Near equi-atomic nickel titanium (NiTi) shape memory alloys (SMAs) are a class of materials characterized by their unique deformation behavior. In these alloys, deformation mechanisms such as mechanical twinning and stress induced phase transformation between a high symmetry phase (austenite) and a low symmetry phase (martensite) additionally occur and influence mechanical behavior and thus their functionality. Consequently, applications of SMAs usually call for precise phase transformation temperatures, which depend on the thermomechanical history and the composition of the alloy. Instrumented indentation, inherently a mechanical characterization technique for small sampling volumes, offers a cost effective means of empirically testing SMAs in the form of centimeter scaled buttons prior to large-scale production. Additionally, it is an effective probe for intricate SMA geometries (e.g., in medical stents, valves etc.), not immediately amenable to conventional mechanical testing. The objective of this work was to study the deformation behavior of NiTi SMAs using instrumented indentation. This involved devising compliance calibration techniques to account for instrument deformation and designing spherical diamond indenters. Substantial quantitative information related to the deformation behavior of the shape memory and superelastic NiTi was obtained for the first time, as opposed to existing qualitative indentation studies. For the case of shape memory NiTi, the elastic modulus of the B19' martensite prior to twinning was determined using spherical indentation to be about 101 GPa, which was comparable to the value from neutron diffraction and was substantially higher than typical values reported from extensometry (68 GPa in this case). Twinning at low stresses was observed from neutron diffraction measurements and was attributed to reducing the elastic modulus estimated by extensometry. The onset of predominantly elastic deformation of the twinned martensite was identified from the nanoindentation response and the elastic modulus of the twinned martensite was estimated to be about 17 GPa. Finite element modeling was used to validate the measurements. For the case of the superelastic NiTi, the elastic modulus of the parent austenite was estimated to be about 62 GPa. The onset of large-scale stress induced martensite transformation and its subsequent elastic deformation were identified from the nanoindentation response. The effect of cycling on the mechanical behavior of the NiTi specimen was studied by repeatedly indenting at the same location. An increase in the elastic modulus value for the austenite and a decrease in the associated hysteresis and residual depth after the initial few cycles followed by stabilization were observed. As for the case of shape memory NiTi, finite element modeling was used to validate the measurements. This work has initiated a methodology for the quantitative evaluation of shape memory and superelastic NiTi alloys with instrumented spherical indentation. The aforementioned results have immediate implications for optimizing thermomechanical processing parameters in prototype button melts and for the mechanical characterization of intricate SMA geometries (e.g., in medical stents, valves etc.) This work was made possible by grants from NASA (NAG3-2751) and NSF (CAREER DMR-0239512) to UCF.

This thesis describes experimental investigation of thermal and combustion phenomena as well as structure for self- propagating combustion synthesis of porous Ni - Ti intermetallic aimed for structural biomedical application. The control parameters for the porosity distribution have been investigated experimentally through varying the preheat temperature, initial porosity, initial elemental particle size, and applied pressure during the fabrication process. Ni and Ti elemental powders are mixed using a 1:1 ratio. The mixture is compressed using several different compression forces to produce cylindrical samples of 1.1 cm diameter and 2-3cm length, with initial porosity ranging from 30% to 40%. The samples are preheated to various initial temperatures and ignited from the top surface such that the flame propagates axially downwards. The combustion reaction is recorded with a motion camera. An infrared sensor is used to record the temperature profile during the combustion process. The samples are then cut using a diamond saw in both longitudinal and transverse directions. Image analysis software is then used to analyze the porosity distribution in each sample.

No description available.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-26T19:19:12Z No. of bitstreams: 1 HENRIQUE MARTINNI RAMOS DE OLIVEIRA - DISSERTAÇÃO PPGEM 2014..pdf: 5119070 bytes, checksum: 23504b03a49c79c4f4d5a4f8815ee9ac (MD5) / Made available in DSpace on 2018-04-26T19:19:12Z (GMT). No. of bitstreams: 1 HENRIQUE MARTINNI RAMOS DE OLIVEIRA - DISSERTAÇÃO PPGEM 2014..pdf: 5119070 bytes, checksum: 23504b03a49c79c4f4d5a4f8815ee9ac (MD5) Previous issue date: 2014-08-01 / CNPq / Capes / As Ligas com Memória de Forma (LMF) devem seu comportamento único a uma transformação de fase reversível entre duas estruturas cristalinas: martensita (baixa temperatura e menor rigidez) e austenita (alta temperatura e maior rigidez). Essa transformação pode ocorrer em consequência de dois estímulos diferentes: uma mudança de temperatura ou aplicação de tensão mecânica, ambos acima de valores críticos característicos desses materiais. Do segundo caso resulta o fenômeno da superelasticidade, que é a capacidade de recuperar totalmente a deformação após o carregamento e descarregamento mecânico na fase de mais alta temperatura (austenita). No decorrer dessa deformação ocorre a transformação de fase induzida por tensão da austenita para a martensita. Esta transformação é exotérmica e tende a se estabilizar após certo número de ciclos de deformação. Estudos sobre as propriedades dinâmicas das LMF mostram que o comportamento superelástico é dependente da taxa de deformação, ou em outras palavras, da frequência de excitação. Este comportamento resulta da combinação complexa entre tensão mecânica, temperatura e taxa de dissipação do calor latente gerado no material. Observou-se também que altas frequências diminuem a capacidade de dissipação de calor latente, resultando no aumento de temperatura do material e valores de tensão de transformação de fase maiores. Considerações como estas são importantes para a modelagem do comportamento dinâmico do material, aplicável, por exemplo, em sistemas de absorção de vibração de construções civis. Nesse contexto, o objetivo deste trabalho é estudar experimentalmente a influência da frequência sobre o comportamento dinâmico superelástico de fios de LMF Ni-Ti pré-estabilizados, assim como os efeitos da geração de calor sobre as propriedades mecânicas avaliadas. Os testes realizados corresponderam a ensaios dinâmicos de tração uniaxial em fios superelásticos de LMF Ni-Ti com variação de freqüência e simultâneo acompanhamento de temperatura do material, usando uma máquina de ensaios da marca MTS modelo MTS 793 series. / Shape Memory Alloys (SMA) owe their behavior unique to a reversible phase transformation between two crystalline structures: martensite (low temperature and stiffness) and austenite (high temperature and stiffness). This phase change can occur as a result of two distinct stimuli: a change in temperature or an applied mechanical stress, both over certain critical values, characteristic of this materials. From the latter it results the phenomenon of the superelasticity, which is the ability to totally recover a deformation after simply ceasing the load. During this deformation occurs a stressinduced martensitic transformation from austenite to martensite, being it an exothermal process and that tends to stabilize after a certain number of cycles. Investigation concerning dynamic properties of SMA demonstrate that its superelastic behavior depends on the strain rate, or in other words, on the excitation frequency. This behavior results from the complex combination of mechanical stress, temperature and rate of latent heat dissipation generated in the material. It was also observed that high frequencies diminish the capacity of dissipation of latent heat, resulting in an increase in the material temperature and, therefore, in higher values of phase transformation stresses. This kind of consideration is fundamental in dynamic behavior modeling, applicable for instance, in vibration absorption systems in civil building. In this context, the objective of this work is experimentally study the influence of the frequency on superelastic behavior of pre-stabilized Ni-Ti SMA superelastic wires, as well as the effects of heat generation on the evaluated mechanical properties. Dynamical tests were performed in a uniaxial tensile mode in Ni-Ti SMA superelastic wires varying the frequency and simultaneously monitoring sample’s temperature, using a test machine from MTS, model MTS 793 series.

Dans cette étude, nous avons élaboréun revêtementde TiO₂ par sol-gel sur des alliages super-élastiques de NiTi. L’idée générale était de développer couche mince de TiO₂ protectrice et flexible. Le film mince est formé en immergeant les échantillons de NiTi, préalablement chimiquement gravés, dans une solution réactive à 7,5 mm/s, puis en effectuant plusieurs traitements thermiques :un premier traitement thermique à 100 °C pendant 45 minutes dans une atmosphère humide, un deuxième traitement à 110 °C pendant 2 heures dans une atmosphère sèche et enfin un dernier traitement à 500 °C pendant 10 minutes. Les couches minces de TiO₂ ont été caractérisé par de la flexion trois points, par MEB, par MET, par AFM, par GIXRD, par XPS et par de la cartographie Raman. Les résultats de l’étude ont montré un film nanocomposite, avec ~100nmde TiO2 amorphe formé à l’interface externe de la couche et d'un mélange de grains cristallisés de ~10 nm, d'anatase et de rutile à l'interface interne métal/oxyde.Cette hétéro-structure est capable de soutenir 6,4% de déformation sans l’apparition de défauts plastiques majeurs (cloques, fissures...). Une faible concentration de Ni a été observé au niveau de la surface externe des couches minces de TiO₂, ce qui se traduit par une augmentation de la biocompatibilité du matériau. La technique sol-gel a été utilisée pour revêtir des instruments endodontiques de RaCe. Ce deuxième système a été testé à la fois en fatigue pour estimer sa durée de vie, et à la résistance à la corrosion en NaClO, et à des températures correspondant aux transformations de phase. Les résultats ont montré une augmentation statistiquement significative de la durabilité en fatigue, en particulier après les essais de corrosion. L'efficacité de la « coupe », mesurée par une procédure originale, a été similaire aux instruments revêtus et non revêtus. Le traitement thermique n'a pas été suffisant efficient pour modifier de façon significative les températures de transformation de phase : le comportement mécanique d'origine de l'instrument a été maintenu. / In this work, a dip-coating sol-gel deposition route was developed to coat superelastic NiTi alloy with a flexible TiO₂ protective layer. The film was formed by emerging the samples at 7.5 mm/s and thermally treating at 100ºC in a humid atmosphere for 45 min, 110ºC in a dry atmosphere for 2 hours and at 500ºC for 10 minutes.The film was first deposited over chemically etched substrates and characterized by SEM, TEM, AFM, GIXRD, XPS, Raman cartographyand three-point bending tests. Results showed that a ~100 nm nanocomposite film constituted of amorphous TiO₂ on the upper half and a mixture of ~10 nm anatase and rutile grains on the oxide/metal interfacewas formed. This film was capable of sustaining up to 6.4% strain without cracking or peeling. A high decrease in the concentration of Ni at the surface was measured, indicating an that an increase in the biocompatibilityof the material was achieved. This route was used to coat RaCe endodontic instruments, which were tested regarding fatigue life, cutting efficiency and corrosion resistance in NaClO. Results showed a statistically significant improvement in fatigue life for the coated instruments, mainly after corrosion tests. Cutting efficiency measured by an original developed technique was similar for coated and uncoated samples. / Neste trabalho foi desenvolvida uma rota de deposição sol-gel por imersão para revestirligas de NiTi superelásticas com uma camada protetora e flexível de TiO2. O filmeformado pela emersão de amostras a 7,5 mm/s seguida de tratamentos térmicos a 100ºCpor 45 minutos em atmosfera úmida, 110ºC por 2 horas em atmosfera seca e 500ºC por10 minutos. O filme foi depositado sobre substratos decapados quimicamente ecaracterizados por MEV, MET, AFM, GIXRD, XPS, cartografia Raman e dobramentode três pontos. Resultados mostraram que um filme nanocompósito com ~100 nmconstituído de TiO2 amorfo na metade superior e uma mistura de grãos de 10 a 50 nmde anatase e rutila na interface metal/óxido foi formado. Este filme é capaz de sustentar6,4% de deformação sem trincar ou descamar. Uma grande redução na concentração deNi na superfície foi detectada, indicando um aumento na biocompatibilidade domaterial. A rota foi usada para revestir instrumentos endodônticos de NiTi modeloRaCe 25/0.06 que foram testados em relação à vida em fadiga, eficiência de corte,resistência à corrosão em NaClO. Detectou-se um aumento estatisticamentesignificativo na vida em fadiga, especialmente após os ensaios de corrosão. A eficiênciade corte, medida por um procedimento original desenvolvido, foi similar parainstrumentos revestidos e não revestidos. O tratamento térmico não foi suficiente paraalterar significativamente as temperaturas de transformação de fases, mantendo ocomportamento mecânico original do instrumento.

Mimicking nature gives rise to many important facets of biomaterials. This study is inspired by nature and reports on the fabrication of an intercalated polymer-NiTi nanocomposite that mimics the structural order of urethral tissue performing micturition. PTFE is chosen due to its hydrophobicity, low surface energy, and thermal and chemical stability. NiTi has been selected as a prime candidate for this research due to its excellent mechanical stability, corrosion resistance, energy absorbance, shape memory and biocompatibility. Nanoscale engineering of intercalated nanocomposites is done by PVD sputtering PTFE and NiTi. FTIR spectroscopy confirms that PTFE reforms as polymer chains after sputtering. Suitable PVD sputtering parameters were selected by investigating their influence on deposition rates, microstructure and properties of PTFE and NiTi thin films. PTFE forms stable nanocomposite coatings with NiTi and displays favourable surface interactions, known as ‘intercalation’. Intercalated PTFE-NiTi films were fabricated as layered and co-sputtered thin films. Co-sputtered nanocomposites contained nearly one-third vacant sites within its internal microstructure because of intercalation while intercalation introduced minute pits in fibrous NiTi columns of layered nanocomposites. These pits allow PTFE to extend their chains and crosslinks, resulting in microstructural and functional changes in the thin films. Intercalated PTFE-NiTi nanocomposites offer a close match to the natural tissue in terms of responding to the fluid contact (wetting angle modifications), and allow the soft and hard matter to incorporate in one framework without any chemical reactions (intercalation). An intercalated microstructure in co-sputtered and layered nanocomposites was verified by EDS-SEM and EDS-TEM techniques. The functional responses were witnessed by changes in water contact angle (WCA) and coefficient of friction (CoF) values measured on the film surface. The WCA (99°) and CoF (0.1 – 0.2) of the intercalated nanocomposite (sample PNT12) were different to the NiTi (top layer). WCA and CoF indicate the internal microstructural interactions because of intercalation. Although the pseudoelastic behaviour of NiTi can provide additional fluid response but the difficulty is an absence of crystallinity in as-deposited NiTi, and the heat treatment that melts PTFE. However, DSC and XRD techniques were employed to find the optimum NiTi composition and transition temperatures for phase transformation related to pseudoelasticity. This study provides the basis to incorporate the shape memory (pseudoelasticity or thermal shape memory effect (shape memory effect)) features of NiTi into the intercalated nanocomposite in future. The intercalated PTFE-NiTi nanocomposite reveals a fascinating research precinct, having the response generating characteristics similar to that of natural tissue.

Les travaux présentés ont consisté à développer des stratégies d'identification performantes des paramètres des lois de comportement superélastique des Alliages à Mémoire de Forme (AMF). L'objectif est de disposer d'une solution complète de caractérisation, d'identification, et de simulation de structures en AMF soumises à des sollicitations complexes. Une base de données expérimentale unifiée pour un alliage de NiTi superélastique a été établie pour une multitude de trajets de déformation multiaxiaux et à différentes températures : en traction homogène, en compression, en traction-compression et en traction-traction. Une caractérisation expérimentale a été développée sur une plate-forme multiaxiale assemblée au laboratoire durant ce travail. L'emploi de la corrélation d'images a permis d'enrichir la base de données expérimentale en déterminant pour chaque essai les champs cinématiques. Cette collection d'essais a permis de montrer l'importante différence de comportement observée entre les directions de laminage et transverse, bien que le matériau soit faiblement texturé. Des procédures d'identification du comportement thermomécanique des AMF ont été mises en place, basées sur la construction et minimisation d'une fonction objectif régularisée. La première est basée sur l'exploitation des courbes contrainte-déformation moyennes sous chargement homogène et unixial. La seconde exploite la richesse des champs de déformations mesurés en essai hétérogène. Les deux stratégies ont permis d'identifier les huit paramètres gouvernant le comportement superélastique du modèle de Chemisky et al. (Chemisky et al. 2011). Des différences entre les jeux de paramètres identifiés sont caractéristiques des effets d'anisotropie observés. Le succès de cette stratégie démontre sa pertinence et est encourageant pour l'identification de paramètres de lois de comportement anisotropes. / In this work, efficient identification strategies were developed to determine the characteristic parameters of the thermomechanical behavior of pseudoelastic Shape Memory Alloys (SMA). The aim is to obtain a complete solution for characterization, identification and numerical simulation of SMA structures undergoing multiaxial loading paths. A unified experimental database has been constructed to characterize the behavior of superelastic NiTi SMAs. This database includes tension, compression, tension-tension and tension-compression multiaxial tests at different temperatures. A characterization methodology has been developed on a multiaxial testing setup, which has been assembled in the laboratory during this Ph.D. project. Vital information about the strain fields for each test is added to the experimental database through the use of Digital Image Correlation. A significant difference in the thermomechanical behavior between the rolling and transverse directions has been observed, even when the specimens are not strongly textured. Two strategies were developed that rely on the minimization of a regularized cost function for identification of thermomechanical constitutive law parameters. The first identification procedure is based on uniaxial homogeneous tests at different temperatures. In the other strategy the information of strain fields of heterogeneous tests are utilized. In each case, the eight material parameters of the constitutive law of Chemisky et al. (Chemisky et al. 2011) have been identified. A difference between the identified parameters in the rolling and transverse direction is noted and corresponds to the effect of anisotropy. Nevertheless, the capabilities of the relevant identification strategies shall allow the determination of the parameters of anisotropic constitutive laws.

No description available.

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.

De nombreux gestes médicaux utilisent des aiguilles. Il est proposé une solution de principe pour contrôler la trajectoire d’une aiguille lors son insertion. Ce contrôle de trajectoire permet d’éviter des obstacles et atteindre une cible avec plus de précision. La solution de principe proposée repose sur l’utilisation des alliages à mémoires de forme de type Nickel-Titane (NiTi) et des traitements thermiques localisés. Une méthode expérimentale originale pour caractériser les alliages NiTi est développée. Cette méthode repose sur l’utilisation d’un dispositif expérimental permettant de faire des mesures et analyses mécaniques dynamiques (DMA) lors d’un essai de traction ou au cours d’un balayage en température sous contrainte. Ces mesures DMA ont permis de détecter les nombreux phénomènes présents dans ces alliages : élasticité, transformation de phase, réorientation,localisation, plasticité. Les résultats des mesures effectuées sur un fil commercial de NiTi sont présentés et analysés. L’analyse de l’évolution du module de conservation a permis de mettre en évidence les différentes séquences de transformation et de définir les domaines d’existence des phases en fonction de la contrainte et de la température. Des valeurs de modules d’élasticité de l’austénite, de la martensite et de la phase R sont proposées. Enfin,des modèles d’évolution du module de conservation lors d’un essai de traction et d’un balayage en température sous contrainte sont proposés. Une dernière partie concerne l’étude des effets des traitements thermiques sur un fil NiTi étiré à froid. Une gamme de traitements thermiques a été réalisée sur un fil NiTi. Les propriétés thermomécaniques ont été investiguées à la fois par des essais de traction isothermes et des mesures DMA en balayage en température sous contrainte. / Many medical procedures use needles. A solution is proposed to control and modifyneedle trajectory during its insertion. This steerable needle must be able to avoid anobstacle and reach the target with more accuracy. The solution uses Nickel Titanium(NiTi) shape memory alloy. A new experimental method is proposed to characterize NiTiwires. This method is based on experimental device wich allows to perform DynamicMechanical Analysis (DMA) during a tensile test or during a temperature sweep understress. DMA measurements can detect many phenomena : elasticity, phase transformation,reorientation, plasticity. Results for a commercial NiTi wire are presented and analyzed.Storage modulus evolution analysis shows multistage phase transformations for which thestress-temperature diagram has been established. Values of elastic modulus are determinedfor austenite, martensite and R phase. Estimation models are proposed to determinestorage modulus evolution during tensile test with DMA and temperature sweep understress with DMA. The last part of this work studies the effect of heat treatment on acold worked Niti wire. A range of heat treatments was performed. Thermomechanicaltreatment effects were investigated both with tensile tests and temperature sweeps understress with DMA.