Au cours des procédés de mise en forme du verre creux, les outillages de verrerie sont soumis à des conditions extrêmes avec des températures pouvant dépasser largement 650 °C. De plus, ces derniers sont exposés à des phénomènes d'abrasion sévères et à des réactions physico-chimiques complexes avec le verre fondu. Ceci est particulièrement accentué par les cycles thermiques dus aux contacts répétés avec le verre. L'objectif de ce travail de thèse est de proposer des solutions innovantes de dépôts de superalliages et/ou traitements de surface destinés à augmenter la durée de vie des outillages. Trois axes d'innovation sont présentés dans ce mémoire. Le premier concerne l'étude du dépôt de poudre composite Co/NiB par soudure PTA (Plasma Transfered Arc) sur des moules en alliage cuivreux. Le second est dédié à l'étude de la faisabilité technique d'un dépôt PVD (Physical Vapor Deposition) multicouche à gradient fonctionnel, présentant des caractéristiques intéressantes pour des applications verrières en termes de dureté et de stabilité thermique, sur des poinçons en acier AISI 431. Enfin, le troisième axe de recherche fait l'objet d'une analyse plus approfondie et concerne l'étude de la nitruration par implantation d'ions azotes multichargés, également sur un acier AISI 431. On observe après implantation une augmentation significative de la dureté (+ 240 %). Une approche multi-expérimentale et multi-échelle est alors proposée afin d'étudier la microstructure du matériau implanté ainsi que son évolution après un recuit de 1h à 650 °C de manière à anticiper le comportement du matériau en production, et de corréler ceci aux propriétés de dureté / Glass moulds have to withstand very high temperatures which can far exceed 650 °C during the glass forming process. They are exposed to very tough conditions such as abrasive wear and physico-chemical reactions, accentuated by thermal shocks due to high speed contact with hot glass melt. The aim of this work is to find innovative solutions for superalloy coating or surface treatments in order to increase the service life of glass tools. Three innovation projects are presented in this report. The first one is dedicated to PTA (Plasma Transferred Arc) welded coating of composite Co/NiB powder on copper alloy moulds. The second one is about technical feasibility of a multilayer PVD (Physical Vapor Deposition) coating with properties congruent to glass production in term of hardness and thermal stability, on AISI 431 plunger stainless steel. Last but not least, the third innovative project is about nitriding by ion implantation with multicharged nitrogen ions on AISI 431 stainless steel. We notice after ion implantation a significant hardness increase (+ 240 %). A multi-experimental and multi-scale approach was carried out in order to study the implanted material microstructure and its evolution after annealing at 650 °C during 1h to predict the material behavior during production and correlate it to hardness properties

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<p>  </p> <p>Stress corrosion cracking (SCC) is a longstanding critical materials challenge in austenitic stainless steels (AuSS). Recently, there has been mounting concern regarding the potential for Chloride-induced stress corrosion cracking (CISCC) along arc weld seams on austenitic stainless-steel canisters used as spent nuclear fuel (SNF) dry storage containers, due to the residual stress from the welding process and exposure to chloride-rich coastal air at storage sites. To ensure the safety of the SNF storage, fundamental understanding and mitigation methods of CISCC are critical in both engineering design and maintenance of the storage canisters before and after their deployment. With the recent development of high-resolution characterization and analysis techniques, a more robust and comprehensive understanding of the fundamental TGCISCC mechanism starts to be more accessible. In this thesis, comprehensive state-of-the-art techniques, including SEM, EBSD, HREBSD, FIB, ATEM, TKD, potential dynamic measurement, XRD, and nanoindentation will be used to further understand the mechanistic mechanism of TGCISCC in AuSS from macroscopic scale down to atomistic scale. </p>

In the past, it has been found that CuZr-based BMG composites containing B2 CuZr crystals in the glassy matrix display significant plasticity with obvious work hardening. In this work, it was tried to provide a strategy for pinpointing the formation of CuZr-based BMG composites, to modify the microstructures of these composites, and to clarify their yielding and deformation mechanisms. In order to pinpoint the formation of CuZr-based BMG composites, the phase formation and structural evolution of 11 kinds of CuZr-based alloy systems, altogether 36 different compositions, during heating and quenching processes were investigated. An endothermic event between the crystallization and melting peaks was found to be associated with a eutectoid transformation of the B2 CuZr phase. With the addition of elements to the CuZr-based alloys, this endothermic peak(s) shifts to lower or higher temperatures, implying that minor element additions can change the thermal stability of the B2 CuZr phase. By considering the thermal stability of the supercooled liquid, i.e. its resistance against crystallization, and the thermal stability of the B2 CuZr phase, a new strategy to select compositions, which form metastable CuZr-based composites consisting of an amorphous phase and B2 CuZr crystals, is proposed. It is characterized by a parameter, K = Tf /TL, where Tf and TL are the final temperature of the eutectoid transformation during heating and the liquidus temperature of the alloy, respectively. Based on this criterion, the present CuZr-based alloys are classified into three types. For Type I alloys with lower K values, it is difficult to obtain bulk metallic glass (BMG) composites. For Type III alloys with higher K values, BMG composites with larger dimensions are prone to be fabricated, whereas only moderate-sized BMG composites can be obtained for Type II possessing intermediate K values. Accordingly, CuZr-based BMG composites containing B2 CuZr phase in the glassy matrix for different alloy systems were successfully fabricated into different dimensions. For the sake of controlling the formation of the B2 CuZr phase in the glassy matrix and then changing the deformability of CuZr-based BMG composites, different methods were also used to fabricate these composites by: (1) introducing insoluable/high-melting particles; (2) appropriate re-melting treatments of master alloys; and (3) a new flash heating and quenching method. It was demonstrated that the volume fraction, size and distribution of the B2 phase in the glassy matrix can be controlled as well using the methods above. In order to clarify the excellent mechanical properties of CuZr-based BMG composites, the yielding and plastic deformation mechanisms of CuZr-based BMG composites were investigated based on SEM, XRD, and TEM observations. With the volume fraction of amorphous phase (famor) decreasing from 100 vol.% to 0 vol.%, a single-to-“double”-to-“triple”-double yielding transition was found. For the monolithic CuZr-based BMGs and their composites with the famor ³ 97.5 ± 0.5 vol.%, only one yielding at a strain of ~2% occurs, which is due to the formation of multiple shear bands in the glassy matrix, and the associative actions of the shear banding and the martensitic transformation (MT), respectively. When the famor is less than 97.5 ± 0.5 vol.%, a “yielding” occurs at a low strain of ~1%, which results from the yielding of B2 CuZr phase and the onset of the MT within B2 CuZr phase. When the famor is larger than 55 ± 3 vol.%, a “yielding” observed at strains >8% is ascribed from the operation of dislocations with a high density as well as partial de-twinning. It was also found that with the famor decreasing, the deformation mechanism gradually changes from a shear-banding dominated process, to a process being governed by the MT in the crystalline phase, resulting in different plastic strains. Owing to the importance of the MT and the shear banding to the deformation of CuZr-based BMG composites, the details of the MT and the shear banding process were investigated. On one hand, it was found that the MT temperatures of CuZr-based martensitic alloys have a clear relationship with the respective electronic structure and the lattice parameter of the equiatomic CuZr intermetallics. The MT temperatures of the studied alloys can be evaluated by the average concentration of valence electrons. Additional elements with larger atomic radius can affect the stacking fault energy and the electronic charge density redistribution, resulting in the difference of the electronic structures. On the other hand, the formation and multiplication of shear bands for CuZr-based BMG composites is associated with the storage and dissipation of the partial elastic energy during the plastic deformation. When microstructural inhomogeneities at different length scales are introduced into the glassy matrix, the elastic energy stored in the sample-machine system during the plastic deformation is redistributed, resulting in a transition of shear banding process from a chaotic behavior to a self-organized critical state. All in all, our studies and observations provide an understanding of the formation, deformation, and microstrcutural optimization of CuZr-based BMG composites and give guidance on how to improve the ductility/toughness of BMGs.:Contents Abstract V Kurzfassung IX 1 Theoretical background 1 1.1 Development of metallic glasses 1 1.2 Formation of metallic glasses 3 1.2.1 Thermodynamic considerations 5 1.2.2 Kinetic considerations 7 1.2.3 Structural considerations 10 1.3 Mechanical properties of metallic glasses 14 1.4 Deformation mechanisms of metallic glasses 18 1.4.1 Shear transformation zone theory 18 1.4.2 Free volume model 20 1.4.3 Potential energy landscape theory 21 1.4.4 Cooperative Shearing Model 22 1.5 Strategies to improve the ductility of metallic glasses 24 1.5.1 Nano-scaled microstructural inhomogeneities 25 1.5.2 Micro-scaled microstructural inhomogeneities 28 1.5.3 CuZr-based BMG composites 31 2 Experimental techniques 37 2.1 Sample preparation 37 2.1.1 Arc melting/suction casting 37 2.1.2 Centrifugal casting 38 2.1.3 High-frequency melting/injection casting 39 2.1.4 Melt spinning 39 2.1.5 Ball milling and powder consolidation 40 2.2 Structure characterizations 41 2.2.1 X-ray diffraction 41 2.2.2 Optical microscopy and scanning electron microscopy 41 2.2.3 Transmission electron microscopy 42 2.3 Thermal analysis 43 2.3.1 Differential scanning calorimetry 43 2.3.2 Dilatometry 44 2.4 Measurement of the elastic constants 44 2.5 Compression and tensile tests 44 3 Strategy for pinpointing the formation of CuZr-based BMG composites 46 3.1 Theoretical analysis for the formation of CuZr-based BMG composites 46 3.2 Nature of the eutectoid B2 CuZr transformation 49 3.2.1 Shift of endothermic peak(s) related to the eutectoid B2 transformation 49 3.2.2 Thermal stability of the B2 CuZr phase 52 3.3 Formation of the amorphous phase and the B2 CuZr phase 54 3.4 A new parameter for pinpointing the formation of CuZr-based BMG composites 57 3.5 Conclusions 59 4 Synthesis of CuZr-based BMG composites 60 4.1 Formation of Type I alloys 60 4.2 Formation of Type II alloys 62 4.2.1 Formation and microstructures of the Cu50Zr50 BMG composites 62 4.2.2 Formation and microstructures of the Cu-Zr-Ti BMG composites 67 4.2.3 Formation and microstructures of the Cu-Zr-Al and Cu-Zr-Ag BMG composites 70 4.3 Formation of Type III alloys 74 4.4 Conclusions 76 5 Processing routes for CuZr-based BMG composites 78 5.1 Influence of the melting current/time 78 5.2 Adjusting the cooling rate 81 5.3 Re-melting of the pre-alloy 82 5.4 Introduction of boron nitride particles 84 5.5 Effect of TaW inoculation 87 5.6 “Flash annealing” 93 5.7 Conclusions 100 6 Yielding and deformation mechanisms of CuZr-based BMG composites 101 6.1 Formation and microstructures of Cu47.5Zr47.5Al5 BMG composites 101 6.2 Deformation behavior of Cu47.5Zr47.5Al5 BMG composites 105 6.3 Yielding and plastic deformation mechanisms 110 6.3.1 Yielding and plastic deformation during stage I 110 6.3.2 Yielding and plastic deformation during stage II 113 6.3.3 Yielding and plastic deformation during stage III 114 6.3.4 Plastic deformation during stage IV 118 6.3.5 Fracture behavior 120 6.4 Modeling of the “yielding” behavior 121 6.5 Conclusions 124 7 Martensitic transformation behavior in CuZr-based alloys 126 7.1 Electronic structures and martensitic transformation 126 7.1.1 Electronic structures of the B2 CuZr phase 127 7.1.2 Electronic structures of CuZr martensites 129 7.2 Effect of minor additions on the martensitic transformation 130 7.2.1 Formation of Cu-Zr-Ti crystalline samples 130 7.2.2 Effect of Ti element on the martensitic transformation 133 7.2.3 Effect of minor elements on the martensitic transformation temperature 135 7.3 Martensitic transformation in rapidly solidified alloys 139 7.3.1 Martensitic transformation in the as-cast Cu50Zr50 alloys 140 7.3.2 Martensitic transformation in the as-cast Cu-Zr-Al alloys 142 7.4 Conclusions 145 8 Shear banding process of CuZr-based BMG composites 146 8.1 Serrated flow in CuZr-based BMG composites 146 8.2 Statistical analysis of the serrations for brittle and ductile BMGs 148 8.3 Different statistical results of the serration events for CuZr-based BMG composites during deformation 152 8.4 Energy criteria for serrations in CuZr-based BMG and their composites 155 8.5 Conclusions 158 9 Summary and Outlook 160 Publications 162 Acknowledgements 163 References 164 Schriftliche Erklärung 191 / In letzter Zeit zeigte sich, dass massive Cu-Zr-basierte metallische Glaskomposite, welche B2 CuZr-Kristallite in der amorphen Matrix enthalten, eine ausgeprägte Plastizität mit klarer Kaltverfestigung aufweisen. Im Rahmen dieser Arbeit wurde versucht, eine Strategie zur zielgenauen Einstellung der Phasenbildung und des dazugehörigen Gefüges von massiven CuZr-basierten Glas-Matrix-Kompositen bereitzustellen, sowie deren Fließ- und Verformungsmechanismen aufzuklären. Es wurden elf verschiedene CuZr-basierte Legierungssysteme, insgesamt 36 verschiedene Zusammensetzungen, während Heiz- und Abschreckprozessen untersucht, um die Phasenbildung samt Gefüge von massiven CuZr-basierten Glas-Matrix-Kompositen zielgenau einzustellen. Bei CuZr-basierten metallischen Gläsern kann eine endotherme Reaktion zwischen Kristallisation und Schmelzvorgang der eutektoiden Umwandlung von B2 CuZr zugeordnet werden. Mit Zugabe verschiedener Elemente zur CuZr-Basislegierung kann diese Umwandlung zu höheren bzw. niedrigeren Temperaturen verschoben werden. Bereits geringe Beimischungen beeinflussen die thermische Stabilität der B2 CuZr-Phase. Unter Berücksichtigung der thermischen Stabilität, sowie des Widerstands gegen Kristallisation der unterkühlten Schmelze und der B2 CuZr-Phase wurde eine neue Strategie zur Auswahl des Zusammensetzungsgebiets metastabiler CuZr-Legierungen verschiedener Durchmesser vorgeschlagen. Dieser Widerstand kann durch den Parameter K=Tf/TL beschrieben werden, wobei Tf die Endtemperatur der eutektoiden Umwandlung und TL die Liquidustemperatur sind. Basierend auf diesem Parameter können die untersuchten CuZr-basierten Legierungen in drei Klassen unterteilt werden. Für Legierungen vom Typ I mit niedrigeren K-Werten, ist es schwer massive metallische Glas-Komposite (BMG-Komposite) zu erhalten. Im Gegensatz dazu lassen sich für Legierungen vom Typ III, mit höheren K-Werten, BMG-Komposite mit größeren Probendurchmessern herstellen und Legierungen vom Typ II mit einem mittleren K-Wert mit moderaten Probendurchmessern erzeugt werden. Folglich wurden CuZr-basierte Glas-Matrix-Komposite verschiedener Legierungssysteme mit B2-Phase in der amorphen Matrix erfolgreich in unterschiedlichen Geometrien hergestellt. Zur Kontrolle der Ausbildung der B2-Phase in der amorphen Matrix wurden unterschiedliche Methoden verwendet, um duktile CuZr-basierte BMG-Komposite herzustellen: (1) Einbringen von unlöslichen, hochschmelzenden Partikeln; (2) geeignete Wiederaufschmelzbehandlungen der Vorlegierungen; (3) eine neue Schnellerhitzungs- und -Abschreckmethode. Es konnte gezeigt werden, dass der Volumenanteil, sowie die Größe und Verteilung der B2-Phase in der amorphen Matrix durch die oben genannten Methoden kontrolliert werden können. Um die mechanischen Eigenschaften hinsichtlich des Fließens und der plastischen Deformationsmechanismen von CuZr-basierten BMG-Kompositen aufzuklären, wurden diese näher mittels Rasterelektronenmikroskopie, Röntgenbeugung und Durchstrahlungs-elektronenmikroskopie untersucht. Mit sinkendem Volumenanteil der amorphen Phase (famor) von 100 vol.% auf 0 vol.% kann ein Übergang von einer über zwei zu drei Fließgrenzen beobachtet werden. Für monolithische CuZr-basierte BMGs und ihre Komposite mit einem Anteil famor ≥ 97.5 ± 0.5vol.% erfolgt das Fließen ab einer Stauchung von ~2% durch Ausbildung von mehreren Scherbänden in der amorphen Matrix bzw. dem Zusammenwirken des dazugehörigen Scherens und der Martensitumwandlung. Bei einem Anteil famor unter 97.5 ± 0.5 vol.% findet ein Fließen bei niedrigerer Stauchung von ~1% statt. Dies geschieht aufgrund des Fließens und der beginnenden martensitischen Umwandlungen der B2 CuZr-Phase. Bei einem Anteil famor größer als 55 ± 3 vol.% kann ein Fließen oberhalb einer Stauchung von 8% durch die Interaktion von Versetzungen bei hoher Versetzungsdichte sowie partiellem „Entzwillingen“, beobachtet werden. Es wurde herausgefunden, dass mit sinkendem famor der Verformungsmechanismus schrittweise von einem Scherband dominierten zu einem von der martensitischen Umwandlung dominierten Mechanismus übergeht. Dieser Übergang führt zu Unterschieden in der plastischen Verformung. Da für das Verformungsverhalten von CuZr-basierten BMG-Kompositen die deformationsinduzierte martensitische Umwandlung und die Entstehung sowie Ausbreitung von Scherbändern von herausragender Bedeutung sind, wurden sie näher untersucht. Einerseits wurde herausgefunden, dass die Umwandlungstemperatur der martensitischen Umwandlung von CuZr-basierten martensitischen Legierungen in klarer Beziehung zur entsprechenden Elektronenstruktur und der Gitterkonstanten der äquiatomaren intermetallischen CuZr-Phasen stehen. Die martensitischen Umwandlungstemperaturen der untersuchten Legierungen können über die mittlere Valenzelektronenkonzentration ausgewertet werden. Zusätzliche Elemente mit größerem Atomradius können die Stapelfehlerenergie und die Ladungsdichteverteilung ändern, was in unterschiedliche Elektronenstrukturen mündet. Andererseits ist die Entstehung und Vervielfachung von Scherbändern in CuZr-basierten BMG-Kompositen verbunden mit der Speicherung und Dissipation der partiellen elastischen Energie während der plastischen Verformung. Durch das Einbringen von Gefügeinhomogenitäten unterschiedlicher Größe in die Glasmatrix, wird die elastische Energie, die im System Probe-Maschine gespeichert ist, während der plastischen Deformation umverteilt. Dies führt zu einem Übergang des Schervorgangs von chaotischem Verhalten zu einem selbstorganisierten kritischen Zustand. Insgesamt stellen unsere Untersuchungen und Beobachtungen ein Verständnis der Ausbildung, Verfomung und Gefügeoptimierung von CuZr-basierten BMG-Kompositen bereit und sollen als Leitfaden zur Verbesserung der Duktilität bzw. Zähigkeit von BMGs dienen.:Contents Abstract V Kurzfassung IX 1 Theoretical background 1 1.1 Development of metallic glasses 1 1.2 Formation of metallic glasses 3 1.2.1 Thermodynamic considerations 5 1.2.2 Kinetic considerations 7 1.2.3 Structural considerations 10 1.3 Mechanical properties of metallic glasses 14 1.4 Deformation mechanisms of metallic glasses 18 1.4.1 Shear transformation zone theory 18 1.4.2 Free volume model 20 1.4.3 Potential energy landscape theory 21 1.4.4 Cooperative Shearing Model 22 1.5 Strategies to improve the ductility of metallic glasses 24 1.5.1 Nano-scaled microstructural inhomogeneities 25 1.5.2 Micro-scaled microstructural inhomogeneities 28 1.5.3 CuZr-based BMG composites 31 2 Experimental techniques 37 2.1 Sample preparation 37 2.1.1 Arc melting/suction casting 37 2.1.2 Centrifugal casting 38 2.1.3 High-frequency melting/injection casting 39 2.1.4 Melt spinning 39 2.1.5 Ball milling and powder consolidation 40 2.2 Structure characterizations 41 2.2.1 X-ray diffraction 41 2.2.2 Optical microscopy and scanning electron microscopy 41 2.2.3 Transmission electron microscopy 42 2.3 Thermal analysis 43 2.3.1 Differential scanning calorimetry 43 2.3.2 Dilatometry 44 2.4 Measurement of the elastic constants 44 2.5 Compression and tensile tests 44 3 Strategy for pinpointing the formation of CuZr-based BMG composites 46 3.1 Theoretical analysis for the formation of CuZr-based BMG composites 46 3.2 Nature of the eutectoid B2 CuZr transformation 49 3.2.1 Shift of endothermic peak(s) related to the eutectoid B2 transformation 49 3.2.2 Thermal stability of the B2 CuZr phase 52 3.3 Formation of the amorphous phase and the B2 CuZr phase 54 3.4 A new parameter for pinpointing the formation of CuZr-based BMG composites 57 3.5 Conclusions 59 4 Synthesis of CuZr-based BMG composites 60 4.1 Formation of Type I alloys 60 4.2 Formation of Type II alloys 62 4.2.1 Formation and microstructures of the Cu50Zr50 BMG composites 62 4.2.2 Formation and microstructures of the Cu-Zr-Ti BMG composites 67 4.2.3 Formation and microstructures of the Cu-Zr-Al and Cu-Zr-Ag BMG composites 70 4.3 Formation of Type III alloys 74 4.4 Conclusions 76 5 Processing routes for CuZr-based BMG composites 78 5.1 Influence of the melting current/time 78 5.2 Adjusting the cooling rate 81 5.3 Re-melting of the pre-alloy 82 5.4 Introduction of boron nitride particles 84 5.5 Effect of TaW inoculation 87 5.6 “Flash annealing” 93 5.7 Conclusions 100 6 Yielding and deformation mechanisms of CuZr-based BMG composites 101 6.1 Formation and microstructures of Cu47.5Zr47.5Al5 BMG composites 101 6.2 Deformation behavior of Cu47.5Zr47.5Al5 BMG composites 105 6.3 Yielding and plastic deformation mechanisms 110 6.3.1 Yielding and plastic deformation during stage I 110 6.3.2 Yielding and plastic deformation during stage II 113 6.3.3 Yielding and plastic deformation during stage III 114 6.3.4 Plastic deformation during stage IV 118 6.3.5 Fracture behavior 120 6.4 Modeling of the “yielding” behavior 121 6.5 Conclusions 124 7 Martensitic transformation behavior in CuZr-based alloys 126 7.1 Electronic structures and martensitic transformation 126 7.1.1 Electronic structures of the B2 CuZr phase 127 7.1.2 Electronic structures of CuZr martensites 129 7.2 Effect of minor additions on the martensitic transformation 130 7.2.1 Formation of Cu-Zr-Ti crystalline samples 130 7.2.2 Effect of Ti element on the martensitic transformation 133 7.2.3 Effect of minor elements on the martensitic transformation temperature 135 7.3 Martensitic transformation in rapidly solidified alloys 139 7.3.1 Martensitic transformation in the as-cast Cu50Zr50 alloys 140 7.3.2 Martensitic transformation in the as-cast Cu-Zr-Al alloys 142 7.4 Conclusions 145 8 Shear banding process of CuZr-based BMG composites 146 8.1 Serrated flow in CuZr-based BMG composites 146 8.2 Statistical analysis of the serrations for brittle and ductile BMGs 148 8.3 Different statistical results of the serration events for CuZr-based BMG composites during deformation 152 8.4 Energy criteria for serrations in CuZr-based BMG and their composites 155 8.5 Conclusions 158 9 Summary and Outlook 160 Publications 162 Acknowledgements 163 References 164 Schriftliche Erklärung 191

<p> The room-temperature fracture behaviour of calcia partially stabilized zirconia (PSZ) was investigated. Fracture energy measurements were made using the standard stress intensity calibration and work to fracture techniques. The detailed nature of the PSZ microstructure was studied using scanning electron microscopy, qualitative X-ray analysis and T.E.M, surface replication. The grain structure was detenninod to be bimodal with small grains of pure zirconia dispersed along the boundaries of large grains. These large grains consist of a binary pure-zirconia/stabilized zirconia mixture. An attempt was made to relate the fracture properties to the nature of the inherent flaws present in the material. </p> <p> The strength of calcia partially stabilised zirconia was observed to depend on the size and distribution of the grain boundary precipitate of pure zirconia. It is postulated that this grain boundary precipitate causes decohesion and weakening of some of the grain boundaries due to the large internal stresses associated with its martensitic phase transformation. This phenomena of grain boundary decohesion leads to elastic nonlinearity and hysteresis. Crack propagation was always observed to proceed in a slow controlled fashion in this material. A model is proposed to explain theses observations based on the formation of a microcrack zone at the tip of a propagation crack. The occurrence of continued stable crack propagation is believed associated with increasing microcrack zone size with increasing crack length. Evidence supporting this model is presented. </p> / Thesis / Master of Science (MSc)

New materials are always being developed to get the best properties possible where needed. The way to create these materials and test them is also developing. When it comes to high-strength steels, a martensitic microstructure is a common choice. Martensite is a diffusionless phase transformation that generates the brittle martensitic microstructure. Tempering is a process where the brittle martensite is heat treated to make it more ductile and tough while simultaneously precipitating secondary phase particles that could help to strengthen the material. This study focuses on a novel dual-hardening martensitic steel that combines two different precipitates: carbides and intermetallics. The investigations are performed using simulations with the Thermo-Calc module TC-PRISMA to analyse the precipitation. The precipitation modelling is also compared to experimental data from the literature to evaluate the accuracy of the modelling. Out of the six alloys in this study, five were supposed to have NiAl precipitates. What was found was that two alloys, Alloy B and Alloy E, had NiAl precipitates that showed in PRISMA. In the three alloys that did not show NiAl precipitates, two of them did not have the phase stable at respective ageing temperatures. In the last alloy, that only had carbides, both of the precipitates showed up in PRISMA. More work needs to be done on co-precipitation, with comparison between simulations and experiments to confirm that the databases are reliable enough to be used to develop the materials of the future. / Nya material utvecklas hela tiden för att få de bästa möjliga egenskaperna där det behövs. Sättet att skapa dessa material, och testa dem, håller också på att utvecklas. När det gäller höghållfastastål är en martensitisk mikrostruktur ett vanligt val. Martensit är en diffusionsfri fasomvandling som genererar denna spröda martensitiska mikrostruktur. Härdning är en process där den spröda martensiten värmebehandlas för att göra den mer seg och duktil samtidigt som den skiljer ut sekundärfas-partiklar som kan hjälpa till att stärka materialet. Denna studie fokuserar på ett nytt dubbelhärdat martensitiskt stål som kombinerar två olika utskiljningar: karbider och intermetalliska utskiljningar. Undersökningarna utförs med hjälp av simuleringar med Thermo-Calc-modulen TC-PRISMA för att analysera utskiljningarna. Utskiljningsmodelleringen jämförs också med experimentella data från litteraturen för att utvärdera modellens noggrannhet. Av de sex legeringarna i denna studie skulle fem ha NiAl-utskiljningar. Det som konstaterade svar att endast två legeringar, legering B och legering E, hade NiAl-utskiljningar som visades i PRISMA. I de tre där det inte visades hade två av dem inte den fasen stabil vid respektiveåldringstemperaturer. Den sista legeringen hade bara karbider och i PRISMA dök de båda två upp. Mer arbete måste göras med samhärdning, med jämförelser mellan simuleringar och experiment för att bekräfta att databaserna är tillförlitliga nog för att kunna användas för att utveckla framtidens material.

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No description available.

Selective laser melting (SLM) has been shown to be an attractive manufacturing route for the production of ??/?? titanium alloys, and in particular Ti-6Al-4V. A thorough understanding of the relationship between the process, microstructure and mechanical properties of the components produced by this technology is however crucial for the establishment of SLM as an alternative manufacturing route. The purpose of the present study is thus to determine the microstructure evolution, crystallographic texture and the mechanical properties of SLM Ti-6Al-4V. The effect of several processing parameters on the density and the microstructure of the SLM samples were initially investigated. It was found that different sets of process parameters can be used to fabricate near fully dense components. It was found that the samples built using the optimised process window consist exclusively of ????? martensitic phase precipitated from prior ?? columnar grains. It was observed that the ?? grain solidification is influenced by the laser scan strategy and that the ?? phase has a strong <001> texture along its grain growth direction. The ????? martensitic laths that originate from the parent ?? grains precipitate according to the Burgers orientation relationship. It was found that ????? laths clusters from the same ?? grain have a specific misorientation that minimise the local shape strain. Texture inheritance across successive deposited layers was also observed and discussed in relation to various variant selection mechanisms. The mechanical properties of as-built and stress relieved SLM Ti-6Al-4V built using the same optimised process parameters were then investigated. It was found that the build orientation affects the tensile properties, and in particular the ductility of the samples. Samples built perpendicularly to the building direction showed higher ductility than those built in the vertical orientation. It was also observed that a stress relief heat treatment was beneficial to the mechanical properties of SLM Ti-6Al-4V. The ductility of the stress relieved samples was indeed higher than those found in the as-built condition. It was found that the predominant fracture mode during tensile testing is inter-granular. In terms of high-cycle fatigue, it was found that SLM Ti-6Al-4V is comparable to HIPed cast Ti-6Al-4V but it has a significantly lower fatigue resistance than that of wrought and annealed alloys. It was observed that porosity and the elongated prior ?? grain boundaries decrease substantially the fatigue life of the components. Cracks propagate either by fatigue striation or ductile tearing mechanisms. Using alternative laser scan strategies it was possible to control the microstructure of the as-built samples. It was observed that the laser scan vector length influences several microstructural features, such as the width of the prior ?? grains and the thickness of the ????? laths. It was found that re-melting the same layer has instead little effect on the microstructure. A novel laser scan strategy characterised by much lower laser power and scan speed than those typically used in SLM enabled finally to fabricate SLM Ti-6Al-4V with a microstructure close to that of conventionally manufactured Ti-6Al-4V. This study investigates for the first time the crystallographic texture evolution in Ti-6Al-4V manufactured by SLM. Further, this research presents for the first time the effect of the characteristic microstructure and crystallographic texture on the mechanical properties and fracture of SLM Ti-6Al-4V. Lastly, for the first time this research shows examples of microstructural control during the SLM fabrication of the same alloy using long laser dwell times.

Die Motivation zur Untersuchung ternärer und quaternären CuZr-Legierungen bestand in der Annahme, dass die Zugabe von Kobalt den Stabilitätsbereich von B2 CuZr bis zur Raumtemperatur erweitert und Aluminium einen signifikanten Effekt auf die Glasbildungsfähigkeit des CuZr-Systems hat. Die vorliegende Dissertation befasst sich mit der Herstellung und Charakterisierung von Cu50-xCoxZr50 (0 ≤ x ≤ 20) und Cu50-xCoxZr45Al5- (x = 2, 5, 10 und 20) Legierungen. Hierbei wurden die Phasenbildung, die thermische Stabilität, die Mikrostruktur, die Martensitbildung und die mechanischen Eigenschaften der Legierungen untersucht. Die Abhängigkeit der Phasenbildung von der Erstarrungsrate und der thermodynamischen Stabilität von Cu-Co-Zr-Legierungen zeigte, dass die Zugabe von Kobalt die Glasbildungsfähigkeit von Cu-Co-Zr-Legierungen absenkt und die stabilen kristallinen Produkte des Systems von Cu10Zr7 + CuZr2 zu (Cu,Co)Zr Phase mit einer B2 Struktur verändert. Die Ergebnisse weisen darauf hin, dass bei den schmelzgesponnene Bänder mit wenigstens 5 Atom-% Co das Glas direkt in B2 (Cu,Co)Zr kristallisiert, während Massivproben mit Co-Gehalten zwischen 0 ≤ x < 5 die monokline (Cu,Co)Zr Phase und Cu10Zr7 sowie CuZr2 beinhalten, wobei für x ≥ 10 die B2 (Cu,Co)Zr Phase bei Raumtemperatur im Gleichgewicht ist. Des Weiteren werden mit steigendem Co-Gehalt die Martensitumwandlungstemperaturen zu niedrigeren Werten verschoben. Die Phasenbildung im ternären System wird im pseudo-binären (Cu,Co)Zr-Phasendiagramm zusammengefasst, welches die Entwicklung neuer Formgedächtnislegierungen sowie metallischer Glas-Komposite bei Zugabe des Glasbildungselementes Aluminium vereinfacht. In den Vierstofflegierungen erhöht Al die Glasübergangs- und Kristallisationstemperaturen und verbessert dadurch die Glasbildungsfähigkeit des Systems. Die röntgenographische Analyse zeigte, dass die Kristallisationsprodukte der schmelzgesponnenen Bänder variieren: von Cu10Zr7 + CuZr2 + AlCu2Zr zu (Cu,Co)Zr + AlCu2Zr, wenn Co ≤ 5 und Co ≥ 10. Die Herstellung von Massivproben mit unterschiedlichen Durchmessern führte zu einem vollständig amorphen Gefüge, einem metallischen Glas-Komposit oder einem vollständig kristallinen Gefüge. Für Co ≤ 5 tritt neben (Cu,Co)Zr und AlCu2Zr ebenfalls Cu10Zr7 auf. Mittels Rasterelektronen (REM)- und Transmissionselektronenmikroskopie (TEM) erfolgte die Analyse des Einflusses von Al- und Co-Zugaben auf die Mikrostruktur von CuZr-Legierungen. Für die Cu-Co-Zr-Al-Legierungen sowie Cu30Co20Zr45Al5 (ø = 4 mm) und Cu45Co5Zr45Al5 (ø = 2 mm) wurden mikrostrukturelle Untersuchungen mittels TEM durchgeführt. Nachfolgend wurde die Heterogenität der Mikrostruktur in der Cu40Co10Zr45Al5 (ø = 2 mm) untersucht. Der Einfluss von Co auf die mechanischen Eigenschaften von rascherstarrten Cu50-xCoxZr50 (x = 2, 5, 10 und 20 Atom-%) Legierungen zeigt, dass das Verformungsverhalten der Stäbe unter Druckbeanspruchung stark von der Mikrostruktur der (Cu,Co)Zr Phase und somit von der Legierungszusammensetzung abhängt. Kobalt beeinflusst die Bruchfestigkeit der Gussproben. Weiterhin zeigen Proben mit martensitischem Gefüge eine Kaltverfestigung. Neben der Kaltverfestigung zeigen die Legierungen mit hohem Co-Gehalt eine verformungsinduzierte Martensitumwandlung und weisen zwei Streckgrenzen auf. Für die Vierstofflegierungen wurde der Einfluss der Kühlrate und der chemischen Zusammensetzung auf die mechanischen Eigenschaften untersucht. Für Cu48Co2Zr45Al5 (ø = 1.5, 2, 3 und 4 mm) und Cu45Co5Zr45Al5 (ø = 3 mm) wurde der Einfluss der Kühlrate und der Heterogenität diskutiert. Die Ergebnisse zeigen, dass die mechanischen Eigenschaften der Cu50-xCoxZr45Al5-Legierungen stark von der Makrostruktur und dem Volumenanteil der amorphen und kristallinen Phase abhängen. Die verformungsinduzierte Martensitumwandlung in Cu40Co10Zr50- und Cu40Co10Zr45Al5-Gussstäben wurde mittels hochenergetischer Röntgenstrahlung durchgeführt. Die In-situ- Druckversuche erfolgten weg- und kraftkontrolliert. Das makroskopische und mikroskopische Spannung-Dehnungs-Verhalten sowie die Phasenumwandlungskinetik wurden dabei betrachtet. Die relativen Veränderungen der vollständig integrierten Intensität der ausgewählten B2- und Martensitreflexe, die auf die Veränderungen der Volumenanteile der entsprechenden Phasen unter Verformung hinweisen, wurden als Phasenumwandlungsvolumen M/M+B2 beschrieben. / The fact that the presence of Co extends the stability range of B2 CuZr to room temperature, together with the significant effect of Al on improving the glass forming ability of the CuZr system was the motivation to investigate the ternary and quaternary CuZr alloys with the aim of synthesizing BMG composites containing B2 (Cu,Co)Zr crystals. This PhD thesis deals with preparation and characterization of Cu50-xCoxZr50 (0 ≤ x ≤ 20) and Cu50-xCoxZr45Al5 (x = 2, 5, 10 and 20) alloys. The phase formation, thermal stability, microstructure, martensitic transformation and mechanical properties of these alloys were investigated. The dependence of phase formation on solidification rate and the thermodynamically stability of Cu-Co-Zr alloys reveals that the addition of Co decreases the glass forming ability (GFA) of the Cu-Co-Zr alloys and changes the stable crystalline products of the system from Cu10Zr7 + CuZr2 to (Cu,Co)Zr phase with a B2 structure. The results indicate that for the melt-spun ribbons with at least 5 % Co, the glass crystallizes directly into B2 (Cu,Co)Zr, while in the case of bulk specimens, compositions with 0 ≤ x < 5 of Co contain the monoclinic (Cu,Co)Zr phase and Cu10Zr7 and CuZr2, whereas, for x ≥ 10, the B2 (Cu,Co)Zr phase is the equilibrium phase at room temperature. Furthermore, increasing the cobalt content decreases the martensitic transformation temperatures to lower temperatures. The phase formation in the ternary system is summarized in a pseudo-binary (Cu,Co)Zr phase diagram, that helps for designing new shape memory alloys, as well as bulk metallic glass composites with the addition of glass former elements. In the quaternary alloys, Al increases the glass transition and crystallization temperatures and hence improves the GFA of the system. The X-ray analysis illustrates that for the melt-spun ribbons, the crystallization products vary from Cu10Zr7 + CuZr2 + AlCu2Zr to (Cu,Co)Zr + AlCu2Zr when Co ≤ 5 and Co ≥ 10, respectively. Depending on the cooling rates, the bulk samples represent a fully amorphous structure or BMG composites or a fully crystalline structure. For Co ≤ 5, beside (Cu,Co)Zr and AlCu2Zr, Cu10Zr7 exists as well. Scanning (SEM) and transmission (TEM) electron microscopy investigations were done to investigate the effect of Al and Co addition to the microstructure of CuZr alloys. In the case of Cu-Co-Zr-Al alloys, Cu30Co20Zr45Al5 (ɸ = 4 mm) and Cu45Co5Zr45Al5 (ɸ = 2 mm) compositions were selected for the microstructure verification using TEM. Later, the heterogeneity of the microstructure in Cu40Co10Zr45Al5 (ɸ = 2 mm) alloy was considered. The effect of Co on the mechanical properties of rapidly solidified Cu50-xCoxZr50 (x = 2, 5, 10 and 20 at.%) alloys depict that the deformation behavior of the rods under compressive loading strongly depends on the microstructure, and as a results, on the alloy composition. Cobalt affects the fracture strength of the as-cast samples; and deformation is accompanied with two yield stresses for high Co-content alloys, which undergo deformation-induced martensitic transformation. Instead samples with a martensitic structure show a work-hardening behavior. For quaternary alloys, the effects of cooling rate and chemical composition on mechanical properties of the alloys were investigated. Cu48Co2Zr45Al5 (ɸ= 1.5, 2, 3 and 4 mm) and Cu45Co5Zr45Al5 (ɸ = 3 mm) compositions were selected to discuss the effect of cooling rate and heterogeneity, respectively. The results depict that the mechanical properties of Cu50-xCoxZr45Al5 alloys strongly depend on the microstructure and the volume fraction of the amorphous and crystalline phases. The deformation-induced martensitic transformation of Cu40Co10Zr50 and Cu40Co10Zr45Al5 as-cast rods, was studied by means of high-energy X-rays. The in situ compression measurements were performed in track control and load control modes. The macroscopic and microscopic stress-strain behavior, as well as the phase transformation kinetics were considered. The relative changes in the fully integrated intensity of the selected B2 and martensite peaks, which indicate the changes in volume fraction of the corresponding phases under deformation, was described as phase transformation volume, M/M+B2.