ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

DESIGN OF EFFICIENT IN-NETWORK DATA PROCESSING AND DISSEMINATION FOR VANETS

By providing vehicle-to-vehicle and vehicle-to-infrastructure wireless communications, vehicular ad hoc networks (VANETs), also known as the “networks on wheels”, can greatly enhance traffic safety, traffic efficiency and driving experience for intelligent transportation system (ITS). However, the unique features of VANETs, such as high mobility and uneven distribution of vehicular nodes, impose critical challenges of high efficiency and reliability for the implementation of VANETs. This dissertation is motivated by the great application potentials of VANETs in the design of efficient in-network data processing and dissemination. Considering the significance of message aggregation, data dissemination and data collection, this dissertation research targets at enhancing the traffic safety and traffic efficiency, as well as developing novel commercial applications, based on VANETs, following four aspects: 1) accurate and efficient message aggregation to detect on-road safety relevant events, 2) reliable data dissemination to reliably notify remote vehicles, 3) efficient and reliable spatial data collection from vehicular sensors, and 4) novel promising applications to exploit the commercial potentials of VANETs. Specifically, to enable cooperative detection of safety relevant events on the roads, the structure-less message aggregation (SLMA) scheme is proposed to improve communication efficiency and message accuracy. The scheme of relative position based message dissemination (RPB-MD) is proposed to reliably and efficiently disseminate messages to all intended vehicles in the zone-of-relevance in varying traffic density. Due to numerous vehicular sensor data available based on VANETs, the scheme of compressive sampling based data collection (CS-DC) is proposed to efficiently collect the spatial relevance data in a large scale, especially in the dense traffic. In addition, with novel and efficient solutions proposed for the application specific issues of data dissemination and data collection, several appealing value-added applications for VANETs are developed to exploit the commercial potentials of VANETs, namely general purpose automatic survey (GPAS), VANET-based ambient ad dissemination (VAAD) and VANET based vehicle performance monitoring and analysis (VehicleView). Thus, by improving the efficiency and reliability in in-network data processing and dissemination, including message aggregation, data dissemination and data collection, together with the development of novel promising applications, this dissertation will help push VANETs further to the stage of massive deployment.

Participation of portuguese manufacturing industry in global value chains

Portugal’s manufacturing sector has a significant importance both in national income and employment. As has been pointed out by several researchers, the traditional methods of analysis fail to grasp all the dimensions of economic competitiveness. This dissertation is then, at its core, an analysis of Portugal’s manufacturing industry in terms of the latter’s value added to production and impact to employment under the framework of global value chains. The current dissertation seeks to study in which way the Portuguese manufacturing industry, and its respective sectors, has a direct and indirect impact on the creation of value added and employment and how this impact can be measured. For development of this work the input-output approach for calculation of multipliers and the new framework proposed by Timmer et al. (2013) for calculation of GVC income and GVC jobs indicators were used, elaborated on the basis of the WIOD project dataset. Moreover, to illustrate the application of the provided methodology the Portuguese textile industry was used as an example. It was found that the changes in final demand of such sectors as Pulp, Paper, Printing and Publishing; Machinery, Nec and Textiles and Textile Products would have a larger impact on generated value added than other manufacturing sectors. At the same time, employment created by the changes in final demand would be more impacted by such sectors as Food, Beverages and Tobacco; Wood and Products of Wood and Cork and Textiles and Textile Products. In this regard, the number of low-skilled workers in Portugal seems to be more effected by changes in final demand, than those occupied by higher -skilled individuals. Moreover, it was found that the distribution of GVC income and GVC jobs for the Portuguese manufacturing industry shares a similar outlook. However, upon closer inspection of GVC labour distribution by skill levels there seems to exist a general progression in which low-skilled jobs requirements are met by local resources, while the need for higher skilled jobs require a greater “off-shoring” of work The results obtained through calculations of presented multipliers provide a powerful tool for policy makers in strategic planning of development of national economy. Using the provided methodology and obtained results, a government and supranational organizations could define which industry would have the greatest impact for an additional unit of output generated through the economy, and thus define the sectors for further investments.

Plan de negocios endúlzate: emprendimiento

En principio, la realización de este proyecto conllevo al desarrollo de mis habilidades y conocimientos adquiridos durante la carrera de administración de Negocios Internacionales. Así mismo, me permitió tener una visión más cercana sobre el proceso de comercio exterior, con el trabajo a diario en Procolombia, empresa en la que realizo mi pasantía, el hacer investigaciones de mercado, el contacto con empresarios exportadores de panela, trabajar con expertos de la empresa en el sector panelero, las diversas capacitaciones en temas de comercio exterior, identificación de mercados potenciales y asuntos legales de la exportación, enriqueció la información y construcción de mi proyecto. El mercado de los endulzantes naturales a nivel mundial, según estudios de Euromonitor Internacional ha venido tenido un protagonismo cada vez más importante en diversos mercados, especialmente en Estados Unidos y Europa. Así, cada vez existe un mayor número de personas que se abstienen del consumo del azúcar refinado, pues temen del padecimiento de enfermedades como la obesidad o el cáncer a causa de productos fabricados con químicos. De esta manera, las tendencias de consumo se encaminan hacia la búsqueda por parte de las personas por alimentos naturales, dentro de los cuales se encuentran los endulzantes sin químicos que aportan un alto valor nutricional. En este sentido, la unión Europea se convierte en un mercado atractivo para la exportación de endulzantes naturales, esto debido a las tendencias de los europeos hacia el consumo de alimentos saludables según lo afirma un estudio de mercado del Ministry of foreign affairs (CBI). De esta manera, el país con mayores índices de consumo de alimentos orgánicos es Alemania, sumado a ello en los hábitos de consumo son importantes los endulzantes pues la ingesta de té y café es alta, haciéndose mayor en época de invierno.

The significant role of third-party logistics (3pl) operators as fosterers of organizational performance in colombian companies

La eliminación de barreras entre países es una consecuencia que llega con la globalización y con los acuerdos de TLC firmados en los últimos años. Esto implica un crecimiento significativo del comercio exterior, lo cual se ve reflejado en un aumento de la complejidad de la cadena de suministro de las empresas. Debido a lo anterior, se hace necesaria la búsqueda de alternativas para obtener altos niveles de productividad y competitividad dentro de las empresas en Colombia, ya que el entorno se ha vuelto cada vez más complejo, saturado de competencia no sólo nacional, sino también internacional. Para mantenerse en una posición competitiva favorable, las compañías deben enfocarse en las actividades que le agregan valor a su negocio, por lo cual una de las alternativas que se están adoptando hoy en día es la tercerización de funciones logísticas a empresas especializadas en el manejo de estos servicios. Tales empresas son los Proveedores de servicios logísticos (LSP), quienes actúan como agentes externos a la organización al gestionar, controlar y proporcionar actividades logísticas en nombre de un contratante. Las actividades realizadas pueden incluir todas o parte de las actividades logísticas, pero como mínimo la gestión y ejecución del transporte y almacenamiento deben estar incluidos (Berglund, 2000). El propósito del documento es analizar el papel de los Operadores Logísticos de Tercer nivel (3PL) como promotores del desempeño organizacional en las empresas colombianas, con el fin de informar a las MIPYMES acerca de los beneficios que se obtienen al trabajar con LSP como un medio para mejorar la posición competitiva del país.

Non-Equilibrium Atmospheric Plasma As A Novel Route To Nanomaterial Synthesis And Processing For Biomedical Applications

Since last century, the rising interest of value-added and advanced functional materials has spurred a ceaseless development in terms of industrial processes and applications. Among the emerging technologies, thanks to their unique features and versatility in terms of supported processes, non-equilibrium plasma discharges appear as a key solvent-free, high-throughput and cost-efficient technique. Nevertheless, applied research studies are needed with the aim of addressing plasma potentialities optimizing devices and processes for future industrial applications. In this framework, the aim of this dissertation is to report on the activities carried out and the results achieved concerning the development and optimization of plasma techniques for nanomaterial synthesis and processing to be applied in the biomedical field. In the first section, the design and investigation of a plasma assisted process for the production of silver (Ag) nanostructured multilayer coatings exhibiting anti-biofilm and anti-clot properties is described. With the aim on enabling in-situ and on-demand deposition of Ag nanoparticles (NPs), the optimization of a continuous in-flight aerosol process for particle synthesis is reported. The stability and promising biological performances of deposited coatings spurred further investigation through in-vitro and in-vivo tests which results are reported and discussed. With the aim of addressing the unanswered questions and tuning NPs functionalities, the second section concerns the study of silver containing droplet conversion in a flow-through plasma reactor. The presented results, obtained combining different analysis techniques, support a formation mechanism based on droplet to particle conversion driven by plasma induced precursor reduction. Finally, the third section deals with the development of a simulative and experimental approach used to investigate the in-situ droplet evaporation inside the plasma discharge addressing the main contributions to liquid evaporation in the perspective of process industrial scale up.

I servizi di investimento nella disciplina dell'imposta sul valore aggiunto: il quadro normativo europeo e la sua attuazione nazionale

Il presente lavoro di ricerca ha ad oggetto i profili fiscali IVA dei servizi di investimento, in ambito sia europeo che nazionale, prestati dalle banche, dalle Sim e da consulenti/società di consulenza finanziaria nei confronti della clientela al dettaglio. Ciò al fine di individuarne il corretto trattamento fiscale nonché le possibili soluzioni agli interrogativi che ancora oggi rimangono aperti, anche alla luce delle indicazioni fornite nel tempo dalla Corte di Giustizia europea. Constatata la profonda differenza esistente tra la classificazione MiFID dei servizi di investimento e quella fiscale delle operazioni finanziarie, oltre alla mancanza di coordinamento tra le relative normative europee, che non si incontrano neanche nell’attività ermeneutica della Corte di giustizia, si è cercato di interpretare la Direttiva IVA alla luce della normativa di settore (MIFID). L’analisi della Direttiva IVA e, più in particolare, del trattamento da essa riservato alle operazioni finanziarie è stata, quindi, svolta cercando di ricondurre queste ultime ai (singoli) servizi di investimento (e, quindi, alla Direttiva MiFID) al fine di tracciare un collegamento che né il legislatore comunitario né la CGE hanno individuato. È, tuttavia, apparso evidente come l’intero sistema dell’IVA, con particolare riferimento alle operazioni finanziarie, si sia ormai consolidato sulle interpretazioni della Corte di giustizia le quali hanno mostrato una elevata resilienza intrinseca. È, pertanto, auspicabile un intervento legislativo, a livello comunitario, finalizzato a rimettere mano alla Direttiva IVA al fine di fornire criteri più chiari e stringenti per l’applicazione delle disposizioni in essa contenute, con particolare riferimento a quelle relative alle operazioni finanziarie.

Optimization of an innovative T6 heat treatment for the AlSi10Mg alloy processed by Laser-based Powder Bed Fusion: effect on microstructure, mechanical properties, and tribological behavior

Laser-based Powder Bed Fusion (L-PBF) technology is one of the most commonly used metal Additive Manufacturing (AM) techniques to produce highly customized and value-added parts. The AlSi10Mg alloy has received more attention in the L-PBF process due to its good printability, high strength/weight ratio, corrosion resistance, and relatively low cost. However, a deep understanding of the effect of heat treatments on this alloy's metastable microstructure is still required for developing tailored heat treatments for the L-PBF AlSi10Mg alloy to overcome the limits of the as-built condition. Several authors have already investigated the effects of conventional heat treatment on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy but often overlooked the peculiarities of the starting supersatured and ultrafine microstructure induced by rapid solidification. For this reason, the effects of innovative T6 heat treatment (T6R) on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy were assessed. The short solution soaking time (10 min) and the relatively low temperature (510 °C) reduced the typical porosity growth at high temperatures and led to a homogeneous distribution of fine globular Si particles in the Al matrix. In addition, it increased the amount of Mg and Si in the solid solution available for precipitation hardening during the aging step. The mechanical (at room temperature and 200 °C) and tribological properties of the T6R alloy were evaluated and compared with other solutions, especially with an optimized direct-aged alloy (T5 alloy). Results showed that the innovative T6R alloy exhibits the best mechanical trade-off between strength and ductility, the highest fatigue strength among the analyzed conditions, and interesting tribological behavior. Furthermore, the high-temperature mechanical performances of the heat-treated L-PBF AlSi10Mg alloy make it suitable for structural components operating in mild service conditions at 200 °C.

Development of processes for the valorization of lignocellulosic biomass based on renewable energies

The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.

ENVIRONMENTAL TEMPERATURES IN FLORIDA DAIRY HOUSING

Environmental conditions in all air-conditioned barn and in evaporatively cooled sprinkler and fall and tunnel-ventilated barns are compared and recommendations for dairy barn design for hot, humid climates arc, given. Temperature Humidity Indexes (THI) observed in the air-conditioned barn were always below 72. Average THIs ill the evaporatively cooled barns during afternoon hours were seldom less than 75. The environmental conditions observed in these studies are typical for many, areas adjacent to the Gulf Coast of the United States and for tropical regions throughout the world. Providing comfortable environmental conditions for cows housed in area with hot, humid climates is difficult using only evaporative cooling and ventilation. Air-conditioning dairy housing is a possible alternative method, particularly for high value cows.

VALOR ECONÔMICO AGREGADO POR HOSPITAIS UNIVERSITÁRIOS PÚBLICOS

The increasing participation of the society in the decision-making process related to public politics stimulates public administration in Brazil to search for mechanisms to demonstrate efficiency and disclosure in resource application. The main objective of this work is to calculate the economic value added to the society by Public University Hospitals. Therefore, a Public University Hospital case study has been carried out and its economic performance evaluated during a period of three years. This study has shown that the economic value added to the society in the long term by the entity is positive. The proposed value measurement has indicated that the society is getting a superior return from the opportunity costs of capital invested, that is, the hospital is constructing economic value and consequently contributing to the social welfare.

Suspension of apatite particles in a self-aerated Denver laboratory flotation cell

Effective solids suspension is a necessary precondition for particle collection, and solids suspension is largely dependent on the hydrodynamics of the flotation cell. This study attempted to correlate the status of the suspension of apatite particles of different sizes in a Denver laboratory flotation cell versus the impeller rotational speed (N) adopted to operate the machine. The latter variable (N) influences the impeller capacity to lift the particles from the bottom of the tank and also to disperse them throughout the volume of the vessel. Such an impeller capacity can be characterized by the critical impeller speed for the accomplishment of solids off-bottom suspension (N(z)) and also by the velocity of the radial water flow discharged by the impeller (U) divided by the particle terminal settling velocity (U(s)). This way, the status of the suspension of apatite particles inside the flotation cell can be characterized by one of three categories: ""segregation"" (N/N(2) < 0.60 and U(s)/U > 0.08); ""suspension"" (0.60 <= N/N(2) < 1 and 0.06 < U(s)/U < 0.10); and ""dragging"" (N/N(2) >= 1 and U(s)/U <= 0.03). The range of impeller rotational speed (N), which was able to suspend the finest particles (D(p) = 90,mu m), was unable to suspend the coarsest particles (D(P) = 254 mu m). Conversely, the high value of N (N > 1,300 rpm), which is adequate to suspend the coarsest particles, may promote the entrainment of the finest particles to the froth layer.

Tax Cost of Investment Projects: the case of ICMS credits

This article discusses the impact on the profitability of firms under Complementary Law 102/2000 (which abrogated the Law 89/96 - Kandir Law) allowing the appropriation of ICMS credits, due to investment in fixed assets goods, at a ratio of 1/48 per month. The paper seeks to demonstrate how this new system - which resulted in the transformation of the ICMS as a value added tax (VAT) consumption-type to an income-type - leads to a loss of approximately 30% of the value of credits to be recovered and the effect it generates on the cost of investment and the profits for small, medium and large firms. From the methodological point of view, it is a descriptive and quantitative research, which proceeded in three stages. Initially, we have obtained estimated value of net sales and volume of investments, based on report Painel de Competitividade prepared by the Federacao das Indtustrias do Estado de Sao Paulo (Fiesp/Serasa). Based on this information, it was possible to obtain estimates of the factors of generation of debits and credits for ICMS, using the model Credit Control of Fixed Assets (CIAP). Finally, we have calculated three indicators: (i) present value of debt recovery/value of credits, (ii) present value of debt recovery / investment value, (iii) present value of debt recovery / sales profitability. We have conclude that the system introduced by Complementary Law 102/2000 implicates great opportunity cost for firms and that legislation should be reviewed from this perspective, aiming to ensure lower costs associated with investment projects.

How rare is too rare to harvest? Management challenges posed by timber species occurring at low densities in the Brazilian Amazon

Tropical forests are characterized by diverse assemblages of plant and animal species compared to temperate forests. Corollary to this general rule is that most tree species, whether valued for timber or not, occur at low densities (<1 adult tree ha(-1)) or may be locally rare. In the Brazilian Amazon, many of the most highly valued timber species occur at extremely low densities yet are intensively harvested with little regard for impacts on population structures and dynamics. These include big-leaf mahogany (Swietenia macrophylla), ipe (Tabebuia serratifolia and Tabebuia impetiginosa), jatoba (Hymenaea courbaril), and freijo cinza (Cordia goeldiana). Brazilian forest regulations prohibit harvests of species that meet the legal definition of rare - fewer than three trees per 100 ha - but treat all species populations exceeding this density threshold equally. In this paper we simulate logging impacts on a group of timber species occurring at low densities that are widely distributed across eastern and southern Amazonia, based on field data collected at four research sites since 1997, asking: under current Brazilian forest legislation, what are the prospects for second harvests on 30-year cutting cycles given observed population structures, growth, and mortality rates? Ecologically `rare` species constitute majorities in commercial species assemblages in all but one of the seven large-scale inventories we analyzed from sites spanning the Amazon (range 49-100% of total commercial species). Although densities of only six of 37 study species populations met the Brazilian legal definition of a rare species, timber stocks of five of the six timber species declined substantially at all sites between first and second harvests in simulations based on legally allowable harvest intensities. Reducing species-level harvest intensity by increasing minimum felling diameters or increasing seed tree retention levels improved prospects for second harvests of those populations with a relatively high proportion of submerchantable stems, but did not dramatically improve projections for populations with relatively flat diameter distributions. We argue that restrictions on logging very low-density timber tree populations, such as the current Brazilian standard, provide inadequate minimum protection for vulnerable species. Population declines, even if reduced-impact logging (RIL) is eventually adopted uniformly, can be anticipated for a large pool of high-value timber species unless harvest intensities are adapted to timber species population ecology, and silvicultural treatments are adopted to remedy poor natural stocking in logged stands. (C) 2008 Elsevier B.V. All rights reserved.

Sugar and ethanol production as a rural development strategy in Brazil: Evidence from the state of Sao Paulo

Sugar and ethanol production are key components of Brazil`s rural development and energy strategies, yet in recent years sugar production has been widely criticized for its environmental and labor practices. This study examines the relationship between rural development and sugarcane, ethanol, and cattle production in the state of Sao Paulo. Our results suggest that the value added components of sugarcane production, which include sugar refining and ethanol production, may have a strong positive affect on local human development in comparison to primary agricultural production activities and other land uses. These results imply that sugar production, when accompanied by a local processing industry can stimulate rural development. However, this paper also highlights the significant environmental and social harms generated by the sugar industry at large, which may undermine its development benefits if not addressed. (C) 2011 Elsevier Ltd. All rights reserved.