Giovanni Spinelli

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.

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.

Numerical investigation on the influence factors of the electrical properties of carbon nanotubes-filled composites

In order to predict the electrical properties of carbon nanotubes-filled composites, a three-dimensional (3D) numerical model is proposed. A random distribution of impenetrable conducting cylinders inside a cubic insulating matrix models the morphology of the considered material. The variation of the macroscopic electrical performances of the simulated structures is estimated through a suitable 3D resistance and capacitance network associated with the different percolating paths. The introduction in the model of the capacitive effects exhibited by the material, usually not considered in other simulation approaches, allows also a significant analysis in the frequency domain. The electron tunneling effect between conducting structures, determinant in the polymer nanocomposites, is also accurately taken into account to study the composite properties. The obtained results are in good agreement with theoretical predictions and experimental data suggesting that the proposed model can properly estimate different...

A morphological and structural approach to evaluate the electromagnetic performances of composites based on random networks of carbon nanotubes

Small quantities of carbon nanotubes (CNTs) in polymer resins allow to obtain new lightweight nanocomposites suitable for microwave applications, such as efficient electromagnetic shielding or radar absorbing materials. The availability of appropriate simulation models taking into account the morphological and physical features of such very interesting composites is very important for design and performance optimization of devices and systems. In this study, a 3-dimensional (3D) numerical structure modeling the morphology of a CNT-based composite is considered in order to carry out a computational analysis of their electromagnetic performances. The main innovative features of the proposed model consists in the identification of a resistance and capacitance network whose values depend on the filler geometry and loading and whose complexity is associated with the percolation paths. Tunneling effect and capacitive interactions between the individual conductive particles are properly taken into account. The o...

Numerical study of electrical behaviour in carbon nanotube composites

A structure aimed at modeling a polymeric nanocomposite loaded with carbon nanotubes (CNTs) is simulated by considering, in a three-dimensional space, a random distribution of impenetrable conducting cylinders inside an insulating cubic matrix. The variation of the electrical conductivity of the structure for different volume loadings of the conducting phase is estimated through a 3D resistor network. The tunneling effect between conducting clusters which is deemed responsible of the global conductivity is taken into account. By using a Monte Carlo method, the electrical conductivity and the percolation thresholds of the obtained structures are analyzed as a function of geometrical and physical influencing parameters.

The effect of filler aspect ratio on the electromagnetic properties of carbon-nanofibers reinforced composites

The effect of filler aspect ratio on the electromagnetic properties of epoxy-amine resin reinforced with carbon nanofibers is here investigated. A heat treatment at 2500 °C of carbon nanofibers seems to increase their aspect ratio with respect to as-received ones most likely due to a lowering of structural defects and the improvement of the graphene layers within the dixie cup conformation. These morphological differences revealed by Ramans spectroscopy and scanning electron microscopy analyses may be responsible for the different electrical properties of the resulting composites. The DC characterization of the nanofilled material highlights an higher electrical conductivity and a lower electrical percolation threshold for the heat-treated carbon nanofibers based composites. In fact, the electrical conductivity is about 0.107 S/m and 1.36 × 10−3 S/m for the nanocomposites reinforced with heat-treated and as received fibers, respectively, at 1 wt. % of nanofiller loading, while the electrical percolation ...