We review the current state of the art of graphene-enhanced thermal interface materials for the management of heat the next generation of electronics. Increased integration densities, speed, and power of electronic and optoelectronic devices require thermal interface materials with substantially higher thermal conductivity, improved reliability, and lower cost. Graphene has emerged as a promising filler material that can meet the demands of future high-speed and high-powered electronics. This review describes the use of graphene as a filler in curing and non-curing polymer matrices. Special attention is given to strategies for achieving the thermal percolation threshold with its corresponding characteristic increase in the overall thermal conductivity. Many applications require high thermal conductivity of the composites while simultaneously preserving electrical insulation. A hybrid filler -- graphene and boron nitride -- approach is presented as possible technology for independent control of electrical and thermal conduction. Reliability and lifespan performance of thermal interface materials is an important consideration towards the determination of appropriate practical applications. The present review addresses these issues in detail, demonstrating the promise of the graphene-enhanced thermal interface materials as compared to alternative technologies.
Polymer composites with thermally conductive nanoscale filler particles, such as graphene and hexagonal boron nitride (h-BN), are promising for certain heat transfer applications. While graphene-polymer composites have been extensively investigated, studies on h-BN-polymer composites has been relatively rare. In this paper, we use molecular dynamics (MD) simulations to study the interfacial thermal conductance (ITC) involved in the h-BN-polymer composites. We first compare the ITC across h-BN/hexane (C6H14) interfaces to that of graphene/hexane interfaces, where we found that the electrostatic…
The recent development of nanoscale fillers, such as carbon nanotube, graphene, and nanocellulose, allows the functionality of polymer nanocomposites to be controlled and enhanced. However, conventional synthesis methods of polymer nanocomposites cannot maximise the reinforcement of these nanofillers at high filler content. Approaches to the synthesis of high content filler polymer nanocomposites are suggested to facilitate future applications. The fabrication methods address design of the polymer nanocomposite architecture, which encompass one, two, and three dimensional morphology. Factors t…
Polymer nanocomposites based on 2D materials as fillers are the target in the industrial sector, but the ability to manufacture them on a large scale is very limited, and there is a lack of tools to scale up the manufacturing process of these nanocomposites. Here, for the first time, a systematic and fundamental study showing how 2D materials are inserted into the polymeric matrix in order to obtain nanocomposites using conventional and industrially scalable polymer processing machines leading to large-scale manufacturing are described. Two new strategies were used to insert pre-exfoliated 2D …
Different types of graphene-related materials (GRM) are industrially available and have been exploited for thermal conductivity enhancement in polymers. These include materials with very different features, in terms of thickness, lateral size and composition, especially concerning the oxygen to carbon ratio and the possible presence of surface functionalization. Due to the variability of GRM properties, the differences in polymer nanocomposites preparation methods and the microstructures obtained, a large scatter of thermal conductivity performance is found in literature. However, detailed cor…
This paper is an attempt to predict the thickness and modulus at the nanometric interphase region with the knowledge on the macroscopic Young's modulus in the polymer-clay nanocomposites. First, a systematic design of 20160 linear elastic finite element simulations are used to derive an analytical equation between the interphase thickness, the interphase modulus, the nanoclay content and the macroscopic Young's modulus of the nanocomposite. Four calibration parameters in this equation are calculated based on the reported data about NYLON6-MMT nanocomposite. Next, an analytical nanoscale equati…
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 …
In the present work, the effect of different nanofiller (BaTiO3, CeO2, Er2O3 or TiO2) on blend solid polymer electrolyte comprising of PEO and PVC complexed with bulky LiPF6 have been explored. The XRD analysis confirms the polymer nanocomposite formation. FTIR provides evidence of interaction among the functional groups of the polymer with the ions and the nanofiller in terms of shifting and changing peak profile. The highest ionic conductivity is ~2.3x10-5 S cm-1 with a wide electrochemical stability window of ~3.5 V for 10 wt. % Er2O3. The real and imaginary part of dielectric permittivity …
The promise of enhanced performance has motivated the study of one dimensional nanomaterials, especially aligned carbon nanotubes (A-CNTs), for the reinforcement of polymeric materials. While early work has shown that CNTs have remarkable theoretical properties, more recent work on aligned CNT polymer matrix nanocomposites (A-PNCs) have reported mechanical properties that are orders of magnitude lower than those predicted by rule of mixtures. This large difference primarily originates from the morphology of the CNTs that reinforce the A-PNCs, which have significant local curvature commonly ref…
This work proposes an investigation of the fracturing behavior of polymer nanocomposites. Towards this end, the study leverages the analysis of a large bulk of fracture tests from the literature with the goal of critically investigating the effects of the nonlinear Fracture Process Zone (FPZ). It is shown that for most of the fracture tests the effects of the nonlinear FPZ are not negligible, leading to significant deviations from Linear Elastic Fracture Mechanics (LEFM) sometimes exceeding 150% depending on the specimen size and nanofiller content. To get a deeper understanding of the charact…
A free standing transparent film of solid state polymer electrolyte based on PEO/PAN + NaPF6 with different compositions of nano sized TiO2 in weight percent (x = 0, 1, 2, 5, 10, 15, 20 ) is synthesized by using standard solution cast technique. The homogeneous surface of above polymer composition is examined by FESEM. The microscopic interaction among polymer, salt and nanoceramic filler has been analyzed by Fourier Transformed Infra-Red (FTIR) spectroscopy. The reduction of ion pair formation in polymeric separator is clearly observed on addition of nanofiller in the polymer salt complex fil…
This work investigated how the structure size affects the quasi-static and fatigue behaviors of graphene polymer nanocomposites, a topic that has been often overlooked. The results showed that both quasi-static and fatigue failure of these materials scale nonlinearly with the structure size due to the presence of a significant Fracture Process Zone (FPZ) ahead of the crack tip induced by graphene nanomodification. Such a complicated size effect and scaling in either quasi-static or fatigue scenario cannot be described by the Linear Elastic Fracture Mechanics (LEFM), but can be well captured by…
Improving lithium-ion batteries (LIBs) safety remains in a challenging task when compared with the tremendous progress made in their performance in recent years. Embedding thermo-responsive polymer switching materials (TRPS) into LIB cells has been proved to be a promising strategy to provide consistent thermal abuse protections at coin-cell level. However, it is unrealistic to achieve large-scale applications without further demonstration in high-capacity pouch cells. Here, we employed tungsten carbide (WC) as a novel conductive filler, and successfully overcame the intrinsic processing diffi…
Advanced electrical conductors that outperform copper and aluminum can revolutionize our lives, enabling billions of dollars in energy savings and facilitating a transition to an electric mobility future. Nanocarbons (carbon nanotubes and graphene) present a unique opportunity for developing advanced conductors for electrical power, communications, electronics, and electric machines for the aerospace, marine, and automotive industries. This paper compiles the major research progress in the field of advanced nanocarbon-based and metal-nanocarbon conductors. It also elucidates the competitivenes…
In this work, a novel electrospun conductive polymer nanocomposite made of polycaprolactone with an exohedral complex made of multiwalled carbon nanotubes and fullerene C60 was prepared and characterized. The preparation was straightforward and the complexes self-assembled within the nanocomposite fibers. The nanocomposite showed electrical switching behavior due to charge accumulation of fullerene C60 upon electrical stimulation. Write-once read-many memory devices were fabricated by electrospinning a nanocomposite with 0.8%wt. fullerene C60 onto interdigitated coplanar electrodes. The device…
Epoxy resins are thermosetting polymers with an extensive set of applications such as anticorrosive coatings, adhesives, matrices for fibre reinforced composites and elements of electronic systems for automotive, aerospace and construction industries.
We demonstrate the use of nanodiamond in constructing holographic nanoparticle-polymer composite transmission gratings with large saturated refractive index modulation amplitudes at both optical and slow-neutron wavelengths, resulting in efficient control of light and slow-neutron beams. Nanodiamond possesses a high refractive index at optical wavelengths and large coherent and small incoherent scattering cross sections with low absorption at slow-neutron wavelengths. We describe the synthesis of nanodiamond, the preparation of photopolymerizable nanodiamond-polymer composite films, the constr…
The work presents a comprehensive methodology to determine the Shielding Effectiveness (SE) of single-walled carbon nanotubes (SWCNTs)/polymer nanocomposites. Here, an algorithm based on Ant Colony Optimization (ACO) was employed to determine the electrical conductivity (σ) of these nanocomposites as a function of SWCNT concentration. Then, these σ values were used to compute the SE values as a function of frequency and concentration. Specifically, a pseudo three-dimensional (3D) percolation model was developed to study the effects of random connectivity of SWCNTs to one another on the σ value…
In this work, the preparation of nanocomposites based on poly(L-lactide) PLLA and graphite nanoplatelets (GNP) was assessed, by applying, for the first time, the reactive extrusion (REX) polymerization approach, which is considered a low environmental impact method to prepare polymer systems and which allows an easy scalability. In particular, ad hoc synthesized molecules, constituted by a pyrene end group and a poly (D-lactide) (PDLA) chain (Pyr-D), capable of interacting with the surface of GNP layers as well as forming stereoblocks during the ring opening polymerization (ROP) of L-lactide, …
There has been a massive growth in the study of transition metal dichalcogenides (TMDs) over the past decade, based upon their interesting and unusual electronic, optical and mechanical properties, such as tuneable and strain-dependent bandgaps. Tungsten disulfide (WS2), as a typical example of TMDs, has considerable potential in applications such as strain engineered devices and the next generation multifunctional polymer nanocomposites. However, controlling the strain, or more practically, monitoring the strain in WS2 and the associated micromechanics have not been so well studied. Both phot…
Polyaniline and graphene nanoplatelets (PANI-GNP) nanocomposites are synthesized by in situ oxidative polymerization of polyaniline using an oxidizing agent, ammonium peroxy disulphate (APS). The mass of GNP in the nanocomposites varied by 5, 10, and 15 wt% compared to PANI. The synthesized polyaniline coated graphene nanoplatelets (PANI-GNP) nanocomposites are chemically characterized and using Fourier Transform Infrared Spectroscopy (FTIR), Raman spectroscopy, Scanning electron microscopy (SEM), UV-Vis spectroscopy, and X-ray diffraction analysis (XRD). FTIR and Raman spectroscopy analysis c…
Materials comprising carbon nanotube (CNT) aligned nanowire (NW) polymer nanocomposites (A-PNCs) are emerging as next-generation materials for use in aerospace structures. Enhanced operating regimes, such as operating temperatures, motivate the study of CNT aligned NW ceramic matrix nanocomposites (A-CMNCs). Here we report the synthesis of CNT A-CMNCs through the pyrolysis of CNT A-PNC precursors, thereby creating carbon matrix CNT A-CMNCs. Characterization reveals that the fabrication of high strength, high temperature, lightweight next-generation aerospace materials is possible using this me…
Thermal conduction in polymer nanocomposites depends on several parameters including the thermal conductivity and geometrical features of the nanoparticles, the particle loading, their degree of dispersion and formation of a percolating networks. To enhance efficiency of thermal contact between free-standing conductive nanoparticles were previously proposed. This work report for the first time the investigation of molecular junctions within a graphene polymer nanocomposite. Molecular dynamics simulations were conducted to investigate the thermal transport efficiency of molecular junctions in p…
Nanocomposite material proves to be the best candidate to match todays technological need as fascinating properties can be achieved by combining two or more nanomaterials. Among various nanomaterials, graphene is able to stand out far ahead of all others because of its novel structure and exclusive characteristics. In particular, graphene metal nanocomposites have attracted enormous interest for their prospective use in various fields, including electronics and electrical and energy related areas. However, for the utmost use of potential of graphene, it has to be homogenously embedded into met…
Polydimethylsiloxane (PDMS) is an insulator and it is commonly used in fabrication of micro-structures but there is a need of electrical conductive PDMS. Therefore, this research is mainly focused on producing PDMS nanocomposites with high electrical conductivity. Thus, we produced highly conductive PDMS nanocomposites which were filled with multiwalled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs). Due to the synergistic effect between CNTs and GNPs inside a polymeric matrix, we expected to obtain more conductive nanocomposites than PDMS nanocomposite filled with only CNTs. Addi…
Carbon-nanofillers are known for improving the desired properties of polymers. The dispersion quality of nanofillers in the matrix is vital for the fabrication of high-performance nanocomposites. An effective approach for improving dispersion states of multi-walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GNPs) was employed via hybrid inclusion of the nanofillers in polyurethane matrix to further enhancing viscoelastic properties. Nanocomposites based on MWCNTs, two groups of graphene and hybrid MWCNT/graphene with varied weight fractions and ratios were fabricated via a simple, qu…
Pyrene-functional PMMAs were prepared via ATRP-controlled polymerization and click reaction, as efficient dispersing agents for the exfoliation of few-layered graphene sheets (GS) in easily processable low boiling point chloroform. In parallel, detailed atomistic simulations showed fine dispersion of the GS/polymer hybrids in good agreement with the experiment. Moreover, the molecular dynamics simulations revealed interesting conformations (bridges, loops, dangling ends, free chains) of GS/polymer hybrids and allowed us to monitor their time evolution both in solution and in the polymer nanoco…
Polyynes are finite chains formed by sp-hybridized carbon atoms with alternating single and triple bonds and displaying intriguing electronic and optical properties. Pulsed laser ablation in liquid (PLAL) is a well assessed technique for the physical synthesis of hydrogen-capped polyynes in solution, however, their limited stability prevents further exploitation in materials for different applications. In this work, polyynes in poly(vinyl alcohol) (PVA) were produced in a single-step PLAL process by ablating graphite directly in aqueous solution of PVA, investigating the role of polymer concen…
Graphene wetting by polymers is a critical issue to both the success of polymer-aided transfer of large size sheets onto specific substrates and to the development of well performing nanocomposites. Here we show for the first time that high temperature contact angle measurements can be performed to investigate the wettability of CVD graphene by molten polymers. In particular, poly(methyl methacrylate), a widely used polymer support for CVD graphene transfer, has been adopted herein for this proof-of-concept study and the values of contact angle and work of adhesion have been provided in the te…
Most polymers are long-lasting and produced from monomers derived from fossil fuel sources. Bio-based and/or biodegradable plastics have been proposed as a sustainable alternative. Amongst those available, polyhydroxyalkanoate (PHA) shows great potential across a large variety of applications but is currently limited to packaging, cosmetics and tissue engineering due to its relatively poor physical properties. An expansion of its uses can be accomplished by developing nanocomposites where PHAs are used as the polymer matrix. Herein, a PHA biopolyester was melt blended with graphene nanoplatele…
In this work, we demonstrate that edge-oxidation of graphene can enable larger enhancement in thermal conductivity (k) of graphene-nanoplatelet (GnP)/polyetherimide (PEI) composites relative to oxidation of the basal plane of graphene. Edge oxidation (EGO) offers the advantage of leaving the basal plane of graphene intact, preserving its high in-plane thermal conductivity (kin > 2000 Wm-1K-1), while, simultaneously, the oxygen groups introduced on graphene edge enhance interfacial thermal conductance through hydrogen bonding with oxygen groups of polyetherimide (PEI), enhancing overall polymer…
The biaxial mechanical properties constitute another remarkable advantage of graphene, but their evaluation has been overlooked in polymer nanocomposites. Herein, we provided an innovative and practical method to characterise biaxial reinforcement from graphene via swelling of elastomers, where graphene nanoplatelets were controlled to be oriented in-plane. The in-plane-aligned graphene imposed a biaxial constraining force to the elastomer during the swelling process that led to the anisotropic swelling behaviour of the bulk nanocomposites.
In order to realise the potential of graphene nanocomposites it is vital to control the degree of dispersion and achieve a strong graphene polymer interface. Herein, we developed a facile grafting to functionalisation approach for graphene nanoplatelets. NH2-terminated graphene nanoplatelets, NH2 GNPs, prepared by a diazonium coupling were used as a platform to covalently graft PMMA chains to the surface of graphene through an amidation between the NH2 groups and PMMA chains, PMMA NH GNPs. A degree of PMMA grafting of 3.8 wt, one chain per 40 carbon atoms, was found to both improve the dispers…
