Integrated analysis and design of optimization and up-scaling of inductively coupled plasma synthesis of nanoparticles

This study is focused on radio-frequency inductively coupled thermal plasma (ICP) synthesis of nanoparticles, combining experimental and modelling approaches towards process optimization and industrial scale-up, in the framework of the FP7-NMP SIMBA European project (Scaling-up of ICP technology for continuous production of Metallic nanopowders for Battery Applications). First the state of the art of nanoparticle production through conventional and plasma routes is summarized, then results for the characterization of the plasma source and on the investigation of the nanoparticle synthesis phenomenon, aiming at highlighting fundamental process parameters while adopting a design oriented modelling approach, are presented. In particular, an energy balance of the torch and of the reaction chamber, employing a calorimetric method, is presented, while results for three- and two-dimensional modelling of an ICP system are compared with calorimetric and enthalpy probe measurements to validate the temperature field predicted by the model and used to characterize the ICP system under powder-free conditions. Moreover, results from the modeling of critical phases of ICP synthesis process, such as precursor evaporation, vapour conversion in nanoparticles and nanoparticle growth, are presented, with the aim of providing useful insights both for the design and optimization of the process and on the underlying physical phenomena. Indeed, precursor evaporation, one of the phases holding the highest impact on industrial feasibility of the process, is discussed; by employing models to describe particle trajectories and thermal histories, adapted from the ones originally developed for other plasma technologies or applications, such as DC non-transferred arc torches and powder spherodization, the evaporation of micro-sized Si solid precursor in a laboratory scale ICP system is investigated. Finally, a discussion on the role of thermo-fluid dynamic fields on nano-particle formation is presented, as well as a study on the effect of the reaction chamber geometry on produced nanoparticle characteristics and process yield.

Agents, nodes & resources: Universal naming system for a coordination middleware

La tesi si propone di sviluppare un modello, l'architettura e la tecnologia per il sistema di denominazione del Middleware Coordinato TuCSoN, compresi gli agenti, i nodi e le risorse. Identità universali che rappresentano queste entità, sia per la mobilità fisica sia per quella virtuale, per un Management System (AMS, NMS, RMS) distribuito; tale modulo si occupa anche di ACC e trasduttori, prevedendo questioni come la tolleranza ai guasti, la persistenza, la coerenza, insieme con il coordinamento disincarnata in rete, come accade con le tecnologie Cloud. All’interno dell’elaborato, per prima cosa si è fatta una introduzione andando a descrivere tutto ciò che è contenuto nell’elaborato in modo da dare una visione iniziale globale del lavoro eseguito. Di seguito (1° capitolo) si è descritta tutta la parte relativa alle conoscenze di base che bisogna avere per la comprensione dell’elaborato; tali conoscenze sono relative a TuCSoN (il middleware coordinato con cui il modulo progettato dovrà interfacciarsi) e Cassandra (sistema server distribuito su cui si appoggia la parte di mantenimento e salvataggio dati del modulo). In seguito (2° capitolo) si è descritto JADE, un middleware da cui si è partiti con lo studio per la progettazione del modello e dell’architettura del modulo. Successivamente (3° capitolo) si è andati a spiegare la struttura e il modello del modulo considerato andando ad esaminare tutti i dettagli relativi alle entità interne e di tutti i legami fra esse. In questa parte si è anche dettagliata tutta la parte relativa alla distribuzione sulla rete del modulo e dei suoi componenti. In seguito (4° capitolo) è stata dettagliata e spiegata tutta la parte relativa al sistema di denominazione del modulo, quindi la sintassi e l’insieme di procedure che l’entità consumatrice esterna deve effettuare per ottenere un “nome universale” e quindi anche tutti i passaggi interni del modulo per fornire l’identificatore all’entità consumatrice. Nel capitolo successivo (5° capitolo) si sono descritti tutti i casi di studio relativi alle interazioni con le entità esterne, alle entità interne in caso in cui il modulo sia o meno distribuito sulla rete, e i casi di studio relativi alle politiche, paradigmi e procedure per la tolleranza ai guasti ed agli errori in modo da dettagliare i metodi di riparazione ad essi. Successivamente (6° capitolo) sono stati descritti i possibili sviluppi futuri relativi a nuove forme di interazione fra le entità che utilizzano questo modulo ed alle possibili migliorie e sviluppi tecnologici di questo modulo. Infine sono state descritte le conclusioni relative al modulo progettato con tutti i dettagli in modo da fornire una visione globale di quanto inserito e descritto nell’elaborato.

Scaled down physical properties of semiconductor nanowires for nanoelectronics scaling up

Semiconductor nanowires (NWs) are one- or quasi one-dimensional systems whose physical properties are unique as compared to bulk materials because of their nanoscaled sizes. They bring together quantum world and semiconductor devices. NWs-based technologies may achieve an impact comparable to that of current microelectronic devices if new challenges will be faced. This thesis primarily focuses on two different, cutting-edge aspects of research over semiconductor NW arrays as pivotal components of NW-based devices. The first part deals with the characterization of electrically active defects in NWs. It has been elaborated the set-up of a general procedure which enables to employ Deep Level Transient Spectroscopy (DLTS) to probe NW arrays’ defects. This procedure has been applied to perform the characterization of a specific system, i.e. Reactive Ion Etched (RIE) silicon NW arrays-based Schottky barrier diodes. This study has allowed to shed light over how and if growth conditions introduce defects in RIE processed silicon NWs. The second part of this thesis concerns the bowing induced by electron beam and the subsequent clustering of gallium arsenide NWs. After a justified rejection of the mechanisms previously reported in literature, an original interpretation of the electron beam induced bending has been illustrated. Moreover, this thesis has successfully interpreted the formation of NW clusters in the framework of the lateral collapse of fibrillar structures. These latter are both idealized models and actual artificial structures used to study and to mimic the adhesion properties of natural surfaces in lizards and insects (Gecko effect). Our conclusion are that mechanical and surface properties of the NWs, together with the geometry of the NW arrays, play a key role in their post-growth alignment. The same parameters open, then, to the benign possibility of locally engineering NW arrays in micro- and macro-templates.

Der Renormierungsgruppen-Fluß der konform-reduzierten Quantengravitation

Wir analysieren die Rolle von "Hintergrundunabhängigkeit" im Zugang der effektiven Mittelwertwirkung zur Quantengravitation. Wenn der nicht-störungstheoretische Renormierungsgruppen-(RG)-Fluß "hintergrundunabhängig" ist, muß die Vergröberung durch eine nicht spezifizierte, variable Metrik definiert werden. Die Forderung nach "Hintergrundunabhängigkeit" in der Quantengravitation führt dazu, daß die funktionale RG-Gleichung von zusätzlichen Feldern abhängt; dadurch unterscheidet sich der RG-Fluß in der Quantengravitation deutlich von dem RG-Fluß einer gewöhnlichen Quantentheorie, deren Moden-Cutoff von einer starren Metrik abhängt. Beispielsweise kann in der "hintergrundunabhängigen" Theorie ein Nicht-Gauß'scher Fixpunkt existieren, obwohl die entsprechende gewöhnliche Quantentheorie keinen solchen entwickelt. Wir untersuchen die Bedeutung dieses universellen, rein kinematischen Effektes, indem wir den RG-Fluß der Quanten-Einstein-Gravitation (QEG) in einem "konform-reduzierten" Zusammenhang untersuchen, in dem wir nur den konformen Faktor der Metrik quantisieren. Alle anderen Freiheitsgrade der Metrik werden vernachlässigt. Die konforme Reduktion der Einstein-Hilbert-Trunkierung zeigt exakt dieselben qualitativen Eigenschaften wie in der vollen Einstein-Hilbert-Trunkierung. Insbesondere besitzt sie einen Nicht-Gauß'schen Fixpunkt, der notwendig ist, damit die Gravitation asymptotisch sicher ist. Ohne diese zusätzlichen Feldabhängigkeiten ist der RG-Fluß dieser Trunkierung der einer gewöhnlichen $phi^4$-Theorie. Die lokale Potentialnäherung für den konformen Faktor verallgemeinert den RG-Fluß in der Quantengravitation auf einen unendlich-dimensionalen Theorienraum. Auch hier finden wir sowohl einen Gauß'schen als auch einen Nicht-Gauß'schen Fixpunkt, was weitere Hinweise dafür liefert, daß die Quantengravitation asymptotisch sicher ist. Das Analogon der Metrik-Invarianten, die proportional zur dritten Potenz der Krümmung ist und die die störungstheoretische Renormierbarkeit zerstört, ist unproblematisch für die asymptotische Sicherheit der konform-reduzierten Theorie. Wir berechnen die Skalenfelder und -imensionen der beiden Fixpunkte explizit und diskutieren mögliche Einflüsse auf die Vorhersagekraft der Theorie. Da der RG-Fluß von der Topologie der zugrundeliegenden Raumzeit abhängt, diskutieren wir sowohl den flachen Raum als auch die Sphäre. Wir lösen die Flußgleichung für das Potential numerisch und erhalten Beispiele für RG-Trajektorien, die innerhalb der Ultraviolett-kritischen Mannigfaltigkeit des Nicht-Gauß'schen Fixpunktes liegen. Die Quantentheorien, die durch einige solcher Trajektorien definiert sind, zeigen einen Phasenübergang von der bekannten (Niederenergie-) Phase der Gravitation mit spontan gebrochener Diffeomorphismus-Invarianz zu einer neuen Phase von ungebrochener Diffeomorphismus-Invarianz. Diese Hochenergie-Phase ist durch einen verschwindenden Metrik-Erwartungswert charakterisiert.

Oblique ionograms automatic scaling and eikonal based ray tracing

A method for automatic scaling of oblique ionograms has been introduced. This method also provides a rejection procedure for ionograms that are considered to lack sufficient information, depicting a very good success rate. Observing the Kp index of each autoscaled ionogram, can be noticed that the behavior of the autoscaling program does not depend on geomagnetic conditions. The comparison between the values of the MUF provided by the presented software and those obtained by an experienced operator indicate that the procedure developed for detecting the nose of oblique ionogram traces is sufficiently efficient and becomes much more efficient as the quality of the ionograms improves. These results demonstrate the program allows the real-time evaluation of MUF values associated with a particular radio link through an oblique radio sounding. The automatic recognition of a part of the trace allows determine for certain frequencies, the time taken by the radio wave to travel the path between the transmitter and receiver. The reconstruction of the ionogram traces, suggests the possibility of estimating the electron density between the transmitter and the receiver, from an oblique ionogram. The showed results have been obtained with a ray-tracing procedure based on the integration of the eikonal equation and using an analytical ionospheric model with free parameters. This indicates the possibility of applying an adaptive model and a ray-tracing algorithm to estimate the electron density in the ionosphere between the transmitter and the receiver An additional study has been conducted on a high quality ionospheric soundings data set and another algorithm has been designed for the conversion of an oblique ionogram into a vertical one, using Martyn's theorem. This allows a further analysis of oblique soundings, throw the use of the INGV Autoscala program for the automatic scaling of vertical ionograms.

Complex tracer mobilities in polymer networks revealed by fluorescence correlation spectroscopy

Gels are elastic porous polymer networks that are accompanied by pronounced mechanical properties. Due to their biocompatibility, ‘responsive hydrogels’ (HG) have many biomedical applications ranging from biosensors and drug delivery to tissue engineering. They respond to external stimuli such as temperature and salt by changing their dimensions. Of paramount importance is the ability to engineer penetrability and diffusion of interacting molecules in the crowded HG environment, as this would enable one to optimize a specific functionality. Even though the conditions under which biomedical devices operate are rather complex, a bottom-up approach could reduce the complexity of mutually coupled parameters influencing tracer mobility. The present thesis focuses on the interaction-induced tracer diffusion in polymer solutions and their homologous gels, probed by means of Fluorescence Correlation Spectroscopy (FCS). This is a single-molecule-sensitive technique having the advantage of optimal performance under ultralow tracer concentrations, typically employed in biosensors. Two different types of hydrogels have been investigated, a conventional one with broad polydispersity in the distance between crosslink points and a so-called ‘ideal’, with uniform mesh size distribution. The former is based on a thermoresponsive polymer, exhibiting phase separation in water at temperatures close to the human body temperature. The latter represents an optimal platform to study tracer diffusion. Mobilities of different tracers have been investigated in each network, varying in size, geometry and in terms of tracer-polymer attractive strength, as perturbed by different stimuli. The thesis constitutes a systematic effort towards elucidating the role of the strength and nature of different tracer-polymer interactions, on tracer mobilities; it outlines that interactions can still be very important even in the simplified case of dilute polymer solutions; it also demonstrates that the presence of permanent crosslinks exerts distinct tracer slowdown, depending on the tracer type and the nature of the tracer-polymer interactions, expressed differently by each tracer with regard to the selected stimulus. In aqueous polymer solutions, the tracer slowdown is found to be system-dependent and no universal trend seems to hold, in contrast to predictions from scaling theory for non-interacting nanoparticle mobility and empirical relations concerning the mesh size in polymer solutions. Complex tracer dynamics in polymer networks may be distinctly expressed by FCS, depending on the specific synergy among-at least some of - the following parameters: nature of interactions, external stimuli employed, tracer size and type, crosslink density and swelling ratio.

Novel algorithms for electronic structure based molecular dynamics with linear system-size scaling

Die vorliegende Arbeit behandelt die Entwicklung und Verbesserung von linear skalierenden Algorithmen für Elektronenstruktur basierte Molekulardynamik. Molekulardynamik ist eine Methode zur Computersimulation des komplexen Zusammenspiels zwischen Atomen und Molekülen bei endlicher Temperatur. Ein entscheidender Vorteil dieser Methode ist ihre hohe Genauigkeit und Vorhersagekraft. Allerdings verhindert der Rechenaufwand, welcher grundsätzlich kubisch mit der Anzahl der Atome skaliert, die Anwendung auf große Systeme und lange Zeitskalen. Ausgehend von einem neuen Formalismus, basierend auf dem großkanonischen Potential und einer Faktorisierung der Dichtematrix, wird die Diagonalisierung der entsprechenden Hamiltonmatrix vermieden. Dieser nutzt aus, dass die Hamilton- und die Dichtematrix aufgrund von Lokalisierung dünn besetzt sind. Das reduziert den Rechenaufwand so, dass er linear mit der Systemgröße skaliert. Um seine Effizienz zu demonstrieren, wird der daraus entstehende Algorithmus auf ein System mit flüssigem Methan angewandt, das extremem Druck (etwa 100 GPa) und extremer Temperatur (2000 - 8000 K) ausgesetzt ist. In der Simulation dissoziiert Methan bei Temperaturen oberhalb von 4000 K. Die Bildung von sp²-gebundenem polymerischen Kohlenstoff wird beobachtet. Die Simulationen liefern keinen Hinweis auf die Entstehung von Diamant und wirken sich daher auf die bisherigen Planetenmodelle von Neptun und Uranus aus. Da das Umgehen der Diagonalisierung der Hamiltonmatrix die Inversion von Matrizen mit sich bringt, wird zusätzlich das Problem behandelt, eine (inverse) p-te Wurzel einer gegebenen Matrix zu berechnen. Dies resultiert in einer neuen Formel für symmetrisch positiv definite Matrizen. Sie verallgemeinert die Newton-Schulz Iteration, Altmans Formel für beschränkte und nicht singuläre Operatoren und Newtons Methode zur Berechnung von Nullstellen von Funktionen. Der Nachweis wird erbracht, dass die Konvergenzordnung immer mindestens quadratisch ist und adaptives Anpassen eines Parameters q in allen Fällen zu besseren Ergebnissen führt.

Effect of smoking on the results of a chlorhexidine digluconate treatment extended up to 3 months after scaling and root planing-a pilot study

The aim of the study was to evaluate the impact of smoking on a prolongated chlorhexidine digluconate regimen after scaling and root planing. Forty-two smokers (test group) and 85 nonsmoking patients (control group) with generalized chronic periodontitis were examined for clinical attachment level (CAL), probing depth (PD), bleeding on probing (BoP), and Plaque Index (Pl) at baseline and after 1 and 3 months. During scaling and root planing, a 0.2% chlorhexidine digluconate solution and a 1% chlorhexidine digluconate gel were used. The subjects used a 0.2% chlorhexidine digluconate solution twice daily for 3 months. The Mann-Whitney U and Wilcoxon tests were used for statistical analysis. There were significant improvements of all studied variables after 1 and 3 months in both groups. After 3 months, the mean improvement in the test group was 1.62 mm for CAL, 2.85 mm for PD, and 48% for BoP; in the control group, the values were 2.18 mm for CAL, 2.81 mm for PD, and 47% for BoP. Only the maximum changes of CAL between 1 and 3 months (test group, 0.32 mm vs 0.69 mm in the control group) and PD (test group, 0.47 mm vs 0.76 mm in the control group) were significantly different between the groups (P < .05 and P = .05, respectively). The present data appear to suggest that the use of chlorhexidine digluconate twice daily during a period of 3 months following nonsurgical periodontal therapy may result in significant clinical improvements in smokers and nonsmokers.

Microbiologic findings 1 year after partial- and full-mouth scaling in the treatment of moderate chronic periodontitis

To investigate the impact on microbiologic variables of full-mouth scaling (FMS) and conventional scaling and root planing (cSRP) after 12 months.

The quality of primary care in a country with universal health care coverage

Standard indicators of quality of care have been developed in the United States. Limited information exists about quality of care in countries with universal health care coverage.

Scaling Ceramic Provenience at Lydian Sardis, Western Turkey

We present a multistage strategy to define the scale and geographic distribution of 'local' ceramic production at Lydian Sardis based on geochemical analysis (NAA) of a large diverse ceramic sample (n = 281). Within the sphere of local ceramic production, our results demonstrate an unusual pattern of reliance on a single resource relative to other contemporary Iron Age centers. When our NAA results are combined with legacy NAA provenience data for production centers in Western Anatolia, we can differentiate ceramic emulation from exchange, establish probable proveniences for the non-local component of the dataset, and define new non-local groups with as yet no known provenience. (C) 2012 Elsevier Ltd. All rights reserved.