Optical Characterization of Organic Gain Materials for UV-emitting Hybrid Complex Coupled VCSELs

In this thesis, optical gain measurement setup based on variable stripe length method is designed, implemented and improved. The setup is characterized using inorganic and organic samples. The optical gain of spiro-quaterphenyl is calculated and compared with measurements from the setup. Films with various thicknesses of spiro-quaterphenyl, methoxy-spiro-quaterphenyl and phenoxy-spiro-quaterphenyl are deposited by a vacuum vapor deposition technique forming asymmetric slab waveguides. The optical properties, laser emission threshold, optical gain and loss coefficient for these films are measured. Additionally, the photodegradation during pumping process is investigated.

Hybrid constraint programming and metaheuristic methods for large scale optimization problems

This work presents hybrid Constraint Programming (CP) and metaheuristic methods for the solution of Large Scale Optimization Problems; it aims at integrating concepts and mechanisms from the metaheuristic methods to a CP-based tree search environment in order to exploit the advantages of both approaches. The modeling and solution of large scale combinatorial optimization problem is a topic which has arisen the interest of many researcherers in the Operations Research field; combinatorial optimization problems are widely spread in everyday life and the need of solving difficult problems is more and more urgent. Metaheuristic techniques have been developed in the last decades to effectively handle the approximate solution of combinatorial optimization problems; we will examine metaheuristics in detail, focusing on the common aspects of different techniques. Each metaheuristic approach possesses its own peculiarities in designing and guiding the solution process; our work aims at recognizing components which can be extracted from metaheuristic methods and re-used in different contexts. In particular we focus on the possibility of porting metaheuristic elements to constraint programming based environments, as constraint programming is able to deal with feasibility issues of optimization problems in a very effective manner. Moreover, CP offers a general paradigm which allows to easily model any type of problem and solve it with a problem-independent framework, differently from local search and metaheuristic methods which are highly problem specific. In this work we describe the implementation of the Local Branching framework, originally developed for Mixed Integer Programming, in a CP-based environment. Constraint programming specific features are used to ease the search process, still mantaining an absolute generality of the approach. We also propose a search strategy called Sliced Neighborhood Search, SNS, that iteratively explores slices of large neighborhoods of an incumbent solution by performing CP-based tree search and encloses concepts from metaheuristic techniques. SNS can be used as a stand alone search strategy, but it can alternatively be embedded in existing strategies as intensification and diversification mechanism. In particular we show its integration within the CP-based local branching. We provide an extensive experimental evaluation of the proposed approaches on instances of the Asymmetric Traveling Salesman Problem and of the Asymmetric Traveling Salesman Problem with Time Windows. The proposed approaches achieve good results on practical size problem, thus demonstrating the benefit of integrating metaheuristic concepts in CP-based frameworks.

Development and testing of an asymmetric capacitor with a nickel-carbon foam positive electrode

Electrochemical capacitors (ECs), also known as supercapacitors or ultracapacitors, are energy storage devices with properties between batteries and conventional capacitors. EC have evolved through several generations. The trend in EC is to combine a double-layer electrode with a battery-type electrode in an asymmetric capacitor configuration. The double-layer electrode is usually an activated carbon (AC) since it has high surface area, good conductivity, and relatively low cost. The battery-type electrode usually consists of PbO2 or Ni(OH)2. In this research, a graphitic carbon foam was impregnated with Co-substituted Ni(OH)2 using electrochemical deposition to serve as the positive electrode in the asymmetric capacitor. The purpose was to reduce the cost and weight of the ECs while maintaining or increasing capacitance and gravimetric energy storage density. The XRD result indicated that the nickel-carbon foam electrode was a typical α-Ni(OH)2. The specific capacitance of the nickel-carbon foam electrode was 2641 F/g at 5 mA/cm2, higher than the previously reported value of 2080 F/g for a 7.5% Al-substituted α-Ni(OH)2 electrode. Three different ACs (RP-20, YP-50F, and Ketjenblack EC-600JD) were evaluated through their morphology and electrochemical performance to determine their suitability for use in ECs. The study indicated that YP-50F demonstrated the better overall performance because of the combination of micropore and mesopore structures. Therefore, YP-50F was chosen to combine with the nickel-carbon foam electrode for further evaluation. Six cells with different mass ratios of negative to positive active mass were fabricated to study the electrochemical performance. Among the different mass ratios, the asymmetric capacitor with the mass ratio of 3.71 gave the highest specific energy and specific power, 24.5 W.h/kg and 498 W/kg, respectively.

Performance evaluation of a novel asymmetric capacitor using a light-weight, carbon foam supported nickel electrode

Electrochemical capacitors have been an important development in recent years in the field of energy storage. Capacitors can be developed by utilizing either double layer capacitance at the electrode/solution interfaces alone or in combination with a battery electrode associated with a faradic redox process in one electrode. An asymmetric capacitor consisting of electrochemically deposited nickel hydroxide, supported on carbon foam as a positive electrode and carbon sheet as a negative electrode has been successfully assembled and cycled. One objective of this study has been to demonstrate the viability of the nickel carbon foam positive electrode, especially in terms of cycle life. Electrochemical characterization shows stable, high cycle performance in 26 wt. % KOH electrolyte with a maximum energy density of 4.1 Wh/Kg and a relaxation time constant of 6.24 s. This cell has demonstrated high cycle life, 14,500 cycles, with efficiency better than 98%. In addition, the cell failure mechanism and self-discharge behavior of the aforesaid capacitor are analyzed.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Two-dimensional assembly and local redox-activity of molecular hybrid structures in an electrochemical environment

The self-assembly and redox-properties of two viologen derivatives, N-hexyl-N-(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-H) and N,N-bis(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-SH), immobilized on Au(111)-(1x1) macro-electrodes were investigated by cyclic voltammetry, surface enhanced infrared spectroscopy (SEIRAS) and in situ scanning tunneling microscopy (STM). Depending on the assembly conditions one could distinguish three different types of adlayers for both viologens: a low coverage disordered and an ordered striped phase of flat oriented molecules as well as a high coverage monolayer composed of tilted viologen moieties. Both molecules, HS-6V6-H and HS-6V6-SH, were successfully immobilized on Au(poly) nano-electrodes, which gave a well-defined redox-response in the lower pA–current range. An in situ STM configuration was employed to explore electron transport properties of single molecule junctions Au(T)|HS-6V6-SH(HS-6V6-H)|Au(S). The observed sigmoidal potential dependence, measured at variable substrate potential ES and at constant bias voltage (ET–ES), was attributed to electronic structure changes of the viologen moiety during the one-electron reduction/re-oxidation process V2+ V+. Tunneling experiments in asymmetric, STM-based junctions Au(T)-S-6V6-H|Au(S) revealed current (iT)–voltage (ET) curves with a maximum located at the equilibrium potential of the redox-process V2+ V+. The experimental iT–ET characteristics of the HS-6V6-H–modified tunneling junction were tentatively attributed to a sequential two-step electron transfer mechanism.

Relevance of porosity and surface chemistry of superactivated carbons in capacitors

We show, through some examples, that chemical activation by alkaline hydroxides permits the preparation of activated carbons with tailored pore volume, pore size distribution, pore structure and surface chemistry, which are useful for their application as electrodes in supercapacitors. Examples are presented discussing the importance of each of these properties on the double layer capacitance, on the kinetics of the electric double-layer charge-discharge process and on the pseudo-capacitative contribution from the surface functional groups or the addition of a conducting polymer.

Carbon–carbon asymmetric aqueous capacitor by pseudocapacitive positive and stable negative electrodes

An asymmetric aqueous capacitor was constructed by employing zeolite-templated carbon (ZTC) as a pseudocapacitive positive electrode and KOH-activated carbon as a stable negative electrode. The asymmetric capacitor can be operated with the working voltage of 1.4 V, and exhibits an energy density that is comparable to those of conventional capacitors utilizing organic electrolytes, thanks to the large pseudocapacitance of ZTC. Despite relatively thick electrode (0.2 mm) configuration, the asymmetric capacitor could be well operated under a current density of 500 mA g −1.

Reverse Geometry Hybrid Contact Lens Fitting in a Case of Donor-Host Misalignment after Keratoplasty

Purpose: To report the successful outcome obtained after fitting a new hybrid contact lens in a cornea with an area of donor-host misalignment and significant levels of irregular astigmatism after penetrating keratoplasty (PKP). Materials and methods: A 41-year-old female with bilateral asymmetric keratoconus underwent PKP in her left eye due to the advanced status of the disease. One year after surgery, the patient referred a poor visual acuity and quality in this eye. The fitting of different types of rigid gas permeable contact lenses was performed, but with an unsuccessful outcome due to contact lens stability problems and uncomfortable wear. Scheimpflug imaging evaluation revealed that a donor-host misalignment was present at the nasal area. Contact lens fitting with a reverse geometry hybrid contact lens (Clearkone, SynergEyes Carlsbad) was then fitted. Visual, refractive, and ocular aberrometric outcomes were evaluated during a 1-year period after the fitting. Results: Uncorrected distance visual acuity improved from a prefitting value of 20/200 to a best corrected postfitting value of 20/20. Prefitting manifest refraction was +5.00 sphere and -5.50 cylinder at 75°, with a corrected distance visual acuity of 20/30. Higher order root mean square (RMS) for a 5 mm pupil changed from a prefitting value of 6.83 µm to a postfitting value of 1.57 µm (5 mm pupil). The contact lens wearing was referred as comfortable, with no anterior segment alterations. Conclusion: The SynergEyes Clearkone contact lens seems to be another potentially useful option for the visual rehabilitation after PKP, especially in cases of donor-host misalignment.

Optimised phase disposition pulse-width modulation strategy for hybrid-clamped multilevel inverters using switching state sequences

This study describes an optimised modulation strategy based on switching state sequences for the hybrid-clamped multilevel converter. Two key control variables defined as 'phase shift angle' and 'switching state change' for a five-level hybrid-clamped inverter are proposed to improve all switches' operation, and by changing their values, different control methods can be obtained for modulation optimisation purposes. Two example methods can solve the voltage imbalance problem of the dc-link capacitors and furthermore avoid two switches' simultaneous switching transitions and improve the inverter's performance as compared with the traditional phase disposition pulse-width modulation strategy. A 6 kW prototype inverter is developed and a range of simulation and experiments are carried out for validation. It is found that simulation and experimental results are in a good agreement and the proposed modulation strategy is verified in terms of low-order harmonic reduction.

Efficiency and power density improvement of grid-connected hybrid renewable energy systems utilizing high frequency-based power converters

High efficiency of power converters placed between renewable energy sources and the utility grid is required to maximize the utilization of these sources. Power quality is another aspect that requires large passive elements (inductors, capacitors) to be placed between these sources and the grid. The main objective is to develop higher-level high frequency-based power converter system (HFPCS) that optimizes the use of hybrid renewable power injected into the power grid. The HFPCS provides high efficiency, reduced size of passive components, higher levels of power density realization, lower harmonic distortion, higher reliability, and lower cost. The dynamic modeling for each part in this system is developed, simulated and tested. The steady-state performance of the grid-connected hybrid power system with battery storage is analyzed. Various types of simulations were performed and a number of algorithms were developed and tested to verify the effectiveness of the power conversion topologies. A modified hysteresis-control strategy for the rectifier and the battery charging/discharging system was developed and implemented. A voltage oriented control (VOC) scheme was developed to control the energy injected into the grid. The developed HFPCS was compared experimentally with other currently available power converters. The developed HFPCS was employed inside a microgrid system infrastructure, connecting it to the power grid to verify its power transfer capabilities and grid connectivity. Grid connectivity tests verified these power transfer capabilities of the developed converter in addition to its ability of serving the load in a shared manner. In order to investigate the performance of the developed system, an experimental setup for the HF-based hybrid generation system was constructed. We designed a board containing a digital signal processor chip on which the developed control system was embedded. The board was fabricated and experimentally tested. The system's high precision requirements were verified. Each component of the system was built and tested separately, and then the whole system was connected and tested. The simulation and experimental results confirm the effectiveness of the developed converter system for grid-connected hybrid renewable energy systems as well as for hybrid electric vehicles and other industrial applications.

Hybrid Power System Intelligent Operation and Protection Involving Plug-in Electric Vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.

Growth, Characterization, and Properties of Hybrid Graphene-Carbon Nanotube Films and Related Carbon Nanostructures

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Hybrid power system intelligent operation and protection involving plug-in electric vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. ^ The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. ^ The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.^

Modeling of Electric Hybrid Vehicles based on Innovative Energy Storage Technologies for Super Sports Cars Applications

Today, the contribution of the transportation sector on greenhouse gases is evident. The fast consumption of fossil fuels and its impact on the environment has given a strong impetus to the development of vehicles with better fuel economy. Hybrid electric vehicles fit into this context with different targets, starting from the reduction of emissions and fuel consumption, but also for performance and comfort enhancement. Vehicles exist with various missions; super sport cars usually aim to reach peak performance and to guarantee a great driving experience to the driver, but great attention must also be paid to fuel consumption. According to the vehicle mission, hybrid vehicles can differ in the powertrain configuration and the choice of the energy storage system. Lamborghini has recently invested in the development of hybrid super sport cars, due to performance and comfort reasons, with the possibility to reduce fuel consumption. This research activity has been conducted as a joint collaboration between the University of Bologna and the sportscar manufacturer, to analyze the impact of innovative energy storage solutions on the hybrid vehicle performance. Capacitors have been studied and modeled to analyze the pros and cons of such solution with respect to batteries. To this aim, a full simulation environment has been developed and validated to provide a concept design tool capable of precise results and able to foresee the longitudinal performance on regulated emission cycles and real driving conditions, with a focus on fuel consumption. In addition, the target of the research activity is to deepen the study of hybrid electric super sports cars in the concept development phase, focusing on defining the control strategies and the energy storage system’s technology that best suits the needs of the vehicles. This dissertation covers the key steps that have been carried out in the research project.