Experimental Study on Friction between Saline Ice and Steel

Understanding the interaction of sea ice with offshore structures is of primary importance for the development of technology in cold climate regions. The rheological properties of sea ice (strength, creep, viscosity) as well as the roughness of the contact surface are the main factors influencing the type of interaction with a structure. A device was developed and designed and small scale laboratory experiments were carried out to study sea ice frictional interaction with steel material by means of a uniaxial compression rig. Sea-ice was artificially grown between a stainless steel piston (of circular cross section) and a hollow cylinder of the same material, coaxial to the former and of the same surface roughness. Three different values for the roughness were tested: 1.2, 10 and 30 μm Ry (maximum asperities height), chosen as representative values for typical surface conditions, from smooth to normally corroded steel. Creep tests (0.2, 0.3, 0.4 and 0.6 kN) were conducted at T = -10 ºC. By pushing the piston head towards the cylinder base, three different types of relative movement were observed: 1) the piston slid through the ice, 2) the piston slid through the ice and the ice slid on the surface of the outer cylinder, 3) the ice slid only on the cylinder surface. A cyclic stick-slip motion of the piston was detected with a representative frequency of 0.1 Hz. The ratio of the mean rate of axial displacement to the frequency of the stick-slip oscillations was found to be comparable to the roughness length (Sm). The roughness is the most influential parameter affecting the amplitude of the oscillations, while the load has a relevant influence on the their frequency. Guidelines for further investigations were recommended. Marco Nanetti - seloselo@virgilio.it

Analisi sperimentale degli effetti di temperature elevate sul comportamento strutturale dei rinforzi in FRP

In questa tesi si è voluta porre l’attenzione sulla suscettibilità alle alte temperature delle resine che li compongono. Lo studio del comportamento alle alte temperature delle resine utilizzate per l’applicazione dei materiali compositi è risultato un campo di studio ancora non completamente sviluppato, nel quale c’è ancora necessità di ricerche per meglio chiarire alcuni aspetti del comportamento. L’analisi di questi materiali si sviluppa partendo dal contesto storico, e procedendo successivamente ad una accurata classificazione delle varie tipologie di materiali compositi soffermandosi sull’ utilizzo nel campo civile degli FRP (Fiber Reinforced Polymer) e mettendone in risalto le proprietà meccaniche. Considerata l’influenza che il comportamento delle resine riveste nel comportamento alle alte temperature dei materiali compositi si è, per questi elementi, eseguita una classificazione in base alle loro proprietà fisico-chimiche e ne sono state esaminate le principali proprietà meccaniche e termiche quali il modulo elastico, la tensione di rottura, la temperatura di transizione vetrosa e il fenomeno del creep. Sono state successivamente eseguite delle prove sperimentali, effettuate presso il Laboratorio Resistenza Materiali e presso il Laboratorio del Dipartimento di Chimica Applicata e Scienza dei Materiali, su dei provini confezionati con otto differenti resine epossidiche. Per valutarne il comportamento alle alte temperature, le indagini sperimentali hanno valutato dapprima le temperature di transizione vetrosa delle resine in questione e, in seguito, le loro caratteristiche meccaniche. Dalla correlazione dei dati rilevati si sono cercati possibili legami tra le caratteristiche meccaniche e le proprietà termiche delle resine. Si sono infine valutati gli aspetti dell’applicazione degli FRP che possano influire sul comportamento del materiale composito soggetto alle alte temperature valutando delle possibili precauzioni che possano essere considerate in fase progettuale.

Effetto di un packaging innovativo sulla qualità di nettarine

L’imballaggio alimentare si può definire come un sistema coordinato per disporre i beni per il trasporto, la distribuzione, la conservazione, la vendita e l’utilizzo. Uno dei materiali maggiormente impiegati, nell’industria alimentare, per la produzione di imballaggi sono le materie plastiche. Esse sono sostanze organiche derivanti da petrolio greggio, sono composti solidi allo stato finito, ma possono essere modellate allo stato fluido. Un imballaggio alimentare deve svolgere determinate funzioni tra cui: - contenimento del prodotto - protezione del prodotto da agenti esterni - logistica - comunicativa - funzionale - ecologica L'ultimo punto sopracitato è il principale problema delle materie plastiche derivanti dal petrolio greggio. Questi materiali sono difficilmente riciclabili perché spesso un imballaggio è composto da più materiali stratificati o perché si trova a diretto contatto con gli alimenti. Inoltre questi materiali hanno un lungo tempo di degradazione (da 100 a 1000 anni) che ne rendono difficile e costoso lo smaltimento. Per questo nell’ultimo decennio è cominciata la ricerca di un materiale plastico, flessibile alle esigenze industriali e nel contempo biodegradabile. Una prima idea è stata quella di “imitare la natura” cercando di replicare macromolecole già esistenti (derivate da amido e zuccheri) per ottenere una sostanza plastico-simile utilizzabile per gli stessi scopi, ma biodegradabile in circa sei mesi. Queste bioplastiche non hanno preso piede per l’alto costo di produzione e perché risulta impossibile riconvertire impianti di produzione in tutto il mondo in tempi brevi. Una seconda corrente di pensiero ha indirizzato i propri sforzi verso l’utilizzo di speciali additivi aggiunti in minima misura (1%) ai classici materiali plastici e che ne permettono la biodegradazione in un tempo inferiore ai tre anni. Un esempio di questo tipo di additivi è l’ECM Masterbatch Pellets che è un copolimero di EVA (etilene vinil acetato) che aggiunto alle plastiche tradizionali rende il prodotto finale completamente biodegradabile pur mantenendo le proprie caratteristiche. Scopo di questo lavoro di tesi è stato determinare le modificazioni di alcuni parametri qualitativi di nettarine di Romagna(cv.-Alexa®) confezionate-con-film-plastici-tradizionali-e-innovativi. I campioni di nettarine sono stati confezionati in cestini in plastica da 1 kg (sigillati con un film flow-pack macroforato) di tipo tradizionale in polipropilene (campione denominato TRA) o vaschette in polipropilene additivato (campione denominato BIO) e conservati a 4°C e UR 90-95% per 7 giorni per simulare un trasporto refrigerato successivamente i campioni sono stati posti in una camera a 20°C e U.R. 50% per 4 giorni al fine di simulare una conservazione al punto vendita. Al tempo 0 e dopo 4, 7, 9 e 11 giorni sono state effettuate le seguenti analisi: - coefficiente di respirazione è stato misurata la quantità di CO2 prodotta - indice di maturazione espresso come rapporto tra contenuto in solidi solubili e l’acidità titolabile - analisi di immagine computerizzata - consistenza della polpa del frutto è stata misurata attraverso un dinamometro Texture Analyser - contenuto in solidi totali ottenuto mediante gravimetria essiccando i campioni in stufa sottovuoto - caratteristiche sensoriali (Test Accettabilità) Conclusioni In base ai risultati ottenuti i due campioni non hanno fatto registrare dei punteggi significativamente differenti durante tutta la conservazione, specialmente per quanto riguarda i punteggi sensoriali, quindi si conclude che le vaschette biodegradabili additivate non influenzano la conservazione delle nettarine durante la commercializzazione del prodotto limitatamente ai parametri analizzati. Si ritiene opportuno verificare se il processo di degradazione del polimero additivato si inneschi già durante la commercializzazione della frutta e soprattutto verificare se durante tale processo vengano rilasciati dei gas che possono accelerare la maturazione dei frutti (p.e. etilene), in quanto questo spiegherebbe il maggiore tasso di respirazione e la più elevata velocità di maturazione dei frutti conservati in tali vaschette. Alimentary packaging may be defined as a coordinate system to dispose goods for transport, distribution, storage, sale and use. Among materials most used in the alimentary industry, for the production of packaging there are plastics materials. They are organic substances deriving from crude oil, solid compounds in the ended state, but can be moulded in the fluid state. Alimentary packaging has to develop determinated functions such as: - Product conteniment - Product protection from fieleders agents - logistic - communicative - functional - ecologic This last term is the main problem of plastic materials deriving from crude oil. These materials are hardly recyclable because a packaging is often composed by more stratified materials or because it is in direct contact with aliments. Beside these materials have a long degradation time(from 100 to 1000 years) that make disposal difficult and expensive. For this reason in the last decade the research for a new plastic material is begin, to make industrial demands more flexible and, at the same time, to make this material biodegradable: At first, the idea to “imitate the nature” has been thought, trying to reply macromolecules already existents (derived from amid and sugars) to obtain a similar-plastic substance that can be used for the same purposes, but it has to be biodegradable in about six months. These bioplastics haven’t more success bacause of the high production cost and because reconvert production facilities of all over the wolrd results impossible in short times. At second, the idea to use specials addictives has been thought. These addictives has been added in minim measure (1%) to classics plastics materials and that allow the biodegradation in a period of time under three years. An example of this kind of addictives is ECM Masterbatch Pellets which is a coplymer of EVA (Ethylene vinyl acetate) that, once it is added to tradizional plastics, make final product completely biodegradable however maintaining their own attributes. The objective of this thesis work has been to determinate modifications of some Romagna’s Nectarines’ (cv. Alexa®) qualitatives parameters which have been packaged-with traditional and innovative-plastic film. Nectarines’ samples have been packaged in plastic cages of 1 kg (sealed with a macro-drilled flow-pack film) of traditional type in polypropylene (sample named TRA) or trays in polypropylene with addictives (sample named BIO) and conservated at 4°C and UR 90-95% for 7 days to simulate a refrigerated transport. After that, samples have been put in a camera at 20°C and U.R. 50% for 4 days to simulate the conservation in the market point. At the time 0 and after 4, 7, 9 and 11 days have been done the following analaysis: - Respiration coefficient wherewith the amount CO2 producted has been misurated - Maturation index which is expressed as the ratio between solid soluble content and the titratable acidity - Analysis of computing images - Consistence of pulp of the fruit that has been measured through Texture Analyser Dynanometer - Content in total solids gotten throught gravimetry by the drying of samples in vacuum incubator - Sensorial characteristic (Panel Test) Consequences From the gotten results, the two samples have registrated no significative different scores during all the conservation, expecially about the sensorial scores, so it’s possible to conclude that addictived biodegradable trays don’t influence the Nectarines’ conservation during the commercialization of the product qualifiedly to analized parameters. It’s advised to verify if the degradation process of the addicted polymer may begin already during the commercialization of the fruit and in particular to verify if during this process some gases could be released which can accelerate the maturation of fruits (p.e. etylene), because all this will explain the great respiration rate and the high speed of the maturation of fruits conservated in these trays.

Development and Characterization of Biopolymers

Development and characterization of biopolymers was done in AIJU’s laboratories. AIJU, Technological Institute for children’s products and leisure is based in Spain. The work has the aim to study qualities and characteristics of bioplastics’ blends, in order to design where improvements can be executed. Biopolymers represent a sector with great development possibilities because they combine high technical potential and eco-sustainability. Nowadays, plastic pollution has becoming increasingly concerning, particularly in terms of management of waste. Bioplastics provide an alternative for the disposal of products, reducing the volume of waste and enhancing the end of life recovery. Despite the growing interest in biopolymers there is some gaps that need be filled. The main objective on this work, is the optimization of bioplastics mechanical properties, to find suitable substitutes, as similar as possible to conventional plastics. Firstly, investigations on processability of biomaterials has been deepen since the project deals with toy manufacturing’s sector. Thus, starting from laboratory scale the work aspires to expand industrially. By working with traditional machines, it was notable that, with some limited modifications, the equipment can perform the same functions. Therefore, operational processes do not emerge as an obstacle to the production chain. Secondly, after processing bio-blends, they are characterized by thermal tests (melt flow index, differential scanning calorimetry-DSC, thermogravimetry-TGA) and mechanical tests (traction and flexural tests, Charpy impact, SHORE D hardness and density). While the compatibility does not show relevant results, mechanical improvements has been visualized with addition of more ductile materials. The study was developed by inclusion of sustainable additive VINNEX® to blends. The thesis has highlighted that integration of more flexible materials provides elasticity without compromising bioplastics’ properties.

Realizzazione grafica del catalogo di nuovi materiali biocompositi con applicazione progettuale nel packaging cosmetico

Il primo capitolo introduce l’importante problema dei rifiuti plastici e l’impatto che hanno nell’ambiente, esaminando sia i rifiuti plastici di grandi dimensioni sia le microplastiche. A riguardo, un documento molto significativo è quello della New Plastics Economy: questo raccoglie rilevanti informazioni sull’andamento della produzione e dei rifiuti plastici negli anni e va a delineare dei suggerimenti, delle linee guida che dovrebbero essere adottate per migliorare questa attuale condizione di crisi ambientale dovuta proprio alle materie plastiche. Il secondo capitolo ha il compito di introdurre i trentasei nuovi biocompositi in fase di produzione e sperimentazione e con loro il primo progetto grafico di tesi del catalogo per l’azienda Arianna Fibers. Una prima parte affronta il tema della valorizzazione dello scarto. Ed è qui che i gusci di frutta secca hanno l’opportunità di trasformarsi da rifiuto in risorsa, da materia di scarto in materia prima. Karà bio-compositi sono dei nuovi materiali composti da una matrice di bioplastica biodegradabile e da scarti di gusci di frutta secca. Il mio obiettivo è stato quello di progettare un catalogo di questi materiali che raccoglie campioni materici, informazioni, foto, render e applicazioni. Il terzo capitolo riguarda la progettazione del packaging cosmetico come applicazione dei nuovi materiali biocompositi precedentemente descritti. Si parla dunque di Impronta Ambientale, LCA ed Ecodesign del packaging cosmetico e da queste ed altre valutazioni su casi studio presenti sul mercato nasce Karà bio-cosmetics: una linea di packaging cosmetici sostenibili realizzati con i materiali biocompositi biodegradabili. La tipologia di materiale scelto è quella dei biocompositi a matrice PHA, unica bioplastica biodegradabile in ambiente aperto. Si tratta di una linea di diversi pezzi associabili a vari tipi di cosmetici che l’utente potrà poi personalizzare.

Polyhydroxyalkanoates production from salted food waste using mixed microbial cultures.

Plastic is an essential asset for the modern lifestyle, given its superiority as a material from the points of view of cost, processability and functional properties. However, plastic-related environmental pollution has become nowadays a very significant problem that can no longer be overlooked. For this reason, in recent decades, the research for new materials that could replace fossil fuel-based plastics has been focused on biopolymers with similar physicochemical properties to fossil fuel-based plastics, such as Polyhydroxyalkanoates (PHA). PHAs are a family of biodegradable polyesters synthesized by many microorganisms as carbon and energy reserves. PHA appears as a good candidate to substitute conventional petroleum-based plastics since it has similar properties, but with the advantage of being biobased and biodegradable, and has a wide range of applications (e.g., packaging). However, the PHA production cost is almost four times higher (€5/kg) than conventional plastic manufacturing. The PHA production by mixed microbial cultures (MMC) allows to reduce production costs as it does not require aseptic conditions and it enables the use of inexpensive by-products or waste streams as these cultures are more amenable to deal with complex feedstocks. Saline wastewaters (WWs), generated by several industries such as seafood, leather and dairy, are often rich in organic compounds and, due to a strong salt inhibition, the biological treatments are inefficient, and their disposal is expensive. These saline WWs are a potential feedstock for PHA production, as they are an inexpensive raw material. Moreover, saline WWs could allow the utilization of seawater in the process as dilution and cleaning agent, further decreasing the operational costs and the environmental burden of the process. The main goal of the current project is to assess and optimize the PHA production from a mixture of food waste and brine wastewater from the fishery industry by MMC.

Optimization of a polyhydroxyalkanoates production process using a halotolerant mixed microbial culture

The rate at which petroleum based plastics are being produced, used and thrown away is increasing every year because of an increase in the global population. Polyhydroxyalkanoates can represent a valid alternative to petroleum based plastics. They are biodegradable polymers that can be produced by some microorganisms as intracellular reserves. The actual problem is represented by the production cost of these bioplastics, which is still not competitive if compared to the one of petroleum based plastics. Mixed microbial cultures can be fed with substrates obtained from the acidogenic fermentation of carbon rich wastes, such as cheese whey, municipal effluents and various kinds of food wastes, that have a low or sometimes even inexisting cost and in this way wastes can be valorized instead of being discharged. The process consists of three phases: acidogenic fermentation in which the substrate is obtained, culture selection in which a PHA-storing culture is selected and enriched eliminating organisms that do not show this property and accumulation, in which the culture is fed until reaching the maximum storage capacity. In this work the possibility to make the process cheaper was explored trying to couple the selection and accumulation steps and a halotolerant culture collected from seawater was used and fed with an artificially salted synthetic substrated made of an aqueous solution containing a mixture of volatile fatty acids in order to explore also if its performance can allow to use it to treat substrates derived from saline effluents, as these streams cannot be treated properly by bacterias found in activated sludge plants due to inhibition caused by high salt concentrations. Generating and selling the produced PHAs obtained from these bacterias it could be possible to lower, nullify or even overcome the costs associated to the new section of a treating plant dedicated to saline effluents.

Optimization and characterization of a wheat-based biocomposite for additive manufacturing

In recent years plastic is a key material, fundamental for a large variety of implications. But its large utilization has the direct consequence of the disposal of tons of wastes, that in the major amount cannot be recycled. To pose a solution to the issue of the increasing amount of plastics that are rapidly accumulating all over the world, it is necessary to switch to biodegradable materials. This dissertation is focused on a biodegradable and biobased plastic (polylactic acid, PLA), in order to set free the material from the market and issues of oil, but the PLA is very expensive. For this reason it was added a part of natural component derived from wastes (wheat middling), that acts as reinforcement and decreases the cost of the final material forming a biocomposite. Since their interaction is difficult, the purpose of this dissertation is to improve the affinity between the PLA and the wheat middling.

Development and scale-up studies of bio-based poly(ester-amide)s

Plastics are polymers of conventional and extensive use in our day-to-day life. This is due to their light weight, adaptability to different uses and low prices. A downside of such extensive use is the environmental pollution arising from plastic production and disposal. Indeed, many commodity polymers are produced from non-renewable resources while other do not bio-degrade after their end-of-life disposal. Consequently, the ideal polymer comes from renewable raw materials and bio-degrades after its disposal, meaning that it would do little or no harm to the environment from the beginning to the end of its life cycle. In this thesis project a class of bio-based and bio-degradable co-polymers, namely poly(ester-amide)s, was investigated because of their tunable mechanical and bio-degradation properties as well as their renewable origin. Such polymers were synthetized and characterized thermically and mechanically. Furthermore, a scale-up procedure was developed and applied to one polymer and processing trials were made with the material obtained after scale-up.

End of life treatment options for bioplastics; a composting efficency case study

The constant increase in plastic production creates many problems, from its oil-based production all the way to end-of-life treatment, as the same proprieties that make plastic useful make conventional plastic into long-lasting waste that’s quickly piling up. One alternative is a different kind of plastic, bioplastic, a polymeric compound that is both functionally like synthetic plastics and largely environmentally sustainable. It is not necessarily enough to solve the plastic waste issue there's a need for effective strategies to manage bioplastic products at their end of life, to avoid undoing the reduction of environmental impact. One such treatment, unique to biodegradable bioplastics, is composting. This prompts a closer study of how efficient this process is in degrading bioplastics.

Monitoring of macro- and microlitter in the Venice lagoon and coastal area

Marine litter and plastics are a significant and growing marine contaminant that has become a global problem. Macrolitter is subject to fragmentation and degradation due to physical, chemical and biological processes, leading to the formation of micro-litter, the so-called microplastics. The purpose of this research is to assess marine litter pollution by using remote sensing tools to identify areas of macrolitter accumulation and to evaluate the concentrations of microplastics in different environmental matrices: water, sediment and biota (i.e. mussels and fish) and to contribute to the European project MAELSTROM (Smart technology for MArinE Litter SusTainable RemOval and Management). The aim is to monitor the presence of macro- and microlitter at two sites of the Venice coastal area: an abandoned mussel farm at sea and a lagoon site near the artificial Island of Sacca Fisola; The results showed that both study areas are characterised by high amounts of marine litter, but the type of observed litter is different. In fact, in the mussel farm area, most of the litter is linked to aquaculture activities (ropes, nets, mooring blocks and floating buoys). In the Venice lagoon site, the litter comes more from urban activities and from the city of Venice (car tyres, crates, wrecks, etc.). Microplastics is present in both sites and in all the analysed matrices. Generally, higher microplastics concentrations were found at Sacca Fisola (i.e., in surface waters, mussels and fish). Moreover, some differences were also observed in shapes and colours comparing the two sites. At Sacca Fisola, white irregular fragments predominate in water samples, blue filaments in sediment and mussels, and transparent irregular fragments in fish. At the Mussel Farm, blue filaments predominate in water, sediment and mussels, while flat black fragments predominate in fish. These differences are related to the different types of macrolitter that characterised the two areas.