First principles calculations of H-storage in sorption materials

A review of various contributions of first principles calculations in the area of hydrogen storage, particularly for the carbon-based sorption materials, is presented. Carbon-based sorption materials are considered as promising hydrogen storage media due to their light weight and large surface area. Depending upon the hybridization state of carbon, these materials can bind the hydrogen via various mechanisms, including physisorption, Kubas and chemical bonding. While attractive binding energy range of Kubas bonding has led to design of several promising storage systems, in reality the experiments remain very few due to materials design challenges that are yet to be overcome. Finally, we will discuss the spillover process, which deals with the catalytic chemisorption of hydrogen, and arguably is the most promising approach for reversibly storing hydrogen under ambient conditions.

Size-dependent density of nanoparticles and nanostructured materials

We discuss the size-dependent density of nanoparticles and nanostructured materials keeping the recent experimental results in mind. The density is predicted to increase with decreasing size for nanoparticles but it can decrease with size for nanostructured materials that corroborates the experimental results reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Carbonaceous nickel oxide nano-composites: as electrode materials in electrochemical capacitor applications

Carbonaceous nickel oxide powder samples have been synthesized from an adducted nickel beta-ketoester complex used as a ``single source precursor'' through a solution-based microwave-assisted chemical route. Comprehensive analysis of the resulting powder material has been carried out using various characterization techniques. These analysis reveal that, depending on the solvent used, either NiO/C or Ni/NiO/C composites are formed, wherein Ni and/or NiO nanocrystals are enveloped in amorphous carbon. As the components emerge from the same molecular source, the composites are homogeneous on a fine scale, making them promising electrode materials for supercapacitors. Electrochemical capacitive behavior of these oxide composites is studied in a three-electrode configuration. With a specific capacitance of 113 F g(-1), Ni/NiO/C is superior to NiO/C as capacitor electrode material, in 0.1 M Na2SO4 electrolyte. This is confirmed by impedance measurements, which show that charge-transfer resistance and equivalent series resistance are lower in Ni/NiO/C than in NiO/C, presumably because of the presence of metallic nickel in the former. The cyclic voltammograms are nearly rectangular and the electrodes display excellent cyclability in different electrolytes: Na2SO4, KOH and Ca(NO3)(2)center dot 4H(2)O. Specific capacitance as high as 143 F g(-1), is measured in Ca(NO3)(2)center dot 4H(2)O electrolyte.

Dielectric and electrical conductivity properties of multi-stage spark plasma sintered HA-CaTiO3 composites and comparison with conventionally sintered materials

One of the different issues limiting the wider application of monolithic hydroxyapatite (HA) as an ideal bone replacement material is the lack of reasonably good electrical transport properties. The comprehensive electrical property characterization to evaluate the efficacy of processing parameters in achieving the desired combination of electroactive properties is considered as an important aspect in the development of HA-based bioactive material. In this perspective, the present work reports the temperature (RT-200 degrees C) and frequency (100 Hz-1 MHz) dependent dielectric properties and AC conductivity for a range of HA-CaTiO3 (HA-CT) composites, densified using both conventional pressureless sintering in air as well as spark plasma sintering in vacuum. Importantly, the AC conductivity of spark plasma sintered ceramics similar to upto 10(-5) (Omega cm)(-1)] are found to be considerably higher than the corresponding pressureless sintered ceramics similar to upto 10(-8) (Omega cm)(-1)]. Overall, the results indicate the processing route dependent functional properties of HA-CaTiO3 composites as well as related advantages of spark plasma sintering route. (C) 2013 Elsevier Ltd. All rights reserved.

In vitro/In vivo assessment and mechanisms of toxicity of bioceramic materials and its wear particulates

With the progress in modern technological research, novel biomaterials are being largely developed for various biomedical applications. Over the past two decades, most of the research focuses on the development of a new generation of bioceramics as substitutes for hard tissue replacement. In reference to their application in different anatomical locations of a patient, newly developed bioceramic materials can potentially induce a toxic/harmful effect to the host tissues. Therefore, prior to clinical testing, relevant biochemical screening assays are to be performed at the cellular and molecular level, to address the issues of biocompatibility and long term performance of the implants. Along with testing strategies in the bulk material toxicity, a detailed evaluation should also be conducted to determine the toxicity of the wear products of the potential bioceramics. This is important as the bioceramics are intended to be implanted in patients with longer life expectancy and notwithstanding, the material will eventually release finer (mostly nanosized) sized debris particles due to continuous wear at articulating surfaces in the hostile corrosive environment of the human body. The wear particulates generated from a biocompatible bioceramic may act in a different way, inducing early/late aseptic loosening at the implant site, resulting in osteolysis and inflammation. Hence, a study on the chronic effects of the wear particulates, in terms of local and systemic toxicity becomes the major criteria in the toxicity evaluation of implantable bioceramics. In this broad perspective, this article summarizes some of the currently used techniques and knowledge in assessing the in vitro and in vivo cytotoxicity and genotoxicity of bioceramic implant materials. It also addresses the need to conduct a broad evaluation before claiming the biocompatibility and clinical feasibility of any new biomaterial. This review also emphasizes some of the case studies based on the experimental designs that are currently followed and its importance in the context of clinical applications.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

Si-mediated fabrication of reduced graphene oxide and its hybrids for electrode materials

Here, we demonstrate a Si-mediated environmentally friendly reduction of graphene oxide (GO) and the fabrication of its hybrids with multiwall carbon nanotubes and nanofibers. The reduction of GO is facilitated by nascent hydrogen generated by the reaction between Si and KOH at similar to 60 degrees C. The overall process takes 5 to 7 minutes and 10 to 15 mu m of Si is consumed each time. We show that Si can be used multiple times and the rGO based hybrids can be used for electrode materials.

Sulfate Chemistry for High-Voltage Insertion Materials: Synthetic, Structural and Electrochemical Insights

Rechargeable batteries based on Li and Na ions have been growing leaps and bounds since their inception in the 1970s. They enjoy significant attention from both the fundamental science point of view and practical applications ranging from portable electronics to hybrid vehicles and grid storage. The steady demand for building better batteries calls for discovery, optimisation and implementation of novel positive insertion (cathode) materials. In this quest, chemists have tried to unravel many future cathode materials by taking into consideration their eco-friendly synthesis, material/process economy, high energy density, safety, easy handling and sustainability. Interestingly, sulfate-based cathodes offer a good combination of sustainable syntheses and high energy density owing to their high-voltage operation, stemming from electronegative SO42- units. This review delivers a sneak peak at the recent advances in the discovery and development of sulfate-containing cathode materials by focusing on their synthesis, crystal structure and electrochemical performance. Several family of cathodes are independently discussed. They are 1) fluorosulfates AMSO(4)F], 2) bihydrated fluorosulfates AMSO(4)F2H(2)O], 3) hydroxysulfate AMSO(4)OH], 4) bisulfates A(2)M(SO4)(2)], 5) hydrated bisulfates A(2)M(SO4)(2)nH(2)O], 6) oxysulfates Fe-2(SO4)(2)O] and 7) polysulfates A(2)M(2)(SO4)(3)]. A comparative study of these sulfate-based cathodes has been provided to offer an outlook on the future development of high-voltage polyanionic cathode materials for next-generation batteries.

Lithium metal borate (LiMBO3) family of insertion materials for Li-ion batteries: a sneak peak

Rechargeable lithium-ion battery remains the leading electrochemical energy-storage device, albeit demanding steady effort of design and development of superior cathode materials. Polyanionic framework compounds are widely explored in search for such cathode contenders. Here, lithium metal borate (LiMBO3) forms a unique class of insertion materials having the lowest weight polyanion (i. e., BO33-), thus offering the highest possible theoretical capacity (ca. 220 mAh/g). Since the first report in 2001, LiMBO3 has rather slow progress in comparison to other polyanionic cathode systems based on PO4, SO4, and SiO4. The current review gives a sneak peak to the progress on LiMBO3 cathode systems in the last 15 years highlighting their salient features and impediments in cathode implementation. The synthesis and structural aspects of borate family are described along with the critical analysis of the electrochemical performance of borate family of insertion materials.

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).

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.

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.