Adhesive durability and joint reliability, strictly related to the bonding agents, are key parameters still under evaluation in civil as well as in other engineering fields. Moisture, different ...environmental agents and temperature (in particular) can strongly affect the performance of the adhesive joints over the time limiting their applicability. The environmental temperature may exceed the glass transition temperature (Tg) of the adhesive formulation entailing relevant changes in its properties, determining, for instance, a transition from a hard to a rubbery behaviour, thus compromising its specific application. Furthermore, due to changes of the temperature values, the structural adhesive can be naturally subjected to a delay or increase in the curing degree. Hence adverse or positive changes in strength and stiffness can be manifested. Within this framework, the topic of the present paper is the study of the hygro-thermal durability of two commercial epoxy resins, suitable for civil engineering applications, respect to the immersion in tap water and sea water for a period of fifteen months at the temperature of 30 °C. To this scope a wide experimental program was developed comprising both End Notch Failure (ENF) tests on the adhesive samples (adherent in glass fiber reinforced polymer, GFRP) for evaluating the pure fracture energy in Mode II of the resins and the water absorption tests for resins and GFRP materials. In general, the results, in terms of fracture energy, show an initial increment (first three-four months) followed by a decrement up to the reaching of a plateau (in the ninth-twelfth month of conditioning). For what concerns the water absorption, the results show that the equilibrium value of both resins is reached in about one month, while that of GFRP samples depend on the type of liquid: three months for tap water and about five months for sea water. Considering the lower activity of the seawater, the longer time to reach the equilibrium value was an expected result.
Carbon nanofibers (CNFs) were heat-treated at 1100 °C (CNF1100) and 2500 °C (CNF2500), respectively, and embedded as fillers at different mass percentages into an epoxy mixture. The paper aims at ...evaluating, through a comparison between the two different types of resulting nanocomposites, the influence of the CNF heat treatment on the thermal, mechanical, and electrical performance of the formulated samples. Thermogravimetric analysis (TGA) showed oxidative stability in the air of CNF2500 approximately 200 °C higher than the CNF1100 ones. The first oxidation stage of the resins embedding the two typologies of CNFs falls between 380 and 480 °C. This means that the temperature of the heat treatment of the nanofiller does not influence the temperature at which the thermodegradation of the nanocomposites starts. Differential Scanning Calorimetry (DSC) data show that the highest degree of cure (DC) was recorded for the epoxy samples filled with CNF2500. CNF thermal treatment increases the direct current (dc) conductivity of the nanocomposite by 3 orders of magnitude around the electrical percolation threshold (EPT) and increases the storage modulus of the CNF2500-based resins up to 60 °C compared with the unfilled resin. The peculiar wall structure of CNF1100 determines a further slight enhancement. Tunneling Atomic Force Microscopy (TUNA) reveals that the CNFs are evenly distributed on the nanodomains showing higher electric current values for samples loaded with CNF2500.
Carbon nanostructured forms, such as one-dimensional (1D) carbon nanofibers (CNFs) and two-dimensional (2D) graphene nanoplatelets (GNPs), are increasingly attracting the attention of scientists ...whose studies are aimed at obtaining superior nanocomposites with unrivaled performance and/or unprecedented properties. In this work, nanocomposites loaded with different mass percentages of carbonaceous nanoparticles (CNFs, GNPs) capable to exhibit discrete electrical conductivity have been investigated using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tunneling atomic force microscopy (TUNA). DSC and DMA investigations highlighted that an appropriate chemical composition of the hosting matrix, together with a suitable two-stage curing cycle allows formulating structural resins characterized by high values of the curing degree (higher than 97%), glass transition temperature (also higher than 250 °C), and storage modulus (higher than 3000 MPa at room temperature). TUNA analysis evidences a satisfactory distribution of the conductive nanofiller on nanometric domains
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Isotactic polypropylene/multi-walled carbon nanotube (iPP/MWCNTs) films have been exposed to accelerated weathering in a UV device for increasing times. The effect of UV irradiation on the structural ...and chemical changes has been investigated. The resistance to accelerated photooxidation of (iPP/MWCNTs) films has been compared to the photooxidation behaviour of unfilled polypropylene films with the same structural organization. The chemical and structural modifications resulting from photooxidation have been followed using infrared spectroscopy, calorimetric and diffractometric analysis. MWCNTs embedded in the polymeric matrix are able to strongly contrast the degradation mechanisms and the structural and morphological rearrangements caused by the UV treatment on the unfilled polymer. MWCNTs determine an induction period (IP) before the increase of the carbonyl and hydroxyl groups. The extent of the IP is strictly correlated to the amount of MWCNTs. The low electrical percolation threshold (EPT) and the electrical conductivity of the nanocomposites, together with their excellent thermal and photooxidative stability, make them promising candidates to fulfill many industrial requirements.
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.
This study focuses on epoxy hybrid systems prepared by incorporating multi-wall carbon nanotubes (MWCNTs) and graphene nanosheets (GNs) at two fixed filler amounts: below (0.1 wt%) and above (0.5 ...wt%), with varying MWCNT:GN mix ratios. The hybrid epoxy systems exhibited remarkable electrical performance, attributed to the π–π bond interactions between the multi-wall carbon nanotubes and the graphene layers dispersed in the epoxy resin matrix. The material’s properties were characterized through dynamic mechanical and thermal analyses over a wide range of temperatures. In addition to excellent electrical properties, the formulated hybrid systems demonstrated high mechanical performance and thermal stability. Notably, the glass transition temperature of the samples reached 255 °C, and high storage modulus values at elevated temperatures were observed. The hybrid systems also displayed thermal stability up to 360 °C in air. By comparing the mechanical and electrical performance, the formulation can be optimized in terms of the electrical percolation threshold (EPT), electrical conductivity, thermostability, and mechanical parameters. This research provides valuable insights for designing advanced epoxy-based materials with multifunctional properties.
Electromagnetic and thermal properties of a non-conventional polymer nanocomposite based on thermoplastic Polylactic acid (PLA, Ingeo™) filled, in different weight percentage, with multi-walled ...carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), as well as a mixture of both fillers (MWCNTs/GNPs), are analyzed. The combination of notable electrical, thermal, and electromagnetic (EM) properties of the carbon fillers, in concentrations above the percolation threshold, together with the good processability of the PLA matrix gives rise to innovative filaments for 3D printing. In particular, the shielding efficiency (SE) in the frequency range 26-37 GHz of samples increases from 0.20 dB of unfilled PLA up to 13.4 dB for composites containing MWCNTs and GNPs, corresponding to 4% and 95% of SE, respectively. The thermal conductivity of the PLA loaded with 12 wt % of GNPs is 263% higher than that of the unfilled polymer, whereas an improvement of about 99% and 190% is detected for the PLA matrix loaded with MWCNTs and both fillers, respectively. The EM and thermal characterization is combined with a morphological investigation allowing us to correlate the dispersion states of the fillers within the polymer matrix with the observed EM and thermal properties. The EM and thermal characteristics exhibited by the nanocomposites make them suitable for packaging applications of electronic devices with electromagnetic interference (EMI) shielding and thermal dissipation features.
Reversible Hydrogen Bonds (RHB) have been explored to confer self-healing function to multifunctional nanocomposites. This study has been carried out through a sequence of different steps. Hydrogen ...bonding moieties, with the intrinsic ability to simultaneously perform the functions of both hydrogen donors and acceptors, have been covalently attached to the walls of carbon nanotubes. The epoxy matrix has been modified to adapt the formulation for hosting self-healing mechanisms. It has been toughened with different percentages of rubber phase covalently linked to the epoxy precursor. The most performant matrix, from the mechanical point of view, has been chosen for the incorporation of MWCNTs. Self-healing performance and electrical conductivities have been studied. The comparison of data related to the properties of nanocomposites containing incorporated functionalized and nonfunctionalized MWCNTs has been performed. The values of the electrical conductivity of the self-healing nanocomposites, containing 2.0% by weight of functionalized multiwalled carbon nanotubes (MWCNTs), range between 6.76 × 10
S/m and 3.77 × 10
S/m, depending on the nature of the functional group. Curing degrees, glass transition temperatures, and storage moduli of the formulated multifunctional nanocomposites prove their potential for application as functional structural materials.
The capability of Atomic Force Microscopy (AFM) to characterize composite material interfaces can help in the design of new carbon-based nanocomposites by providing useful information on the ...structure-property relationship. In this paper, the potentiality of AFM is explored to investigate the dispersion and the morphological features of aeronautical epoxy resins loaded with several carbon nanostructured fillers. Fourier Transform Infrared Spectroscopy (FTIR) and thermal investigations of the formulated samples have also been performed. The FTIR results show that, among the examined nanoparticles, exfoliated graphite (EG) with a predominantly two-dimensional (2D) shape favors the hardening process of the epoxy matrix, increasing its reaction rate. As evidenced by the FTIR signal related to the epoxy stretching frequency (907 cm
), the accelerating effect of the EG sample increases as the filler concentration increases. This effect, already observable for curing treatment of 60 min conducted at the low temperature of 125 °C, suggests a very fast opening of epoxy groups at the beginning of the cross-linking process. For all the analyzed samples, the percentage of the curing degree (DC) goes beyond 90%, reaching up to 100% for the EG-based nanocomposites. Besides, the addition of the exfoliated graphite enhances the thermostability of the samples up to about 370 °C, even in the case of very low EG percentages (0.05% by weight).
In the present study, polylactic acid (PLA) enriched with carbonaceous particles like multi-walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs) or a combination of both up 12 wt % of loading ...are used for producing 3D-printed specimens with fused deposition modeling (FDM) technology which are then experimentally and theoretically investigated. The goal is to propose a non-conventional filaments indicated for additive manufacturing process with improved dielectric and thermal properties, compared to the performances exhibited by the unfilled polymer. In the light of the above, a wide dielectric spectroscopy and a thermal analysis, supported by a morphological investigation, are performed. The results highlight that the introduction of 1-dimensional filler (MWCNTs) are more suitable for improving the dielectric properties of the resulting materials, due to the enhancement of the interfacial polarization and the presence of functionalized groups, whereas 2-dimensional nanoparticles (GNPs) better favor the thermal conduction mechanisms thanks to the lower thermal boundary resistance between the two phases, polymer/filler. In particular, with a loading of 12 wt % of MWCNTs the relative permittivity reaches the value of 5.35 × 103 much greater than that of 3.7 measured for unfilled PLA while for the thermal conductivity the enhancement with 12 wt % of GNPs is about 261% respect the thermal behavior of the neat polymer. The experimental results are correlated to theoretical findings, whereas a design of experiment (DoE) approach is adopted for investigating how the different fillers influence the dielectric and thermal performances of the 3D-printed parts, thus assisting the design of such innovative materials that appear promising for development and applications in the electromagnetic (EM) field and heat transfer.
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