Core-shell particles and their application for superhydrophobic surfaces

During the last years great effort has been devoted to the fabrication of superhydrophobic surfaces because of their self-cleaning properties. A water drop on a superhydrophobic surface rolls off even at inclinations of only a few degrees while taking up contaminants encountered on its way. rnSuperhydrophobic, self-cleaning coatings are desirable for convenient and cost-effective maintenance of a variety of surfaces. Ideally, such coatings should be easy to make and apply, mechanically resistant, and long-term stable. None of the existing methods have yet mastered the challenge of meeting all of these criteria.rnSuperhydrophobicity is associated with surface roughness. The lotus leave, with its dual scale roughness, is one of the most efficient examples of superhydrophobic surface. This thesis work proposes a novel technique to prepare superhydrophobic surfaces that introduces the two length scale roughness by growing silica particles (~100 nm in diameter) onto micrometer-sized polystyrene particles using the well-established Stöber synthesis. Mechanical resistance is conferred to the resulting “raspberries” by the synthesis of a thin silica shell on their surface. Besides of being easy to make and handle, these particles offer the possibility for improving suitability or technical applications: since they disperse in water, multi-layers can be prepared on substrates by simple drop casting even on surfaces with grooves and slots. The solution of the main problem – stabilizing the multilayer – also lies in the design of the particles: the shells – although mechanically stable – are porous enough to allow for leakage of polystyrene from the core. Under tetrahydrofuran vapor polystyrene bridges form between the particles that render the multilayer-film stable. rnMulti-layers are good candidate to design surfaces whose roughness is preserved after scratch. If the top-most layer is removed, the roughness can still be ensured by the underlying layer.rnAfter hydrophobization by chemical vapor deposition (CVD) of a semi-fluorinated silane, the surfaces are superhydrophobic with a tilting angle of a few degrees. rnrnrn

Analysis and modelling of the performance of technologies for flue gas treatment in Waste-to-Energy processes

Waste management represents an important issue in our society and Waste-to-Energy incineration plants have been playing a significant role in the last decades, showing an increased importance in Europe. One of the main issues posed by waste combustion is the generation of air contaminants. Particular concern is present about acid gases, mainly hydrogen chloride and sulfur oxides, due to their potential impact on the environment and on human health. Therefore, in the present study the main available technological options for flue gas treatment were analyzed, focusing on dry treatment systems, which are increasingly applied in Municipal Solid Wastes (MSW) incinerators. An operational model was proposed to describe and optimize acid gas removal process. It was applied to an existing MSW incineration plant, where acid gases are neutralized in a two-stage dry treatment system. This process is based on the injection of powdered calcium hydroxide and sodium bicarbonate in reactors followed by fabric filters. HCl and SO2 conversions were expressed as a function of reactants flow rates, calculating model parameters from literature and plant data. The implementation in a software for process simulation allowed the identification of optimal operating conditions, taking into account the reactant feed rates, the amount of solid products and the recycle of the sorbent. Alternative configurations of the reference plant were also assessed. The applicability of the operational model was extended developing also a fundamental approach to the issue. A predictive model was developed, describing mass transfer and kinetic phenomena governing the acid gas neutralization with solid sorbents. The rate controlling steps were identified through the reproduction of literature data, allowing the description of acid gas removal in the case study analyzed. A laboratory device was also designed and started up to assess the required model parameters.

Waste management in Forlì-Cesena province: Life Cycle Assessment (LCA) of Forlì incinerator

This work assesses the environmental impact of a municipal solid waste incinerator with energy recovery in Forlì-Cesena province (Emilia-Romagna region, Italy). The methodology used is Life Cycle Assessment (LCA). As the plant already applies the best technologies available in waste treatment, this study focuses on the fate of the residues (bottom and fly ash) produced during combustion. Nine scenarios are made, based on different ash treatment disposing/recycling techniques. The functional unit is the amount of waste incinerated in 2011. Boundaries are set from waste arrival in the plant to the disposal/recovery of the residues produced, with energy recovery. Only the operative period is considered. Software used is GaBi 4 and the LCIA method used is CML2001. The impact categories analyzed are: abiotic depletion, acidification, eutrophication, freshwater aquatic ecotoxicity, global warming, human toxicity, ozone layer depletion, photochemical oxidant formation, terrestrial ecotoxicity and primary energy demand. Most of the data are taken from Herambiente. When primary data are not available, data from Ecoinvent and GaBi databases or literature data are used. The whole incineration process is sustainable, due to the relevant avoided impact given by co-generator. As far as regards bottom ash treatment, the most influential process is the impact savings from iron recovery. Bottom ash recycling in road construction or as building material are both valid alternatives, even if the first option faces legislative limits in Italy. Regarding fly ash inertization, the adding of cement and Ferrox treatment results the most feasible alternatives. However, this inertized fly ash can maintain its hazardous nature. The only method to ensure the stability of an inertized fly ash is to couple two different stabilization treatments. Ash stabilization technologies shall improve with the same rate of the flexibility of the national legislation about incineration residues recycling.

Massenspektrometrische Untersuchungen des Komplexierungsverhaltens von Actinid-Ionen in Lösung

Da die Langzeit-Radiotoxizität von abgebrannten Kernbrennstoffen von Plutonium und den minoren Actiniden dominiert wird, sind diese Elemente im Fokus der Untersuchungen bezüglich der Entsorgung der radioaktiven Abfälle.rnUm ein besseres Verständnis der Selektivität der Partitioning-Liganden BTP und BTBP bezüglich der Extraktion von trivalenten Actiniden zu erlangen, wurden die Komplexe, die diese mit Lanthaniden in octanolischer Lösung bilden charakterisiert. Das unterschiedliche Extraktionsverhalten der Lanthaniden untereinander konnte dabei auf unterschiedliche Präferenz zur Bildung von Ln(BTP)3-Komplexen abhängig vom Ionenradius der Lanthaniden zurückgeführt werden. Darüber hinaus konnte gezeigt werden, dass abhängig vom sterischen Anspruch der BTBP-Liganden in Eu(BTBP)2-Komplexen Nitratliganden in der ersten Koordinationssphäre gebunden werden. rnDa das Verhalten von Plutonium unter geochemischen Bedingungen von besonderem Interesse für die Risikoabschätzung von nuklearen Endlagern ist, widmet sich der zweite Teil der Arbeit dem Hydrolyse- und Kolloidbildungsverhalten von wässrigen Plutoniumlösungen in den Oxidationsstufen IV bis VI. Daher wurden die Lösungsspezies von sowohl Zirconium(IV) als Analogon für Plutonium(IV), als auch die von Uran(VI) und Plutonium(VI) direkt mittels massenspektrometrischer Methoden charakterisiert und quantifiziert. Darüber hinaus wurde die kinetische Hemmung der Reduktion von Pu(V) zu Pu(IV) und nachfolgender Kolloidbildung untersucht, welche sich durch oberflächeninduzierte Reduktion an kolloidalen Kristallisationskeimen deutlich beschleunigen lässt.rn

Morphological instability analysis of a misfit strained core-shell nanowire for the growth of quantum dots

Nell'ambito delle nanostrutture, un ruolo primario è svolto dai punti quantici. In questo lavoro siamo interessati all'analisi teorica del processo di creazione dei punti quantici: esso può avvenire per eteroepitassia, in particolare secondo il metodo studiato da Stranski-Krastanov. Un film di Germanio viene depositato su un substrato di Silicio in modo coerente, cioè senza dislocazioni, e, a causa del misfit tra le maglie dei due materiali, c'è un accumulo di energia elastica nel film. A una certa altezza critica questa energia del film può essere ridotta se il film si organizza in isole (punti quantici), dove la tensione può essere rilassata lateralmente. L'altezza critica dipende dai moduli di Young (E, υ), dal misfit tra le maglie (m) e dalla tensione superficiali (γ). Il trasporto di materiale nel film è portato avanti per diffusione superficiale. Il punto focale nell'analisi delle instabilità indotte dal misfit tra le maglie dei materiali è la ricerca delle caratteristiche che individuano il modo di crescita più rapido dei punti quantici. In questo lavoro siamo interessati ad un caso particolare: la crescita di punti quantici non su una superficie piana ma sulla superficie di un nanofilo quantico a geometria cilindrica. L'analisi delle instabilità viene condotta risolvendo le equazioni all'equilibrio: a tal fine sono state calcolate le distribuzioni del tensore delle deformazioni e degli sforzo di un nanofilo core-shell con una superficie perturbata al primo ordine rispetto all'ampiezza della perturbazione. L'analisi è stata condotta con particolari condizioni al contorno ed ipotesi geometriche, e diverse scelte dello stato di riferimento del campo degli spostamenti. Risolto il problema elastico, è stata studiata l'equazione dinamica di evoluzione descrivente la diffusione di superficie. Il risultato dell'analisi di instabilità è il tasso di crescita in funzione del numero d'onda q, con diversi valori del raggio del core, spessore dello shell e modo normale n, al fine di trovare il più veloce modo di crescita della perturbazione.

Valorisation of organic waste: new developments from proton nuclear magnetic resonance characterization

The last half-century has seen a continuing population and consumption growth, increasing the competition for land, water and energy. The solution can be found in the new sustainability theories, such as the industrial symbiosis and the zero waste objective. Reducing, reusing and recycling are challenges that the whole world have to consider. This is especially important for organic waste, whose reusing gives interesting results in terms of energy release. Before reusing, organic waste needs a deeper characterization. The non-destructive and non-invasive features of both Nuclear Magnetic Resonance (NMR) relaxometry and imaging (MRI) make them optimal candidates to reach such characterization. In this research, NMR techniques demonstrated to be innovative technologies, but an important work on the hardware and software of the NMR LAGIRN laboratory was initially done, creating new experimental procedures to analyse organic waste samples. The first results came from soil-organic matter interactions. Remediated soils properties were described in function of the organic carbon content, proving the importance of limiting the addition of further organic matter to not inhibit soil processes as nutrients transport. Moreover NMR relaxation times and the signal amplitude of a compost sample, over time, showed that the organic matter degradation of compost is a complex process that involves a number of degradation kinetics, as a function of the mix of waste. Local degradation processes were studied with enhanced quantitative relaxation technique that combines NMR and MRI. The development of this research has finally led to the study of waste before it becomes waste. Since a lot of food is lost when it is still edible, new NMR experiments studied the efficiency of conservation and valorisation processes: apple dehydration, meat preservation and bio-oils production. All these results proved the readiness of NMR for quality controls on a huge kind of organic residues and waste.

Microchannel heat exchangers: An attractive option for the regenerator of a mobile orc waste heat recovery system

The performance of microchannel heat exchangers was assessed in gas-to-liquid applications in the order of several tens of kWth . The technology is suitable for exhaust heat recovery systems based on organic Rankine cycle. In order to design a light and compact microchannel heat exchanger, an optimization process is developed. The model employed in the procedure is validated through computational fluid-dynamics analysis with commercial software. It is shown that conjugate effects have a significant impact on the heat transfer performance of the device.

Quantum dot cytotoxicity in vitro: An investigation into the cytotoxic effects of a series of different surface chemistries and their core/shell materials

Abstract The aim of this study was to assess the effects of a series of different surface coated quantum dots (QDs) (organic, carboxylated [COOH] and amino [NH(2)] polytethylene glycol [PEG]) on J774.A1 macrophage cell viability and to further determine which part of the QDs cause such toxicity. Cytotoxic examination (MTT assay and LDH release) showed organic QDs to induce significant cytotoxicity up to 48 h, even at a low particle concentration (20 nM), whilst both COOH and NH(2) (PEG) QDs caused reduced cell viability and cell membrane permeability after 24 and 48 h exposure at 80 nM. Subsequent analysis of the elements that constitute the QD core, core/shell and (organic QD) surface coating showed that the surface coating drives QD toxicity. Elemental analysis (ICP-AES) after 48 h, however, also observed a release of Cd from organic QDs. In conclusion, both the specific surface coating and core material can have a significant impact on QD toxicity.

Analysis of llicit and illicit drugs in waste, surface and lake water samples using large volume direct injection high performance liquid chromatography – Electrospray tandem mass spectrometry (HPLC–MS/MS)

http://www.sciencedirect.com/science/article/pii/S0045653510008891

Dimorphism in Shell Shape and Strength in Two Species of Emydid Turtle

This study investigates the mechanical implications of shell shape differences between males and females of two North American turtle species: Chrysemys picta and Glyptemys insculpta. These species show patterns of sexual dimorphism that are common to many species of turtle. Females have wider and more highly domed shells, whereas males tend to have flatter, more streamlined shells. In addition, the males of many terrestrial species have concave plastra, most likely to accommodate the domed shells of the females while mating. The purpose of this study was to determine whether the known morphological differences in male and female turtle shells are also associated with differences in shell strength. Landmark coordinate data were collected from the shells of males and females of both species. These data were used to create digital models of each shell for finite-element (FE) analysis. FE models were generated by transforming a single base model of a turtle shell to match the shapes of each specimen examined in this study. All models were assigned the same material properties and restraints. Twelve load cases, each representing a predator’s bite at a different location on the carapace, were applied separately to the models. Subsequently, Von Mises stresses were extracted for each element of each model. Overall, the shells of females of both species exhibited significantly lower maximum and average stresses for a given load than those of their male counterparts. Male G. insculpta exhibited significant increases in stresses because of the concave shape of their plastra. We suggest that the mechanical implications of shell shape differences between males and females may have a large impact on many aspects of the biology of these turtle species.

Finite Element Modeling of Shell Shape in the Freshwater Turtle Pseudemys concinna Reveals a Trade-Off between Mechanical Strength and Hydrodynamic Efficiency

Aquatic species can experience different selective pressures on morphology in different flow regimes. Species inhabiting lotic regimes often adapt to these conditions by evolving low-drag (i.e., streamlined) morphologies that reduce the likelihood of dislodgment or displacement. However, hydrodynamic factors are not the only selective pressures influencing organismal morphology and shapes well suited to flow conditions may compromise performance in other roles. We investigated the possibility of morphological trade-offs in the turtle Pseudemys concinna. Individuals living in lotic environments have flatter, more streamlined shells than those living in lentic environments; however, this flatter shape may also make the shells less capable of resisting predator-induced loads. We tested the idea that ‘‘lotic’’ shell shapes are weaker than ‘‘lentic’’ shell shapes, concomitantly examining effects of sex. Geometric morphometric data were used to transform an existing finite element shell model into a series of models corresponding to the shapes of individual turtles. Models were assigned identical material properties and loaded under identical conditions, and the stresses produced by a series of eight loads were extracted to describe the strength of the shells. ‘‘Lotic’’ shell shapes produced significantly higher stresses than ‘‘lentic’’ shell shapes, indicating that the former is weaker than the latter. Females had significantly stronger shell shapes than males, although these differences were less consistent than differences between flow regimes. We conclude that, despite the potential for many-to-one mapping of shell shape onto strength, P. concinna experiences a trade-off in shell shape between hydrodynamic and mechanical performance. This trade-off may be evident in many other turtle species or any other aquatic species that also depend on a shell for defense. However, evolution of body size may provide an avenue of escape from this trade-off in some cases, as changes in size can drastically affect mechanical performance while having little effect on hydrodynamic performance.

Biomechanics on the Half Shell: Functional Performance Influences Patterns of Morphological Variation in the Emydid Turtle carapace

This study uses the carapace of emydid turtles to address hypothesized differences between terrestrial and aquatic species. Geometric morphometrics are used to quantify shell shape, and performance is estimated for two shell functions: shell strength and hydrodynamics. Aquatic turtle shells differ in shape from terrestrial turtle shells and are characterized by lower frontal areas and presumably lower drag. Terrestrial turtle shells are stronger than those of aquatic turtles; many-to-one mapping of morphology to function does not entirely mitigate a functional trade-off between mechanical strength and hydrodynamic performance. Furthermore, areas of morphospace characterized by exceptionally poor performance in either of the functions are not occupied by any emydid species. Though aquatic and terrestrial species show no significant differences in the rate of morphological evolution, aquatic species show a higher lineage density, indicative of a greater amount of convergence in their evolutionary history. The techniques employed in this study, including the modeling of theoretical shapes to assess performance in unoccupied areas of morphospace, suggest a framework for future studies of morphological variation.

Optimal Solid Waste Policy with Centralized Recycling Opportunities

Economic models have demonstrated the efficiency of curbside collection taxes. This paper demonstrates that such efficiencies disappear in economies with centralized recycling options - where recyclable materials can be removed from the waste stream either by households or at a centralized recycling facility. In such economies a curbside garbage tax not only fails to encourage the centralized recycler to internalize the external costs of waste disposal, but introduces inefficiencies to the cost-minimizing mix of household and centralized recycling efforts. The optimal waste policy is a tax assessed further downstream at the landfill rather than at the curb.