Identification of stock units of Mullus barbatus (Linnaeus, 1758) in the Italian seas: development of genomic 2b-RAD markers and biological variation analysis.

This thesis is settled within the STOCKMAPPING project, which represents one of the studies that were developed in the framework of RITMARE Flagship project. The main goals of STOCKMAPPING were the creation of a genomic mapping for stocks of demersal target species and the assembling of a database of population genomic, in order to identify stocks and stocks boundaries. The thesis focuses on three main objectives representing the core for the initial assessment of the methodologies and structure that would be applied to the entire STOCKMAPPING project: individuation of an analytical design to identify and locate stocks and stocks boundaries of Mullus barbatus, application of a multidisciplinary approach to validate biological methods and an initial assessment and improvement for the genotyping by sequencing technique utilized (2b-RAD). The first step is the individuation of an analytical design that has to take in to account the biological characteristics of red mullet and being representative for STOCKMAPPING commitments. In this framework a reduction and selection steps was needed due to budget reduction. Sampling areas were ranked according the individuation of four priorities. To guarantee a multidisciplinary approach the biological data associated to the collected samples were used to investigate differences between sampling areas and GSAs. Genomic techniques were applied to red mullet for the first time so an initial assessment of molecular protocols for DNA extraction and 2b-RAD processing were needed. At the end 192 good quality DNAs have been extracted and eight samples have been processed with 2b-RAD. Utilizing the software Stacks for sequences analyses a great number of SNPs markers among the eight samples have been identified. Several tests have been performed changing the main parameter of the Stacks pipeline in order to identify the most explicative and functional sets of parameters.

Stock boundaries of Parapenaeus longirostris (Lucas, 1846) populations in the Italian seas: Development of genomic 2b-RAD markers and biological variation analysis.

This thesis is developed in the contest of Ritmare project WP1, which main objective is the development of a sustainable fishery through the identification of populations boundaries in commercially important species in Italian Seas. Three main objectives are discussed in order to help reach the main purpose of identification of stock boundaries in Parapenaeus longirostris: 1 -Development of a representative sampling design for Italian seas; 2 -Evaluation of 2b-RAD protocol; 3 -Investigation of populations through biological data analysis. First of all we defined and accomplished a sampling design which properly represents all Italian seas. Then we used information and data about nursery areas distribution, abundance of populations and importance of P. longirostris in local fishery, to develop an experimental design that prioritize the most important areas to maximize the results with actual project funds. We introduced for the first time the use of 2b-RAD on this species, a genotyping method based on sequencing the uniform fragments produced by type IIB restriction endonucleases. Thanks to this method we were able to move from genetics to the more complex genomics. In order to proceed with 2b-RAD we performed several tests to identify the best DNA extraction kit and protocol and finally we were able to extract 192 high quality DNA extracts ready to be processed. We tested 2b-RAD with five samples and after high-throughput sequencing of libraries we used the software “Stacks” to analyze the sequences. We obtained positive results identifying a great number of SNP markers among the five samples. To guarantee a multidisciplinary approach we used the biological data associated to the collected samples to investigate differences between geographical samples. Such approach assures continuity with other project, for instance STOCKMED, which utilize a combination of molecular and biological analysis as well.

Ultra-Low Power and Non-intrusive Wireless Monitoring for Smart Buildings

Wireless Sensor Networks (WSNs) offer a new solution for distributed monitoring, processing and communication. First of all, the stringent energy constraints to which sensing nodes are typically subjected. WSNs are often battery powered and placed where it is not possible to recharge or replace batteries. Energy can be harvested from the external environment but it is a limited resource that must be used efficiently. Energy efficiency is a key requirement for a credible WSNs design. From the power source's perspective, aggressive energy management techniques remain the most effective way to prolong the lifetime of a WSN. A new adaptive algorithm will be presented, which minimizes the consumption of wireless sensor nodes in sleep mode, when the power source has to be regulated using DC-DC converters. Another important aspect addressed is the time synchronisation in WSNs. WSNs are used for real-world applications where physical time plays an important role. An innovative low-overhead synchronisation approach will be presented, based on a Temperature Compensation Algorithm (TCA). The last aspect addressed is related to self-powered WSNs with Energy Harvesting (EH) solutions. Wireless sensor nodes with EH require some form of energy storage, which enables systems to continue operating during periods of insufficient environmental energy. However, the size of the energy storage strongly restricts the use of WSNs with EH in real-world applications. A new approach will be presented, which enables computation to be sustained during intermittent power supply. The discussed approaches will be used for real-world WSN applications. The first presented scenario is related to the experience gathered during an European Project (3ENCULT Project), regarding the design and implementation of an innovative network for monitoring heritage buildings. The second scenario is related to the experience with Telecom Italia, regarding the design of smart energy meters for monitoring the usage of household's appliances.

Development of a microgrid with renewable energy sources and electrochemical storage system integration

Beside the traditional paradigm of "centralized" power generation, a new concept of "distributed" generation is emerging, in which the same user becomes pro-sumer. During this transition, the Energy Storage Systems (ESS) can provide multiple services and features, which are necessary for a higher quality of the electrical system and for the optimization of non-programmable Renewable Energy Source (RES) power plants. A ESS prototype was designed, developed and integrated into a renewable energy production system in order to create a smart microgrid and consequently manage in an efficient and intelligent way the energy flow as a function of the power demand. The produced energy can be introduced into the grid, supplied to the load directly or stored in batteries. The microgrid is composed by a 7 kW wind turbine (WT) and a 17 kW photovoltaic (PV) plant are part of. The load is given by electrical utilities of a cheese factory. The ESS is composed by the following two subsystems, a Battery Energy Storage System (BESS) and a Power Control System (PCS). With the aim of sizing the ESS, a Remote Grid Analyzer (RGA) was designed, realized and connected to the wind turbine, photovoltaic plant and the switchboard. Afterwards, different electrochemical storage technologies were studied, and taking into account the load requirements present in the cheese factory, the most suitable solution was identified in the high temperatures salt Na-NiCl2 battery technology. The data acquisition from all electrical utilities provided a detailed load analysis, indicating the optimal storage size equal to a 30 kW battery system. Moreover a container was designed and realized to locate the BESS and PCS, meeting all the requirements and safety conditions. Furthermore, a smart control system was implemented in order to handle the different applications of the ESS, such as peak shaving or load levelling.

Phenothiazine based polymers for energy and data storage application

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung von Polymeren mit redox-funktionalen Phenothiazin-Seitenketten. Phenothiazin und seine Derivate sind kleine Redoxeinheiten, deren reversibles Redoxverhalten mit electrochromen Eigenschaften verbunden ist. Das besondere an Phenothiazine ist die Bildung von stabilen Radikalkationen im oxidierten Zustand. Daher können Phenothiazine als bistabile Moleküle agieren und zwischen zwei stabilen Redoxzuständen wechseln. Dieser Schaltprozess geht gleichzeitig mit einer Farbveränderung an her.rnrnIm Rahmen dieser Arbeit wird die Synthese neuartiger Phenothiazin-Polymere mittels radikalischer Polymerisation beschrieben. Phenothiazin-Derivate wurden kovalent an aliphatischen und aromatischen Polymerketten gebunden. Dies erfolgte über zwei unterschiedlichen synthetischen Routen. Die erste Route beinhaltet den Einsatz von Vinyl-Monomeren mit Phenothiazin Funktionalität zur direkten Polymerisation. Die zweite Route verwendet Amin modifizierte Phenothiazin-Derivate zur Funktionalisierung von Polymeren mit Aktivester-Seitenketten in einer polymeranalogen Reaktion. rnrnPolymere mit redox-funktionalen Phenothiazin-Seitenketten sind aufgrund ihrer Elektron-Donor-Eigenschaften geeignete Kandidaten für die Verwendung als Kathodenmaterialien. Zur Überprüfung ihrer Eignung wurden Phenothiazin-Polymere als Elektrodenmaterialien in Lithium-Batteriezellen eingesetzt. Die verwendeten Polymere wiesen gute Kapazitätswerte von circa 50-90 Ah/kg sowie schnelle Aufladezeiten in der Batteriezelle auf. Besonders die Aufladezeiten sind 5-10 mal höher als konventionelle Lithium-Batterien. Im Hinblick auf Anzahl der Lade- und Entladezyklen, erzielten die Polymere gute Werte in den Langzeit-Stabilitätstests. Insgesamt überstehen die Polymere 500 Ladezyklen mit geringen Veränderungen der Anfangswerte bezüglich Ladezeiten und -kapazitäten. Die Langzeit-Stabilität hängt unmittelbar mit der Radikalstabilität zusammen. Eine Stabilisierung der Radikalkationen gelang durch die Verlängerung der Seitenkette am Stickstoffatom des Phenothiazins und der Polymerhauptkette. Eine derartige Alkyl-Substitution erhöht die Radikalstabilität durch verstärkte Wechselwirkung mit dem aromatischen Ring und verbessert somit die Batterieleistung hinsichtlich der Stabilität gegenüber Lade- und Entladezyklen. rnrnDes Weiteren wurde die praktische Anwendung von bistabilen Phenothiazin-Polymeren als Speichermedium für hohe Datendichten untersucht. Dazu wurden dünne Filme des Polymers auf leitfähigen Substraten elektrochemisch oxidiert. Die elektrochemische Oxidation erfolgte mittels Rasterkraftmikroskopie in Kombination mit leitfähigen Mikroskopspitzen. Mittels dieser Technik gelang es, die Oberfläche des Polymers im nanoskaligen Bereich zu oxidieren und somit die lokale Leitfähigkeit zu verändern. Damit konnten unterschiedlich große Muster lithographisch beschrieben und aufgrund der Veränderung ihrer Leitfähigkeit detektiert werden. Der Schreibprozess führte nur zu einer Veränderung der lokalen Leitfähigkeit ohne die topographische Beschaffenheit des Polymerfilms zu beeinflussen. Außerdem erwiesen sich die Muster als besonders stabil sowohl mechanisch als auch über die Zeit.rnrnZum Schluss wurden neue Synthesestrategien entwickelt um mechanisch stabile als auch redox-funktionale Oberflächen zu produzieren. Mit Hilfe der oberflächen-initiierten Atomtransfer-Radikalpolymerisation wurden gepfropfte Polymerbürsten mit redox-funktionalen Phenothiazin-Seitenketten hergestellt und mittels Röntgenmethoden und Rasterkraftmikroskopie analysiert. Eine der Synthesestrategien geht von gepfropften Aktivesterbürsten aus, die anschließend in einem nachfolgenden Schritt mit redox-funktionalen Gruppen modifiziert werden können. Diese Vorgehensweise ist besonders vielversprechend und erlaubt es unterschiedliche funktionelle Gruppen an den Aktivesterbürsten zu verankern. Damit können durch Verwendung von vernetzenden Gruppen neben den Redoxeigenschaften, die mechanische Stabilität solcher Polymerfilme optimiert werden. rn rn

Design and Prototyping High Endurance Multi-Rotor

The topic of this thesis fo cus on the preliminary design and the p erformance analysis of a multirotor platform. A multirotor is an electrically p owered Vertical Take Off (VTOL) machine with more than two rotors that lift and control the platform. Multirotor are agile, compact and robust, making them ideally suited for b oth indo or and outdo or application especially to carry-on several sensors like electro optical multisp ectral sensor or gas sensor. The main disadvantage is the limited endurance due to heavy Li-Po batteries and high disk loading through the use of different small prop ellers. At the same time, the design of the multirotor do es not follow any engineering principle but it follow the ideas of amateurs’ builder. An adaptation of the classic airplane design theory for the preliminary design is implemented to fill the gap and detailed study of the endurance is p erformed to define the right way to make this kind of VTOL platforms.

Controllable assembly of graphene hybrid materials and their application in energy storage and conversion

Hybrid Elektrodenmaterialien (HEM) sind der Schlüssel zu grundlegenden Fortschritten in der Energiespeicherung und Systemen zur Energieumwandlung, einschließlich Lithium-Ionen-Batterien (LiBs), Superkondensatoren (SCs) und Brennstoffzellen (FCs). Die faszinierenden Eigenschaften von Graphen machen es zu einem guten Ausgangsmaterial für die Darstellung von HEM. Jedoch scheitern traditionelle Verfahren zur Herstellung von Graphen-HEM (GHEM) scheitern häufig an der fehlenden Kontrolle über die Morphologie und deren Einheitlichkeit, was zu unzureichenden Grenzflächenwechselwirkungen und einer mangelhaften Leistung des Materials führt. Diese Arbeit konzentriert sich auf die Herstellung von GHEM über kontrollierte Darstellungsmethoden und befasst sich mit der Nutzung von definierten GHEM für die Energiespeicherung und -umwandlung. Die große Volumenausdehnung bildet den Hauptnachteil der künftigen Lithium-Speicher-Materialien. Als erstes wird ein dreidimensionaler Graphen Schaumhybrid zur Stärkung der Grundstruktur und zur Verbesserung der elektrochemischen Leistung des Fe3O4 Anodenmaterials dargestellt. Der Einsatz von Graphenschalen und Graphennetzen realisiert dabei einen doppelten Schutz gegen die Volumenschwankung des Fe3O4 bei dem elektrochemischen Prozess. Die Leistung der SCs und der FCs hängt von der Porenstruktur und der zugänglichen Oberfläche, beziehungsweise den katalytischen Stellen der Elektrodenmaterialien ab. Wir zeigen, dass die Steuerung der Porosität über Graphen-basierte Kohlenstoffnanoschichten (HPCN) die zugängliche Oberfläche und den Ionentransport/Ladungsspeicher für SCs-Anwendungen erhöht. Desweiteren wurden Stickstoff dotierte Kohlenstoffnanoschichten (NDCN) für die kathodische Sauerstoffreduktion (ORR) hergestellt. Eine maßgeschnittene Mesoporosität verbunden mit Heteroatom Doping (Stickstoff) fördert die Exposition der aktiven Zentren und die ORR-Leistung der metallfreien Katalysatoren. Hochwertiges elektrochemisch exfoliiertes Graphen (EEG) ist ein vielversprechender Kandidat für die Darstellung von GHEM. Allerdings ist die kontrollierte Darstellung von EEG-Hybriden weiterhin eine große Herausforderung. Zu guter Letzt wird eine Bottom-up-Strategie für die Darstellung von EEG Schichten mit einer Reihe von funktionellen Nanopartikeln (Si, Fe3O4 und Pt NPs) vorgestellt. Diese Arbeit zeigt einen vielversprechenden Weg für die wirtschaftliche Synthese von EEG und EEG-basierten Materialien.

Synthesis, characterization and formulation of a cathode active material: Copper nitroprusside

Nowadays, rechargeable Li-ion batteries play an important role in portable consumer devices. Formulation of such batteries is improvable by researching new cathodic materials that present higher performances of cyclability and negligible efficiency loss over cycles. Goal of this work was to investigate a new cathodic material, copper nitroprusside, which presents a porous 3D framework. Synthesis was carried out by a low-cost and scalable co-precipitation method. Subsequently, the product was characterized by means of different techniques, such as TGA, XRF, CHN elemental analysis, XRD, Mössbauer spectroscopy and cyclic voltammetry. Electrochemical tests were finally performed both in coin cells and by using in situ cells: on one hand, coin cells allowed different formulations to be easily tested, on the other operando cycling led a deeper insight to insertion process and both chemical and physical changes. Results of several tests highlighted a non-reversible electrochemical behavior of the material and a rapid capacity fading over time. Moreover, operando techniques report that amorphisation occurs during the discharge.

The binding mode of side chain- and C3-modified epothilones to tubulin

The tubulin-binding mode of C3- and C15-modified analogues of epothilone A (Epo A) was determined by NMR spectroscopy and computational methods and compared with the existing structural models of tubulin-bound natural Epo A. Only minor differences were observed in the conformation of the macrocycle between Epo A and the C3-modified analogues investigated. In particular, 3-deoxy- (compound 2) and 3-deoxy-2,3-didehydro-Epo A (3) were found to adopt similar conformations in the tubulin-binding cleft as Epo A, thus indicating that the 3-OH group is not essential for epothilones to assume their bioactive conformation. None of the available models of the tubulin-epothilone complex is able to fully recapitulate the differences in tubulin-polymerizing activity and microtubule-binding affinity between C20-modified epothilones 6 (C20-propyl), 7 (C20-butyl), and 8 (C20-hydroxypropyl). Based on the results of transferred NOE experiments in the presence of tubulin, the isomeric C15 quinoline-based Epo B analogues 4 and 5 show very similar orientations of the side chain, irrespective of the position of the nitrogen atom in the quinoline ring. The quinoline side chain stacks on the imidazole moiety of beta-His227 with equal efficiency in both cases, thus suggesting that the aromatic side chain moiety in epothilones contributes to tubulin binding through strong van der Waals interactions with the protein rather than hydrogen bonding involving the heteroaromatic nitrogen atom. These conclusions are in line with existing tubulin polymerization and microtubule-binding data for 4, 5, and Epo B.

Assessing Commonality and Differentiation for Packaging-Family Planning with Application to Medication Labels

This thesis presents a metric for assessing the commonality and differentiation of packaging-family planning with application to medical labels along with supporting background research and findings. Consumable products such as medications rely on the package or label to represent the contents. Package confusion has been widely recognized as a major problem for both over-the-counter and pharmacy-dispensed medications with potentially lethal consequences. It is critical to identify a medication as a member of a product family and differentiate its contributing elements based on visual features on the package or label to avoid consumer confusion and reduce dispensing errors. Indices that indicate degrees of commonality and differentiation of features in consumer products such as batteries, light bulbs, handles, etc for platforms have been shown to benefit development of engineered product families [6]. It is possible to take a similar approach for visual features in packaging such as typography, shape/form, imagery and color to benefit packaging-family development. This thesis establishes a commonality differentiation index for prominence of visual features on over-the-counter and pharmacy-dispensed medications based on occurrence, size, and location of features. It provides a quantitative measure to assist package designers in evaluating alternatives to satisfy strategic goals and improve safety. The index is demonstrated with several medications that have been identified by the Institute for Safe Medication Practice as commonly confused.

Crystal structure of the Leishmania major phosphodiesterase LmjPDEB1 and insight into the design of the parasite-selective inhibitors

Human leishmaniasis is a major public health problem in many countries, but chemotherapy is in an unsatisfactory state. Leishmania major phosphodiesterases (LmjPDEs) have been shown to play important roles in cell proliferation and apoptosis of the parasite. Thus LmjPDE inhibitors may potentially represent a novel class of drugs for the treatment of leishmaniasis. Reported here are the kinetic characterization of the LmjPDEB1 catalytic domain and its crystal structure as a complex with 3-isobutyl-1-methylxanthine (IBMX) at 1.55 A resolution. The structure of LmjPDEB1 is similar to that of human PDEs. IBMX stacks against the conserved phenylalanine and forms a hydrogen bond with the invariant glutamine, in a pattern common to most inhibitors bound to human PDEs. However, an extensive structural comparison reveals subtle, but significant differences between the active sites of LmjPDEB1 and human PDEs. In addition, a pocket next to the inhibitor binding site is found to be unique to LmjPDEB1. This pocket is isolated by two gating residues in human PDE families, but constitutes a natural expansion of the inhibitor binding pocket in LmjPDEB1. The structure particularity might be useful for the development of parasite-selective inhibitors for the treatment of leishmaniasis.

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.

Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

RF-sputter fabrication of magnetic garnet thin films and simulation modeling for 1-D magnetic photonic crystal waveguide devices

One dimensional magnetic photonic crystals (1D-MPC) are promising structures for integrated optical isolator applications. Rare earth substituted garnet thin films with proper Faraday rotation are required to fabricate planar 1D-MPCs. In this thesis, flat-top response 1D-MPC was proposed and spectral responses and Faraday rotation were modeled. Bismuth substituted iron garnet films were fabricated by RF magnetron sputtering and structures, compositions, birefringence and magnetooptical properties were studied. Double layer structures for single mode propagation were also fabricated by sputtering for the first time. Multilayer stacks with multiple defects (phase shift) composed of Ce-YIG and GGG quarter-wave plates were simulated by the transfer matrix method. The transmission and Faraday rotation characteristics were theoretically studied. It is found that flat-top response, with 100% transmission and near 45o rotation is achievable by adjusting the inter-defect spacing, for film structures as thin as 30 to 35 μm. This is better than 3-fold reduction in length compared to the best Ce-YIG films for comparable rotations, thus allows a considerable reduction in size in manufactured optical isolators. Transmission bands as wide as 7nm were predicted, which is considerable improvement over 2 defects structure. Effect of repetition number and ratio factor on transmission and Faraday rotation ripple factors for the case of 3 and 4 defects structure has been discussed. Diffraction across the structure corresponds to a longer optical path length. Thus the use of guided optics is required to minimize the insertion losses in integrated devices. This part is discussed in chapter 2 in this thesis. Bismuth substituted iron garnet thin films were prepared by RF magnetron sputtering. We investigated or measured the deposition parameters optimization, crystallinity, surface morphologies, composition, magnetic and magnetooptical properties. A very high crystalline quality garnet film with smooth surface has been heteroepitaxially grown on (111) GGG substrate for films less than 1μm. Dual layer structures with two distinct XRD peaks (within a single sputtered film) start to develop when films exceed this thickness. The development of dual layer structure was explained by compositional gradient across film thickness, rather than strain gradient proposed by other authors. Lower DC self bias or higher substrate temperature is found to help to delay the appearance of the 2nd layer. The deposited films show in-plane magnetization, which is advantageous for waveguide devices application. Propagation losses of fabricated waveguides can be decreased by annealing in an oxygen atmosphere from 25dB/cm to 10dB/cm. The Faraday rotation at λ=1.55μm were also measured for the waveguides. FR is small (10° for a 3mm long waveguide), due to the presence of linear birefringence. This part is covered in chapter 4. We also investigated the elimination of linear birefringence by thickness tuning method for our sputtered films. We examined the compressively and tensilely strained films and analyze the photoelastic response of the sputter deposited garnet films. It has been found that the net birefringence can be eliminated under planar compressive strain conditions by sputtering. Bi-layer GGG on garnet thin film yields a reduced birefringence. Temperature control during the sputter deposition of GGG cover layer is critical and strongly influences the magnetization and birefringence level in the waveguide. High temperature deposition lowers the magnetization and increases the linear birefringence in the garnet films. Double layer single mode structures fabricated by sputtering were also studied. The double layer, which shows an in-plane magnetization, has an increased RMS roughness upon upper layer deposition. The single mode characteristic was confirmed by prism coupler measurement. This part is discussed in chapter 5.

PROPERTIES AND STRUCTURES OF Li-N BASED HYDROGEN STORAGE MATERIALS

Traditional transportation fuel, petroleum, is limited and nonrenewable, and it also causes pollutions. Hydrogen is considered one of the best alternative fuels for transportation. The key issue for using hydrogen as fuel for transportation is hydrogen storage. Lithium nitride (Li3N) is an important material which can be used for hydrogen storage. The decompositions of lithium amide (LiNH2) and lithium imide (Li2NH) are important steps for hydrogen storage in Li3N. The effect of anions (e.g. Cl-) on the decomposition of LiNH2 has never been studied. Li3N can react with LiBr to form lithium nitride bromide Li13N4Br which has been proposed as solid electrolyte for batteries. The decompositions of LiNH2 and Li2NH with and without promoter were investigated by using temperature programmed decomposition (TPD) and X-ray diffraction (XRD) techniques. It was found that the decomposition of LiNH2 produced Li2NH and NH3 via two steps: LiNH2 into a stable intermediate species (Li1.5NH1.5) and then into Li2NH. The decomposition of Li2NH produced Li, N2 and H2 via two steps: Li2NH into an intermediate species --- Li4NH and then into Li. The kinetic analysis of Li2NH decomposition showed that the activation energies are 533.6 kJ/mol for the first step and 754.2 kJ/mol for the second step. Furthermore, XRD demonstrated that the Li4NH, which was generated in the decomposition of Li2NH, formed a solid solution with Li2NH. In the solid solution, Li4NH possesses a similar cubic structure as Li2NH. The lattice parameter of the cubic Li4NH is 0.5033nm. The decompositions of LiNH2 and Li2NH can be promoted by chloride ion (Cl-). The introduction of Cl- into LiNH2 resulted in the generation of a new NH3 peak at low temperature of 250 °C besides the original NH3 peak at 330 °C in TPD profiles. Furthermore, Cl- can decrease the decomposition temperature of Li2NH by about 110 °C. The degradation of Li3N was systematically investigated with techniques of XRD, Fourier transform infrared (FT-IR) spectroscopy, and UV-visible spectroscopy. It was found that O2 could not affect Li3N at room temperature. However, H2O in air can cause the degradation of Li3N due to the reaction between H2O and Li3N to LiOH. The produced LiOH can further react with CO2 in air to Li2CO3 at room temperature. Furthermore, it was revealed that Alfa-Li3N is more stable in air than Beta-Li3N. The chemical stability of Li13N4Br in air has been investigated by XRD, TPD-MS, and UV-vis absorption as a function of time. The aging process finally leads to the degradation of the Li13N4Br into Li2CO3, lithium bromite (LiBrO2) and the release of gaseous NH3. The reaction order n = 2.43 is the best fitting for the Li13N4Br degradation in air reaction. Li13N4Br energy gap was calculated to be 2.61 eV.