A Comprehensive Review on the Thermal Stability Assessment of Polymers and Composites for Aeronautics and Space Applications.

This review article provides an exhaustive survey on experimental investigations regarding the thermal stability assessment of polymers and polymer-based composites intended for applications in the aeronautical and space fields. This review aims to: (1) come up with a systematic and critical overview of the state-of-the-art knowledge and research on the thermal stability of various polymers and composites, such as polyimides, epoxy composites, and carbon-filled composites; (2) identify the key factors, mechanisms, methods, and challenges that affect the thermal stability of polymers and composites, such as the temperature, radiation, oxygen, and degradation; (3) highlight the current and potential applications, benefits, limitations, and opportunities of polymers and composites with high thermal stability, such as thermal control, structural reinforcement, protection, and energy conversion; (4) give a glimpse of future research directions by providing indications for improving the thermal stability of polymers and composites, such as novel materials, hybrid composites, smart materials, and advanced processing methods. In this context, thermal analysis plays a crucial role in the development of polyimide-based materials for the radiation shielding of space solar cells or spacecraft components. The main strategies that have been explored to improve the processability, optical transparency, and radiation resistance of polyimide-based materials without compromising their thermal stability are highlighted. The combination of different types of polyimides, such as linear and hyperbranched, as well as the incorporation of bulky pendant groups, are reported as routes for improving the mechanical behavior and optical transparency while retaining the thermal stability and radiation shielding properties. Furthermore, the thermal stability of polymer/carbon nanocomposites is discussed with particular reference to the role of the filler in radiation monitoring systems and electromagnetic interference shielding in the space environment. Finally, the thermal stability of epoxy-based composites and how it is influenced by the type and content of epoxy resin, curing agent, degree of cross-linking, and the addition of fillers or modifiers are critically reviewed. Some studies have reported that incorporating mesoporous silica micro-filler or microencapsulated phase change materials (MPCM) into epoxy resin can enhance its thermal stability and mechanical properties. The mesoporous silica composite exhibited the highest glass transition temperature and activation energy for thermal degradation among all the epoxy-silica nano/micro-composites. Indeed, an average activation energy value of 148.86 kJ/mol was recorded for the thermal degradation of unfilled epoxy resin. The maximum activation energy range was instead recorded for composites loaded with mesoporous microsilica. The EMC-5p50 sample showed the highest mean value of 217.6 kJ/mol. This remarkable enhancement was ascribed to the polymer invading the silica pores and forging formidable interfacial bonds.

Erratum: Effect of Porosity and Crystallinity on 3D Printed PLA Properties. Polymers 2019, 11, 1487.

The authors wish to make a change to the published paper [...].

Electrical Current Map and Bulk Conductivity of Carbon Fiber-Reinforced Nanocomposites.

A suitably modified resin film infusion (RFI) process was used for manufacturing carbon fiber-reinforced composites (CFRCs) impregnated with a resin containing nanocages of glycidyl polyhedral oligomeric silsesquioxane (GPOSS) for enhancing flame resistance and multi-wall carbon nanotubes (MWCNTs) to contrast the electrical insulating properties of the epoxy resin. The effects of the different numbers (7, 14 and 24) of the plies on the equivalent direct current (DC) and alternating current (AC) electrical conductivity were evaluated. All the manufactured panels manifest very high values in electrical conductivity. Besides, for the first time, CFRC strings were analyzed by tunneling atomic force microscopy (TUNA) technique. The electrical current maps highlight electrically conductive three-dimensional networks incorporated in the resin through the plies of the panels. The highest equivalent bulk conductivity is shown by the seven-ply panel characterized by the parallel (σ//0°) in-plane conductivity of 16.19 kS/m. Electrical tests also evidence that the presence of GPOSS preserves the AC electrical stability of the panels.

Effect of Porosity and Crystallinity on 3D Printed PLA Properties.

Additive manufacturing (AM) is a promising technology for the rapid tooling and fabrication of complex geometry components. Among all AM techniques, fused filament fabrication (FFF) is the most widely used technique for polymers. However, the consistency and properties control of the FFF product remains a challenging issue. This study aims to investigate physical changes during the 3D printing of polylactic acid (PLA). The correlations between the porosity, crystallinity and mechanical properties of the printed parts were studied. Moreover, the effects of the build-platform temperature were investigated. The experimental results confirmed the anisotropy of printed objects due to the occurrence of orientation phenomena during the filament deposition and the formation both of ordered and disordered crystalline forms (α and δ, respectively). A heat treatment post-3D printing was proposed as an effective method to improve mechanical properties by optimizing the crystallinity (transforming the δ form into the α one) and overcoming the anisotropy of the 3D printed object.

Different Methods of Dispersing Carbon Nanotubes in Epoxy Resin and Initial Evaluation of the Obtained Nanocomposite as a Matrix of Carbon Fiber Reinforced Laminate in Terms of Vibroacoustic Performance and Flammability.

Different industrial mixing methods and some of their combinations ((1) ultrasound; (2) mechanical stirring; (3) by roller machine; (4) by gears machine; and (5) ultrasound radiation + high stirring) were investigated for incorporating multi-walled carbon nanotubes (MWCNT) into a resin based on an aeronautical epoxy precursor cured with diaminodiphenylsulfone (DDS). The effect of different parameters, ultrasound intensity, number of cycles, type of blade, and gear speed on the nanofiller dispersion were analyzed. The inclusion of the nanofiller in the resin causes a drastic increase in the viscosity, preventing the homogenization of the resin and a drastic increase in temperature in the zones closest to the ultrasound probe. To face these challenges, the application of high-speed agitation simultaneously with the application of ultrasonic radiation was applied. This allowed, on the one hand, a homogeneous dispersion, and on the other hand, an improvement of the dissipation of heat generated by ultrasonic radiation. The most efficient method was a combination of ultrasound radiation assisted by a high stirring method with the calendar, which was used for the preparation of a carbon fiber reinforced panel (CFRP). The manufactured panel was subjected to dynamic and vibroacoustic tests in order to characterize structural damping and sound transmission loss properties. Under both points of view, the new formulation demonstrated an improved efficiency with reference to a standard CFRP equivalent panel. In fact, for this panel, the estimated damping value was well above the average of the typical values representative of the carbon fiber laminates (generally less than 1%), and also a good vibroacoustic performance was detected as the nanotube based panel exhibited a higher sound transmission loss (STL) at low frequencies, in correspondence with the normal mode participation region. The manufactured panel was also characterized in terms of fire performance using a cone calorimeter and the results were compared to those obtained using a commercially available monocomponent RTM6 (Hexcel composites) epoxy aeronautic resin with the same process and the same fabric and lamination. Compared to the traditional RTM6 resin, the panel with the epoxy nanofilled resin exhibits a significant improvement in fire resistance properties both in terms of a delay in the ignition time and in terms of an increase in the thermal resistance of the material. Compared to the traditional panel, made in the same conditions as the RTM6 resin, the time of ignition of the nanotube-based panel increased by 31 seconds while for the same panel, the heat release rate at peak, the average heat release rate, and the total heat release decreased by 21.4%, 48.5%, and 15%, respectively. The improvement of the fire performance was attributed to the formation of a non-intumescent char due to the simultaneous presence of GPOSS and carbon nanotubes.

Reversible Self-Healing Carbon-Based Nanocomposites for Structural Applications.

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 × 10-3 S/m and 3.77 × 10-2 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.

Multifunctional Performance of a Nano-Modified Fiber Reinforced Composite Aeronautical Panel.

The adoption of multifunctional flame-resistant composites is becoming increasingly attractive for many components of aircrafts and competition cars. Compared to conventional alloy solutions, the reduced weight and corrosion resistance are only a couple of the relevant advantages they can offer. In this paper, a carbon fiber reinforced panel (CFRP) was impregnated with an epoxy resin enhanced using a combination of 0.5 wt% of carbon nanotubes (CNTs) and 5 wt% of Glycidyl-Polyhedral Oligomeric Silsesquioxanes (GPOSS). This formulation, which is peculiar to resins with increased electrical conductivity and flame-resistance properties, has been employed for manufacturing a carbon fiber reinforced panel (CFRP) composed of eight plies through a liquid infusion technique. Vibro-acoustic tests have been performed on the panel for the characterization of the damping performance, as well the transmission loss properties related to micro-handling treatments. The spectral excitation has been provided by an acoustic source simulating the aerodynamic pressure load agent on the structure. The incorporation of multi-walled carbon nanotubes MWCNTs in the epoxy matrix determines a non-trivial improvement in the dynamic performance of the laminate. An increased damping loss factor with reference to standard CFRP laminate and also an improvement of the sound insulation parameter was found for the specific test article.

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.

Nano-Charged Polypropylene Application: Realistic Perspectives for Enhancing Durability.

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.

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.