Rational molecular dynamics scheme for predicting optimum concentration loading of nano-additive in phase change materials

The present study deals with the diffusion and phase transition behaviour of paraffin reinforced with carbon nano-additives namely graphene oxide (GO) and surface functionalized single walled carbon nanotubes (SWCNT). Bulk disordered systems of paraffin hydrocarbons impregnated with carbon nano-additives have been generated in realistic equilibrium conformations for potential application as latent heat storage systems. Ab initio molecular dynamics(MD) in conjugation with COMPASS forcefield has been implemented using periodic boundary conditions. The proposed scheme allows determination of optimum nano-additive loading for improving thermo-physical properties through analysis of mass, thermal and transport properties; and assists in determination of composite behaviour and related performance from microscopic point of view. It was observed that nanocomposites containing 7.8% surface functionalised SWCNT and 55% GO loading corresponds to best latent heat storage system. The propounded methodology could serve as a by-pass route for economically taxing and iterative experimental procedures required to attain the optimum composition for best performance. The results also hint at the large unexplored potential of ab-initio classical MD techniques for predicting performance of new nanocomposites for potential phase change material applications. (C) 2015 Author(s).

An efficient strategy to develop microwave shielding materials with enhanced attenuation constant

A mutually miscible homopolymer (here polymethyl methacrylate; PMMA) was employed to tailor the interfacial properties of immiscible polycarbonate/styrene acrylonitrile (PC/SAN) blends. In order to design materials that can shield microwave radiation, one of the key properties i.e. electrical conductivity was targeted here using a conducting inclusion; multiwall carbon nanotubes (MWNTs). Owing to higher polarity, MWNTs prefer PC over SAN which though enhance the electrical conductivity of the blends, they don't improve the interfacial properties and results in poor mechanical properties. Hence, an efficient strategy has been adopted here to simultaneously enhance the mechanical, electrical and microwave attenuation properties. Herein, the MWNTs were wrapped by PMMA via in situ polymerization of MMA (methyl methacrylate). This strategy resulted in the migration of PMMA modified MWNTs towards the blend's interface and resulted in an effective stress transfer across the interface leading to improved mechanical and dynamic mechanical properties. Interestingly, the bulk electrical conductivity of the blends was also enhanced, manifesting the improved dispersion of the MWNTs. The state of dispersion of the MWNTs and the phase morphology were assessed using scanning electron microscopy. The microwave attenuation properties were evaluated using a vector network analyzer (VNA) in the X and K-u-band frequencies. The blends with PMMA wrapped MWNTs manifested a -21 dB of shielding effectiveness which suggests attenuation of more than 99% of the incoming microwave radiation. More interestingly, the attenuation constant could be tuned here employing this unique strategy. This study clearly opens a new tool box in designing materials that show improved mechanical, dynamic mechanical, electrical conductivity and microwave shielding properties.

Tetrahedrites as thermoelectric materials: an overview

Tetrahedrites are natural earth-abundant minerals consisting of environmentally-friendly elements of copper and sulphur. Recently, research has been focused on the natural and synthetic minerals of tetrahedrite materials for thermoelectric applications. The thermoelectric figure of merit zT of around unity at similar to 723 K for many doped and natural tetrahedrite materials in the past 2-3 years was determined and this value is comparable to conventional p-type TE materials. In this review, a brief history of tetrahedrite materials is followed by information about its crystal structure and chemical bonding, electronic band structure and transport properties. Different synthesis approaches have been summarized. Also, this review outlines the effect of different doping elements on the thermoelectric properties of tetrahedrite materials, and the natural mineral tetrahedrite that can be used as thermoelectric materials.

Hetero-atom Doped Carbon Nanotubes for Dye Degradation and Oxygen Reduction Reaction

We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min(-1). The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes

In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established by single crystal X-ray diffraction analysis. Furthermore, a detailed experimental and theoretical study has been performed to understand the effect of substitution of symmetric and non-symmetric functional groups on optical, thermal and electrochemical properties of fluoranthene. These materials exhibit a deep blue emission and high PLQY in solution and solid state. The vacuum deposited, non-doped electroluminescent devices with the device structure ITO/NPD (15 nm)/CBP (15 nm)/EML (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al were fabricated and characterized. A systematic shift in the peak position of EL emission was observed from sky blue to bluish-green with EL maxima from 477 nm to 490 nm due to different functional groups on the periphery of fluoranthene. In addition, a high luminance of >= 2000 cd m(-2) and encouraging external quantum efficiency (EQE) of 1.1-1.4% were achieved. A correlation of the molecular structure with device performance has been established.

Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)(3) polysulphate: 3.8V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

Boron clusters in luminescent materials

In recent times, luminescent materials with tunable emission properties have found applications in almost all aspects of modern material sciences. Any discussion on the recent developments in luminescent materials would be incomplete if one does not account for the versatile photophysical features of boron containing compounds. Apart from triarylboranes and tetra-coordinate borate dyes, luminescent materials consisting of boron clusters have also found immense interest in recent times. Recent studies have unveiled the opportunities hidden within boranes, carboranes and metalloboranes, etc. as active constituents of luminescent materials. From simple illustrations of luminescence, to advanced applications in LASERs, OLEDs and bioimaging, etc., the unique features of such compounds and their promising versatility have already been established. In this review, recent revelations about the excellent photophysical properties of such materials are discussed.

Two-Phase Metallic Thermal Interface Materials Processed Through Liquid Phase Sintering Followed by Accumulative Roll Bonding

Thermal interface materials (TIMs) form a mechanical and thermal link between a heat source and a heat sink. Thus, they should have high thermal conductivity and high compliance to efficiently transfer heat and accommodate any differential strain between the heat source and the sink, respectively. This paper reports on the processing and the characterization of potential metallic TIM composite solders comprising of Cu, a high conductivity phase, uniformly embedded in In matrix, a highly compliant phase. We propose the fabrication of such a material by a two-step fabrication technique comprising of liquid phase sintering (LPS) followed by accumulative roll bonding (ARB). To demonstrate the efficacy of the employed two-step processing technique, an In-40 vol. % Cu composite solder was produced first using LPS with short sintering periods (30 or 60 s at 160 degrees C) followed by ARB up to five passes, each pass imposing a strain of 50%. Mechanical response and electrical and thermal conductivities of the fabricated samples were evaluated. It was observed that processing through ARB homogenizes the distribution of Cu in an In matrix, disintegrates the agglomerates of Cu powders, and also significantly increases thermal and electrical conductivities, almost attaining theoretically predicted values, without significantly increasing the flow stress. Furthermore, the processing technique also allows the insertion of desired foreign species, such as reduced graphene oxide, in In-Cu for further enhancing a target property, such as electrical conductivity.

Optical-Phonon-Limited High-Field Transport in Layered Materials

An optical-phonon-limited velocity model has been employed to investigate high-field transport in a selection of layered 2-D materials for both, low-power logic switches with scaled supply voltages, and high-power, high-frequency transistors. Drain currents, effective electron velocities, and intrinsic cutoff frequencies as a function of carrier density have been predicted, thus providing a benchmark for the optical-phonon-limited high-field performance limits of these materials. The optical-phonon-limited carrier velocities for a selection of multi-layers of transition metal dichalcogenides and black phosphorus are found to be modest compared to their n-channel silicon counterparts, questioning the utility of biasing these devices in the source-injection dominated regime. h-BN, at the other end of the spectrum, is shown to be a very promising material for high-frequency, high-power devices, subject to the experimental realization of high carrier densities, primarily due to its large optical-phonon energy. Experimentally extracted saturation velocities from few-layer MoS2 devices show reasonable qualitative and quantitative agreement with the predicted values. The temperature dependence of the measured v(sat) is discussed and compared with the theoretically predicted dependence over a range of temperatures.

Conceptual design of three-dimensional scaffolds of powder-based materials for bone tissue engineering applications

Purpose - The purpose of this paper is to investigate the possibility to construct tissue-engineered bone repair scaffolds with pore size distributions using rapid prototyping techniques. Design/methodology/approach - The fabrication of porous scaffolds with complex porous architectures represents a major challenge in tissue engineering and the design aspects to mimic complex pore shape as well as spatial distribution of pore sizes of natural hard tissue remain unexplored. In this context, this work aims to evaluate the three-dimensional printing process to study its potential for scaffold fabrication as well as some innovative design of homogeneously porous or gradient porous scaffolds is described and such design has wider implication in the field of bone tissue engineering. Findings - The present work discusses biomedically relevant various design strategies with spatial/radial gradient in pore sizes as well as with different pore sizes and with different pore geometries. Originality/value - One of the important implications of the proposed novel design scheme would be the development of porous bioactive/biodegradable composites with gradient pore size, porosity, composition and with spatially distributed biochemical stimuli so that stem cells loaded into scaffolds would develop into complex tissues such as those at the bone-cartilage interface.

A dilation-driven vortex flow in sheared granular materials explains a rheometric anomaly

Granular flows occur widely in nature and industry, yet a continuum description that captures their important features is yet not at hand. Recent experiments on granular materials sheared in a cylindrical Couette device revealed a puzzling anomaly, wherein all components of the stress rise nearly exponentially with depth. Here we show, using particle dynamics simulations and imaging experiments, that the stress anomaly arises from a remarkable vortex flow. For the entire range of fill heights explored, we observe a single toroidal vortex that spans the entire Couette cell and whose sense is opposite to the uppermost Taylor vortex in a fluid. We show that the vortex is driven by a combination of shear-induced dilation, a phenomenon that has no analogue in fluids, and gravity flow. Dilatancy is an important feature of granular mechanics, but not adequately incorporated in existing models.

Understanding the Growth of Interfacial Reaction Product Layers between Dissimilar Materials

When one starts to analyze the evolution of the interfacial reaction product layers between dissimilar materials it is often found out that as the number of interacting species grows, the complexity of the analysis increases extremely rapidly. It may even appear that the task is just too difficult to be completed. In this article we present the thermodynamic-kinetic method, which can be used to rationalize the evolution of interfacial reaction layers and bring back the physics to the analyses. The method is conceptually very simple. It combines energetics-what can happen-with kinetics-how fast things take place. Yet the method is flexible enough that it can utilize quantitative and qualitative data starting from the atomistic simulations up to the experiments carried out with bulk materials. Several examples about how to utilize this method in material scientific problems are given.

Thermoelectric Properties of In-Doped Cu2ZnGeSe4

Recently, much research has been focused on finding new thermoelectric materials. Cu-based quaternary chalcogenides that belong to A(2)BCD(4) (A = Cu; B = Zn, Cd; C = Sn, Ge; D = S, Se, Te) are wide band gap materials and one of the potential thermoelectric materials due to their complex crystal structures. In this study, In-doped quaternary compounds Cu2ZnGe1-xInxSe4 (x = 0, 0.025, 0.05, 0.075, 0.1) were prepared by a solid state synthesis method. Powder x-ray diffraction patterns of all the samples showed a tetragonal crystal structure (space group I-42m) of the main phase with a trace amount of impurity phases, which was further confirmed by Rietveld analysis. The elemental composition of all the samples showed a slight deviation from the nominal composition with the presence of secondary phases. All the transport properties were measured in the temperature range 373-673 K. The electrical resistivity of all the samples initially decreased up to similar to 470 K and then increased with increase in temperature upto 673 K, indicating the transition from semiconducting to metallic behavior. Positive Seebeck coefficients for all the samples revealed that holes are the majority carriers in the entire temperature range. The substitution of In3+ on Ge4+ introduces holes and results in the decrease of resistivity as well as the Seebeck coefficient, thereby leading to the optimization of the power factor. The lattice thermal conductivity of all the samples decreased with increasing temperature, indicating the presence of phonon-phonon scattering. As a result, the thermoelectric figure of merit (zT) of the doped sample showed an increase as compared to the undoped compound.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

Effective thermal conductivity of reactive packed beds of hydriding materials

Applications of hydriding materials for solid state hydrogen storage, hydrogen compression, thermal energy storage and sorption heating and cooling systems have been demonstrated successfully. However, the performance of these devices significantly depends upon heat and mass transfer characteristics of the reactive packed beds. One of the important parameters regulating heat and mass transfer in the hydriding bed is its effective thermal conductivity (ETC), which is dependent on several operating parameters such as pressure and temperature. ETC also varies significantly due to the variation of hydrogen concentration during the hydriding and dehydriding processes. Based on the extensive studies done by the authors on ETC of metal hydride beds, a review of experimental methods, mathematical studies and augmentation techniques is presented in this paper, with emphasis on the effects of operating parameters on ETC. (C) 2016 Elsevier Ltd. All rights reserved.