Wet chemistry synthesis towards nanostructures of thermoelectric antimonides

Die vorliegende Arbeit befasst sich mit der Synthese von nanostrukturierten Antimoniden, wobei die folgenden beiden Themen bearbeitet wurden: rnAus chemischer Sicht wurden neue Synthesewege entwickelt, um Nanopartikel der Verbindungen in den binären Systemen Zn-Sb und Fe-Sb herzustellen (Zn4Sb3, ZnSb, FeSb2, Fe1+xSb). Anders als in konventionellen Festkörperreaktionen, die auf die Synthese von Bulk-Materialien oder Einkristallen zielen, muss die Synthese von Nanopartikeln Agglomerate und Ostwald-Wachstum vermeiden. Daher benötigen annehmbare Reaktionszeiten und vergleichsweise tiefe Reaktionstemperaturen kurze Diffusionswege und tiefe Aktivierungsbarrieren. Demzufolge bedient sich die Synthese der Reaktion von Antimon-Nanopartikeln und geeigneten molekularen oder nanopartikulären Edukten der entsprechenden Übergangsmetalle. Zusätzlich wurden anisotrope ZnSb Strukturen synthetisiert, indem eine Templat-Synthese mit Hilfe von anodisierten Aluminiumoxid- oder Polycarbonat-Membranen angewandt wurde. rnDie erhaltenen Produkte wurden hauptsächlich durch Röntgen-Diffraktion und Elektronenmikroskopie untersucht. Die Auswertung der Pulver Röntgendiffraktions-Daten stellte eine Herausforderung dar, da die Nanostrukturierung und die Anwesenheit von mehreren Phasen zu verbreiterten und überlagernden Reflexen führen. Zusätzliche Fe-Mößbauer Messungen wurden im Falle der Fe-Sb Produkte vorgenommen, um detailliertere Informationen über die genaue Zusammensetzung zu erhalten. Die erstmals hergestellte Phase Zn1+xSb wurde einer detaillierten Kristallstrukturanalyse unterzogen, die mit Hilfe einer neuen Diffraktionsmethode, der automatisierten Elektronen Diffraktions Tomographie, durchgeführt wurde.rnrnAus physikalischer Sicht sind Zn4Sb3, ZnSb und FeSb2 interessante thermoelektrische Materialien, die aufgrund ihrer Fähigkeit thermische in elektrische Energie umzuwandeln, großes Interesse geweckt haben. Nanostrukturierte thermoelektrische Materialien zeigen dabei eine höhere Umwandlungseffizienz zu erhöhen, da deren thermische Leitfähigkeit herabgesetzt ist. Da thermoelektrische Bauteile aus dichten Bulk-Materialien gefertigt werden, spielte die Verfestigung der synthetisierten nanopartikulären Pulver eine große Rolle. Die als „Spark Plasma Sintering“ bezeichnete Methode wurde eingesetzt, um die Proben zu pressen. Dies ermöglicht schnelles Heizen und Abkühlen der Probe und kann so das bei klassischen Heißpress-Methoden unvermeidliche Kristallitwachstum verringern. Die optimalen Bedingungen für das Spark Plasma Sintern zu finden, ist Inhalt von bestehender und weiterführender Forschung. rnEin Problem stellt die Stabilität der Proben während des Sinterns dar. Trotz des schnellen Pressens wurde eine teilweise Zersetzung im Falle des Zn1+xSb beobachtet, wie mit Hilfe von Synchrotrondiffraktionsuntersuchungen aufgedeckt wurde. Morphologie und Dichte der verschiedenen verfestigten Materialien wurden mittels Rasterelektronenmikroskopie und Lasermikroskopie bestimmt. Die Gitterdynamik wurde mit Hilfe von Wärmekapazitätsmessungen- und inelastischer Kern-Streuung untersucht. Die Wärmeleitfähigkeit der nanostrukturierten Materialien ist im Vergleich zu den Festkörpern ist drastisch reduziert - im Falle des FeSb2 um mehr als zwei Größenordnungen. Abhängig von der Zusammensetzung und mechanischen Härte wurden für einen Teil der verfestigten Nanomaterialien die thermoelektrische Eigenschaften, wie Seebeck Koeffizient, elektrische und Wärmeleitfähigkeit, gemessen.rn

Geological and hydrogeological features affecting migration, multi-phase partitioning and degradation of chlorinated hydrocarbons through unconsolidated porous media.

Chlorinated solvents are the most ubiquitous organic contaminants found in groundwater since the last five decades. They generally reach groundwater as Dense Non-Aqueous Phase Liquid (DNAPL). This phase can migrate through aquifers, and also through aquitards, in ways that aqueous contaminants cannot. The complex phase partitioning to which chlorinated solvent DNAPLs can undergo (i.e. to the dissolved, vapor or sorbed phase), as well as their transformations (e.g. degradation), depend on the physico-chemical properties of the contaminants themselves and on features of the hydrogeological system. The main goal of the thesis is to provide new knowledge for the future investigations of sites contaminated by DNAPLs in alluvial settings, proposing innovative investigative approaches and emphasizing some of the key issues and main criticalities of this kind of contaminants in such a setting. To achieve this goal, the hydrogeologic setting below the city of Ferrara (Po plain, northern Italy), which is affected by scattered contamination by chlorinated solvents, has been investigated at different scales (regional and site specific), both from an intrinsic (i.e. groundwater flow systems) and specific (i.e. chlorinated solvent DNAPL behavior) point of view. Detailed investigations were carried out in particular in one selected test-site, known as “Caretti site”, where high-resolution vertical profiling of different kind of data were collected by means of multilevel monitoring systems and other innovative sampling and analytical techniques. This allowed to achieve a deep geological and hydrogeological knowledge of the system and to reconstruct in detail the architecture of contaminants in relationship to the features of the hosting porous medium. The results achieved in this thesis are useful not only at local scale, e.g. employable to interpret the origin of contamination in other sites of the Ferrara area, but also at global scale, in order to address future remediation and protection actions of similar hydrogeologic settings.

Assessment and optimization of chemical industrial processes from a life cycle perspective

During the PhD program in chemistry, curriculum in environmental chemistry, at the University of Bologna the sustainability of industry was investigated through the application of the LCA methodology. The efforts were focused on the chemical sector in order to investigate reactions dealing with the Green Chemistry and Green Engineering principles, evaluating their sustainability in comparison with traditional pathways by a life cycle perspective. The environmental benefits associated with a reduction in the synthesis steps and the use of renewable feedstock were assessed through a holistic approach selecting two case studies with high relevance from an industrial point of view: the synthesis of acrylonitrile and the production of acrolein. The current approach wants to represent a standardized application of LCA methodology to the chemical sector, which could be extended to several case studies, and also an improvement of the current databases, since the lack of data to fill the inventories of the chemical productions represent a huge limitation, difficult to overcome and that can affects negatively the results of the studies. Results emerged from the analyses confirms that the sustainability in the chemical sector should be evaluated from a cradle-to-gate approach, considering all the stages and flows involved in each pathways in order to avoid shifting the environmental burdens from a steps to another. Moreover, if possible, LCA should be supported by other tools able to investigate the other two dimensions of sustainability represented by the social and economic issues.

Formation of DNA complexes in aqueous and organic solvents

From a physical-chemical point of view, it is challenging to form complexes with polyelectrolytes, consisting of only molecule of the largest component, i.e. the component with the highest number of charges. In this study, complexes are formed with DNA because of its potential applications as an artificial vector for gene delivery. The aim of this work is to prepare complexes in aqueous solutions as well as in organic solvents containing only one DNA molecule. For this purpose, the topology, equilibrium and conformation of complexes between a supercoiled DNA pUC19 (2686 base pairs) and spermine containing hydrophilic and/or hydrophobic moieties or a polylysine with a hydrophilic block are determined by means of dynamic (DLS) and static light scattering (SLS), atomic force microscopy (AFM), and circular dichroism (CD) spectroscopy. It is demonstrated that all of these complexes consisted of only one molecule of the polyanion. Only the polylysine-b-polyethylene glycol copolymer satisfied the conditions: 1) 100% neutralization of DNA charges and with a small excess of the cation (lower than 30%) and 2) form stable complexes at every charge ratio. rnDNA complex formation is also investigated in organic solvents. Precipitation is induced by neutralizing the charge of the supercoiled DNA pUC19 with the surfactants dodecyltrimethylammonium bromide (DTAB) and tetradecyltrimethylammonium bromide (TTAB). After isolation and drying of the solids, the complexes are dissolved in organic solvents. DNA-TTA complexes are only soluble in methanol and DNA-DTA in DMF. The complexes again consisted of only one DNA molecule. The final topology of the complexes is different in methanol than in DMF. In the former case, DNA seems to be compacted whereas in the latter case, the DNA-DTA complexes seem to have an expanded conformation. Upon complex formation with polycations in organic solvents (with polyvilylpyridine brush (b-PVP) in methanol and with a protected polylysine in DMF), DNA aggregates and precipitates. rnDNA is linearized with an enzyme (SmaI) to investigate the influence of the initial topology of the polyanion on the final conformation of the complexes in organic solvents. Two main differences are evidenced: 1. Complexes in organic solvents formed with linear DNA have in general a more expanded conformation and a higher tendency to aggregate. 2. If a polycation, i.e. the b-PVP, is added to the linear DNA-TTA complexes in methanol, complexes with the polycation are formed at a higher charge ratio. In DMF, the addition of the same b-PVP and of b-PLL did not lead to the formation of complexes.rn

Investigation of the reactivity of metal oxide catalysts for the gas-phase phenol methylation

The gas-phase phenol methylation with methanol was investigated both from catalitic and spectroscopic point of view. In particular, the work focus on the behavior of metal oxide catalysts, like iron(III) vanadate and aluminum vanadate. Spectroscopic studies include: X-ray diffraction and Raman analysis for catalyst charactrerization; Diffuse reflectance infrared fourier transform spectroscopy and in-situ Infrared spectroscopy in vacuum for investigation of interactions between reactants and surface of catalysts.

Enhancement of inductive power transfer with flat spiral resonators

The aim of this thesis is to develop a depth analysis of the inductive power transfer (or wireless power transfer, WPT) along a metamaterial composed of cells arranged in a planar configuration, in order to deliver power to a receiver sliding on them. In this way, the problem of the efficiency strongly affected by the weak coupling between emitter and receiver can be obviated, and the distance of transmission can significantly be increased. This study is made using a circuital approach and the magnetoinductive wave (MIW) theory, in order to simply explain the behavior of the transmission coefficient and efficiency from the circuital and experimental point of view. Moreover, flat spiral resonators are used as metamaterial cells, particularly indicated in literature for WPT metamaterials operating at MHz frequencies (5-30 MHz). Finally, this thesis presents a complete electrical characterization of multilayer and multiturn flat spiral resonators and, in particular, it proposes a new approach for the resistance calculation through finite element simulations, in order to consider all the high frequency parasitic effects. Multilayer and multiturn flat spiral resonators are studied in order to decrease the operating frequency down to kHz, maintaining small external dimensions and allowing the metamaterials to be supplied by electronic power converters (resonant inverters).

Characterization of integrated Bragg gratings in silicon-on-insulator

Silicon-on-insulator (SOI) is rapidly emerging as a very promising material platform for integrated photonics. As it combines the potential for optoelectronic integration with the low-cost and large volume manufacturing capabilities and they are already accumulate a huge amount of applications in areas like sensing, quantum optics, optical telecommunications and metrology. One of the main limitations of current technology is that waveguide propagation losses are still much higher than in standard glass-based platform because of many reasons such as bends, surface roughness and the very strong optical confinement provided by SOI. Such high loss prevents the fabrication of efficient optical resonators and complex devices severely limiting the current potential of the SOI platform. The project in the first part deals with the simple waveguides loss problem and trying to link that with the polarization problem and the loss based on Fabry-Perot Technique. The second part of the thesis deals with the Bragg Grating characterization from again the point of view of the polarization effect which leads to a better stop-band use filters. To a better comprehension a brief review on the basics of the SOI and the integrated Bragg grating ends up with the fabrication techniques and some of its applications will be presented in both parts, until the end of both the third and the fourth chapters to some results which hopefully make its precedent explanations easier to deal with.

Molecular genetic causes of columnar growth in apple (Malus x domestica)

The columnar growth habit of apple is interesting from an economic point of view as the pillar-like trees require little space and labor. Genetic engineering could be used to speed up breeding for columnar trees with high fruit quality and disease resistance. For this purpose, this study dealt with the molecular causes of this interesting phenotype. The original bud sport mutation that led to the columnar growth habit was found to be a novel nested insertion of a Gypsy-44 LTR retrotransposon on chromosome 10 at 18.79 Mb. This subsequently causes tissue-specific differential expression of nearby downstream genes, particularly of a gene encoding a 2OG-Fe(II) oxygenase of unknown function (dmr6-like) that is strongly upregulated in developing aerial tissues of columnar trees. The tissue-specificity of the differential expression suggests involvement of cis-regulatory regions and/or tissue-specific epigenetic markers whose influence on gene expression is altered due to the retrotransposon insertion. This eventually leads to changes in genes associated with stress and defense reactions, cell wall and cell membrane metabolism as well as phytohormone biosynthesis and signaling, which act together to cause the typical phenotype characteristics of columnar trees such as short internodes and the absence of long lateral branches. In future, transformation experiments introducing Gypsy-44 into non-columnar varieties or excising Gypsy-44 from columnar varieties would provide proof for our hypotheses. However, since site-specific transformation of a nested retrotransposon is a (too) ambitious objective, silencing of the Gypsy-44 transcripts or the nearby genes would also provide helpful clues.

A river runs through it - ancient DNA data on the neolithic populations of the Great Hungarian Plain

This thesis was part of a multidisciplinary research project funded by the German Research Foundation (“Bevölkerungsgeschichte des Karpatenbeckens in der Jungsteinzeit und ihr Einfluss auf die Besiedlung Mitteleuropas”, grant no. Al 287/10-1) aimed at elucidating the population history of the Carpathian Basin during the Neolithic. The Carpathian Basin was an important waypoint on the spread of the Neolithic from southeastern to central Europe. On the Great Hungarian Plain (Alföld), the first farming communities appeared around 6000 cal BC. They belonged to the Körös culture, which derived from the Starčevo-Körös-Criş complex in the northern Balkans. Around 5600 cal BC the Alföld-Linearbandkeramik (ALBK), so called due to its stylistic similarities with the Transdanubian and central European LBK, emerged in the northwestern Alföld. Following a short “classical phase”, the ALBK split into several regional subgroups during its later stages, but did not expand beyond the Great Hungarian Plain. Marking the beginning of the late Neolithic period, the Tisza culture first appeared in the southern Alföld around 5000 cal BC and subsequently spread into the central and northern Alföld. Together with the Herpály and Csőszhalom groups it was an integral part of the late Neolithic cultural landscape of the Alföld. Up until now, the Neolithic cultural succession on the Alföld has been almost exclusively studied from an archaeological point of view, while very little is known about the population genetic processes during this time period. The aim of this thesis was to perform ancient DNA (aDNA) analyses on human samples from the Alföld Neolithic and analyse the resulting mitochondrial population data to address the following questions: is there population continuity between the Central European Mesolithic hunter-gatherer metapopulation and the first farming communities on the Alföld? Is there genetic continuity from the early to the late Neolithic? Are there genetic as well as cultural differences between the regional groups of the ALBK? Additionally, the relationships between the Alföld and the neighbouring Transdanubian Neolithic as well as other European early farming communities were evaluated to gain insights into the genetic affinities of the Alföld Neolithic in a larger geographic context. 320 individuals were analysed for this study; reproducible mitochondrial haplogroup information (HVS-I and/or SNP data) could be obtained from 242 Neolithic individuals. According to the analyses, population continuity between hunter-gatherers and the Neolithic cultures of the Alföld can be excluded at any stage of the Neolithic. In contrast, there is strong evidence for population continuity from the early to the late Neolithic. All cultural groups on the Alföld were heavily shaped by the genetic substrate introduced into the Carpathian Basin during the early Neolithic by the Körös and Starčevo cultures. Accordingly, genetic differentiation between regional groups of the ALBK is not very pronounced. The Alföld cultures are furthermore genetically highly similar to the Transdanubian Neolithic cultures, probably due to common ancestry. In the wider European context, the Alföld Neolithic cultures also highly similar to the central European LBK, while they differ markedly from contemporaneous populations of the Iberian Peninsula and the Ukraine. Thus, the Körös culture, the ALBK and the Tisza culture can be regarded as part of a “genetic continuum” that links the Neolithic Carpathian Basin to central Europe and likely has its roots in the Starčevo -Körös-Criş complex of the northern Balkans.

Stochastic foundations of dynamic trade and labor market models

This dissertation consists of three self-contained papers that are related to two main topics. In particular, the first and third studies focus on labor market modeling, whereas the second essay presents a dynamic international trade setup.rnrnIn Chapter "Expenses on Labor Market Reforms during Transitional Dynamics", we investigate the arising costs of a potential labor market reform from a government point of view. To analyze various effects of unemployment benefits system changes, this chapter develops a dynamic model with heterogeneous employed and unemployed workers.rn rnIn Chapter "Endogenous Markup Distributions", we study how markup distributions adjust when a closed economy opens up. In order to perform this analysis, we first present a closed-economy general-equilibrium industry dynamics model, where firms enter and exit markets, and then extend our analysis to the open-economy case.rn rnIn Chapter "Unemployment in the OECD - Pure Chance or Institutions?", we examine effects of aggregate shocks on the distribution of the unemployment rates in OECD member countries.rn rnIn all three chapters we model systems that behave randomly and operate on stochastic processes. We therefore exploit stochastic calculus that establishes clear methodological links between the chapters.

Numerical and semi-analytical models of sliding masses: application to the 1783 Scilla tsunamigenic landslide

The Scilla rock avalanche occurred on 6 February 1783 along the coast of the Calabria region (southern Italy), close to the Messina Strait. It was triggered by a mainshock of the Terremoto delle Calabrie seismic sequence, and it induced a tsunami wave responsible for more than 1500 casualties along the neighboring Marina Grande beach. The main goal of this work is the application of semi-analtycal and numerical models to simulate this event. The first one is a MATLAB code expressly created for this work that solves the equations of motion for sliding particles on a two-dimensional surface through a fourth-order Runge-Kutta method. The second one is a code developed by the Tsunami Research Team of the Department of Physics and Astronomy (DIFA) of the Bologna University that describes a slide as a chain of blocks able to interact while sliding down over a slope and adopts a Lagrangian point of view. A wide description of landslide phenomena and in particular of landslides induced by earthquakes and with tsunamigenic potential is proposed in the first part of the work. Subsequently, the physical and mathematical background is presented; in particular, a detailed study on derivatives discratization is provided. Later on, a description of the dynamics of a point-mass sliding on a surface is proposed together with several applications of numerical and analytical models over ideal topographies. In the last part, the dynamics of points sliding on a surface and interacting with each other is proposed. Similarly, different application on an ideal topography are shown. Finally, the applications on the 1783 Scilla event are shown and discussed.

Micropollutants affect the ability of phytoplankton communities to track environmental changes

Human activities strongly influence environmental processes, and while human domination increases, biodiversity progressively declines in ecosystems worldwide. High genetic and phenotypic variability ensures functionality and stability of ecosystem processes through time and increases the resilience and the adaptive capacity of populations and communities, while a reduction in functional diversity leads to a decrease in the ability to respond in a changing environment. Pollution is becoming one of the major threats in aquatic ecosystem, and pharmaceutical and personal care products (PPCPs) in particular are a relatively new group of environmental contaminants suspected to have adverse effects on aquatic organisms. There is still a lake of knowledge on the responses of communities to complex chemical mixtures in the environment. We used an individual-trait-based approach to assess the response of a phytoplankton community in a scenario of combined pollution and environmental change (steady increasing in temperature). We manipulated individual-level trait diversity directly (by filtering out size classes) and indirectly (through exposure to PPCPs mixture), and studied how reduction in trait-diversity affected community structure, production of biomass and the ability of the community to track a changing environment. We found that exposure to PPCPs slows down the ability of the community to respond to an increasing temperature. Our study also highlights how physiological responses (induced by PPCPs exposure) are important for ecosystem processes: although from an ecological point of view experimental communities converged to a similar structure, they were functionally different.

On the recurrence of random walks in Lévy random environments

This thesis investigates one-dimensional random walks in random environment whose transition probabilities might have an infinite variance. The ergodicity of the dynamical system ''from the point of view of the particle'' is proved under the assumptions of transitivity and existence of an absolutely continuous steady state on the space of the environments. We show that, if the average of the local drift over the environments is summable and null, then the RWRE is recurrent. We provide an example satisfying all the hypotheses.

Design of an indirectly fired gas turbine integrated with an organic rankine cycle unit for combined heat and power production

In the last years, the European countries have paid increasing attention to renewable sources and greenhouse emissions. The Council of the European Union and the European Parliament have established ambitious targets for the next years. In this scenario, biomass plays a prominent role since its life cycle produces a zero net carbon dioxide emission. Additionally, biomass can ensure plant operation continuity thanks to its availability and storage ability. Several conventional systems running on biomass are available at the moment. Most of them are performant either in the large-scale or in the small power range. The absence of an efficient system on the small-middle scale inspired this thesis project. The object is an innovative plant based on a wet indirectly fired gas turbine (WIFGT) integrated with an organic Rankine cycle (ORC) unit for combined heat and power production. The WIFGT is a performant system in the small-middle power range; the ORC cycle is capable of giving value to low-temperature heat sources. Their integration is investigated in this thesis with the aim of carrying out a preliminary design of the components. The targeted plant output is around 200 kW in order not to need a wide cultivation area and to avoid biomass shipping. Existing in-house simulation tools are used: They are adapted to this purpose. Firstly the WIFGT + ORC model is built; Zero-dimensional models of heat exchangers, compressor, turbines, furnace, dryer and pump are used. Different fluids are selected but toluene and benzene turn out to be the most suitable. In the indirectly fired gas turbine a pressure ratio around 4 leads to the highest efficiency. From the thermodynamic analysis the system shows an electric efficiency of 38%, outdoing other conventional plants in the same power range. The combined plant is designed to recover thermal energy: Water is used as coolant in the condenser. It is heated from 60°C up to 90°C, ensuring the possibility of space heating. Mono-dimensional models are used to design the heat exchange equipment. Different types of heat exchangers are chosen depending on the working temperature. A finned-plate heat exchanger is selected for the WIFGT heat transfer equipment due to the high temperature, oxidizing and corrosive environment. A once-through boiler with finned tubes is chosen to vaporize the organic fluid in the ORC. A plate heat exchanger is chosen for the condenser and recuperator. A quasi-monodimensional model for single-stage axial turbine is implemented to design both the WIFGT and the ORC turbine. The system simulation after the components design shows an electric efficiency around 34% with a decrease by 10% compared to the zero-dimensional analysis. The work exhibits the system potentiality compared to the existing plants from both technical and economic point of view.

How to assess the external validity of therapeutic trials: a conceptual approach

Background External validity of study results is an important issue from a clinical point of view. From a methodological point of view, however, the concept of external validity is more complex than it seems to be at first glance. Methods Methodological review to address the concept of external validity. Results External validity refers to the question whether results are generalizable to persons other than the population in the original study. The only formal way to establish the external validity would be to repeat the study for that specific target population. We propose a three-way approach for assessing the external validity for specified target populations. (i) The study population might not be representative for the eligibility criteria that were intended. It should be addressed whether the study population differs from the intended source population with respect to characteristics that influence outcome. (ii) The target population will, by definition, differ from the study population with respect to geographical, temporal and ethnical conditions. Pondering external validity means asking the question whether these differences may influence study results. (iii) It should be assessed whether the study's conclusions can be generalized to target populations that do not meet all the eligibility criteria. Conclusion Judging the external validity of study results cannot be done by applying given eligibility criteria to a single target population. Rather, it is a complex reflection in which prior knowledge, statistical considerations, biological plausibility and eligibility criteria all have place.