Magnetische Formgedächtnislegierungen sind Festkörper, die eine Phasenumwandlung erster Ordnung von einer hochsymmetrischen Phase (Austenit) zu einer niedersymmetrischen Phase (Martensit) durchlaufen. Dies kann in der Nähe von Raumtemperatur stattfinden und sowohl durch Temperaturänderung, als auch durch äußere Magnetfelder, mechanische Spannungen oder hydrostatischen Druck induziert werden. Daraus ergeben sich funktionale Eigenschaften, wie der magnetokalorische und der elastokalorische Effekt, eine magnetfeldinduzierte Dehnung und ein großer Magnetowiderstand. Zwillingsgrenzen im Martensit können durch äußere Magnetfelder bewegt werden, was zu großen reversiblen Längenänderungen führt. Der Ablauf der Phasenumwandlung und das Gefüge des Martensits werden dabei durch die elastischen Randbedingungen an der Phasengrenze bestimmt. In dieser Arbeit werden deshalb die Nukleation und das Wachstum des Martensits untersucht. Als Modellsystem werden epitaktische Schichten der Heuslerlegierung Ni-Mn-Ga verwendet. In der martensitischen Phase weist diese Legierung eine modulierte Kristallstruktur auf, die im Konzept des adaptiven Martensits durch eine Verzwillingung auf der atomaren Skala interpretiert werden kann. Im ersten Teil wird mit Röntgenbeugung die modulierte Struktur untersucht. Die Intensität der Überstrukturreflexe wird mit einer kinematischen Beugungssimulation verglichen. Dabei wird nachgewiesen, dass es sich um ein nanoverzwillingtes Gefüge mit einer hohen Dichte an Stapelfehlern handelt. Im zweiten Teil wird das martensitische Gefüge mit Elektronenbeugung im Rasterelektronenmikroskop und Texturmessungen durch Röntgenbeugung untersucht. Das martensitische Gefüge kann im Rahmen der phänomenologischen Martensittheorie quantitativ erklärt werden. Daraus ergibt sich ein geometrisches Modell des martensitischen Nukleus und seiner Wachstumsstadien. Die Phasenumwandlung wird temperaturabhängig im Elektronen- und im Atomkraftmikroskop untersucht und mit dem geometrischen Modell verglichen. Die begrenzte Gültigkeit des geometrischen Modells an makroskopischen Zwillingsgrenzen und an der Grenzfläche zum Schichtsubstrat werden diskutiert. Schließlich kann die Bildung des gesamten hierarchischen Zwillingsgefüges erklärt werden. Im dritten Teil wird die Energiebarriere der Nukleation untersucht. Da die Umwandlung bei konstanter Temperatur abläuft, wird geschlussfolgert, dass Autonukleationsprozesse zu einer starken Verringerung der Nukleationsbarrieren führen. Schließlich wird gezeigt, dass durch Nanoindentation die Nukleation gezielt beeinflusst werden kann. / Magnetic shape memory alloys are solids that undergo a first order phase transition from a high symmetry phase (austenite) into a low symmetry phase (martensite). This can happen close to room temperature and can be induced by changes of temperature, external magnetic fields, mechanical stresses or hydrostatic pressure. This leads to functional properties like the magnetocaloric and elastocaloric effect, a magnetic-field-induced strain and giant magnetoresistance. Twin boundaries in the martensite can be moved by external magnetic fields, which leads to giant reversible length changes. The process of the phase transition and the microstructure of martensite are determined by the elastic boundary conditions at the phase interface. In this work, nucleation and growth of the martensite are studied. Epitaxial films of the Heusler alloy Ni-Mn-Ga are used as a model system. This alloy exhibits a modulated crystal structure which is interpreted as twinning on the atomic scale in the framework of adaptive martensite. In the first part, the modulated structure is studied by X-ray diffraction. The intensity of the superstructure is compared to a kinematic diffraction simulation and it is shown that it is a nanotwinned microstructure with a high density of stacking faults. In the seond part, the martensitic microstructure is studied by electron diffraction in the scanning electron microscope and by texture measurements using X-ray diffraction. The martensitic microstructure can be explained quantitatively in the framework of the phenomenological theory of martensite. This leads to a geometrical model of the martensitic nucleus and its growth stages. The phase transformation is studied as a function of temperature in the scanning electron microscope and atomic force microscope and is compared to the geometric model. The limits of the geometrical model at macroscopic twin boundaries and at interfaces to the substrate are discussed. Finally, the formation of the entire twin microstructure can be explained. In the third part, the energy barrier of nucleation is studied. The transformation is isothermal which leads to the conclusion that autonucleation processes decrease the nucleation barrier significantly. Finally, the influence of nanoindentation on the nucleation is shown.

Slat-band chains are used as conveyors by the food industry, breweries and bottling plants. The operating conditions require abrasion resistance and strength which are at the limit of the capabilities of the current material of choice, cold worked type 430. In an unconventional way of strengthening this material, Mintek developed a process in which the cold worked material is aged between 450°C and 500°C. The present work aims to elucidate the strengthening mechanism, using type 430 stainless steel containing 16.42% Cr and 0.036% C, in the cold-rolled condition (38% reduction in area), with and without prior solution heat treatment. The Cr-rich precipitate α" may form in the 450°C to 500°C range (due to the miscibility gap in the Fe-Cr system), resulting in the increased hardness and lowered ductility. Mossbauer studies confirmed that the α", at this composition and temperature, forms through the process of nucleation and growth. Hardening due to α" precipitation was only observed after aging for 64 hours or more, however. After increasing the dissolved interstitial content by solution heat treatments (in the vicinity of 900°C), increases in Vickers hardness of 30-50 kg/mm2 could be obtained after only 8 minutes at 475°C. This hardness increase corresponds to an increase in tensile strength of more than 100 MPa. The increased hardness does not appear to be caused by strain aging, and presumably results from fine carbide or nitride precipitation. Solution treatment at 930°C also introduced some martensite (α') into the microstructure, which raised the hardness of the unaged cold worked material. Overaging of the carbide and nitride precipitates was observed at 475°C, but not at 450°C, probably due to the lower diffusion rates at the lower temperature. No averaging of the α" precipitates occurred, for aging times up to 2072 hours. Samples aged for selected periods of time at 475°C had low impact strengths - even well before the formation of α" - and revealed predominantly cleavage fracture with some ductile fracture areas, mostly at grain boundaries. Both impact strength and lateral expansion indicated that embrittlement accompanies the increased hardness obtained by aging. Calculation of critical crack lengths from the impact data, however, revealed that a maximum flaw length of 0.8 mm, for specimens solution treated at 880°C, could be tolerated before catastrophic failure. Since it is not expected that flaws of that size would exist in the as manufactured links, fatigue will probably determine the lifetime of the chains, although the lower K1c values indicate that less crack propagation will be tolerated before brittle fracture. During the aging treatment, the strength may be lowered by recrystallisation of the coldworked material. Transmission electron microscopy (TEM) revealed the start of recovery, but no recrystallisation. Some large precipitates (around lμm in diameter) were present. These were identified, through their diffraction patterns, as M23C6; these carbides were present in both aged and unaged material and hence represent precipitates which had not dissolved during the initial solution treatments. The α" precipitates- and the presumed newly formed nitride and carbide precipitates - were too fine for detection by TEM. Potentiodynamic testing of the treated material in a 0.5M H2SO4 solution indicated that, although the probable hardening mechanisms imply localised Cr depletion of the matrix, the general corrosion resistance and passivation behaviour were not affected. It is concluded that the strength of the chain may be increased markedly by short-term heat treatments at 475°C, with lowered toughness, but with no decrease in corrosion resistance. Martensite, work hardening, and precipitation of carbides and nitrides all contribute to the final strength, with α" formation only becoming significant after longer aging times. / Dissertation (MEng)--University of Pretoria, 2013. / Materials Science and Metallurgical Engineering / unrestricted

No presente trabalho foram estudados os fenômenos de encruamento e, principalmente, a formação e reversão da martensita alfa-linha (a\', cúbica de corpo centrado, CCC, ferromagnética) induzida por deformação em um aço inoxidável dúplex UNS S31803 e um super dúplex UNS S32520. Inicialmente, as microestruturas dos dois materiais na condição solubilizada foram caracterizadas com auxílio de várias técnicas complementares de análise microestrutural. Foram determinadas fração volumétrica, estrutura cristalina, composição química, tamanho e morfologia das duas fases (ferrita e austenita). Posteriormente, os dois aços foram deformados por dois métodos: a laminação a frio, dividida em vários estágios, com menores graus de deformação e a limagem, sendo que o cavaco limado resultante apresenta altos graus de deformação. Algumas amostras deformadas foram recozidas. Os fenômenos de encruamento, formação e reversão de martensita induzida por deformação na austenita, recuperação, recristalização da austenita e da ferrita no cavaco limado foram estudados predominantemente por difratometria de raios X e usando o método de Rietveld. A difratometria de raios X também foi utilizada para determinação das microdeformações residuais e tamanhos de cristalito (subgrão), calculadas a partir do alargamento dos picos de difração causado pelas deformações. Desta forma, puderam-se comparar os níveis de deformação da laminação e limagem. Qualitativamente, a formação e reversão da martensita induzida por deformação também foi estudada por meio de medidas magnéticas utilizando-se dados de saturação magnética das curvas de histerese obtidas com o auxílio de um magnetômetro de amostra vibrante. Observou-se que para o aço inoxidável dúplex, tanto a laminação quanto a limagem causaram a formação de martensita induzida por deformação e para o aço inoxidável super dúplex, apenas a limagem promoveu essa transformação. Em comparação com o aço dúplex, o aço super dúplex apresentou maior resistência à formação de martensita induzida por deformação, pois apresenta uma austenita mais rica em nitrogênio e uma maior propensão à formação de fase sigma durante o recozimento, pois apresenta uma ferrita mais rica em cromo e nitrogênio. / In the present work the phenomena of strain hardening, formation and reversion of the strain induced alpha-prime martensite (a\', body centered cubic, BCC, Ferromagnetic) in an UNS S31803 duplex and UNS S32520 super duplex stainless steels have been studied. Firstly, the microstructures of both materials in the solution annealed condition were characterized with the aid of several microstructural analysis complementary techniques. The volume fraction, crystalline structure, chemical composition, size and morphology of the two phases (ferrite and austenite) have been determined. Further, both steels were deformed by two methods: cold rolling, divided into several stages, with lower strain levels than filing, which the chips resulting had higher strain levels. The phenomena of strain hardening, formation and reversion of strain induced martensite in the austenite phase, recovery and recrystallization of austenite and ferrite phases have been studied, mainly using X-ray diffraction and the Rietveld method. X-ray diffraction was also used to determine the residual microstrain and crystallite size (sub grain), calculated from the diffraction peak broadening caused by straining. Thus, the levels of cold rolling and filing strains could be compared. Qualitatively, the formation and reversion of strain induced martensite was also studied by magnetic measurements using data from magnetic saturation of hysteresis curves obtained with the aid of a vibrating sample magnetometer. It has been observed that for the duplex stainless steel, both filing as well as cold rolling promoted strain induced martensite. On the other hand, for the super duplex stainless steel, just filing promoted this transformation. In the comparing with duplex, the super duplex stainless steel austenite is more stable that is why is richer in nitrogen, so, the strain induced martensite formation is more difficult. The easier sigma phase precipitation during annealing as well in the super duplex stainless steel is due higher levels of chrome and molybdenum than the duplex stainless steel.

The synthesis of in-situ bulk metallic glass composites (BMGCs) with crystals that undergo a martensitic transformation under loading is possibly the most effective method to improve the plasticity of metallic glasses at room temperature. These martensitic or shape memory BMGCs are typically fabricated via solidification of glass-forming melts, which requires the meticulous selection of the chemical composition and the proper choice of the processing parameters (particularly the cooling rate) in order to ensure that the glassy matrix coexists with the desired amount of austenitic phase having suitable morphology and characteristics. Unfortunately, a relatively limited number of alloy systems, where austenite and glassy matrix coexist over a wide range of compositions, is available. Additionally, the necessity for rapid heat extraction and the corresponding high cooling rates essential for glass formation by melt solidification set an inherent limit to the achievable dimensions of BMGs and BMGCs specimens. The aim of this thesis is to study the effectiveness of powder metallurgy as an alternative to solidification for the synthesis of shape memory BMGCs. Ni50.6Ti49.4 and Zr48Cu36Al8Ag8 metallic glass powders were selected as the constituents of the composites because they have been extensively investigated and represent well the characteristic behavior of metallic glass and shape memory phases. BMGCs with different volume fractions of NiTi phase were fabricated using pressure-assisted sintering via hot pressing and their microstructure, mechanical properties and deformation mechanism were investigated. Particular focus was placed upon identifying the individual contributions of the martensitic transformation and shear band formation to plasticity as well as their mutual interaction at different length scales using a multidisciplinary approach involving experiments and simulations. BMG composites were synthesized by hot pressing of powder mixtures consisting of Zr48Cu36Al8Ag8 metallic glass and different amounts of Ni50.6Ti49.4 particles (10, 20, 40 and 60 vol.%) using the optimized consolidation parameters (temperature-time-pressure) determined for the monolithic BMG. All composites are characterized by a relatively uniform particle distribution and good interface bonding without any sign of reaction between the metallic glass and NiTi. The NiTi particles are progressively less isolated with increasing volume fraction of NiTi up to 40 % and, for the BMGC with 60 vol.% NiTi, the glassy particles are no longer connected and the NiTi phase becomes the continuous matrix. This is not a trivial achievement as the change of matrix while maintaining the structure of the constituent phases would not be easily obtained by solidification of melts with such different compositions. The size of the samples (10 mm diameter and 9 - 11 mm height) is larger than the characteristic BMGCs synthesized by casting and can, in principle, be scaled up to larger dimensions, demonstrating the effectiveness of this approach for overcoming the size limitation inherent to glass formation via solidification. In contrast to the monolithic BMG, which does not show any sign of plasticity, the BMGCs exhibit macroscopic plastic deformation that progressively increases with increasing NiTi content along with distinct strain-hardening. The BMG composites have similar fracture strength, which is comparable with the monolithic BMG, and exhibit a distinct double yield behavior, similar to shape memory BMGCs fabricated by casting. The deformed BMGCs exhibit a high density of shear bands, again in agreement with what observed for similar BMGCs fabricated by casting. These findings not only demonstrate that BMGCs with tunable microstructures and thus with optimized deformability can be synthesized by pressure-assisted sintering but, thanks to the phase stability of the components across such a wide range of compositions, also offer an excellent platform to examine fundamental aspects in the field of martensitic BMGCs. The confining stress exerted by the surrounding glassy matrix was quantified at the macroscale via a hybrid Voigt-Reuss mixture, which considers intermediate weighted combinations of stiff and compliant behaviors. In this way, the macroscopic stress required to initiate the martensitic transformation from B2 to B19´ can be described with rather good accuracy. The confining effect was further investigated by in-situ high-energy X-ray diffraction to have access to the strain tensor of the B2 phase as a function of loading. The results indicate that the confining stress along the direction perpendicular to the loading axis is particularly strong because the expansion of the B2 phase is constrained by the elastic matrix. A mechanism responsible for shear band formation in shape memory BMGCs is proposed. The stress field generated by the martensitic transformation in the contiguous glass would activate the adjacent shear transformation zone (STZ, the elementary units of plasticity in BMGs). The stress field induced by the activated STZ in the surrounding material then triggers the activation of the following STZs along the path of a potential shear band, in an autocatalytic process resembling the domino effect. The shear band formed in this way propagates through the glassy phase and, when impinging a B2 particle, the associated stress field would locally trigger the martensitic transformation, starting again the process. Molecular dynamics (MD) simulations of a martensitic BMGC show that the structural perturbation generated by the martensitic transformation is indeed transmitted to the adjacent glassy matrix and, in turn, to the developing shear band, in agreement with the proposed mechanism. The individual contribution of the glassy phase to the residual strain after each loading-unloading cycle was quantified assuming that the NiTi phase behaves in the same manner across the different specimens. The glass contribution was then correlated to the shear band density to obtain the plastic strain resulting from shear banding for a given amount of NiTi phase, a quantity that could be effectively used in the design of plastically-deformable BMGCs with shape memory particles. The martensitic transformation in the composites becomes progressively more irreversible with increasing strain. A large contribution to the martensite stabilization may come from the residual stress induced by the shear bands, in accordance with the finite element method (FEM) simulations, showing that residual stresses in the composites suppress the reverse transformation after unloading. These finding corroborates the hypothesis that the residual elastic stress field generated by the shear bands may be fundamental for stabilizing the martensitic phase by restraining the atoms at the glass-crystal interface from rearranging back to form austenite. This process can be reversed by proper heat treatment. The findings presented in this thesis offer the opportunity to synthesize shape memory BMG composites with enhanced plasticity and strain-hardening capability along with larger dimensions than those typically achieved by solidification. The powder metallurgy approach provides the necessary versatility in materials design and resulting properties of the composites via the control over the fundamental microstructural features, such as volume fraction, size, morphology and distribution of the second phase. Additionally, materials processing in the solid state gives a virtually infinite choice among the possible composite components, a degree of freedom not usually given when processing via solidification.:Abstract iii Kurzfassung vii Motivation and objectives xi 1 Theoretical background and state-of-the-art 1 1.1 Bulk metallic glasses (BMGs) 1 1.1.1 Formation of metallic glasses 2 1.1.2 Mechanical properties of BMGs 5 1.1.3 Shear bands in metallic glasses 8 1.2 Bulk metallic glass matrix composites 19 1.2.1 Fabrication of BMG composites 20 1.2.2 In-situ BMG composites 27 1.2.3 Ex-situ BMG composites 43 2 Experiments and simulations 57 2.1 Sample preparation 57 2.1.1 Starting materials 57 2.1.2 Powder mixing 59 2.1.3 Powder consolidation 60 2.2 Materials characterization 61 2.2.1 Composition analysis 61 2.2.2 Laboratory X-ray diffraction 61 2.2.3 High-energy X-ray diffraction and strain analysis 62 2.2.4 Viscosity measurements 63 2.2.5 Differential scanning calorimetry 64 2.2.6 Density measurements 64 2.2.7 X-ray computed tomography 65 2.2.8 Optical microscopy and scanning electron microscopy 65 2.2.9 Transmission electron microscopy 66 2.2.10 Elastic constants measurements 66 2.2.11 Mechanical tests 67 2.3 Molecular dynamic simulations 67 2.4 Finite element simulations 68 3 Pressure-assisted sintering of single-phase Zr48Cu36Al8Ag8 metallic glass and Ni50.6Ti49.4 powders 73 3.1 Synthesis and properties of single-phase Zr48Cu36Al8Ag8 bulk metallic glass 73 3.2 Synthesis and properties of single-phase Ni50.6Ti49.4 shape memory alloy 80 4 Pressure-assisted sintering of BMG composites with shape memory crystals: Microstructure and mechanical properties 87 4.1 Microstructure of BMG composites 87 4.2 Effect of NiTi volume fraction on mechanical properties 90 4.3 Effect of confinement of the glassy phase on the martensitic transformation 95 5 Deformation mechanism of shape memory BMG composites 101 5.1 Martensitic transformation and shear band formation 101 5.2 Mechanism of shear band formation in shape memory BMG composites 107 6 Reversibility of the martensitic transformation in shape memory BMG composites 113 6.1 Martensite stabilization in NiTi alloy and BMG composites 113 6.2 Simulation of the martensite stabilization effect in BMG composites 119 6.3 Effect of heat treatment on the martensitic reverse transformation 121 7 Summary and outlook 125 References 131 Acknowledgements 155 Publications 157 Erklärung 159

Heat treatment influences structure and characteristics of treatmented material. Good heat treatment of steels for bearings ensures hardness of matrix 60 - 65 HRC, whereas structure has be formed by tempered fine needle-shaped martensite with definite part of residual austenite. Carbides should be evenly dispersed, they mustn´t create carbide network and carbide lines. Quality of steels for bearings is also influenced by volume and morphology of inclusions in the matrix. In this diploma thesis various conditions of heat treatment were to be set up with the aim of choose the optimal ones. These ensures perfect martensite transformation and full hardening of all component. Quenching from 760 °C – 770 °C was quite unsatisfactory. At this temperature resulting structure was ferritic-perlitic, because martensite transformation did not pass. Too long hold on hardening temperature also had unfavourable influence on resulting structure and characteristics. In this case, structure was created by very coarse needle-shaped martensite. Coarsening of martensite needle locally exceeded maximum allowed level. In the structure there was also possible to watch partly soluted globular carbides. Optimal heat treatment is quenching from 850 °C – 870 °C followed by tempering at 220 °C. Resulting structure quite agree with above-mentioned needs. This heat treatment can be recommended for technical practise.

Magnetische Formgedächtnislegierungen sind Festkörper, die eine Phasenumwandlung erster Ordnung von einer hochsymmetrischen Phase (Austenit) zu einer niedersymmetrischen Phase (Martensit) durchlaufen. Dies kann in der Nähe von Raumtemperatur stattfinden und sowohl durch Temperaturänderung, als auch durch äußere Magnetfelder, mechanische Spannungen oder hydrostatischen Druck induziert werden. Daraus ergeben sich funktionale Eigenschaften, wie der magnetokalorische und der elastokalorische Effekt, eine magnetfeldinduzierte Dehnung und ein großer Magnetowiderstand. Zwillingsgrenzen im Martensit können durch äußere Magnetfelder bewegt werden, was zu großen reversiblen Längenänderungen führt. Der Ablauf der Phasenumwandlung und das Gefüge des Martensits werden dabei durch die elastischen Randbedingungen an der Phasengrenze bestimmt. In dieser Arbeit werden deshalb die Nukleation und das Wachstum des Martensits untersucht. Als Modellsystem werden epitaktische Schichten der Heuslerlegierung Ni-Mn-Ga verwendet. In der martensitischen Phase weist diese Legierung eine modulierte Kristallstruktur auf, die im Konzept des adaptiven Martensits durch eine Verzwillingung auf der atomaren Skala interpretiert werden kann. Im ersten Teil wird mit Röntgenbeugung die modulierte Struktur untersucht. Die Intensität der Überstrukturreflexe wird mit einer kinematischen Beugungssimulation verglichen. Dabei wird nachgewiesen, dass es sich um ein nanoverzwillingtes Gefüge mit einer hohen Dichte an Stapelfehlern handelt. Im zweiten Teil wird das martensitische Gefüge mit Elektronenbeugung im Rasterelektronenmikroskop und Texturmessungen durch Röntgenbeugung untersucht. Das martensitische Gefüge kann im Rahmen der phänomenologischen Martensittheorie quantitativ erklärt werden. Daraus ergibt sich ein geometrisches Modell des martensitischen Nukleus und seiner Wachstumsstadien. Die Phasenumwandlung wird temperaturabhängig im Elektronen- und im Atomkraftmikroskop untersucht und mit dem geometrischen Modell verglichen. Die begrenzte Gültigkeit des geometrischen Modells an makroskopischen Zwillingsgrenzen und an der Grenzfläche zum Schichtsubstrat werden diskutiert. Schließlich kann die Bildung des gesamten hierarchischen Zwillingsgefüges erklärt werden. Im dritten Teil wird die Energiebarriere der Nukleation untersucht. Da die Umwandlung bei konstanter Temperatur abläuft, wird geschlussfolgert, dass Autonukleationsprozesse zu einer starken Verringerung der Nukleationsbarrieren führen. Schließlich wird gezeigt, dass durch Nanoindentation die Nukleation gezielt beeinflusst werden kann. / Magnetic shape memory alloys are solids that undergo a first order phase transition from a high symmetry phase (austenite) into a low symmetry phase (martensite). This can happen close to room temperature and can be induced by changes of temperature, external magnetic fields, mechanical stresses or hydrostatic pressure. This leads to functional properties like the magnetocaloric and elastocaloric effect, a magnetic-field-induced strain and giant magnetoresistance. Twin boundaries in the martensite can be moved by external magnetic fields, which leads to giant reversible length changes. The process of the phase transition and the microstructure of martensite are determined by the elastic boundary conditions at the phase interface. In this work, nucleation and growth of the martensite are studied. Epitaxial films of the Heusler alloy Ni-Mn-Ga are used as a model system. This alloy exhibits a modulated crystal structure which is interpreted as twinning on the atomic scale in the framework of adaptive martensite. In the first part, the modulated structure is studied by X-ray diffraction. The intensity of the superstructure is compared to a kinematic diffraction simulation and it is shown that it is a nanotwinned microstructure with a high density of stacking faults. In the seond part, the martensitic microstructure is studied by electron diffraction in the scanning electron microscope and by texture measurements using X-ray diffraction. The martensitic microstructure can be explained quantitatively in the framework of the phenomenological theory of martensite. This leads to a geometrical model of the martensitic nucleus and its growth stages. The phase transformation is studied as a function of temperature in the scanning electron microscope and atomic force microscope and is compared to the geometric model. The limits of the geometrical model at macroscopic twin boundaries and at interfaces to the substrate are discussed. Finally, the formation of the entire twin microstructure can be explained. In the third part, the energy barrier of nucleation is studied. The transformation is isothermal which leads to the conclusion that autonucleation processes decrease the nucleation barrier significantly. Finally, the influence of nanoindentation on the nucleation is shown.

Ti-Nb alloys are characterized by a diverse metallurgy which allows obtaining a wide palette of microstructural configurations and physical properties via careful selection of chemical composition, heat treatment and mechanical processing routes. The present work aims to expand the current state of knowledge about martensite forming Ti-Nb alloys by studying 15 binary Ti-c_{Nb}Nb (9wt.% ≤ c_{Nb} ≤ 44.5wt.%) alloy formulations in terms of their structural and mechanical properties, as well as their thermal stability. The crystal structures of the martensitic phases, α´ and α´´, and the influence of the Nb content on the lattice (Bain) strain and on the volume change related to the β → α´/α´´ martensitic transformations are analyzed on the basis of Rietveld-refinements. The magnitude of the shuffle component of the β → α´/α´´ martensitic transformations is quantified in relation to the chemical composition. The largest transformation lattice strains are operative in Nb-lean alloys. Depending on the composition, both a volume dilatation and contraction are encountered and the volume change may influence whether hexagonal martensite α´ or orthorhombic martensite α´´ forms from β upon quenching. The mechanical properties and the deformation behavior of martensitic Ti-Nb alloys are studied by complementary methods including monotonic and cyclic uniaxial compression, nanoindentation, microhardness and impulse excitation technique. The results show that the Nb content strongly influences the mechanical properties of martensitic Ti-Nb alloys. The elastic moduli, hardness and strength are minimal in the vicinity of the limiting compositions bounding the interval in which orthorhombic martensite α´´ forms by quenching. Uniaxial cyclic compressive testing demonstrates that the elastic properties of strained samples are different than those of unstrained ones. Also, experimental evidence indicates a deformation-induced martensite to austenite (α´´ → β) conversion. The influence of Nb content on the thermal stability and on the occurrence of decomposition reactions in martensitic Ti-Nb alloys is examined by isochronal differential scanning calorimetry, dilatometry and in-situ synchrotron X-ray diffraction complemented by transmission electron microscopy. The thermal decomposition and transformation behavior exhibits various phase transformation sequences during heating into the β-phase field in dependence of composition. Eventually, the transformation temperatures, interval, hysteresis and heat of the β ↔ α´´ martensitic transformation are investigated in relation to the Nb content. The results obtained in this study are useful for the development and optimization of β-stabilized Ti-based alloys for structural, Ni-free shape memory and/or superelastic, as well as for biomedical applications. / Ti-Nb Legierungen zeichnen sich durch eine vielfältige Metallurgie aus, die es nach sorgfältiger Auswahl der chemischen Zusammensetzung sowie der thermischen und mechanischen Prozessierungsroute ermöglicht eine große Bandbreite mikrostruktureller Konfigurationen und physikalischer Eigenschaften zu erhalten. Das Ziel der vorliegenden Arbeit ist es den gegenwärtigen Wissensstand über martensitbildende Ti-Nb Legierungen zu erweitern. Zu diesem Zweck werden 15 binäre Ti-c_{Nb} Nb (9 Gew.% ≤ c_{Nb} ≤ 44.5 Gew.%) Legierungen hinsichtlich ihrer strukturellen und mechanischen Eigenschaften sowie ihrer thermischen Stabilität untersucht. Die Kristallstrukturen der martensitischen Phasen, α´ und α´´, sowie der Einfluss des Nb-Gehalts auf die Gitterverzerrung (Bain-Verzerrung), auf die Verschiebungswellenkomponente (Shuffle-Komponente) und auf die Volumenänderung der martensitischen β → α´/α´´ Transformationen werden anhand von Rietveld-Verfeinerungen analysiert. In Abhängigkeit des Nb-Gehalts tritt entweder eine Volumendilatation oder -kontraktion auf, die bestimmen könnte ob hexagonaler Martensit α´ oder orthorhombischer Martensit α´´ aus β bei Abkühlung gebildet wird. Die mechanischen Eigenschaften und das Verformungsverhalten martensitischer Ti-Nb Legierungen werden mit einer Reihe komplementärer Methoden (monotone und zyklische einachsige Druckversuche, Nanoindentation, Mikrohärte, Impulserregungstechnik) untersucht. Die Ergebnisse zeigen durchgehend, dass die mechanischen Eigenschaften martensitischer Ti-Nb Legierungen stark vom Nb-Gehalt beeinflusst werden. Die mechanischen Kennwerte sind minimal in der Nähe der Zusammensetzungen, innerhalb derer β → α´´ bei Abkühlung auftritt. Aus Druckversuchen geht hervor, dass die elastischen Eigenschaften verformter Proben verschieden zu denen unverformter sind. Die experimentellen Ergebnisse weisen außerdem auf eine verformungsinduzierte Umwandlung von Martensit in Austenit (α´´ → β) hin. Der Einfluss des Nb-Gehalts auf die thermische Stabilität und das Auftreten von Zerfallsreaktionen in martensitischen Ti-Nb Legierungen wird anhand von dynamischer Differenzkalorimetrie, Dilatometrie, und in-situ Synchrotronröntgenbeugung in Kombination mit Transmissionselektronenmikroskopie untersucht. Das thermische Zerfalls- und Umwandlungsverhalten ist durch das Auftreten einer Vielzahl von in Abhängigkeit des Nb-Gehalts unterschiedlichen Phasentransformationssequenzen gekennzeichnet. Abschließend werden die Transformationstemperaturen und -wärmen, das Transformationsinterval und die thermische Hysterese der martensitischen β ↔ α´´ Umwandlung untersucht. Die Ergebnisse dieser Arbeit sind für die Entwicklung und Optimierung β-stabilisierter Ti-Legierungen für strukturelle und biomedizinische Anwendungen sowie Ni-freier Komponenten, die Formgedächtniseffekt und/oder Superelastizität aufweisen, von Nutzen.

Heat treatment of different steel products have existed for thousands of years. It has always been an important tool to get the microstructure and resulting properties such as hardness and case hardness and it is even more important today than ever before. This project concentrated on the quenching process and means to decrease the distortion caused by this process. The effect of different oils, temperatures, agitation and if gas quenching could give better results were investigated. The results showed that Miller´s 75 quench oil was better than Park´s 420 at slow agitation and that the viscosity of the oils influenced how much changes in agitation speed and oil temperature affected the distortion. It also shows that gas quenching is an alternative to oil quenching if the microstructure can be improved. Otherwise using Miller´s 75 with low agitation in the Surface combustion furnace will give best results.

Research on bainite and martensite structures has indicated that lower bainite needles have a refining effect on the lath martensitic structure. Lower bainte needles partitions prior austenite grains and will consequently have a refining effect on the subsequent formed lath martensite. Smaller austenite grains will result in smaller lath martensitic packets and blocks and will result in enhanced mechanical properties.   In order to create a variation of lower bainte structure in a matrix of martensite, two different heat treating methods were tested. The work was focused towards the formation of lower bainite during isothermal heat treating in molten salt, above and below the MS-temperature. Both un-tempered and tempered samples were analyzed .Two different materials were tested, both were AISI 4140 but with a slightly difference in hardenability. The material provided by Ovako Steel is 326C and 326F the later had a higher hardenability. In order to better distinguish the two structures from each other when studied under a microscope, a variation of etching methods were tested.  It was possible to create a variation of lower bainite structures in a matrix of martensite.  326F shows less amount of lower bainite and provides a higher average surface hardness before tempering.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23507号 / 工博第4919号 / 新制||工||1768(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 安田 秀幸, 教授 奥田 浩司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM