In the present work, the multi-objective optimization by genetic algorithms is investigated and applied to heat transfer problems. Firstly, the work aims to compare different reproduction processes employed by genetic algorithms and two new promising processes are suggested. Secondly, in this work two heat transfer problems are studied under the multi-objective point of view. Specifically, the two cases studied are the wavy fins and the corrugated wall channel. Both these cases have already been studied by a single objective optimizer. Therefore, this work aims to extend the previous works in a more comprehensive study.

New concepts on porosity appraisal in ancient and modern construction materials. The role of Fractal Geometry on porosity characterization and transport phenomena. This work studied the potential of Fractal Geometry to the characterization of porous materials. Besides the descriptive aspects of the pore size distribution, the fractal dimensions have led to the development of rational relations for the prediction of permeability coefficients to fluid and heat transfer. The research considered natural materials used in historical buildings (rock and earth) as well as currently employed materials as hydraulic cement and technologically advanced materials such as silicon carbide or YSZ ceramics. The experimental results of porosity derived from the techniques of mercury intrusion and from the image analysis. Data elaboration was carried out according to established procedures of Fractal Geometry. It was found that certain classes of materials are clearly fractal and respond to simple patterns such as Sierpinski and Menger models. In several cases, however, the fractal character is not recognised because the microstructure of the material is based on different phases at different dimensional scales, and in consequence the “fractal dimensions” calculated from porosimetric data do not come within the standard range (less than 3). Using different type and numbers of fractal units is possible, however, to obtain “virtual” microstructures that have the fraction of voids and pore size distribution equivalent with the experimental ones for almost any material. Thus it was possible to take the expressions for the permeability and the thermal conduction which does not require empirical “constants”, these expressions have also provided values that are generally in agreement with the experimental available data. More problematic has been the fractal discussion of the geometry of the rupture of the material subjected to mechanical stress both external and internal applied. The results achieved on these issues are qualitative and prone to future studies. Keywords: Materials, Microstructure, Porosity, Fractal Geometry, Permeability, Thermal conduction, Mechanical strength.

No description available.

This work focuses on magnetohydrodynamic (MHD) mixed convection flow of electrically conducting fluids enclosed in simple 1D and 2D geometries in steady periodic regime. In particular, in Chapter one a short overview is given about the history of MHD, with reference to papers available in literature, and a listing of some of its most common technological applications, whereas Chapter two deals with the analytical formulation of the MHD problem, starting from the fluid dynamic and energy equations and adding the effects of an external imposed magnetic field using the Ohm's law and the definition of the Lorentz force. Moreover a description of the various kinds of boundary conditions is given, with particular emphasis given to their practical realization. Chapter three, four and five describe the solution procedure of mixed convective flows with MHD effects. In all cases a uniform parallel magnetic field is supposed to be present in the whole fluid domain transverse with respect to the velocity field. The steady-periodic regime will be analyzed, where the periodicity is induced by wall temperature boundary conditions, which vary in time with a sinusoidal law. Local balance equations of momentum, energy and charge will be solved analytically and numerically using as parameters either geometrical ratios or material properties. In particular, in Chapter three the solution method for the mixed convective flow in a 1D vertical parallel channel with MHD effects is illustrated. The influence of a transverse magnetic field will be studied in the steady periodic regime induced by an oscillating wall temperature. Analytical and numerical solutions will be provided in terms of velocity and temperature profiles, wall friction factors and average heat fluxes for several values of the governing parameters. In Chapter four the 2D problem of the mixed convective flow in a vertical round pipe with MHD effects is analyzed. Again, a transverse magnetic field influences the steady periodic regime induced by the oscillating wall temperature of the wall. A numerical solution is presented, obtained using a finite element approach, and as a result velocity and temperature profiles, wall friction factors and average heat fluxes are derived for several values of the Hartmann and Prandtl numbers. In Chapter five the 2D problem of the mixed convective flow in a vertical rectangular duct with MHD effects is discussed. As seen in the previous chapters, a transverse magnetic field influences the steady periodic regime induced by the oscillating wall temperature of the four walls. The numerical solution obtained using a finite element approach is presented, and a collection of results, including velocity and temperature profiles, wall friction factors and average heat fluxes, is provided for several values of, among other parameters, the duct aspect ratio. A comparison with analytical solutions is also provided, as a proof of the validity of the numerical method. Chapter six is the concluding chapter, where some reflections on the MHD effects on mixed convection flow will be made, in agreement with the experience and the results gathered in the analyses presented in the previous chapters. In the appendices special auxiliary functions and FORTRAN program listings are reported, to support the formulations used in the solution chapters.

The object of the present study is the process of gas transport in nano-sized materials, i.e. systems having structural elements of the order of nanometers. The aim of this work is to advance the understanding of the gas transport mechanism in such materials, for which traditional models are not often suitable, by providing a correct interpretation of the relationship between diffusive phenomena and structural features. This result would allow the development new materials with permeation properties tailored on the specific application, especially in packaging systems. The methods used to achieve this goal were a detailed experimental characterization and different simulation methods. The experimental campaign regarded the determination of oxygen permeability and diffusivity in different sets of organic-inorganic hybrid coatings prepared via sol-gel technique. The polymeric samples coated with these hybrid layers experienced a remarkable enhancement of the barrier properties, which was explained by the strong interconnection at the nano-scale between the organic moiety and silica domains. An analogous characterization was performed on microfibrillated cellulose films, which presented remarkable barrier effect toward oxygen when it is dry, while in the presence of water the performance significantly drops. The very low value of water diffusivity at low activities is also an interesting characteristic which deals with its structural properties. Two different approaches of simulation were then considered: the diffusion of oxygen through polymer-layered silicates was modeled on a continuum scale with a CFD software, while the properties of n-alkanthiolate self assembled monolayers on gold were analyzed from a molecular point of view by means of a molecular dynamics algorithm. Modeling transport properties in layered nanocomposites, resulting from the ordered dispersion of impermeable flakes in a 2-D matrix, allowed the calculation of the enhancement of barrier effect in relation with platelets structural parameters leading to derive a new expression. On this basis, randomly distributed systems were simulated and the results were analyzed to evaluate the different contributions to the overall effect. The study of more realistic three-dimensional geometries revealed a prefect correspondence with the 2-D approximation. A completely different approach was applied to simulate the effect of temperature on the oxygen transport through self assembled monolayers; the structural information obtained from equilibrium MD simulations showed that raising the temperature, makes the monolayer less ordered and consequently less crystalline. This disorder produces a decrease in the barrier free energy and it lowers the overall resistance to oxygen diffusion, making the monolayer more permeable to small molecules.

Fenomeni di trasporto ed elettrostatici in membrane da Nanofiltrazione La capacità di predire le prestazioni delle membrane da nanofiltrazione è molto importante per il progetto e la gestione di processi di separazione a membrana. Tali prestazioni sono strettamente legate ai fenomeni di trasporto che regolano il moto dei soluti all’interno della matrice della membrana. Risulta, quindi, di rilevante importanza la conoscenza e lo studio di questi fenomeni; l’obiettivo finale è quello di mettere a punto modelli di trasporto appropriati che meglio descrivano il flusso dei soluti all’interno della membrana. A fianco dei modelli di trasporto ricopre, quindi, una importanza non secondaria la caratterizzazione dei parametri aggiustabili propri della membrana sulla quale si opera. La procedura di caratterizzazione di membrane deve chiarire le modalità di svolgimento delle prove sperimentali e le finalità che esse dovrebbero conseguire. Tuttavia, nonostante i miglioramenti concernenti la modellazione del trasporto di ioni in membrana ottenuti dalla ricerca negli ultimi anni, si è ancora lontani dall’avere a disposizione un modello univoco in grado di descrivere i fenomeni coinvolti in maniera chiara. Oltretutto, la palese incapacità del modello di non riuscire a prevedere gli andamenti sperimentali di reiezione nella gran parte dei casi relativi a miscele multicomponenti e le difficoltà legate alla convergenza numerica degli algoritmi risolutivi hanno fortemente limitato gli sviluppi del processo anche e soprattutto in termini applicativi. Non da ultimo, si avverte la necessità di poter prevedere ed interpretare l’andamento della carica di membrana al variare delle condizioni operative attraverso lo sviluppo di un modello matematico in grado di descrivere correttamente il meccanismo di formazione della carica. Nel caso di soluzioni elettrolitiche, infatti, è stato riconosciuto che la formazione della carica superficiale è tra i fattori che maggiormente caratterizzano le proprietà di separazione delle membrane. Essa gioca un ruolo importante nei processi di trasporto ed influenza la sua selettività nella separazione di molecole caricate; infatti la carica di membrana interagisce elettrostaticamente con gli ioni ed influenza l’efficienza di separazione degli stessi attraverso la partizione degli elettroliti dalla soluzione esterna all’interno dei pori del materiale. In sostanza, la carica delle membrane da NF è indotta dalle caratteristiche acide delle soluzioni elettrolitiche poste in contatto con la membrana stessa, nonché dal tipo e dalla concentrazione delle specie ioniche. Nello svolgimento di questo lavoro sono stati analizzati i principali fenomeni di trasporto ed elettrostatici coinvolti nel processo di nanofiltrazione, in particolare si è focalizzata l’attenzione sugli aspetti relativi alla loro modellazione matematica. La prima parte della tesi è dedicata con la presentazione del problema generale del trasporto di soluti all’interno di membrane da nanofiltrazione con riferimento alle equazioni alla base del modello DSP&DE, che rappresenta una razionalizzazione dei modelli esistenti sviluppati a partire dal modello DSPM, nel quale sono stati integrarti i fenomeni di esclusione dielettrica, per quanto riguarda la separazione di elettroliti nella filtrazione di soluzioni acquose in processi di Nanofiltrazione. Il modello DSP&DE, una volta definita la tipologia di elettroliti presenti nella soluzione alimentata e la loro concentrazione, viene completamente definito da tre parametri aggiustabili, strettamente riconducibili alle proprietà della singola membrana: il raggio medio dei pori all’interno della matrice, lo spessore effettivo e la densità di carica di membrana; in più può essere considerato un ulteriore parametro aggiustabile del modello il valore che la costante dielettrica del solvente assume quando confinato in pori di ridotte dimensioni. L’impostazione generale del modello DSP&DE, prevede la presentazione dei fenomeni di trasporto all’interno della membrana, descritti attraverso l’equazione di Nerst-Planck, e lo studio della ripartizione a ridosso dell’interfaccia membrana/soluzione esterna, che tiene in conto di diversi contributi: l’impedimento sterico, la non idealità della soluzione, l’effetto Donnan e l’esclusione dielettrica. Il capitolo si chiude con la presentazione di una procedura consigliata per la determinazione dei parametri aggiustabili del modello di trasporto. Il lavoro prosegue con una serie di applicazioni del modello a dati sperimentali ottenuti dalla caratterizzazione di membrane organiche CSM NE70 nel caso di soluzioni contenenti elettroliti. In particolare il modello viene applicato quale strumento atto ad ottenere informazioni utili per lo studio dei fenomeni coinvolti nel meccanismo di formazione della carica; dall’elaborazione dei dati sperimentali di reiezione in funzione del flusso è possibile ottenere dei valori di carica di membrana, assunta quale parametro aggiustabile del modello. che permettono di analizzare con affidabilità gli andamenti qualitativi ottenuti per la carica volumetrica di membrana al variare della concentrazione di sale nella corrente in alimentazione, del tipo di elettrolita studiato e del pH della soluzione. La seconda parte della tesi relativa allo studio ed alla modellazione del meccanismo di formazione della carica. Il punto di partenza di questo studio è rappresentato dai valori di carica ottenuti dall’elaborazione dei dati sperimentali di reiezione con il modello di trasporto, e tali valori verranno considerati quali valori “sperimentali” di riferimento con i quali confrontare i risultati ottenuti. Nella sezione di riferimento è contenuta la presentazione del modello teorico “adsorption-amphoteric” sviluppato al fine di descrivere ed interpretare i diversi comportamenti sperimentali ottenuti per la carica di membrana al variare delle condizioni operative. Nel modello la membrana è schematizzata come un insieme di siti attivi di due specie: il gruppo di siti idrofobici e quello de siti idrofilici, in grado di supportare le cariche derivanti da differenti meccanismi chimici e fisici. I principali fenomeni presi in considerazione nel determinare la carica volumetrica di membrana sono: i) la dissociazione acido/base dei siti idrofilici; ii) il site-binding dei contro-ioni sui siti idrofilici dissociati; iii) l’adsorbimento competitivo degli ioni in soluzione sui gruppi funzionali idrofobici. La struttura del modello è del tutto generale ed è in grado di mettere in evidenza quali sono i fenomeni rilevanti che intervengono nel determinare la carica di membrana; per questo motivo il modello permette di indagare il contributo di ciascun meccanismo considerato, in funzione delle condizioni operative. L’applicazione ai valori di carica disponibili per membrane Desal 5-DK nel caso di soluzioni contenenti singoli elettroliti, in particolare NaCl e CaCl2 permette di mettere in evidenza due aspetti fondamentali del modello: in primis la sua capacità di descrivere andamenti molto diversi tra loro per la carica di membrana facendo riferimento agli stessi tre semplici meccanismi, dall’altra parte permette di studiare l’effetto di ciascun meccanismo sull’andamento della carica totale di membrana e il suo peso relativo. Infine vengono verificate le previsioni ottenute con il modello dal suddetto studio attraverso il confronto con dati sperimentali di carica ottenuti dall’elaborazione dei dati sperimentali di reiezione disponibili per il caso di membrane CSM NE70. Tale confronto ha messo in evidenza le buone capacità previsionali del modello soprattutto nel caso di elettroliti non simmetrici quali CaCl2 e Na2SO4. In particolare nel caso un cui lo ione divalente rappresenta il contro-ione rispetto alla carica propria di membrana, la carica di membrana è caratterizzata da un andamento unimodale (contraddistinto da un estremante) con la concentrazione di sale in alimentazione. Il lavoro viene concluso con l’estensione del modello ADS-AMF al caso di soluzioni multicomponenti: è presentata una regola di mescolamento che permette di ottenere la carica per le soluzioni elettrolitiche multicomponenti a partire dai valori disponibili per i singoli ioni componenti la miscela.

This doctoral work gains deeper insight into the dynamics of knowledge flows within and across clusters, unfolding their features, directions and strategic implications. Alliances, networks and personnel mobility are acknowledged as the three main channels of inter-firm knowledge flows, thus offering three heterogeneous measures to analyze the phenomenon. The interplay between the three channels and the richness of available research methods, has allowed for the elaboration of three different papers and perspectives. The common empirical setting is the IT cluster in Bangalore, for its distinguished features as a high-tech cluster and for its steady yearly two-digit growth around the service-based business model. The first paper deploys both a firm-level and a tie-level analysis, exploring the cases of 4 domestic companies and of 2 MNCs active the cluster, according to a cluster-based perspective. The distinction between business-domain knowledge and technical knowledge emerges from the qualitative evidence, further confirmed by quantitative analyses at tie-level. At firm-level, the specialization degree seems to be influencing the kind of knowledge shared, while at tie-level both the frequency of interaction and the governance mode prove to determine differences in the distribution of knowledge flows. The second paper zooms out and considers the inter-firm networks; particularly focusing on the role of cluster boundary, internal and external networks are analyzed, in their size, long-term orientation and exploration degree. The research method is purely qualitative and allows for the observation of the evolving strategic role of internal network: from exploitation-based to exploration-based. Moreover, a causal pattern is emphasized, linking the evolution and features of the external network to the evolution and features of internal network. The final paper addresses the softer and more micro-level side of knowledge flows: personnel mobility. A social capital perspective is here developed, which considers both employees’ acquisition and employees’ loss as building inter-firm ties, thus enhancing company’s overall social capital. Negative binomial regression analyses at dyad-level test the significant impact of cluster affiliation (cluster firms vs non-cluster firms), industry affiliation (IT firms vs non-IT fims) and foreign affiliation (MNCs vs domestic firms) in shaping the uneven distribution of personnel mobility, and thus of knowledge flows, among companies.

ABSTRACT: The dimension stone qualification through the use of non-destructive tests (NDT) is a relevant research topic for the industrial characterisation of finite products, because the competition of low-costs products can be sustained by an offer of highqualification and a top-guarantee products. The synthesis of potentialities offered by the NDT is the qualification and guarantee similar to the well known agro-industrial PDO, Protected Denomination of Origin. In fact it is possible to guarantee both, the origin and the quality of each stone product element, even through a Factory Production Control on line. A specific disciplinary is needed. A research developed at DICMA-Univ. Bologna in the frame of the “OSMATER” INTERREG project, allowed identifying good correlations between destructive and non-destructive tests for some types of materials from Verbano-Cusio-Ossola region. For example non conventional ultrasonic tests, image analysis parameters, water absorption and other measurements showed to be well correlated with the bending resistance, by relationships varying for each product. In conclusion it has been demonstrated that a nondestructive approach allows reaching several goals, among the most important: 1) the identification of materials; 2) the selection of products; 3) the substitution of DT by NDT. Now it is necessary to move from a research phase to the industrial implementation, as well as to develop new ND technologies focused on specific aims.

No description available.

This thesis wad aimed at the study and application of titanium dioxide photocatalytic activity on ceramic materials. As a matter of fact, photocatalysis is a very promising method to face most of the problems connected with the increasing environmental pollution. Furthermore, titanium dioxide, in its anatase crystallographic phase, is one of the most investigated photocatalytic material and results to be perfectly compatible with silicate body mixes. That goal was pursued by two different strategies: 1. the addition to a body mix used for heavy clay products of several titania powders, with different mean crystallite size, surface area, morphology and anatase/rutile ratio and a titania nanosuspension as well. The titania addition followed two procedures: bulk and spray addition over the ceramic samples surface. Titania was added in two different percentages: 2.5 and 7.5 wt.% in both of the methods. The ceramic samples were then fired at three maximum temperatures: 900, 950 and 1000 °C. Afterwards, the photocatalytic activity of the prepared ceramic samples was evaluated by following the degradation of an organic compound in aqueous medium, under UV radiation. The influence of titania morphological characteristics on the photoactivity of the fired materials was studied by means of XRD and SEM observations. The ceramic samples, sprayed with a slip containing 7.5 wt.% of titania powder and fired at 900 °C, have the best photoactivity, with a complete photo-decomposition of the organic compound. At 1000 °C no sample acted as a photocatalyst due to the anatase-to-rutile phase transformation and to the reaction between titania and calcium and iron oxides in the raw materials. 2. The second one foresaw the synthesis of TiO2-SiO2 solid solutions, using the following stoichiometry: Ti1-xSixO2 where x = 0, 0.1, 0.3 and 0.5 atoms per formula unit (apfu). The mixtures were then fired following two thermal cycles, each with three maximum temperatures. The effect of SiO2 addition into the TiO2 crystal structure and, consequently, on its photocatalytic activity when fired at high temperature, was thoroughly investigated by means of XRD, XPS, FE-SEM, TEM and BET analysis. The photoactivity of the prepared powders was assessed both in gas and liquid phase. Subsequently, the TiO2-SiO2 solid solutions, previously fired at 900 °C, were sprayed over the ceramic samples surface in the percentage of 7.5 wt.%. The prepared ceramic samples were fired at 900 and 1000 °C. The photocatalytic activity of the ceramic samples was evaluated in liquid phase. Unfortunately, that samples did not show any appreciable photoactivity. In fact, samples fired at 900 °C showed a pretty low photoactivity, while the one fired at 1000 °C showed no photoactivity at all. This was explained by the excessive coarsening of titania particles. To summarise, titania particle size, more than its crystalline phase, seems to have a relevant role in the photocatalytic activity of the ceramic samples.