freezing. Recently developed MGCs, with in situ crystalline ductile phase, demonstrate a combination of mechanical properties and fracture behavior unseen in known structural metals. The composites showed higher wear rates but lower coefficient of friction compared to monolithic amorphous glasses. No tribolayer formation was seen for the composites in sharp contrast to that of the monolithic metallic glasses. Corrosion was evaluated by open circuit potential (OCP) analysis and potentiodynamic polarization. Site-specific corrosion behavior was studied by scanning vibration electrode technique (SVET) to identify formation of galvanic couples. Scanning kelvin probe microscope was used to map elecropositivity difference between the phases and linked to wear/corrosion behavior. Phases with higher elecropositivity were more susceptible to surface degradation. Wear and corrosion synergy in marine environment was evaluated for two high entropy alloys (HEAs), CoCrFeMnNi and Al0.1CoCrFeNi. Between the two alloys, Al0.1CoCrFeNi showed better wear resistance compared to CoCrFeMnNi in dry and marine conditions due to quicker passivation, a higher magnitude of polarization resistance and significantly larger pitting resistance.

No description available.

Bulk metallic glasses (BMGs) are a new class of structural materials and exhibit unique combinations of mechanical properties. As a result, their mechanical behavior has been an active area of scientific pursuit in the recent past and considerable emphasis has been paid to understand plastic deformation in them. It is now well accepted that shear transformation zones (STZs), aided by free volume, are the fundamental carriers of plasticity. At a microscopic level, deformation at low temperatures and high stresses tends to localize into shear bands. Most BMGs posses high fracture toughness despite high yield strengths and poor global ductility. However, the micro-mechanisms of fracture and fatigue in this new class of materials are not fully understood yet. The overall objective of this study is to provide insights into the fracture and fatigue response of amorphous alloys, which is important both from scientific and technological perspectives. The key questions we seek to answer through this study are the following. Do amorphous alloys undergo a ductile-brittle transition (DBT), and if so what are the reasons for it? What are the parameters that influence fatigue crack initiation in amorphous alloys and whether fatigue life can be improved by surface treatments? A related question is whether the BMGs are susceptible to deformation-induced crystallization (DIC). A Zr-based BMG, Zr41.2Ti13.75Cu12.5Ni10Be22.5 was utilized to conduct this study. By comparing the fracture and fatigue behaviors in the as-cast and annealed states {annealing was carried out below the glass transition temperature (Tg) because of established embrittlement effects}, we seek to provide answers for the questions posed above. We begin by examining the influence of temperature on the toughness of BMGs. Impact toughness measurements show that the annealed samples, which are brittle at room temperature, recover the lost toughness beyond a critical temperature (TDB) and exhibit a sharp DBT. However, the hardness remains unaffected across the TDB. Fractography reveals nano-scale patterning and cleavage fracture in the brittle state, while the formation of thick vein-patterns and shear fracture are characteristics of the ductile state of the annealed samples. We explore various micro-mechanistic possibilities for explaining the features of this transition, including a critical Poisson’s ratio-toughness correlation. Next, to understand the origins of fatigue crack initiation, we study the un-notched fatigue response of as-cast and sub-Tg annealed Zr-based BMG specimens. Because of embrittlement and nano-crystallization at the crack initiation region, the annealed specimens exhibit a lower fatigue life than the as-cast specimens. Shot-peening of the as-cast specimens did not exhibit significant improvement in their fatigue performance because of competing effects between the compressive residual stress field (CRSF) and deformation-induced softening. To further investigate surface and repeated loading effects, the tribological response of the as-cast Zr-based BMG was compared with specimens annealed above and below the Tg. A good correlation between the hardness (increasing as a function of the annealing temperature) and wear rate was obtained. The formation and peeling of the oxide layer formed during testing was the primary wear mechanism in all the specimens. Lastly, crystallization was observed within the deformed region of the as-cast Zr-based BMG repeatedly scratched with a sharp diamond indenter. But, transmission electron microscopy (TEM) does not reveal any evidence of crystallization within the indents formed within an electron transparent film formed by laser deposition of the as-cast Zr-based BMG. Absence of crystallization in deformed regions obtained by designing critical experiments, which avoid artifacts generated during sample preparation, suggests that the occasional observation of DIC might be an exception rather than the rule in BMGs.