High pressure and low temperature study of ammonia borane and lithium amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the "hydrogen economy" faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH 3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. ^ Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. ^ Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn2 1 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.^

Low Temperature Sintering Semiconductive Barium Strontium Titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1,0.2,0.3,0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ñmax/ñmin ratio (ñmax is the highest resistivity at temperatures above Tc, ñmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ñmax and ñmin. Also, ñmax/ñmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ñmax/ñmin ratio value.

Design and analysis of micro-channel heat-exchanger embedded in Low Temperature Co-fire Ceramic (LTCC)

Increased device density, switching speeds of integrated circuits and decrease in package size is placing new demands for high power thermal-management. The convectional method of forced air cooling with passive heat sink can handle heat fluxes up-to 3-5W/cm2; however current microprocessors are operating at levels of 100W/cm2, This demands the usage of novel thermal-management systems. In this work, water-cooling systems with active heat sink are embedded in the substrate. The research involved fabricating LTCC substrates of various configurations - an open-duct substrate, the second with thermal vias and the third with thermal vias and free-standing metal columns and metal foil. Thermal testing was performed experimentally and these results are compared with CFD results. An overall thermal resistance for the base substrate is demonstrated to be 3.4oC/W-cm2. Addition of thermal vias reduces the effective resistance of the system by 7times and further addition of free standing columns reduced it by 20times.

Controllo ultra-low power di un modulatore back-scattering per applicazioni di localizzazione in sistemi RFID

In questa tesi viene elaborata un'applicazione ultra-low power (ULP) basata su microcontrollore, per implementare la procedura di controllo di diversi circuiti di un tag RFID. Il tag preso in considerazione è pensato per lavorare in assenza di batteria, da cui la necessita' di ridurre i consumi di potenza. La sua attivazione deve essere inoltre comandata attraverso un'architettura Wake up Radio (WuR), in cui un segnale di controllo radio indirizza e attiva il circuito. Nello specifico, la rete di decodifica dell'indirizzo è stata realizzata mediante il modulo di comunicazione seriale del microcontrollore. Nel Capitolo 1 verrà introdotto il tema dell'Energy Harvesting. Nel Capitolo 2 verrà illustrata l'architettura del sistema nel suo complesso. Nel Capitolo 3 verrà spiegato dettagliatamente il funzionamento del microcontrollore scelto. Il Capitolo 4 sarà dedicato al firmware implementato per svolgere le operazioni fondamentali imputate al micro per i compiti di controllo. Verrà inoltre introdotto il codice VHDL sviluppato per emulare l'output del modulo WuR mediante un FPGA della famiglia Cyclone II. Nel Capitolo 5 verrà presentata una stima dei consumi del microcontrollore in funzione dei parametri di configurazione del sistema. Verrà inoltre effettuato un confronto con un altro microcontrollore che in alcune condizioni potrebbe rappresentare iun'alternativa valida di progetto. Nei Capitoli 6 e 7 saranno descritti possibili sviluppi futuri e conclusioni del progetto. Le specifiche di progetto rilevanti della tesi sono: 1. minimo consumo energetico possibile del microcontrollore ULP 2. elevata rapidità di risposta per la ricezione dei tag, per garantire la ricezione di un numero maggiore possibile di indirizzi (almeno 20 letture al secondo), in un range di tempo limitato 3. generazione di un segnale PWM a 100KHz di frequenza di commutazione con duty cycle 50% su cui basare una modulazione in back-scattering.

Haematite natural crystals: non-linear initial susceptibility at low temperature

Several works have reported that haematite has non-linear initial susceptibility at room temperature, like pyrrhotite or titanomagnetite, but there is no explanation for the observed behaviours yet. This study sets out to determine which physical property (grain size, foreign cations content and domain walls displacements) controls the initial susceptibility. The performed measurements include microprobe analysis to determine magnetic phases different to haematite; initial susceptibility (300 K); hysteresis loops, SIRM and backfield curves at 77 and 300 K to calculate magnetic parameters and minor loops at 77 K, to analyse initial susceptibility and magnetization behaviours below Morin transition. The magnetic moment study at low temperature is completed with measurements of zero field cooled-field cooled and AC susceptibility in a range from 5 to 300 K. The minor loops show that the non-linearity of initial susceptibility is closely related to Barkhausen jumps. Because of initial magnetic susceptibility is controlled by domain structure it is difficult to establish a mathematical model to separate magnetic subfabrics in haematite-bearing rocks.

Genome-wide association of multiple complex traits in outbred mice by ultra low-coverage sequencing

We thank the High-Throughput Genomics Group at the Wellcome Trust Centre for Human Genetics and the Wellcome Trust Sanger Institute for the generation of the sequencing data. This work was funded by Wellcome Trust grant 090532/Z/09/Z (J.F.). Primary phenotyping of the mice was supported by the Mary Lyon Centre and Mammalian Genetics Unit (Medical Research Council, UK Hub grant G0900747 91070 and Medical Research Council, UK grant MC U142684172). D.A.B acknowledges support from NIH R01AR056280. The sleep work was supported by the state of Vaud (Switzerland) and the Swiss National Science Foundation (SNF 14694 and 136201 to P.F.). The ECG work was supported by the Netherlands CardioVascular Research Initiative (Dutch Heart Foundation, Dutch Federation of University Medical Centres, the Netherlands Organization for Health Research and Development, and the Royal Netherlands Academy of Sciences) PREDICT project, InterUniversity Cardiology Institute of the Netherlands (ICIN; 061.02; C.A.R., C.R.B). Na Cai is supported by the Agency of Science, Technology and Research (A*STAR) Graduate Academy. The authors wish to acknowledge excellent technical assistance from: Ayako Kurioka, Leo Swadling, Catherine de Lara, James Ussher, Rachel Townsend, Sima Lionikaite, Ausra S. Lionikiene, Rianne Wolswinkel and Inge van der Made. We would like to thank Thomas M Keane and Anthony G Doran for their help in annotating variants and adding the FVB/NJ strain to the Mouse Genomes Project.

Nanowires for 3d silicon interconnection – low temperature compliant nanowire-polymer film for z-axis interconnect

Semiconductor chip packaging has evolved from single chip packaging to 3D heterogeneous system integration using multichip stacking in a single module. One of the key challenges in 3D integration is the high density interconnects that need to be formed between the chips with through-silicon-vias (TSVs) and inter-chip interconnects. Anisotropic Conductive Film (ACF) technology is one of the low-temperature, fine-pitch interconnect method, which has been considered as a potential replacement for solder interconnects in line with continuous scaling of the interconnects in the IC industry. However, the conventional ACF materials are facing challenges to accommodate the reduced pad and pitch size due to the micro-size particles and the particle agglomeration issue. A new interconnect material - Nanowire Anisotropic Conductive Film (NW-ACF), composed of high density copper nanowires of ~ 200 nm diameter and 10-30 µm length that are vertically distributed in a polymeric template, is developed in this work to tackle the constrains of the conventional ACFs and serves as an inter-chip interconnect solution for potential three-dimensional (3D) applications.