Production and Electrical Characterization of Low Density Polyethylene-based Micro- and Nano-dielectrics containing Graphene Oxide, Functionalized Graphene and Carbon Black additives

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*.

Influence of additives on the performance of a PVDF membrane

The field of use of membranes is wide and ranges from the automotive industry to biomedical uses. Many formulations and compositions find a niche where they are able to improve efficiency, running cost and quality of the product. The aim of this research is to expand GVS’s product portfolio introducing a new membrane formulation. A series of additives were researched and evaluated, adding them to the membrane solutions, which were then cast and characterised using techniques like Scanning Electron Microscopy (SEM), poroscopy, FT-IT ATR and measurements like Water Break Through (WBT), Air Flow (AF), thickness. This study ultimately focused on one additive, which effect on the membranes was studied in various compositions. Interesting insights were also collected on the stability of the polymer solutions over time, which was found to change the membrane properties significantly, mainly affecting airflow and water breakthrough. Properties of the membranes were studied to find possible correlations to the amount of additive. The additive seems however to change the membrane porometry considerably depending on the time of immersion in the water bath. A new procedure to yield uniform unsupported polymeric membranes for tensile tests was developed. The additive was found to reduce elongation at break and decrease tensile strength of the membranes, possibly hinting toward plasticization of the product.

Idrogenazione selettiva del 5-idrossimetilfurfurale in fase omogenea: studio dell'attività catalitica del complesso di Shvo

Il presente lavoro di tesi è frutto di una collaborazione fra il Dipartimento di Chimica Fisica ed Inorganica (gruppo del Prof. Valerio Zanotti – Mattia Vaccari, Dr. Rita Mazzoni) ed il Dipartimento di Chimica Industriale e dei Materiali (gruppo del Prof. Angelo Vaccari – Dr. Thomas Pasini, Dr. Stefania Albonetti, Prof. Fabrizio Cavani) e si inserisce il un progetto volto a valutare l’attività e la selettività del catalizzatore di idrogenazione di Shvo 1, verso l’idrogenazione selettiva del doppio legame polare del 5-idrossimetilfurfurale (HMF) in fase omogenea. L’HMF è un composto di natura organica facilmente ottenibile dalle biomasse, il quale può essere impiegato come building block per ottenere prodotti ad alto valore aggiunto per la chimica fine o additivi per biocarburanti aventi un elevato potere calorifico. In particolare la nostra attenzione si è rivolta alla produzione del 2,5-diidrossimetilfurano (BHMF), un importante building block per la produzione di polimeri e schiume poliuretaniche. Il lavoro di tesi da me svolto ha riguardato la messa a punto di una nuova metodologia sintetica per la preparazione del catalizzatore di Shvo e lo studio della sua attività catalitica nella riduzione di HMF a BHMF. Il comportamento del catalizzatore è stato monitorato studiando la resa in BHMF in funzione di tutti i parametri di reazione: temperatura, pressione di H2, solvente, rapporto molare substrato/catalizzatore, concentrazione, tempo. Successivamente è stata valutata la possibilità di riciclare il catalizzatore recuperando il prodotto di estrazione con acqua, per precipitazione o eseguendo la reazione in miscela bifasica (toluene/H2O). The present work is a collaboration between the Department of Physics and Inorganic Chemistry (group of Prof. Valerio Zanotti - Mattia Vaccari, Dr. Rita Mazzoni) and the Department of Industrial Chemistry and Materials (Group of Prof. Angelo Vaccari - Dr. Thomas Pasini, Dr. Stefania Albonetti, Prof. Fabrizio Cavani), and it’s a project devoted to evaluate the activity and selectivity of the Shvo catalyst, in the selective hydrogenation of polar double bond of 5 -hydroxymethylfurfural (HMF) in homogeneous phase. The HMF is an organic compound easily obtained from biomass, which can be used as a building block for fine chemicals abd polymer production or additives for biofuels with a high calorific value. In particular, our attention turned to the production of 2.5-bishydroxymethylfuran (BHMF), an important building block for the production of polymers and polyurethane foams. This thesis has involved the development of a new synthetic methodology for the preparation of Shvo’s catalyst and the study of its catalytic activity in the reduction of HMF to BHMF. The behavior of the catalyst was monitored by studying the yield in BHMF as a function of all the reaction parameters: temperature, pressure of H2, solvent, substrate to catalyst molar ratio, concentration, time. Subsequently it was evaluated the possibility of recycling the catalyst recovering the product of extraction with water, by precipitation or performing the reaction in biphasic mixture (toluene/H2O).

α-ossidazione asimmetrica organocatalizzata di aldeidi ramificate con dibenzoil perossido

In this thesis, the development of an enantioselective oxidation of α-branched aldehydes using covalent organocatalysis is described. At state of the art, the asymmetric organocatalysis approach, gave often serous difficulties for these kind of substrate respect “classic” aldehydes. We have used a primary cinchona alkaloid derived amine (specially the 9-epi-NH2-CDA) to develop the reaction in combinations with additives. With benzoyl peroxide as oxidant and 2-phenylpropionaldehyde as reference substrate, we have tried to optimize this system but we not found great results about enantiomeric excess.

Complessi carbenici N-eterociclici di rutenio: catalizzatori omogenei in reazioni di idrogenazione e deidrogenazione

Il presente lavoro di tesi si inserisce in un progetto di ricerca volto alla sintesi di nuovi complessi di metalli di transizione per lo sviluppo di catalizzatori bifunzionali metallo-legante da impiegare in reazioni di catalisi omogenea, in particolare in reazioni redox quali idrogenazione e deidrogenazione attraverso il trasferimento di idrogeno. Il mio progetto ha riguardato la messa a punto della sintesi di complessi di Ru(0) che combinano leganti ciclopentadienonici e carbeni N-eterociclici e la sintesi dei corrispondenti complessi cationici per protonazione. Inoltre, è stato sintetizzato e caratterizzato un nuovo complesso cationico attraverso la metilazione del corrispettivo complesso neutro. I complessi sintetizzati sono stati utilizzati come precursori di catalizzatori nella riduzione tramite trasferimento di idrogeno del 4-fluoroacetofenone, valutandone l’attività catalitica in relazione a leganti, additivi e controioni. Allo scopo di delineare qualche ipotesi sul meccanismo di reazione sono stati effettuati diversi studi sulla reattività dei complessi impiegati in catalisi, in particolare usando la piridina come agente di “trapping”. Infine, è stato condotto uno studio preliminare dell’attività catalitica dei complessi sintetizzati nell’ossidazione di benzilalcol a benzaldeide. The present work is part of a research project that involves the study of new ruthenium-based transition metal complexes in order to develop new metal-ligand bifunctional catalysts to employ in homogeneous catalytic systems, in particular in redox reactions such as hydrogenation and dehydrogenation through hydrogen transfer. My project is focused on the optimization of the synthesis of Ru(0) complexes that combines different ligands as tetraphenylcyclopentadienone and N-heterocyclic carbenes and the synthesis of the corresponding cationic complexes by protonation. Furthermore, it is reported the synthesis and characterization of a new cationic complex obtained by methylation of the corresponding neutral complex. All the prepared complexes were employed as catalyst precursors in the transfer hydrogenation of 4-fluoroacetophenone and their performances were investigated in relation to the type of ligands, additives and counterions. The reactivity of these ruthenium complexes was also investigated with the aim of delineate some hypothesis on the reaction mechanism, in particular employing pyridine as a trapping agent. Finally, preliminary studies on the oxidation of benzyl alcohol have been carried out.

In vivo and in vitro effects of antioxidant compounds and PPAR γ modulators on rainbow trout oxidative stress and lipid metabolism.

The aquafeed use of raw plant materials, as protein and lipid sources, has been considered and approved as a sustainable alternative to fish products (fish meal and oils) because the current trend to use high-lipid diets has been shown to induce undesirable increase in fat depots or further physiological alterations, such as induction of oxidative stress. In the aquaculture perspective, the addition of natural substances with antioxidant properties is an emerging strategy for protecting biological systems and foodstuffs from oxidative damage. Among natural substances, hydroxytyrosol (HT) and caffeic acid (CA) have attracted considerable attention as food antioxidant additives and modulators of physiological and molecular pathways involved in energy metabolism and adiposity. The aim of this study was to evaluate the effects of CA and HT on lipid metabolism and oxidative stress of rainbow trout (Oncorhynchus mykiss). In vitro results showed the potential anti-obesogenic effects of the compounds CA and HT on the adipose tissue of the rainbow trout. To support these data, in vitro assays performed (MTT, ORO, immunofluorescence) resulted in accordance among them; only results from proliferating cell nuclear antigen (PCNA) assay were not significant. In vivo results showed a possible anti-obesogenic effect of CA in liver and HT in adipose tissue. Regarding oxidative stress, we could hypothesize a possible anti-oxidant role of CA in liver.

Investigation on performance characteristics of dense graded hot mix asphalt with RAP and Crumb Rubber

The use of recycled materials in asphalt mixtures such as reclaimed asphalt pavements (RAP) have become widely accepted as a replacement for virgin asphalt binder or virgin aggregates. In this study, the RAP content was 30%, and CR additives were blended with the soft unmodified binder by using dry processes. The objective of this study was to investigate and evaluate the engineering properties of dry method application of crumb rubber influences on reclaimed asphalt pavement (RAP) mixtures. To evaluate the effect of rubber-bitumen interaction on the mixture’s mechanical properties, a laboratory investigation has been conducted on a range of dense graded and 30% RAP by dry process crumb rubber modified (CRM) asphalt mixtures containing 0% (control), 1% crumb rubber by the total aggregate mass. The experimental program in this research include the binder extraction for estimating the amount of aged binder in the both fine and coarse RAP material. Before extracting the binder the RAP sieve analysis, have been done to provide the Black grading curve. In continue after the binder extraction the material sieved again to providing the white curve. The comparison of Black and White curve indicated that there is a remarkable difference between the aggregate grading even for the fine RAP. The experimental program was continued by fabricating 12 specimens in different 4 types of mixtures. For the first group no RAP, no rejuvenator and no crumb rubber were used. For the second group 30% of virgin aggregates substituted by RAP material and the third group was similar to the second group just with 0.01% rejuvenator. the forth group was the group, which in that the specimens contain RAP, rejuvenator and crumb rubber. Finally the specimens were tested for Indirect tensile strength. The results indicated that the addition of crumb rubber increased the optimum amount of binder in the mixture with 30% RAP.

Investigation on performance characteristics of dense graded hot mix asphalt with RAP and crumb rubber

The objective of this study was to fundamentally characterize the laboratory performance of traditional hot mix asphalt (HMA) mixtures incorporating high RAP content and waste tire crumb rubber through their fundamental engineering properties. The nominal maximum aggregates size was chosen for this research was 12mm (considering the limitation of aggregate size for surface layer) and both coarse and fine aggregates are commonly used in Italy that were examined and analyzed in this study. On the other hand, the RAP plays an important role in reducing production costs and enhancing the environmentally sustainable pavements instead of using virgin materials in HMA. Particularly, this study has aimed to use 30% of RAP content (25% fine aggregate RAP and 5% coarse aggregate RAP) and 1% of CR additives by the total weight of aggregates for mix design. The mixture of aggregates, RAP and CR were blended with different amount of unmodified binder through dry processes. Generally, the main purposes of this study were investigating on capability of using RAP and CR in dense graded HMA and comparing the performance of rejuvenator in RAP with CR. In addition, based on the engineering analyses during the study, we were able compare the fundamental Indirect Tensile Strength (ITS) value of dense graded HMA and also mechanical characteristics in terms of Indirect Tensile Stiffness Modulus (ITSM). In order to get an extended comparable data, four groups of different mixtures such as conventional mixture with only virgin aggregates (DV), mixture with RAP (DR), mixture with RAP and rejuvenator (DRR), and mixture with RAP, rejuvenator, CR (DRRCr) were investigated in this research experimentally. Finally, the results of those tests indicated that the mixtures with RAP and CR had the high stiffness and less thermal sensitivity, while the mixture with virgin aggregates only had very low values in comparison.

Rheology of bituminous mastics and mortars containing crumb rubber from tyres: a novel dry-hybrid technology

This report studied the effect of crumb rubber in the asphalt mixture. The mixtures were also having limestone filler as a modifier. Mastic and mortar (mastic-fine aggregate system) mixture having different quantities of crumb rubber and limestone filler modifiers have been tested in order to find the best rutting resistance combination with an acceptable stiffness. The rheological tests on bituminous mastics and mortars have done in the laboratories in Nottingham Transport Engineering Centre (NTEC) and University of Bologna (DICAM). In the second chapter, an extensive literature review about the binders, additives, asphalt mixtures, various modelling and testing methods have been reviewed. In the third chapter, the physical and rheological properties of the binders have been investigated using both traditional devices and DSRs. The forth chapter is dedicated to finding the behaviour of the modified mastics (Binder-modifier system) with different combinations. Five different combinations of crumb rubber and limestone filler mastic tested with various methods using Dynamic Shear Rheometers. In the fifth chapter, in order to find the effect of the modifiers in the rheological properties of the complete asphalt mixture, the fine aggregates added to the same mastic combinations. In this phase, the behaviour of the system so-called mortar; binder, rubber, filler and fine aggregates) has been studied using the DSR device and the traditional tests. The results show that using fine crumb rubber reduces the thermo sensibility of the mastic (Binder Bitumen System) and improves its elasticity. Limestone filler in the other hand increases the mixture stiffness at high Frequencies. Another important outcome of this research was that the rheological properties of the mortars were following the same trend of the mastics, therefore study the rheological properties of the mastic gives an upright estimation of the mortar.

Rheological Characterization of Bitumen and Asphalt including the effect of Added-recycled Material

This thesis evaluates the rheological behaviour of asphalt mixtures and the corresponding extracted binders from the mixtures containing different amounts of Reclaimed Asphalt (RA). Generally, the use of RA is limited to certain amounts. The study materials are Stone Mastic Asphalts including a control sample with 0% RA, and other samples with RA rates of 30%, 60% and 100%. Another set of studied mixtures are Asphalt Concretes (AC) types with again a control mix having 0% RA rate and the other mixtures designs containing 30%, 60% and 90% of reclaimed asphalt which also contain additives. In addition to the bitumen samples extracted from asphalt mixes, there are bitumen samples directly extracted from the original RA. To characterize the viscoelastic behaviour of the binders, Dynamic Shear Rheometer (DSR) tests were conducted on bitumen specimens. The resulting influence of the RA content in the bituminous binders are illustrated through master curves, black diagrams and Cole-Cole plots with regressing these experimental data by the application of the analogical 2S2P1D and the analytical CA model. The advantage of the CA model is in its limited number of parameters and thus is a simple model to use. The 2S2P1D model is an analogical rheological model for the prediction of the linear viscoelastic properties of both asphalt binders and mixtures. In order to study the influence of RA on mixtures, the Indirect Tensile Test (ITT) has been conducted. The master curves of different mixture samples are evaluated by regressing the test data points to a sigmoidal function and subsequently by comparing the master curves, the influence of RA materials is studied. The thesis also focusses on the applicability and also differences of CA model and 2S2P1D model for bitumen samples and the sigmoid function for the mixtures and presents the influence of the RA rate on the investigated model parameters.