Nonlinear mechanics and nonlinear material properties in micromechanical resonators

Microelectromechanical Systems are ubiquitous in modern technology, with applications ranging from accelerometers in smartphones to ultra-high precision motion stages used for atomically-precise positioning. With the appropriate selection of materials and device design, MEMS resonators with ultra-high quality factors can be fabricated at minimal cost. As the sizes of such resonators decrease, however, their mechanical, electrical, and material properties can no longer be treated as linear, as can be done for larger-scale devices. Unfortunately, adding nonlinear effects to a system changes its dynamics from exactly-solvable to only solvable in specific cases, if at all. Despite (and because of) these added complications, nonlinear effects open up an entirely new world of behaviors that can be measured or taken advantage of to create even more advanced technologies. In our resonators, oscillations are induced and measured using aluminum nitride transducers. I used this mechanism for several separate highly-sensitive experiments. In the first, I demonstrate the incredible sensitivity of these resonators by actuating a mechanical resonant mode using only the force generated by the radiation pressure of a laser at room temperature. In the following three experiments, which use similar mechanisms, I demonstrate information transfer and force measurements by taking advantage of the nonlinear behavior of the resonators. When nonlinear resonators are strongly driven, they exhibit sum and difference frequency generation, in which a large carrier signal can be mixed with a much smaller modulation to produce signals at sum and difference frequencies of the two signals. These sum and difference signals are used to detect information encoded in the modulation signal using optical radiation pressure and acoustic pressure waves. Finally, in my experiments, I probe the nonlinear nature of the piezoelectric material rather than take advantage of the nonlinear resonator behavior. The relative sizes of the linear and nonlinear portions of the piezoelectric constant can be determined because the force applied to the resonator by a transducer is independent of the dielectric constant. This method allowed me to quantify the nonlinear constants

The shape – morphing performance of magnetoactive soft materials

Magnetoactive soft materials (MSMs) are soft polymeric composites filled with magnetic particles that are an emerging class of smart and multifunctional materials with immense potentials to be used in various applications including but not limited to artificial muscles, soft robotics, controlled drug delivery, minimally invasive surgery, and metamaterials. Advantages of MSMs include remote contactless actuation with multiple actuation modes, high actuation strain and strain rate, self-sensing, and fast response etc. Having broad functional behaviours offered by the magnetic fillers embedded within non-magnetic matrices, MSMs are undoubtedly one of the most promising materials in applications where shape-morphing, dynamic locomotion, and reconfigurable structures are highly required. This review article provides a comprehensive picture of the MSMs focusing on the materials, manufacturing processes, programming and actuation techniques, behaviours, experimental characterisations, and device-related achievements with the current state-of-the-art and discusses future perspectives. Overall, this article not only provides a comprehensive overview of MSMs’ research and development but also functions as a systematic guideline towards the development of multifunctional, shape-morphing, and sophisticated magnetoactive devices

Structure and Reactivity of Terrestrial and Extraterrestrial Pyrrhotite

Pyrrhotite (Fe1−xS) is a non-stoichiometric iron monosulfide common in terrestrial rocks, ore deposits, and many extraterrestrial materials. The non-stoichiometry due to metal vacancies relates to a variety of composition-dependent crystallographic superstructures, but little of the existing structural and microstructural complexity has been explored yet. This thesis investigates the occurrences and nature of pyrrhotite superstructures, examines the related nano- and microstructural phenomena, and explores their effects on chemical reactivity. The goal is to comprehend the relations of the nanoscale real structure of pyrrhotite to its physicochemical properties. A central tool in these studies is analytical transmission electron microscopy (TEM), which has been extensively used to study terrestrial and extraterrestrial samples. In three studies, published or submitted as scientific research articles, it is shown that structural complexity of pyrrhotites is a widespread feature in terrestrial and extraterrestrial materials and is strongly interrelated with its physicochemical properties and environments of formation and alteration. A new model based on translation interface modulation is being introduced to provide a realistic description of the structural state of natural NC-pyrrhotites. Novel insights into the thermodynamically stable phase assemblages in the Fe-S system at ambient temperatures are presented and the crystallography and connected thermochemistry of pyrrhotites are deployed to reach new conclusions about the petrogenetic history of chondritic meteorites and the alteration processes they were involved in. Finally, an experimental alteration study reveals for the fist time quantitatively that the vacancy superstructures and anisotropy of pyrrhotites have tremendous effects on their kinetic behaviors during dissolution under acidic and oxidizing conditions. Intrinsic reactivity differences between 4C- and NC-pyrrhotite are clearly resolved and discusses in the framework of the newly established structure model

Synthesis and gas sensing properties of inorganic semiconducting, p-n heterojunction nanomaterials

En aquesta tesis utilitzant principalment Aerosol Assited Chemical Vapor Deposition, AACVD, com a metodologia de síntesis d'òxid de tungstè nanoestructurat s'han fabricat diferents sensors de gasos. Per tal d'estudiar la millora en la selectivitat i la sensibilitat dels sensors de gasos basats en òxid de tungstè aquest s'han decorat, via AACVD, amb nanopartícules d'altres òxids metàl·lics per a crear heterojuncions per tal d'obtenir un increment en la sensibilitat electrònica, les propietats químiques del material o bé ambdues. En particular, s'han treballat en diferents sensors de nanofils d'òxid de tungstè decorats amb nanopartícules d'òxid de níquel, òxid de cobalt i òxid d'iridi resultant en sensors amb un gran increment de resposta i selectivitat cap al sulfur d'hidrogen, per a l'amoníac i per a l'òxid de nitrogen respectivament a concentracions traça. A més a més, s'han estudiat els mecanismes de reacció que tenen lloc entre les espècies d'oxigen adsorbides a la superfície del sensor quan interactua amb un gas. I també s'ha treballat en intentar controlar el potencial de superfície de les capes nanoestructurades per tal de controlar la deriva en la senyal al llarg del temps, quan el sensor està operant, a través d'un control de temperatura.En esta tesis utilizando principalmente Aerosol Assited Chemical Vapor Deposition, AACVD, como metodología de síntesis de óxido de tungsteno nanoestructurado se han fabricado diferentes sensores de gases. Para estudiar la mejora en la selectividad y la sensibilidad de los sensores de gases basados en óxido de tungsteno estos se han decorado, vía AACVD, con nanopartículas de otros óxidos metálicos para crear heterouniones para obtener un incremento en la sensibilidad electrónica, las propiedades químicas del material o bien ambas. En particular, se han trabajado en diferentes sensores de nanohilos de óxido de tungsteno decorados con nanopartículas de óxido de níquel, óxido de cobalto y óxido de iridio resultante en sensores con un gran incremento de respuesta y selectividad hacia el sulfuro de hidrógeno, para el amoníaco y para el óxido de nitrógeno respectivamente a concentraciones traza. Además, se han estudiado los mecanismos de reacción que tienen lugar entre las especies de oxígeno adsorbidas en la superficie del sensor cuando interactúa con un gas. Y también se ha trabajado en intentar controlar el potencial de superficie de las capas nanoestructuradas para controlar la deriva en la señal a lo largo del tiempo, cuando el sensor está trabajando, a través de un control de temperatura.In this thesis, using mainly Aerosol Assited Chemical Vapor Deposition, AACVD, as a synthesis methodology for nanostructured tungsten oxide, different gas sensors have been manufactured. To study the improvement in the selectivity and sensitivity of gas sensors based on tungsten oxide, they have been decorated, via AACVD, with nanoparticles of other metal oxides to create heterojunctions to obtain an increase in electronic sensitivity, in the chemical properties of the material or at the same time in both. Particularly, we have worked on different tungsten oxide nanowire sensors decorated with nanoparticles of nickel oxide, cobalt oxide and iridium oxide resulting in sensors with a large increase in response and selectivity towards hydrogen sulfide, for ammonia. and for nitrogen oxide respectively at trace concentrations. In addition, the reaction mechanisms that take place between oxygen species adsorbed on the sensor surface when it interacts with a gas have been also studied. Furthermore, efforts have been put on trying to control the surface potential of the nanostructured layers to control the drift in the signal over time, when operating the sensors, through temperature control

Influence of Electrolyte on the Stability and Activity of WO3 for Photoelectrochemical Oxidation Reactions

Metal oxide semiconductors provide a platform for absorption of solar energy to generate a chemical potential gradient, driving an uphill chemical transformation in a photoelectrochemical (PEC) reaction. However, the stability of the metal oxide material is also an important consideration. In this thesis, tungsten oxide (WO3 ) films were made by spin casting aqueous ammonium metatungstate solutions on fluorine tin oxide substrate. The tungsten oxide films were used to investigate water oxidation and chloride oxidation, two important reactions in solar fuel production. WO3 has generally been regarded as a poor choice of metal oxide light absorber for performing water oxidation due to degradation in the photocurrent density during normal operation. However in this work, electrochromic tungsten bronze impurities (HxWO3) were shown to oxidize during PEC water oxidation operation, resulting in a loss of donor density, causing the loss of photocurrent density observed. The regeneration of tungsten bronze donor species can induced by light in a photochromic mechanism, resulting in a recovery in the photocurrent density and demonstrates that photocurrent density loss during water oxidation is reversible. The rate of water oxidation was determined by detecting oxygen gas, the product of water oxidation, with flow cell gas chromatography. After photochromic regeneration of tungsten bronze donors, the rate of water oxidation recovered alongside the overall photocurrent. Because of the importance of tungsten bronze species in the PEC behavior of tungsten oxide, it is referred to as HxWO3 in the thesis chapters to better describe the material used. Tungsten bronze donor species are electrochemically active and suppressing the rate of donor oxidation will increase the stability in PEC photocurrent. To this end, chloride oxidation was explored as a possible alternative to water oxidation for solar fuel formation. Improvement in PEC photocurrent stability was observed in 0.5 M sodium chloride electrolytes compared to 0.1 M potassium phosphate electrolytes at the same pH. Chloride more rapidly injects electrons into the HxWO3 material, eliminating photogenerated holes before oxidation of tungsten bronze impurities can occur. The oxidation of donors was also prevented by applying an FeOOH electrocatalyst to the surface of the Hx WO3 because the electronic states of FeOOH are well positioned to inject electron density into HxWO3 , similar to chloride oxidation. Using chloride electrolytes with HxWO3 materials leads to higher stability in the photocurrent density during solar fuel producing reactions. The hypochlorous acid produced by Hx WO3 is a strong oxidant capable of performing many useful chemical transformations. The oxidation of aqueous primary and secondary alcohols was investigated using ethanol and 2-propanol and 1 M chloride electrolytes. The yield was monitored using 1 H-NMR. The yield of products was high for both ethanol and 2-propanol. Proton activity influenced the yield of acetic acid and acetone, but no influence was observed in the acetaldehyde yield. Because hypochlorous acid undergoes light induced homolytic cleavage, generating radical species, alcohol oxidation was also performed using a platinum electrode in the same electrolyte. Comparing the product yield of alcohol oxidation using platinum in the dark and under illumination, only the acetaldehyde yield exhibited a dependence on the illumination with no difference observed in the acetic acid and acetone yields. These observations were used to rationalize the mechanism of hypochlorous oxidation for the observed products.PHDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/162940/1/breuhaa_1.pd

Continuous Hydrothermal Synthesis of Inorganic Nanoparticles: Applications and Future Directions

Nanomaterials are at the leading edge of the emerging field of nanotechnology. Their unique and tunable size-dependent properties (in the range 1-100 nm) make these materials indispensable in many modern technological applications. In this Review, we summarize the state-of-art in the manufacture and applications of inorganic nanoparticles made using continuous hydrothermal flow synthesis (CHFS) processes. First, we introduce ideal requirements of any flow process for nanoceramics production, outline different approaches to CHFS, and introduce the pertinent properties of supercritical water and issues around mixing in flow, to generate nanoparticles. This Review then gives comprehensive coverage of the current application space for CHFS-made nanomaterials including optical, healthcare, electronics (including sensors, information, and communication technologies), catalysis, devices (including energy harvesting/conversion/fuels), and energy storage applications. Thereafter, topics of precursor chemistry and products, as well as materials or structures, are discussed (surface-functionalized hybrids, nanocomposites, nanograined coatings and monoliths, and metal-organic frameworks). Later, this Review focuses on some of the key apparatus innovations in the field, such as in situ flow/rapid heating systems (to investigate kinetics and mechanisms), approaches to high throughput flow syntheses (for nanomaterials discovery), as well as recent developments in scale-up of hydrothermal flow processes. Finally, this Review covers environmental considerations, future directions and capabilities, along with the conclusions and outlook

INVESTIGATION OF MAGNESIUM ION CHARGE STORAGE MECHANISM IN MANGANESE DIOXIDE

Magnesium (Mg) battery is considered as a promising candidate for the next generation battery technology that could potentially replace the current lithium (Li)-ion batteries due to the following factors. Magnesium possesses a higher volumetric capacity than commercialized Li-ion battery anode materials. Additionally, the low cost and high abundance of Mg compared to Li makes Mg batteries even more attractive. Moreover, unlike metallic Li anodes which have a tendency to develop a dendritic structure on the surface upon the cycling of the battery, Mg metal is known to be free from such a hazardous phenomenon. Due to these merits of Mg as an anode, the topic of rechargea¬ble Mg batteries has attracted considerable attention among researchers in the last few decades. However, the aforementioned advantages of Mg batteries have not been fully utilized due to the serious kinetic limitation of Mg2+ diffusion process in many hosting compounds which is believed to be due to a strong electrostatic interaction between divalent Mg2+ ions and hosting matrix. This serious kinetic hindrance is directly related to the lack of cathode materials for Mg battery that provide comparable electrochemical performances to that of Li-based system. Manganese oxide (MnO2) is one of the most well studied electrode materials due to its excellent electrochemical properties, including high Li+ ion capacity and relatively high operating voltage (i.e., ~ 4 V vs. Li/Li+ for LiMn2O4 and ~ 3.2 V vs. Mg/Mg2+). However, unlike the good electrochemical properties of MnO2 realized in Li-based systems, rather poor electrochemical performances have been reported in Mg based systems, particularly with low capacity and poor cycling performances. While the origin of the observed poor performances is believed to be due to the aforementioned strong ionic interaction between the Mg2+ ions and MnO2 lattice resulting in a limited diffusion of Mg2+ ions in MnO2, very little has been explored regarding the charge storage mechanism of MnO2 with divalent Mg2+ ions. This dissertation investigates the charge storage mechanism of MnO2, focusing on the insertion behaviors of divalent Mg2+ ions and exploring the origins of the limited Mg2+ insertion behavior in MnO2. It is found that the limited Mg2+ capacity in MnO2 can be significantly improved by introducing water molecules in the Mg electrolyte system, where the water molecules effectively mitigated the kinetic hindrance of Mg2+ insertion process. The combination of nanostructured MnO2 electrode and water effect provides a synergic effect demonstrating further enhanced Mg2+ insertion capability. Furthermore, it is demonstrated in this study that pre-cycling MnO2 electrodes in water-containing electrolyte activates MnO2 electrode, after which improved Mg2+ capacity is maintained in dry Mg electrolyte. Based on a series of XPS analysis, a conversion mechanism is proposed where magnesiated MnO2 undergoes a conversion reaction to Mg(OH)2 and MnOx and Mn(OH)y species in the presence of water molecules. This conversion process is believed to be the driving force that generates the improved Mg2+ capacity in MnO2 along with the water molecule’s charge screening effect. Finally, it is discussed that upon a consecutive cycling of MnO2 in the water-containing Mg electrolyte, structural water is generated within the MnO2 lattice, which is thought to be the origin of the observed activation phenomenon. The results provided in this dissertation highlight that the divalency of Mg2+ ions result in very different electrochemical behaviors than those of the well-studied monovalent Li+ ions towards MnO2