Cassava root husks as a sorbent material for the uptake and pre-concentration of cadmium(II) from aqueous media

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo da influência do tratamento térmico a laser nas características dos aços avançados de alta resistência dual phase 600 e transformed induced plasticity 750

Pós-graduação em Engenharia Mecânica - FEG

Plasmid DNA partitioning and separation using poly(ethylene glycol)/poly(acrylate)/salt aqueous two-phase systems

Phase diagrams of poly(ethylene glycol)/polyacrylate/Na2SO4 systems have been investigated with respect to polymer size and pH. Plasmid DNA from Escherichia coil can depending on pH and polymer molecular weight be directed to a poly(ethylene glycol) or to a polyacrylate-rich phase in an aqueous two-phase system formed by these polymers. Bovine serum albumin (BSA) and E. coil homogenate proteins can be directed opposite to the plasmid partitioning in these systems. Two bioseparation processes have been developed where in the final step the pDNA is partitioned to a salt-rich phase giving a total process yield of 60-70%. In one of them the pDNA is partitioned between the polyacrylate and PEG-phases in order to remove proteins. In a more simplified process the plasmid is partitioned to a PEG-phase and back-extracted into a Na2SO4-rich phase. The novel polyacrylate/PEG system allows a strong change of the partitioning between the phases with relatively small changes in composition or pH. (C) 2012 Elsevier B.V. All rights reserved.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

A LED Based Photometer for Solid Phase Photometry: Zinc Determination in Pharmaceutical Preparation Employing a Multicommuted Flow Analysis Approach

In this work, a LED (light emitting diode) based photometer for solid phase photometry is described. The photometer was designed to permit direct coupling of a light source (LED) and a photodiode to a flow cell with an optical pathlength of 4 mm. The flow cell was filled with adsorbing solid phase material (C-18), which was used to immobilize the chromogenic reagent 1-(2-thiazolylazo)-2-naphthol (TAN). Aiming to allow accuracy assessment, samples were also analyzed employing ICP OES (inductively coupled plasma optical emission spectrometry) methodology. Applying the paired t-test at the 95% confidence level, no significant difference was observed. Other useful features were also achieved: linear response ranging from 0.05 to 0.85 mg L-1 Zn, limit of detection of 9 mu g L-1 Zn (3 sigma criterion), standard deviation of 1.4% (n = 10), sampling throughput of 36 determinations per h, and a waste generation and reagent consumption of 1.7 mL and of 0.03 mu g per determination, respectively.

The effects of the pressing step on the microstructure and aging of NdFeB bonded magnets

The effects of the compaction step on the (micro)structural features and aging behavior of polymer coated NdFeB-based bonded magnets is reported. Due to the fracture of the material during pressing, it is estimated an increase of at least 14% in the particles' area which is not coated. Such uncoated surfaces, when exposed to the environment, reduce the magnetic performance of the magnets aged/cured in air by 19% in the conditions evaluated in this investigation. Furthermore, XRD results interpreted by Rietveld analyses show a lattice parameter change in the tetragonal structure of the hard magnetic phase after pressing. Such change varies as a function of the height of the compacted part and it is ascribed to macro-elastic stress arising from the pressure distribution in the magnet. An aging/curing step during 24 h is able to relief such macro-elastic stress. (C) 2012 Elsevier B.V. All rights reserved.

A LED based photometer for solid phase photometry: zinc determination in pharmaceutical preparation employing a multicommuted flow analysis approach

Neste trabalho é proposto um fotômetro baseado em LED (diodo emissor de luz) para fotometria em fase sólida. O fotômetro foi desenvolvido para permitir o acoplamento da fonte de radiação (LED) e do fotodetector direto na cela de fluxo, tendo um caminho óptico de 4 mm. A cela de fluxo foi preenchida com material sólido (C18), o qual foi utilizado para imobilizar o reagente cromogênico 1-(2-tiazolilazo)-2-naftol (TAN). A exatidão foi avaliada empregando dados obtidos através da técnica ICP OES (espectrometria de emissão por plasma indutivamente acoplado). Aplicando-se o teste-t pareado não foi observada diferença significativa em nível de confiança de 95%. Outros parâmetros importantes encontrados foram faixa de resposta linear de 0,05 a 0,85 mg L-1 Zn, limite de detecção de 9 µg L-1 Zn (n = 3), desvio padrão de 1,4 % (n = 10), frequência de amostragem de 36 determinações por h, e uma geração de efluente e consumo de reagente de 1,7 mL e 0,03 µg por determinação, respectivamente.

Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions.

Size effects on phase stability and phase transitions in technologically relevant materials have received growing attention. Several works reported that metastable phases can be retained at room temperature in nanomaterials, these phases generally corresponding to the high-temperature polymorph of the same material in bulk state. Additionally, size-dependent shifts in solubility limits and/or in the transition temperatures for on heating or on cooling cycles have been observed. ZrO2-Sc2O3 (zirconia-scandia) solid solutions are known to exhibit very high oxygen ion conductivity provided their structure is composed of cubic and/or pseudocubic tetragonal phases. Unfortunately, for solid zirconia-scandia polycrystalline samples with typical micrometrical average crystal sizes, the high-conductivity cubic phase is only stable above 600°C. Depending on composition, three low-conductivity rhombo-hedral phases (β, γ and δ) are stable below 600°C down to room temperature, within the compositional range of interest for SOFCs. In previous investigations, we showed that the rhombohedral phases can be avoided in nanopowders with average crystallite size lower than 35 nm.

Adaptation and Constraint in the Plant Reproductive Phase

Conservatism is a central theme of organismic evolution. Related species share characteristics due to their common ancestry. Some concern have been raised among evolutionary biologists, whether such conservatism is an expression of natural selection or of a constrained ability to adapt. This thesis explores adaptations and constraints within the plant reproductive phase, particularly in relation to the evolution of fleshy fruit types (berries, drupes, etc.) and the seasonal timing of flowering and fruiting. The different studies were arranged along a hierarchy of scale, with general data sets sampled among seed plants at the global scale, through more specific analyses of character evolution within the genus Rhamnus s.l. L. (Rhamnaceae), to descriptive and experimental field studies in a local population of Frangula alnus (Rhamnaceae). Apart from the field study, this thesis is mainly based on comparative methods explicitly incorporating phylogenetic relationships. The comparative study of Rhamnus s.l. species included the reconstruction of phylogenetic hypotheses based on DNA sequences. Among geographically overlapping sister clades, biotic pollination was not correlated with higher species richness when compared to wind pollinated plants. Among woody plants, clades characterized by fleshy fruit types were more species rich than their dry-fruited sister clades, suggesting that the fleshy fruit is a key innovation in woody habitats. Moreover, evolution of fleshy fruits was correlated with a change to more closed (darker) habitats. An independent contrast study within Rhamnus s.l. documented allometric relations between plant and fruit size. As a phylogenetic constraint, allometric effects must be considered weak or non-existent, though, as they did not prevail among different subclades within Rhamnus s.l. Fruit size was correlated with seed size and seed number in F. alnus. This thesis suggests that frugivore selection on fleshy fruit may be important by constraining the upper limits of fruit size, when a plant lineage is colonizing (darker) habitats where larger seed size is adaptive. Phenological correlations with fruit set, dispersal, and seed size in F. alnus, suggested that the evolution of reproductive phenology is constrained by trade-offs and partial interdependences between flowering, fruiting, dispersal, and recruitment phases. Phylogenetic constraints on the evolution of phenology were indicated by a lack of correlation between flowering time and seasonal length within Rhamnus cathartica and F. alnus, respectively. On the other hand, flowering time was correlated with seasonal length among Rhamnus s.l. species. Phenological differences between biotically and wind pollinated angiosperms also suggested adaptive change in reproductive phenology.

Studio di biomateriali usati come scaffold per Tissue Engineering e loro caratterizzazione con tecniche spettroscopiche vibrazionali e di analisi termica

This research investigated someone of the main problems connected to the application of Tissue Engineering in the prosthetic field, in particular about the characterization of the scaffolding materials and biomimetic strategies adopted in order to promote the implant integration. The spectroscopic and thermal analysis techniques were usefully applied to characterize the chemico-physical properties of the materials such as – crystallinity; – relative composition in case of composite materials; – Structure and conformation of polymeric and peptidic chains; – mechanism and degradation rate; – Intramolecular and intermolecular interactions (hydrogen bonds, aliphatic interactions). This kind of information are of great importance in the comprehension of the interactions that scaffold undergoes when it is in contact with biological tissues; this information are fundamental to predict biodegradation mechanisms and to understand how chemico-physical properties change during the degradation process. In order to fully characterize biomaterials, this findings must be integrated by information relative to mechanical aspects and in vitro and in vivo behavior thanks to collaborations with biomedical engineers and biologists. This study was focussed on three different systems that correspond to three different strategies adopted in Tissue Engineering: biomimetic replica of fibrous 3-D structure of extracellular matrix (PCL-PLLA), incorporation of an apatitic phase similar to bone inorganic phase to promote biomineralization (PCL-HA), surface modification with synthetic oligopeptides that elicit the interaction with osteoblasts. The characterization of the PCL-PLLA composite underlined that the degradation started along PLLA fibres, which are more hydrophylic, and they serve as a guide for tissue regeneration. Moreover it was found that some cellular lines are more active in the colonization of the scaffold. In the PCL-HA composite, the weight ratio between the polymeric and the inorganic phase plays an essential role both in the degradation process and in the biomineralization of the material. The study of self-assembling peptides allowed to clarify the influence of primary structure on intermolecular and intermolecular interactions, that lead to the formation of the secondary structure and it was possible to find a new class of oligopeptides useful to functionalize materials surface. Among the analytical techniques used in this study, Raman vibrational spectroscopy played a major role, being non-destructive and non-invasive, two properties that make it suitable to degradation studies and to morphological characterization. Also micro-IR spectroscopy was useful in the comprehension of peptide structure on oxidized titanium: up to date this study was one of the first to employ this relatively new technique in the biomedical field.

L'eredità di Aldo Rossi nella Penisola Iberica. La costruzione della città e il progetto contemporaneo

Descrizione, tema e obiettivi della ricerca La ricerca si propone lo studio delle possibili influenze che la teoria di Aldo Rossi ha avuto sulla pratica progettuale nella Penisola Iberica, intende quindi affrontare i caratteri fondamentali della teoria che sta alla base di un metodo progettuale ed in particolar modo porre l'attenzione alle nuove costruzioni quando queste si confrontano con le città storiche. Ha come oggetto principale lo studio dei documenti, saggi e scritti riguardanti il tema della costruzione all'interno delle città storiche. Dallo studio di testi selezionati di Aldo Rossi sulla città si vuole concentrare l'attenzione sull'influenza che tale teoria ha avuto nei progetti della Penisola Iberica, studiare come è stata recepita e trasmessa successivamente, attraverso gli scritti di autori spagnoli e come ha visto un suo concretizzarsi poi nei progetti di nuove costruzioni all'interno delle città storiche. Si intende restringere il campo su un periodo ed un luogo precisi, Spagna e Portogallo a partire dagli anni Settanta, tramite la lettura di un importante evento che ha ufficializzato il contatto dell'architetto italiano con la Penisola Iberica, quale il Seminario di Santiago de Compostela tenutosi nel 1976. Al Seminario parteciparono numerosi architetti che si confrontarono su di un progetto per la città di Santiago e furono invitati personaggi di fama internazionale a tenere lezioni introduttive sul tema di dibattito in merito al progetto e alla città storica. Il Seminario di Santiago si colloca in un periodo storico cruciale per la Penisola Iberica, nel 1974 cade il regime salazarista in Portogallo e nel 1975 cade il regime franchista in Spagna ed è quindi di rilevante importanza capire il legame tra l'architettura e la nuova situazione politica. Dallo studio degli interventi, dei progetti che furono prodotti durante il Seminario, della relazione tra questo evento ed il periodo storico in cui esso va contestualizzato, si intende giungere alla individuazione delle tracce della reale presenza di tale eredità. Presupposti metodologici. Percorso e strumenti di ricerca La ricerca può quindi essere articolata in distinte fasi corrispondenti per lo più ai capitoli in cui si articola la tesi: una prima fase con carattere prevalentemente storica, di ricerca del materiale per poter definire il contesto in cui si sviluppano poi le vicende oggetto della tesi; una seconda fase di impronta teorica, ossia di ricerca bibliografica del materiale e delle testimonianze che provvedono alla definizione della reale presenza di effetti scaturiti dai contatti tra Rossi e la Penisola Iberica, per andare a costruire una eredità ; una terza fase che entra nel merito della composizione attraverso lo studio e la verifica delle prime due parti, tramite l'analisi grafica applicata ad uno specifico esempio architettonico selezionato; una quarta fase dove il punto di vista viene ribaltato e si indaga l'influenza dei luoghi visitati e dei contatti intrattenuti con alcuni personaggi della Penisola Iberica sull'architettura di Rossi, ricercandone i riferimenti. La ricerca è stata condotta attraverso lo studio di alcuni eventi selezionati nel corso degli anni che si sono mostrati significativi per l'indagine, per la risonanza che hanno avuto sulla storia dell'architettura della Penisola. A questo scopo si sono utilizzati principalmente tre strumenti: lo studio dei documenti, le pubblicazioni e le riviste prodotte in Spagna, gli scritti di Aldo Rossi in merito, e la testimonianza diretta attraverso interviste di personaggi chiave. La ricerca ha prodotto un testo suddiviso per capitoli che rispetta l'organizzazione in fasi di lavoro. A seguito di determinate condizioni storiche e politiche, studiate nella ricerca a supporto della tesi espressa, nella Penisola Iberica si è verificato il diffondersi della necessità e del desiderio di guardare e prendere a riferimento l'architettura europea e in particolar modo quella italiana. Il periodo sul quale viene focalizzata l'attenzione ha inizio negli anni Sessanta, gli ultimi prima della caduta delle dittature, scenario dei primi viaggi di Aldo Rossi nella Penisola Iberica. Questi primi contatti pongono le basi per intense e significative relazioni future. Attraverso l'approfondimento e la studio dei materiali relativi all'oggetto della tesi, si è cercato di mettere in luce il contesto culturale, l'attenzione e l'interesse per l'apertura di un dibattito intorno all'architettura, non solo a livello nazionale, ma europeo. Ciò ha evidenziato il desiderio di innescare un meccanismo di discussione e scambio di idee, facendo leva sull'importanza dello sviluppo e ricerca di una base teorica comune che rende coerente i lavori prodotti nel panorama architettonico iberico, seppur ottenendo risultati che si differenziano gli uni dagli altri. E' emerso un forte interesse per il discorso teorico sull'architettura, trasmissibile e comunicabile, che diventa punto di partenza per un metodo progettuale. Ciò ha reso palese una condivisione di intenti e l'assunzione della teoria di Aldo Rossi, acquisita, diffusa e discussa, attraverso la pubblicazione dei suoi saggi, la conoscenza diretta con l'architetto e la sua architettura, conferenze, seminari, come base teorica su cui fondare il proprio sapere architettonico ed il processo metodologico progettuale da applicare di volta in volta negli interventi concreti. Si è giunti così alla definizione di determinati eventi che hanno permesso di entrare nel profondo della questione e di sondare la relazione tra Rossi e la Penisola Iberica, il materiale fornito dallo studio di tali episodi, quali il I SIAC, la diffusione della rivista "2C. Construccion de la Ciudad", la Coleccion Arquitectura y Critica di Gustavo Gili, hanno poi dato impulso per il reperimento di una rete di ulteriori riferimenti. E' stato possibile quindi individuare un gruppo di architetti spagnoli, che si identificano come allievi del maestro Rossi, impegnato per altro in quegli anni nella formazione di una Scuola e di un insegnamento, che non viene recepito tanto nelle forme, piuttosto nei contenuti. I punti su cui si fondano le connessioni tra l'analisi urbana e il progetto architettonico si centrano attorno due temi di base che riprendono la teoria esposta da Rossi nel saggio L'architettura della città : - relazione tra l'area-studio e la città nella sua globalità, - relazione tra la tipologia edificatoria e gli aspetti morfologici. La ricerca presentata ha visto nelle sue successive fasi di approfondimento, come si è detto, lo sviluppo parallelo di più tematiche. Nell'affrontare ciascuna fase è stato necessario, di volta in volta, operare una verifica delle tappe percorse precedentemente, per mantenere costante il filo del discorso col lavoro svolto e ritrovare, durante lo svolgimento stesso della ricerca, gli elementi di connessione tra i diversi episodi analizzati. Tale operazione ha messo in luce talvolta nodi della ricerca rimasti in sospeso che richiedevano un ulteriore approfondimento o talvolta solo una rivisitazione per renderne possibile un più proficuo collegamento con la rete di informazioni accumulate. La ricerca ha percorso strade diverse che corrono parallele, per quanto riguarda il periodo preso in analisi: - i testi sulla storia dell'architettura spagnola e la situazione contestuale agli anni Settanta - il materiale riguardante il I SIAC - le interviste ai partecipanti al I SIAC - le traduzioni di Gustavo Gili nella Coleccion Arquitectura y Critica - la rivista "2C. Construccion de la Ciudad" Esse hanno portato alla luce una notevole quantità di tematiche, attraverso le quali, queste strade vengono ad intrecciarsi e a coincidere, verificando l'una la veridicità dell'altra e rafforzandone il valore delle affermazioni. Esposizione sintetica dei principali contenuti esposti dalla ricerca Andiamo ora a vedere brevemente i contenuti dei singoli capitoli. Nel primo capitolo Anni Settanta. Periodo di transizione per la Penisola Iberica si è cercato di dare un contesto storico agli eventi studiati successivamente, andando ad evidenziare gli elementi chiave che permettono di rintracciare la presenza della predisposizione ad un cambiamento culturale. La fase di passaggio da una condizione di chiusura rispetto alle contaminazioni provenienti dall'esterno, che caratterizza Spagna e Portogallo negli anni Sessanta, lascia il posto ad un graduale abbandono della situazione di isolamento venutasi a creare intorno al Paese a causa del regime dittatoriale, fino a giungere all'apertura e all'interesse nei confronti degli apporti culturali esterni. E' in questo contesto che si gettano le basi per la realizzazione del I Seminario Internazionale di Architettura Contemporanea a Santiago de Compostela, del 1976, diretto da Aldo Rossi e organizzato da César Portela e Salvador Tarragó, di cui tratta il capitolo secondo. Questo è uno degli eventi rintracciati nella storia delle relazioni tra Rossi e la Penisola Iberica, attraverso il quale è stato possibile constatare la presenza di uno scambio culturale e l'importazione in Spagna delle teorie di Aldo Rossi. Organizzato all'indomani della caduta del franchismo, ne conserva una reminescenza formale. Il capitolo è organizzato in tre parti, la prima si occupa della ricostruzione dei momenti salienti del Seminario Proyecto y ciudad historica, dagli interventi di architetti di fama internazionale, quali lo stesso Aldo Rossi, Carlo Aymonino, James Stirling, Oswald Mathias Ungers e molti altri, che si confrontano sul tema delle città storiche, alle giornate seminariali dedicate all’elaborazione di un progetto per cinque aree individuate all’interno di Santiago de Compostela e quindi dell’applicazione alla pratica progettuale dell’inscindibile base teorica esposta. Segue la seconda parte dello stesso capitolo riguardante La selezione di interviste ai partecipanti al Seminario. Esso contiene la raccolta dei colloqui avuti con alcuni dei personaggi che presero parte al Seminario e attraverso le loro parole si è cercato di approfondire la materia, in particolar modo andando ad evidenziare l’ambiente culturale in cui nacque l’idea del Seminario, il ruolo avuto nella diffusione della teoria di Aldo Rossi in Spagna e la ripercussione che ebbe nella pratica costruttiva. Le diverse interviste, seppur rivolte a persone che oggi vivono in contesti distanti e che in seguito a questa esperienza collettiva hanno intrapreso strade diverse, hanno fatto emergere aspetti comuni, tale unanimità ha dato ancor più importanza al valore di testimonianza offerta. L’elemento che risulta più evidente è il lascito teorico, di molto prevalente rispetto a quello progettuale che si è andato mescolando di volta in volta con la tradizione e l’esperienza dei cosiddetti allievi di Aldo Rossi. Negli stessi anni comincia a farsi strada l’importanza del confronto e del dibattito circa i temi architettonici e nel capitolo La fortuna critica della teoria di Aldo Rossi nella Penisola Iberica è stato affrontato proprio questo rinnovato interesse per la teoria che in quegli anni si stava diffondendo. Si è portato avanti lo studio delle pubblicazioni di Gustavo Gili nella Coleccion Arquitectura y Critica che, a partire dalla fine degli anni Sessanta, pubblica e traduce in lingua spagnola i più importanti saggi di architettura, tra i quali La arquitectura de la ciudad di Aldo Rossi, nel 1971, e Comlejidad y contradiccion en arquitectura di Robert Venturi nel 1972. Entrambi fondamentali per il modo di affrontare determinate tematiche di cui sempre più in quegli anni si stava interessando la cultura architettonica iberica, diventando così ¬ testi di riferimento anche nelle scuole. Le tracce dell’influenza di Rossi sulla Penisola Iberica si sono poi ricercate nella rivista “2C. Construccion de la Ciudad” individuata come strumento di espressione di una teoria condivisa. Con la nascita nel 1972 a Barcellona di questa rivista viene portato avanti l’impegno di promuovere la Tendenza, facendo riferimento all’opera e alle idee di Rossi ed altri architetti europei, mirando inoltre al recupero di un ruolo privilegiato dell’architettura catalana. A questo proposito sono emersi due fondamentali aspetti che hanno legittimato l’indagine e lo studio di questa fonte: - la diffusione della cultura architettonica, il controllo ideologico e di informazione operato dal lavoro compiuto dalla rivista; - la documentazione circa i criteri di scelta della redazione a proposito del materiale pubblicato. E’ infatti attraverso le pubblicazioni di “2C. Construccion de la Ciudad” che è stato possibile il ritrovamento delle notizie sulla mostra Arquitectura y razionalismo. Aldo Rossi + 21 arquitectos españoles, che accomuna in un’unica esposizione le opere del maestro e di ventuno giovani allievi che hanno recepito e condiviso la teoria espressa ne “L’architettura della città”. Tale mostra viene poi riproposta nella Sezione Internazionale di Architettura della XV Triennale di Milano, la quale dedica un Padiglione col titolo Barcelona, tres epocas tres propuestas. Dalla disamina dei progetti presentati è emerso un interessante caso di confronto tra le Viviendas para gitanos di César Portela e la Casa Bay di Borgo Ticino di Aldo Rossi, di cui si è occupato l’ultimo paragrafo di questo capitolo. Nel corso degli studi è poi emerso un interessante risvolto della ricerca che, capovolgendone l’oggetto stesso, ne ha approfondito gli aspetti cercando di scavare più in profondità nell’analisi della reciproca influenza tra la cultura iberica e Aldo Rossi, questa parte, sviscerata nell’ultimo capitolo, La Penisola Iberica nel “magazzino della memoria” di Aldo Rossi, ha preso il posto di quello che inizialmente doveva presentarsi come il risvolto progettuale della tesi. Era previsto infatti, al termine dello studio dell’influenza di Aldo Rossi sulla Penisola Iberica, un capitolo che concentrava l’attenzione sulla produzione progettuale. A seguito dell’emergere di un’influenza di carattere prettamente teorica, che ha sicuramente modificato la pratica dal punto di vista delle scelte architettoniche, senza però rendersi esplicita dal punto di vista formale, si è preferito, anche per la difficoltà di individuare un solo esempio rappresentativo di quanto espresso, sostituire quest’ultima parte con lo studio dell’altra faccia della medaglia, ossia l’importanza che a sua volta ha avuto la cultura iberica nella formazione della collezione dei riferimenti di Aldo Rossi. L’articolarsi della tesi in fasi distinte, strettamente connesse tra loro da un filo conduttore, ha reso necessari successivi aggiustamenti nel percorso intrapreso, dettati dall’emergere durante la ricerca di nuovi elementi di indagine. Si è pertanto resa esplicita la ricercata eredità di Aldo Rossi, configurandosi però prevalentemente come un’influenza teorica che ha preso le sfumature del contesto e dell’esperienza personale di chi se ne è fatto ricevente, diventandone così un continuatore attraverso il proprio percorso autonomo o collettivo intrapreso in seguito. Come suggerisce José Charters Monteiro, l’eredità di Rossi può essere letta attraverso tre aspetti su cui si basa la sua lezione: la biografia, la teoria dell’architettura, l’opera. In particolar modo per quanto riguarda la Penisola Iberica si può parlare dell’individuazione di un insegnamento riferito alla seconda categoria, i suoi libri di testo, le sue partecipazioni, le traduzioni. Questo è un lascito che rende possibile la continuazione di un dibattito in merito ai temi della teoria dell’architettura, della sue finalità e delle concrete applicazioni nelle opere, che ha permesso il verificarsi di una apertura mentale che mette in relazione l’architettura con altre discipline umanistiche e scientifiche, dalla politica, alla sociologia, comprendendo l’arte, le città la morfologia, la topografia, mediate e messe in relazione proprio attraverso l’architettura.

Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Biomass Gasification - Process analysis and dimensioning aspects for downdraft units and gas cleaning lines

In such territories where food production is mostly scattered in several small / medium size or even domestic farms, a lot of heterogeneous residues are produced yearly, since farmers usually carry out different activities in their properties. The amount and composition of farm residues, therefore, widely change during year, according to the single production process periodically achieved. Coupling high efficiency micro-cogeneration energy units with easy handling biomass conversion equipments, suitable to treat different materials, would provide many important advantages to the farmers and to the community as well, so that the increase in feedstock flexibility of gasification units is nowadays seen as a further paramount step towards their wide spreading in rural areas and as a real necessity for their utilization at small scale. Two main research topics were thought to be of main concern at this purpose, and they were therefore discussed in this work: the investigation of fuels properties impact on gasification process development and the technical feasibility of small scale gasification units integration with cogeneration systems. According to these two main aspects, the present work was thus divided in two main parts. The first one is focused on the biomass gasification process, that was investigated in its theoretical aspects and then analytically modelled in order to simulate thermo-chemical conversion of different biomass fuels, such as wood (park waste wood and softwood), wheat straw, sewage sludge and refuse derived fuels. The main idea is to correlate the results of reactor design procedures with the physical properties of biomasses and the corresponding working conditions of gasifiers (temperature profile, above all), in order to point out the main differences which prevent the use of the same conversion unit for different materials. At this scope, a gasification kinetic free model was initially developed in Excel sheets, considering different values of air to biomass ratio and the downdraft gasification technology as particular examined application. The differences in syngas production and working conditions (process temperatures, above all) among the considered fuels were tried to be connected to some biomass properties, such elementary composition, ash and water contents. The novelty of this analytical approach was the use of kinetic constants ratio in order to determine oxygen distribution among the different oxidation reactions (regarding volatile matter only) while equilibrium of water gas shift reaction was considered in gasification zone, by which the energy and mass balances involved in the process algorithm were linked together, as well. Moreover, the main advantage of this analytical tool is the easiness by which the input data corresponding to the particular biomass materials can be inserted into the model, so that a rapid evaluation on their own thermo-chemical conversion properties is possible to be obtained, mainly based on their chemical composition A good conformity of the model results with the other literature and experimental data was detected for almost all the considered materials (except for refuse derived fuels, because of their unfitting chemical composition with the model assumptions). Successively, a dimensioning procedure for open core downdraft gasifiers was set up, by the analysis on the fundamental thermo-physical and thermo-chemical mechanisms which are supposed to regulate the main solid conversion steps involved in the gasification process. Gasification units were schematically subdivided in four reaction zones, respectively corresponding to biomass heating, solids drying, pyrolysis and char gasification processes, and the time required for the full development of each of these steps was correlated to the kinetics rates (for pyrolysis and char gasification processes only) and to the heat and mass transfer phenomena from gas to solid phase. On the basis of this analysis and according to the kinetic free model results and biomass physical properties (particles size, above all) it was achieved that for all the considered materials char gasification step is kinetically limited and therefore temperature is the main working parameter controlling this step. Solids drying is mainly regulated by heat transfer from bulk gas to the inner layers of particles and the corresponding time especially depends on particle size. Biomass heating is almost totally achieved by the radiative heat transfer from the hot walls of reactor to the bed of material. For pyrolysis, instead, working temperature, particles size and the same nature of biomass (through its own pyrolysis heat) have all comparable weights on the process development, so that the corresponding time can be differently depending on one of these factors according to the particular fuel is gasified and the particular conditions are established inside the gasifier. The same analysis also led to the estimation of reaction zone volumes for each biomass fuel, so as a comparison among the dimensions of the differently fed gasification units was finally accomplished. Each biomass material showed a different volumes distribution, so that any dimensioned gasification unit does not seem to be suitable for more than one biomass species. Nevertheless, since reactors diameters were found out quite similar for all the examined materials, it could be envisaged to design a single units for all of them by adopting the largest diameter and by combining together the maximum heights of each reaction zone, as they were calculated for the different biomasses. A total height of gasifier as around 2400mm would be obtained in this case. Besides, by arranging air injecting nozzles at different levels along the reactor, gasification zone could be properly set up according to the particular material is in turn gasified. Finally, since gasification and pyrolysis times were found to considerably change according to even short temperature variations, it could be also envisaged to regulate air feeding rate for each gasified material (which process temperatures depend on), so as the available reactor volumes would be suitable for the complete development of solid conversion in each case, without even changing fluid dynamics behaviour of the unit as well as air/biomass ratio in noticeable measure. The second part of this work dealt with the gas cleaning systems to be adopted downstream the gasifiers in order to run high efficiency CHP units (i.e. internal engines and micro-turbines). Especially in the case multi–fuel gasifiers are assumed to be used, weightier gas cleaning lines need to be envisaged in order to reach the standard gas quality degree required to fuel cogeneration units. Indeed, as the more heterogeneous feed to the gasification unit, several contaminant species can simultaneously be present in the exit gas stream and, as a consequence, suitable gas cleaning systems have to be designed. In this work, an overall study on gas cleaning lines assessment is carried out. Differently from the other research efforts carried out in the same field, the main scope is to define general arrangements for gas cleaning lines suitable to remove several contaminants from the gas stream, independently on the feedstock material and the energy plant size The gas contaminant species taken into account in this analysis were: particulate, tars, sulphur (in H2S form), alkali metals, nitrogen (in NH3 form) and acid gases (in HCl form). For each of these species, alternative cleaning devices were designed according to three different plant sizes, respectively corresponding with 8Nm3/h, 125Nm3/h and 350Nm3/h gas flows. Their performances were examined on the basis of their optimal working conditions (efficiency, temperature and pressure drops, above all) and their own consumption of energy and materials. Successively, the designed units were combined together in different overall gas cleaning line arrangements, paths, by following some technical constraints which were mainly determined from the same performance analysis on the cleaning units and from the presumable synergic effects by contaminants on the right working of some of them (filters clogging, catalysts deactivation, etc.). One of the main issues to be stated in paths design accomplishment was the tars removal from the gas stream, preventing filters plugging and/or line pipes clogging At this scope, a catalytic tars cracking unit was envisaged as the only solution to be adopted, and, therefore, a catalytic material which is able to work at relatively low temperatures was chosen. Nevertheless, a rapid drop in tars cracking efficiency was also estimated for this same material, so that an high frequency of catalysts regeneration and a consequent relevant air consumption for this operation were calculated in all of the cases. Other difficulties had to be overcome in the abatement of alkali metals, which condense at temperatures lower than tars, but they also need to be removed in the first sections of gas cleaning line in order to avoid corrosion of materials. In this case a dry scrubber technology was envisaged, by using the same fine particles filter units and by choosing for them corrosion resistant materials, like ceramic ones. Besides these two solutions which seem to be unavoidable in gas cleaning line design, high temperature gas cleaning lines were not possible to be achieved for the two larger plant sizes, as well. Indeed, as the use of temperature control devices was precluded in the adopted design procedure, ammonia partial oxidation units (as the only considered methods for the abatement of ammonia at high temperature) were not suitable for the large scale units, because of the high increase of reactors temperature by the exothermic reactions involved in the process. In spite of these limitations, yet, overall arrangements for each considered plant size were finally designed, so that the possibility to clean the gas up to the required standard degree was technically demonstrated, even in the case several contaminants are simultaneously present in the gas stream. Moreover, all the possible paths defined for the different plant sizes were compared each others on the basis of some defined operational parameters, among which total pressure drops, total energy losses, number of units and secondary materials consumption. On the basis of this analysis, dry gas cleaning methods proved preferable to the ones including water scrubber technology in al of the cases, especially because of the high water consumption provided by water scrubber units in ammonia adsorption process. This result is yet connected to the possibility to use activated carbon units for ammonia removal and Nahcolite adsorber for chloride acid. The very high efficiency of this latter material is also remarkable. Finally, as an estimation of the overall energy loss pertaining the gas cleaning process, the total enthalpy losses estimated for the three plant sizes were compared with the respective gas streams energy contents, these latter obtained on the basis of low heating value of gas only. This overall study on gas cleaning systems is thus proposed as an analytical tool by which different gas cleaning line configurations can be evaluated, according to the particular practical application they are adopted for and the size of cogeneration unit they are connected to.

A model for diffusive and displacive phase transitions in steels

Heat treatment of steels is a process of fundamental importance in tailoring the properties of a material to the desired application; developing a model able to describe such process would allow to predict the microstructure obtained from the treatment and the consequent mechanical properties of the material. A steel, during a heat treatment, can undergo two different kinds of phase transitions [p.t.]: diffusive (second order p.t.) and displacive (first order p.t.); in this thesis, an attempt to describe both in a thermodynamically consistent framework is made; a phase field, diffuse interface model accounting for the coupling between thermal, chemical and mechanical effects is developed, and a way to overcome the difficulties arising from the treatment of the non-local effects (gradient terms) is proposed. The governing equations are the balance of linear momentum equation, the Cahn-Hilliard equation and the balance of internal energy equation. The model is completed with a suitable description of the free energy, from which constitutive relations are drawn. The equations are then cast in a variational form and different numerical techniques are used to deal with the principal features of the model: time-dependency, non-linearity and presence of high order spatial derivatives. Simulations are performed using DOLFIN, a C++ library for the automated solution of partial differential equations by means of the finite element method; results are shown for different test-cases. The analysis is reduced to a two dimensional setting, which is simpler than a three dimensional one, but still meaningful.