Ultrasonication Influence on the Morphological Characteristics of Graphene Nanoplatelet Nanocomposites and Their Electrical and Electromagnetic Interference Shielding Behavior.

Graphene nanoplatelets (GNPs)/epoxy composites have been fabricated via gravity molding. The electrical and thermal properties of the composites have been studied with variable GNP type (C300, C500, and C750, whose surface areas are ~300, 500, and 750 m2/g, respectively), GNP loading (5, 10, 12, and 15 wt.%), and dispersion time via ultrasonication (0, 30, 60, and 120 min). By increasing the time of sonication of the GNP into the epoxy matrix, the electrical conductivity decreases, which is an effect of GNP fragmentation. The best results were observed with 10-12% loading and a higher surface area (C750), as they provide higher electrical conductivity, thereby preserving thermal conductivity. The influence of sonication over electrical conductivity was further analyzed via the study of the composite morphology by means of Raman spectroscopy and X-ray diffraction (XRD), providing information about the aspect ratio of GNPs. Moreover, electromagnetic shielding (EMI) has been studied up to 4 GHz. Composites with C750 and 120 min ultrasonication show the best performance in EMI shielding, influenced by their higher electrical conductivity.

Electromechanical Properties of Smart Vitrimers Reinforced with Carbon Nanotubes for SHM Applications.

The Structural Health Monitoring (SHM) capabilities of a well-studied self-healing epoxy resin based on disulfide bonds, through the addition of carbon nanotubes (CNTs), are studied. Since these materials demonstrated, in recent works, a high dependency of the dynamic hardener content on the repair performance, this study aimed to analyze the effect of the vitrimeric chemistry on the electromechanical properties by studying different 2-aminophenyl disulfide (2-AFD) hardener and CNT contents. The electrical conductivity increases with both the CNT and AFD contents, in general. Moreover, an excess of AFD close to the stoichiometric ratio with a low CNT content improved the tensile strength by 45%, while higher AFD contents promoted its detriment by 41% due to a reduced crosslinking density. However, no significant difference in the mechanical properties was observed at a higher CNT content, regardless of the AFD ratio. The developed materials demonstrate a robust electromechanical response at quasi-static conditions. The sensitivity significantly increases at higher AFD ratios, from 0.69 to 2.22 for the 0.2 wt.%. CNT system, which is advantageous due to the enhanced repair performance of these vitrimeric materials with a higher hardener content. These results reveal the potential use of self-healing vitrimers as integrated SHM systems capable of detecting damages and self-repairing autonomously.

Recyclable Multifunctional Nanocomposites Based on Carbon Nanotube Reinforced Vitrimers with Shape Memory and Joule Heating Capabilities.

The present study focuses on the multifunctional capabilities of carbon nanotube (CNT)-reinforced vitrimers. More specifically, the thermomechanical properties, the Joule effect heating capabilities, the electrical conductivity, the shape memory, and the chemical recycling capacity are explored as a function of the CNT content and the NH2/epoxy ratio. It is observed that the electrical conductivity increases with the CNT content due to a higher number of electrical pathways, while the effect of the NH2/epoxy ratio is not as prevalent. Moreover, the Tg of the material decreases when increasing the NH2/epoxy ratio due to the lower cross-link density, whereas the effect of the CNTs is more complex, in some cases promoting a steric hindrance. The results of Joule heating tests prove the suitability of the proposed materials for resistive heating, reaching average temperatures above 200 °C when applying 100 V for the most electrically conductive samples. Shape memory behavior shows an outstanding shape fixity ratio in every case (around 100%) and a higher shape recovery ratio (95% for the best-tested condition) when decreasing the NH2/epoxy ratio and increasing the CNT content, as both hinder the rearrangement of the dynamic bonds. Finally, the results of the recyclability tests show the ability to regain the nanoreinforcement for their further use. Therefore, from a multifunctional analysis, it can be stated that the proposed materials present promising properties for a wide range of applications, such as Anti-icing and De-icing Systems (ADIS), Joule heating devices for comfort or thermotherapy, or self-deployable structures, among others.

Electrical and Joule Heating Capabilities of Multifunctional Coatings based on Recycled Carbon Fiber from Prepreg Scrap.

The continuous growth in the use of preimpregnated semielaborated products to manufacture continuous carbon fiber-reinforced polymer parts has led the industry to face an important challenge in the management of the prepreg scrap, as the amount of waste produced can reach almost 75% due to the inefficiency of the cutting phase. In this context, this industry is pushed to move toward a circular economy approach by conferring a new use to their waste. The main problem arises from the fact that shortening carbon fiber leads to nonefficient mechanical reinforcement and that other thermal or chemical recycling approaches are environmentally hazardous. In this work, mechanical recycling of carbon fiber prepregs from expired virgin prepregs or scrap from an automated manufacturing operation is proposed as an economical and environmentally efficient method to obtain multifunctional coatings with Joule effect heating capabilities, which are demanded by different industries as a high-value product. As a coating, mechanical performance is not so relevant; nevertheless, obtaining high electrical conductivity by the incorporation of proper size and distributed short recycled carbon fiber can lead to a self-heating coating that could be used for anti- and deicing purposes or any other thermally activated function with very low power consumption. In this way, electrical conductivities up to 2 S/m were obtained, which allowed for achieving temperatures of 200 °C by the Joule effect in all samples in less than 17 s by the application of voltages below 48 V for bulk materials and 100 V for the coating.

An Analysis of the Effect of Activation Temperature and Crack Geometry on the Healing Efficiency of Polycaprolactone (PCL)/Epoxy Blends.

Self-healing materials have attracted great interest in recent years. Particularly, the use of thermoset/thermoplastics blends has emerged as a good option with relatively low activation temperatures and potential infinite healing cycles. Nevertheless, a methodical study of healing conditions and evaluation is still required for further industrial development. The effect of activation temperature and crack morphology in polycaprolactone (PCL)/epoxy blends are explored. For this purpose, PCL content was varied (5, 10, and 15 wt %) with contents lower than critical composition. Therefore, the morphology of all studied blends is the epoxy matrix with a separated PCL phase. In this sense, an increase in PCL content leads to a reduction in the Tg, due to the partial PCL miscibility, and the presence of larger PCL domains. It was observed that a higher temperature (150 °C) and PCL content led to a more efficient self-healing process because of both the lower viscosity of the melted PCL at higher temperatures and the presence of larger PCL reservoirs when increasing the PCL content. Crack morphology influence was studied by inducing cracks with different tools: a custom crack machine with a cutting blade, a scalpel, and a pin. The results show that the recovery was better when the cracks were smaller and shallower, that is, with the pin. In addition, the healing efficiency by means of both parameters, crack volume and depth change, showed more similar results in slimmer cracks, due to a lower crack width-to-depth ratio.

Electrical, Thermo-Electrical, and Electromagnetic Behaviour of Epoxy Composites Reinforced with Graphene Nanoplatelets with Different Average Surface Area.

The influence of the average surface area of different graphene nanoplatelets (GNP) on the thermo-electrical behaviour, associated with Joule heating, and the attenuation of electromagnetic signals of epoxy composites has been studied, analysing the effect of the morphology obtained as a function of the dispersion time by ultrasonication and the GNP content added. Gravity moulding was used as the first stage in the scaling-up, oriented to the industrial manufacture of multilayer coatings, observing a preferential self-orientation of nanoparticles and, in several conditions, a self-stratification too. The increase of sonication time during the GNP dispersion provides a decrease in the electrical conductivity, due to the GNP fragmentation. Instead, the thermal conductivity is enhanced due to the higher homogeneous distribution of GNPs into the epoxy matrix. Finally, the lower surface area of GNPs reduces the thermal and electrical conductivity due to a greater separation between nanosheets. Regarding the study of the attenuation of electromagnetic waves, it has been discovered that in the frequency range from 100 Hz to 20 MHz, this attenuation is independent of the direction of analysis, the type of graphene, the sonication time, and the state of dispersion of the nano-reinforcement in the matrix. Furthermore, it has also been observed that the conservation of the constant shielding values for the three types of GNPs are in a range of average frequencies between 0.3 and 3 MHz.

Secondary Raw Materials from Residual Carbon Fiber-Reinforced Composites by An Upgraded Pyrolysis Process.

This paper presents a process where carbon fibers and hydrogen can be recovered simultaneously through a two-stage thermal treatment of an epoxy-carbon fiber composite. For this purpose, some pieces of epoxy resin reinforced with carbon fiber fabrics have been fabricated and, after curing, have been pyrolyzed in an installation consisting of two reactors. In the first one, the thermal decomposition of the resin takes place, and in the second one, the gases and vapors coming from the first reactor are thermally treated. Once this process is completed, the solid generated is oxidized with air to eliminate the resin residues and carbonaceous products from the fibers surface. The recovered carbon fiber fabrics have been reused to make new cured parts and their electrical and mechanical properties have been measured. The results show that it is possible to obtain carbon fiber fabrics that can be processed as they leave the recycling process and that retain 80% of the tensile modulus, 70% of the flexural strength, and 50% of the interlaminar shear strength. At the same time, a gaseous stream with more than 66% by volume of hydrogen can be obtained, reaching a maximum of 81.7%.

Carbon Nanotube Reinforced Poly(ε-caprolactone)/Epoxy Blends for Superior Mechanical and Self-Sensing Performance in Multiscale Glass Fiber Composites.

In this paper, a novel carbon nanotube (CNT) polycaprolactone (PCL), epoxy, and glass fiber (GF) composite is reported. Here, the nanoreinforced composites show a flexural strength increase of around 30%, whereas the interlaminar shear strength increases by 10-15% in comparison to unenhanced samples. This occurs because the addition of the CNTs induces a better PCL/epoxy/GF interaction. Furthermore, the nanoparticles also give novel functionalities to the multiscale composite, such as strain and damage monitoring. Here, the electrical response of the tensile- and compressive-subjected faces was simultaneously measured during flexural tests as well as the transverse conductivity in interlaminar tests, showing an exceptional capability for damage detection. Moreover, it was observed that the electrical sensitivity increases with PCL content due to a higher efficiency of the dispersion process that promotes the creation of a more uniform electrical network.

Electrical Properties and Strain Sensing Mechanisms in Hybrid Graphene Nanoplatelet/Carbon Nanotube Nanocomposites.

Electrical and electromechanical properties of hybrid graphene nanoplatelet (GNP)/carbon nanotube (CNT)-reinforced composites were analyzed under two different sonication conditions. The electrical conductivity increases with increasing nanofiller content, while the optimum sonication time decreases in a low viscosity media. Therefore, for samples with a higher concentration of GNPs, an increase of sonication time of the hybrid GNP/CNT mixture generally leads to an enhancement of the electrical conductivity, up to values of 3 S/m. This means that the optimum sonication process to achieve the best performances is reached in the longest times. Strain sensing tests show a higher prevalence of GNPs at samples with a high GNP/CNT ratio, reaching gauge factors of around 10, with an exponential behavior of electrical resistance with applied strain, whereas samples with lower GNP/CNT ratio have a more linear response owing to a higher prevalence of CNT tunneling transport mechanisms, with gauge factors of around 3-4.

Complex Geometry Strain Sensors Based on 3D Printed Nanocomposites: Spring, Three-Column Device and Footstep-Sensing Platform.

Electromechanical sensing devices, based on resins doped with carbon nanotubes, were developed by digital light processing (DLP) 3D printing technology in order to increase design freedom and identify new future and innovative applications. The analysis of electromechanical properties was carried out on specific sensors manufactured by DLP 3D printing technology with complex geometries: a spring, a three-column device and a footstep-sensing platform based on the three-column device. All of them show a great sensitivity of the measured electrical resistance to the applied load and high cyclic reproducibility, demonstrating their versatility and applicability to be implemented in numerous items in our daily lives or in industrial devices. Different types of carbon nanotubes-single-walled, double-walled and multi-walled CNTs (SWCNTs, DWCNTs, MWCNTs)-were used to evaluate the effect of their morphology on electrical and electromechanical performance. SWCNT- and DWCNT-doped nanocomposites presented a higher Tg compared with MWCNT-doped nanocomposites due to a lower UV light shielding effect. This phenomenon also justifies the decrease of nanocomposite Tg with the increase of CNT content in every case. The electromechanical analysis reveals that SWCNT- and DWCNT-doped nanocomposites show a higher electromechanical performance than nanocomposites doped with MWCNTs, with a slight increment of strain sensitivity in tensile conditions, but also a significant strain sensitivity gain at bending conditions.

Highly Multifunctional GNP/Epoxy Nanocomposites: From Strain-Sensing to Joule Heating Applications.

A performance mapping of GNP/epoxy composites was developed according to their electromechanical and electrothermal properties for applications as strain sensors and Joule heaters. To achieve this purpose, a deep theoretical and experimental study of the thermal and electrical conductivity of nanocomposites has been carried out, determining the influence of both nanofiller content and sonication time. Concerning dispersion procedure, at lower contents, higher sonication times induce a decrease of thermal and electrical conductivity due to a more prevalent GNP breakage effect. However, at higher GNP contents, sonication time implies an enhancement of both electrical and thermal properties due to a prevalence of exfoliating mechanisms. Strain monitoring tests indicate that electrical sensitivity increases in an opposite way than electrical conductivity, due to a higher prevalence of tunneling mechanisms, with the 5 wt.% specimens being those with the best results. Moreover, Joule heating tests showed the dominant role of electrical mechanisms on the effectiveness of resistive heating, with the 8 wt.% GNP samples being those with the best capabilities. By taking the different functionalities into account, it can be concluded that 5 wt.% samples with 1 h sonication time are the most balanced for electrothermal applications, as shown in a radar chart.

Mechanical and Strain-Sensing Capabilities of Carbon Nanotube Reinforced Composites by Digital Light Processing 3D Printing Technology.

Mechanical and strain sensing capabilities of carbon nanotube (CNT) reinforced composites manufactured by digital light processing (DLP) 3D printing technology have been studied. Both CNT content and a post-curing treatment effects have been analyzed. It has been observed that post-curing treatment has a significant influence on mechanical properties, with an increase of Young's modulus and glass transition temperature whereas their effect in electrical properties is not so important. Furthermore, the strain sensing tests show a linear response of electrical resistance with applied strain, with higher values of sensitivity when decreasing CNT content due to a higher interparticle distance. Moreover, the electrical sensitivity of bending tests is significantly lower than in tensile ones due to the compression subjected face effect. Therefore, the good gauge factor values (around 2-3) and the high linear response proves the applicability of the proposed nanocomposites in structural health monitoring applications.

Influence of Morphology on the Healing Mechanism of PCL/Epoxy Blends.

Polycaprolactone (PCL) is being researched as a self-healing agent blended with epoxy resins by several reasons: low melting point, differential expansive bleeding (DBE) of PCL, and reaction induced phase separation (RIPS) of PCL/epoxy blends. In this work, PCL/epoxy blends were prepared with different PCL ratios and two different epoxy networks, cured with aliphatic and aromatic amine hardeners. The curing kinetic affects to the blend morphology, varying its critical composition. The self-healing behavior is strongly affected by the blend morphology, reaching the maximum efficiency for co-continuous phases. Blends with dispersed PCL phase into epoxy matrix can also show high self-healing efficiency because of the low PCL domains that act as reservoir of self-healing agent. In this last case, it was confirmed that the most efficient self-healable blends are one whose area occupied by PCL phase is the largest. These blends remain the good thermal and mechanical behavior of epoxy matrix, in contrast to the worsened properties of blends with bicontinuous morphology. In this work, the self-healing mechanism of blends is studied in depth by scanning electron microscopy. Furthermore, the influence of the geometry of the initial surface damage is also evaluated, affecting to the measurement of self-healing efficiency.

Carbon Nanotube-Doped Adhesive Films for Detecting Crack Propagation on Bonded Joints: A Deeper Understanding of Anomalous Behaviors.

A novel nanoreinforced adhesive film has been developed to detect adhesive deformation and crack propagation along the bonding line by means of the electrical response of the material. Adhesive films were doped by spraying an aqueous dispersion of carbon nanotubes (CNTs) over the surface. To determine the sensitivity of bonded joints, single lap shear (SLS) and mode-I fracture energy tests have been carried out while their electrical response has been measured. It has been found that CNT-doped adhesive films are able to detect adhesive deformation and final failure for SLS specimens and crack initiation and propagation along the bonding line for mode-I specimens with a high sensitivity. Sudden increases on electrical resistance are correlated to a rapid growing of the crack length due to instability on crack propagation in a tick-slip case, whereas specimens with a more uniform crack propagation are linked to a steadier increase on electrical resistance, and both of them are properly correlated to the mechanical response. By analyzing more in detail the electrical response and comparing with theoretical approaches, the stick-slip behavior is associated with the presence of porosity and lack of adhesives because of possible manufacturing issues such as adhesive overflowing. These statements are also validated by microstructural analysis. Therefore, the potential and applicability of the proposed adhesive films for evaluating the structural integrity has been demonstrated.

Strain Sensing Based on Multiscale Composite Materials Reinforced with Graphene Nanoplatelets.

The electrical response of NH2-functionalized graphene nanoplatelets composite materials under strain was studied. Two different manufacturing methods are proposed to create the electrical network in this work: (a) the incorporation of the nanoplatelets into the epoxy matrix and (b) the coating of the glass fabric with a sizing filled with the same nanoplatelets. Both types of multiscale composite materials, with an in-plane electrical conductivity of ~10-3 S/m, showed an exponential growth of the electrical resistance as the strain increases due to distancing between adjacent functionalized graphene nanoplatelets and contact loss between overlying ones. The sensitivity of the materials analyzed during this research, using the described procedures, has been shown to be higher than commercially available strain gauges. The proposed procedures for self-sensing of the structural composite material would facilitate the structural health monitoring of components in difficult to access emplacements such as offshore wind power farms. Although the sensitivity of the multiscale composite materials was considerably higher than the sensitivity of metallic foils used as strain gauges, the value reached with NH2 functionalized graphene nanoplatelets coated fabrics was nearly an order of magnitude superior. This result elucidated their potential to be used as smart fabrics to monitor human movements such as bending of fingers or knees. By using the proposed method, the smart fabric could immediately detect the bending and recover instantly. This fact permits precise monitoring of the time of bending as well as the degree of bending.