Development and characterization of innovative graphene-based composites

Over the last decade, graphene and related materials (GRM) have drawn significant interest and resources for their development into the next generation of composite materials. This is because these nanoparticles have the ability to operate as reinforcing additives capable of imparting considerable mechanical property increases while also embedding multi-functional advantages on the host matrix. Because graphene and 2D materials are still in their early stages, the relative maturity of different types of composite systems varies. As a result, certain nanocomposite systems are currently commercially accessible, while others are not yet sufficiently developed to enter the market. A substantial emphasis has been placed on developing thermoplastic and thermosetting materials that combine a variety of mechanical and functional qualities. These include higher strength and stiffness, increased thermal and electrical conductivity, improved barrier properties, fire retardancy, and others, with the ultimate goal of providing multifunctionality to already employed composites. The work presented in this thesis investigates the use and benefits that GRM could bring to composites for a variety of applications, with the goal of realizing multifunctional components with improved properties that leads to lightweight and, as a result, energy and cost savings and pollution reduction in the environment. In particular, we worked on the following topics: • Benchmarking of commercial GRM-based master batches; • GRM-coatings for water uptake reduction; • GRM as thermo-electrical anti-icing /de-icing system; • GRM for Out of Oven curing of composites.

Electrospinning of polymeric composites with GRMs for different industrial applications

Electrospinning is the most common and industrially scalable technique for the production of polymeric nanofibers. Currently, nanocomposites are drawing much interest for their excellent properties in terms of flexibility, electrical conductivity and high surface area, which enhances the interaction with the surrounding environment. The objective of this thesis was the optimization of different electrospinning setups for the production of nanostructured polymeric composites using graphene-related materials as nanofillers. Such composites were obtained using different polymers as matrix (polyamide 6, polyinylidene fluoride and polylactic acid) that were selected and combined with the appropriate reinforcements based on their properties and their interest for specific applications. Moreover, this study highlighted the possibility to tune the morphology and size of the produced nanofibers by the addition of appropriate nanofillers even in low amounts. The addition of only 0.5% of GO allowed the production of smooth nanofibers with diameters up to 75% thinner (in the case of PLA) than the ones obtained from the pristine polymer. PVdF was charged with GO to produce triboelectric materials that can be exploited in a wearable nanogenerator for the conversion of human motion energy in electrical energy. The addition of GO improved the open-circuit voltage and power-output of a generator prototype by 3.5 times. Electrospun PA6 membranes were coated with rGO using a simple two-step technique to produce conductive textiles for wearable electronic applications. The sheet resistance of the produced materials was measured in approximately 500 Ω/sq and their resistance to washing and bending was successfully tested. These materials could be exploited as strain sensors or heating elements in smart textiles. PLA was co-electrospun with GO and cellulose nanofibers to produce high-surface area and porosity mats that could be exploited for the production of functionalized highly selective adsorption membranes with low pressure drops.

Enhancing predictive capability of models for solubility and permeability in polymers and composites

The interpretation of phase equilibrium and mass transport phenomena in gas/solvent - polymer system at molten or glassy state is relevant in many industrial applications. Among tools available for the prediction of thermodynamics properties in these systems, at molten/rubbery state, is the group contribution lattice-fluid equation of state (GCLF-EoS), developed by Lee and Danner and ultimately based on Panayiotou and Vera LF theory. On the other side, a thermodynamic approach namely non-equilibrium lattice-fluid (NELF) was proposed by Doghieri and Sarti to consistently extend the description of thermodynamic properties of solute polymer systems obtained through a suitable equilibrium model to the case of non-equilibrium conditions below the glass transition temperature. The first objective of this work is to investigate the phase behaviour in solvent/polymer at glassy state by using NELF model and to develop a predictive tool for gas or vapor solubility that could be applied in several different applications: membrane gas separation, barrier materials for food packaging, polymer-based gas sensors and drug delivery devices. Within the efforts to develop a predictive tool of this kind, a revision of the group contribution method developed by High and Danner for the application of LF model by Panayiotou and Vera is considered, with reference to possible alternatives for the mixing rule for characteristic interaction energy between segments. The work also devotes efforts to the analysis of gas permeability in polymer composite materials as formed by a polymer matrix in which domains are dispersed of a second phase and attention is focused on relation for deviation from Maxwell law as function of arrangement, shape of dispersed domains and loading.

Effects of Accelerated Hygroscopic Ageing on Interlaminar Shear Strength and Glass Transition Temperature of CFRP

This study, which is undertaken in cooperation with Riba-COMPOSITES, investigates the effects of hygroscopic ageing on the Interlaminar Shear Strength and Glass Transition Temperature of short-beams made of carbon fibre reinforced polymer (CFRP) composites provided by two different vendors. The materials have the same weave pattern but differ in the epoxy resin formulation. The tests are done in accordance with ASTM. Accelerated ageing techniques are carried out by immersion of the specimens in deionized water at 70°C for different periods of time, developing different degrees of ageing. The results of the tests confirm that hygroscopic ageing causes a loss of properties and a depression of the glass transition temperature in both the materials. However, since one of the two materials shows more constant property degradation, its behaviour in service conditions should be more easily predictable.

Analisi e standardizzazione del ciclo commessa dei materiali in conto lavoro: il caso HP Composites S.p.A.

HP Composites, azienda leader nella produzione di componenti in fibra di carbonio, a seguito della crescita di ordini commissionati dai suoi clienti, ha deciso di affidare a dei fornitori la produzione di alcune commesse, in alcune o in tutte le fasi del loro ciclo. L’elaborato di tesi nasce da un’esperienza di tirocinio nell’ufficio pianificazione di HP Composites, e si pone l’obiettivo di analizzare tutte le attività che, evitando di dedicare risorse alle lavorazioni selezionate, deve compiere per supportare il fornitore; l’analisi è stata effettuata tramite la costruzione di un diagramma di flusso e fornendo un indicazione del tempo richiesto da ogni attività, per poi poi avanzare delle proposte di ottimizzazione. Il ciclo commessa può essere suddiviso in quattro fasi: scelta della commessa e selezione del fornitore, attivazione del fornitore, gestione settimanale dell’evasione degli ordini e gestione del fine commessa. L’ufficio acquisti nel tempo si è specializzato individuando i temi da chiarire prima di attivare la fornitura per evitare l’insorgere di problematiche a produzione già attivata. Per quanto riguarda la gestione settimanale del fornitore, è stato istituito il ruolo del responsabile delle esternalizzazioni, una figura che funga da intermediario con il fornitore e monitori la produzione esterna: questa figura apporta un'alta quantità di interazioni, ma HP valuta maggiori i vantaggi di questa gestione centralizzata. Inoltre nel tempo le attività pianificazione sono state ottimizzate grazie alla stesura di file precompilati da aggiornare. Un’attività fonte di inefficienza è quella dell’emissione dei documenti di trasporto, soprattutto nel caso in cui il compito di consegnare il prodotto al cliente è deputato al fornitore di conto lavoro: HP Composites ha intenzione di implementare un lettore barcode per l’emissione del documento che ridurrebbe i tempi richiesti dall’attività e permetterebbe una gestione del conto lavoro a sistema più corretta.

Cure Induced Residual Stresses on Thick Composite Components Manufactured by Additive Process

This study investigates the effect of an additive process in manufacturing of thick composites. Airstone 780 E epoxy resin and 785H Hardener system is used in the analysis since it is widely used wind turbine blade, namely thick components. As a fiber, fabric by SAERTEX (812 g/m2) with a 0-90 degrees layup direction is used. Temperature overshoot is a major issue during the manufacturing of thick composites. A high temperature overshoot leads to an increase in residual stresses. These residual stresses are causing warping, delamination, dimensional instability, and undesired distortion of composite structures. A coupled thermo-mechanical model capable of predicting cure induced residual stresses have been built using the commercial FE software Abaqus®. The possibility of building thick composite components by means of adding a finite number of sub-laminates has been investigated. The results have been compared against components manufactured following a standard route. The influence of pre-curing of the sub-laminates has also been addressed and results compared with standard practice. As a result of the study, it is found that introducing additive process can prevent temperature overshoot to occur and benefits the residual stresses generation during the curing process. However, the process time required increases by 50%, therefore increasing the manufacturing costs. An optimized cure cycle is required to minimize process time and cure induced defects simultaneously.

A Microleakage Study Of Gutta-percha/ah Plus And Resilon/real Self-etch Systems After Different Irrigation Protocols.

The development and maintenance of the sealing of the root canal system is the key to the success of root canal treatment. The resin-based adhesive material has the potential to reduce the microleakage of the root canal because of its adhesive properties and penetration into dentinal walls. Moreover, the irrigation protocols may have an influence on the adhesiveness of resin-based sealers to root dentin. The objective of the present study was to evaluate the effect of different irrigant protocols on coronal bacterial microleakage of gutta-percha/AH Plus and Resilon/Real Seal Self-etch systems. One hundred ninety pre-molars were used. The teeth were divided into 18 experimental groups according to the irrigation protocols and filling materials used. The protocols used were: distilled water; sodium hypochlorite (NaOCl)+eDTA; NaOCl+H3PO4; NaOCl+eDTA+chlorhexidine (CHX); NaOCl+H3PO4+CHX; CHX+eDTA; CHX+ H3PO4; CHX+eDTA+CHX and CHX+H3PO4+CHX. Gutta-percha/AH Plus or Resilon/Real Seal Se were used as root-filling materials. The coronal microleakage was evaluated for 90 days against Enterococcus faecalis. Data were statistically analyzed using Kaplan-Meier survival test, Kruskal-Wallis and Mann-Whitney tests. No significant difference was verified in the groups using chlorhexidine or sodium hypochlorite during the chemo-mechanical preparation followed by eDTA or phosphoric acid for smear layer removal. The same results were found for filling materials. However, the statistical analyses revealed that a final flush with 2% chlorhexidine reduced significantly the coronal microleakage. A final flush with 2% chlorhexidine after smear layer removal reduces coronal microleakage of teeth filled with gutta-percha/AH Plus or Resilon/Real Seal SE.

Effect Of Composite Containing An Iodonium Salt On The Bond Strength Of Brackets To Bovine Enamel.

This study investigated the effect of the incorporation of an iodonium salt in experimental composites, on the bond strength of metallic brackets bonded to bovine teeth. Two hundred and seventy bovine teeth were embedded in self-curing acrylic resin and divided into 18 groups (n=15), according to the experimental composite with an iodonium salt at molar concentrations 0 (control), 0.5, or 1%; the light-activation times (8, 20 and 40 s); and the storage times (10 min or 24 h). Metallic brackets were fixed on the tooth surface using experimental composites. Photoactivation was performed with a quartz-tungsten-halogen light-curing unit curing unit for 8, 20 and 40 s. The specimens were stored in distilled water at 37 °C for 10 min or 24 h and submitted to bond strength test at 0.5 mm/min. The data were subjected to three-way ANOVA and Tukey's test (α=0.05). The Adhesive Remnant Index (ARI) was used to classify the failure modes. The shear bond strengths (MPa) at 10 min for light-activation times of 8, 20 and 40 s were: G1 - 4.6, 6.9 and 7.1; G2 - 8.1, 9.2 and 9.9; G3 - 9.1, 10.4 and 10.7; and at 24 h were: G1 - 10.9, 11.1 and 11.7; G2 - 11.8, 12.7 and 14.2; G3 - 12.1, 14.4 and 15.8. There was a predominance of ARI score 3 for groups with 10 min storage time, and ARI score 2 for groups with 24 h storage time. In conclusion, the addition of iodonium salt (C05 and C1) to the experimental composite may increase the bond strength of brackets to bovine enamel using reduced light exposure times.

Photoelastic And Finite Element Analyses Of Occlusal Loads In Mandibular Body.

This study proposed to evaluate the mandibular biomechanics in the posterior dentition based on experimental and computational analyses. The analyses were performed on a model of human mandible, which was modeled by epoxy resin for photoelastic analysis and by computer-aided design for finite element analysis. To standardize the evaluation, specific areas were determined at the lateral surface of mandibular body. The photoelastic analysis was configured through a vertical load on the first upper molar and fixed support at the ramus of mandible. The same configuration was used in the computer simulation. Force magnitudes of 50, 100, 150, and 200 N were applied to evaluate the bone stress. The stress results presented similar distribution in both analyses, with the more intense stress being at retromolar area and oblique line and alveolar process at molar level. This study presented the similarity of results in the experimental and computational analyses and, thus, showed the high importance of morphology biomechanical characterization at posterior dentition.

Durabilidade de compósito biomassa vegetal-cimento modificado por polímero

The durability of the cellulose-cement composites is a decisive factor to introduce such material in the market. Polymers have been used in concrete and mortar production to increase its durability. The goal of this work was the physical and mechanical characterization of cellulose-cement composites modified by a polymer and the subsequent durability evaluation. The work also evaluated the dispersion of acrylic polymer in composites made of Pinus caribaea residues. The physical properties observed were water absorption by immersion and bulk density. Rupture modulus and toughness were determined by flexural test. The specimens were obtained from pads, produced by pressing and wet curing. Samples were subjected to accelerated aging tests by repeated wetting and drying cycles and hot-water bath and natural aging. The scanning electron microscopy (SEM) allowed verifying the fiber and composite characteristics along the time. For the composite range analyzed, it was observed the polymer improved the mechanical properties of composites besides a significant decreasing in water absorption. The use of polymer improved the performance of vegetable fiber-cement composites when compared to the conventional mortar, due to water absorption decreasing.

Effect of laser welding on the titanium composite tensile bond strength

The aim of this study was to analyze the shear bond strength between commercially pure titanium, with and without laser welding, after airbone-particle abrasion (Al2O3) and 2 indirect composites. Sixty-four specimens were cast and divided into 2 groups with and without laser welding. Each group was divided in 4 subgroups, related to Al2O3 grain size: A - 250 µm; B - 180 µm; C- 110 µm; and D - 50 µm. Composite rings were formed around the rods and light polymerized using UniXS unit. Specimens were invested and their shear bond strength at failure was measured with a universal testing machine at a crosshead speed of 2.0 mm/min. Statistical analysis was carried out with ANOVA and Tukey's test (α=0.05). The highest bond strength means were recorded in 250 µm group without laser welding. The lowest shear bond strength means were recorded in 50 µm group with laser welding. Statistically significant differences (p<0.05) were found between all groups. In conclusion, airborne particle abrasion yielded significantly lower bond strength as the Al2O3 particle size decreased. Shear bond strength decreased in the laser welded specimens.

Adhesion of an endodontic sealer to dentin and gutta-percha: shear and push-out bond strength measurements and SEM analysis

The use of an adequate method for evaluation of the adhesion of root canal filling materials provides more reliable results to allow comparison of the materials and substantiate their clinical choice. The aims of this study were to compare the shear bond strength (SBS) test and push-out test for evaluation of the adhesion of an epoxy-based endodontic sealer (AH Plus) to dentin and gutta-percha, and to assess the failure modes on the debonded surfaces by means of scanning electron microscopy (SEM). Three groups were established (n=7): in group 1, root cylinders obtained from human canines were embedded in acrylic resin and had their canals prepared and filled with sealer; in group 2, longitudinal sections of dentin cylinders were embedded in resin with the canal surface smoothed and turned upwards; in group 3, gutta-percha cylinders were embedded in resin. Polyethylene tubes filled with sealer were positioned on the polished surface of the specimens (groups 2 and 3). The push-out test (group 1) and the SBS test (groups 2 and 3) were performed in an Instron universal testing machine running at crosshead speed of 1 mm/min. Means (±SD) in MPa were: G1 (8.8±1.13), G2 (5.9±1.05) and G3 (3.8±0.55). Statistical analysis by ANOVA and Student's t-test (a=0.05) revealed statistically significant differences (p<0.01) among the groups. SEM analysis showed a predominance of adhesive and mixed failures of AH Plus sealer. The tested surface affected significantly the results with the sealer reaching higher bond strength to dentin than to gutta-percha with the SBS test. The comparison of the employed methodologies showed that the SBS test produced significantly lower bond strength values than the push-out test, was skilful in determining the adhesion of AH Plus sealer to dentin and gutta-percha, and required specimens that could be easily prepared for SEM, presenting as a viable alternative for further experiments.

Evaluating resin-enamel bonds by microshear and microtensile bond strength tests: effects of composite resin

OBJECTIVES: The aims of this study were to evaluate the effect of resin composite (Filtek Z250 and Filtek Flow Z350) and adhesive system [(Solobond Plus, Futurabond NR (VOCO) and Adper Single Bond (3M ESPE)] on the microtensile (μTBS) and microshear bond strength (μSBS) tests on enamel, and to correlate the bond strength means between them. MATERIAL AND METHODS: Thirty-six extracted human molars were sectioned to obtain two tooth halves: one for μTBS and the other one for μSBS. Adhesive systems and resin composites were applied to the enamel ground surfaces and light-cured. After storage (37(0)C/24 h) specimens were stressed (0.5 mm/min). Fracture modes were analyzed under scanning electron microscopy. The data were analyzed using two-way ANOVA and Tukey's test (α=0.05). RESULTS: The correlation between tests was estimated with Pearson's product-moment correlation statistics (α =0.05). For both tests only the main factor resin composite was statistically significant (p<0.05). The correlation test detected a positive (r=0.91) and significant (p=0.01) correlation between the tests. CONCLUSIONS: The results were more influenced by the resin type than by the adhesives. Both microbond tests seem to be positive and linearly correlated and can therefore lead to similar conclusions.

Resíduos de sisal como reforço em compósitos de polipropileno virgem e reciclado

Foram estudadas as propriedades térmicas e mecânicas de compósitos de polipropileno, virgem e reciclado, reforçados com 30% em massa de fibras residuais de sisal, assim como o perfil de processamento e a morfologia da matriz polimérica. Para tanto, foram determinadas a resistência à tração, o módulo de Young, alongamento na ruptura, e energia de impacto. As amostras também foram caracterizadas por MEV, DMTA e TG. Para ambos os compósitos de polipropileno, virgem e reciclado, com a adição das fibras, o alongamento na ruptura mostrou uma queda significativa, enquanto que a resistência à tração não sofreu grandes variações. Houve um aumento significativo nos valores de tração na ruptura e de energia de impacto com a adição das fibras de sisal na matriz de polipropileno. As análises térmicas mostraram ligações secundárias, como as ligações polares, entre as fibras e a matriz, concordando com o comportamento mecânico dos compósitos. Constatou-se que a temperatura de transição vítrea não variou após a adição da fibra.

Biocompósitos de matriz glioxal-fenol reforçada com celulose microcristalina

Glioxal pode ser obtido a partir de biomassa (como da oxidação de lipídeos) e não é tóxico ou volátil, tendo sido por isso utilizado no presente trabalho como substituto de formaldeído na preparação de resina fenólica do tipo novolaca, sendo usado como catalisador o ácido oxálico, que também pode ser obtido de fontes renováveis. A resina glioxal-fenol foi utilizada na preparação de compósitos reforçados com celulose microcristalina (CM, 30, 50 e 70% em massa), uma celulose com elevada área superficial. As imagens de microscopia eletrônica de varredura (MEV) das superfícies fraturadas demonstraram que os compósitos apresentaram boa interface reforço/matriz, consequência da elevada área superficial da CM e presença de grupos polares (hidroxilas) tanto na matriz como na celulose, o que permitiu a formação de ligações hidrogênio, favorecendo a compatibilidade entre ambas. A análise térmica dinâmico-mecânica (DMTA) demonstrou que todos os compósitos apresentaram elevado módulo de armazenamento à temperatura ambiente. Além disso, o compósito reforçado com 30% de CM apresentou baixa absorção de água, comparável à do termorrígido fenólico, que é utilizado em escala industrial. Os resultados demonstraram que compósitos com boas propriedades podem ser preparados usando elevada proporção de materiais obtidos de biomassa.