This work identifies alloy terminal freezing range, columnar growth, grain coarsening, liquid availability towards the terminal stage of solidification, and segregation towards boundaries as primary factors affecting the hot-cracking susceptibility of fusion-based additive manufacturing (F-BAM) processed alloys. Additionally, an integrated computational materials engineering (ICME)-based approach has been formulated to design novel Al alloys, and high entropy alloys for F-BAM processing. The ICME-based approach has led to heterogeneous nucleation-induced grain refinement, terminal eutectic solidification-enabled liquid availability, and segregation-induced coalescence of solidification boundaries during laser-powder bed fusion (L-PBF) processing. In addition to exhibiting a wide crack-free L-PBF processing window, the designed alloys exhibited microstructural heterogeneity and hierarchy (MHH), and thus could leverage the unique process dynamics of L-PBF to produce a fine-tunable MHH and mechanical behavior. Furthermore, alloy chemistry-based fine tuning of the stacking fault energy has led to transformative damage tolerant alloys. Such alloys can shield defects stemming from the stochastic powder bed in L-PBF, and consequently can prevent catastrophic failure despite the solidification defects. A modified materials systems approach that explicitly includes alloy chemistry as a means to modify the printability, properties and performance with F-BAM is also presented. Overall, this work is expected to facilitate application specific manufacture with F-BAM and eventually facilitate widespread adoption of F-BAM in structural application.

The high entropy alloys (HEAs) have been developed based on the concept of entropic stabilization associated with a large number of constituent elements. The high configurational entropy in HEAs is expected to cause promising characteristic properties, i.e. high microstructural stability and high mechanical properties. In this study, the equiatomic fcc-structured FeNiCoCrMn and the bcc-structured TiNbHfTaZr single phase high entropy alloys (HEAs) were investigated regarding the effect of multiple atom species on microstructure, intrinsic lattice strain and mechanical properties. In a comparison with the HEAs, the sub-alloys having less chemical complexity were studied. The selected sub-alloys of the FeNiCoCrMn HEA were FeNiCoCr, FeNiCo, FeNi alloys and pure Ni, while equiatomic TiNbHfTa, TiNbHf, TiNb alloys and pure Nb were studied to compare with the TiNbHfTaZr HEA. The samples in this study were prepared by arc-melting, cold-crucible casting and thermomechanical treatment. The thermal phase stability of the FeNiCoCrMn HEA, TiNbHfTaZr HEA and their sub-alloys were observed and no second phase was formed between 300 - 1500 K. In high entropy alloys, the random arrangement of multiple atom species is assumed to cause large atomic displacements at lattice sites, which give rise to a severe lattice distortion. The evidences of lattice distortion in HEAs have been limitedly reported due to a difficulty of experimental investigation. In this work, the pair distribution function (PDF) method was used to assess local strain with analysis of diffuse intensities on total synchrotron X-ray scattering data. The current study found that the level of local lattice strain associated with atomic displacement was a function of atomic size misfit. The local lattice strain of the FeNiCoCrMn HEA was small and comparable to that of the sub-alloys which obtain similar values of the atomic size misfit. In contrast to the FeNiCoCrMn system, the magnitude of the local lattice strain increased with the value of atomic size misfit from the unary Nb sample to the quinary TiNbHfTaZr HEA. The lattice distortion was evident in the TiNbHfTaZr HEA due to large local lattice strain, but the local lattice strain of the FeNiCoCrMn HEA was not anomalously large. The level of lattice strain determines the solid solution hardening as a consequence of the elastic interaction between dislocations and atoms. The comparable level of the lattice strain in the FeNiCoCrMn HEA, its sub-alloys and Ni sample led to narrow range of hardness (64 – 132 HV) and tensile yield strength (60 – 192 MPa). For the bcc-structured samples, the hardness and the yield strength significantly varied depending on the level of local lattice strain, between 80 – 327 HV of hardness and 207 – 985 MPa of tensile yield strength. It is clear from the result that the atomic size misfit influences the level of the local lattice strain and the solid solution hardening. Cold rotary swaging was used to study the work hardening in the HEAs because it can delay fracture by large hydrostatic stresses. The large plastic deformability was observed in the FeNiCoCrMn and TiNbHfTaZr HEAs. The TiNbHfTaZr HEA was cold-swaged by 90% reduction of the cross-sectional area without intermediate annealing. The FeNiCoCrMn HEA was swaged until 85% reduction of the cross-sectional area; however, it was observed that it could be further deformed. The dislocation densities of the HEAs and its sub-alloys after the cold deformation were calculated as in the range between 1014 - 1015 m-2, in a good agreement with reported values of conventional metals after severe plastic deformation. This finding suggested that the level of dislocation density storage was correlated with the number of the constituent elements, the level of lattice distortion associated with atomic size misfit and the intrinsic properties (i.e. the stacking fault energy and the melting point). Whereas the intrinsic lattice strains of the FeNiCoCrMn HEA and its sub-alloys were comparable, the levels of dislocation storage were different possibly due to a difference of stacking fault energy. For the bcc-structured samples, the dislocation densities of the TiNbHfTaZr HEA, TiNbHfTa and TiNbHf alloys were large due to the large atomic size misfits. The high dislocation density leads to strong interactions between dislocations, which results in high resistance to dislocation motions. The high mechanical properties (hardness and yield strength) in the as-deformed FeNiCoCrMn and TiNbHfTaZr HEA were presented with the evidence of high dislocation densities. Moreover, the hardness and yield strength of the FeNiCoCrMn HEA significantly increased by the deformation, while those of the TiNbHfTaZr HEA after the deformation were slightly changed from the undeformed HEA. The large work hardenability of the FeNiCoCrMn HEA is possibly caused by small solid solution hardening and ease of twin formation. The research results suggest a further step towards designing an alloy composition for a development of microstructure and mechanical properties of high entropy alloys. It is evidently clear from the findings that the large number of constituent elements (in a term of high configurational entropy) is not only a factor in the determination of lattice distortion, microstructure and mechanical properties, but the type and the combination of constituent elements including the atomic interactions (i.e. atomic size misfit) have also an effect.:Abstract v Zusammenfassung ix Contents xiii 1. Motivation and objectives 1 2. Fundamentals 5 2.1 Concept of high entropy alloys 5 2.1.1 Phase formation and thermodynamic 5 2.1.2 Four core effects 10 2.2 Alloy classification of high entropy alloys 13 2.3 Mechanical properties of high entropy alloys 14 3. Experiments 19 3.1 Alloy preparation 19 3.1.1 Alloy selection 19 3.1.2 Melting and casting 21 3.1.3 Thermomechanical treatment 23 3.2 Sample characterization 27 3.2.1 Chemical analyses 27 3.2.2 Differential scanning calorimetry (DSC) 27 3.2.3 Scanning electron microscopy and microstructural analyses 28 3.2.4 X-ray diffraction (XRD) 29 3.2.5 High energy synchrotron X-ray diffraction 29 3.2.6 Mechanical Properties 33 4. Thermal phase stability of single phase high entropy alloys 35 5. An assessment of lattice strain in single phase high entropy alloys 49 5.1 Analysis of micro lattice strain on fcc- and bcc-structured high entropy alloys 50 5.2 Analysis of local lattice strain on fcc- and bcc-structured high entropy alloys 56 6. Solid solution hardening in single phase high entropy alloys 65 6.1 Hardness of fcc- and bcc-structured high entropy alloys 65 6.2 Tensile strength of fcc- and bcc-structured high entropy alloys 70 6.3 Correlation between atomic size misfit and solid solution hardening in Ti-Nb-Hf-Ta-Zr system 82 7. Work hardening in single phase high entropy alloys 91 7.1 Work hardenability of fcc- and bcc-structured high entropy alloys 91 7.2 Dislocation density of fcc- and bcc-structured high entropy alloys after cold swaging 93 8. Summary and outlook 109 8.1 Summary 109 8.2 Outlook 112 References 113 Acknowledgements 131 Erklärung 133 / Die Hochentropielegierungen (HELen) wurden auf der Grundlage des Konzepts der entropischen Stabilisierung entwickelt, was eine große Anzahl von Legierungselementen beinhaltet. Es wird erwartet, dass die hohe Konfigurationsentropie in HELen vielversprechende charakteristische Eigenschaften hervorruft, d.h. hohe mikrostrukturelle Stabilität und hohe mechanische Eigenschaften. In dieser Studie wurden die äquiatomare kfz-strukturierte FeNiCoCrMn und die krz-strukturierte TiNbHfTaZr Einphasen-Hochentropielegierung hinsichtlich der Wirkung mehrerer Atomarten auf das Gefüge, die intrinsische Gitterdehnung und die mechanischen Eigenschaften untersucht. Im Vergleich zu den HELen wurden die Sublegierungen mit geringerer chemischer Komplexität untersucht. Die ausgewählten Sublegierungen der FeNiCoCrMn HEL waren FeNiCoCr, FeNiCo, FeNi-Legierungen und reines Ni, während äquiatomare TiNbHfTa, TiNbHf, TiNbHf, TiNb-Legierungen und reines Nb im Vergleich zur TiNbHfTaZr HEL untersucht wurden. Die Proben in dieser Studie wurden durch Lichtbogenschmelzen, Kalttiegelguss und thermomechanische Behandlung hergestellt. Die thermische Phasenstabilität der FeNiCoCrMn HEL, der TiNbHfTaZr HEL und ihrer Sublegierungen wurde untersucht und es wurde keine zweite Phase zwischen 300 - 1500 K gebildet. Bei Hochentropielegierungen wird angenommen, dass die zufällige Anordnung mehrerer Atomarten zu großen Atomverschiebungen an den Gitterplätzen führt, die eine starke Gitterverzerrung hervorrufen. Aufgrund der Schwierigkeit der experimentellen Untersuchung wurden Beweise für Gitterverzerrungen bei HELen nur begrenzt berichtet. In dieser Studie wurde die Methode der Paarverteilungsfunktion (PDF) verwendet, um die lokale Dehnung mit Analyse der diffusen Intensitäten der gesamten Synchrotron-Röntgenstreuungsdaten zu beurteilen. Die aktuelle Studie ergab, dass die Höhe der lokalen Gitterdehnung, die mit der atomaren Verschiebung einhergeht, eine Funktion der Differenz der Atomgröße ist. Die lokale Gitterdehnung der FeNiCoCrMn HEL war klein und vergleichbar mit der der Sublegierungen, für die ähnliche Werte für die Atomgrößen-Unterschiede ermittelt wurden. Im Gegensatz zum FeNiCoCrMn-System stieg die Größe der lokalen Gitterdehnung mit dem Wert der Atomgrößendifferenz von der unären Nb-Probe bis zur quinären TiNbHfTaZr HEL. Die Gitterverzerrung war in der TiNbHfTaZr HEL aufgrund der großen lokalen Gitterdehnung offensichtlich, wohingegen die lokale Gitterdehnung der FeNiCoCrMn HEL nicht ungewöhnlich groß war. Die Höhe der Gitterdehnung bestimmt die Mischkristallverfestigung als Folge der elastischen Wechselwirkung zwischen Versetzungen und Atomen. Der vergleichbare Wert der Gitterdehnung in der FeNiCoCrMn HEL, seinen Sublegierungen und den Ni-Proben führte zu einem engen Härte- (64 - 132 HV) und Streckgrenzenbereich (60 - 192 MPa). Für die krz-strukturierten Proben variierten die Härte und die Streckgrenze dagegen je nach Höhe der lokalen Gitterdehnung signifikant, d.h zwischen 80 - 327 HV hinsichtlich der Härte und zwischen 207 - 985 MPa hinsichtlich der Streckgrenze. Aus dem Ergebnis ist ersichtlich, dass die Differenz der Atomgröße einen Einfluss auf die Höhe der lokalen Gitterdehnung und die Mischkristallverfestigung hat. Das Kalthämmen wurde für die Untersuchung der Kaltverfestigung in den HELen genutzt, da es den Bruch durch die großen hydrostatischen Spannungen verzögern kann. Die große plastische Verformbarkeit wurde bei den FeNiCoCrMn und TiNbHfTaZr HELen beobachtet. Die TiNbHfTaZr HEL wurde ohne Zwischenglühen um 90% der Querschnittsfläche kaltgehämmert. Die FeNiCoCrMn HEL wurde bis zu einer Verkleinerung der Querschnittsfläche von 85% gehämmert, wobei jedoch eine weitere Verformung möglich gewesen wäre. Die Versetzungsdichten der HELen und ihrer Sublegierungen wurden nach dem Verformung in einem Bereich zwischen 1014 - 1015 m-2 berechnet, was in guter Übereinstimmung mit den berichteten Werten konventioneller Metalle nach starker plastischer Verformung ist. Dieses Ergebnis deutete darauf hin, dass die Höhe der gespeicherten Versetzungsdichte mit der Anzahl der beinhaltenden Elemente, dem Grad der Gitterverzerrung im Zusammenhang mit der Differenz der Atomgröße und den intrinsischen Eigenschaften (d.h. der Stapelfehlerenergie und dem Schmelzpunkt) korreliert. Obwohl die intrinsischen Gitterdehnungen der FeNiCoCrMn HEL und seiner Sublegierungen vergleichbar waren, waren die Werte der gespeicherten Versetzungen unterschiedlich, was möglicherweise an einer Differenz der Stapelfehlerenergie lag. Für die krz-strukturierten Proben waren die Versetzungsdichten der TiNbHfTaZr HEL, der TiNbHfTa- und der TiNbHf-Legierungen aufgrund der großen Atomgrößenunterschiede hoch. Die hohe Versetzungsdichte bewirkt starke Wechselwirkungen zwischen den Versetzungen, was zu einem hohen Widerstand gegen Versetzungsbewegungen führt. Die hohen mechanischen Eigenschaften (Härte und Streckgrenze) in den verformten FeNiCoCrMn und TiNbHfTaZr HELen wurden mit dem Nachweis hoher Versetzungsdichten belegt. Darüber hinaus wurden die Härte und die Streckgrenze des FeNiCoCrMn HEL durch das Kalthämmern deutlich erhöht, während die der TiNbHfTaZr HEL nach dem Hämmerprozess nur leicht gegenüber der unverformten HEL verändert wurden. Die große Kaltverfestigung der FeNiCoCrMn HEL ist möglicherweise auf eine geringe Mischkristallhärtung und eine geringfügige Zwillingsbildung zurückzuführen. Die Forschungsergebnisse empfehlen für die Entwicklung des Gefüges und der mechanischen Eigenschaften von Hochentropielegierungen weitere Schritte hinsichtlich eines zielführenden Legierungsdesigns durchzuführenhin. Aus den Ergebnissen geht eindeutig hervor, dass die große Anzahl an Legierungselementen ( hinsichtlich einer hochkonfigurativen Entropie) nicht die einzige Einflussgrößebei der Bestimmung von Gitterverzerrungen, dem Gefüge und der mechanischen Eigenschaften darstellt, sondern auch die Art und die Kombination der Legierungselementen einschließlich der atomaren Wechselwirkungen (d.h. Atomgrößenunterschiede) einen Effekt haben.:Abstract v Zusammenfassung ix Contents xiii 1. Motivation and objectives 1 2. Fundamentals 5 2.1 Concept of high entropy alloys 5 2.1.1 Phase formation and thermodynamic 5 2.1.2 Four core effects 10 2.2 Alloy classification of high entropy alloys 13 2.3 Mechanical properties of high entropy alloys 14 3. Experiments 19 3.1 Alloy preparation 19 3.1.1 Alloy selection 19 3.1.2 Melting and casting 21 3.1.3 Thermomechanical treatment 23 3.2 Sample characterization 27 3.2.1 Chemical analyses 27 3.2.2 Differential scanning calorimetry (DSC) 27 3.2.3 Scanning electron microscopy and microstructural analyses 28 3.2.4 X-ray diffraction (XRD) 29 3.2.5 High energy synchrotron X-ray diffraction 29 3.2.6 Mechanical Properties 33 4. Thermal phase stability of single phase high entropy alloys 35 5. An assessment of lattice strain in single phase high entropy alloys 49 5.1 Analysis of micro lattice strain on fcc- and bcc-structured high entropy alloys 50 5.2 Analysis of local lattice strain on fcc- and bcc-structured high entropy alloys 56 6. Solid solution hardening in single phase high entropy alloys 65 6.1 Hardness of fcc- and bcc-structured high entropy alloys 65 6.2 Tensile strength of fcc- and bcc-structured high entropy alloys 70 6.3 Correlation between atomic size misfit and solid solution hardening in Ti-Nb-Hf-Ta-Zr system 82 7. Work hardening in single phase high entropy alloys 91 7.1 Work hardenability of fcc- and bcc-structured high entropy alloys 91 7.2 Dislocation density of fcc- and bcc-structured high entropy alloys after cold swaging 93 8. Summary and outlook 109 8.1 Summary 109 8.2 Outlook 112 References 113 Acknowledgements 131 Erklärung 133

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Fundamental understanding of high strain rate deformation behavior of materials is critical in designing new alloys for wide-ranging applications including military, automobile, spacecraft, and industrial applications. High entropy alloys, consisting of multiple elements in (near) equimolar proportions, represent a new paradigm in structural alloy design providing ample opportunity for achieving excellent performance in high strain rate applications by proper selection of constituent elements and/or thermomechanical processing. This dissertation is focused on fundamental understanding of high strain-rate deformation behavior of several high entropy alloy systems with widely varying microstructures. Ballistic impact testing of face centered cubic Al0.1CoCrFeNi high entropy alloy showed failure by ductile hole growth. The deformed microstructure showed extensive micro-banding and micro-twinning at low velocities while adiabatic shear bands and dynamic recrystallization were seen at higher velocities. The Al0.7CoCrFeNi and AlCoCrFeNi2.1 eutectic high entropy alloys, with BCC and FCC phases in lamellar morphology, showed failure by discing. A network of cracks coupled with small and inhomogeneous plastic deformation led to the brittle mode of failure in these eutectic alloys. Phase-specific mechanical behavior using small-scale techniques revealed higher strength and strain rate sensitivity for the B2 phase compared to the L12 phase. The interphase boundary demonstrated good stability without any cracks at high compressive strain rates. The Al0.3CoCrFeNi high entropy alloy with bimodal microstructure demonstrated an excellent combination of strength and ductility. Ballistic impact testing of Al0.3CoCrFeNi alloy showed failure by ductile hole growth and demonstrated superior performance compared to all the other high entropy alloy systems studied. The failure mechanism was dominated by micro-banding, micro-twining, and adiabatic shear localization. Comparison of all the high entropy alloy systems with currently used state-of-the-art rolled homogenous armor (RHA) steel showed a strong dependence of failure modes on microstructural features.

High-entropy alloys (HEAs) have attracted significant interest in the materials science community over the last 15 years. At the first moment, what caught the attention was the fact that these alloys tend to form solid solutions at room temperature, despite being composed of multiple elements in equiatomic or near-equiatomic concentrations. It was initially concluded that the configurational entropy plays a key role in the stabilization of the solid solutions. Later studies revealed the importance of lattice strain enthalpies, enthalpies of mixing, structural mismatch of constituents, and kinetics in phase formation/stability. The study presented in this thesis was branched into three major parts, all related to understanding phase formation, stability, or metastability in this class of alloys. The first part deals with developing an empirical method to predict single-phase solid solution formation in multi-principal element alloys. The second, which makes the core of this thesis, are non-equilibrium solidification studies of CrFeNi and CoCrNi medium-entropy alloys, and CoCrFeNi, Al0.3CoCrFeNi, and NbTiVZr high-entropy alloys. The last part is devoted to understanding the thermophysical properties of CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys. An empirical approach, based on the theoretical elastic-strain energy, has been developed to predict the phase formation and its stability for complex concentrated alloys. The conclusiveness of this approach is compared with the traditional empirical rules based on the atomic-size mismatch, enthalpy of mixing, and valence-electron concentration for a database of 235 alloys. The proposed “elastic-strain energy vs. valence-electron concentration” criterion shows an improved ability to distinguish between single-phase solid solutions, mixtures of solid solutions, and intermetallic phases when compared to the available empirical rules used to date. The criterion is especially strong for alloys that precipitate the μ phase. The elastic-strain-energy parameter can be combined with other known parameters, such as those noted above, to establish new criteria which can help in designing novel complex concentrated alloys with the on-demand combination of mechanical properties. The solidification behavior of the CoCrFeNi high-entropy alloy and the ternary CrFeNi and CoCrNi medium-entropy suballoys has been studied in situ using high-speed video-camera and synchrotron X-ray diffraction (XRD) on electromagnetically levitated samples at Leibniz Institute for Solid State and Materials Research Dresden (IFW Dresden) and German Synchrotron DESY, Hamburg. In all alloys, the formation of a primary metastable body-centered cubic bcc phase was observed if the melt was sufficiently undercooled. The delay time for the onset of the nucleation of the stable face-centered cubic fcc phase, occurring within bcc crystals, is inversely proportional to the melt undercooling. The experimental findings agree with the stable and metastable phase equilibria for the (CoCrNi)-Fe section. Crystal-growth velocities for the CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys, extracted from the high-speed video sequences in the present study, are comparable to the literature data for Fe-rich Fe-Ni and Fe-Cr-Ni alloys, evidencing the same crystallization kinetics. The effect of melt undercooling on the microstructure of solidified samples is analyzed and discussed in the thesis. To understand the effect of Al addition on the non-equilibrium solidification behavior of the equiatomic CoCrFeNi alloy, the Al0.3CoCrFeNi HEA has been studied. While the quaternary alloy melt could be significantly undercooled, this was not possible in the five-component alloy. Therefore, the investigations on phase formation, crystal growth, and microstructural evolution were confined to the low undercooling regime. In situ XRD measurements revealed that the liquid crystallized into a fcc single-phase solid solution at this undercooling level. However, ex situ XRD revealed the precipitation of the ordered L12 phase for a sample solidified with ΔT = 30 K. Crystal growth velocities are shown to be smaller than in the CoCrFeNi, CrFeNi, and CoCrNi alloys; nonetheless, they are in the same order of magnitude. Spontaneous grain refinement, without the formation of crystal twins, is observed at low undercooling of ΔT = 70 K, which could be explained by the dendrite tip radius dependence on melt undercooling. In situ studies of the equiatomic NbTiVZr refractory high-entropy alloys revealed the effect of processing conditions on the high-temperature phase formation. When the melt was undercooled over 80 K, it crystallized as a bcc single-phase solid solution despite solute partitioning between the dendritic and interdendritic regions. When the sample was solidified from the semisolid state, it resulted in the formation of two additional bcc phases at the interdendritic regions. The crystal growth velocity, as estimated from the high-speed videos, showed pronounced sluggish kinetics: it is 1 to 2 orders of magnitude smaller compared to literature data of other medium and high-entropy alloys. The study of the linear expansion coefficient α and heat capacity at constant pressure 𝐶𝑝 of the equiatomic CoCrFeNi and the medium-entropy CrFeNi and CoCrNi alloys revealed an anomalous behavior with S-shaped curves in the temperature range of 700 – 950 K. The anomalous behavior is shown to be reversible as it occurred during the first and second heating. However, a minimum is only observed on the first heating, while in the second heating a sudden increase of both the α and 𝐶𝑝 occurs at the temperature of the onset of the minima in the first heating. Magnetic moment measurements as a function of temperature showed that the observed anomaly is not associated with the Curie temperature. Consideration of the structural and microstructural evaluation discards a first-order phase transformation or recrystallization as probable causes, at least for the CoCrFeNi and CoCrNi alloys. Based on literature evidence, the anomalies in the temperature dependences of the linear expansion coefficient and heat capacity are believed to be caused by a chemical short-range order transition known as the K-state effect. However, to reveal the exact nature of this phenomenon, further experimental and theoretical studies are required, which is outside the frame of the present work.:Abstract ....................................................................................................................... I Kurzfassung .............................................................................................................. IV Chapter 1: Motivation and Fundamentals .................................................................. 1 1.1 Introduction .......................................................................................................... 1 1.2 The high-entropy alloy (HEA) design concept ...................................................... 4 1.3 Empirical rules of phase formation for HEAs ....................................................... 6 1.4 Calculation of phase diagrams of HEAs ............................................................. 18 1.5 The core effects of HEAs ................................................................................... 20 1.5.1 Lattice distortion .............................................................................................. 20 1.5.2 Sluggish diffusion ............................................................................................ 22 1.5.3 Cocktail effect................................................................................................... 23 1.6 Mechanical properties ........................................................................................ 24 1.6.1 Lightweight high-entropy alloys ....................................................................... 24 1.6.2 Overcoming the strength-ductility tradeoff ...................................................... 26 1.6.3 Cryogenic high-entropy alloys ......................................................................... 28 1.6.4 Refractory high-entropy alloys ........................................................................ 30 1.7 Functional properties .......................................................................................... 33 1.7.1 Soft magnetic properties ................................................................................. 33 1.7.2 Magnetocaloric properties ............................................................................... 35 1.7.3 Hydrogen storage ............................................................................................ 36 Chapter 2: Experimental .......................................................................................... 38 2.1 Sample preparation ............................................................................................ 38 2.2 Electromagnetic levitation .................................................................................. 40 2.3 In situ X-ray diffraction ........................................................................................ 43 2.4 Microstructural and structural analysis ............................................................... 44 2.5 Thermal analysis ................................................................................................ 45 2.6 Dilatometry ......................................................................................................... 45 2.7 Magnetic moment ............................................................................................... 46 2.8 Heat treatment ................................................................................................... 46 Chapter 3: In situ study of non-equilibrium solidification of CoCrFeNi high-entropy alloy and CrFeNi and CoCrNi ternary suballoys ...................................................... 47 3.1 Introduction ........................................................................................................ 47 3.2 Results ............................................................................................................... 48 3.2.1 In situ synchrotron X-ray diffraction ................................................................. 48 3.2.2 High-speed video imaging ............................................................................... 52 3.2.3 Microstructure of the solidified samples .......................................................... 62 3.3 Discussion .......................................................................................................... 64 3.3.1 bcc-fcc nucleation and growth competition ..................................................... 64 3.3.2. Crystal growth kinetics ................................................................................... 68 3.3.3. Microstructural evolution ................................................................................ 70 Chapter 4: The effect of Al addition to the CoCrFeNi alloy on the non-equilibrium solidification behaviour.............................................................................................. 72 4.1 Introduction ........................................................................................................ 72 4.2 Results and Discussion ...................................................................................... 73 Chapter 5: Non-equilibrium solidification of the NbTiVZr refractory high-entropy alloy ................................................................................................................................. 84 5.1 Introduction ........................................................................................................ 84 5.2 Results ............................................................................................................... 85 5.2.1 In situ synchrotron X-ray diffraction ................................................................. 85 5.2.2 Room temperature synchrotron X-ray diffraction ............................................ 88 5.2.3 High-speed video imaging ............................................................................... 89 5.2.4 Microstructure and structure analysis ............................................................. 91 5.3 Discussion .......................................................................................................... 94 5.3.1 Phase formation upon solidification ................................................................ 94 5.3.2 Crystal growth kinetics .................................................................................... 98 5.3.3 Structural and microstructural features............................................................ 99 Chapter 6: Solid-state thermophysical properties of CrFeNi, CoCrNi, and CoCrFeNi medium- and high-entropy alloys ........................................................................... 101 6.1 Introduction ...................................................................................................... 101 6.2 Results ............................................................................................................. 102 6.3 Discussion ........................................................................................................ 106 6.3.1 Thermophysical properties ............................................................................ 106 6.3.2 Short-range order in medium- and high-entropy alloys ................................. 109 Chapter 7: Summary ............................................................................................... 111 7.1 Empirical rule of phase formation of complex concentrated alloys ................... 111 7.2 Non-equilibrium solidification of medium- and high-entropy alloys ................... 111 7.3 Thermophysical properties of the medium- and high-entropy alloys ................ 113 Chapter 8: Outlook ................................................................................................. 115 Appendix 1 .............................................................................................................. 117 Appendix 2 ............................................................................................................. 123 Appendix 3 ............................................................................................................. 133 Appendix 4 ............................................................................................................. 134 References.............................................................................................................. 140 Acknowledgments .................................................................................................. 164 List of publications .................................................................................................. 166 Erklärung ......................................................................................................................... 167

High-entropy alloys (HEAs) represent a special group of solid solutions containing five or more principal elements. The new design strategy has attracted extensive attention from the materials science community. The design and development of HEAs with desired properties have become an important subject in materials science and technology. For understanding the basic properties of HEAs, here we investigate the magnetic properties, Curie temperatures, electronic structures, phase stabilities, and elastic properties of paramagnetic (PM) body-centered cubic (bcc) and face-centered cubic (fcc) AlxCrMnFeCoNi (0 ≤ x ≤ 5, in molar fraction) HEAs using the first-principles exact muffin-tin orbitals (EMTO) method in combination with the coherent potential approximation (CPA) for dealing with the chemical and magnetic disorder. Whenever possible, we compare the theoretical predictions to the available experimental data in order to verify our methodology. In addition, we make use of the previous theoretical investigations carried out on AlxCrFeCoNi HEAs to reveal and understand the role of Mn in the present HEAs. The theoretical lattice constants are found to increase with increasing x, which is in good agreement with the available experimental data. The magnetic transition temperature for the bcc structure strongly decreases with x, whereas that for the fcc structure shows a weak composition dependence. Within their own stability fields, both structures are predicted to be PM at ambient conditions. Upon Al addition, the crystal structure changes from fcc to bcc with a broad two-phase field region, in line with the observations. Bain path calculations suggest that within the duplex region both phases are dynamically stable. Comparison with available experimental data demonstrates that the employed approach describes accurately the elastic moduli of the present HEAs. The elastic parameters exhibit complex composition dependences, although the predicted lattice constants increase monotonously with Al addition. The elastic anisotropy is unusually high for both phases. The brittle/ductile transitions formulated in terms of Cauchy pressure and Pugh ratio become consistent only when the strong elastic anisotropy is accounted for. The negative Cauchy pressure of CrMnFeCoNi is found to be due to the relatively low bulk modulus and C12 elastic constant, which in turn are consistent with the relatively low cohesive energy. Our findings in combination with the experimental data suggest anomalous metallic character for the present HEAs system. The work and results presented in this thesis give a good background to go further and study the plasticity of AlxCrMnFeCoNi type of HEAs as a function of chemistry and temperature. This is a very challenging task and only a very careful pre-study concerning the phase stability, magnetism and elasticity can provide enough information to turn my plan regarding ab initio description of the thermo-plastic deformation mechanisms in AlxCrMnFeCoNi HEAs into a successful research.

Vývoj nových materiálů pro součásti v moderních technologiích vystavené extrémním podmínkám má v současné době rostoucí význam. Děje se tak v důsledku neustále se zvyšujících požadavků průmyslových odvětví na lepší konstrukční vlastnosti nosných materiálů. Ve světle těchto faktů si tato studie klade za cíl posoudit nové složení slitin s vysokou entropií, které se vyznačují vysokým aplikačním potenciálem pro kritické aplikace. Slitiny jsou připravovány práškovou metalurgií, t.j. kombinací mechanického legování a slinování v pevné fázi. Pro účely srovnávaní vlastností jsou vybrané kompozice vyrobeny také tradičními metalurgickými metodami v roztaveném stavu, jako je vakuové indukční tavení a následné lití nebo vakuové obloukové tavení. Prášková metalurgie umožňuje postupný vývoj kompozitů s kovovou matricí (MMC) prostřednictvím přípravy oxidicky zpevněných HEA slitin. To je možné díky inherentním in-situ reakcím během procesu výroby. Když se naopak zvolí výrobní postup z taveniny, připravený kovový materiál vykazuje velké rozdíly v mikrostrukturách a souvisejících vlastnostech, v porovnání se stejným materiálem vyrobeným práškovou cestou (PM). Vyrobené práškové a tavené materiály jsou detailně charakterizovány s ohledem na komplexní vyhodnocení vlivu různých metod zpracování. Práce se zejména orientuje na mikrostrukturní charakteristiky materiálů a jejich mechanické vlastnosti, včetně vlivu tepelného zpracování na fázové transformaci a mikrostrukturní stabilitu připravených materiálů.

<p dir="ltr">Advancements in material science are accelerating technological evolution, driven by initiatives like the Materials Genome Project, which integrates computational and experi- mental strategies to expedite material discovery. In this work, we focus on the reliability of advanced materials under extreme conditions, a critical area for enhancing their technological applications.</p><p dir="ltr">Multi-principal component alloys (MPEAs) exhibit remarkable properties under extreme conditions. However, their vast compositional space makes a brute-force exploration of potential alloys prohibitive. We address this challenge by employing a Bayesian approach to explore the oxidation resistance of hundreds of alloys, applying computational techniques to accurately calculate and quantify errors in the melting temperatures of MPEAs, and investigating the compositional biases and short-range order in their nucleation behaviors.</p><p dir="ltr">Furthermore, we scrutinize the role of wide bandgap semiconductors, which are essential in high-power applications due to their superior breakdown voltage, drift velocity, and sheet charge density. The lack of lattice-matched substrates often results in strained films, which enhances piezoelectric effects crucial for device reliability. Our research advances the pre- diction of piezoelectric and dielectric responses as influenced by biaxial strain and doping in gallium nitride (GaN). Additionally, we delve into how various common defects affect the formation of trap states, significantly impacting the electronic properties of these materials. These studies offer significant advancements in understanding MPEAs and wide bandgap semiconductors under extreme conditions. We also provide foundational insights for developing robust and efficient materials essential for next-generation applications.</p>

Yes / This paper describes some underlying principles of multicomponent and high entropy alloys, and gives some examples of these materials. Different types of multicomponent alloy and different methods of accessing multicomponent phase space are discussed. The alloys were manufactured by conventional and high speed solidification techniques, and their macroscopic, microscopic and nanoscale structures were studied by optical, X-ray and electron microscope methods. They exhibit a variety of amorphous, quasicrystalline, dendritic and eutectic structures.

[ES] Las aleaciones biomédicas de alta entropía (Bio-HEA) con propiedades no tóxicas, sintetizadas mediante métodos de pulvimetalurgia, han recibido una atención limitada a pesar de su potencial para un rendimiento mecánico y biológico favorable. Este estudio tuvo como objetivo investigar sistemáticamente las características microestructurales, mecánicas, electroquímicas y de liberación de iones de distintas composiciones de aleaciones porosas organizadas en tres grupos. El grupo uno consta de cuatro aleaciones porosas de TNZT EB con distintas proporciones de Ti/Ta, mientras que el grupo dos consta de dos aleaciones porosas de TNZTM EB con diferentes proporciones de Ti/Mo. Por último, el grupo tres incluye dos aleaciones más densas de TNZT SPS con diferentes proporciones de Ti/Ta. En el análisis de la microestructura de las aleaciones TNZT EB, es evidente la presencia de fase (matriz) BCC semiequiaxial y micrométrica con un pequeño contenido de fase HCP. Propiedades mecánicas, que abarcan módulos elásticos (83-100 GPa), dureza (373-430 HVN), flexión máxima (225-476 MPa), resistencia a la tracción (120-256 MPa) y compresión (713-1410 MPa); además, la velocidad de corrosión electroquímica (4,5-9,6 ¿m año-1) y la liberación de iones (toxicidad, 0,04-1,1 ¿m año-1), se encuentran dentro de los límites aceptables para los biomateriales de implantes. Sorprendentemente, aumentar el contenido de Ti (y disminuir Ta) muestra ventajas en la mejora de la resistencia mecánica y reduce el módulo elástico. La microestructura del grupo dos, específicamente las aleaciones Ti20 EB TNZTM, exhibe fases (matriz) BCC semiequiaxiales y micrométricas con proporciones disminuidas de fases Zr FCC y HCP. Por el contrario, en Ti25 EB TNZTM, la microestructura comprende fases FCC (matriz) micrométricas y semiequiaxiales con cantidades reducidas de fases HCP y BCC. Es digno de mención subrayar el desafío de la débil homogeneidad que conduce a una heterogeneidad evidente en las aleaciones TNZTM EB. Las propiedades mecánicas, incluidos módulos elásticos (78-80 GPa), dureza (257-294 HVN), flexión máxima (186-210 MPa), resistencia a la tracción (121-144 MPa), compresión (661-774 MPa), corrosión electroquímica. (5-6,6 ¿m año-1) y la liberación de iones (toxicidad, 0,3-0,8 ¿m año-1) están también dentro de rangos aceptables para biomateriales de implantes. La reducción ventajosa del módulo elástico y la liberación de iones se logra disminuyendo el contenido de Ti (y aumentando el Mo), mientras que la mejora del fortalecimiento mecánico se facilita al aumentar el contenido de Ti (y disminuyendo el Mo). El grupo tres, aleaciones TNZT SPS, exhibe una microestructura con fases BCC (matriz) micrométricas y semiequiaxiales y un menor contenido de fases HCP y FCC. Los módulos elásticos (85-88 GPa), dureza (268-349 HVN), flexión máxima (225-476 MPa) y corrosión electroquímica (4,7-5,1 ¿m año-1) resultan ligeramente inferiores que en las aleaciones de polvos elementales. El aumento del contenido de Ti (y la disminución de Ta) muestran ventajas en cuanto a la reducción del módulo elástico y mejoran la dureza. El valor moderado del módulo elástico tiene beneficios potenciales para aliviar el efecto de apantallamiento de tensiones entre los implantes y el tejido orgánico. Sin embargo, en el caso del grupo uno (TNZT EB), la velocidad de corrosión mostró una tendencia ascendente, mientras que la liberación de iones metálicos disminuyó con el aumento del contenido de Ti. Por el contrario, para el grupo dos (TNZTM EB), tanto la velocidad de corrosión como la liberación de iones metálicos disminuyeron en respuesta al aumento del contenido de Ti. Dentro del grupo tres (TNZT SPS) hubo un aumento en la velocidad de corrosión a medida que aumentaba el contenido de Ti. Con base en lo anterior, las aleaciones porosas de TNZT EB con contenidos de Ti medios y altos (Ti30 EB y Ti35 EB) resultan los candidatos más prometedores para aplicaciones de implantes biomédicos. / [CA] Els aliatges biomèdics d'alta entropia (Bio-HEA) amb propietats no tòxiques, sintetitzats mitjançant mètodes de pulvimetal·lúrgia, han rebut una atenció limitada malgrat el seu potencial per a un rendiment mecànic i biològic favorable. Aquest estudi te com a objectiu investigar sistemàticament les característiques microestructurals, mecàniques, electroquímiques i d'alliberament d'ions de diferents composicions d'aliatges porosos organitzats en tres grups. El grup u consta de quatre aliatges porosos de TNZT EB amb diferents proporcions de Ti/Ta, mentre que el grup dos consta de dos aliatges porosos de TNZTM EB amb diferents proporcions de Ti/Mo. Finalment, el grup tres inclou dos aliatges més denses de TNZT SPS amb diferents proporcions de Ti/Ta. A l'anàlisi de la microestructura dels aliatges TNZT EB, és evident la presència de fase (matriu) BCC semiequiaxial i micromètrica amb un petit contingut de fase HCP. Propietats mecàniques, que abasten mòduls elàstics (83-100 GPa), duresa (373-430 HVN), flexió màxima (225-476 MPa), resistència a la tracció (120-256 MPa) i compressió (713-1410 MPa); a més, la velocitat de corrosió electroquímica (4.5-9.6 ¿m any-1) i l'alliberament d'ions (toxicitat, 0.04-1.1 ¿m any-1), es troben dins dels límits acceptables per als biomaterials d'implants. Sorprenentment, augmentar el contingut de Ti (i disminuir Ta) mostra avantatges en la millora de la resistència mecànica i redueix el mòdul elàstic. La microestructura del grup dos, específicament els aliatges Ti20 EB TNZTM, exhibeix fases (matriu) BCC semiequiaxials i micromètriques amb proporcions disminuïdes de fases Zr FCC i HCP. Per contra, a Ti25 EB TNZTM, la microestructura comprèn fases FCC (matriu) micromètriques i semiequiaxials amb quantitats reduïdes de fases HCP i BCC. És digne de menció subratllar el desafiament de la feble homogeneïtat que condueix a una heterogeneïtat química evident en els aliatges TNZTM EB. Les propietats mecàniques, inclosos mòduls elàstics (78-80 GPa), duresa (257-294 HVN), flexió màxima (186-210 MPa), resistència a la tracció (121-144 MPa), compressió (661-774 MPa), corrosió electroquímica. (5-6.6 ¿m any-1) i l'alliberament d'ions (toxicitat, 0,3-0,8 ¿m any-1) estan també dins de rangs acceptables per a biomaterials d'implants. La reducció avantatjosa del mòdul elàstic i l'alliberament d'ions s'aconsegueix disminuint el contingut de Ti (i augmentant el Mo), mentre que la millora de l'enfortiment mecànic es facilita en augmentar el contingut de Ti (i disminuint el Mo). El grup tres, aliatges TNZT SPS, exhibeix una microestructura amb fases BCC (matriu) micromètriques i semiequiaxials i un menor contingut de fases HCP i FCC. Els mòduls elàstics (85-88 GPa), duresa (268-349 HVN), flexió màxima (225-476 MPa) i corrosió electroquímica (4.7-5.1 ¿m any-1) resulten lleugerament inferiors que en els aliatges de pols elementals. L'augment del contingut de Ti (i la disminució de Ta) mostren avantatges quant a la reducció del mòdul elàstic i milloren la duresa. El valor moderat del mòdul elàstic té beneficis potencials per alleujar l'efecte d'apantallament de tensions entre els implants i el teixit orgànic. Tot i això, en el cas del grup u (TNZT EB), la velocitat de corrosió va mostrar una tendència ascendent, mentre que l'alliberament d'ions metàl·lics va disminuir amb l'augment del contingut de Ti. Per contra, per al grup dos (TNZTM EB), tant la velocitat de corrosió com l'alliberament d'ions metàl·lics van disminuir en resposta a l'augment del contingut de Ti. Dins el grup tres (TNZT SPS) hi va haver un augment en la velocitat de corrosió a mesura que augmentava el contingut de Ti. Amb base a això, els aliatges porosos de TNZT EB amb continguts de Ti mitjans i alts (Ti30 EB i Ti35 EB) resulten els candidats més prometedors per a aplicacions d'implants biomèdics. / [EN] Biomedical high entropy alloys (Bio-HEAs) with non-toxic properties, synthesized through powder metallurgy methods, have received limited attention despite their potential for favorable mechanical and biological performance. This study aimed to systematically investigate the microstructural, mechanical, electrochemical, and ion release features of distinct porous alloy compositions organized into three groups. Group one consisted of four porous TNZT EB alloys with varied Ti/Ta ratios, while group two comprised two porous TNZTM EB alloys with different Ti/Mo ratios. Lastly, group three included two porous TNZT SPS alloys with varying Ti/Ta ratios. In the microstructure analysis of TNZT EB alloys, the presence of semi-equiaxed and micrometric BCC phases (matrix) with lower HCP phase content was evident. Mechanical properties, encompassing elastic moduli (83-100 GPa), hardness (373-430 HVN), ultimate bending (225-476 MPa), tensile (120-256 MPa) strength, and compression (713-1410 MPa), in addition to electrochemical corrosion (4.5-9.6 ¿m year-1) and ion release (toxicity, 0.04-1.1 ¿m year-1), fell within acceptable limits for implant biomaterials. Remarkably, augmenting the Ti content (and decreasing Ta) exhibited advantages in improving mechanical strength and reducing the elastic modulus. The microstructure of group two, specifically the Ti20 EB TNZTM alloys, exhibited semi-equiaxed and micrometric BCC phases (matrix) with diminished proportions of FCC and HCP phases. Conversely, in Ti25 EB TNZTM, the microstructure comprised semi-equiaxed and micrometric FCC-phases (matrix) with reduced quantities of HCP and BCC phases. It is noteworthy to underscore the challenge of weak homogeneity leading to evident heterogeneity in TNZTM EB alloys. The mechanical properties, including elastic moduli (78-80 GPa), hardness (257-294 HVN), ultimate bending (186-210 MPa), tensile (121-144 MPa) strength, compression (661-774 MPa), electrochemical corrosion (5-6.6 ¿m year-1), and ion release (toxicity, 0.3-0.8 ¿m year-1), fell within acceptable ranges for implant biomaterials. The advantageous reduction of elastic modulus and ion releases was achieved by decreasing the Ti content (and increasing Mo), whereas enhancing mechanical strengthening was facilitated by increasing the Ti content (and decreasing Mo). Group three, TNZT SPS alloys, exhibited a microstructure with semi-equiaxed and micrometric BCC-phases (matrix) and lower HCP and FCC phase content. The elastic moduli (85-88 GPa), hardness (268-349 HVN), and ultimate bending (225-476 MPa), and electrochemical corrosion (4.7-5.1 ¿m year-1). Increasing Ti content (and decreasing Ta) were advantageous for reducing the elastic modulus and improving hardness. The moderate elastic modulus value holds potential benefits in alleviating the mechanical incongruence between the implant and organic tissue. Nevertheless, in the case of group one (TNZT EB), the corrosion rate exhibited an upward trend, while the metallic ion release declined with increasing Ti content. In contrast, for group two (TNZTM EB), both the corrosion rate and metallic ion release diminished in response to escalating Ti content. Within group three (TNZT SPS) there was increase in the corrosion rate as the Ti content escalated. Based on the above, porous TNZT EB alloys with medium and highest Ti contents (Ti30 EB and Ti35 EB) emerged as promising candidates for biomedical implant applications / Kamel Mohammad Al-Hawajreh, G. (2024). Performance Effect of the Content of Alloying Elements in the Development of High Entropy Alloys of the Ti-Nb-Zr-Ta-Mo Family for Biomedical Applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/208235