The superior effect of edge functionalization relative to basal plane functionalization of graphene in enhancing the thermal conductivity of polymer-graphene nanocomposites - a combined molecular dynamics and Green's functions study.

To achieve polymer-graphene nanocomposites with high thermal conductivity (k), it is critically important to achieve efficient thermal coupling between graphene and the surrounding polymer matrix through effective functionalization schemes. In this work, we demonstrate that edge-functionalization of graphene nanoplatelets (GnPs) can enable a larger enhancement of effective thermal conductivity in polymer-graphene nanocomposites relative to basal plane functionalization. Effective thermal conductivity for the edge case is predicted, through molecular dynamics simulations, to be up to 48% higher relative to basal plane bonding for 35 wt% graphene loading with 10 layer thick nanoplatelets. The beneficial effect of edge bonding is related to the anisotropy of thermal transport in graphene, involving very high in-plane thermal conductivity (∼2000 W m-1 K-1) compared to the low out-of-plane thermal conductivity (∼10 W m-1 K-1). Likewise, in multilayer graphene nanoplatelets (GnPs), the thermal conductivity across the layers is even lower due to the weak van der Waals bonding between each pair of layers. Edge functionalization couples the polymer chains to the high in-plane thermal conduction pathway of graphene, thus leading to overall high thermal conductivity of the composite. Basal-plane functionalization, however, lowers the thermal resistance between the polymer and the surface graphene sheets of the nanoplatelet only, causing the heat conduction through inner layers to be less efficient, thus resulting in the basal plane scheme to be outperformed by the edge scheme. The present study enables fundamentally novel pathways for achieving high thermal conductivity polymer nanocomposites.

Length dependence thermal conductivity of zinc selenide (ZnSe) and zinc telluride (ZnTe) - a combined first principles and frequency domain thermoreflectance (FDTR) study.

In this study, we report the length dependence of thermal conductivity (k) of zinc blende-structured Zinc Selenide (ZnSe) and Zinc Telluride (ZnTe) for length scales between 10 nm and 10 µm using first-principles computations, based on density-functional theory. The k value of ZnSe is computed to decrease significantly from 22.9 W m-1 K-1 to 1.8 W m-1 K-1 as the length scale is diminished from 10 µm to 10 nm. The k value of ZnTe is also observed to decrease from 12.6 W m-1 K-1 to 1.2 W m-1 K-1 for the same decrease in length. We also measured the k of bulk ZnSe and ZnTe using the Frequency Domain Thermoreflectance (FDTR) technique and observed a good agreement between the FDTR measurements and first principles calculations for bulk ZnSe and ZnTe. Understanding the thermal conductivity reduction at the nanometer length scale provides an avenue to incorporate nanostructured ZnSe and ZnTe for thermoelectric applications.

Strain tuned high thermal conductivity in boron phosphide at nanometer length scales - a first-principles study.

Breakdown of Fourier law of heat conduction at nanometer length scales significantly diminishes thermal conductivity, leading to challenges in thermal management of nanoelectronic applications. In this work we demonstrate using first-principles computations that biaxial strain can enhance k at a nanoscale in boron phosphide (BP), yielding nanoscale k values that exceed even the bulk k value of silicon. At a length scale of L = 200 nm, k of 4% biaxially strained BP is enhanced by 25% to a value of 150.4 W m-1 K-1, relative to 120 W m-1 K-1 computed for unstrained BP at 300 K. The enhancement in k at a nanoscale is found to be due to the suppression of anharmonic scattering in the higher frequency range where phonon meanfreepaths are in nanometers, mediated by an increase in the phonon band gap in strained BP. Such a suppression in scattering enhances the meanfreepaths in the nanometer regime, thus enhancing nanoscale k. First-principles computations based on deriving harmonic and anharmonic force interactions from density-functional theory are used to provide detailed understanding of the effect in terms of individual scattering channels.

Advances in Nickel-Containing High-Entropy Alloys: From Fundamentals to Additive Manufacturing.

High-entropy alloys (HEAs) are recognized as a class of advanced materials with outstanding mechanical properties and corrosion resistance. Among these, nickel-based HEAs stand out for their impressive strength, ductility, and oxidation resistance. This review delves into the latest advancements in nickel-containing HEAs, covering their fundamental principles, alloy design strategies, and additive manufacturing techniques. We start by introducing HEAs and their unique properties, emphasizing the crucial role of nickel. This review examines the complex relationships between alloy composition, valence electron concentration (VEC), and the resulting crystal structures. This provides insights into design principles for achieving desired microstructures and mechanical properties. Additive manufacturing (AM) techniques like selective laser melting (SLM), electron beam melting (EBM), and laser metal deposition (LMD) are highlighted as powerful methods for fabricating intricate HEA components. The review addresses the challenges of AM processes, such as porosity, fusion defects, and anisotropic mechanical properties, and discusses strategies to mitigate these issues through process optimization and improved powder quality. The mechanical behavior of AM-processed nickel-based HEAs is thoroughly analyzed, focusing on compressive strength, hardness, and ductility. This review underscores the importance of microstructural features, including grain size, phase composition, and deformation mechanisms, in determining the mechanical performance of these alloys. Additionally, the influence of post-processing techniques, such as heat treatment and hot isostatic pressing (HIP) on enhancing mechanical properties is explored. This review also examines the oxidation behavior of nickel-containing HEAs, particularly the formation of protective oxide scales and their dependence on aluminum content. The interplay between composition, VEC, and oxidation resistance is discussed, offering valuable insights for designing corrosion resistant HEAs. Finally, this review outlines the potential applications of nickel-based HEAs in industries such as aerospace, automotive, and energy, and identifies future research directions to address challenges and fully realize the potential of these advanced materials.

Superior enhancement in thermal conductivity of epoxy/graphene nanocomposites through use of dimethylformamide (DMF) relative to acetone as solvent.

This method article describes the fabrication of graphene-epoxy nanocomposites using two different solvents, dimethylformamide (DMF) and acetone, and validates the resulting thermal conductivity improvements. The study compared the two solvents at a filler composition of 7 wt% and found that DMF resulted in more uniform dispersion of graphene nanoparticles in the epoxy matrix, leading to a 44% improvement in thermal conductivity compared to acetone. Laser scanning confocal microscopy (LSCM) imaging showed that DMF-based composites had more evenly dispersed graphene nanoplatelets than acetone-based composites, which exhibited larger graphene agglomerations. Effective medium theory calculations showed that DMF led to almost 35% lower interface thermal resistance between graphene and epoxy compared to acetone. The validated fabrication method and findings provide new possibilities for developing high thermal conductivity graphene-epoxy nanocomposites for various thermal management applications.•This article describes methods for fabricating graphene-epoxy composites using acetone and DMF as solvents, and validates that DMF is better for achieving higher thermal conductivity in the composite.

Chemically Edge-Carboxylated Graphene Enhances the Thermal Conductivity of Polyetherimide-Graphene Nanocomposites.

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 offers the advantage of leaving the basal plane of graphene intact, preserving its high in-plane thermal conductivity (kin > 2000 W m-1 K-1), while, simultaneously, the oxygen groups introduced on the graphene edge enhance interfacial thermal conductance through hydrogen bonding with oxygen groups of PEI, enhancing the overall polymer composite thermal conductivity. Edge oxidation is achieved in this work by oxidizing graphene in the presence of sodium chlorate and hydrogen peroxide, thereby introducing an excess of carboxyl groups on the edge of graphene. Basal plane oxidation of graphene, on the other hand, is achieved through the Hummers method, which distorts the sp2 carbon-carbon network of graphene, dramatically lowering its intrinsic thermal conductivity, causing the BGO/PEI (BGO = basal-plane oxidized graphene or basal-plane-functionalized graphene oxide) composite's k value to be even lower than pristine GnP/PEI composite's k value. The resulting thermal conductivity of the EGO/PEI (EGO = edge-oxidized graphene or edge-functionalized graphene oxide) composite is found to be enhanced by 18%, whereas that of the BGO/PEI composite is diminished by 57%, with respect to the pristine GnP/PEI composite with 10 wt % GnP content. Two-dimensional Raman mapping of GnPs is used to confirm and distinguish the location of oxygen functional groups on graphene. The superior effect of edge bonding presented in this work can lead to fundamentally novel pathways for achieving high thermal conductivity polymer composites.

Large Enhancement in Thermal Conductivity of Solvent-Cast Expanded Graphite/Polyetherimide Composites.

We demonstrate in this work that expanded graphite (EG) can lead to a very large enhancement in thermal conductivity of polyetherimide-graphene and epoxy-graphene nanocomposites prepared via solvent casting technique. A k value of 6.6 W⋅m-1⋅K-1 is achieved for 10 wt% composition sample, representing an enhancement of ~2770% over pristine polyetherimide (k~0.23 W⋅m-1⋅K-1). This extraordinary enhancement in thermal conductivity is shown to be due to a network of continuous graphene sheets over long-length scales, resulting in low thermal contact resistance at bends/turns due to the graphene sheets being covalently bonded at such junctions. Solvent casting offers the advantage of preserving the porous structure of expanded graphite in the composite, resulting in the above highly thermally conductive interpenetrating network of graphene and polymer. Solvent casting also does not break down the expanded graphite particles due to minimal forces involved, allowing for efficient heat transfer over long-length scales, further enhancing overall composite thermal conductivity. Comparisons with a recently introduced effective medium model show a very high value of predicted particle-particle interfacial conductance, providing evidence for efficient interfacial thermal transport in expanded graphite composites. Field emission environmental scanning electron microscopy (FE-ESEM) is used to provide a detailed understanding of the interpenetrating graphene-polymer structure in the expanded graphite composite. These results open up novel avenues for achieving high thermal conductivity polymer composites.

Lattice Instability and Ultralow Lattice Thermal Conductivity of Layered PbIF.

Understanding the interplay between various design strategies (for instance, bonding heterogeneity and lone pair induced anharmonicity) to achieve ultralow lattice thermal conductivity (κl) is indispensable for discovering novel functional materials for thermal energy applications. In the present study, we investigate layered PbXF (X = Cl, Br, I), which offers bonding heterogeneity through the layered crystal structure, anharmonicity through the Pb2+ 6s2 lone pair, and phonon softening through the mass difference between F and Pb/X. The weak interlayer van der Waals bonding and the strong intralayer ionic bonding with partial covalent bonding result in a significant bonding heterogeneity and a poor phonon transport in the out-of-plane direction. Large average Grüneisen parameters (≥2.5) demonstrate strong anharmonicity. The computed phonon dispersions show flat bands, which suggest short phonon lifetimes, especially for PbIF. Enhanced Born effective charges are due to cross-band-gap hybridization. PbIF shows lattice instability at a small volume expansion of 0.1%. The κl values obtained by the two channel transport model are 20-50% higher than those obtained by solving the Boltzmann transport equation. Overall, ultralow κl values are found at 300 K, especially for PbIF. We propose that the interplay of bonding heterogeneity, lone pair induced anharmonicity, and constituent elements with high mass difference aids the design of low κl materials for thermal energy applications.

Effect of Alignment on Enhancement of Thermal Conductivity of Polyethylene-Graphene Nanocomposites and Comparison with Effective Medium Theory.

Thermal conductivity (k) of polymers is usually limited to low values of ~0.5 W in comparison to metals (>20 W). The goal of this work is to enhance thermal conductivity (k) of polyethylene-graphene nanocomposites through simultaneous alignment of polyethylene (PE) lamellae and graphene nanoplatelets (GnP). Alignment is achieved through the application of strain. Measured values are compared with predictions from effective medium theory. A twin conical screw micro compounder is used to prepare polyethylene-graphene nanoplatelet (PE-GnP) composites. Enhancement in k value is studied for two different compositions with GnP content of 9 weight% and 13 weight% and for applied strains ranging from 0% to 300%. Aligned PE-GnP composites with 13 weight% GnP displays ~1000% enhancement in k at an applied strain of 300%, relative to k of pristine unstrained polymer. Laser Scanning Confocal Microscopy (LSCM) is used to quantitatively characterize the alignment of GnP flakes in strained composites; this measured orientation is used as an input for effective medium predictions. These results have important implications for thermal management applications.

Thermal conductivity of hexagonal BC2P - a first-principles study.

In this work, we report a high thermal conductivity (k) of 162 W m-1 K-1 and 52 W m-1 K-1 at room temperature, along the directions perpendicular and parallel to the c-axis, respectively, of bulk hexagonal BC2P (h-BC2P), using first-principles calculations. We systematically investigate elastic constants, phonon group velocities, phonon linewidths and mode thermal conductivity contributions of transverse acoustic (TA), longitudinal acoustic (LA) and optical phonons. Interestingly, optical phonons are found to make a large contribution of 30.1% to the overall k along a direction perpendicular to the c-axis at 300 K. BC2P is also found to exhibit high thermal conductivity at nanometer length scales. At 300 K, a high k value of ∼47 W m-1 K-1 is computed for h-BC2P at a nanometer length scale of 50 nm, providing avenues for achieving efficient nanoscale heat transfer.