Preparazione di una resina epossidica bio-based e studio delle relative proprietà

Epoxy resins are very diffused materials due to their high added value deriving from high mechanical proprieties and thermal resistance; for this reason they are widely used both as metallic coatings in aerospace and in food packaging. However, their preparation uses dangerous reagents like bisphenol A and epichlorohydrin respectively classified as suspected of causing damage to fertility and to be carcinogen. Therefore, to satisfy the ever-growing attention to environmental problems and human safeness, we are considering alternative “green” processes through the use of reagents obtained as by-products from other processes and mild experimental conditions, and also economically sustainable and attractive for industries. Following previous results, we carried out the reaction leading to the formation of diphenolic acid (DPA), its allylation and the following epoxidation of the double bonds, all in aqueous solvent. In a second step the obtained product were cross-linked at high temperature with and without the use of hardeners. Then, on the obtained resin, some tests were performed like release in aqueous solution, scratch test and DSC analysis.

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.

Formulazione e caratterizzazione di idropitture con materie prime “Bio-Based”

The market for paint products with raw materials derived from renewable sources is growing rapidly in the building industry. When high performance in wet scrub resistance is required, “washable” paints are used. However, formulating products with Bio-Based raw materials generally results in a decrease in performances compared to similar products with raw materials from fossil sources. Therefore, a new formulation approach is needed to characterize polymeric binders from renewable sources and to consider the synergistic effects given by blends of polymeric binders of different origin and chemical structure. To date, the development of new formulations that imply less environmental impact is necessary if these products have to remain competitive in the marketplace. During the trainingship in IVAS S.p.A., washable paints with different PVC (Pigment Volume Concentration) were formulated and tested, evaluating whether the performance of paints with polymeric binders obtained from renewable sources was comparable to those with polymeric binders from fossil sources. The binders were chemically characterized by DSC, FT-IR and NMR analysis. Characterization tests of paints were focused on the evaluation of degree of whiteness, hiding power, dirt setting, and wet scrub resistance. Following the results obtained from the available binder combinations, it was possible to formulate two washable paints with comparable performances to those from fossil sources: paint A with 20 % of alkydic polymer and 80 % styrene/acrylic polymer and paint B with 40 % of alkydic polymer and 60 % styrene/acrylic polymer. Finally, the formulation was completed by adding the mainly Bio-Based derived additives generally used for this category of paints.

Sostituzione dell'epicloridrina con derivati del glicerolo nella preparazione di prepolimeri per resine epossidiche bio-based.

La recente e innovativa filosofia della green chemistry che si sta diffondendo nell’industria chimica e l’incombente esaurimento di risorse fossili, stanno indirizzando la ricerca del settore chimico verso la realizzazione di processi sempre più sostenibili. Tra i processi che necessitano maggiormente di questi cambiamenti, vi è quello della produzione di resine epossidiche che per il 90% è costituito attualmente da resine a base di bisfenolo-A, neuro tossico e pericoloso per la riproduzione umana, ed epicloridrina cancerogena; entrambi ottenuti da risorse fossili. Per tali motivi, in questo elaborato si è cercato di sviluppare un processo di sintesi il più possibile “green”, per l’ottenimento di una molecola derivante da risorse rinnovabili, da sostituire all’epicloridrina nella sintesi di prepolimeri per resine epossidiche bio-based. Lo sviluppo del lavoro è avvenuto tramite lo studio dei reagenti, solventi e parametri operativi, ottenendo il glicidil tosilato a partire da glicerolo e tosil cloruro attraverso una reazione in sistema bifasico, semplice dal punto di vista pratico e senza l’utilizzo di composti tossici. Il glicidil tosilato è meno problematico in quanto meno volatile rispetto all’epicloridrina, ed inoltre le prove di reazione con il bisfenolo-A hanno portato all’ottenimento del prepolimero con rese maggiori rispetto a quelle ottenute nelle stesse condizioni con epicloridrina.

Nuovi copoliesteri multiblocco bio-based per applicazioni biomedicali: Correlazioni proprieta-struttura.

Sintesi e caratterizzazione di nuovi poliesteri alifatici per uso biomedicale.

Dithienopyrrole-based materials: development of new polymeric derivatives

The possibility to control molar mass and termination of the growing chain is fundamental to create well-defined, reproducible materials. For this reason, in order to apply polydithienopyrrole (PDTP) as organic conjugated polymer, the possibility of controlled polymerization needs to be verified. Another aspect that is still not completely explored is bound to the optical activity of the PDTP, which bearing appropriate substituents may adopt a helical conformation. The configuration of the helix, built up from achiral co-monomers, can be established in an enantiopure way by using only a small percentage of the chiral monomer co-polymerized with achiral co-monomer. The effect, called “sergeants and soldiers effect”, is expressed by the nonlinear increase of the chiral response vs the ratio of the chiral co-monomer used for the polymerization. To date, this effect is still not completely explored for PDTP. In this framework the project will investigate, firstly, the possibility to obtain a controlled polymerization of PDTP. Then, monomers with different side chains and organometallic functions will be screened for a CTCP-type polymerization. Also a Lewis-acid based cationic polymerization will be performed. Moreover the chemical derivatization of dithienopyrrole DTP is explored: the research is going to concern also block copolymers, built up by DTP and monomers of different nature. The research will be extended also to the investigation of optically active derivates of PDTP, using a chiral monomer for the synthesis. The possibility to develop a supramolecular distribution of the polymeric chains, together with the “sergeants and soldiers effect” will be checked investigating a series of polymers with increasing amounts of chiral monomer.

Resine bio-based da oli vegetali: applicazioni industriali in prodotti vernicianti rinnovabili a basso impatto ambientale

La tesi riguarda lo studio di resine polimeriche derivanti da oli vegetali, impiegabili come leganti nei prodotti vernicianti per l’edilizia ed altri settori. I prodotti vernicianti plant-based sono stati confrontati con altri prodotti attualmente commercializzati, provenienti da fonti fossili. Considerata la produzione ingente dei prodotti vernicianti su base mondiale (8,31 kg/persona) sarebbe determinante impiegare delle fonti rinnovabili per garantirne una produzione sostenibile, diminuendo l’inquinamento, ritardando l’esaurimento del petrolio e riducendo le emissioni di CO2 e di conseguenza l’effetto serra ed il cambiamento climatico. Sono state trattate, quindi, alcune vie di sintesi “green” di leganti poliuretanici ed epossidici per prodotti vernicianti ad elevate prestazioni. Gli oli vegetali sono stati scelti come materie prime in quanto relativamente economici e disponibili in grandi quantità, risultando adatti per produzioni su scala industriale. Sono inoltre riportati i metodi di formulazione di uno smalto opaco bio-based per esterni (ad es. infissi e staccionate) e una vernice opaca per parquet (interni). Le formulazioni sperimentali sono state poi caratterizzate e confrontate con altri prodotti fossil-based presenti in commercio. I prodotti vernicianti sono stati sottoposti a test di brillantezza (gloss), adesione, presa di sporco, durezza, resistenza all’abrasione e resistenza chimica.

Extraction of antioxidants from corn by-products for applications in bio-based polymer matrices

The objective of this dissertation is the evaluation of the exploitability of corn cobs as natural additives for bio-based polymer matrices, in order to hone their properties while keeping the fundamental quality of being fully bio-derived. The first part of the project has the purpose of finding the best solvent and conditions to extract antioxidants and anti-degrading molecules from corn cobs, exploiting room and high-temperature processes, traditional and advanced extraction methods, as well as polar and nonpolar solvents. The extracts in their entirety are then analysed to evaluate their antioxidant content, in order to select the conditions able to maximise their anti-degrading properties. The second part of the project, instead, focuses on assessing chemical and physical properties of the best-behaving extract when inserted in a polymeric matrix. To achieve this, low-density polyethylene (LDPE) and poly (butylene succinate – co – adipate) (PBSA) are employed. These samples are obtained through extrusion and are subsequently characterised exploiting the DSC equipment and a sinusoidally oscillating rheometer. In addition, extruded polymeric matrices are subjected to thermal and photo ageing, in order to identify their behaviour after different forms of degradation and to assess their performances with respect to synthetically produced anti-degrading additives.

Natural Wax-Based Water Vapour Barrier Coatings on PLA for MAP Food Packaging

PLA is a bio-based polymer that is obtained from renewable resources and it is very promising for a sustainable packaging manufacturing. However, its gas and vapour barrier properties are not enough to comply with the requirements of MAP packaging of fresh foods, which need specific concentration of water and oxygen to avoid spoilage and to keep the organoleptic properties unaltered throughout their shelf-life. The use of waxes from natural renewable sources such as plants (e.g., candelilla wax, carnauba wax, rice bran wax, sunflower wax) or animals (e.g., beeswax) could tackle down the permeation of water vapour through the packaging without affecting its bio-based content. The core of this work is developing wax-based coatings with enhanced thermo-mechanical properties so that they can undergo thermoforming and a proper adhesion to the PLA substrate can be ensured. Chemical modifications and crosslinking of waxes are performed to produce wax-based alkyd resins. The synthesised materials are characterised both by DSC and FTIR. Films of the wax-based alkyds are produced in order to assess their water vapour permeability.

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.

A new method for continuous quality control of nsm cfrp systems

In the last decade the near-surface mounted (NSM) strengthening technique using carbon fibre reinforced polymers (CFRP) has been increasingly used to improve the load carrying capacity of concrete members. Compared to externally bonded reinforcement (EBR), the NSM system presents considerable advantages. This technique consists in the insertion of carbon fibre reinforced polymer laminate strips into pre-cut slits opened in the concrete cover of the elements to be strengthened. CFRP reinforcement is bonded to concrete with an appropriate groove filler, typically epoxy adhesive or cement grout. Up to now, research efforts have been mainly focused on several structural aspects, such as: bond behaviour, flexural and/or shear strengthening effectiveness, and energy dissipation capacity of beam-column joints. In such research works, as well as in field applications, the most widespread adhesives that are used to bond reinforcements to concrete are epoxy resins. It is largely accepted that the performance of the whole application of NSM systems strongly depends on the mechanical properties of the epoxy resins, for which proper curing conditions must be assured. Therefore, the existence of non-destructive methods that allow monitoring the curing process of epoxy resins in the NSM CFRP system is desirable, in view of obtaining continuous information that can provide indication in regard to the effectiveness of curing and the expectable bond behaviour of CFRP/adhesive/concrete systems. The experimental research was developed at the Laboratory of the Structural Division of the Civil Engineering Department of the University of Minho in Guimar\~aes, Portugal (LEST). The main objective was to develop and propose a new method for continuous quality control of the curing of epoxy resins applied in NSM CFRP strengthening systems. This objective is pursued through the adaptation of an existing technique, termed EMM-ARM (Elasticity Modulus Monitoring through Ambient Response Method) that has been developed for monitoring the early stiffness evolution of cement-based materials. The experimental program was composed of two parts: (i) direct pull-out tests on concrete specimens strengthened with NSM CFRP laminate strips were conducted to assess the evolution of bond behaviour between CFRP and concrete since early ages; and, (ii) EMM-ARM tests were carried out for monitoring the progressive stiffness development of the structural adhesive used in CFRP applications. In order to verify the capability of the proposed method for evaluating the elastic modulus of the epoxy, static E-Modulus was determined through tension tests. The results of the two series of tests were then combined and compared to evaluate the possibility of implementation of a new method for the continuous monitoring and quality control of NSM CFRP applications.

Nuove procedure sintetiche sostenibili per la preparazione di strutture poliuretaniche

Questo lavoro di tesi si inserisce in un contesto di ricerca molto attuale, il quale, studia nuove procedure sintetiche sostenibili per la preparazione di strutture poliuretaniche. Partendo dall’etilene carbonato e dall’esametilendiammina, due molecole che possono essere ricavate da fonti rinnovabili, sono state ottimizzate la sintesi e la purificazione di un carbammato: bis(2-idrossietil)-esan-1,6-diildicarbammato (BHEDC), senza l’impiego di solventi ed in condizioni blande. Il BHEDC è conosciuto in letteratura, ma è poco studiato e non viene attualmente utilizzato come monomero. In questo lavoro il bis(2-idrossietil)-esan-1,6-diildicarbammato è stato polimerizzato in massa con diverse percentuali di bis(2-idrossietil)-tereftalato (BHET), il quale non è ricavabile da fonti naturali ma è ottenibile dal riciclo chimico del Poli-Etilene Tereftalato (PET). Sono state successivamente analizzate la struttura chimica e le proprietà termiche nonché spettroscopiche dei nuovi composti poliuretanici, così da poterne definire le correlazioni tra la struttura e le prestazioni finali. Infine, è stata messa a punto una procedura di tipo one-pot per la preparazione dei poliuretani sopra citati; questa prevede la sintesi diretta dei polimeri senza la necessità dello stadio di purificazione del bis(2-idrossietil)-esan-1,6-diildicarbammato.

PEDOT:PSS thin films: Applications in Bioelectronics

Owing to their capability of merging the properties of metals and conventional polymers, Conducting Polymers (CPs) are a unique class of carbon-based materials capable of conducting electrical current. A conjugated backbone is the hallmark of CPs, which can readily undergo reversible doping to different extents, thus achieving a wide range of electrical conductivities, while maintaining mechanical flexibility, transparency and high thermal stability. Thanks to these inherent versatility and attracting properties, from their discovery CPs have experienced incessant widespread in a great plethora of research fields, ranging from energy storage to healthcare, also encouraging the spring and growth of new scientific areas with highly innovative content. Nowadays, Bioelectronics stands out as one of the most promising research fields, dealing with the mutual interplay between biology and electronics. Among CPs, the polyelectrolyte complex poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), especially in the form of thin films, has been emphasized as ideal platform for bioelectronic applications. Indeed, in the last two decades PEDOT:PSS has played a key role in the sensing of bioanalytes and living cells interfacing and monitoring. In the present work, development and characterization of two kinds of PEDOT:PSS-based devices for applications in Bioelectronics are discussed in detail. In particular, a low-cost amperometric sensor for the selective detection of Dopamine in a ternary mixture was optimized, taking advantage of the electrocatalytic and antifouling properties that render PEDOT:PSS thin films appealing tools for electrochemical sensing of bioanalytes. Moreover, the potentialities of this material to interact with live cells were explored through the fabrication of a microfluidic trapping device for electrical monitoring of 3D spheroids using an impedance-based approach.

Valutazione dell’adenina come indurente da fonte rinnovabile per resine epossidiche commerciali e per la produzione di materiali compositi

Le resine più utilizzate industrialmente per la produzione di materiali compositi sono quelle epossidiche a base di diglicidil etere del bisfenolo A. Tipicamente, a livello industriale vengono utilizzate diammine sintetizzate da precursori tossici per l’ambiente e per l’uomo. Prendendo atto dell’intrinseca pericolosità di questi sistemi, sono state valutate delle alternative per rendere il processo di produzione dei materiali compositi più sostenibile e sensibile verso l’ambiente e la salute degli operatori. Questo progetto di tesi di laurea sperimentale è il proseguimento di un lavoro precedentemente svolto dal gruppo di ricerca che ha individuato l’adenina come un’alternativa non tossica e bio-based agli attuali agenti reticolanti. Nel presente lavoro di tesi, sono stati effettuati studi di formulazione e reticolazione dell’adenina con resine epossidiche commerciali da infusione e da impregnazione già utilizzate a livello industriale. L’obbiettivò è stato quello di ottenere formulati di resina e adenina capaci di dare un prodotto completamente reticolato, utilizzabile commercialmente e con elevati valori di Tg. Le formulazioni più promettenti così ottenute per ogni tipo di resina sono state utilizzate insieme a fibre di carbonio (vergini e riciclate), fibre di lino e di juta per la produzione di materiali compositi a fibra corta. Le formulazioni di resina e i compositi ottenuti sono stati caratterizzati mediante Analisi Termogravimetrica (TGA), Calorimetria Differenziale a Scansione (DSC) e Analisi Dinamico Meccanica (DMA).

Studio dell’adenina come indurente per resine epossidiche e produzione di materiali compositi da fonti rinnovabili

A causa di una maggiore preoccupazione ambientale, la ricerca si sta muovendo verso lo sviluppo di nuovi prodotti bio-based. Il progetto è stato incentrato sulla possibilità di produrre materiali compositi utilizzando un sistema resina-indurente interamente ottenuto da fonti rinnovabili con fibre naturali totalmente green e sintetiche. In particolare, è stata studiata la possibilità di utilizzare l’adenina, una molecola atossica e derivante da fonte rinnovabile, per la produzione di compositi con fibre di lino, juta, carbonio vergine e riciclato con resina epossidica da fonte bio. In particolare è stato ottimizzato il ciclo di cura e sono state caratterizzate le proprietà termiche e meccaniche dei materiali prodotti mediante analisi DSC (Differential Scanning Calorimetry), DMA (Dynamic Mechanical Analysis) e TGA (Termo-Gravimetric-Analysis). Per comprendere meglio la reticolazione delle resine epossidiche, si è studiato il meccanismo di reazione tra l’adenina e un precursore epossidico attraverso spettroscopia 1H-NMR (Nuclear Magnetic Resonance).