This research deals with the synthesis and characterization (transmission electron microscopy and optical spectroscopy) of composite nanocondensates produced by pulse laser ablation (PLA) on Zn, Zn-Cu and Cu-Au targets in liquid or vacuum. First, wurtzite-type (W)-ZnO and

The purpose of this work is to reveal the governing mechanisms responsible for the magnetic field-induced i) martensite reorientation in Ni2MnGa single crystals, ii) stress-assisted phase transformation in Ni2MnGa single crystals and iii) phase transformation in NiMnCoIn alloys. The ultimate goal of utilizing these mechanisms is to increase the actuation stress levels in magnetic shape memory alloys (MSMAs). Extensive experimental work on magneto-thermo-mechanical (MTM) characterization of these materials enabled us to i) better understand the ways to increase the actuation stress and strain and decrease the required magnetic field for actuation in MSMAs, ii) determine the effects of main MTM parameters on reversible magnetic field induced phase transformation, such as magnetocrystalline anisotropy energy (MAE), Zeeman energy (ZE), stress hysteresis, thermal hysteresis, critical stress for the stress induced phase transformation and crystal orientation, iii) find out the feasibility of employing polycrystal MSMAs, and iv) formulate a thermodynamical framework to capture the energetics of magnetic field-induced phase transformations in MSMAs. Magnetic shape memory properties of Ni2MnGa single crystals were characterized by monitoring magnetic field-induced strain (MFIS) as a function of compressive stress and stress-induced strain as a function of magnetic field. It is revealed that the selection of the operating temperature with respect to martensite start and Curie temperatures is critical in optimizing actuator performance. The actuation stress of 5 MPa and work output of 157 kJm−3 are obtained by the field-induced variant reorientation in NiMnGa alloys. Reversible and one-way stress-assisted field-induced phase transformations are observed in Ni2MnGa single crystals under low field magnitudes (<0.7T) and resulted in at least an order of magnitude higher actuation stress levels. It is very promising to provide higher work output levels and operating temperatures than variant reorientation mechanisms in NiMnGa alloys. Reversible field-induced phase transformation and shape memory characteristics of NiMnCoIn single crystals are also studied. Reversible field-induced phase transformation is observed only under high magnetic fields (>4T). Necessary magnetic and mechanical conditions, and materials design and selection guidelines are proposed to search for field-induced phase transformation in other ferromagnetic materials that undergo thermoelastic martensitic phase transformation.

Previous experimental observations have shown that the pseudoelastic response of NiTi shape memory alloys (SMA) is localized in nature and proceeds through nucleation and propagation of localized deformation bands. It has also been observed that the mechanical response of SMAs is strongly affected by loading rate and cyclic degradation. These behaviors significantly limit the accurate modeling of SMA elements used in various devices and applications. The aim of this work is to provide engineers with a constitutive model that can accurately describe the dynamic, unstable pseudoelastic response of SMAs, including their cyclic response, and facilitate the reliable design of SMA elements. A 1-D phenomenological model is developed to simulate the localized phase transformations in NiTi wires during both loading and unloading. In this model, it is assumed that the untransformed particles located close to the transformed regions are less stable than those further away from the transformed regions. By consideration of the thermomechanical coupling among the stress, temperature, and latent heat of transformation, the analysis can account for strain-rate effects. Inspired by the deformation theory of plasticity, the 1-D model is extended to a 3-D macromechanical model of localized unstable pseudoelasticity. An important feature of this model is the reorientation of the transformation strain tensor with changes in stress tensor. Unlike previous modeling efforts, the present model can also capture the propagation of localized deformation during unloading. The constitutive model is implemented within a 2-D finite element framework to allow numerical investigation of the effect of strain rate and boundary conditions on the overall mechanical response and evolution of localized transformation bands in NiTi strips. The model successfully captures the features of the transformation front morphology, and pseudoelastic response of NiTi strip samples observed in previous experiments. The 1-D and 3-D constitutive models are further extended to include the plastic deformation and degradation of material properties as a result of cyclic loading.

Shape memory alloys (SMAs) are widely used in a broad variety of applications in multiscale devices ranging from nano-actuators used in nano-electrical-mechanical systems (NEMS) to large energy absorbing elements in civil engineering applications. This research introduces a multiscale analysis for SMAs, particularly Nickel-Titanium alloys (NiTi). SMAs are studied in a variety of length scales ranging from macroscale to nanoscale. In macroscale, a phenomenological constitutive framework is adopted and developed by adding the effect of phase transformation latent heat. Analytical closed-form solutions are obtained for modeling the coupled thermomechanical behavior of various large polycrystalline SMA devices subjected to different loadings, including uniaxial loads, torsion, and bending. Thermomechanical responses of several SMA devices are analyzed using the introduced solutions and the results are validated by performing various experiments on some large SMA elements. In order to study some important properties of polycrystalline SMAs that the macroscopic phenomenological frameworks cannot capture, including the texture and intergranular effects in polycrystalline SMAs, a micromechanical framework with a realistic modeling of the grains based on Voronoi tessellations is used. The local form of the first law of thermodynamics is used and the energy balance relations for the polycrystalline SMAs are obtained. Generalized coupled thermomechanical governing equations considering the phase transformation latent heat are derived for polycrystalline SMAs. A three-dimensional finite element framework is used and different polycrystalline samples are modeled. By considering appropriate distributions of crystallographic orientations in the grains obtained from experimental texture measurements of NiTi samples the effects of texture and the tension-compression asymmetry on the thermomechanical response of polycrystalline SMAs are studied. The interaction between the stress state (tensile or compressive), number of grains, and the texture on the thermomechanical response of polycrystalline SMAs is also studied. For studying some aspects of the thermomechanical properties of SMAs that cannot be studied neither by the phenomenological constitutive models nor by the micromechanical models, molecular dynamics simulations are used to explore the martensitic phase transformation in NiTi alloys at the atomistic level. The martensite reorientation, austenite to martensite phase transformation, and twinning mechanisms in NiTi nanostructures are analyzed and the effect of various parameters including the temperature and size on the phase transformation at the atomistic level is studied. Results of this research provide insight into studying pseudoelasticity and shape memory response of NiTi alloys at different length scales and are useful for better understanding the solid-to-solid phase transformation at the atomistic level, and the effects of this transformation on the microstructure of polycrystal SMAs and the macroscopic response of these alloys.

Over the last few decades, Shape Memory Alloys (SMAs) have been increasingly explored in order to take advantage of their unique properties (i.e., pseudoelasticity and shape memory effect), in various actuation, sensing and absorption applications. In order to achieve an effective design of SMA-based devices a thorough investigation of their behavior in the presence of cracks is needed. In particular, it is important to understand the effect of phase transformation on their fracture response. The aim of the present work is to study the effect of stress-induced as well as thermo-mechanically-induced phase transformation on several characteristics of the fracture response of SMAs. The SMA thermomechanical response is modeled through an existing constitutive phenomenological model, developed within the framework of continuum thermodynamics, which has been implemented in a finite element frame-work. The effect of stress-induced phase transformation on the mechanical fields in the vicinity of a stationary crack and on the toughness enhancement associated with crack advance in an SMA subjected to in-plane mode I loading conditions is examined. The small scale transformation assumption is employed in the analysis according to which the size of the region occupied by the transformed material forming close to the crack tip is small compared to any characteristic length of the problem (i.e. the size of the transformation zone is thirty times smaller than the size of the cracked ligament). Given this assumption, displacement boundary conditions, corresponding to the Irwin’s solution for linear elastic fracture mechanics, are applied on a circular region in the austenitic phase that encloses the stress-induced phase transformation zone. The quasi-static stable crack growth is studied by assuming that the crackpropagates at a certain critical level of the crack-tip energy release rate. The Virtual Crack Closure Technique (VCCT) is employed to calculate the energy release rate. Fracture toughness enhancement associated with transformation dissipation is observed and its sensitivity on the variation of key characteristic non-dimensional parameters related to the constitutive response is investigated. Moreover, the effect of the dissipation due plastic deformation on the fracture resistance is analyzed by using a Cohesive Zone Model (CZM). The effect of thermo-mechanically-induced transformation on the driving force for crack growth is analyzed in an infinite center-cracked SMA plate subjected to thermal actuation under isobaric mode I loading. The crack-tip energy release rate is identified as the driving force for crack growth and is measured over the entire thermal cycle by means of the VCCT. A substantial increase of the crack-tip energy release rate – an order of magnitude for some material systems – is observed during actuation as a result of phase transformation, i.e., martensitic transformation occurring during actuation causes anti-shielding that might cause the energy release rate to reach the critical value for crack growth. A strong dependence of the crack-tip energy release rate on the variation of the thermomechanical parameters characterizing the material response is examined. Therefore, it is implied that the actual shape of the strain- temperature curve is important for the quantitative determination of the change of the crack-tip energy release rate during actuation.

The press hardening belongs to state-of-the-art technology at sheet metal forming to gain high strength and crash resistant parts in automotive industry. This process could establish due to its cost- and esourceefficiency. According to ongoing developments on direct press hardening processes it is necessary to describe and understand the thermo-mechanical treatment of 22MnB5. Therefore the flow behavior and phase transformation during cooling with simultaneous forming is investigated. The experimental process considers industrial parameters in order to get industry-oriented results. In deep drawing processes the sheet metal is roped into the draw die and bended around the die edge. Thereby sheets perform different stages of compressive and tensile strain at the die oriented side and the punch oriented side of the sheet. There are different stages and values of stress and strain according to several layers of the sheet over its cross-section. The values of stress, strain and forming rate were FEcalculated for industry-relevant bending radii and sheet thicknesses of manganese-boron steel 22MnB5. According to the calculations different cooling and forming strategies were performed by dilatometric tests. The forming behavior is described by the microstructural development with regard to the cooling rate and temperature. Beside the influence of austenite forming on the phase transformation and mechanical properties is considered. A prospective view is given to illustrate ongoing examinations under compressive and combined tensional and compressive forces.

The exciting thermomechanical properties of nickel-titanium shape memory alloys have sparked significant research efforts seeking to exploit their exotic capabilities. Until recently, the performance capabilities of nickel-titanium devices have been inhibited by the retention of only one thermomechanical characteristic. However, laser processing technology promises to deliver enhanced material offerings which are capable of multiple functional responses. Presented in this thesis, is an investigation of the effects of laser processing on the thermomechanical behaviour of nickel-titanium shape memory alloys. In the context of this work, laser processing refers to removal of alloy constituents, as in the case of laser ablation, or alternatively, addition of elements through laser alloying. The effects of laser ablation on the composition, crystallography and phase transformation temperatures of a nickel-titanium strip have been studied. Application of laser energy was shown to ablate nickel constituents, induce an austenite-martensite phase change and cause an increase in phase transformation onset temperatures, which correlated well with reported findings. Laser processing of a nickel-titanium wire was shown to locally embed an additional thermomechanical response which manifested as unique shape memory and pseudoelastic properties. Localized alloying of ternary species via laser processing of nickel-titanium strip was investigated. Synthesis of a ternary shape memory intermetallic within the laser processing region was achieved through melting of copper foils. Results from thermoanalytical testing indicated that the ternary compound possessed a higher phase transformation temperature and reduced transformation hysteresis in comparison to the reference alloy. Indentation testing was used to demonstrate the augmented thermomechanical characteristics of the laser processed shape memory alloy. In order to demonstrate the enhanced functionality of laser processed nickel-titanium shape memory alloys, a self-positioning nickel-titanium microgripper was fabricated. The microgripper was designed to actuate through four different positions, corresponding to activation of three embedded shape memory characteristics. Thermoanalytical and tensile testing instrumentations were used to characterize the thermomechanical performance of the laser processed nickel-titanium microgripper. Results indicated that each of the laser processed microgripper components possessed unique mechanical and shape memory recovery properties.

Previous experimental observations have shown that the pseudoelastic response of NiTi shape memory alloys (SMA) is localized in nature and proceeds through nucleation and propagation of localized deformation bands. It has also been observed that the mechanical response of SMAs is strongly affected by loading rate and cyclic degradation. These behaviors significantly limit the accurate modeling of SMA elements used in various devices and applications. The aim of this work is to provide engineers with a constitutive model that can accurately describe the dynamic, unstable pseudoelastic response of SMAs, including their cyclic response, and facilitate the reliable design of SMA elements. A 1-D phenomenological model is developed to simulate the localized phase transformations in NiTi wires during both loading and unloading. In this model, it is assumed that the untransformed particles located close to the transformed regions are less stable than those further away from the transformed regions. By consideration of the thermomechanical coupling among the stress, temperature, and latent heat of transformation, the analysis can account for strain-rate effects. Inspired by the deformation theory of plasticity, the 1-D model is extended to a 3-D macromechanical model of localized unstable pseudoelasticity. An important feature of this model is the reorientation of the transformation strain tensor with changes in stress tensor. Unlike previous modeling efforts, the present model can also capture the propagation of localized deformation during unloading. The constitutive model is implemented within a 2-D finite element framework to allow numerical investigation of the effect of strain rate and boundary conditions on the overall mechanical response and evolution of localized transformation bands in NiTi strips. The model successfully captures the features of the transformation front morphology, and pseudoelastic response of NiTi strip samples observed in previous experiments. The 1-D and 3-D constitutive models are further extended to include the plastic deformation and degradation of material properties as a result of cyclic loading.

Les aciers Dual-Phase sont largement utilisés dans le secteur de l’automobile enraison de leurs propriétés mécaniques remarquables et du bon compromis résistanceductilité qui lui donne d’intéressante potentialités comme absorbeur d’énergiemécanique. Cependant, la recherche de bons compromis entre les propriétésmécaniques en traction et celles de formabilité nécessite une optimisation desparamètres microstructuraux. Ce travail de thèse s’inscrit dans cet optique. Dans unepremière partie, l’étude bibliographique proposée permet de mieux cerner lesparamètres influençant la formation des microstructures ainsi que les propriétés desaciers DP. Dans une seconde partie, nous proposons un travail expérimental originalpermettant de mieux comprendre la formation des microstructures des aciers DP etde découpler l’effet de certains paramètres microstructuraux sur les propriétés deces aciers. Enfin, la modélisation micromécanique proposée permet de compléter etd’interpréter les données expérimentales acquises. Ce travail ouvre des voiesintéressantes de « design » des microstructures des aciers DP en vue de développerdes aciers de nouvelles générations possédant des propriétés optimisées. / Ferrite-martensite dual-phase (DP) steels have been widely used in automotiveindustry due to their excellent mechanical properties, such as high work-hardeningrate and a good compromise between strength and ductility allowing high energyabsorbing performance. In order to fully exploit the potential of DP steels and extendthe application, the dual-phase microstructure has to be optimized for bettercombination of strength and formability that is characterized by uniform strainand/or fracture strain. As a starting point, detailed literature review is made on themicrostructure development and mechanical properties of DP steels, and the keyfactors controlling microstructural features and determining mechanical propertiesare identified. Through experimental investigation, microstructures are developed inorder to decouple the effects of various microstructural features, and themicrostructure—mechanical properties relationship is systematically studied.Micromechanical modeling is used to further understand the experimental resultswithin a quantitative framework, and to provide a support for microstructurerefinement of DP steels by parametric study. Strategies of designing DP steels tofulfill specific forming operation have been proposed, and the concept of DP steelswith graded martensite islands has been discussed with FEM analysis as a possibilityof improving strength—formability trade-off.

Pesquisas anteriores sobre aÃos ferrÃticos experimentais com alto teor de molibdÃnio (Mo) constataram que embora o Mo seja responsÃvel por aumentar a resistÃncia à corrosÃo em meios ricos em Ãcidos naftÃnicos e em complexos de enxofre, teores acima de 5% Mo favorecem a formaÃÃo de fases deletÃrias e reduzem a tenacidade do aÃo. Para melhorar a tenacidade dessas ligas, mantendo-se a estabilidade da fase ferrÃtica, o presente trabalho adicionou nÃquel (Ni) à composiÃÃo, elevou o teor de cromo (Cr) para 25% e manteve o elevado teor de Mo. Essas novas ligas pertencem a uma famÃlia de aÃos denominados aÃos inoxidÃveis superferrÃticos, desenvolvidos inicialmente para uso em trocadores de calor e ambientes marinhos. Este trabalho faz parte de um estudo para adaptar a composiÃÃo de aÃos superferrÃticos comerciais para utilizaÃÃo em plantas petrolÃferas que refinam petrÃleos ricos em compostos de enxofre atravÃs do aumento do teor de Mo na liga. A cinÃtica de precipitaÃÃo de fases em ligas com composiÃÃes experimentais (Fe25%Cr5-7%Mo2-4%Ni) com adiÃÃo de niÃbio (Nb) e titÃnio (Ti) foi estudada para temperaturas de 400ÂC a 900ÂC em diferentes tempos de tratamento. Foi realizado o estudo termodinÃmico das ligas empregando o Thermo-Calc para determinar a temperatura de estabilidade da fase ferrÃtica e identificar as possÃveis fases intermetÃlicas precipitadas em condiÃÃes de equilÃbrio. As ligas foram envelhecidas a 400 e 475ÂC para estudar a precipitaÃÃo da fase alfa linha (&#945;â) e seus efeitos nas propriedades mecÃnicas, magnÃticas e de resistÃncia à corrosÃo. Foram realizados tratamentos isotÃrmicos de 600 a 900ÂC para estudar a cinÃtica de precipitaÃÃo das fases intermetÃlicas. As alteraÃÃes microestruturais, nas propriedades mecÃnicas e na resistÃncia à corrosÃo devido a variaÃÃo da composiÃÃo e do tratamento tÃrmico foram estudadas. Os resultados obtidos nas ligas experimentais tratadas a 400 e 475ÂC indicaram aumento na dureza e reduÃÃo da fase ferrita, acompanhada de aumento da suscetibilidade a corrosÃo por pite sendo mais crÃtico a 475ÂC, com melhor desempenho observado para a liga 5Mo4Ni. Para as amostras tratadas de 600 a 900ÂC a liga 7Mo2Ni apresentou a menor quantidade de fases deletÃrias precipitadas e menor suscetibilidade a corrosÃo por pite. Ocorreu precipitaÃÃo de austenita para as ligas contendo 4%Ni tratadas a 800ÂC e 900ÂC. A liga 7Mo4Ni apresentou pior desempenho comparada Ãs outras ligas experimentais em todas as condiÃÃes estudadas. / Previous research on experimental ferritic steel with high Mo content showed that Mo increases the resistance to naphthenic corrosion and sulfur complexes. However, Mo content above 5 wt% favored the formation of deleterious phases and reduced the toughness of the steel. To improve the toughness of these alloys and keep the ferrite phase stable, was added Ni, increased Cr content to 25% and maintained high Mo content. These new alloys belong to a family of steels known as superferritic stainless steels. They were originally developed for use in heat exchangers and marine environments. There is a current trend to use these alloys in the oil industry driving the research on the effect of the increase of Mo content on the microstructure of these steels. The kinetics of phase precipitation in experimental compositions (Fe25%Cr 5-7%Mo 2-4%Ni) with addition of Nb and Ti will be investigated for temperatures from 400  C to 900  C for different treatment times. In this first stage, Thermo-Calc software was used to determine the temperature stability of the ferritic phase and to identify possible intermetallic phases precipitated at thermodynamic equibrium. The alloys were aged at 400 and 475ÂC for study the alfa prime phase precipitation and their effects on the mechanical, magnetic and corrosion properties. Isothermal treatments were carried out 600 ÂC to 900  C to study the kinetics of precipitation of intermetallic phases. The microstructural changes on the mechanical and corrosion properties due to variation in composition and heat treatment were studied. The results obtained in the experimental alloys treated at 400 and 475ÂC indicated an increase in hardness, while wt% of ferrite had decreased, accompanied by increased susceptibility to pitting corrosion, the best performance observed for 5Mo4Ni alloy these conditions. For samples treated 600 to 900ÂC the 7Mo2Ni alloy showed the smallest amount deleterious phase precipitated and less susceptibility to pitting corrosion. Austenite phase precipitation occurred for the alloys containing 4%Ni treated at 800ÂC and 900ÂC. The 7Mo4Ni alloy showed worse performance compared to other experimental alloys in all conditions studied.