Dissertations / Theses on the topic 'Densità energetica'

The sequence of events that, in Italy, has characterised the development of Social Housing since the Second World War until today has made it necessary to face the renovation of social residential buildings. Despite the short period of time that has elapsed since their construction, the condition of large housing estates built in our country between the 1960s and 1980s are not only largely unfit for purpose but they also present substantial limitations with regards to energy efficiency. In this respect, research has defined a methodology to approach the regeneration of buildings of reference and has assumed some strategies to improve energy efficiency. After outlining the latest developments regarding public and private housing construction both in Italy and in Europe since the post-war period, some representative Italian residential areas with high density living have been analysed taking into particular consideration their most important features. Among these areas, an suitably representative case study has been identified in the “Virgolone” housing development which is located in the Pilastro district of Bologna. In this large housing estate, consisting of more than two thousand units, the technical and architectural features of the three main urban sections have been firstly identified. This sections correspond, in turn, to three periods of construction (1964-1986) whose predominant differences have been highlighted. The variety of housing types, of building systems and of management policies has characterized a diversified development which, depending on the building, has sometimes produced a variety of results in the same housing estate. Defining a strategy for effective renovation necessitates acquiring a preliminary and detailed knowledge of the building of reference, based on an analysis of a multiplicity of elements, in particular of those elements which are most affected by obsolescence and that influence its performance directly. The cognitive survey investigated the performance deficit of technological units which make up the building envelope and assessed the degradation phenomena related to structural and construction features, contextualizing the choices in a given historical moment. This survey has been followed by a critical evaluation of the qualitative analysis carried out and of the instrumental data acquired, which has allowed to focus the attention on the most important problems of the individual residential units and to gain a basic knowledge necessary to undertake the following phase, which consists of defining the possible intervention of renovation. In this regard, the energy consumption of the building has been calculated, comparing it with the energy performance index defined by legislation. The results of this in-depth analysis has contributed to formulating scenarios of intervention through following transformation stages, proposing different project hypotheses for solutions for which assessments of the intervention costs and of the time it would take to have a return on the investment have been calculated.

2011/2012
Il presente lavoro è stato condotto nella Riserva Naturale della Foce dell’Isonzo, in un'area caratterizzata da un ampio invaso d’acqua dolce, soggetto a prosciugamento in periodo estivo. Lo scopo di questo studio è stato quello di analizzare struttura ed abbondanza della comunità macrozoobentonica e valutare il contenuto energetico dei taxa più rappresentativi, in relazione all’importante ruolo che questa comunità assume da un punto di vista trofico in questi ambienti. I macroinvertebrati bentonici ricoprono tutti i ruoli trofici dei consumatori e sono la componente più importante della dieta di Pesci ed Uccelli limicoli. Sono state scelte 5 stazioni di campionamento sulla base della diversa profondità dell’acqua, diversa copertura vegetale del substrato e diversa durata della fase bagnata. Mensilmente, a partire dal gennaio 2009 fino a ottobre 2012 è stata rilevata la profondità assieme ad alcuni parametri chimico-fisici, quali: ossigeno disciolto (mg l-1), temperatura (°C), pH e conduttività (mS cm-1). I dati evidenziano per la profondità una tendenza inversa rispetto alla temperatura, legata al ciclo stagionale di prosciugamento/riallagamento a cui è soggetta l’area di studio, e tra temperatura e ossigeno disciolto. La conduttività tende ad aumentare in corrispondenza dell’aumento di temperatura in estate, mente il pH si mantiene su valori neutri tendenti leggermente al basico, oscillando entro un range piuttosto ristretto. Durante l’ultimo anno di attività (novembre 2011-ottobre 2012) sono state monitorate le concentrazioni di alcuni nutrienti (mg l-1), quali NH4, NO3, NO2, PO4, all’interno del sedimento. Per tale scopo sono stati prelevati mensilmente campioni di sedimento mediante un carotiere manuale, e stagionalmente campioni a carico della colonna d’acqua. I risultati denunciano un’alta concentrazione di nutrienti, in particolare dei composti dell’azoto, rispetto a quanto atteso in ambienti dilciacquicoli, verosimilmente, in relazione al carico organico dovuto alla presenza dell’avifauna nell’area di studio. Allo scopo di effettuare analisi granulometriche e misurazioni del C organico, nell’inverno ed autunno 2009, sono stati analizzati campioni di sedimento, in collaborazione con il Dipartimento di Matematica e Geoscienze dell’Università di Trieste. Le analisi granulometriche hanno evidenziato in febbraio la presenza di silt sabbioso in tutte le stazioni, ad eccezione della stazione 2, in cui è stato invece rinvenuto silt argilloso. In ottobre anche nelle stazioni 3 e 4 è stato osservato silt argilloso, mentre non vi sono variazioni nelle restanti stazioni. L’analisi del carbonio organico mostra sempre valori simili nei due campionamenti, con valori più alti nella stazione 1 (3,29% in febbraio, 3,93% in ottobre) e più bassi nelle stazioni 2 e 5 (rispettivamente 1,73% e 1,71% in febbraio e 1,18% e 1,14% in ottobre). Per quanto attiene le comunità macrozoobentoniche, sono stati effettuati campionamenti mediante utilizzo di due tecniche: 1) mediante box corer manuale, strumento dotato di un’area di presa definita (289 cm²), che garantisce un campionamento di tipo quantitativo e minimizza le perdite del campione; 2) tramite la tecnica dei pacchetti fogliari che simulano il naturale accumulo di detrito e che permettono di analizzare i processi decompositivi ed i taxa che riescono a colonizzare i pacchetti. I campionamenti che hanno visto l’utilizzo del box corer si sono svolti nell’aprile 2009 e a cavallo tra ottobre e novembre 2009, e hanno visto il prelievo di 6 subcampionamenti per stazione. La determinazione tassonomica si è spinta fino a livello di famiglia o di genere e, per alcuni taxa raccolti nella primavera, a livello di specie, grazie anche alla collaborazione della Dott.ssa Boggero (CNR, Pallanza) e del Prof. Rossaro (Università di Milano). Le campagne di campionamento mediante pacchi fogliari si sono svolte per tre anni consecutivi, dall’autunno 2009 all’estate 2012, durante le stagioni autunnale, primaverile ed estiva. I pacchi sono stati realizzati con foglie di Phragmites australis, raccolte all’interno della Riserva, seguendo il protocollo indicato da Basset et al., 2006. Sono state organizzate tre unità subcampionarie per ogni stazione, messe in posa con evento unico e raccolte a scaglioni (una per stazione) con cadenza quindicinale. Dopo la raccolta i macroinvertebrati sono stati separati immediatamente dalla componente fogliare, in attesa della determinazione che si è spinta allo stesso livello indicato per i campioni raccolti con box-corer. La struttura della comunità macrozoobentonica è risultata esser costituita principalmente da Crostacei (Classe Ostracoda, famiglie Asellidae e Gammaridae), Oligocheti (famiglie Lumbricidae, Tubificidae, Naididae) ed Insetti. Tra questi ultimi il taxon dominante è risultato essere quello dei Ditteri Chironomidi, i quali rappresentano sempre oltre il 90% degli Insetti rinvenuti. Tale strutura di comunità è stata riscontrata, pur variando i rapporti tra le frequenze percentuali dei vari taxa, nelle diverse stagioni, con entrambi i metodi di campionamento. Numerosità e diversità (espressa come numero dei taxa rinvenuti) sono risultate maggiori durante la primavera rispetto all’autunno, sia nei campioni raccolti con box corer che con le trappole trofiche. Sulla base dei pesi dei pacchetti fogliari post periodo di permanenza nelle stazioni sono stati calcolati i tassi di decomposizione della sostanza organica vegetale (gg-1), utilizzando il modello di Olson (1963). Il modello è stato trasformato da esponenziale a lineare e sono stati effettuati dei confronti a livello inter- e intrastagionale mediante analogo dell’ ANCOVA. La pianificazione del protocollo di campionamento è stata organizzata con la collaborazione con il Dipartimento di Scienze e Tecnologie Biologiche e Ambientali dell’Università degli Studi del Salento. Il tasso di decomposizione della sostanza organica vegetale è risultato esser compreso tra 0,0066 e 0,0075 gg-1 in autunno e tra 0,0108 e 0,0158 gg-1 in primavera. I confronti hanno permesso di mettere in evidenza differenze significative tra i tassi di decomposizione autunnale e primaverile per ogni anno di attività (p>0,05). Non sono state osservate differenze significative tra i tassi autunnali, mentre tali differenze sono sempre emerse a livello della stagione primaverile (p<0,0001). Le campagne di campionamento estive non sono state completate con successo a causa del prosciugamento dell’area, per cui non è stato possibile effettuare paragoni. Confronti intra stagionali non hanno evidenziato (salvo due eccezioni) differenze tra le stazioni (p>0,05). Si può concludere quindi che il sistema degrada la sostanza organica vegetale alla stessa velocità in ogni sua parte nelle stagioni esaminate. Per i taxa per cui numerosità e peso secco lo hanno reso possibile, (Ditteri Chironimidi appartenenti alla tribù dei Chironomini e due famiglie di Crostacei: Gammaridae e Asellidae) sono state effettuate misure a carico della densità energetica ED (cal g-1, peso secco). I taxa sono stati trattati in stufa a 60 °C per 72 ore e in seguito polverizzati. Con il materiale ottenuto sono state prodotte delle pastiglie in seguito processate in un calorimetro adiabatico a bomba Parr 1425 (Parr Instrument Company, U.S.A.). I valori ottenuti sono stati confrontati (quando possibile) mediante statistica non parametrica (test di Kruskal e Wallis per i Chironomini e test U di Mann e Whitney per i Gammaridae), allo scopo di indagare differenze stagionali tra i valori di ogni taxon. Le misure sono state effettuate presso il Dipartimento di Scienze e Tecnologie Biologiche e Ambientali dell’Università degli Studi del Salento. I valori di densità energetica per la tribù dei Chironomini sono risultati esser compresi tra 3398,7 cal g-1 (valore autunnale) e 3483,6 cal g-1 (valore primaverile), mentre per i Gammaridae i valori sono risultati pari a 3863,7 cal g-1 in primavera e 40008,6 cal g-1 in autunno. Il valore della densità energetica per il taxon degli Asellidi è risultato pari a 3856,1 cal g-1 . Non è stato possibile evidenziare differenze significative a livello stagionale né per i Chironomini né per i Gammaridae. Per la tribù dei Chironomini e la famiglia dei Gammaridae sono state costruite curve di regressione lunghezza/peso secco. Per tale scopo è stata rilevata la lunghezza L (mm) ed è stato misurato o stimato il peso secco DW (g) per almeno 50 esemplari per ciascun taxon. Dall’analisi delle comunità macrozoobentoniche osservate all’interno del Ripristino emerge come il sistema rappresentato da quest’area sia assimilabile a una sorta di “laboratorio naturale” che torna praticamente a una condizione di “zero” a seguito del prosciugamento che avviene durante i mesi estivi. Al termine della fase secca, segue una fase di riallagamento, che si completa durante la stagione autunnale, con conseguente ricolonizzazione dei microhabitat da parte dei macroinvertebrati. La ricolonizzazione porta però a strutture di popolazione che possono essere ben diverse da quelle osservate in precedenza. Si può quindi affermare che il Ripristino è un sistema in uno stato di “perenne ricolonizzazione”. Questa conclusione è ulteriormente supportata dall’analisi dei tassi di decomposizione, i quali sono risultati esser praticamente identici nella stagione autunnale (a seguito dell’azzeramento del sistema) e sempre diversi in primavera, variando di anno in anno. I risultati fin qui ottenuti, forniscono nuove conoscenze riguardo ad aspetti finora poco studiati nell’area di studio (tassi di decomposizione della sostanza organica vegetale e densità energetice dei macroinvertebrati bentonici), e supportano la teoria secondi cui il mondo ecologico è un mondo di “non-equilibrio”, in cui i fenomeni di disturbo sono comuni e possono esser sempre diversi di volta. Questi fenomeni, possono portare a direzioni non facilmente prevedibili, e ogni ecosistema è dunque unico, irriproducibile e intendibile come fenimeno pro tempore.
XXIV Ciclo
1976

First-principles calculations employing density functional theory (DFT) were performed on the energetic materials PETN, HMX, RDX, nitromethane, and a recently discovered material, nitrate ester 1 (NEST-1). The aims of the study were to accurately predict the isothermal equation of state for each material, improve the description of these molecular crystals in DFT by introducing a correction for dispersion interactions, and perform uniaxial compressions to investigate physical properties that might contribute to anisotropic sensitivity. For each system, hydrostatic-compression simulations were performed. Important properties calculated from the simulations such as the equilibrium structure, isothermal equation of state, and bulk moduli were compared with available experimental data to assess the agreement of the calculation method. The largest contribution to the error was believed to be caused by a poor description of van der Waals (vdW) interactions within the DFT formalism. An empirical van der Waals correction to DFT was added to VASP to increase agreement with experiment. The average agreement of the calculated unit-cell volumes for six energetic crystals improved from approximately 9% to 2%, and the isothermal EOS showed improvement for PETN, HMX, RDX, and nitromethane. A comparison was made between DFT results with and without the vdW correction to identify possible advantages and limitations.  Uniaxial compressions perpendicular to seven low-index crystallographic planes were performed on PETN, HMX, RDX, nitromethane, and NEST-1. The principal stresses, shear stresses, and band gaps for each direction were compared with available experimental information on shock-induced sensitivity to determine possible correlations between physical properties and sensitivity. The results for PETN, the only system for which the anisotropic sensitivity has been thoroughly investigated by experiment, indicated a possible correlation between maximum shear stress and sensitivity. The uniaxial compressions that corresponded to the greatest maximum shear stresses in HMX, RDX, solid nitromethane, and NEST-1 were identified and predicted as directions with possibly greater sensitivity. Experimental data is anticipated for comparison with the predictions.

This thesis investigates the response of a circumstellar accretion disc to the fly-by of a perturbing mass on a parabolic orbit, both with and without the presence of dissipation. Observed protostellar number densities and velocity dispersions imply that collisions between protostellar systems are likely during the pre-main sequence phase of their evolution. Observations of the Orion Nebula have revealed 'truncated' discs and with this in mind the post-encounter material distributions are examined and are found to be promising candidates for the observed systems. Finally, the isolated evolution of the disc remnants are studied with a view to studying the motions of 'precessing' or 'wandering' jets.

The detailed study of the structure and electron density distributions of polymorphic and phase transition materials is presented. Understanding and predicting the appearance of polymorphism and phase transitions in organic and organometallic materials is of considerable interest in fields such as pharmaceutical science, solid-state chemistry, and materials science. However, the small lattice energy difference between the different molecular conformations and packing between these materials are often particularly challenging in this area. Consequently, obtaining the most accurate description of the atomic positions and the electronic distributions plays an extremely important role in obtaining the best estimation of the lattice energies. In the present work,high-resolution X-ray diffraction as well as neutron diffraction tehniques have been used in reaching these aims. For minimizing the data collection times, synchrotron sources were also used for obtaining X-ray diffraction data, including Diamond, I19 beam line and Soleil, CRYSTAL beam line. Molecular complexes of lutidine isomers and chloranilic acid are also studied, in both 1:1 and 2:1 ratios, in order to investigate their relative stabilities through hydrogen bond contributions towards stabilising stoichiometrically different ‘compositional polymorphs’. The energy stability rankings in small organic molecules and transition metal complexes which exhibit polymorphism or displacive phase transitions are calculated using experimental charge density and fully theoretical approaches. The effect of the hydrogen bonds in the rank stabilities is also investigated. The pharmaceutical sulfathiazole and piracetam compounds are identified to have very small lattice energy differences between the polymorphs studied and the ranking stability orders are not maintained in the approaches used. Studies of the coordination complex [Ni(en)3]2+(NO3-)2 show that, contrary to expectation, the higher temperature phase is calculated to be the most stable one, showing the strongest intermolecular interaction energies. Overall, the presented studies show that current methodologies for estimating solid state lattice energies, even using high quality diffraction data and complex modeling of the electron density, are not sufficiently accurate to allow reliable estimation of polymorph energy differences. The results obtained for all studied polymorphic and phase transition materials using the experimental charge density approach show a high dependence of the lattice energies on the multipole model used.

This study investigates the multipolar expansion of the magnetic flux density in toroidal harmonics, with the main purpose of identifying a valid procedure for the calculation of the multipole coefficients. Because of the analytical complexities introduced by the toroidal coordinates system, numerous verifications are necessary to validate the expressions of the magnetic flux density components. The methodology developed for the evaluation of the multipole coefficients is based on fitting procedures. The only requirement for the application of this technique is the knowledge of the magnetic flux density values (or of the scalar potential) in defined points of a toroidal shape surface. Furthermore, a possible numerical strategy is introduced for the acquisition of the magnetic flux density values on the points of the mentioned grid.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Aeronautics and Astronautics, 2008.
Includes bibliographical references (p. 75-76).
Charged-particle radiography, specifically protons and alphas, has recently been used to image various High-Energy-Density Physics objects of interest, including Inertial Confinement Fusion capsules during their implosions, Laser-Plasma Interactions, and Rayleigh-Taylorinstability growth. An imploded D23He-filled glass capsule - the backlighter - provides monoenergetic 15-MeV and 3-MeV protons and 3.6-MeV alphas for radiographing these various phenomena. Because the backlighter emits mono-energetic particles, information about areal density and electromagnetic fields in imaged systems can be obtained simultaneously. One of the most important characteristics of the backlighter is the fusion product yield, so understanding the experiment parameters that affect it is essential to the future of chargedparticle radiography. Empirical studies of backlighter performance under a variety of conditions are presented, along with proton yield parameterizations based on backlighter and laser parameters. In order to investigate the limits and capabilities of this diagnostic, the Geant4 Transport Toolkit is introduced as the supplementary simulation tool to accompany this novel diagnostic; benchmark simulations with experimental data are presented.
by Mario John-Errol Manuel.
S.M.

The effect of varying substituents on structure and energies of bisketenes was studied using ab initio methods. Effect of substituents on ring closing reaction of bisketenes to the corresponding cyclobutenediones was also studied using ab initio methods. One or two of the following substituents were used to study the effect of varying substituents: BH2, CH3, NH2, OH, F, AlH2, SiH3, PH2, SH, Cl. Studies were done at the Hartree-Fock (HF), Møller-Plesset (MP2), and Density Functional Theory (B3LYP) levels of theory using the 6-31G* basis set.

Computational chemistry has led to the greater understanding of the molecular world, from the interaction of molecules, to the composition of molecular species and materials. Of the families of computational chemistry approaches available, the main families of electronic structure methods that are capable of accurate and/or reliable predictions of energetic, structural, and spectroscopic properties are ab initio methods and density functional theory (DFT). The focus of this dissertation is to improve the accuracy of predictions and computational efficiency (with respect to memory, disk space, and computer processing time) of some computational chemistry methods, which, in turn, can extend the size of molecule that can be addressed, and, for other methods, DFT, in particular, gain greater insight into which DFT methods are more reliable than others. Much, though not all, of the focus of this dissertation is upon transition metal species – species for which much less method development has been targeted or insight about method performance has been well established. The ab initio approach that has been targeted in this work is the correlation consistent composite approach (ccCA), which has proven to be a robust, ab initio computational method for main group and first row transition metal-containing molecules yielding, on average, accurate thermodynamic properties, i.e., within 1 kcal/mol of experiment for main group species and within 3 kcal/mol of experiment for first row transition metal molecules. In order to make ccCA applicable to systems containing any element from the periodic table, development of the method for second row transition metals and heavier elements, including lower p-block (5p and 6p) elements was pursued. The resulting method, the relativistic pseudopotential variant of ccCA (rp-ccCA), and its application are detailed for second row transition metals and lower p-block elements. Because of the computational cost of ab initio methods, DFT is a popular choice for the study of transition metals. Despite this, the most reliable density functionals for the prediction of energetic properties (e.g. enthalpy of formation, ionization potential, electron affinity, dissociation energy) of transition metal species, have not been clearly identified. The examination of DFT performance for first and second row transition metal thermochemistry (i.e., enthalpies of formation) was conducted and density functionals for the study of these species were identified. And, finally, to address the accuracy of spectroscopic and energetic properties, improvements for a series of density functionals have been established. In both DFT and ab initio methods, the harmonic approximation is typically employed. This neglect of anharmonic effects, such as those related to vibrational properties (e.g. zero-point vibrational energies, thermal contributions to enthalpy and entropy) of molecules, generally results in computational predictions that are not in agreement with experiment. To correct for the neglect of anharmonicity, scale factors can be applied to these vibrational properties, resulting in better alignment with experimental observations. Scale factors for DFT in conjunction with both the correlation and polarization consistent basis sets have been developed in this work.

This dissertation focuses on computational study of the geometry and energetics small molecules and nanoclusters involving transition metals (TM). These clusters may be used for various industrial applications including catalysis and photonics. Specifically, in this work we have studied hydrides and carbides of 3d-transition metal systems (Sc through Cu), small nickel and gold clusters. Qualitatively correct description of the bond dissociation is ensured by allowing the spatial and spin symmetry to break. We have tested applicability of new exchange-correlation functional and alternative theoretical descriptions (spin-contamination correction in broken symmetry DFT and ensemble Kohn-Sham (EKS)) as well. We studies TM hydrides and carbides systems to understand the importance of underlying phenomenon of bond breaking in catalytic processes. We have tested several exchange-correlation functionals including explicit dependence on kinetic energy density for the description of hydrides (both neutral and cationic) and carbides formed by 3d-transition metals. We find M05-2x and BMK dissociation energies are in better agreement with experiment (where available) than those obtained with high level wavefunction theory methods, published previously. This agreement with experiment deteriorates quickly for other functionals when the fraction of the Hartree-Fock exchange in DFT functional is decreased. Higher fraction of HF exchange is also essential in EKS formalism, but it does not help when spin-adapted unrestricted approach is employed. We analyze the electron spin densities using Natural Bond Orbital population analysis and find that simple description of 3d electrons as non-bonding in character is rarely correct. Unrestricted formalism results in appreciable spin-contamination for some of the systems at equilibrium, which motivated us to investigate it further in details. In order to correct the spin contamination effect on the energies, we propose a new scheme to correct for spin contamination arising in broken-symmetry DFT approach. Unlike conventional schemes, our spin correction is introduced for each spin-polarized electron pair individually and therefore is expected to yield more accurate energy values. We derive an expression to extract the energy of the pure singlet state from the energy of the broken-symmetry DFT description of the low spin state and the energies of the high spin states (pentuplet and two spin-contaminated triplets in the case of two spin-polarized electron pairs). We validate our spin-contamination correction approach by a simple example of H2 and applied to more complex MnH system. Ensemble KS formalism is also applied to investigate the dissociation of C2 molecule. We find that high fraction of HF exchange is essential to reproduce the results of EKS treatment with exact exchange-correlation functional. We analyze the geometry and energetics of small nickel clusters (Ni2-Ni5) for several lowest energy isomers. We also study all possible spin states of small nickel cluster isomers and report observed trends in energetics. Finally we determine the geometry and energetics of ten lowest energy isomers of four small gold clusters (Au2, Au4, Au6, and Au8). We have also investigated the influence of cluster geometry, ligation, solvation and relativistic effects on electronic structure of these gold clusters. The effect of one-by-one ligand attachment in vacuum and solvent environment is also studied. Performance of five DFT functionals are tested as well; Local Spin Density Approximation (SVWN5), Generalized Gradient Approximation (PBE), kinetic energy density-dependent functional (TPSS), hybrid DFT (B3LYP), and CAM-B3LYP which accounts for long-range exchange effects believed to be important in the analysis of metal bonding in gold complexes and clusters. Our results exhibit the ligand induced stability enhancement of otherwise less stable isomers of Au4, Au6 and Au8. Ligands are found to play a crucial role in determining the 2D to 3D transition realized in small gold clusters. In order to select an appropriate theory level to use in this study, we investigate the effect of attachment of four different ligands (NH3, NMe3, PH3, PMe3) on cluster geometry and energetics of Au2 and Au4 in vacuum and in solution. Our results benchmark the applicability of DFT functional model and polarization functions in the basis set for calculations of ligated gold cluster systems. We employ five different basis sets with increasing amount of polarization and diffuse functions; LANL2DZ, LANL2DZ-P, def2-SVP, def2-TZVP, and def2-QZVP. We obtain NMe3 = NH3 < PH3 < PMe3 order of ligand binding energies and observe shallow potential energy surfaces in all molecules. Our results suggest appropriate quantum-chemical methodologies to model small noble metal clusters in realistic ligand environment to provide reliable theoretical analysis in order to complement experiments.
Ph.D.
Department of Chemistry
Sciences
Chemistry PhD

Social insects are used as models for understanding the evolution of sociality because they show seemingly complex behavioral and physiological traits that enforce group cohesion, collective organization, and group level reproduction. Social organization in insect societies requires workers to share information. Information sharing allows workers to efficiently perform and switch among tasks to meet colony needs. For many species that nest in preformed cavities, colony growth results in crowding inside the nest which can affect colony productivity and fitness. How does colony size and social density affect individual and collective behavior? Using a combination of laboratory and field experiments, I have begun to answer this question. In Temnothorax rugatulus ants, high social density resulted in greater colony energy use. In addition, larger colonies used proportionally less energy compared to smaller colonies, but showed reduced brood production. These results indicate that the way colonies use energy changes with social density and group size. In analyzing the effects of colony size and density on worker behavior, I found that high density increased worker connectivity and information sharing. Workers in larger colonies showed less connectivity compared to workers in smaller colonies. Interestingly, workers with more interactions spent less time in brood care. This study shows that workers' access to information and the overall pattern of information flow are affected by social density and colony size, and changes in worker connectivity can influence task behavior. The next study shows that field colonies maintained a relatively constant level of intranidal density irrespective of colony size; this suggests that Temnothorax ants actively regulate social density. When colonies were established in high density nests, they showed greater foraging and scouting activities, and this led to a higher probability for becoming polydomous, i.e., occupying multiple nests. When polydomy occurred, colonies divided evenly between two nests, but distributed fewer, heavier workers and brood to the supplemental nests. Taken together, the first four studies indicate that social density is an important colony phenotype that affects individual and collective behavior and energetics in ants, and the collective management of social density may be a group adaptation in ants and other social insects. Lastly, because crowding affects polydomy behavior, the final two experiments tested whether colony emigration and nest construction and dispersion, two strategies for reducing intranidal crowding, are influenced by food distribution. Temnothorax colonies preferred to emigrate to nests positioned closer to food, and weaver ants (Oecophylla smaragdina) positioned newly constructed nests in food-rich areas. Furthermore, weaver ants used the newly constructed nests to more rapidly retrieve and safeguard valuable food items. Thus, strategic emigrations and adaptive nest dispersion can remedy intranidal crowding and at the same time allow growing colonies to acquire adequate food to meet colony needs.

Iron is a material of fundamental importance in the industrial and economic processes of our society as it is the major constituent of steels. With advances in computational science, much progress has been made in the understanding of the microscopic mechanisms that determine the macroscopic properties of such material at ordinary or extreme conditions. Ab initio quantum mechanical calculations based on density-functional theory (DFT), in particular, proved to be a unique tool for this purpose. Nevertheless, in order to study large enough systems up to length- and time-scales comparable with those accessible in experiments, interatomic potentials are needed. These are typically based on functional forms driven by physical intuition and fitted on experimental data at zero/low temperature and/or on available first-principles data. Despite their vast success, however, their low flexibility limits their systematic improvement upon database extension. Moreover, their accuracy at intermediate and high temperature remains questionable. In this thesis, we first survey a selection of embedded atom method (EAM) potentials to understand their strengths and limitations in reproducing experimental thermodynamic, vibrational and elastic properties of bcc iron at finite temperature. Our calculations show that, on average, all the potentials rapidly deviate from experiments as temperature is increased. At the same time, they suggest that, despite an anomalous rapid softening of its C44 shear constant, the Mendelev03 parameterization is the most accurate among those considered in this work. As a second step, we compute the same finite-temperature properties from DFT. We verify our plane-wave spin-polarized pseudopotential implementation against selected zero temperature all-electron calculations, thus highlighting the difficulties of the semi-local generalized gradient approximation exchange and correlation functional in describing the electronic properties of iron. On the other hand, we demonstrate that after accounting for the vibrational degrees of freedom, DFT provides a good description of the thermal behavior of thermodynamic and elastic properties of α-iron up to a good fraction of the Curie temperature without the explicit inclusion of magnetic transverse degrees of freedom. Electronic entropy effects are also analyzed and shown to be of secondary importance. Finally, we attempt at generating a set of highly flexible Gaussian approximation potentials (GAP) for bcc iron that retain ab initio accuracy both at zero and finite temperature. To this end, we use a non-linear, non-parametric Gaussian-process regression, and construct a training database of total energies, stresses and forces taken from first-principles molecular dynamics simulations. We cover approximately 105 local atomic environments including pristine and defected bulk systems, and surfaces with different crystallographic orientations. We then validate the different GAP models against DFT data not directly included in the dataset, focusing on the prediction of thermodynamic, vibrational, and elastic properties and of the energetics of bulk defects.

La dispersion, c’est-à-dire le déplacement d’un individu entre deux sites de reproduction, est un processus clé pour la dynamique des métapopulations et les flux de gènes. Son succès peut être modulé par des différences de phénotype ou syndromes de dispersion. Cependant, les contraintes environnementales (externes) et physiologiques (internes) qui sous-tendent ces syndromes restent mal connus. Ce projet vise à clarifier l’impact des variations environnementales et des contraintes oxydatives (liées aux espèces réactives de l’oxygène produites durant la respiration) sur les phénotypes associés à la dispersion chez un passereau, le gobemouche à collier Ficedula albicollis. La demande énergétique a été expérimentalement (i) augmentée en manipulant la surface alaire ou (ii) diminuée par une supplémentation en nourriture. L’équilibre oxydo-réducteur des gobemouches en reproduction est influencé par des interactions complexes entre facteurs intrinsèques (statut de dispersion) et extrinsèques (densité de couples reproducteurs, année, traitement expérimental). La capacité antioxydante dépend principalement des différences permanentes entre individus, alors que les pro-oxydants présentent de grandes variations intra-individu. Les variations environnementales et les contraintes énergétiques modulent aussi les différences de succès reproducteur et de comportement parental liées au statut de dispersion. Nos résultats confirment que les oiseaux dispersants et philopatriques diffèrent dans leur gestion de l’équilibre oxydo-réducteur lorsqu’il est en compétition avec l’investissement reproducteur. Ces différences pourraient avoir des conséquences à long terme sur la valeur sélective et compenser les différences de succès reproducteur entre individus dispersants et philopatriques dans les habitats de faible qualité. Ce travail souligne que les traits associés à la dispersion sont souvent déterminés par des normes de réaction à l’environnement et non des différences fixées entre individus, et améliore notre compréhension des syndromes de dispersion
Dispersal, i.e. individual movement between breeding sites, is a key process for metapopulation dynamics and gene flow. Its success can be modulated by phenotypic differences between dispersing and philopatric individuals, or dispersal syndromes. However, the environmental (external) and physiological (internal) constraints underlying such syndromes remain poorly known. This project aimed at clarifying the impact of environmental variation and oxidative constraints, linked to the reactive oxygen species produced during respiration, on phenotypes associated to dispersal in a passerine bird, the collared flycatcher Ficedulla albicollis. Energetic demand was experimentally (i) increased through a wing load manipulation or (ii) relieved through food supplementation. The oxidative balance of breeding flycatchers was influenced by complex interactions of dispersal status and extrinsic factors (breeding density, year, experimental treatments). Interestingly, antioxidant capacity was influenced both by permanent individual differences and by food availability, whereas measures of pro-oxidants were highly variables within individuals. Environmental variation and energetic constraints also modulated the differences in reproduction associated with dispersal: dispersing and philopatric birds differ in their management of the oxidative balance when it is competing with reproductive investment. This thesis highlights that reaction norms, rather than fixed differences, often shape traits associated to dispersal

Questo progetto è incentrato sulla modellizzazione del plasma di bordo dei reattori a fusione nucleare attualmente più conosciuti e diffusi al mondo, i tokamak. Nel divertore, la regione dedicata all'interazione plasma-parete, le condizioni devono garantire le transizioni da un regime caratterizzato da un plasma ionizzante e quindi con una popolazione di atomi neutri molto piccola, ad uno stato con un forte accoppiamento tra i neutri e il plasma, separati da un fronte di ionizzazione, per ottenere infine uno stato di plasma ricombinante dominato dagli atomi neutri. In questo quadro quindi, si è studiato approfonditamente il modello a due punti, un modello teorico ampiamente utilizzato nell'ambito della fisica dei plasmi di bordo. Questo modello trova un'applicazione pratica nello sviluppo di un codice a basso sforzo computazionale per la descrizione del plasma di bordo chiamato SOLDIV, che è stato sviluppato all'IRFM, istituto di ricerca sede del periodo di tirocinio. Parte del lavoro di tesi è consistito nel miglioramento del modulo per la descrizione del divertore, attraverso l'implementazione di elementi fisici aggiuntivi come il grado di detachment, con il vincolo del mantenimento di un basso tempo di calcolo. La particolare geometria del tokamak induce l'insorgere di forti flussi di calore nella zona di bordo, anche detta scrape-off layer. Questo fenomeno può avere conseguenze macroscopiche e incidere sull'efficienza della macchina se non venisse controllato, ed è stato infine oggetto di studio nel presente elaborato. L'obiettivo dell'analisi è stato quello di determinare la posizione del fronte di ionizazzione e di trovare un modello semplice 1D per poterne prevedere la locazione e il comportamento degli aspetti fisici che dominano la regione del divertore quali il fenomeno della biforcazione.

Direct hydrocarbon fuel cells are fuel cells than use hydrocarbons directly as fuel instead of the most commonly used fuel in a fuel cell, hydrogen. Studies are being done on direct hydrocarbon fuel cells because they have the potential to be energetically more efficient than hydrogen fuel cells. There are many different hydrocarbons that are available to use as a feed stock and each one reacts at different reaction rates. As the current density of a fuel cell is linked to the reaction rate, it is important to know the energetics of an oxidation reaction that is occurring. Density Functional Theory (DFT) is a technique that can be used to predict the energy states of intermediate reaction steps in a given mechanism. The focus of this study is the using DFT to explore the energetics of the oxidation of ethane to ethylene in a nickel-anode catalyst fuel cell. DFT was used in adsorption runs to optimize the geometries beginning (adsorbed ethane) and end (adsorbed ethylene) of the oxidation reaction. DFT was then used to calculate the energy of transition states by varying bond lengths. It was determined the removal of the second hydrogen from the ethyl radical is the most energy intensive step and, thus, the rate limiting step. Hydrogen, ethane, and ethylene were all explored in this study. The heats of adsorption varied from largest to smallest in the order of ethylene, hydrogen, and ethane. It was determined that the heat of adsorption of hydrogen is sufficient to meet the energy requirements for the dissociation reaction. This may help explain why hydrogen reacts so readily in fuel cells. Conversely, the heats of adsorption for the hydrocarbons did not meet the energy requirements for the dissociation reactions. This may help explain why ethane and ethylene react more slowly in a fuel cell as compared to hydrogen. Also, the oxidation of ethane to ethylene requires two large activation energies. These two additional activation energies may help explain why ethylene reacts more readily than ethane in a fuel cell.

Oggigiorno la ricerca di nuovi materiali per gradatori di campo da impiegarsi in accessori di cavi ha iniziato a studiare alcuni materiali nano dielettrici con proprietà elettriche non lineari con la tensione ed aventi proprietà migliorate rispetto al materiale base. Per questo motivo in questo elaborato si sono studiati materiali nanostrutturati a base di polietilene a bassa densità (LDPE) contenenti nano polveri di grafene funzionalizzato (G*), ossido di grafene (GO) e carbon black (CB). Il primo obiettivo è stato quello di selezionare e ottimizzare i metodi di fabbricazione dei provini. La procedura di produzione è suddivisa in due parti. Nella prima parte è stata utilizzatala tecnica del ball-milling, mentre nella seconda un pressa termica (thermal pressing). Mediante la spettroscopia dielettrica a banda larga (BDS) si sono misurate le componenti reali e immaginarie della permettività e il modulo della conducibilità del materiale, in tensione alternata. Il miglioramento delle proprietà rispetto al provino di base composto dal solo polietilene si sono ottenute quando il quantitativo delle nanopolveri era maggiore. Le misure sono state effettuate sia a 3 V che a 1 kV. Attraverso misurazioni di termogravimetria (TGA) si è osservato l’aumento della resistenza termica di tutti i provini, soprattutto nel caso quando la % di nanopolveri è maggiore. Per i provini LDPE + 0.3 wt% GO e LDPE + 0.3 wt% G* si è misurata la resistenza alle scariche parziali attraverso la valutazione dell’erosione superficiale dei provini. Per il provino contenente G* è stato registrato una diminuzione del 22% del volume eroso, rispetto al materiale base, mentre per quello contenente GO non vi sono state variazioni significative. Infine si è ricercata la resistenza al breakdown di questi ultimi tre provini sopra citati. Per la caratterizzazione si è fatto uso della distribuzione di Weibull. Lo scale parameter α risulta aumentare solo per il provino LDPE + 0.3 wt% G*.

xx, 229 p. : ill. (some col.)
Reproductive effort is a central element of human biology and ecology. Particularly for females, reproduction is energetically demanding, with elevated metabolic costs during pregnancy and lactation, followed by high child care costs. To satisfy energetic needs, women can adopt various physiological and behavioral strategies. On a physiological level, the energetic requirements of offspring may be met by adjusting metabolic allocation and/or drawing on maternal bodily reserves. On a behavioral level, women may reduce energy expenditure and/or increase energy intake. This study examined reproductive trade-offs in activity and skeletal health among the indigenous Shuar forager-horticulturalists of Ecuadorian Amazonia and had two main objectives. First, this research examined trade-offs in energy use during female reproductive states and behavioral adjustments made by females and males to meet high reproductive demands. Second, this study investigated skeletal health profiles among Shuar, as well non-Shuar Colonos, to identify the relationships between female reproductive factors and skeletal health. Research was conducted among adults in four Morona-Santiago communities. Skeletal health was measured using calcaneal ultrasonometry, and physical activity was measured using accelerometry. Extensive information on sociodemographics and reproduction was assessed through structured interviews. Age-related declines in bone mineral density (BMD) were observed for Shuar and Colonos, while Shuar BMD was significantly higher than that of other populations. These results suggest that normative data from developed countries may reflect suboptimal bone density levels. Regarding reproductive effects on skeletal health, results indicate that earlier menarcheal age and greater stature are associated with better bone health in postmenopausal life. These conclusions suggest the importance of the timing of early developmental stages in establishing bone status in adulthood. Results demonstrate that physical activity levels were similar between pregnant/lactating (P/L) and other women. However, P/L women appear to compensate for elevated energetic demands by relying on a male partner who has increased his energy expenditure, suggesting greater participation in subsistence activities. Overall, this study demonstrates the importance of biocultural strategies among women to meet high reproductive costs. Further, it emphasizes the utility of a life history framework for identifying trade-offs in physiology and behavior. This dissertation contains previously published and unpublished co-authored material.
Committee in charge: Dr. J. Josh Snodgrass, Chair; Dr. Lawrence S. Sugiyama, Member; Dr. John Lukacs, Member; Dr. John Halliwell, Outside Member

Thesis (M.S.)--West Virginia University, 2007.
Title from document title page. Document formatted into pages; contains v, 36 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 21).

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Hylodes fredi é um anfíbio anuro endêmico da Mata Atlântica da Ilha Grande, estado do Rio de Janeiro. Os girinos desta rã são encontrados nos remansos dos córregos de floresta de águas límpidas, substrato rochoso e em áreas de água rasa, onde os machos adultos podem ser visualizados em atividade de canto. Buscando aumentar a compreensão da dinâmica populacional das larvas de H. fredi, comparamos suas ocorrência, densidade e condição energética em quatro córregos na porção sul da Ilha Grande em um período de doze meses, relacionando inclusive com parâmetros físico-químicos da água. A condição energética foi calculada como o resíduo da relação entre o logaritmo natural da massa e o logaritmo natural do comprimento do corpo de todas as larvas amostradas desta espécie. A densidade e a condição energética dos girinos de H. fredi variaram entre os córregos. Todas as variáveis da água medidas (oxigênio dissolvido, condutividade, temperatura e profundidade), com exceção do pH, influenciaram na diferenciação entre os córregos. A ocorrência de girinos de diferentes tamanhos e massas ao longo de todos os meses, sem uma clara tendência de crescimento sazonal, sugere que H. fredi possui um extenso período reprodutivo durante todo o ano. Tanto os fatores ambientais da água quanto as densidades dos girinos de H. fredi diferenciaram entre as mesmas áreas. Entretanto não houve diferenciação coincidente na condição energética das larvas de H. fredi e nos fatores abióticos entre os mesmos córregos. As diferen as nas densidades e nas condições energéticas médias dos girinos de H. fredi entre as estações seca e chuvosa sugerem que as condições do ambiente são mais apropriadas na estação chuvosa, com uma maior disponibilidade de recursos. As larvas de H. fredi vivendo em córregos com maiores densidades de girinos da família Hylodidae (H. fredi e Crossodactylus gaudichaudii) possuem, em média, condição energética mais reduzida. Isso provavelmente pode ser explicado pelo compartilhamento de recursos, uma vez que, quando limitados, estes seriam mais escassos para cada indivíduo. A densidade de girinos de H. fredi foi mais influenciada por fatores físico-químicos do ambiente enquanto a condição energética dessas larvas foi mais influenciada por fatores biológicos do ambiente. Assim, os girinos de H. fredi variam na densidade e na condição energética como resultado de um balanço entre os parâmetros bióticos e abióticos dos córregos em que as larvas ocorrem. Neste trabalho, nós também descrevemos o girino de H. fredi.
Hylodes fredi is an endemic frog from Ilha Grande, an Atlantic Forest island, located in Rio de Janeiro state, southeast Brazil. The tadpoles of this species are found in clear stream backwaters in the forest, rocky substrate, in shallow waters where calling male frogs can be found. In order to improve the population dynamic knowledge of H. fredi larval stage, we compared their occurrence, density and energetic condition in four streams from the south portion of Ilha Grande in twelve months, relating them to the physicochemical parameters of the water. Energetic condition was calculated as residual of the relationship between the natural logarithm of mass and the natural logarithm of body length of all the H. fredi tadpoles sampled. Density and condition of the H. fredi larvaes varied between the streams. All variables of water measured (dissolved oxygen, conductivity, temperature and depth), except for pH, influenced the discrimination between the streams. The occurrence of tadpoles with different sizes and masses in all the months, without a clear seasonal variation, suggests that H. fredi has an extensive reproductive period along the year. Both environmental factors of the water and H. fredi tadpoles densities were different between the same streams. However, the energetic condition of the larvaes and the abiotic factors did not differentiated between the same streams. The differences found in density and energetic condition of H. fredi tadpoles between dry and wet seasons indicate that environmental conditions are more appropriate in the wet season, with greater availability of resources. Hylodes fredi larvaes living in streams with higher densities of Hylodidae tadpoles (H. fredi and Crossodactylus gaudichaudii) have smaller energetic condition values. This result seems to be probably due to the sharing of the limited resources, once these would be scarcer for each individual. Density of H. fredi tadpoles was more influenced by the physicochemical factors of the environment, while energetic condition of these tadpoles was more influenced by the biological factors of the environment. Then, density and energetic condition of H. fredi tadpoles vary in result of a balance between the abiotic and biotic parameters of the streams in which the larvaes occur. In this study, we also describe the tadpole of H. fredi.

Energetická náročnost a ekonomická životaschopnost jsou často skloňované pojmy spojené s aquaponickým způsobem produkce potravin. Tato práce si klade za cíl nalézt opatření, která by zvýšila ziskovost podnikání v oblasti aquaponie a zároveň by snížila energetickou náročnost procesu a spotřebu dalších zdrojů. Součástí práce je následné ověření vybraných opatření na zkušební aquaponické farmě. K vyřešení otázky úspory energie a vody byly použity optimalizační metody vycházející z procesního inženýrství. Pro účely automatického monitoringu růstu rostlin, jakožto hlavního zdroje příjmů v aquaponii, byla využita technologie počítačového vidění. Za využití optimalizační metody zvané P-graph, integrace procesů a hledání procesních alternativ bylo nalezeno nejlepší možné uspořádání procesní sítě, které vykazovalo více než devítinásobný čistý roční příjem ve srovnání se současným uspořádáním procesních zařízení v aquaponické farmě. Dalších úspor energie a vody bylo dosaženo instalací reflexních fólií na okraje pěstebních boxů a dalším využitím odpadní vody z aquaponické části farmy v hydroponické sekci určené k pěstování sazenic. Tato opatření mohou napomoci aquaponickým farmám zvýšit konkurenceschopnost a snížit jejich dopad na životní prostředí.

This thesis describes methods of high frequency noise and vibrations computation of cabin part of EV–55M (aircraft developed by Evektor Kunovice). There is a brief summary of methods used for determining high frequency noise and vibrations in the first part of the thesis. Detailed explanation is given for Statistical Energy Analysis (SEA) which is nowadays the most dominant method in this area. The energy balance equation is derived in this chapter and SEA parameters such as modal density, damping loss factor, coupling loss factor and power input are introduced here. Next part deals with main noise sources of propeller driven and jet aircraft and passive and active noise controls are discussed. Practical part of this thesis deals with modeling aircraft EV–55M fuselage using VA One SEA module. Two models were created. First of them is only an outside fuselage with aircraft flooring and the second one is extended by interior trim panels and is applicable for simulation of noise control treatments. Computational modeling is accompanied by experimental measurement of passive noise control material characteristics. Postprocessing of information obtained from impedance tube measurement was performed in FOAM – X. Determined characteristics of porous material were used as inputs to VA One and reduction of sound pressure level in fuselage cavities by using noise control treatment was found. In conclusion there is a summary of noise transmission paths from sources to interior cavity and some treatments of them are simulated

Thesis (Ph. D.)--University of Georgia, 2003.
Directed by Paul v.R. Schleyer. Includes articles published in Journal of organic chemistry, and Organic letters, and an article submitted to Science. Includes bibliographical references.

This research aims at exploring meaning, quality and analytical capacity of density concept and its potential interpretations in architecture and sustainability fields. Its goal is to determine the relationships among built environment, energy and form of urban textures in Mediterranean compact city, taken density as useful parameter to illustrate their features. Despite the growing unsustainability of today’s city facing an effective energy and environmental crisis, recent statistics have confirmed the increasing attractive power of metropolitan areas. Within the context of European compact city, new building models, based on energy conservation, account for an insignificant percentage compared to existing city whose functioning remarkably affects the efficiency of the whole metropolitan system. Therefore, an approach determining instruments and design methods at both urban and architectural scale, should be found in order to set out conditions more appropriate to the compact city. In respect of this kind of scale, the relationship between energy and form takes a central role in the variation of energy performances; at the same time the concept of density has showed itself as an efficient instrument of analysis of the morphological performances of the built form. This research is composed by five interconnected parts. The first one examines urban and energy dynamics’ current conditions to comprehend the role and contribution of the building industry considering the scientific progress and the implementation of present operational instruments. The second one investigates role and evolution of the density concept as parameter, design instrument and basis of theoretical categories, especially referring to interactions with urban form and sustainability. In the third part the analytical abilities of density are employed to prove the environmental implications and verify the existence of interactions among urban sustainability indicators and density. Then, the fourth one enquires into the relationships among density and energy at the urban scale. Finally, the fifth part investigates such relationships in the compact fabrics in Rome and Barcelona by models and simulations set up in order to control the correspondent factors. The influence of urban morphology, built-form and constructive features on solar access and energy demand for heating and cooling is shown by different definitions of density indicators. Among these, are determined those more suitable to express reliable trends in relation with solar access and energy demand. Firstly results point out that the contribution of the built environment to the complex energy issue arisen by metropolitan systems must be focused on the reduction of the demand - even before on the consumption and impact - operating with multi-scale methods and instruments for the transformation of existing city. Density has a preferred role in the relationship between sustainability and form, thanks to its interpretative skills and meanings undertaken as theoretical and design category. At the metropolitan scale, urban sustainability indicators and density do not always show evident relationships with energy and environmental implications. Built-form, typology and constructive features are the main factors that occur on energy performances variation of urban fabrics. The investigation of these kinds of performances by density parameters permit the comprehension of the different energy behaviors in each urban texture, offering a contribution to the instruments of energy analysis at urban scale and permitting more efficient conditions for the built environment leading to the concept of sustainable density. Methodological structure and the determined parametrical instruments show themselves as knowledge base for aware transformations of Mediterranean compact city.