Design, synthesis and Chemical-physical characterization of photocatalytic inorganic nanocrystals for technological applications

This work was based on the synthesis and characterization of innovative crystals for biomedical and technological applications. Different types of syntheses were developed in order to obtain crystals with high photocatalytic properties. A hydrothermal synthesis was also processed to correlate the chemical-physical characteristics with synthesis parameters obtaining synthesis of nanoparticles of titanium dioxide with different morphology, size and crystalline phase depending on the variation of the synthesis parameters. Also a synthesis in water at 80 °C temperature and low pressure was developed from which anatase containing a small percentage of brookite nanoparticles were obtained, presenting a high photocatalytic activity. These particles have been used to obtain the microcrystals formed by an inorganic core of hydroxyapatite surface covered by TiO2 nanoparticles. Micrometer material with higher photocatalytic has been produced. The same nanoparticles have been functionalized with resorcinol oxidized in order to increase the photocatalytic efficiency. Photodegradation test results have confirmed this increase. Finally, synthetic nanoparticles with a waterless synthesis using formic acid and octanol, through esterification "in situ" were synthesized. Nanoparticles superficially covered by carboxylic residues able to bind a wide range of molecules to obtain further photocatalytic properties were obtained.

Investigation of a superthermal ultracold neutron source based on a solid deuterium converter for the TRIGA Mainz reactor

Research in fundamental physics with the free neutron is one of the key tools for testing the Standard Model at low energies. Most prominent goals in this field are the search for a neutron electric dipole moment (EDM) and the measurement of the neutron lifetime. Significant improvements of the experimental performance using ultracold neutrons (UCN) require reduction of both systematic and statistical errors.rnThe development and construction of new UCN sources based on the superthermal concept is therefore an important step for the success of future fundamental physics with ultracold neutrons. rnSignificant enhancement of today available UCN densities strongly correlates with an efficient use of an UCN converter material. The UCN converter here is to be understood as a medium which reduces the velocity of cold neutrons (CN, velocity of about 600 m/s) to the velocity of UCN (velocity of about 6 m/s).rnSeveral big research centers around the world are presently planning or constructing new superthermal UCN sources, which are mainly based on the use of either solid deuterium or superfluid helium as UCN converter.rnThanks to the idea of Yu.Pokotilovsky, there exists the opportunity to build competitive UCN sources also at small research reactors of the TRIGA type. Of course these smaller facilities don't promise high UCN densities of several 1000 UCN/cm³, but they are able to provide densities around 100 UCN/cm³ for experiments.rnIn the context of this thesis, it was possible to demonstrate succesfully the feasibility of a superthermal UCN source at the tangential beamport C of the research reactor TRIGA Mainz. Based on a prototype for the future UCN source at the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII) in munich, which was planned and built in collaboration with the Technical University of Munich, further investigations and improvements were done and are presented in this thesis. rnIn parallel, a second UCN source for the radial beamport D was designed and built. The comissioning of this new source is foreseen in spring 2010.rnAt beamport D with its higher thermal neutron flux, it should be possible to increase the available UCN densities of 4 UCN/cm³ by minimum one order of magnitude.

Processi integrati per l’intensificazione di processo: reazione di fotocatalisi accoppiata alla pervaporazione, la dialisi e all’ozonizzazione

L’accoppiamento di diverse operazioni unitarie può in certi casi portare ad una cosiddetta “intensificazione di processo”, cioè ad un aumento sostanziale delle rese, dell’efficienza e della sostenibilità. Nel presente lavoro sono state pertanto analizzate le potenzialità di accoppiamento della fotocatalisi, il più studiato tra i “processi di ossidazione avanzata”, sia con alcuni processi a membrana per la sintesi verde di aromi sia con l’ozonizzazione per la depurazione di acque. È stato dimostrato che in entrambi i casi l’ottenimento di una significativa intensificazione di processo dipende in gran parte dai parametri operativi, in particolare dal rapporto, delta, tra la velocità caratteristica di fotocatalisi e quella del processo accoppiato. Nel caso della sintesi di aromi, in cui la fotocatalisi viene accoppiata con la pervaporazione o con la dialisi ricircolando al reattore il retentato dalla cella con la membrana. Il parametro delta dipende dalla velocità di reazione, dalle proprietà di trasporto delle membrane e naturalmente dal volume del rettore e dall’area della membrana. La reazione fotocatalitica produce l’aroma, ad esempio vanillina da acido ferulico, per ossidazione parziale e grazie al recupero del prodotto se ne evita l’ulteriore ossidazione aumentandone pertanto la resa. L’operare in apparati separati offre diversi vantaggi come la possibilità di variare senza vincoli il rapporto tra area della membrana e volume del reattore, ma impone di considerare anche il grado effettivo di accoppiamento dei processi. In questo caso, come evidenziato dal modello matematico, un sufficientemente elevato rapporto di ricircolo consente comunque di integrare efficacemente i processi. Nell’ozonizzazione fotocatalitica si hanno due importanti vantaggi: l’aumento della velocità di degradazione grazie alla sinergia tra i processi e la capacità di controllare la formazione di prodotti pericolosi. La sinergia viene massimizzata ad un valore ottimale di delta, mentre la formazione dei prodotti indesiderati viene controllata operando secondo le procedure che sono state individuate.

Development and application of a thermo-hydraulic model supporting the design and the deterministic safety analysis in a sodium cooled fast reactor

Il CP-ESFR è un progetto integrato di cooperazione europeo sui reattori a sodio SFR realizzato sotto il programma quadro EURATOM 7, che unisce il contributo di venticinque partner europei. Il CP-ESFR ha l'ambizione di contribuire all'istituzione di una "solida base scientifica e tecnica per il reattore veloce refrigerato a sodio, al fine di accelerare gli sviluppi pratici per la gestione sicura dei rifiuti radioattivi a lunga vita, per migliorare le prestazioni di sicurezza, l'efficienza delle risorse e il costo-efficacia di energia nucleare al fine di garantire un sistema solido e socialmente accettabile di protezione della popolazione e dell'ambiente contro gli effetti delle radiazioni ionizzanti. " La presente tesi di laurea è un contributo allo sviluppo di modelli e metodi, basati sull’uso di codici termo-idraulici di sistema, per l’ analisi di sicurezza di reattori di IV Generazione refrigerati a metallo liquido. L'attività è stata svolta nell'ambito del progetto FP-7 PELGRIMM ed in sinergia con l’Accordo di Programma MSE-ENEA(PAR-2013). Il progetto FP7 PELGRIMM ha come obbiettivo lo sviluppo di combustibili contenenti attinidi minori 1. attraverso lo studio di due diverse forme: pellet (oggetto della presente tesi) e spherepac 2. valutandone l’impatto sul progetto del reattore CP-ESFR. La tesi propone lo sviluppo di un modello termoidraulico di sistema dei circuiti primario e intermedio del reattore con il codice RELAP5-3D© (INL, US). Tale codice, qualificato per il licenziamento dei reattori nucleari ad acqua, è stato utilizzato per valutare come variano i parametri del core del reattore rilevanti per la sicurezza (es. temperatura di camicia e di centro combustibile, temperatura del fluido refrigerante, etc.), quando il combustibile venga impiegato per “bruciare” gli attinidi minori (isotopi radioattivi a lunga vita contenuti nelle scorie nucleari). Questo ha comportato, una fase di training sul codice, sui suoi modelli e sulle sue capacità. Successivamente, lo sviluppo della nodalizzazione dell’impianto CP-ESFR, la sua qualifica, e l’analisi dei risultati ottenuti al variare della configurazione del core, del bruciamento e del tipo di combustibile impiegato (i.e. diverso arricchimento di attinidi minori). Il testo è suddiviso in sei sezioni. La prima fornisce un’introduzione allo sviluppo tecnologico dei reattori veloci, evidenzia l’ambito in cui è stata svolta questa tesi e ne definisce obbiettivi e struttura. Nella seconda sezione, viene descritto l’impianto del CP-ESFR con attenzione alla configurazione del nocciolo e al sistema primario. La terza sezione introduce il codice di sistema termico-idraulico utilizzato per le analisi e il modello sviluppato per riprodurre l’impianto. Nella sezione quattro vengono descritti: i test e le verifiche effettuate per valutare le prestazioni del modello, la qualifica della nodalizzazione, i principali modelli e le correlazioni più rilevanti per la simulazione e le configurazioni del core considerate per l’analisi dei risultati. I risultati ottenuti relativamente ai parametri di sicurezza del nocciolo in condizioni di normale funzionamento e per un transitorio selezionato sono descritti nella quinta sezione. Infine, sono riportate le conclusioni dell’attività.

Nanoparticle preparation process using novel microjet reactor technology for enhancing dissolution rates of poorly water soluble drugs

In this study a novel method MicroJet reactor technology was developed to enable the custom preparation of nanoparticles. rnDanazol/HPMCP HP50 and Gliclazide/Eudragit S100 nanoparticles were used as model systems for the investigation of effects of process parameters and microjet reactor setup on the nanoparticle properties during the microjet reactor construction. rnFollowing the feasibility study of the microjet reactor system, three different nanoparticle formulations were prepared using fenofibrate as model drug. Fenofibrate nanoparticles stabilized with poloxamer 407 (FN), fenofibrate nanoparticles in hydroxypropyl methyl cellulose phthalate (HPMCP) matrix (FHN) and fenofibrate nanoparticles in HPMCP and chitosan matrix (FHCN) were prepared under controlled precipitation using MicroJet reactor technology. Particle sizes of all the nanoparticle formulations were adjusted to 200-250 nm. rnThe changes in the experimental parameters altered the system thermodynamics resulting in the production of nanoparticles between 20-1000 nm (PDI<0.2) with high drug loading efficiencies (96.5% in 20:1 polymer:drug ratio).rnDrug releases from all nanoparticle formulations were fast and complete after 15 minutes both in FaSSIF and FeSSIF medium whereas in mucodhesiveness tests, only FHCN formulation was found to be mucoadhesive. Results of the Caco-2 studies revealed that % dose absorbed values were significantly higher (p<0.01) for FHCN in both cases where FaSSIF and FeSSIF were used as transport buffer.rn

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid–solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U.S., by using less than 0.7% of the U.S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H-2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid-solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H-2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H-2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U. S., by using less than 0.7% of the U. S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

Parameter identification of a copper-zeolite SCR catalyst model using reactor data

The selective catalytic reduction system is a well established technology for NOx emissions control in diesel engines. A one dimensional, single channel selective catalytic reduction (SCR) model was previously developed using Oak Ridge National Laboratory (ORNL) generated reactor data for an iron-zeolite catalyst system. Calibration of this model to fit the experimental reactor data collected at ORNL for a copper-zeolite SCR catalyst is presented. Initially a test protocol was developed in order to investigate the different phenomena responsible for the SCR system response. A SCR model with two distinct types of storage sites was used. The calibration process was started with storage capacity calculations for the catalyst sample. Then the chemical kinetics occurring at each segment of the protocol was investigated. The reactions included in this model were adsorption, desorption, standard SCR, fast SCR, slow SCR, NH3 Oxidation, NO oxidation and N2O formation. The reaction rates were identified for each temperature using a time domain optimization approach. Assuming an Arrhenius form of the reaction rates, activation energies and pre-exponential parameters were fit to the reaction rates. The results indicate that the Arrhenius form is appropriate and the reaction scheme used allows the model to fit to the experimental data and also for use in real world engine studies.

Supplemental Data - Bioremediation of polluted air from an industrial plant using rotating biofilter reactor-based technology

Two microbial isolates (HDB, Hydrogen-Degrading Bacteria) obtained from industrial wastewater were inoculated into the rotating biofilter reactor 'Biowheel 2.0' and tested for the ability to purify gaseous flows containing benzene and non-methane volatile organic compounds (NMVOCs) released at an industrial plant. Different classes of gaseous flow were tested, namely 'cold box', 'in shell', and 'mix', all of them associated with the industrial process of 'mold-casting'. A significant increase in Removal Efficiency (RE) was recorded for benzene and NMVOCs in the inoculated 'Biowheel 2.0' biofilter, compared to uninoculated control. For each type of gaseous flow, odor impact was evaluated in the inlet and outlet flows at the industrial plant, using the test panel method and electronic nose technology. A significant drop in the amount of Olfactometric Units (O.U.) m-3 occurred in the gaseous flows treated with the bacterial consortium. The reported data demonstrate the ability of the consortium to degrade hydrocarbons, revealing its potential for bioremediation of polluted air emissions occurring at industrial plants.

Isotopic prediction calculation methodologies: application to Vandellos-II Reactor cycles 7-11

Determining as accurate as possible spent nuclear fuel isotopic content is gaining importance due to its safety and economic implications. Since nowadays higher burn ups are achievable through increasing initial enrichments, more efficient burn up strategies within the reactor cores and the extension of the irradiation periods, establishing and improving computation methodologies is mandatory in order to carry out reliable criticality and isotopic prediction calculations. Several codes (WIMSD5, SERPENT 1.1.7, SCALE 6.0, MONTEBURNS 2.0 and MCNP-ACAB) and methodologies are tested here and compared to consolidated benchmarks (OECD/NEA pin cell moderated with light water) with the purpose of validating them and reviewing the state of the isotopic prediction capabilities. These preliminary comparisons will suggest what can be generally expected of these codes when applied to real problems. In the present paper, SCALE 6.0 and MONTEBURNS 2.0 are used to model the same reported geometries, material compositions and burn up history of the Spanish Van de llós II reactor cycles 7-11 and to reproduce measured isotopies after irradiation and decay times. We analyze comparisons between measurements and each code results for several grades of geometrical modelization detail, using different libraries and cross-section treatment methodologies. The power and flux normalization method implemented in MONTEBURNS 2.0 is discussed and a new normalization strategy is developed to deal with the selected and similar problems, further options are included to reproduce temperature distributions of the materials within the fuel assemblies and it is introduced a new code to automate series of simulations and manage material information between them. In order to have a realistic confidence level in the prediction of spent fuel isotopic content, we have estimated uncertainties using our MCNP-ACAB system. This depletion code, which combines the neutron transport code MCNP and the inventory code ACAB, propagates the uncertainties in the nuclide inventory assessing the potential impact of uncertainties in the basic nuclear data: cross-section, decay data and fission yields

Isotopic prediction simulations applied to high burnup samples irradiated in VANDELLÓS-II Reactor core

Isotopic content assessment has a paramount importance for safety and storage reasons. During the latest years, a great variety of codes have been developed to perform transport and decay calculations, but only those that couple both in an iterative manner achieve an accurate prediction of the final isotopic content of irradiated fuels. Needless to say, them all are supposed to pass the test of the comparison of their predictions against the corresponding experimental measures.

Temperature Evolution and Light Species Diffusion in Armor and Structural Material for Inertial Fusion Reactor Chambers: a Case for HiPER 4a

One of the most advance designs for HiPER fusion reactor is a spherical chamber 10 m in diameter based on dry wall concept. In this system, the first wall will have to withstand short energy pulses of 5 to 20 MJ at a repetition rate of 0.5-10 Hz mostly in form of X-rays and charged particles. To avoid melting of the inner surface, the first wall consists on a thin armor attached to the structural material. Thickness (th) and material of each layer have to be chosen to assure the proper functioning of the facility during its planned lifetime.

Air-steam gasification of sewage sludge in a bubbling bed reactor: Effect of alumina as a primary catalyst

Numerous references can be found in scientific literature regarding biomass gasification. However, there are few works related to sludge gasification. A study of sewage sludge gasification process in a bubbling fluidised bed gasifier on a laboratory scale is here reported. The aim was to find the optimum conditions for reducing the production of tars and gain more information on the influx of different operating variables in the products resulting from the gasification of this waste. The variables studied were the equivalence ratio (ER), the steam-biomass ratio (SB) and temperature. Specifically, the ER was varied from 0.2 to 0.4, the SB from 0 to 1 and the temperature from 750 °C (1023 K) to 850 °C (1123 K). Although it was observed that tar production could be considerably reduced (up to 72%) by optimising the gasification conditions, the effect of using alumina (aluminium oxide, of proven efficacy in destroying the tar produced in biomass gasification) as primary catalyst in air and air-steam mixture tests was also verified. The results show that by adding small quantities of alumina to the bed (10% by weight of fed sludge) considerable reductions in tar production can be obtained (up to 42%) improving, at the same time, the lower heating value (LHV) of the gas and carbon conversion.

Silica final lenses under HiPER laser fusion reactor operation conditions

We have studied the thermo-mechanical response and atomistic degradation of final lenses in HiPER project. Final silica lenses are squares of 75 × 75 cm2 with a thickness of 5 cm. There are two scenarios where lenses are located at 8 m from the centre: •HiPER 4a, bunches of 100 shots (maximum 5 DT shots <48 MJ at ≈0.1 Hz). No blanket in chamber geometry. •HiPER 4b, continuous mode with shots ≈50 MJ at 10 Hz to generate 0.5 GW. Liquid metal blanket in chamber design.

Análisis de Estimación Óptima del Accidente de Pérdida de Refrigerante por Rotura Pequeña de 1”en Cabeza de Vasija en un Reactor tipo PWR

En el año 2002 durante una inspección se localizó una importante corrosión en la cabeza de la vasija de Davis Besse NPP. Si no se hubiera producido esa detección temprana, la corrosión hubiera provocado una pequeña rotura en la cabeza de la vasija. La OECD/NEA consideró la importancia de simular esta secuencia en la instalación experimental ROSA, la cual fue reproducida posteriormente por grupos de investigación internacionales con varios códigos de planta. En este caso el código utilizado para la simulación de las secuencias experimentales es TRACE. Los resultados de este test experimental fueron muy analizados internacionalmente por la gran influencia que dos factores tenía sobre el resultado: las acciones del operador relativas a la despresurización y la detección del descubrimiento del núcleo por los termopares que se encuentran a su salida. El comienzo del inicio de la despresurización del secundario estaba basado en la determinación del descubrimiento del núcleo por la lectura de los temopares de salida del núcleo. En el experimento se registró un retraso importante en la determinación de ese descubrimiento, comenzando la despresurización excesivamente tarde y haciendo necesaria la desactivación de los calentadores que simulan el núcleo del reactor para evitar su daño. Dada las condiciones excesivamente conservadoras del test experimentale, como el fallo de los dos trenes de inyección de alta presión durante todo el transitorio, en las aplicaciones de los experimentos con modelo de Almaraz NPP, se ha optado por reproducir dicho accidente con condiciones más realistas, verificando el impacto en los resultados de la disponibilidad de los trenes de inyección de alta presión o los tiempos de las acciones manuales del operador, como factores más limitantes y estableciendo el diámetro de rotura en 1”