Porous TiNi alloys (Ti-50.4 at. %Ni and Ti-50.6 at. %Ni) with porosities in the range 21%-81% were prepared successfully applying a new powder metallurgy fabrication route in which magnesium was used as space holder resulting in either single austenite phase or a mixture of austenite and martensite phases dictated by the composition of the starting prealloyed powders but entirely free from secondary brittle intermetallics, oxides, nitrides and carbonitrides. Magnesium vapor do not only prevents secondary phase formation and contamination but also provides higher temperature sintering opportunity preventing liquid phase formation at the eutectic temperature, 1118 &deg / C resulting from Ni enrichment due to oxidation. By two step sintering processing (holding the sample at 1100 &deg / C for 30 minutes and subsequently sintering at temperatures higher than the eutectic temperature, 1118 &deg / C) magnesium may allow sintering probably up to the melting point of TiNi. The processed alloys exhibited interconnected (partially or completely depending on porosity content) open macro-pores spherical in shape and irregular micro-pores in the cell walls resulting from incomplete sintering. It has been found that porosity content of the foams have no influence on the phase transformation temperatures while deformation and oxidation are severely influential. Porous TiNi alloys displayed excellent superelasticity and shape memory behavior. Space holder technique seems to be a promising method for production of porous TiNi alloys. Desired porosity level, pore shape and accordingly mechanical properties were found to be easily adjustable.

NiTiHf alloys have attracted considerable attention as potential high temperature Shape Memory Alloy (SMA) but the instability in transformation temperatures and significant irrecoverable strain during thermal cycling under constant stress remains a major concern. The main reason for irrecoverable strain and change in transformation temperatures as a function of thermal cycling can be attributed to dislocation formation due to relatively large volume change during transformation from austenite to martensite. The formation of dislocations decreases the elastic stored energy, and during back transformation a reduced amount of strain is recovered. All these observations can be attributed to relatively soft lattice that cannot accommodate volume change by other means. We have used Equal Channel Angular Extrusion (ECAE), hot rolling and marforming to strengthen the 49.8Ni-42.2Ti-8Hf (in at. %) material and to introduce desired texture to overcome these problems in NiTiHf alloys. ECAE offers the advantage of preserving billet cross-section and the application of various routes, which give us the possibility to introduce various texture components and grain morphologies. ECAE was performed using a die of 90º tool angle and was performed at high temperatures from 500ºC up to 650ºC. All extrusions went well at these temperatures. Minor surface cracks were observed only in the material extruded at 500 °C, possibly due to the non-isothermal nature of the extrusion. It is believed that these surface cracks can be eliminated during isothermal extrusion at this temperature. This result of improved formability of NiTiHf alloy using ECAE is significant because an earlier review of the formability of NiTiHf using 50% rolling reduction concluded that the minimum temperature for rolling NiTi12%Hf alloy without cracks is 700°C. The strain level imposed during one 90° ECAE pass is equivalent to 69% rolling reduction. Subsequent to ECAE processing, a reduction in irrecoverable strain from 0.6% to 0.21% and an increase in transformation strain from 1.25% to 2.18% were observed at a load of 100 MPa as compared to the homogenized material. The present results show that the ECAE process permits the strengthening of the material by work hardening, grain size reduction, homogeneous distribution of fine precipitates, and the introduction of texture in the material. These four factors contribute in the increase of stability of the material. In this thesis I will be discussing the improvement of mechanical behavior and stability of the material achieved after various passes of ECAE.

Magnetic shape memory (MSM) materials are a new class of smart materials which exhibit shape deformation under the influence of an external magnetic field. They are interesting for various types of applications, including actuators, displacement/force sensors, and motion dampers. Due to the huge strain and the magnetic field-driven nature, MSM materials show definite advantages over other smart materials, e.g. conventional thermal shape memory materials, in terms of displacement and speed. The principle behind the magnetic field induced strain (MFIS) is the strong coupling between magnetization and lattice structure. The investigation of both static and dynamic magnetic domain structures in MSM materials is a key step in optimizing the properties for future possible devices. In this work, optical polarization microscopy is applied to investigate the twin boundary and magnetic domain wall motion in bulk NiMnGa single crystals. Surface magnetic domain patterns on adjacent sides of bulk crystals are revealed for the first time providing comprehensive information about the domain arrangement inside the bulk and at the twin boundary. The tilting of the easy axis with respect to the sample surface determines the preferable domain size and leads to spike domain formation on the surface. Out-of-plane surface domains extend into the bulk within a single variant, while a twin boundary mirrors the domain pattern from adjacent variants. Furthermore, magnetic domain evolution during twin boundary motion is observed. The partial absence of domain wall motion throughout the process contradicts currently proposed models. The magnetic state alternates along a moving twin boundary. With the abrupt nucleation of the second variant this leads to the formation of sections of magnetically highly charged head-on domain structures at the twin boundaries. On the other hand, a dynamic actuation experimental setup, which is capable to provide high magnetic fields in a wide range of frequency, was developed in the course of this study. The observation of reversible twin boundary motion up to 600 Hz exhibits the dependence of strain, hysteresis, and twin boundary velocity on the actuation speed. MFIS increases with frequency, while the onset field is similar in all observed cases. Twin boundary mobility enhancement by fast twin boundary motion is proposed to explain the increase in MFIS. The twin boundary velocity is shown to be inversely proportional to the twin boundary density. No limit of twin boundary velocity is observed in the investigated frequency range.

Magnetic Shape Memory Alloys (MSMAs) have the unique ability to change their shape within a magnetic field, or in the presence of stress and a change in temperature. MSMAs have been widely investigated in the past decade due to their ability to demonstrate large magnetic field induced strain and higher frequency response than conventional shape memory alloys (SMAs). NiMn-based alloys are the workhorse of metamagnetic shape memory alloys since they are able to exhibit magnetic field induced phase transformation. In these alloys, martensite and austenite phases have different magnetization behavior, such as the parent phase can be ferromagnetic and martensite phase can be weakly magnetic. The magnetization difference between the transforming phases creates Zeeman energy, which is the main source for magnetic field induced phase transformation, is unlimited with applied field and orientation independent. Thus, metamagnetic shape memory alloys can be employed in polycrystalline form and provide higher actuation stress than conventional MSMAs. High actuation stress levels and frequencies in metamagnetic shape memory alloys are promising for magnetic actuation applications. Effects of heat treatments and cooling rates on the transformation temperatures, magnetization response and shape memory behavior under compressive stress were explored in Ni45Mn36.5Co5In13.5 [100] oriented single crystalline alloys to obtain high transformation temperatures, large magnetization difference, and low hysteresis behavior. It was found that transformation temperatures increase with higher heat treatment temperatures and decrease drastically at lower cooling rates. Temperature hysteresis decreased with increasing heat treatment temperatures. It was revealed that transformation temperatures, hysteresis, and magnetization response can be tailored by heat treatments via modifying interatomic order. Magnetic and mechanical results of NiMn-based metamagnetic alloys in single and polycrystalline forms as functions of composition, stress, temperature and magnetic field (up to 9 Tesla) were revealed through thermal-cycling under stress and magnetic field; stress-cycling as functions of temperature and magnetic field; and magnetic-field-cycling under stress at several temperatures experiments. Single crystalline samples of NiMnCoIn showed recoverable strain of 1.5 % due to magnetic field induced reversible phase transformation under constant stress and strain of 3.7 % by magnetic field induced recovery after variant reorientation of martensite. The magnetic field effect on the superelasticity and shape memory effects were also explored in selected orientations of [100], [110] and [111]. Fe-based ferromagnetic shape memory alloys have received considerable attention due to their better workability, strength, and lower cost compared with commercial NiTi based SMAs. The shape memory properties of a ferrous single crystalline alloy, FeNiCoAlNb, were investigated along the [100] orientation by thermal cycling under constant stress and superelasticity tests in both tension and compression. Aging was used to form nano-size precipitates to demonstrate shape memory behavior and tailor the shape memory properties. It was found that after proper heat treatments, [001] oriented FeNiCoAlNb showed a compressive strain of 15%, low temperature dependent superelastic behavior, high compression-tension asymmetry, and high compressive strength (~3GPa). The orientation dependence of the mechanical properties of FeNiCoAlNb single crystals were investigated along the [100], [110], [012] and [113] orientations. In addition, martensite phase showed higher magnetization than austenite phase as opposed to NiMn-based metamagnetic shape memory alloys. This magnetization difference is promising because it can allow magnetic field induced forward transformation. Ferrous alloys have great potential for high strength, temperature independent, and large scale actuator applications.

Η παρούσα διδακτορική διατριβή περιγράφει το σχεδιασμό και την ανάπτυξη ενός εκπτυσσόμενου Ενδομυελικού Ήλου Επιμήκυνσης των Μακρών Οστών των Κάτω Άκρων. Η επιμήκυνση των κάτω άκρων είναι μία χειρουργική διαδικασία βαθμιαίας επιμήκυνσης των μακρών οστών των κάτω άκρων και των μαλακών μορίων που τα περιβάλουν. Γενικά, η επιμήκυνση των κάτω άκρων στοχεύει στην εξίσωση των σκελών ή αύξηση του μήκους των οστών και στα δύο άκρα. Η τεχνική αύξησης του μήκους των οστών των κάτω άκρων επινοήθηκε από τις αρχές του περασμένου αιώνα [1] και έχει καταξιωθεί στη μοντέρνα χειρουργική από τις αρχές του 1960, λόγω της ενασχόλησης του G.A.Ilizarov. Ο επιστήμονας και χειρουργός G.A.Ilizarov αφιέρωσε όλη τη θεωρητική και πρακτική του έρευνα [2] στη βελτίωση της διαδικασίας επιμήκυνσης των οστών και την ανάπτυξη εξωτερικής συσκευής σταθεροποίησης που φέρει το όνομα του. Η μέθοδος αυτή καθώς και η συσκευή Ilizarov χρησιμοποιήθηκαν πάρα πολύ για να διορθώσουν τόσο βλάβες όσο και παραμορφώσεις των κάτω άκρων. Η ευελιξία αυτής της συσκευής την κάνει ένα εξαιρετικό εργαλείο το οποίο μπορεί να χρησιμοποιηθεί για τη διόρθωση διαφόρων βλαβών όπως π.χ. σταθεροποίηση συνθέτων καταγμάτων, στροφικές διορθώσεις, διορθώσεις οστών με διαφορές μήκους. Τόσο όμως η συσκευή του Ilizarov όσο και οι υπόλοιποι μονόπακτοι εξωτερικοί σταθεροποιητές που παρουσιάσθηκαν αργότερα παρουσιάζουν μειονεκτήματα [3] όπως είναι π.χ. οι σύνθετες χειρουργικές διαδικασίες, οι συνδέσεις και οι βελόνες που διαπερνούν το δέρμα και που οδηγούν σε μολύνσεις, η μειωμένη δυνατότητα φόρτισης και η ταλαιπωρία λόγω του μεγέθους του σταθεροποιητή ειδικά στις περιπτώσεις εκείνες που η ευελιξία του σταθεροποιητή δεν είναι απαραίτητη. Πολλοί ασθενείς που χρειάζονται μία διόρθωση του μήκους ενός άκρου χωρίς άλλες παραμορφώσεις θα μπορούσαν να βοηθηθούν και από μία συσκευή μικρότερης ευελιξίας χωρίς τα μειονεκτήματα των εξωτερικών μονόπακτων σταθεροποιητών. / The technique to increase the length of the long bones is the subject of research for the orthopedic surgeons for many years. The technique is used for the treatment of a limb shortening due to malformation or to a deficit for other reasons e.g. the fracture of a long bone after a car accident, osteomyelitis, or malignancy. The procedure to increase the length of a bone is difficult and may become quite hazardous for the soft tissues surrounding the area. The two parts of the bone are stabilized to eliminate the possibility of relative torsion and bending. Then they align axially with respect to each other and move with a constant rate of elongation of 1mm per day. The elongation is usually achieved by 4 steps of 0,25mm every 6 hours. The application of internal distraction osteogenesis using shape memory alloys has all the advantages of internal osteosynthesis. The only part of these mechanisms that is found externally is the activation mechanism that is connected by the necessary cables of activation with the interior of the bone where the internal distraction device is placed. The basic problem of all designs is the high constructional complexity of activation and control of shift of the two parts of the bone, something that makes this systems non user friendly and with continuous fractures and blockings of the elements of the mechanisms. In the present work, all the advantages of the mechanism of internal distraction osteogenesis are combined with the fundamental advantage; the simplicity of manufacture of the mechanism and the simplicity of operation via the restriction of the moving elements.

Shape memory polymers (SMPs) are a relatively new class of active materials that can store a temporary shape and return to the original configuration upon application of a stimulus such as temperature. This shape changing ability has led to increased interest in their use for biomedical and aerospace applications. A major challenge, however, in the advancement of these applications is the ability to accurately predict the material behavior for complex geometries and boundary conditions. This work addresses this challenge by developing an experimentally calibrated and validated constitutive model that is implemented as a user material subroutine in Abaqus ? a commercially available finite element software package. The model is formulated in terms of finite deformations and assumes the SMP behaves as a thermoelastic material, for which the response is modeled using a compressible neo-Hookean constitutive equation. An internal state variable, the glassy volume fraction, is introduced to account for the phase transformation and associated stored deformation upon cooling from the rubbery phase to the glassy phase and subsequently recovered upon heating. The numerical implementation is performed such that a system of equations is solved using a Newton-Raphson method to find the updated stress in the material. The conductive heat transfer is incorporated through solving Fourier's law simultaneously with the constitutive equations. To calibrate and validate the model parameters, thermomechanical experiments are performed on an amorphous, thermosetting polyurethane shape memory polymer. Strains of 10-25% are applied and both free recovery (zero load) and constrained displacement recovery boundary conditions are considered for each value of applied strain. Using the uniaxial experimental data, the model is then calibrated and compared to the 1-D experimental results. The validated finite element analysis tool is then used to model biomedical devices, including cardiovascular tubes and thrombectomy devices, fabricated from shape memory polymers. The effects of heat transfer and complex thermal boundary conditions are evaluated using coupled thermal-displacement analysis, for which the thermal material properties were experimentally calibrated.

The purpose of this research was to investigate the surface modifications that take place during the machining of NiTi SMA and Ti-6Al-4V with micro-EDM. This was done by creating an array of blind holes and micro-patterns on both work-pieces. To analyze the machined surface and investigate the results, scanning electron microscope (SEM), energy dispersive X- ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques were employed. In addition, the effects of various operating parameters on the machining performance was studied to identify the optimum parameters for micro-EDM of NiTi SMA and Ti-6Al-4V. Recently, aerospace and biomedical industries have placed a high demand on nonconventional machining processes, which can be used to machine high strength and hardto- cut materials such as Titanium alloys, Shape Memory Alloys (SMA) and Super Alloys. Electrical Discharge Machining (EDM) is one of the non-traditional technologies that remove materials from the workpiece through a series of electrical sparks that occur between the workpiece and cutting tool with the presence of dielectric liquid. Obtaining smooth and defect-free surfaces on both workpieces was one of the challenges due to the re-solidified debris on the machined surface. The experimental results showed that there was significant amount of re-casting and formation of resolidification of debris on the Ti surface after machining. On the other hand, the surface generated in NiTi SMA were comparatively smoother with lesser amount of resolidified debris on the surface. By analyzing the results from XRD and EDS, some elements of electrode and dielectric materials such as Tungsten, Carbon and Oxygen were observed on NiTi and Ti surface after machining. In the study of effect of operating parameters, it was found that the voltage, capacitance and tool rotational speed had significant effect on machining time. The machining time was reduced by increasing the voltage, capacitance and tool rotational speed. The machining time was found to be comparatively higher for machining NiTi SMA than Ti alloy. Comparing all the parameters, the voltage of 60 V, capacitance of 1000 PF, and tool rotational speed of 3500 RPM were selected as optimum parameters for this study. Although signs of tool electrode wear and debris particles on the machined surface were observed for both workpieces during the micro-EDM process, Ti alloy and NiTi SMA could be machined successfully using the micro-EDM process.

Shape memory polymers (SMPs) have been candidate materials for morphing applications. However, the SMPs have not been fully tested to work in relevant environments required for Air Force missions. In this study, an epoxy-based SMP was separately exposed to moisture, lubricating oil and UV radiation, which are simulated service environments designed to be reflective of anticipated performance requirements. The thermomechanical properties and shape memory effects were studied by using novel high-temperature nanoindentation technique. Results show that environmental conditions have affected the glass transition temperature and mechanical properties of the SMPs. In most cases, the conditioned SMPs exhibited higher elastic moduli than the unconditioned SMP. The shape recovery ability of the SMP was assessed by creating an indent and then observing the corresponding recovery according to the standard shape memory cycle. It was found that the deformation was mostly recovered for both conditioned and unconditioned SMP samples on heating the material above its glass transition temperature.

Cubic-phase silicon carbide (andamp;acirc;-SiC) nanostructures were successfully synthesized by the reaction of silicon monoxide (SiO) powder with multi-walled carbon nanotubes (MWCNTs) at high temperatures. Experiments were conducted under vacuum or in the presence of argon gas in a high-temperature furnace and the fabrication parameters of temperature (1300 -1500andamp;deg;C), time, and reactant material mass were varied to optimize the material. The resulting samples were then physically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD analysis revealed the presence of dominant andamp;acirc;-silicon carbide phases. SEM images depicted morphologies similar to the starting MWCNTs, having relatively larger diameter sizes, shorter lengths and reduced curvature. TEM observations showed the presence of solid and hollow nanostructures with both crystalline and amorphous regions. Additional experiments were performed to investigate de-aggregation and dispersion procedures for the andamp;acirc;-SiC nanostructures fabricated. Optimum results for these experiments were achieved by ultrasonication of 0.01 wt.% andamp;acirc;-SiC in N,N dimethyl formamide (DMF) and dispersion using a spin coater. A methodology for electrical testing of andamp;acirc;-SiC nanostructures was developed using the de-aggregation and dispersion process established. SEM observations revealed that the random nature of the dispersion procedure used was not efficient in forming contacts regions that would allow electrical measurements of andamp;acirc;-SiC nanostructures on the pre-patterned silicon substrate.

Microfluidic devices have found applications in a number of areas, such as medical analysis, chemical synthesis, biological study, and drug delivery. Because of the small channel dimensions used in these systems, most microchannels exhibit laminar flow due to their low Reynold’s number, making mixing of fluids very challenging. Mixing at this size scale is diffusion-limited, so inducing chaotic flow patterns can increase the interface surface area between two fluids, thereby decreasing overall mixing time. One method to create a chaotic flow within the channel is through the introduction of internal protrusions into the channel. In such an application protrusions that create a rotational flow within the channel are preferred due to their effectiveness in folding the two fluids over one another. The novel mixer outlined in this paper uses a Ti-Ni shape memory alloy for the creation of protrusions that can be turned controlled through material temperature. Controllability of the alloy allows users to turn the chaotic flow created by the protrusions off and on by varying the temperature of the mixer. This ability contributes to the idea of a continuous microfluidic system that can be turned on only when necessary as well as recycle unmixed fluids while turned off.