Luigi Vertuccio

Development of epoxy mixtures for application in aeronautics and aerospace

This work describes a successful attempt toward the development of composite materials based on nanofilled epoxy resins for the realization of structural aeronautic components providing efficient lightning strike protection. The epoxy matrix is prepared by mixing a tetrafunctional epoxy precursor with a reactive diluent which allows the moisture content to be reduced and facilitates the nanofiller dispersion step. The reactive diluent also proves to be beneficial for improving the curing degree of nanofilled epoxy mixtures. It increases the mobility of reactive groups resulting in a higher cure degree than the epoxy precursor alone. This effect is particularly advantageous for nanofilled resins where higher temperature treatments are needed, compared to the unfilled resin, to reach the same cure degree. As nanofiller, different carbon nanostructured fiber-shaped fillers are embedded in the epoxy matrix with the aim of improving the electrical properties of the resin. The results highlight a strong influence of the nanofiller nature on the electrical properties especially in terms of electrical percolation threshold (EPT) and electrical conductivity beyond the EPT. Among the analyzed nanofillers, the highest electrical conductivity is obtained by using multiwalled carbon nanotubes (MWCNTs) and heat-treated carbon nanofibers (CNFs). The achieved results are analyzed by considering the nanofiller morphological parameters and characteristics with respect to the impact on their dispersion effectiveness.

The role of carbon nanofiber defects on the electrical and mechanical properties of CNF-based resins

Heat treatment of carbon nanofibers has proven to be an effective method in removing defects from carbon nanofibers, causing a strong increase in their structural perfection and thermal stability. It affects the bonding states of carbon atoms in the nanofiber structure and causes a significant transformation in the hybridization state of the bonded carbon atoms.Nanofilled resins made of heat-treated CNF show significant increases in their electrical conductivity even at low concentrations. This confirms that enhancement in the perfection of the fiber structure with consequent change in the morphological features plays a prominent role in affecting the electrical properties. Indeed heat-treated CNFs display a stiff structure and a smooth surface which tends to lower the thickness of the unavoidable insulating epoxy layer formed around the CNF which, in turn, plays a fundamental role in the electrical transport properties along the conducting clusters. This might be very beneficial in terms of electrical conductivity but might have negligible effect on the mechanical properties.

Epoxy/MWCNT Composite as Temperature Sensor and Electrical Heating Element

An epoxy/carbon nanotubes (CNTs) composite material with a low concentration of multiwalled CNTs (0.5 wt%) has been shown to be applicable in a wide temperature range (up to 160°C) as heating and temperature-sensing element. It can be prepared in any type of geometry allowing a simple application to all kinds of surfaces that have to be sensed and heated. The composite material itself and the electric contacts have demonstrated excellent stability even under extreme ambient conditions. The electrical resistivity of the composite has shown a temperature dependence consistent with the fluctuation-induced tunneling model. This model assumes that the electrical resistance of the nanotube network is dominated by the interconnections between the individual nanotubes rather than by the nanotube resistance itself.

Optimization of graphene-based materials outperforming host epoxy matrices

The degree of graphite exfoliation and edge-carboxylated layers can be controlled and balanced to design lightweight materials characterized by both low electrical percolation thresholds (EPT) and improved mechanical properties. So far, this challenging task has been undoubtedly very hard to achieve. The results presented in this paper highlight the effect of exfoliation degree and the role of edge-carboxylated graphite layers to give self-assembled structures embedded in the polymeric matrix. Graphene layers inside the matrix may serve as building blocks of complex systems that could outperform the host matrix. Improvements in electrical percolation and mechanical performance have been obtained by a synergic effect due to finely balancing the degree of exfoliation and the chemistry of graphene edges which favors the interfacial interaction between polymer and carbon layers. In particular, for epoxy-based resins including two partially exfoliated graphite samples, differing essentially in the content of carboxylated groups, the percolation threshold reduces from 3 wt% down to 0.3 wt%, as the carboxylated group content increases up to 10 wt%. Edge-carboxylated nanosheets also increase the nanofiller/epoxy matrix interaction, determining a relevant reinforcement in the elastic modulus.

Effective formulation and processing of nanofilled carbon fiber reinforced composites

This work describes a successful approach toward the development of a carbon fiber-reinforced composite based on an optimized nanofilled resin for industrial applications. The epoxy matrix is prepared by mixing a tetrafunctional epoxy precursor with a reactive diluent which allows reduction of the viscosity of the epoxy precursor and facilitation of the dispersion of 0.5% wt multiwall carbon nanotubes. The proper choice of the viscosity value and the infusion technique allow improvement of the electrical properties of the panels. The obtained in-plane electrical conductivity is about 20 kS m � 1 , whereas a value of 3.9 S m � 1 is achieved for the out of plane value. Such results confirm that the fibers govern the conduction mechanisms in the direction parallel to the fibers, whereas the percolating path created by the effective distribution of carbon nanotubes achieved by resin formulation and adopted processing approach lead to a significant enhancement of the overall electrical performance of the composites.

Simulation and experimental characterization of polymer/carbon nanotubes composites for strain sensor applications

In this paper, a numerical model is presented in order to analyze the electrical characteristics of polymer composites filled by carbon nanotubes (CNTs) subject to tensile stress and investigate the possible usage of such materials as innovative sensors for small values of strain. The simulated mechano-electrical response of the nanocomposite is obtained through a multi-step approach which, through different modeling stages, provides a simple and effective tool for material analysis and design. In particular, at first, the morphological structures of the composites are numerically simulated by adopting a previously presented model based on a Monte Carlo procedure in which uniform distributions of the CNTs, approximated as of solid cylinders and ensuring some physical constraints, are dispersed inside a cubic volume representing the polymer matrix. Second, a geometrical analysis allows to obtain the percolation paths detected in the simulated structures. Suitable electrical networks composed by resistors and capacitors associated to the complex charge transport and polarization mechanisms occurring in the percolation paths are then identified. Finally, the variations of these circuit parameters, which are differently affected by the mechanical stresses applied to the composites, are considered to analyze the electromechanical characteristics of the composites and hence their performances as stress sensors. The proposed approach is used to investigate the impact on the electro-mechanical response of some physical properties of the base materials, such as the type of carbon nanotube, the height of energy barrier of polymer resin, as well as characteristics of the composite, i.e., the volume fraction of the filler. The tunneling effect between neighboring nanotubes is found to play a dominant role in determining the composite sensitivity to mechanical stresses. The simulation results are also compared with the experimental data obtained by performing stress tests on samples of a multi walled CNT filled composite based on poly (e-caprolactone), a polymer which is of interest for its biocompatibility. Model simulations and measured data show generally satisfactory agreement, confirming the effectiveness of the proposed approach to account for the impact of the interactions between CNTs and the insulating resin on the electromechanical response of the composite.

Influence of carbon nanoparticles/epoxy matrix interaction on mechanical, electrical and transport properties of structural advanced materials

The focus of this study is to design new nano-modified epoxy formulations using carbon nanofillers, such as carbon nanotubes, carbon nanofibers and graphene-based nanoparticles (CpEG), that reduce the moisture content and provide additional functional performance. The chemical structure of epoxy mixture, using a non-stoichiometric amount of hardener, exhibits unique properties in regard to the water sorption for which the equilibrium concentration of water (C eq) is reduced up to a maximum of 30%. This result, which is very relevant for several industrial applications (aeronautical, shipbuilding industries, wind turbine blades, etc), is due to a strong reduction of the polar groups and/or sites responsible to bond water molecules. All nanofillers are responsible of a second phase at lower glass transition temperature (Tg). Compared with other carbon nanofillers, functionalized graphene-based nanoparticles exhibit the best performance in the multifunctionality. The lowest moisture content, the high performance in the mechanical properties, the low electrical percolation threshold (EPT) have been all ascribed to particular arrangements of the functionalized graphene sheets embedded in the polymeric matrix. Exfoliation degree and edge carboxylated groups are responsible of self-assembled architectures which entrap part of the resin fraction hindering the interaction of water molecules with the polar sites of the resin, also favouring the EPT paths and the attractive/covalent interactions with the matrix.

Influence of carbon nanofillers on the curing kinetics of epoxy-amine resin

The cure kinetics of an epoxy resin based on the tetrafunctional epoxy precursor N,N′-tetraglycidyl methylene dianiline-(TGMDA) hardened with 4,4-diaminodiphenyl sulfone is investigated. The influence of carbon nanofillers (carbon nanotubes, carbon nanofibers, and graphene based nanoparticles) on the cure kinetic is studied. Kinetic analysis is performed by dynamic and isothermal differential scanning calorimetry (DSC). In dynamic experiments, the activation energy was computed using an advanced isoconversional method while under isothermal conditions, the Kamal’s model of diffusion control was applied to simulate the systems throughout the curing process. The isothermal analysis shows that the introduction of the diluent decreases, particularly the activation energy of secondary amine-epoxy reaction. A similar effect was obtained by the dynamic DSC analysis that shows a decrease in the activation energy for α > 0.7, a value of conversion for which it is considered that the reaction of secondary amines is active. The inclusion in the resin of one-dimensional fillers does not lead to big differences in the curing kinetics behaviour with respect to the raw epoxy. An increase in the activation energy is found in the case of highly exfoliated graphite. This is likely due to a reduction of free molecular segments of the epoxy network trapped inside the self-assembly structures.

Behavior of epoxy composite resins in environments at high moisture content

Three different organo-modified clays have been incorporated by sonication into a high performance epoxy resin before the cross-linking reaction. The X-ray analysis indicated that, depending on the organoclay type, partially exfoliated and partially intercalated composites have been obtained. As shown by the DSC analysis, the clay addition seems to interact with the cross-linking reaction. The incorporation of organoclay into epoxy increased free volume and micro-voids in the samples. Sorption of water in the composite samples resulted higher than that of the pristine resin, whereas the diffusion coefficient is significantly lower. The lower value of diffusion makes the permeability at ambient conditions lower than the pristine resin. The elastic modulus of the composite sample results higher than that of the pristine resin, especially in the temperature region around the glass transition. The presence of organoclay in epoxy matrix decreased the glass transition temperature, whether the nanocomposites were in a dry or wet condition.

Toughening of epoxy adhesives by combined interaction of carbon nanotubes and silsesquioxanes

The extensive use of adhesives in many structural applications in the transport industry and particularly in the aeronautic field is due to numerous advantages of bonded joints. However, still many researchers are working to enhance the mechanical properties and rheological performance of adhesives by using nanoadditives. In this study the effect of the addition of Multi-Wall Carbon Nanotubes (MWCNTs) with Polyhedral Oligomeric Silsesquioxane (POSS) compounds, either Glycidyl Oligomeric Silsesquioxanes (GPOSS) or DodecaPhenyl Oligomeric Silsesquioxanes (DPHPOSS) to Tetraglycidyl Methylene Dianiline (TGMDA) epoxy formulation, was investigated. The formulations contain neither a tougher matrix such as elastomers nor other additives typically used to provide a closer match in the coefficient of thermal expansion in order to discriminate only the effect of the addition of the above-mentioned components. Bonded aluminium single lap joints were made using both untreated and Chromic Acid Anodisation (CAA)-treated aluminium alloy T2024 adherends. The effects of the different chemical functionalities of POSS compounds, as well as the synergistic effect between the MWCNT and POSS combination on adhesion strength, were evaluated by viscosity measurement, tensile tests, Dynamic Mechanical Analysis (DMA), single lap joint shear strength tests, and morphological investigation. The best performance in the Lap Shear Strength (LSS) of the manufactured joints has been found for treated adherends bonded with epoxy adhesive containing MWCNTs and GPOSS. Carbon nanotubes have been found to play a very effective bridging function across the fracture surface of the bonded joints.