Title: Martensite microstructures in thin films and monocrystals of Heusler alloys Ni-Mn-Ga Author: Kristýna Onderková Department: Department of Surface and Plasma Science Supervisor: Mgr. Ing. Oleg Heczko, Dr., Institute of Physics of the Czech Academy of Sciences Abstract: The submitted thesis examines mainly the first thin films from Ni-Mn-Ga Heusler alloy prepared by magnetron sputtering on the new equipment at Institute of Physics of Charles University. However, the work also analysed the thin films prepared in IFW Dresden and bulk material. The main focus of the work is primarily on the martensitic microstructures, because of the significant effect that their twin boundaries have on the magnetic shape memory phenomena. Microscopic techniques used for the research were mainly Scanning Electron Microscopy (SEM), but also Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). As the Ni-Mn-Ga properties are stronly dependent on chemical composition, the composition was evaluated by two different methods (Electron Dispersive X-ray Spectroscopy and X-ray Fluorescence) and observed differences discussed. Finally the results were compared with X-ray diffraction (XRD) measurements and the films were further characterised by magnetic measurements using Vibrating Sample Magnetometer (VSM)....

Kupferbasierte Legierungen mit Formgedächtniseffekt (z.B. Cu-Al-Ni-Mn) sind vergleichsweise kostengünstige Vertreter im Bereich der Hochtemperatur-Formgedächtnislegierungen mit vielversprechenden Umwandlungseigenschaften. Üblicherweise werden diese über konventionelle schmelzmetallurgische Prozesse hergestellt und dann einer thermomechanischen Behandlung unterzogen. Für die vorliegende Arbeit wurden die Formgedächtnislegierungen Cu-11.85Al-3.2Ni-3Mn und Cu-11,35Al-3,2Ni-3Mn-0,5Zr (m-%) unter Nutzung des selektiven Laserschmelzens (Selective Laser Melting – SLM) verarbeitet und Bauteile, nach einer Optimierung der Prozessparameter, mit einer hohen relativen Dichte (ca. 99%) hergestellt. Anschließend wurde der Einfluss des Energieeintrags, eines zusätzlichen Umschmelzschrittes (Mehrfachbelichtung) und einer Substratheizung auf das Gefüge, das Umwandlungsverhalten, die mechanischen Eigenschaften und die Rückverformung (Zweiweg-Effekt, Pseudoelastizität) untersucht. Zum Vergleich wurden weitere Probenkörper mittels Rascherstarrung der Schmelze hergestellt. Besonders die Korngröße und die thermische Stabilisierung der unterschiedlichen Phasen wirken sich unmittelbar auf die Umwandlungstemperaturen sowie das Rückverformungsverhalten aus. Durch die Nutzung des selektiven Laserschmelzens ergeben sich neue Möglichkeiten bei der Herstellung von endkonturnahen sowie geometrisch komplexen Bauteilen mit Formgedächtniseffekt. Zudem können die Gefüge, und damit die Umwandlungseigenschaften des Materials, bereits während der Herstellung eingestellt werden.

Formgedächtnislegierungen wie Nickel-Titan (NiTi) können sich nach einer plastischen Verformung und anschließendem Aufheizen an ihre ursprüngliche Form „erinnern“ und diese wieder einnehmen. Als meistverwendete Formgedächtnislegierung kann NiTi als Aktor, zur Dämpfung und zur elastokalorischen Kühlen verwendet werden und kommt von der Medizintechnik bis hin zur Luft- und Raumfahrt zum Einsatz. Der Formgedächtniseffekt basiert auf der martensitischen Phasenumwandlung, einer diffusionslosen Strukturänderung, bei der sich die Kristallsymmetrie ändert. Bei NiTi mit etwa 50 At.-% Ni wandelt die kubische Hochtemperaturphase (Austenit) in die monokline Tieftemperaturphase (Martensit) um. Während dieser Umwandlung entsteht eine Vielzahl an Grenzflächen, wodurch sich ein komplexes martensitisches Gefüge – eine Art dreidimensionales „Puzzle“ bildet. Um NiTi-Formgedächtnislegierungen auf verschiedene Anwendungen zuzuschneiden und deren Eigenschaften zu verbessern, ist es wichtig, das Gefüge zu verstehen. Die häufig eingesetzten polykristallinen NiTi-Schichten haben dabei den Nachteil, dass die enthaltenen Korngrenzen einen zusätzlichen Parameter darstellen, der Gefügeuntersuchungen erschwert. Dagegen werden epitaktische Schichten bereits für andere magnetische Formgedächtnislegierungen als Modellsystem eingesetzt und tragen zu einem besseren Verständnis der martensitischen Umwandlung bei. Epitaktische Schichten sind einkristallin, sodass der Einfluss von Korngrenzen ausgeklammert werden kann. Außerdem dient das Substrat, das die Orientierung der Schicht vorgibt, als festes Referenzsystem. In dieser Arbeit wurden epitaktische NiTi-Schichten mit Magnetron-Sputterdeposition hergestellt, die bei Raumtemperatur martensitisch sind. Dabei wurde der Einfluss von Parametern wie Herstellungstemperatur, chemische Zusammensetzung, Wärmebehandlungsszenarien und Pufferschichten auf das Wachstum und die Eigenschaften der Schichten untersucht. So konnten Schichten in zwei unterschiedlichen Orientierungen, (100) und (111), hergestellt werden. Die so optimierten Schichten wurden anschließend dafür genutzt, das martensitische Gefüge skalenübergreifend zu untersuchen. Mit einer Kombination von Mikroskopie- und Röntgenbeugungsmethoden wurden die auftretenden Zwillingsgrenzen, Habitusebenen und Variantenorientierungen analysiert. So lässt sich feststellen, welche Martensitcluster entstehen, wie sie nukleieren und wachsen und welche Grenzflächen auftreten. Dabei ließ sich ein hierarchischer Aufbau des martensitischen Gefüges feststellen, wobei drei Zwillingsgrenzen auf unterschiedlichen Längenskalen für die Beschreibung des Gefüges nötig sind. Die auftretenden Zwillingsgrenzen sind aus Massivmaterialien bekannt, was zeigt, dass sich die Schichten gut als Modellsystem eignen. Das identifizierte, dreidimensionale Modell des Gefüges wurde mit Röntgenmethoden global bestätigt. Dazu wurden die experimentellen Ergebnisse mit zwei unterschiedlichen Martensittheorien, der phänomenologischen Martensittheorie (PTMC) und der Korrespondenztheorie (CT) verglichen. Der hierarchische Aufbau des Gefüges lässt sich zum Großteil mit den Theorien beschreiben. Die Schichten zeigen aber auch die Limitierungen der bisherigen Theorien und bieten so eine Möglichkeit für deren Weiterentwicklung.

Shape memory alloys (SMAs) can recover large strains (e.g., up to 8%) by undergoing a temperature-induced phase transformation. This strain recovery can occur against large forces, resulting in their use as actuators. The SMA elements in such actuators integrate both sensory and actuation functions. This is possible because SMAs can inherently sense a change in temperature and actuate by undergoing a shape change, associated with the temperature-induced phase transformation. The objective of this work is to develop an SMA based cryogenic thermal conduction switch for operation between dewars of liquid methane and liquid oxygen in a common bulk head arrangement for NASA. The design of the thermal conduction switch is based on a biased, two-way SMA actuator and utilizes a commercially available NiTi alloy as the SMA element to demonstrate the feasibility of this concept. This work describes the design from concept to implementation, addressing methodologies and issues encountered, including: a finite element based thermal analysis, various thermo-mechanical processes carried out on the NiTi SMA elements, and fabrication and testing of a prototype switch. Furthermore, recommendations for improvements and extension to NASA's requirements are presented. Such a switch has potential application in variable thermal sinks to other cryogenic tanks for liquefaction, densification, and zero boil-off systems for advanced spaceport applications. The SMA thermal conduction switch offers the following advantages over the currently used gas gap and liquid gap thermal switches in the cryogenic range: (i) integrates both sensor and actuator elements thereby reducing the overall complexity, (ii) exhibits superior thermal isolation in the open state, and (iii) possesses high heat transfer ratios between the open and closed states. This work was supported by a grant from NASA Kennedy Space Center (NAG10-323) with William U. Notardonato as Technical Officer.

No description available.

Dans ce travail, des modèles thermomécaniques basés sur une approche non-locale sont proposés pour décrire le comportement des Alliages à Mémoire de Forme (AMF) avec la prise en compte des effets de la localisation et de la chaleur latente lors de la transformation de phase. Ces modèles sont obtenus comme des extensions d’un modèle local existant. Pour décrire la localisation de la transformation de phase, l’extension du modèle initial a consisté à le réécrire dans un contexte non-local par l’introduction d’une nouvelle variable, définie comme la contrepartie non-locale de la fraction volumique de martensite déjà présente dans le modèle local. L’exploitation de ce modèle a nécessité le développement d’un élément fini spécial dans ABAQUS avec la fraction volumique non-locale de martensite comme un degré de liberté supplémentaire. Les simulations réalisées montrent la pertinence d’une telle approche dans la description de la transformation de phase dans des structures minces en AMF, soumises à des chargements thermomécaniques. Pour décrire les effets de la chaleur latente, une équation d’équilibre thermique ayant comme terme source des contributions dépendant de la transformation de phase a été adjointe au modèle initial. Là encore, l’exploitation du modèle a nécessité le développement d’un élément fini qui prend en compte le couplage thermomécanique et la formulation proposée pour l’équilibre thermique. Les simulations numériques réalisées ont montré l’effet retardant sur la transformation de phase de la chaleur latente, et le caractère hétérogène possible de la transformation dans ce cas. Ces effets sont d’autant plus importants que la vitesse de déformation est élevée / In this Phd thesis, thermo-mechanical models based on a nonlocal approach are proposed in order to describe the behavior of Shape Memory Alloys (SMA), taking into account localization and latent heat effects during phase transformation. These models are obtained as extensions of an existing local model. In order to describe the localization of phase transformation, the extension of the initial model consisted of rewriting it in a nonlocal context through the introduction of a new variable, defined as the nonlocal counterpart of the martensite volume fraction. The use of this model has required the development of a specific finite element in ABAQUS with the nonlocal martensite volume fraction as an additional degree of freedom. The simulations show the relevance of such an approach in the description of the phase transformation occurring in thin SMA structures subjected to thermo-mechanical loadings. To achieve the description of the latent heat effects, a heat balance equation with a source term depending on contributions of the phase transformation was added to the constitutive equations of the initial model. Even there, the use of the model required the development of a finite element which takes into account the thermo-mechanical coupling and considers the proposed formulation for the thermal balance. Numerical simulations have shown the delaying effect of the latent heat on phase transformation and the possible heterogeneous character of the phase transformation in this case. These effects are even more important as the strain rate is high

No description available.

NiTi based shape memory alloys (SMA) cover most of the commercially produced shape memory devices and components. The reversible martensitic transformation between the phases B2 (austenite) and B19′ (martensite) is responsible for the shape memory effect in these alloys. The amount of strain which can be regained after a permanent deformation through thermal activation, known as the recoverable strain, is a strong function of crystallographic texture and microstructure. Texture influences the activation of a specific martensite variant during stress induced martensitic (SIM) transformation and also the re-orientation of twinned variants during further deformation. The variant selection decides the amount of recoverable strain. Since the NiTi based shape memory alloys inevitably undergo thermo-mechanical processing in the course of component design, the consequent evolution of texture and microstructure regulate the shape memory behavior. The present thesis is aimed to address this issue in some NiTi alloys that are technologically important for different applications, namely a binary Ni-rich NiTi alloy, a copper containing NiTi alloy and a hafnium containing NiTi alloy. The Ni rich NiTi alloy displays pseudoelastic behavior that can be used for couplings, the NiTiCu alloy provides a controlled thermal hysteresis suitable for actuator applications and the NiTiHf alloy can be used for high temperature applications. The first Chapter of the thesis provides a detailed overview of the existing knowledge related to evolution of microstructure and texture during processing, the transformation texture and its role on the shape memory behavior in NiTi alloys. The second chapter includes the experimental procedure followed to generate different textures, namely unidirectional and cross rolling with and without a subsequent annealing and also the details of the techniques used to characterize the structure, microstructure, texture and mechanical properties. The evolution of texture during thermo-mechanical processing of a Ni rich NiTi alloy and its impact on shape memory behavior is addressed in Chapter 3. The two modes of rolling employed at higher temperature led to the formation of different textures. The texture of unidirectionally rolled samples was characterized by a strong <111>||ND fiber, while a strong Goss {100}<110> component along with <111>||ND fiber was observed in the texture of the cross rolled samples. Annealing of the unidirectionally rolled samples generated a strong <100>||ND fiber, and a weak <111>||ND fiber was observed for the cross rolled samples. Microtexture analyses indicated that dynamically recrystallized grains had significantly different texture compared to the statically annealed material. One of the salient features of this study is the analysis of different twin boundaries with coincident site lattice (CSL) relations that has been observed in the hot rolled material. The origin of these twins has been attributed to deformation. The evolution of twin boundaries with CSL relation has strong influence on texture formation. A few of the important texture components have been found to have CSL relation amongst them. The origin of different texture components were found using intra-grain misorientation parameters. In-situ transformation studies in a scanning electron microscope have confirmed the formation of different types of twins at very low amount of strain in the Ni rich NiTi alloy. A Schmid factor based criterion was used to identify the activation of a particular variant. Trace analysis of the surface relief due to SIM transformation was utilized to confirm the theoretically predicted variant. Schmid criterion has been found to be valid in all the cases. Modulus variation with temperature and strain was studied using dynamical mechanical analysis. Microstructural changes during thermal and thermo-mechanical cycling revealed higher orientation gradient along grain boundaries compared to grain interior. The compatibility condition at the grain boundaries were attributed to higher misorientation development. Misorientation development during cycling loading process is also found to be a strong function of texture. Processing condition and texture has a strong influence on the recoverable strain. Particularly, the strength of <111>||ND fiber is influential in deciding the recoverable strain. Study of microstructure and texture evolution in the TiNiCu SMA and subsequent study on its impact on recoverable strain is presented in Chapter 4. Convincing evidences for the mechanisms operating during different dynamic restoration processes have been presented through microstructural investigation. Texture analysis of the austenite phase showed the formation of <111>||ND fiber. Despite the weakening of texture at larger strain, strength of certain deformation texture components like S {123}<634> and Cu {112}<111> increased, which suggested that texture evolution in TiNiCu alloy deviates from the texture of binary NiTi at large strains. Transformation texture analysis was carried out through electron back scattered diffraction technique, using an in-situ heating stage. The analysis of the results showed predominant activation of <011> type II as well as {11 1 } type I twins. A comparison of martensite and austenite pole figures indicated strong variant selection during phase transformation. Like the binary NiTi alloy, cross rolling of TiNiCu alloy also showed ample changes in the texture of martensite phase through the formation of different texture components. Annealing of both unidirectionally and cross rolled samples led to the weakening of texture. The change in volume fraction of Ti2NiCu precipitates, resulting from different processing conditions, influenced the transformation temperature. In this case also, texture and large intra-grain misorientation governed the recoverable strain. Chapter 5 is dedicated to the study of high temperature NiTiHf alloy. X-ray diffraction and differential scanning calorimetric studies confirmed a two step martensitic transformation, a B19` monoclinic and rhombohedral R-phase martensite in the studied alloy (Ni49.4Ti38.6Hf12). Microstructural investigations showed the formation of dendritic (Ti,Hf)2Ni precipitates along the grain boundary. Evolution of R-phase martensite was always observed along with (Ti,Hf)2Ni precipitates, irrespective of the processing condition. Dissolution of (Ti,Hf)2Ni precipitates by solution treatment suppressed the R phase formation. Strong texture of R-phase martensite confirmed variant selection during martensitic transformation. On the contrary, texture of B19` martensite was always weak, suggesting no preference for variant selection. Rolled material with a relatively strong texture exhibited higher recoverable strain compared to annealed material. Finally, all the significant outcomes of the present investigation are summarized in Chapter 6. Based on the conclusions, suggestions for future work have been mentioned.

The objective of this research is to thoroughly investigate the shape memory effect in polymers, characterize, and optimize these polymers for applications in information storage systems. Previous research effort in this field concentrated on shape memory metals for biomedical applications such as stents. Minimal work has been done on shape memory poly- mers; and the available work on shape memory polymers has not characterized the behaviors of this category of polymers fully. Copolymer shape memory materials based on diethylene glycol dimethacrylate (DEGDMA) crosslinker, and tert butyl acrylate (tBA) monomer are designed. The design encompasses a careful control of the backbone chemistry of the materials. Characterization methods such as dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC); and novel nanoscale techniques such as atomic force microscopy (AFM), and nanoindentation are applied to this system of materials. Designed experiments are conducted on the materials to optimize spin coating conditions for thin films. Furthermore, the recovery, a key for the use of these polymeric materials for information storage, is examined in detail with respect to temperature. In sum, the overarching objectives of the proposed research are to: (i) design shape memory polymers based on polyethylene glycol dimethacrylate (PEGDMA) and diethylene glycol dimethacrylate (DEGDMA) crosslinkers, 2-hydroxyethyl methacrylate (HEMA) and tert-butyl acrylate monomer (tBA). (ii) utilize dynamic mechanical analysis (DMA) to comprehend the thermomechanical properties of shape memory polymers based on DEGDMA and tBA. (iii) utilize nanoindentation and atomic force microscopy (AFM) to understand the nanoscale behavior of these SMPs, and explore the strain storage and recovery of the polymers from a deformed state. (iv) study spin coating conditions on thin film quality with designed experiments. (iv) apply neural networks and genetic algorithms to optimize these systems.

Objetivou-se nessa pesquisa comparar oito tipos de fios de NiTi superelásticos e termoativos, de seis empresas comerciais (GAC, TP, ORMCO, MASEL, MORELLI e UNITEK) àqueles com adição de cobre (CuNiTi 27 e 35OC, ORMCO), observando se as propriedades mecânicas dos dois últimos justificariam sua escolha clínica. Para tal foram realizados ensaios de tração e microscopia eletrônica de varredura. Os ensaios de tração foram realizados em máquina de ensaios mecânicos da marca EMIC, modelo DL10000, de 10 toneladas de capacidade, no Instituto Militar de Engenharia (IME). A composição química e a topografia superficial dos fios foram determinadas através da microscopia eletrônica de varredura em microscópio da marca JEOL, modelo JSM-5800 LV com sistema de microanálise EDS (energy dispersive spectroscopy). Os resultados mostraram que, de forma geral, os fios de NiTi termoativados apresentaram cargas mais suaves de desativação em relação aos superelásticos. Entre os fios que apresentaram as cargas biologicamente mais adequadas de desativação estão os termoativados da GAC e da UNITEK. Entre os fios de NiTi superelásticos, os de CuNiTi 27C da ORMCO foram os que apresentaram as cargas mais suaves de desativação, sendo semelhantes, estatisticamente (ANOVA), às apresentadas pelos fios de NiTi termoativados da UNITEK para a deformação de 4%. Quando comparados os fios de CuNiTi a 27 e a 35C, observou-se que os primeiros apresentaram forças de desativação de, aproximadamente, 1/3 das apresentadas pelos últimos, para a deformação de 4%. Quando analisada a microscopia eletrônica de varredura de superfície, os fios de NiTi superelásticos que apresentaram melhores acabamentos foram os da MASEL e MORELLI e os que apresentaram os piores acabamentos foram os de NiTi e CuNiTi 27C da ORMCO. Entre os termoativados, todos apresentaram marcas e ranhuras de trefilação bastante visíveis, com características inadequadas em termos de topografia de superfície, sendo que os de CuNiTi 35C da ORMCO e os da UNITEK apresentaram os piores acabamentos de superfície graças à presença de microcavidades formadas devido aos arrancamento de partículas, possivelmente de NiTi4. Quando analisada a morfologia da região de fratura observou-se a presença de deformação plástica, e de microcavidades, características de fratura do tipo dúctil com redução macroscópica do diâmetro, para todos os grupos de fios NiTi e CuNiTi ensaiados, sendo que os de CuNiTi 27 C e os termoativados da UNITEK apresentaram as menores microcavidades e os melhores acabamentos à fratura. Concluiu-se que os fios de CuNiTi 35C, além de terem apresentado as maiores cargas de desativação entre os fios de NiTi termoativados, apresentaram os piores acabamentos das superfícies, o que não justificaria sua escolha como os primeiros fios para utilização clínica. / Leveling and aligning orthodontic wires must be able to generate light and continuous forces. Thus need to have high springback and flexibility. For this purpose it was suggested a variety of supereslatic and termoactivated Nickel-Titanium (NiTi) wires that may offer a load-deformation curve, in a constant plataform. Copper NiTi wires are presented as exhibiting better thermoactivating properties for optimum-forces system with better dental movement control. The aim of this study was to compare 8 NiTi superelastic and thermoactivated wires of six different brands (GAC, TP, ORMCO, MASEL, MORELLI and UNITEK) to Copper addicted wires (CuNiTi 270C and 350C, ORMCO) to verify if the mechanical properties of Copper NiTi would support its clinical use. Stress-strain tests were done in Engeneering Military Institute (IME-Brazil), through test machine (EMIC- DL 10000 model). Scanning electronic microscope with energy dispersive spectroscopy (JOEL, JSM-5800 LV model) was used to determine chemical composition and superficial topography of the wires. Results showed that, in general, thermoactivated NiTi wires exhibited lower deactivation loads when compared to NiTi superelastics. Among the thermoactivated, the GAC and UNITEK ones are the lighter ones. Among the superelastics, the Copper NiTi 270C (ORMCO) were the lighter ones, statistically similar (ANOVA) to thermoactivated NiTi from UNITEK, for 4% strain. Once Copper NiTi 270C showed deactivated loads 62% lower than Copper NiTi 350C , under 4% strain. As regard to Scanning Electronic Microscopy results for superelastic NiTi wires, better superficial burnishing were found for MASEL and MORELLI ones. On the other hand, the worst were ORMCO Superelastic NiTi and CuNiTi 270C. The thermoactivated ones were superficially visibly marked with inadequate superficial topography. Copper NiTi 350 C and UNITEK showed the worst burnishing among the thermoactivated wires, linked to microtags. It was concluded that CuNiTi 350 C showed the greatest deactivation loads and not favorable superficial burning.