Many industries including the medical, aerospace, and automobile industries have increasingly adopted the use of shape memory alloys (SMAs) for a plethora of applications due to their unique thermomechanical properties. From the commercially available SMAs in the market, binary NiTi SMAs have shown the most desirable properties. However, SMA properties can be significantly affected by the fabrication process. One of the most familiar applications of NiTi SMAs is in the design of actuating devices where the shape memory effect properties are highly advantageous. Spring NiTi SMA actuators are among the most commonly used and are generally made by torsion loading a straight wire. Consequently, stress concentrations are formed causing a reduction in recovery force. Other methods for producing springs and other NiTi SMA components is the fast emerging manufacturing method of additive manufacturing (AM). AM often uses metal powders to produce the near-net shape components. A major challenge for SMAs, in particular, is their well-known composition sensitivity. Therefore, it is critical to control composition in NiTi SMAs. In this thesis, a novel method for processing NiTi SMAs for pre-alloyed NiTi SMA powders and springs is presented. A low pressure and low temperature hydriding-pulverization-dehydriding method is used for preparing the pre-alloyed NiTi SMA powders with well-controlled compositions, size, and size distributions from wires. By hydrogen charging as-drawn martensitic NiTi SMA wires in a heated H3PO4 solution, pulverizing, and dehydriding, pre-alloyed NiTi powders of various well-controlled sizes are produced. In addition, a low pressure and low temperature hydriding-dehydriding method is used for producing NiTi SMA helixes from wires. The helix pattern in the pre-alloyed NiTi SMA wires was obtained by hydrogen charging NiTi SMA 500 μm diameter wires at different time intervals, followed by dehydriding to remove the hydrogen. The wires, powders, and resulting helixes were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and x-ray diffraction (XRD). The relationship between the wire diameter, powder particle size, and helix geometry as a function of hydrogen charging time is investigated. Lastly, the recovery behavior due to the shape memory effect is also investigated after dehydriding.

Shape memory alloys (SMAs) are a new generation material which exhibits unique nonlinear deformations due to a phase transformation which allows it to return to its original shape after removal of stress or a change in temperature. It shows a shape memory effect (martensitic condition) and pseudoelasticity (austenitic condition) properties depends on various heat treatment conditions. The reason for these properties depends on phase transformation through temperature changes or applied stress. Many technological applications of austenite SMAs involve cyclical mechanical loading and unloading in order to take advantage of pseudoelasticity, but are limited due to poor fatigue life. In this thesis, I investigated two important mechanical feature to fatigue behavior in pseudoelastic NiTi SMA wires using high energy synchrotron radiation X-ray diffraction (SR-XRD). The first of these involved simple bending and the second of these involved relaxation during compression loading. Differential scanning calorimetry (DSC) was performed to identify the phase transformation temperatures. Scanning electron microscopy (SEM) images were collected for the initial condition of the NiTi SMA wires and during simple bending, SEM revealed that micro-cracks in compression regions of the wire propagate with increasing bend angle, while tensile regions tend to not exhibit crack propagation. SR-XRD patterns were analyzed to study the phase transformation and investigate micromechanical properties. By observing the various diffraction peaks such as the austenite (200) and the martensite (100), (110), and (101) planes, intensities and residual strain values exhibit strong anisotropy depending upon whether the sample is in compression or tension during simple bending. This research provides insight into two specific mechanical features in pseudoelastic NiTi SMA wires.

The area of research dealing with joining of dissimilar metals has been active in recent time. Although fusion and non-fusion techniques of joining have been effectively used for manufacturing components, a comprehensive scientific understanding of the process is lacking. This void exists both in fusion and non-fusion welding methods. The present investigation addresses some of these aspects. The investigation consists of two sections - Part A and Part B. Part A is on Friction welding and Part B deals with Fusion welding using laser. Each section has two chapters each. Following an introductory chapter, basic aspects of friction welding is presented in chapter 2. Chapter 3 deals with the work on friction welding of Fe-Cu couple. Fe-Cu couple is a system with positive heat of mixing. After a brief introduction on various non-equilibrium processes that can occur in this system, experimental details and results are presented. Using the results an attempt is made to understand the flash formation, formation of pores at the interface and the formation of chemically altered zone. It is observed that a chemically altered layer forms predominantly on the Cu side of the interface. It consists of Fe entrapped as fragments/fine crystals and as solid solution in Cu matrix. This zone has higher thickness at the edges than at the center. The mechanism of formation of this interfacial layer which is central to the joining process is related to the fracture and transport of fragments during plastic deformation. Fe forms solid solution in copper under non-equilibrium conditions promoted by shear energy. Using the concept of ballistic mixing, the formation of solid solution is explored. Using nano-indentation experiments mechanical properties of the weldment is estimated and an attempt is made to correlate mechanical properties with the amount of second element present in that location. The chapter 4 in part A deals with the friction welding of Ni-Ti couple. Ni-Ti system has negative heat of mixing and it forms a number of intermetallics. After a brief introduction to the chapter, various experimental techniques and strategies followed to carry out the experiments are explained. Following these, the results are presented. It is observed that TiNi3 formed at initial stage. Theories based on effective heat of formation and surface energy also predict the nucleation of TiNi3. With the continuation of frictional processes, the formation of TiNi and Ti2Ni phases were also observed. Formation of Ti2Ni was shown to greatly accelerate due to shear process. In this system two complementary processes like ballistic mixing and thermal assisted diffusion accelerate Ti2Ni formation. From mechanical tests it is found that Ti2Ni layer in the weldment is weak and hence formation of Ti2Ni in the weldment is detrimental. In chapter 5 an introduction to fusion welding of dissimilar metals is presented as background materials for the subsequent chapters. Chapter 6 deals with nature of segregation of Ag during laser welding of Fe-Ni couple. Ag is used as a tracer to probe fluid flow in the Fe-Ni couple during laser welding. Ag is immiscible both in Fe and Ni whereas Fe and Ni form a complete solution at an elevated temperature and in liquid state. Besides the experimental work, numerical simulation of the weld pool were carried out using homogeneous mixture model using SIMPLER algorithm. Experiments and simulations indicate that fluid flow is asymmetrical and in the deep penetration welding strong convection in the pool drives the tracer to the top of the pool. Overall distribution of the tracer is due to the combined effect of convection and diffusion. In shallow welding there exists a boundary region where tracer does not penetrate. In chapter 7 the results of instrumented indentation experiments on laser welded Fe-Cu weldment has been presented. It was earlier reported that during laser welding of Fe-Cu couple, a variety of microstructures evolves at various locations in the weldment and hardness of the weldment were found to be very high. Here an attempt has been made to explore in details the origin of such a high hardness. The chapter starts with a description of various microstructures that are observed in this weldment followed by the various procedures used for extracting data from instrumented indentation tests. It is followed by the presentation of the experimental results. It is found that rule of mixture along with Hall-Petch strengthening explains the observed increase in hardness of the weldment. The fine scale microstructure consisting of alternate Fe rich and Cu rich layers increases the hardness of the weldment. On copper side of the weldment, composition and scale of microstructure fluctuates and so also the hardness. Finally in chapter 8 overall conclusions of the various chapters in the thesis have been summarised.

L'optimisation des états de surface constitue un enjeu majeur pour les biomatériaux utilisés dans le domaine biomédical. Le titane (Ti) et ses alliages à base de nickel (NiTi) restent à ce jour les biomatériaux métalliques de prédilection dans nos applications cliniques en Odontologie (implants dentaires, instruments endodontiques, et arcs orthodontiques). Le but de nos recherche est d'optimiser les surfaces du Ti et NiTi en les fonctionnalisant par des films multicouches de polyélectrolytes (FMP). Notre travail propose d'étudier différents paramètres devant être impérativement validés avant d'envisager une quelconque application biomédicale in vivo avec ce type de revêtement. Une recherche bibliographique exhastive appuie notre recherche expérimentale. Le premier axe du travail propose de déterminer si des FMP peuvent effectivement s'adsorber chimiquement sur le Ti et le NiTi. qui plus est, une étude biologique est réalisée avec des cellules humaines pour tester la biocompatibilité des ces surfaces fonctionnalisées. La deuxième partie se concentre sur la biocompatibilité de la couche précurseur des FMP à base de polyéthyléneimine (PEI). Les résultats mettent en lumière une certaine cytotoxicité de la PEI envers des ostéoblastes et des fibroblastes gingivaux humain. Pour clore ce travail, nous réalisons des essais de stérilisation afin d'évaluer l'influence d'un tel procédé sur les FMP en terme de caractérisations physico-chimique et biologique des surfaces. La perspective d'une application biomédicale avec les FMP semble prometteuse, notamment en y introduisant des molécules bioactives. Cependant, bien d'autres paramètres sont encore à étudier avant d'envisager une application expérimentale et/ou clinique in vivo. Nous pouvons citer par exemple, le vieillissement des FMP, leur comportement en milieu salivaire ou fluoré, ou encore leur résistance à l'usure. Ces différents éléments rentrent dans les perspectives d'un projet post-doctoral. / Optimization of surface properties is a fundamental priority for biomaterials uses in biomedical applications. Titanium (Ti) and nickel-titanium alloys (NiTi) are the references in terms of metallic biomaterials for clinical applications in Odontology (Dental implants, endodontic instrumentations, and orthodontic arches). The aim of our work is to study the Ti and NiTi surfaces coated with polyelectrolytes multilayers films (PEM). Our work study various parameters needed to be validated before using this functionalized surface treatment for biomedical and clinical applictions in vivo. The first part of this work aims at defining the possibility to chemically adsorb PEM coating on Ti and on NiTi surfaces. Moreover, we have realized a biological study with human cells to test the biocompatibility of functionalized surfaces. In the second part of this thesis, we tested the biocompatibility of the multilayered structure in regards to the precursor base layer of PEM, the polyethyleneimine (PEI). Our reuslts show that the PEI is not cytotoxic towards osteoblasts and human gingival fibroblasts. Finally, we relaized tests of sterilization to evaluate PEM stability in terms of physico-chemical and biological surface characterizations. The development of specific biomedical applications for PEM is an exciting perspective, especially when these firms are functionalized with bioactive molecules. However, many other parameters murst be studied before imagining an experimental or clinical application in vivo. As an example, PEM degradation as well as behaviour in salivary or fluoride solution, still needs to be tested.

Shape memory alloys (SMAs) operating as solid-state actuators pose economic and environmental benefits to the aerospace industry due to their lightweight, compact design, which provides potential for reducing fuel emissions and overall operating cost in aeronautical equipment. Despite wide applicability, the implementation of SMA technology into aerospace-related actuator applications is hindered by harsh environmental conditions, which necessitate extremely high or low transformation temperatures. The versatility of the NiTi-based SMA system shows potential for meeting these demanding material constraints, since transformation temperatures in NiTi can be significantly raised or lowered with ternary alloying elements and/or Ni:Ti ratio adjustments. In this thesis, the expansive transformation capabilities of the NiTi-based SMA system are demonstrated with a low and high-temperature NiTi-based SMA; each encompassing different stages of the SMA development process. First, exploratory work on the NiTiSn SMA system is presented. The viability of NiTiSn alloys as low-temperature SMAs (LTSMAs) was investigated over the course of five alloy heats. The site preference of Sn in near-equiatomic NiTi was examined along with the effects of solution annealing, Ni:Ti ratio adjustments, and precipitation strengthening on the thermomechanical properties of NiTiSn LTSMAs. Second, the thermomechanical processability of NiTiHf high-temperature SMA (HTSMA) wires is presented. The evolution of various microstructural features (grain size reduction, oxide growth, and nano-precipitation) were observed at incremental stages of the hot rolling process and linked to the thermal and mechanical responses of respective HTSMA rods/wires. This work was carried out in an effort to optimize the rolling/drawing process for NiTiHf HTSMAs.