Cold vapour generation electrothermal atomic absorption spectrometry and solid phase extraction based on a new nanosorbent for sensitive HG determination in environmental samples (sea water and river water)

Mercury is not an essential element for plant or animal life and it is a potential environmental toxic because of its tendency to form covalent bonds with organic molecules and the high stability of the Hg-C bond. Reports estimate a total mercury concentration in natural waters ranging from 0.2 to 100 ng L-1. Due to this fact, highly sensitive methods are required for direct determination of such extremely low levels. In this work, a rapid and simple method was developed for separation and preconcentration of mercury by flow injection solid phase extraction coupled with on-line chemical vapour generation electrothermal atomic absorption spectrometry. The system is based on chelating retention of the analyte onto the mini column filled with a mesoporous silica functionalized with 1,5 bis (di-2-pyridyl) methylene thiocarbohydrazide. The main aim of this work was to develop a precise and accurate method for the determination of the Hg. Under the optima conditions and 120 s preconcentration time, the detection limit obtained was 0.009 μg L-1, with RSDs 3.7 % for 0.2 μg L-1, 4.8 % for 1 μg L-1 and enrichment factor 4, Furthermore, the method proposed has permitted the determination of Hg with a reduction in the analysis time, the sample throughput was about 18 h-1, low consumption of reagents and sample volume. The method was applied to the determination of Hg in sea water and river water. For the quality control of the analytical performance and the validation of the newly developed method, the analysis of two certified samples, TMDA 54.4 Fortified Lake, and LGC6187 River sediment was addressed. The results showed good agreement with the certified values.

Effects of Drive Speed Modulation on Dynamics of Slender Rotating Structures

Slender rotating structures are used in many mechanical systems. These structures can suffer from undesired vibrations that can affect the components and safety of a system. Furthermore, since some these structures can operate in a harsh environment, installation and operation of sensors that are needed for closed-loop and collocated control schemes may not be feasible. Hence, the need for an open-loop non-collocated scheme for control of the dynamics of these structures. In this work, the effects of drive speed modulation on the dynamics of slender rotating structures are studied. Slender rotating structures are a type of mechanical rotating structures, whose length to diameter ratio is large. For these structures, the torsion mode natural frequencies can be low. In particular, for isotropic structures, the first few torsion mode frequencies can be of the same order as the first few bending mode frequencies. These situations can be conducive for energy transfer amongst bending and torsion modes. Scenarios with torsional vibrations experienced by rotating structures with continuous rotor-stator contact occur in many rotating mechanical systems. Drill strings used in the oil and gas industry are an example of rotating structures whose torsional vibrations can be deleterious to the components of the drilling system. As a novel approach to mitigate undesired vibrations, the effects of adding a sinusoidal excitation to the rotation speed of a drill string are studied. A portion of the drill string located within a borewell is considered and this rotating structure has been modeled as an extended Jeffcott rotor and a sinusoidal excitation has been added to the drive speed of the rotor. After constructing a three-degree-of-freedom model to capture lateral and torsional motions, the equations of motions are reduced to a single differential equation governing torsional vibrations during continuous stator contact. An approximate solution has been obtained by making use of the Method of Direct Partition of Motions with the governing torsional equation of motion. The results showed that for a rotor undergoing forward or backward whirling, the addition of sinusoidal excitation to the drive speed can cause an increase in the equivalent torsional stiffness, smooth the discontinuous friction force at contact, and reduce the regions of negative slope in the friction coefficient variation with respect to speed. Experiments with a scaled drill string apparatus have also been conducted and the experimental results show good agreement with the numerical results obtained from the developed models. These findings suggest that the extended Jeffcott rotordynamics model can be useful for studies of rotor dynamics in situations with continuous rotor-stator contact. Furthermore, the results obtained suggest that the drive speed modulation scheme can have value for attenuating drill-string vibrations.

Nano-Engineering of Densely Packed Electrochemical Energy Storage Architectures by Atomic Layer Deposition

Nanostructures are highly attractive for future electrical energy storage devices because they enable large surface area and short ion transport time through thin electrode layers for high power devices. Significant enhancement in power density of batteries has been achieved by nano-engineered structures, particularly anode and cathode nanostructures spatially separated far apart by a porous membrane and/or a defined electrolyte region. A self-aligned nanostructured battery fully confined within a single nanopore presents a powerful platform to determine the rate performance and cyclability limits of nanostructured storage devices. Atomic layer deposition (ALD) has enabled us to create and evaluate such structures, comprised of nanotubular electrodes and electrolyte confined within anodic aluminum oxide (AAO) nanopores. The V2O5- V2O5 symmetric nanopore battery displays exceptional power-energy performance and cyclability when tested as a massively parallel device (~2billion/cm2), each with ~1m3 volume (~1fL). Cycled between 0.2V and 1.8V, this full cell has capacity retention of 95% at 5C rate and 46% at 150C, with more than 1000 charge/discharge cycles. These results demonstrate the promise of ultrasmall, self-aligned/regular, densely packed nanobattery structures as a testbed to study ionics and electrodics at the nanoscale with various geometrical modifications and as a building block for high performance energy storage systems[1, 2]. Further increase of full cell output potential is also demonstrated in asymmetric full cell configurations with various low voltage anode materials. The asymmetric full cell nanopore batteries, comprised of V2O5 as cathode and prelithiated SnO2 or anatase phase TiO2 as anode, with integrated nanotubular metal current collectors underneath each nanotubular storage electrode, also enabled by ALD. By controlling the amount of lithium ion prelithiated into SnO2 anode, we can tune full cell output voltage in the range of 0.3V and 3V. This asymmetric nanopore battery array displays exceptional rate performance and cyclability. When cycled between 1V and 3V, it has capacity retention of approximately 73% at 200C rate compared to 1C, with only 2% capacity loss after more than 500 charge/discharge cycles. With increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density. This configuration presents a more realistic test - through its asymmetric (vs symmetric) configuration – of performance and cyclability in nanoconfined environment. This dissertation covers (1) Ultra small electrochemical storage platform design and fabrication, (2) Electron and ion transport in nanostructured electrodes inside a half cell configuration, (3) Ion transport between anode and cathode in confined nanochannels in symmetric full cells, (4) Scale up energy and power density with geometry optimization and low voltage anode materials in asymmetric full cell configurations. As a supplement, selective growth of ALD to improve graphene conductance will also be discussed[3]. References: 1. Liu, C., et al., (Invited) A Rational Design for Batteries at Nanoscale by Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 23-30. 2. Liu, C.Y., et al., An all-in-one nanopore battery array. Nature Nanotechnology, 2014. 9(12): p. 1031-1039. 3. Liu, C., et al., Improving Graphene Conductivity through Selective Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 133-138.

Single-Polarization Double Refraction in Plasmonic Crystals: Considerations on Energy Flow

We examined the optical properties of nanolayered metal-dielectric lattices. At subwavelength regimes, the periodic array of metallic nanofilms demonstrates nonlocality-induced double refraction, conventional positive and as well as negative. In particular, we report on energy-flow considerations concerning both refractive behaviors concurrently. Numerical simulations provide transmittance of individual beams in Ag-TiO2 metamaterials under different configurations. In regimes of the effective-medium theory predicting elliptic dispersion, negative refraction may be stronger than the expected positive refraction.

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Ultrafast transient absorption spectroscopy: principles and applications

The study of photophysical and photochemical processes crosses the interest of many fields of research in physics, chemistry and biology. In particular, the photophysical and photochemical reactions, after light absorption by a photosynthetic pigment-protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. Among the experimental approaches developed for this purpose, the advent of ultrafast transient absorption spectroscopy has become a powerful and widely used technique.[1,2] Focusing on the process of photosynthesis, it relies upon the efficient absorption and conversion of the radiant energy from the Sun. Chlorophylls and carotenoids are the main players in the process. Photosynthetic pigments are typically arranged in a highly organized fashion to constitute antennas and reaction centers, supramolecular devices where light harvesting and charge separation take place. The very early steps in the photosynthetic process take place after the absorption of a photon by an antenna system, which harvests light and eventually delivers it to the reaction center. In order to compete with internal conversion, intersystem crossing, and fluorescence, which inevitably lead to energy loss, the energy and electron transfer processes that fix the excited-state energy in photosynthesis must be extremely fast. In order to investigate these events, ultrafast techniques down to a sub-100 fs resolution must be used. In this way, energy migration within the system as well as the formation of new chemical species such as charge-separated states can be tracked in real time. This can be achieved by making use of ultrafast transient absorption spectroscopy. The basic principles of this notable technique, instrumentation, and some recent applications to photosynthetic systems[3] will be described. Acknowledgements M. Moreno Oliva thanks the MINECO for a “Juan de la Cierva-Incorporación” research contract. References [1] U. Megerle, I. Pugliesi, C. Schriever, C.F. Sailer and E. Riedle, Appl. Phys. B, 96, 215 – 231 (2009). [2] R. Berera, R. van Grondelle and J.T.M. Kennis, Photosynth. Res., 101, 105 – 118 (2009). [3] T. Nikkonen, M. Moreno Oliva, A. Kahnt, M. Muuronen, J. Helaja and D.M. Guldi, Chem. Eur. J., 21, 590 – 600 (2015).

Caractérisation des structures de septines hautement organisées chez la drosophile et leur interaction avec le cytosquelette d’actine

Les septines sont des GTPases conservées dérégulées dans le cancer et les maladies neurodégénératives. Elles servent de protéines d’échafaudage et forment une barrière de diffusion à la membrane plasmique et au corps central lors de la cytokinèse. Elles interagissent avec l’actine et s’organisent en complexes qui polymérisent et forment des structures hautement organisées (anneaux et filaments). Leur dynamique d’assemblage et leur rôle dans la cellule restent à être élucidés. La Drosophile est un modèle simple pour l’étude des septines puisqu’on n’y retrouve que 5 gènes (sep1, sep2, sep4, sep5, peanut) comparativement aux 13 gènes chez l’humain. À l’aide d’un anticorps contre Pnut, nous avons identifié des structures tubulaires dans 30% des cellules S2 de Drosophile. Mon projet a comme but de caractériser ces tubes en élucidant leurs constituants, leur comportement et leurs propriétés pour mieux clarifier le mécanisme par lequel les septines forment des structures hautement organisées et interagissent avec le cytosquelette d’actine. Par immunofluorescence, j’ai pu démontrer que ces tubes sont cytoplasmiques, en mitose ou interphase, ce qui suggère qu’ils ne sont pas régulés par le cycle cellulaire. Pour investiguer la composition et les propriétés dynamiques de ces tubes, j’ai généré une lignée cellulaire exprimant Sep2-GFP qui se localise aux tubes et des ARNi contre les cinq septines. Trois septines sont importantes pour la formation de ces tubes et anneaux notamment Sep1, Sep2 et Pnut. La déplétion de Sep1 cause la dispersion du signal GFP en flocons, tandis que la déplétion de Sep2 ou de Pnut mène à la dispersion du signal GFP uniformément dans la cellule. Des expériences de FRAP sur la lignée Sep2-GFP révèlent un signal de retour très lent, ce qui indique que ces structures sont très stables. J’ai aussi démontré une relation entre l’actine et les septines. Le traitement avec la Latrunculin A (un inhibiteur de la polymérisation de l’actine) ou la Jasplakinolide (un stabilisateur des filaments d’actine) mène à la dépolymérisation rapide (< 30 min) des tubes en anneaux flottants dans le cytoplasme, même si ces tubes ne sont pas reconnus suite à un marquage de la F-actine. L’Actin05C-mCherry se localise aux tubes, tandis que le mutant déficient de la polymérisation, Actin05C-R62D-mCherry perd cette localisation. On observe aussi que la déplétion de la Cofiline et de l’AIP1 (ce qui déstabilise l’actine) mène au même phénotype que le traitement avec la Latrunculine A ou la Jasplakinolide. Alors on peut conclure qu’un cytosquelette d’actine dynamique est nécessaire pour la formation et le maintien des tubes de septines. Les futures études auront comme but de mieux comprendre l’organisation des septines en structures hautement organisées et leur relation avec l’actine. Ceci sera utile pour l’élaboration du réseau d’interactions des septines qui pourra servir à expliquer leur dérégulation dans le cancer et les maladies neurodégénératives.

Optical Waveguides and Structures for Short Haul Optical Communication Channels within Printed Circuit Boards

Optical waveguides have shown promising results for use within printed circuit boards. These optical waveguides have higher bandwidth than traditional copper transmission systems and are immune to electromagnetic interference. Design parameters for these optical waveguides are needed to ensure an optimal link budget. Modeling and simulation methods are used to determine the optimal design parameters needed in designing the waveguides. As a result, optical structures necessary for incorporating optical waveguides into printed circuit boards are designed and optimized. Embedded siloxane polymer waveguides are investigated for their use in optical printed circuit boards. This material was chosen because it has low absorption, high temperature stability, and can be deposited using common processing techniques. Two sizes of waveguides are investigated, 50 $unit{mu m}$ multimode and 4 - 9 $unit{mu m}$ single mode waveguides. A beam propagation method is developed for simulating the multimode and single mode waveguide parameters. The attenuation of simulated multimode waveguides are able to match the attenuation of fabricated waveguides with a root mean square error of 0.192 dB. Using the same process as the multimode waveguides, parameters needed to ensure a low link loss are found for single mode waveguides including maximum size, minimum cladding thickness, minimum waveguide separation, and minimum bend radius. To couple light out-of-plane to a transmitter or receiver, a structure such as a vertical interconnect assembly (VIA) is required. For multimode waveguides the optimal placement of a total internal reflection mirror can be found without prior knowledge of the waveguide length. The optimal placement is found to be either 60 µm or 150 µm away from the end of the waveguide depending on which metric a designer wants to optimize the average output power, the output power variance, or the maximum possible power loss. For single mode waveguides a volume grating coupler is designed to couple light from a silicon waveguide to a polymer single mode waveguide. A focusing grating coupler is compared to a perpendicular grating coupler that is focused by a micro-molded lens. The focusing grating coupler had an optical loss of over -14 dB, while the grating coupler with a lens had an optical loss of -6.26 dB.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

MICROWAVE ABSORPTION PROPERTIES OF TIRES

The waste tire is belonging to insoluble high polymer elastic materials. It takes hundreds of years to resolve the macromolecules of waste tire into the standard which does not pollute the environment. More and more waste tires are air stored which causes space occupation and mosquito-breeding in the places that will spread diseases. The disposal methods include landfill, stockpiles, dumping and incising into particles. However, all these methods are not technically and economically efficient. The trend for the development of waste tire treatment processes is low cost, on-site, and high product recovery at high energy efficiency. In this project, microwave energy has been applied for treatment of the waste tire in laboratory scale. Experimental conditions were varied in order to find the optimum processing parameters such as temperature and atmosphere. The microwave absorption capability of waste tire rubber was investigated by measuring its dielectric properties from room temperature to 800°C in stagnant air and pure nitrogen atmospheres, respectively, at both 915 and 2466MHz.The dielectric parameters data increase steadily at temperatures below 400°C. At temperatures above 400°C, the relative dielectric loss factor and relative dielectric constant begin to decrease. This is due to the solid phase of tire rubber begins to transform to gas phase and the release of volatiles. The calculations of microwave half-power depth and penetration depth of waste tire rubber show that the pyrolysis process significantly improves the microwave absorption capability of the waste tire rubber at low temperatures. The calculated reflection loss of the waste tire rubber suggests that its maximum microwave absorption can be obtained when the rubber has a thickness of 25mm at 915MHz. The sample dimension has a significant effect on the overall performance of microwave absorption in waste tire during pyrolysis and thus on the efficiency of microwave waste tire rubber pyrolysis.

Applications of advanced and dual energy computed tomography in proton therapy

This thesis focuses on advanced reconstruction methods and Dual Energy (DE) Computed Tomography (CT) applications for proton therapy, aiming at improving patient positioning and investigating approaches to deal with metal artifacts. To tackle the first goal, an algorithm for post-processing input DE images has been developed. The outputs are tumor- and bone-canceled images, which help in recognising structures in patient body. We proved that positioning error is substantially reduced using contrast enhanced images, thus suggesting the potential of such application. If positioning plays a key role in the delivery, even more important is the quality of planning CT. For that, modern CT scanners offer possibility to tackle challenging cases, like treatment of tumors close to metal implants. Possible approaches for dealing with artifacts introduced by such rods have been investigated experimentally at Paul Scherrer Institut (Switzerland), simulating several treatment plans on an anthropomorphic phantom. In particular, we examined the cases in which none, manual or Iterative Metal Artifact Reduction (iMAR) algorithm were used to correct the artifacts, using both Filtered Back Projection and Sinogram Affirmed Iterative Reconstruction as image reconstruction techniques. Moreover, direct stopping power calculation from DE images with iMAR has also been considered as alternative approach. Delivered dose measured with Gafchromic EBT3 films was compared with the one calculated in Treatment Planning System. Residual positioning errors, daily machine dependent uncertainties and film quenching have been taken into account in the analyses. Although plans with multiple fields seemed more robust than single field, results showed in general better agreement between prescribed and delivered dose when using iMAR, especially if combined with DE approach. Thus, we proved the potential of these advanced algorithms in improving dosimetry for plans in presence of metal implants.

Effects in ultrafast laser micromachining PMMA-based optical fibre grating

Ultrafast laser owns extreme small beam size and high pulse intensity which enable spatial localised modification either on the surface or in the bulk of materials. Therefore, ultrafast laser has been widely used to micromachine optical fibres to alter optical structures. In order to do the precise control of the micromachining process to achieve the desired structure and modification, investigations on laser parameters control should be carried out to make better understanding of the effects in the laser micromachining process. These responses are important to laser machining, most of which are usually unknown during the process. In this work, we report the real time monitored results of the reflection of PMMA based optical fibre Bragg gratings (POFBGs) during excimer ultraviolet laser micromachining process. Photochemical and thermal effects have been observed during the process. The UV radiation was absorbed by the PMMA material, which consequently induced the modifications in both spatial structure and material properties of the POFBG. The POFBG showed a significant wavelength blue shift during laser micromachining. Part of it attributed to UV absorption converted thermal energy whilst the other did not disappear after POFBG cooling off, which attributed to UV induced photodegradation in POF.