Self-repair of structural and functional composites with intrinsically self-healing polymer matrices: A review

Self-healing is a smart and promising way to make materials more reliable and longer lasting. In the case of structural or functional composites based on a polymer matrix, very often mechanical damage in the polymer matrix or debonding at the matrix–filler interface is responsible for the decrease in intended properties. This review describes the healing behavior in structural and functional polymer composites with a so-called intrinsically self-healing polymer as the continuous matrix. A clear similarity in the healing of structural and functional properties is demonstrated which can ultimately lead to the design of polymer composites that autonomously restore multiple properties using the same self-healing mechanism.     

Unusual toughening effect of graphene oxide on the graphene oxide/nylon 11 composites prepared by in situ melt polycondensation

Graphene oxide/nylon 11 composites were prepared by in situ melt polycondensation. These composites displayed better mechanical properties including stiffness and toughness than the pure nylon 11 matrix. The enhanced toughness was ascribed to the change of crystal form of nylon 11, namely the triclinic α crystal form to the pseudo-hexagonal δ′ crystal form transition trend with the incorporation of GO. Scanning electron microscopy and transmission electron microscopy images showed that GO bundles and stacks with an average thickness of 20 nm are homogeneously dispersed over the nylon 11 matrix with almost no large agglomerates.     

Healable and Mechanically Super‐Strong Polymeric Composites Derived from Hydrogen‐Bonded Polymeric Complexes

It is challenging to fabricate mechanically super‐strong polymer composites with excellent healing capacity because of the significantly limited mobility of polymer chains. The fabrication of mechanically super‐strong polymer composites with excellent healing capacity by complexing polyacrylic acid (PAA) with polyvinylpyrrolidone (PVPON) in aqueous solution followed by molding into desired shapes is presented. The coiled PVPON can complex with PAA in water via hydrogen‐bonding interactions to produce transparent PAA–PVPON composites homogenously dispersed with nanoparticles of PAA–PVPON complexes. As healable materials, the PAA–PVPON composite materials with a glass transition temperature of ≈107.9 °C exhibit a super‐high mechanical strength, with a tensile strength of ≈81 MPa and a Young's modulus of ≈4.5 GPa. The PAA–PVPON composites are stable in water because of the hydrophobic interactions among pyrrolidone groups. The super‐high mechanical strength of the PAA–PVPON composite materials originates from the highly dense hydrogen bonds between PAA and PVPON and the reinforcement of in situ formed PAA–PVPON nanoparticles. The reversibility of the relatively weak but dense hydrogen bonds enables convenient healing of the mechanically strong PAA–PVPON composite materials from physical damage to restore their original mechanical strength.     

Natural silica fiber as reinforcing filler of nylon 6

Short silica fiber (SF) content on the mechanical and morphological properties of composites based on nylon 6 and rubber-toughened nylon 6 matrices was examined. Binary nylon 6/SF and ternary [nylon 6/EPDM-g-MA (ethylene–propylene–diene grafted with maleic anhydride)/SF] composites containing 0–20 wt% SF were formulated. The flexural modulus increased with the SF content at all fiber compositions investigated; however, the value of this property gradually diminished when 20 wt% rubber was added to the polymer. Notched Izod impact strength of 80/20 nylon 6/EPDM-g-MA blend was reduced up to 50% with the addition of 5 wt% SF. However, these composites still retained good stiffness and toughness and presented a good interfacial adhesion between the phases. The results suggest that silica fibers can be employed as an alternative reinforcement of nylon 6 matrices, resulting in materials with useful properties.     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

Structural,electrical and electrochemical parameters of PEO–NaClO3 composite for battery applications

Polyethylene oxide–NaClO₃ composite have been prepared by solution casting technique with different weight percentages as a polymer electrolyte for battery application. The prepared composites were characterized by various tools like XRD, FTIR and SEM. The X-ray diffraction analysis shows the complexation of polymer with salt and existence of both crystalline and amorphous phases. From FTIR spectra confirms the formation of PEO–NaClO₃ composites. SEM images shows the grains are highly agglomerated and its average size increases with increase in salt ratio. Frequency dependence of dielectric property and ac electrical conductivity of polymer electrolytes were studied within the frequency range of 50 Hz to 5 MHz using complex impedance analysis technique. Ionic conductivity follows Arrhenius type behavior as a function of temperature. The fabricated cell of 25 wt.% of PEO–NaClO₃ composites generated high current of 1.79 A.     

Micromechanical analysis of fiber and titanium matrix interface by shear lag method

The model based on fracture mechanics is developed to evaluate the fracture toughness Γ of the fiber/matrix interface in titanium alloys reinforced by SiC monofilaments. Theoretical model for single fiber push-out testing is obtained by shear-lag method. The influences of several key factors (such as the applied stress needed for crack advance, crack length, and interfacial frictional shear stress) are discussed. Using the model, the interfacial toughness of typical composites including Sigma1240/Ti-6-4, SCS-6/Ti-6-4, SCS-6/Timetal 834, SCS-6/Timetal 21s, SCS-6/Ti-24-11 and SCS-6/Ti-15-3 are successfully predicted compared with previous results of these composites. It is verified that the model can reliably predict the interfacial toughness of the titanium matrix composites as well as other metal matrix composites, due to interfacial debonding usually occurs at the bottom face of the samples in such composites.     

Improving the interlaminar properties of polymer composites using a situ accumulation method to construct the multi-scale reinforcement of carbon nanofibers/carbon fibers

A novel method was developed to realize the situ accumulation of carbon nanofibers (CNFs) in the carbon fiber reinforced polymer composites (CFRPs) to construct the multi-scale reinforcement for improving the interlaminar properties. In this method, the prepreg was sealed by the nanomicroporous nylon membrane, and the excess resin was extracted from the prepreg by the vacuum-assisted method. It was found that the use of nylon membrane resulted in effective CNFs accumulation, especially in the interlayer by scanning electron microscopy. Short-beam strength tests and the end-notched flexure tests were conducted respectively to evaluate the interlaminar properties of CFRPs under shear loading. The results indicated that the interlaminar shear strength (ILSS) and the Mode II interlaminar fracture toughness (G_IIC) of CFRPs made by the filtering membrane-assisted method remarkably increased compared with those prepared without using filtering membrane.     

Electromagnetic shielding effectiveness and mechanical property of polymer–matrix composites containing metallized conductive porous flake-shaped diatomite

The porous flake-shaped diatomite particles with different micropores diameter were used as forming templates for the fabrication of the conductive core–shell functional fillers by electroless silver plating. The surface morphologies and phase structures of the surface coatings onto diatomite particles with different micropores diameter were evaluated. The effects of micropores diameter on electrical resistivity, electromagnetic shielding effectiveness and mechanical property of polymer–matrix composites containing silver-coated diatomite particles were also investigated in detail. The results show that the micropores onto initial diatomite particles after plating are completely covered with the coating, while the micropores onto diatomite particles with expanding pores are still visible. The expanding micropores onto diatomite particles in certain size range have less impact on the phase structures, electrical resistivity and electromagnetic shielding effectiveness. However, the mechanical properties of composites are improved significantly after expanding micropores by HF acid corrosion.     

Heat treated wood–nylon 6 composites

Heat treatment is a relatively benign modification method that is growing as an industrial process to improve hygroscopicity, dimensional stability and biological resistance of lignocellulosic fillers. There also has been increased interest in the use of lignocellulosic fillers in numerous automotive applications. This study investigated the influence of untreated and heat treated wood fillers on the mechanical and rheological properties of wood filled nylon 6 composites for possible under-the-hood applications in the automobile industry where conditions are too severe for commodity plastics to withstand. In this study, exposure of wood to high temperatures (212 °C for 8 h) improved the thermal stability and crystallinity of wood. Heat treated pine and maple filled nylon 6 composites (at 20 wt.% loading) had higher tensile strengths among all formulations and increased tensile strength by 109% and 106% compared to neat nylon 6, respectively. Flexural modulus of elasticity (FMOE) of the neat nylon 6 was 2.34 GPa. The FMOE increased by 101% and 82% with the addition of 30 wt.% heat treated pine and 20 wt.% heat treated maple, where it reached maximum values of 4.71 GPa and 4.27 GPa, respectively. The rheological properties of the composites correlated with the crystallinity of wood fillers after the heat treatment. Wood fillers with high crystallinity after heat treatment contributed to a higher storage modulus, complex viscosity and steady shear viscosity and low loss factor in the composites. This result suggests that heat treatment substantially affects the mechanical and rheological properties of wood filled nylon 6 composites. The mechanical properties and thermogravimetric analysis indicated that the heat treated wood did not show significant thermal degradation under 250 °C, suggesting that the wood-filled nylon composites could be especially relevant in thermally challenging areas such as the manufacture of under-the-hood automobile components.     

Mechanical properties of carbon nanotube reinforced polymer nanocomposites: A coarse-grained model

In this work, a coarse-grained (CG) model of carbon nanotube (CNT) reinforced polymer matrix composites is developed. A distinguishing feature of the CG model is the ability to capture interactions between polymer chains and nanotubes. The CG potentials for nanotubes and polymer chains are calibrated using the strain energy conservation between CG models and full atomistic systems. The applicability and efficiency of the CG model in predicting the elastic properties of CNT/polymer composites are evaluated through verification processes with molecular simulations. The simulation results reveal that the CG model is able to estimate the mechanical properties of the nanocomposites with high accuracy and low computational cost. The effect of the volume fraction of CNT reinforcements on the Young's modulus of the nanocomposites is investigated. The application of the method in the modeling of large unit cells with randomly distributed CNT reinforcements is examined. The established CG model will enable the simulation of reinforced polymer matrix composites across a wide range of length scales from nano to mesoscale.     

Mechanical properties of epoxy composites with high contents of nanodiamond

Mechanical properties and thermal conductivity of composites made of nanodiamond with epoxy polymer binder have been studied in a wide range of nanodiamond concentrations (0-25 vol.%). In contrast to composites with a low content of nanodiamond, where only small to moderate improvements in mechanical properties were reported before, the composites with 25 vol.% nanodiamond showed an unprecedented increase in Young’s modulus (up to 470%) and hardness (up to 300%) as compared to neat epoxy. A significant increase in scratch resistance and thermal conductivity of the composites were observed as well. The improved thermal conductivity of the composites with high contents of nanodiamond is explained by direct contacts between single diamond nanoparticles forming an interconnected network held together by a polymer binder.     

Parallel carbon nanotube stripes in polymer thin film with tunable microstructures and anisotropic conductive properties

It is known that shear-flow can induce units to assemble into vorticity-aligned stripe-structures in confined geometries. This study shows that the microstructure and the property of the stripe in polymer thin film can be well tuned by adjusting the viscosity ratio between dispersed phase and continuous phase. Polypropylene (PP)/poly(styrene–ethylene/butadiene–styrene) (SEBS)/octadecylamine functionalized multiwalled carbon nanotubes (ODA-MWCNTs) composites with different viscosity ratios were prepared by either pre-compounding ODA-MWCNT into PP or SEBS in a microcompounder. Under the induction of shear-flow, ODA-MWCNT and SEBS spontaneously assembled into vorticity-aligned stripes in PP thin films for all the composites with different viscosity ratios, resulting in the property of conductive anisotropy for the film. Interestingly, it was found that both the microstructures and the electrical properties of MWCNT stripes in PP thin films prepared from the composites with different viscosity ratios were significantly different.     

Thermoplastic–epoxy interactions and their potential applications in joining composite structures – A review

This paper presents a literature survey on the theoretical backgrounds and the past research efforts in relation to the interactions between certain thermoplastics and epoxies, and their applications in polymer blending, epoxy toughening and composite joining. The main objectives are to understand the possible mechanisms of interfacial adhesion between thermoplastic and thermoset polymers, and also to explore the feasible approaches to improve interfacial adhesion for the purposes of joining fibre reinforced polymer (FRP) composite structures by fusion bonding. Further, it is expected that the review would provide some visions to the potential applications of the thermoplastic–thermoset interfacial interactions for the quick assembly of composite structures in cost-effective manufacturing of composite structures, through the uses of the technologies, such as thermoset composite fusion bonding, welding of thermoplastic composites with thermoset composites, and thermoplastic article attachment on thermoset composites.     

Development of a biocomposite based on green epoxy polymer and natural cellulose fabric (bark cloth) for automotive instrument panel applications

Natural fiber reinforced composites have attracted interest due to their numerous advantages such as biodegradability, dermal non-toxicity and with promising mechanical strength. The desire to mitigate climate change due to greenhouse gas emissions, biodegradable resins are explored as the best forms of polymers for composites apart from their synthetic counterparts which are non-renewable. In this study biodegradable bark cloth reinforced green epoxy composites are developed with view of application to automotive instrument panels. The optimum curing temperature of green epoxy was shown to be 120 °C. The static properties showed a tensile strength of 33 MPa and flexural strength of 207 MPa. The dynamic mechanical properties, frequency sweep showed excellent fiber-matrix bonding of the alkali treated fabric with the green epoxy polymer with glass transition temperature in the range of 160 °C–180 °C. Treatment of the fabric with alkali positively influenced the mechanical properties of the fabric reinforced biocomposites.     

Compressive mechanical properties of closed-cell aluminum foam–polymer composites

The compressive mechanical properties of two kinds of closed-cell aluminum foam–polymer composites (aluminum–epoxy, aluminum–polyurethane) were studied. The nonhomogeneous deformation features of the composites are presented based on the deformation distributions measured by the digital image correlation (DIC) method. The strain fluctuations rapidly grow with an increase in the compressive load. The uneven level of the deformation for the aluminum–polyurethane composite is lower than that for the aluminum–epoxy composite. The region of the preferentially fractured aluminum cell wall can be predicted by the strain distributions in two directions. The mechanical properties of the composites are investigated and compared to those of the aluminum foams. The enhancement effect of the epoxy resin on the Young’s modulus, the Poisson’s ratio and the compressive strength of the aluminum foams is greater than that of the polyurethane resin.     

Thermomechanical modelling the fire properties of fibre–polymer composites

Simple-to-use models are presented in this paper for determining the residual tension, compression and flexural properties of burnt fibre reinforced polymer composite materials following a fire. The post-fire mechanical properties are calculated using analytical equations that combine the properties of the fire-damaged (i.e. char) and undamaged regions of a composite. Fire tests were performed on composites containing carbon, glass or Kevlar fibres with an epoxy, polyester, vinyl ester or phenolic resin matrix to assess the accuracy of the models. The composites were tested to a wide range of fire conditions with temperatures from 525 to 850 °C for times up to 30 min. It is found that the post-fire properties drop rapidly with increasing heat flux and duration of a fire due to the thermal degradation of the polymer matrix. It is shown that the reduction to the post-fire properties of the burnt composites can be accurately determined using the models. In almost all test cases, the agreement between the calculated and measured residual mechanical properties is within 10%.     

Review of the mechanical properties of carbon nanofiber/polymer composites

In this paper, the mechanical properties of vapor grown carbon nanofiber (VGCNF)/polymer composites are reviewed. The paper starts with the structural and intrinsic mechanical properties of VGCNFs. Then the major factors (filler dispersion and distribution, filler aspect ratio, adhesion and interface between filler and polymer matrix) affecting the mechanical properties of VGCNF/polymer composites are presented. After that, VGCNF/polymer composite mechanical properties are discussed in terms of nanofibers dispersion and alignment, adhesion between the nanofiber and polymer matrix, and other factors. The influence of processing methods and processing conditions on the properties of VGCNF/polymer composite is also considered. At the end, the possible future challenges for VGCNF and VGCNF/polymer composites are highlighted.     

Optical and mechanical anisotropies of aligned electrospun nanofibers reinforced transparent PMMA nanocomposites

This study aims to assess the nanofiber directionality effects on optomechanical properties of a widely used transparent thermoplastic poly(methyl methacrylate) (PMMA). Aligned fiber-hybrid mats consisted of nylon-6 (PA-6) nanofibers and PMMA microfibers are prepared using a self-blending co-electrospinning method, followed by hot press molding to fabricate into transparent nanocomposites. Effects of nanofiber orientation degree in two orthogonal directions and loading fraction on the optomechanical behavior of the nanocomposites are examined. Optical transmittance differences parallel and perpendicular to the nanofibers’ orientation are found to vary in a range of 3.9–5.4% at 589 nm, and strong mechanical anisotropy is observed with the 1% PA-6/PMMA nanocomposites. A maximal of 3% PA-6 nanofiber loading maintains the nanocomposite high transmittance (>75%) with improved strength and toughness along the nanofiber axis. This study reveals evident anisotropic optomechanical properties of transparent nanocomposites, and highlights the great designability of transparent nanocomposites by using aligned nanofibers as the designing elements.     

Processing parameters and characterisation of flax fibre reinforced engineering plastic composites with flame retardant fillers

This work studies the possibility of compounding natural fibres (flax) into engineering plastics (PA6 and PB6) and comparing the results with counterpart glass fibre composites. The problem in compounding is the difficulty to compound the fibres with such polymers of high melting temperatures without decomposing the natural fibre thermally. Preliminary experiments are tried to define the possible processing window using the kneader namely temperature, compounding time and shear rate. Fibre content is tried in range of 0–50 wt.% with 10% step. The mixing temperature covers the range around the melting temperature ‘Tm’ [Tm−20, Tm+20]°C. The use of pre-melting temperature in compounding would utilise the energy evolving by fibres mutual rubbing. Compounding time is optimised at the minimum level. Shearing rate is tried at 25, 50, 75 and 100 rpm. Optimum conditions are defined to be 210–230 °C and 200–210 °C for PBT and PA6 respectively. Shearing rate is also defined to lie within 25–50 rpm.Two different additives of non-organic mineral and organic phosphate flame retardants are tried with the prepared composites either alone or in combination with each other. The loading of flame retardants is limited to 20 wt.% in order to leave a space for natural fibres as well as the polymer and to keep in turn the overall composite mechanical properties. A mix of 1:1 ratio between the both types of retardants is needed to reach V0 flame retardation level. Mechanical properties are even improved 30% in E-modulus and 4% in strength with respect to composites without flame retardants. However, the injection moulding is reported to be difficult because of the high viscosity and the parameters should be optimised regarding the desired flame retardance level and the required mechanical properties as well as keeping the fibres not damaged.