Les travaux de recherches développés dans cette thèse concernent la réalisation de couchesminces, à partir de l’alliage à mémoire de forme (AMF) NiTi mécanoélaboré et de structurenanocristalline, en vue de leur intégration dans des microsystèmes. Le but est d’améliorer lespropriétés AMF de leurs homologues de structure microcristalline, dits conventionnels.Les techniques de caractérisation physico-chimiques (DRX, MET, MEB) nous ont permisd’une part, de suivre le mécanisme de formation de l’intermétallique B2-NiTi en fonction dutemps de broyage et d’autre part, de déterminer les paramètres microstructuraux à savoir, lataille des cristallites, le taux de microdéformations et la densité de dislocations des élémentspurs ainsi que ceux de la phase B2-NiTi. Ces paramètres révèlent le caractère nanocristallin etdésordonné des poudres broyées.Par ailleurs, nous avons fabriqué pour la première fois une cible B2-NiTi de structurenanocristalline, par l’intermédiaire d’une méthode alternative (mécanosynthèse et procédé deprojection à froid).Nous avons montré également qu’il est possible de déposer sous forme de couche mincel’intermétallique NiTi nanostructuré. Ce film mince d’épaisseur 447 nm a été déposé parpulvérisation cathodique à magnétron à partir de la cible élaborée par projection à froid (coldspray). / The research work developed in this thesis is related to preparing a thin film of NiTi shapememory alloy used to integrate into microsystems. The goal is to improve the properties oftheir counterparts of microcrystalline structure (conventional target).Physical and chemical techniques of characterization (XRD, TEM and SEM) have allowed onthe one hand, to follow the mechanism of intermetallic NiTi formation as a function ofmilling time and on the other hand, to determine the microstructural parameters : crystallitesize, the microstrain and dislocation density of the pure elements and the B2-NiTi phase.These parameters reveal the character of the disordered nanocrystalline of the milled powders.Furthermore, we fabricated a target of B2-NiTi nanocrystalline structure by an alternativemethod (mechanical alloying and cold spray).We also showed that it is possible to deposit the nanocrystalline NiTi intermetallic thin film.This film with a thickness of about 447 nm was deposited by magnetron sputtering techniquefrom the NiTi target.

The utilization of ferromagnetic shape memory alloys (FSMAs) in small scale devices has attracted considerable attention within the last decade. However, the lack of sufficient studies on their reversible shape change mechanisms, i.e, superelasticity, magnetic field-induced martensite variant reorientation and martensitic phase transformation, at the micron and submicron length scales prevent the further development and the use of FSMAs in small scale devices. Therefore, investigating the size effects in these mechanisms has both scientific and technological relevance. Superelastic behavior of Ni54Fe19Ga27 shape memory alloy single crystalline pillars was studied under compression as a function of pillar diameter. Multiple pillars with diameters ranging between 200 nm and 10 µm were cut on a single crystalline bulk sample oriented along the [110] direction in the compression axis and with fully reversible two-stage martensitic transformation. The results revealed size dependent two-stage martensitic transformation which was suppressed for pillar sizes of 1 µm and below. We also demonstrated that the reduction in pillar diameter decreases the transformation temperature due to the difficulty of martensite nucleation in small scales. Size effects in the magnetic field-induced martensite variant reorientation were investigated in the Ni50Mn28.3Ga21.7 single crystals oriented along the [100] direction of the austenite phase. Single crystalline compression pillars were fabricated on the martensite twins between the sizes of 630 nm and 20 µm. It was found that the stress-induced and magnetic field-induced martensite variant reorientation are size dependent and became more difficult with the reduction in sample size. Surprisingly, it was still possible to magnetically activate the shape change in the micropillars which indicates the fact that magnetocrystalline anisotropy energy increases with the reduction in sample dimensions. Ni45Mn36.6Co5In13.4 pillars between the 600 nm and 10 µm diameters were investigated along the [100] direction of the austenite to study the size effects in the magnetic field-induced phase transformation (MFIPT). MFIPT was obtained down to 5 µm size in these pillars with reasonable magnetic field levels similar to their bulk counterparts.

This dissertation addresses new developments in the constitutive modeling and structural analysis pertaining to rate-independent and rate-dependent irrecoverable inelasticity in Shape Memory Alloys (SMAs). A new model for fully recoverable SMA response is derived that accounts for material behaviors not previously addressed. Rate-independent and rate-dependent irrecoverable deformations (plasticity and viscoplasticity) are then considered. The three phenomenological models are based on continuum thermodynamics where the free energy potentials, evolution equations, and hardening functions are properly chosen. The simultaneous transformation-plastic model considers rate-independent irrecoverable strain generation and uses isotropic and kinematic plastic hardening to capture the interactions between irrecoverable plastic strain and recoverable transformation strain. The combination of theory and implementation is unique in its ability to capture the simultaneous evolution of recoverable transformation strains and irrecoverable plastic strains. The simultaneous transformation-viscoplastic model considers rate-dependent irrecoverable strain generation where the theoretical framework is modfii ed such that the evolution of the viscoplastic strain components are given explicitly. The numerical integration of the constitutive equations is formulated such that objectivity is maintained for SMA structures undergoing moderate strains and large displacements. Experimentally validated analysis results are provided for the fully recoverable model, the simultaneous transformation-plastic yield model, and the transformation-viscoplastic creep model.

In an effort to mitigate damage caused by earthquakes to the built environment, civil engineers have been commissioned to research, design, and build increasingly robust and resilient structural systems. Innovative means to accomplish this task have emerged, such as integrating Shape Memory Alloys (SMAs) into structural systems. SMAs are a unique class of materials that have the ability to spontaneously recover strain of up to 8%. With proper placement in a structural system, SMAs can act as superelastic "structural fuses", absorbing large deformations, dissipating energy, and recentering the structure after a loading event. Though few applications have made it into practice, the potential for widespread use has never been better due to improvements in material behavior and reductions in cost. In this research, three different SMA-based structural applications are developed and tested. The first is a tension/compression damper that utilizes nickel-titanium (NiTi) Belleville washers. The second is a partially restrained beam-column connection utilizing NiTi bars. The third is an articulated quadrilateral bracing system utilizing NiTi wire bundles in parallel with c-shape dampers. Each system was uniquely designed to allow a structure to undergo large drift demands and dissipate energy while retaining strength and recentering ability. This exploratory work highlights the potential for SMA-based structural applications to enhance seismic structural performance and community resilience.

NiTiHf shape memory alloys have been receiving considerable attention for high temperature and high strength applications since they could have transformation temperatures above 100 °C, shape memory effect under high stress (above 500 MPa) and superelasticity at high temperatures. Moreover, their shape memory properties can be tailored by microstructural engineering. However, NiTiHf alloys have some drawbacks such as low ductility and high work hardening in stress induced martensite transformation region. In order to overcome these limitations, studies have been focused on microstructural engineering by aging, alloying and processing. Shape memory properties and microstructure of four Ni-rich NiTiHf alloys (Ni50.3Ti29.7Hf20, Ni50.7Ti29.3Hf20, Ni51.2Ti28.8Hf20, and Ni52Ti28Hf20 (at. %)) were systematically characterized in the furnace cooled condition. H-phase precipitates were formed during furnace cooling in compositions with greater than 50.3Ni and the driving force for nucleation increased with Ni content. Alloy strength increased while recoverable strain decreased with increasing Ni content due to changes in precipitate characteristics. The effects of the heat treatments on the transformation characteristics and microstructure of the Ni-rich NiTiHf shape memory alloys have been investigated. Transformation temperatures are found to be highly annealing temperature dependent. Generation of nanosize precipitates (~20 nm in size) after three hours aging at 450 °C and 550 °C improved the strength of the material, resulting in a near perfect dimensional stability under high stress levels (> 1500 MPa) with a work output of 20–30 J cm– 3. Superelastic behavior with 4% recoverable strain was demonstrated at low and high temperatures where stress could reach to a maximum value of more than 2 GPa after three hours aging at 450 and 550 °C for alloys with Ni great than 50.3 at. %. Shape memory properties of polycrystalline Ni50.3Ti29.7Hf20 alloys were studied via thermal cycling under stress and isothermal stress cycling experiments in tension. Recoverable strain of ~5% was observed for the as-extruded samples while it was decreased to ~4% after aging due to the formation of precipitates. The aged alloys demonstrated near perfect shape memory effect under high tensile stress level of 700 MPa and perfect superelasticity at high temperatures up to 230 °C. Finally, the tensioncompression asymmetry observed in NiTiHf where recoverable tensile strain was higher than compressive strain. The shape memory properties of solutionized and aged Ni-rich Ni50.3Ti29.7Hf20 single crystals were investigated along the [001], [011], and [111] orientations in compression. [001]-oriented single crystals showed high dimensional stability under stress levels as high as 1500 MPa in both the solutionized and aged conditions, but with transformation strains of less than 2%. Perfect superelasticity with recoverable strain of more than 4% was observed for solutionized and 550 °C-3h aged single crystals along the [011] and [111] orientations, and general superelastic behavior was observed over a wide temperature range. The calculated transformation strains were higher than the experimentally observed strains since the calculated strains could not capture the formation of martensite plates with (001) compound twins.

Η παρούσα διδακτορική διατριβή πραγματεύεται την κατασκευή και τον έλεγχο ενός καινοτόμου τεχνητού χεριού, για προσθετικές κυρίως εφαρμογές, κάνοντας χρήση βιομιμητικών ενεργοποιητών και πιο συγκεκριμένα ειδικά κατεργασμένων λεπτών κυλινδρικών αγωγών από μορφομνήμονα μεταλλικά κράματα νικελίου-τιτανίου. Εκμεταλλευόμενοι τα συγκριτικά πλεονεκτήματα των ενεργοποιητών αυτών έναντι των αντίστοιχων συμβατικών, αναπτύσσεται μια πλήρως λειτουργική συσκευή με μικρό μέγεθος και βάρος, ανθρωπομορφική εμφάνιση, αθόρυβη λειτουργία και χαμηλό κόστος κατασκευής και συντήρησης, ικανή να εκπληρώσει σε μεγάλο βαθμό τις απαιτήσεις των ατόμων με αναπηρία στα άνω άκρα. Για τη φυσική υλοποίηση του σκελετού του τεχνητού αυτού χεριού χρησιμοποιείται η τεχνολογία της ταχείας προτυποποίησης. Καθένα από τα πέντε δάκτυλά του ελέγχεται ανεξάρτητα μέσω ενός υπο-ενεργοποιούμενου μηχανισμού κίνησης με τεχνητούς τένοντες. Για τον έλεγχο θέσης κάθε δακτύλου, αναπτύσσεται και εφαρμόζεται μία νέα μέθοδος ελέγχου βασισμένη στην έμφυτη δυνατότητα ανάδρασης θέσης των προαναφερθέντων ενεργοποιητών μέσω μέτρησης της ηλεκτρικής τους αντίστασης. Επιπλέον, αναπτύσσεται κατάλληλος αλγόριθμος για τον σχηματισμό διαφόρων θέσεων και συλλήψεων του τεχνητού χεριού. Για τη βελτίωση του ελέγχου, το χέρι εξοπλίζεται με αισθητήρες αφής στα ακροδάκτυλα, καθώς και με τη δυνατότητα οδήγησης συσκευών οπτικής και απτικής ανάδρασης. Όλα τα ηλεκτρονικά κυκλώματα που είναι απαραίτητα για την οδήγηση των ενεργοποιητών και τον έλεγχο του χεριού αναπτύσσονται και ενσωματώνονται στο εσωτερικό του φυσικού πρωτοτύπου. Με τη βοήθεια ειδικού προγραμματιστικού πακέτου, σχεδιάζεται μία γραφική διεπαφή ελέγχου μέσω της οποίας μελετάται και αξιολογείται η δυνατότητα του αναπτυχθέντος χεριού σε πειράματα σύλληψης διαφόρων αντικειμένων. Τέλος, προτείνονται διάφορες τεχνικές ελέγχου του χεριού από τους χρήστες του, ενώ αναπτύσσεται και κατάλληλος αλγόριθμος ελέγχου βασισμένος στη χρήση ηλεκτρομυογραφικών σημάτων. / This doctoral thesis presents the development and control of an innovative artificial hand, mostly for use in prosthetic applications, utilizing biomimetic actuators, and, more specifically, specially processed thin cylindrical wires made of shape memory nickel-titanium alloys. By exploiting the comparative advantages of these actuators over the conventional ones, a fully functional device is developed, of low size and weight, anthropomorphic appearance, silent operation, low fabrication and maintenance cost, which is capable of satisfying to a great extent the needs of the upper limb amputees. The physical implementation of the chassis of this artificial hand has been performed using rapid prototyping technology. Each of its five digits is independently controlled via a tendon-driven underactuated mechanism. For the position control of each digit, a novel control scheme is devised and implemented based on the inherent position feedback capability of these actuators via the measurement of their electrical resistance. In addition, the necessary algorithm is developed for the formation of various hand postures and prehension patterns. In order to improve the overall hand control, the hand is equipped with tactile sensors at its fingertips, and is also capable of driving optical and tactile feedback devices. All the necessary electronics for driving the actuators and controlling the hand are developed and embedded inside the physical prototype. Using a special programming package, a graphical user interface is designed, through which the grasp capabilities of the developed hand are studied and evaluated for various objects. Finally, several user control techniques of the hand are proposed, and a control algorithm based on the use of electromyographic signals is also developed.

NiTi is the most commonly used shape memory alloy (SMA) and has been widely used for bio-medical, electrical and mechanical applications. Nickel rich NiTi shape memory alloys are coming into prominence due to their distinct superelasticity and shape memory properties as compared to near equi-atomic NiTi shape memory alloys. Besides, their lower density and higher work output than steels makes these alloys an excellent candidate for aerospace and automotive industry. Shape memory properties and phase transformation behavior of high Ni-rich Ni54Ti46 (at.%) polycrystals and Ni-rich Ni51Ti49 (at.%) single-crystals are determined. Their properties are sensitive to heat treatments that affect the phase transformation behavior of these alloys. Phase transformation properties and microstructure were investigated in aged Ni54Ti46 alloys with differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) to reveal the precipitation characteristics and R-phase formation. It was found that Ni54Ti46 has the ability to exhibit perfect superelasticity under high stress levels (~2 GPa) with 4% total strain after 550°C-3h aging. Stress independent R-phase transformation was found to be responsible for the change in shape memory behavior with stress. The shape memory responses of [001], [011] and [111] oriented Ni51Ti49 single-crystals alloy were reported under compression to reveal the orientation dependence of their shape memory behavior. It has been found that transformation strain, temperatures and hysteresis, Classius-Clapeyron slopes, critical stress for plastic deformation are highly orientation dependent. The effects of precipitation formation and compressive loading at selected temperatures on the two-way shape memory effect (TWSME) properties of a [111]-oriented Ni51Ti49 shape memory alloy were revealed. Additionally, aligned Ni4Ti3 precipitates were formed in a single crystal of Ni51Ti49 alloy by aging under applied compression stress along the [111] direction. Formation of a single family of Ni4Ti3 precipitates were exhibited significant TWSME without any training or deformation. When the homogenized and aged specimens were loaded in martensite, positive TWSME was observed. After loading at high temperature in austenite, the homogenized specimen did not show TWSME while the aged specimen revealed negative TWSME.

The objective of this work is to understand the structure-property relationships in a pseudoelastic composition of polycrystalline NiTiPt (Ti-42.7 at% Ni-7.5 at% Pt). Structural characterization of the alloy includes grain size determination and texture analysis while the thermo-mechanical properties are explored using tensile testing. Variation in heat treatment is used as a vehicle to modify microstructure. The results are compared to experiments on Ni-rich NiTi alloy wires (Ti-51.0 at% Ni), which are in commercial use in various biomedical applications. With regards to microstructure, both alloys exhibit a <111> fiber texture along the wire drawing axis, however the NiTiPt alloy's grain size is smaller than that of the Ni-rich NiTi wires, while the latter materials contain second phase precipitates. Given the nanometer scale grain size in NiTiPt and the dispersed, nanometer scale precipitate size in NiTi, the overall strength and ductility of the alloys are essentially identical when given appropriate heat treatments. Property differences include a much smaller stress hysteresis and smaller temperature dependence of the transformation stress for NiTiPt alloys compared to NiTi alloys. Potential benefits and implications for use in vascular stent applications are discussed.

Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2017-08-30T12:06:28Z No. of bitstreams: 1 DissMRS.pdf: 7292710 bytes, checksum: b518987951bcfa31933df3cece2f16cf (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-09-06T18:24:26Z (GMT) No. of bitstreams: 1 DissMRS.pdf: 7292710 bytes, checksum: b518987951bcfa31933df3cece2f16cf (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-09-06T18:33:14Z (GMT) No. of bitstreams: 1 DissMRS.pdf: 7292710 bytes, checksum: b518987951bcfa31933df3cece2f16cf (MD5) / Made available in DSpace on 2017-09-06T18:34:27Z (GMT). No. of bitstreams: 1 DissMRS.pdf: 7292710 bytes, checksum: b518987951bcfa31933df3cece2f16cf (MD5) Previous issue date: 2017-02-10 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Shape memory alloys (SMA) are alloys that undergo martensitic transformation due to an external solicitation (temperature, stress, strain or magnetic field) and are capable of recovering permanent deformation when heated above a critical temperature. The most used shape memory alloys are Ti-Ni- and Cu-based. Cu-based SMA have some advantages due to better thermal and electrical conductivity, lower production cost and are easier to process. The main disadvantage of Cu-based SMA is its low ductility. This property is improved by decreasing the grain size and by a reduction of microstructural heterogeneities. This can be achieved at the surface of structural components after LASER remelting, through which the surface of the material is remelted by a LASER beam and solidifies under extremely high cooling rates. In this context, the aim of the present work is to investigate the influence of LASER surface remelting in the microstructure, thermal stability and mechanical properties of Cu-11.8Al-3.2Ni-3Mn (wt. %) SMA plates obtained by suction casting. The samples were characterized by optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, electron backscatter diffraction, X-ray computed tomography, X-ray diffraction, differential scanning calorimetry as well as by tensile and microhardness tests. The results show that small shifts in the transformation temperatures occur due to the LASER treatment. It was observed that only the monoclinic β’1 martensitic phase formed in the as cast and LASER treated samples. The LASER treatment provided an improvement in mechanical properties with an increase of up to 162 MPa in fracture stress, up to 2.2% in fracture strain and up to 21 HV in microhardness when compared with the as-cast sample. This makes the surface remelting treatment a promising method for improving the mechanical properties of Cu-based SMA. / Ligas com memória de forma (LMF) sofrem transformação martensítica devido a uma solicitação externa (temperatura, tensão, deformação ou campo magnético) e são capazes de recuperar deformações permanentes quando aquecidas acima de uma temperatura crítica. Dentre as LMF mais utilizadas se destacam aquelas à base de Ti e Ni e aquelas à base de Cu. As à base de Cu apresentam vantagens devido a melhor condutividade térmica e elétrica, menor custo de produção e maior facilidade de processamento. A principal desvantagem das LMF à base de cobre é a baixa ductilidade. Uma forma de melhorar essa propriedade é promovendo uma diminuição no tamanho de grão e uma redução das heterogeneidades microestruturais. Isso pode ser obtido no tratamento de refusão superficial a LASER, no qual a superfície do material é refundida por um feixe de LASER e solidificada sob altas taxas de resfriamento. Nesse contexto, o objetivo da presente dissertação de mestrado é analisar a influência do tratamento de refusão superficial a LASER na microestrutura, na estabilidade térmica e nas propriedades mecânicas de placas da LMF Cu-11,8Al-3,2Ni-3Mn (% peso) obtidas através de fundição por sucção. As amostras foram caracterizadas por microscopia óptica e eletrônica de varredura, espectometria de energia dispersiva de raios X, difração de elétrons retroespalhados, tomografia computacional por raios X, calorimetria diferencial de varredura, difração de raios X, ensaio de tração e microdureza. A análise dos resultados mostrou que as temperaturas de transformação sofreram pequenas variações e nenhuma nova fase foi observada após o tratamento de refusão a LASER, sendo observada apenas a presença da fase monoclínica martensítica β’1. O tratamento propiciou uma melhoria nas propriedades mecânicas das placas obtidas por fundição por sucção, com um aumento em até 162 MPa na tensão de fratura, em até 2,2 % na deformação de fratua e em até 21 HV na microdureza, fazendo deste tratamento um método promissor para melhorar as propriedades mecânicas das LMF à base de Cu. / CNPq: 132132/2015-0 / FAPESP: 2015/04134-7

Orientador: Gustavo Luiz Chagas Manhães de Abreu / Resumo: Diversos estudos relacionados à atenuação de vibrações utilizando materiais inteligentes vem sendo amplamente explorados no meio acadêmico. Neste âmbito, as Ligas de Memória de Forma (LMF) se destacam por apresentarem dissipação de energia vibratória devido ao seu comportamento histerético promovido pelo efeito pseudoelástico. No presente trabalho, dois sistemas com um e dois graus de liberdade, contendo mola helicoidal de LMF como elemento resiliente, são implementados numericamente para demonstrar a atenuação de vibrações ocasionada pelas transformações de fase presentes no material. Para cada um dos sistemas mecânicos investigados, dois modelos termomecânicos são confrontados numericamente visando a obtenção das características de cada modelo em representar a atenuação de vibrações dos sistemas submetidos à carregamentos termo-mecânicos. O trabalho termina comentando as potencialidades da proposta apresentada, discutindo as facilidades e dificuldades encontradas na sua implementação e apontando para o desenvolvimento de futuros estudos. / Mestre