A thermodynamics-based constitutive model is derived which predicts the nonlinear strain and magnetization response that magnetic shape memory alloys (MSMAs) exhibit when subjected to mechanical and magnetic loads. The model development is conducted on the basis of an extended thermo-magneto-mechanical framework. A novel free energy function for MSMAs is proposed, from which the constitutive equations are derived in a thermodynamically-consistent manner. The nonlinear and hysteretic nature of the macroscopic material behavior is captured through the evolution of internal state variables which are motivated by the crystallographic and magnetic microstructures of MSMAs. Model predictions are presented for different relevant loading cases and analyzed in detail. Finally, magnetostatic boundary value problems for MSMAs are considered and numerically solved using the finite element method. For these computations the developed constitutive model provides the nonlinear magnetic properties of the MSMA. The knowledge of the magnetic field distribution in the computational domain as a function of the applied field, which results from this magnetostatic analysis, is useful for the proper interpretation of experimental results as well as the design of experiments and applications.

The electropolymerisation of a range of indole derivatives results in the formation of redox active films. These redox films have been observed to be highly luminescent. Earlier studies have investigated electrochemical and photophysical properties, for potential applications such as fast response potentiometric sensors or novel materials for light emitting devices. The work in this thesis extends this approach to electrochemical and computational studies of a range of novel redox-active aromatic systems. This work has exploited the continuing increase of computing power, employing powerful quantum computational models to complement and augment electrochemical methods. Density Functional Theory has been used to show that prediction of oxidation potentials in good agreement with experimental values is achievable for a wide range of aromatic systems. Calculation of the electron spin density of the radical cations has also helped to elucidate the likely coupling locations for the formation of electroactive layers. It is observed that the nature of substituents and additional hetero groups to the aromatic systems can have a profound effect on electron spin density distributions. The redox-active species formed from indole dimers and 5-methylindolocarbazole have also been characterised. The species formed from electropolymerisation of 5- methylindolocarbazole has been found to be a mixture of three isomers of a 5- methylindolocarbazole dimer. Full characterisation of the product of the electropolymerisation of indole dimers was not possible; fluorescence work however suggests this to be a species with a greater degree of conjugation than either indole dimers or trimers. It is thought likely that this product is either a tetramer or longer chain polymer. This work demonstrates the applicability of a combination of computational and electrochemical methods to the characterisation of novel heteroaromatic systems.

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A new sensor technology based on optical diffraction of visible light shows promise for sensing metal ions and other species that employ chemically-responsive metal oxide and conducting polymer grating elements. These materials undergo reversible redox processes upon interaction with a chemical analyte that subsequently induces changes in the materials refractive index. The two key design parameters of this sensing technique involve preparation of micropatterned sensor elements and the evaluation of appropriate wavelengths for detection of diffracted light. Much of the ability to “tune” a desired sensing response is dictated by the understanding of how factors of size, dimension, crystallinity, morphology, porosity, and heterogeneity influence analyte/sensor interactions (i.e., adsorption, binding, and transport). The effect of composition, structure, and morphology of MoO₃, WO₃, Moₓ W₁₋ₓO₃, IrOₓ and polyaniline grating materials on chemical, electrochemical and optical properties of these systems will be examined by a range of spectroscopic and electrochemical techniques. Comprehensive evaluation and correlation of materials’ optical properties to diffraction-based detection will advance understanding of the capabilities and limitations for the diffraction-based sensing methodology. This information can then used to determine optimal sensing parameters to improve detection limits, enhance sensitivity and increase the dynamic range for detection of model analytes. / text

<p>A variety of intriguing surface patterns have been observed on developing natural systems, ranging from corrugated surface of white blood cells at nanometer scales to wrinkled dog skins at millimeter scales. To mimetically harness functionalities of natural morphologies, artificial transformative skin systems by using soft active materials have been rationally designed to generate versatile patterns for a variety of engineering applications. The study of the mechanics and design of these dynamic surface patterns on soft active materials are both physically interesting and technologically important. </p><p>This dissertation starts with studying abundant surface patterns in Nature by constructing a unified phase diagram of surface instabilities on soft materials with minimum numbers of physical parameters. Guided by this integrated phase diagram, an electroactive system is designed to investigate a variety of electrically-induced surface instabilities of elastomers, including electro-creasing, electro-cratering, electro-wrinkling and electro-cavitation. Combing experimental, theoretical and computational methods, the initiation, evolution and transition of these instabilities are analyzed. To apply these dynamic surface instabilities to serving engineering and biology, new techniques of Dynamic Electrostatic Lithography and electroactive anti-biofouling are demonstrated.</p> / Dissertation

Genom sin forskning har Innventia lyckats uppfinna ett mekano-aktivt (rörligt) papper. Syftet med mitt arbete var att göra en studie av konsumentfördelarna med mekano-aktiva förpackningar, vilket skulle leda till framtagning av koncept eller prototyper baserade på konsumentfördelarna. Studien är utförd åt Innventia, för att bistå dem i deras fortsatta arbete med att ta fram mekano-aktiva förpackningar baserade på verkliga konsumentbehov.Studien genomfördes med hjälp av att tre fokusgrupper svarade på en enkät och deltog i workshops. Fokusgrupperna var indelade i följande kategorier: ungdomar, äldre med nedsatt rörelseförmåga samt småbarnsföräldrar, varje fokusgrupp bestod av sex deltagare.Resultatet visade att 89 % av deltagarna uppgav att de någon gång upplevde sig ha svårigheter att hantera förpackningar. Samtliga deltagare tror att dagens förpackningar kan förbättras med mekano-aktiva förpackningar. Deltagarna i studien hade en väldigt positiv inställning till mekano-aktiva förpackningar och resultatet (fick mig att dra slutsatsen) indikerade att det kan finnas (finns) en marknad för mekano-aktiva förpackningslösningar som uppfyller verkliga konsumentbehov. / Through research Innventia has successfully invented a mechano-active (motioned) paper. The purpose of the current work was to do a survey of consumer benefits of mechano-active packages, leading to creation of 1-5 simple concepts and (or) prototypes of mechano-active packages based on consumer benefits. This survey is executed for Innventia in order to help them, in their continuing work with developing mechano-active consumer based packages based on real consumer needs.Using three targeting groups answering a questionnaire and participating in workshops have carried out the survey. The targeting groups were divided into three categories: youth of today, older with reduced mobility and parents with small children; each targeting group contained six participants.The results revealed that 89 % of the participants at sometimes find packages difficult to handle. All of the participants believe that the packages of today can improve with mechano-active packages. The participants in this survey were very open-minded towards the prospect of mechano-active packages and the results (helped me come to the conclusion) indicate that there might be (is) a market for mechano-active packaging solutions that fulfil real consumer needs.

Les travaux de cette thèse portent sur la caractérisation du polymères piézoélectriques de PVDF et celles de ses composites avec un alliage à mémoire de forme, pour des applications de récupération l'énergie thermique. Tout d'abord, une discussion est donnée sur les avancées actuelles des technologies de récupération d'énergie ainsi que leurs intérêts économiques. Des valeurs typiques de l'énergie pouvant être générée sont estimées, ainsi que des énergies nécessaires pour certaines applications.Une attention particulière est accordée aux principes de fonctionnement des matériaux pyroélectriques et piézoélectriques. Le PVDF et l'alliage à mémoire de forme NiTiCu sont également introduits.Des techniques de caractérisation adaptées sont introduites pour par voie direct caractériser le PVDF en tant que générateur de charges électriques, et son aptitude à la récolte de l'énergie thermique. Puisque le PVDF est un matériau très souple, la flexion à quatre points, la flexion sur tube, et la machine de traction sont utilisés pour étudier sa réponse piézoélectriques directe en mode quasi-statique, ainsi que les changements de propriétés piézoélectriques sous contrainte. Des mesures d'auto-décharge sous différents champs électriques appliqués, températures et contraintes sont effectuées pour étudier la stabilité du matériau.Un concept de récupération d'énergie utilisant des composites de matériaux fonctionnels de familles différentes est introduit. Ici, le couplage entre un matériau piézo-/pyroélectrique et un alliage à mémoire de forme est proposé. Le voltage pyroélectrique simple est combiné avec un voltage piézoélectrique induit par la transformation de phase de l'alliage à mémoire de forme, pour augmenter l'énergie totale générée par le système en chauffant. Une preuve de concept est présentée d'abord pour un matériau semi-flexible basé sur une céramique PZT, et ensuite pour le PVDF qui est entièrement flexible.Enfin, un circuit de gestion d'énergie a été conçu et intégré au récupérateur d'énergie en PVDF. Les hauts pics de tension générés lors du chauffage or refroidissement sont abaissés par un convertisseur de type buck à deux étages jusqu'au une tension de sortie utile stable. L'énergie de sortie est utilisée pour alimenter une carte d'émission sans fil. Ainsi, une chaîne complète de génération d'énergie, exploitant des variations de température et allant jusqu'au l'émission de données représentatives de l'événement thermique survenu est présentée.Les résultats de ces travaux concernent un large spectre d'applications potentiels, particulièrement les capteurs autonomes sans fil, et des objets de l'Internet of Things, avec une flexibilité mécanique élevée, une épaisseur réduite et de faible coût de maintenance. / This work deals with the characterization of piezoelectric polymers PVDF and its composites with shape memory alloys, for thermal energy harvesting applications. First, we discuss current advancements on energy harvesting technologies as well as their economical interests. Typical values of energy that can be generated are given together with energies typically needed for applications.Particular attention is given to the functioning principles of pyroelectric and piezoelectric materials. PVDF and shape memory alloy NiTiCu are also introduced.Custom characterization techniques are introduced to characterize PVDF piezoelectric properties relevant to generator applications and to evaluate its suitability for thermal energy harvesting. Since PVDF is a very flexible material, four-point bending, tube bending and a tensile machine experiments are used to study its piezoelectric response in quasi-static mode, as well as changes in piezoelectric properties with increased strain. Self-discharge measurements under various applied electric fields, temperatures and strains are performed to study the stability of material.A concept of composite energy harvesting, utilizing two materials of different families, is introduced. Here, we propose the coupling of piezo-/pyroelectric material and shape memory alloy. The pure pyroelectric voltage is combined with generated piezoelectric voltage, induced by shape memory alloy transformation, to increase the total energy generated by the system during heating. The proof of concept is shown first for ceramic PZT-based semi-flexible material and then for fully flexible PVDF.Finally, a power management circuit was designed and integrated with the PVDF energy harvester. High generated voltage peaks at heating are lowered by a two-step buck converter to a useful stable output voltage. Output energy are used to power a wireless emission card. Thus, a complete power generation chain from temperature variations to data emission is presented.The results of this work concern a wide range of applications, especially modern autonomous wireless sensors and Internet of Things objects, with low profile, high mechanical flexibility and low maintenance costs.

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.

<p dir="ltr">As the demand for energy rises and the threat of climate change looms, the need for clean, reliable, and affordable energy solutions like renewable energies has been more crucial. Energy storage systems (ESSs) are indispensable in addressing the intermittent nature of renewable energies and optimizing grid efficiency. Redox flow batteries (RFBs), thanks to their scalability, independent energy and power, swift response time, and minimal environmental impact, are a particularly promising ESS technology for long-duration storage applications. Despite the technological maturity of aqueous RFBs, nonaqueous organic RFBs (NAORFBs) are a prospective solution due to their wider operational voltage, potentially higher energy density, and larger pool of redox-active materials. However, the current state-of-the-art NAORFBs face challenges due to the lack of suitable organic redox-active materials (ORMs).</p><p dir="ltr">Despite the development of new materials, how their variables influence the total system cost of RFBs remains an unsolved challenge. With this regard, we established a techno-economic (TE) model to calculate the capital cost of nonaqueous hybrid RFBs (NAHRFBs). Prior to this work, NAHRFBs, which employs lithium metal as the anode, were regarded as an RFB system with the highest energy density. However, the correlation between their features and the system cost remained unclear, leaving a research gap for new ORMs. In our model, we selected a state-of-the-art NAHRFB system where 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) serves as the catholyte and lithium metal functions as the anode. Thereafter, sensitivity analyses identified several key factors that determine the system cost, including operational current density, area-specific resistance, cell voltage, electrolyte composition, and both the price and equivalent molecular weight of the ORM. To enhance the cost-competitiveness of current NAHRFBs, it is advised to increase the current density by 10 times and modulate the ORM-related characteristics. The virtually optimized condition manifests that the system cost of NAHRFB can meet the long-term cost target set by the U. S. Department of Energy.</p><p dir="ltr">Informed by the TE model, we discovered that elevating the oxidation potential of catholyte ORMs is instrumental in reducing the system cost of RFBs. To explore this possibility, we incorporated fluorine atoms, a potent electron-withdrawing group (EWG), into a dimethoxybenzene (DMB) derivative, yielding a new ORM (ANL-C46) with an oxidation potential enhanced by ~0.41 V. Surprisingly, ANL-C46 demonstrated superior kinetic and electrochemical stability compared to its parent molecule, as indicated by electron paramagnetic resonance (EPR) study and bulk electrolysis. In particular, the cycling performance of ANL-46 during the bulk electrolysis outperformed most reported high-potential (> 1 V vs. Ag/Ag⁺) ORMs. Density functional theory (DFT) calculations reveals that the introduced fluorine substituents suppress the typical side reaction pathways of the DMB series. These findings offer valuable insights into molecular engineering strategies that concurrently improve multiple desired ORM properties.</p><p dir="ltr">The stability of ORMs is critical for ensuring the extended lifetime of RFBs. We conducted a systematic exploration of the conjugation effect, which potentially stabilizes the ORMs by facilitating a more homogeneous distribution of delocalized charges. This was applied to tailor the electrochemical and physical properties of several DMB derivatives with varying aromatic ring counts. As we extended the aromatic core from 1,4-dimethoxybenzene (1,4-DMB) to 1,4-dimethoxynaphthalene (1,4-DMN), we noted a decrease in oxidation potential, enhanced kinetic stability, and an extended cycling life. However, further extending the aromatic core to 2-ethyl-9,10-dimethyanthracene (EDMA) results in rapid dealkylation of the radical cation due to increased strain in the methoxy substituents. Additionally, 1,4-DMN shows cross-reactions between radical cations, likely via disproportionation. This study demonstrates that extending the π-conjugation changes reactivity in multiple ways. Therefore, attempts to lower oxidation potential and improve ORMs stability through π-conjugation should be pursued with caution.</p>

The transition dynamics in silicon rubber based isotropic magnetorheological (MR) elastomers in terms of the normal force induced by an external homogeneous magnetic field is experimentally addressed. The primary goal was to evaluate dynamic performances of the MR elastic isotropic composite using a transparently presented measuring system with known characteristics in contrast to few previous studies on the topic. It was found that an increase in the magnetic field leads to an increase in the induced force and a decrease in the response time of the MR elastomer. At the same time, both the use of coarse particles as magnetic filler and a significant reduction in the stiffness of the polymer matrix reduce the response time of the MR elastomer under study. The analysis carried out takes into account the dynamics of the electromagnetic coil and the eddy currents induced in the magnet circuit. The shortest response times obtained for various MR elastomer samples are in the range of 27–72 ms for the maximal used magnetic field with an induction of 230 mT. These times correspond to the fastest previously reported ones for MR elastomers and MR elastomer based systems. In addition, the obtained results indicate the presence of different mechanisms responsible for the measured magnetodeformational effect observed in MR elastomers.