Pulsed LASER deposition (PLD) is widely recognized as excellent deposition technique owing to stoichiometric transfer of target material, easy preparation and high quality. Thin films from few nanometers to micrometer regime can be fabricated with equal ease. Although a batch process is not suitable for mass scale industrial production, PLD is a versatile technique, efficient and convenient for high quality basic research.  This thesis illustrates the use of PLD technique to study the emerging trends in tailoring multifunctional magnetic thin films both from basic nanoscience and device development point of view.      After a comprehensive review of magnetism in chapter 1: entitled ‘A journey through classical to modern trends in magnetism, and multifunctional thin film devices’ followed by a reasonably thorough discussion on Pulsed Laser thin film technique in Chapter 2, we present: Studies of tailoring composite high energy product permanent magnetic FePtB based thin films for applications in NEMS /MEMS, (Chapter 3). Study of search for new multiferroic materials by investigating the properties of Chromites. Crystalline Chromites are antiferromagnetic below 150oC.  However depositing thin films by PLD of the crystalline 95.5% dense targets produced by Surface Plasma Sintering, we discovered that the resulting films were amorphous and ferromagnetic beyond room temperature. Moreover advanced spectroscopic techniques revealed that the amorphized state is metallic with Cr in a mixed valence state.   An understanding of the underlying physics of the observed phenomenon has been carried out based on first principles calculations.  These results are now being considered for publication in a high profile journal.  Extensive studies on the films showing that these materials are ferromagnetic, but not ferroelectric are discussed in chapter 4. A preliminary presentation of these studies was pier reviewed and published in MRS symposium proceedings. Fabrication of Room temperature, Transparent, high moment soft ferromagnetic amorphous Bulk metallic glass based FeBNbY thin films by PLD, suitable for Nanolithography in NEMS/MEMS device development .  (Chapter 5) From a basic study point of view on new trends on magnetism we present: 4. The use of PLD technique to demonstrate room temperature ferromagnetism in undoped MgO, and V-doped MgO thin films.  Both of these oxides which do not contain any intrinsically magnetic elements and are diamagnetic in their bulk form belong to a new class of magnetic films, the so called d0magnets signifying that robust above room temperature ferromagnetism arising from defects and controlled carriers and no occupied d-states can be tailored in semiconductors and insulators.  These, mostly ZnO and MgO based thin films which may be classified as Dilute Magnetic Semiconductors, DMS, and Dilute Magnetic Insulators, DMI, are now the materials of active interest in future Electronics involving components which exploit both charge and spin of electrons in the arena of SPINTRONICS. Extensive characterization of magnetic, electrical, optical properties and microscopic structure has ensured development of high quality magnetic materials for future applications. Further research on these promising materials is expected to yield new generation spintronic devices for better performance in terms of efficiency, energy consumption and miniaturization of sizes. / QC 20120511

Nitric oxide (NO) is a mediator of vascular smooth muscle tension that metabolises rapidly in blood. NO delivered by inhalation can therefore be used as a selective pulmonary vasodilator to relieve pulmonary hypertension or to improve oxygenation with no systemic effects. In artificial ventilation nitric oxide has been administered in inspiration gas as a continuous gas flow or to form constant inspired concentration. Homogeneous inspired gas mixture has been regarded essential for successful therapy and the therapy has been characterized by the mixture NO concentration. The response in oxygenation on NO therapy has, however, been variable. Administration of NO as a short pulse synchronously with inspiration has been suggested to improve the response. In this study the NO administration was examined theoretically and experimentally with the aim to relieve pulmonary hypertension and improve oxygenation during artificial ventilation. For the experimental study a system for the synchronized administration was developed. The effect on oxygenation was studied during equine anaesthesia where hypoxemia develops regularly secondary to left-to-right shunt caused by atelectasis. By administering the NO as a short pulse in early inspiration to well ventilated lung areas the oxygenation could be effectively improved. Delayed administration to low ventilated lung areas was found possible for a negative contribution on oxygenation, which reduces the improvement gained in the well-ventilated lung areas. When NO is delivered into the whole inspiration, the net effect on oxygenation is the sum of these negative and positive contributions, whereas with pulsed delivery to the early inspiration the negative contribution can be avoided. This finding may be the main explanation for the varying response in oxygenation detected in patients as a response to NO inhalation. When the NO therapy aimed for the relief of induced pulmonary hypertension in pigs, no difference was observed between NO delivery as a short pulse or given to the whole inspiration. Maximum vasodilatation was observed with 105 nmol/min delivery rate. A larger delivery rate only contributed to an abrupt increase in pulmonary pressure at cessation of the delivery. The NO uptake from alveoli to tissue depends on the alveolar NO partial pressure. In a simulation this partial pressure was shown to be independent of the administration mode. Also the relationship between the NO uptake and delivery setting was not explicit. With pulsed delivery, expired NO can be reduced which was confirmed by the experimental results. This is important when the NO therapy is given in rebreathing circuit.

Even though electrophoretic NMR (eNMR) experiments may provide unique chemical information and have been performed for three decades, the technique is still rarely applied, mainly because several experimental sources of artifacts have to be controlled to achieve accurate results. In this thesis, new experimental setups and protocols for accurate and precise eNMR experiments are presented. These include a novel eNMR sample cell, a radiofrequency filter and methods to suppress bulk flow effects. These developments improved the signal-to-noise ratio by roughly an order of magnitude compared to the U-tube setup previously used for eNMR. Convection-compensated pulse sequences in combination with a phase correction method were found to efficiently suppress bulk flow effects in the experiments and greatly increase experimental accuracy. These experimental setups and protocols were applied to probe association of ions and molecules in solution. It is particularly illustrated that the combination of diffusion and eNMR has great potential to provide quantitative results on ionic and molecular association in a variety of systems. The extent to which ionic surfactants associate with uncharged cyclodextrin probed by eNMR yielded very similar results to those obtained by diffusion NMR experiments. Complexation of a large set of small mono- and polyvalent metal cations to poly(ethylene oxide) was quantified by estimating the effective charge of the polymer through combined diffusion and eNMR information. Significant association was found for cations that have a surface charge density below a critical value. Ion pairing between tetramethylammonium cations and a series of anions in several solvents was also probed by diffusion NMR and eNMR experiments. For the monovalent anions in ethanol and ethanol-water mixture a dependence on ionic size was demonstrated. In water, dimethylsulfoxide, and methanol no such trend and very little pairing was observed. In acetonitrile, a different pattern was seen that did not correlate well with any single ionic parameter. An experimental cell and procedures for electrokinetic studies of solvated proton-conducting polymer materials is also presented. Electro-osmotic flow and diffusion were studied for each molecular component in water-methanol mixtures that swell Nafion membranes. / Elektroforetisk NMR (eNMR) är en experimentell metod som funnits i tre decennier och som kan ge unik kemisk information. Ändå används den sällan då flera experimentella artefakter måste korrigeras för, om man ska få korrekta resultat. I denna avhandling presenteras nya experimentella uppställningar och protokoll ämnade att uppnå korrekta och noggranna resultat. Dessa inkluderar en ny mätcell, ett radiofrekvensfilter och metoder för att minimera effekten av samtidiga bulkflöden i provlösningen. Sammantaget uppnås ungefär en storleksordning högre signal-brus-förhållande jämfört med den U-rörsuppställning som tidigare använts. Konvektions-kompenserande pulssekvenser i kombination med en faskorrektionsteknik minskade också bulkflödeseffekter effektivt, vilket ökade resultatens noggrannhet högst avsevärt. De experimentella uppställningarna och protokollen användes här för att mäta association av joner och molekyler i lösning. Mätningarna visar att kombinationen diffusions- och eNMR har en stor potential att kvantitativt kunna bestämma associationgraden i många olika typer av kemiska system. Associationsgraden mellan joniska tensider och cyklodextriner undersöktes både med eNMR och diffusions-NMR, och resultaten var mycket lika. Komplex-bildningen mellan en serie enkel- och flerladdade metalljoner och poly-(etylenoxid) kvantifierades genom att uppskatta polymerens effektiva laddning från kombinerad diffusions- och eNMR. Betydande komplexbildning hittades för katjoner med ytladdningstäthet under ett kritiskt värde. Jonparbildning mellan tetrametylammoniumjoner och en serie av anjoner i flera olika lösningsmedel undersöktes också med diffusions- och eNMR. För de monovalenta anjonerna i etanol och etanol-vatten-blandning påvisades ett samband med jonstorleken. I vatten, dimetylsulfoxid och metanol var däremot jonparbildningen låg och inget liknande samband hittades. I acetonitril observerades ett annat mönster, som inte korrelerade bra med någon av anjonernas normala joniska karakteristika. Slutligen presenteras en mätcell och procedurer för elektrokinetiska studier i de solvatiserade protonledande polymermaterial som bland annat används i bränsleceller. Elektroosmotiskt flöde och diffusion uppmättes för varje molekylär komponent i Nafion-membran solvatiserade av vatten-metanol-blandningar. / QC20100709

Introduced in 1991, solid ink color printing technology is widely used in the office printing, prepress proofing, and wide format color printing markets. Ink droplets are first deposited on a rotating drum and then transferred to paper to reproduce images with high print quality. The objective of this thesis is to develop scientific knowledge of ink droplet deposition, which is needed for precise image buildup on the drum surface. The first problem studied in the thesis is droplet formation from the printhead with varied working voltages and jetting frequencies. Attention is paid to the formation of satellite droplets, the contraction of ligaments and the startup of high frequency jetting. The jetting conditions for obtaining consistent droplet generation with satellites are determined. A theoretical model is developed to predict the lifetime of ligaments. The second problem we studied is the deposition of single droplets on solid surfaces. The surface texture and final shape of deposited droplets are correlated with impact conditions, which include printhead temperature, substrate temperature, distance from printhead to substrate, and the type of substrate surface. An analytical model is developed to evaluate the interaction of oscillation and viscous damping in the droplet during impact. The third problem covered in the thesis is the deposition of multiple ink droplets on the drum surface. Interaction between droplets causes drawback effect, which degrades print quality. We define a parameter to quantify the drawback effect with varied deposition conditions. A simple model is provided to predict conditions for making continuous lines based on the results of two ink droplets deposition. To understand the hydrodynamics in causing drawback effect, a series of experiments using large liquid droplets are carried out. Focus is put on the evolution of spread length and dynamics of contact line. Correlations for maximum and minimum spread lengths are developed, which are used to reveal the cause of drawback effect in the deposition of ink droplets.

Introduced in 1991, solid ink color printing technology is widely used in the office printing, prepress proofing, and wide format color printing markets. Ink droplets are first deposited on a rotating drum and then transferred to paper to reproduce images with high print quality. The objective of this thesis is to develop scientific knowledge of ink droplet deposition, which is needed for precise image buildup on the drum surface. The first problem studied in the thesis is droplet formation from the printhead with varied working voltages and jetting frequencies. Attention is paid to the formation of satellite droplets, the contraction of ligaments and the startup of high frequency jetting. The jetting conditions for obtaining consistent droplet generation with satellites are determined. A theoretical model is developed to predict the lifetime of ligaments. The second problem we studied is the deposition of single droplets on solid surfaces. The surface texture and final shape of deposited droplets are correlated with impact conditions, which include printhead temperature, substrate temperature, distance from printhead to substrate, and the type of substrate surface. An analytical model is developed to evaluate the interaction of oscillation and viscous damping in the droplet during impact. The third problem covered in the thesis is the deposition of multiple ink droplets on the drum surface. Interaction between droplets causes drawback effect, which degrades print quality. We define a parameter to quantify the drawback effect with varied deposition conditions. A simple model is provided to predict conditions for making continuous lines based on the results of two ink droplets deposition. To understand the hydrodynamics in causing drawback effect, a series of experiments using large liquid droplets are carried out. Focus is put on the evolution of spread length and dynamics of contact line. Correlations for maximum and minimum spread lengths are developed, which are used to reveal the cause of drawback effect in the deposition of ink droplets.

Pulsed power generators are a key component in compact systems for generation of high-power microwaves (HPM). HPM generation by virtual cathode devices such as Vircators put high demands on the source. The rise time and the pulse length of the source voltage are two key issues in the generation of HPM radiation. This thesis describes the construction and tests of several inductive high power pulse generators. The pulse generators were designed with the intent to deliver a pulse with fast rise time and rectangular voltage. Therefore, the pulse generators are all based on discharges of transmission lines. The transmission lines used in the pulse generators are modern high voltage cables normally used in power transmission. All tested pulse generators have step up transformers as intermediate magnetic energy storage. Further, the pulse generators have contributed to the knowledge of compact designs. Closing switches is another important device in pulse generator architectures. In general, high power switching involving large currents and high voltages requires the use of robust switches. The switches used in the pulse generators of this thesis are of gas and liquid type.

No description available.

A series of experiments was carried out to compare the structural and electronic properties of intrinsic nanocrystalline silicon (nc-Si:H) thin films deposited via continuous wave (cw) and pulsed (p)-PECVD at 150°C substrate temperature. Working at this temperature allows for the easy transfer of film recipes from glass to plastic substrates in the future. During the p-PECVD process the pulsing frequency was varied from 0.2 to 50 kHz at 50% duty cycle. Approximately 15% drop in the deposition rate was observed for the samples fabricated in p-PECVD compared to cw-PECVD. The optimum crystallinity and photo (σph) and dark conductivity (σD) were observed at 5 kHz pulsing frequency, with ~10% rise in crystallinity and about twofold rise in the σph and σD compared to cw-PECVD. However, for both the cw and p-PECVD nc-Si:H films, the observed σph and σD were one to two orders and three orders of magnitude higher respectively than those reported in literature. The average activation energy (EA) of 0.16 ∓ 0.01 eV for nc-Si:H films deposited using p-PECVD confirmed the presence of impurities, which led to the observation of the unusually high conductivity values. It was considered that the films were contaminated by the impurity atoms after they were exposed to air. Following the thin film characterization procedure, the optimized nc-Si:H film recipes, from cw and p-PECVD, were used to fabricate the absorber layer of thin film solar cells. The cells were then characterized for J-V and External Quantum Efficiency (EQE) parameters. The cell active layer fabricated from p-PECVD demonstrated higher power conversion efficiency (η) and a maximum EQE of 1.7 ∓ 0.06 % and 54.3% respectively, compared to 1.00 ∓ 0.04 % and 48.6% respectively for cw-PECVD. However, the observed η and EQE of both the cells were lower than a reported nc-Si:H cell fabricated via p-PECVD with similar absorber layer thickness. This was due to the poor Short-circuit Current Density (Jsc), Open-circuit Voltage (Voc), and Fill Factor (FF) of the cw and p-PECVD cells respectively, compared to the reported cell. The low Jsc resulted from the poor photocarrier collection at longer and shorter wavelengths and high series resistance (Rseries). On the other hand, the low Voc stemmed from the low shunt resistance (Rsh). It was inferred that the decrease in the Rsh occurred due to the inadequate electrical isolation of the individual cells and the contact between the n – layer and the front TCO contact at the edge of the p-i-n deposition area. Additionally, the net effect of the high Rseries and the low Rsh led to a decrease in the FF of the cells.

The ionization of chemicals in solids or liquids under ambient conditions, known as ambient ionization mass spectrometry, is currently a fruitful research area in mass spectrometry. To classify those ambient ionization techniques from preexisting atmospheric pressure ionization methods, the former are commonly defined as those mass spectrometric ionization methods that operate under ambient conditions and require minimal or no sample pretreatment. A characteristic of this technology is that sample introduction and ionization are usually separate events, thereby allowing independent control of each set of conditions. A two-step ESI-based technique, named electrospray laser desorption ionization (ELDI), has been developed to characterize nonvolatile analyte molecules directly from the surfaces of solid samples in 2005 by J. Shiea and his co-workers. The analyte molecules are produced by laser irradiating of the sample surfaces, and then post-ionized in an ESI plume. However, the pulsed laser used in ELDI-MS system is quite expensive. Our aim in this research is to develop simple, convenient, and cheap desorption methods and coupled them to post-ionization techniques for direct analysis of liquid and solid sample analysis. They includes: (a) the use of continuous wave (CW) laser instead of pulsed laser to desorb analytes in liquid samples and ointments, and (b) the use of thermal probe to desorb analytes in solid and liquid samples. All of the desorbed neutral species like molecules or droplets are then post-ionized via ESI or APCI processes. The first topic of the research is to develop a cheaper laser system to introduce analytes in solids or liquids into reaction region for post-ionization. In this section, we use a CW laser instead of a pulsed laser for the sampling of analytes. The titanium foil and stainless steel foil sample plate is quite useful and shows a great of desorption efficiency for liquid samples while irradiating by a CW laser. The detection limit by using a CW laser for sampling and ESI for post-ionization is 0.1 £gM for Benzethonium chloride and 1 £gM for cytochrome c, respectively. The combination of CW laser desorption and ESI post-ionization mass spectrometry can be applied in drug components, food safety and biomedical sample analysis. As a result of small size, lightness and lower prices of CW laser system, it not only shows large potential to use as a high efficiency desorption device for novel ionization source of mass spectrometer but also available for a wide range of useful application in many fields. The second topic of the research is to develop a new thermal probe for the direct desorption of sample surface. The home-made thermal probe is used to touch surface of solid sample or liquid sample to generate gas phase molecules or micro analyte droplets. Those neutral analytes are then post-ionized via ESI or APCI processes. In this study, the setting temperature of thermal probe is 250¢J. When the thermal probe touches liquid sample, it makes droplets boiling away explosively and then fused with ESI plume to generate ions. The detection limit by using a thermal probe for sampling and ESI or APCI for post-ionization is 1 £gM for both melamine and cytochrome c. This technique is also applied to analyze controversial additives in drinks. It also shows large potential to use as a high efficiency desorption device for novel ionization source of mass spectrometer and useful for a wide range of useful application in many fields.

In the first part of this thesis, CaCO3 (calcite) powder ball-milled to micro/nano scale were subjected to isothermal firing in the temperature range of 450-600 ¢XC in an open air furnace in order to study specific-surface area reduction as a result of early-stage sintering/coarsening/coalescence/repacking (denoted as SCCR process) of the fine particles. The surface area and pore size distributions were obtained from the BET and BJH methods, respectively. The H1 type adsorption/desorption hysteresis loop of the type IV isotherm was used as an indicator of cylindrical pore formation upon dry pressing and firing of the powder. The apparent activation energy for the onset SCCR of the dry-pressed calcite powder turned out to be 57.5¡Ó1.0 kJ/mol based on t0.5, i.e. time for 50 % specific surface area reduction. The minimum temperature for such an incipient SCCR process was estimated to be 590K (317¢J) by extrapolating the specific-surface-area reduction rate to null. The mechanism of specific surface area change includes the Brownian motion, coarsening and coalescence/repacking of calcite particles besides sintering via synchronizing diffusion of calcium ion and carbonic acid ion along grain surface and boundary. In the second part of this thesis, pulsed laser ablation on micrometer-sized calcite (type I) powder in liquid H2O (PLAL) was conducted to study the structure and optical property change of calcium carbonate under a dynamic high-temperature. high-pressure aqueous condition. X-ray diffraction (XRD) indicated the fragmented calcite I powder via such a PLAL process change predominantly into a metastable CaCO3 II phase presumably by a displacive type transformation from calcite I and/or nucleated from atom clusters. The refined XRD lattice parameters indicate a significant internal compressive stress (up to 1.5 GPa) was retained for the predominant CaCO3 II nanoparticles having well-developed (013), (010) and (013) faces as revealed by transmission electron microscopy (TEM). Minor calcium carbonate nanoparticles were also identified by TEM to be other high-pressure polymorphs (type III and aragonite), hydrated (monohydrocalcite, ikaite), amorphized (amorphous calcium carbonate), and even decomposed as cubic lime (CaO). Monohydrocalcite occasionally occurred as epitaxial intergrowths within the predominant CaCO3 II matrix. Vibrational spectroscopy (Raman and FTIR) indicated the structure units of the overall nanoparticles by the PLAL process were considerably modified as a combined results of size miniature, protonation and internal compressive stress. The UV-visible absorption results further indicate that the minimum band gap of the colloidal solution was narrowed down to ca. 5 eV and 3 eV for the predominant CaCO3 II and minor accessory phases, respectively, thus shedding light on their potential opto-catalytic applications.