Digestive ripening: a synthetic method par excellence for core-shell, alloy, and composite nanostructured materials

The solvated metal atom dispersion (SMAD) method has been used for the synthesis of colloids of metal nanoparticles. It is a top-down approach involving condensation of metal atoms in low temperature solvent matrices in a SMAD reactor maintained at 77 K. Warming of the matrix results in a slurry of metal atoms that interact with one another to form particles that grow in size. The organic solvent solvates the particles and acts as a weak capping agent to halt/slow down the growth process to a certain extent. This as-prepared colloid consists of metal nanoparticles that are quite polydisperse. In a process termed as digestive ripening, addition of a capping agent to the as-prepared colloid which is polydisperse renders it highly monodisperse either under ambient or thermal conditions. In this, as yet not well-understood process, smaller particles grow and the larger ones diminish in size until the system attains uniformity in size and a dynamic equilibrium is established. Using the SMAD method in combination with digestive ripening process, highly monodisperse metal, core-shell, alloy, and composite nanoparticles have been synthesized. This article is a review of our contributions together with some literature reports on this methodology to realize various nanostructured materials.

Multi-component, Self-assembled, Functional Soft Materials

Supramolecular chemistry is an emerging tool for devising materials that can perform specified functions. The self-assembly of facially amphiphilic bile acid molecules has been extensively utilized for the development of functional soft materials. Supramolecular hydrogels derived from the bile acid backbone act as useful templates for the intercalation of multiple components. Based on this, synthesis of gel-nanoparticle hybrid materials, photoluminescent coating materials, development of a new enzyme assay technique, etc. were achieved in the author's laboratory. The present account highlights some of these achievements.

Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions

Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

Soil stabilization with waste materials based binder

This paper describes a laboratory trial to study the effectiveness of a waste-based binder to stabilize expansive soils. The proposed binders viz., Fly ash and/or Ground granulated Blast furnace slag (GGBS) were mixed with the expansive soil along with a small amount of lime to increase soil pH and enable pozzolanic reactions. The geotechnical characteristics of the various combinations of samples were investigated through the compaction tests, unconfined compression tests etc. It was found that the addition of GGBS with and without fly ash and lime has significant influence on the geotechnical characteristics of the soil.

Tribological response of soft materials sliding against hard surface textures at various numbers of cycles

In the present investigation, various kinds of textures were attained on the steel surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Pins made of pure Al, Al-4Mg alloy and pure Mg were then slid against prepared steel plate surfaces at various numbers of cycles using an inclined pin-on-plate sliding tester. Tests were conducted at a sliding velocity of 2mms(-1) in ambient conditions under both dry and lubricated conditions. Normal loads were increased up to 110N during the tests. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plate were measured using an optical profilometer. In the experiments, it was observed that the coefficient of friction and formation of a transfer layer (under dry and lubricated conditions) only depended on surface texture during the first few sliding cycles. The steady-state variation in the coefficient of friction under both dry and lubrication conditions was attributed to the self-organisation of texture of the surfaces at the interface during sliding. Copyright (C) 2012 John Wiley & Sons, Ltd.

Conditions for the onset of elastic and material instabilities in hyperelastic materials

Several constitutive inequalities have been proposed in the literature to quantify the notion that ‘stress increases with strain’ in an elastic material. Due to some inherent shortcomings in them, which we discuss, we propose a new tensorial criterion for isotropic materials. We also present necessary conditions in terms of elasticity tensors for the onset of elastic instabilities.

Cavitation in materials with distributed weak zones: Implications on the origin of brittle fracture in metallic glasses

Several experimental studies have shown that fracture surfaces in brittle metallic glasses (MGs) generally exhibit nanoscale corrugations which may be attributed to the nucleation and coalescence of nanovoids during crack propagation. Recent atomistic simulations suggest that this phenomenon is due to large spatial fluctuations in material properties in a brittle MG, which leads to void nucleation in regions of low atomic density and then catastrophic fracture through void coalescence. To explain this behavior, we propose a model of a heterogeneous solid containing a distribution of weak zones to represent a brittle MG. Plane strain continuum finite element analysis of cavitation in such an elastic-plastic solid is performed with the weak zones idealized as periodically distributed regions having lower yield strength than the background material. It is found that the presence of weak zones can significantly reduce the critical hydrostatic stress for the onset of cavitation which is controlled uniquely by the local yield properties of these zones. Also, the presence of weak zones diminishes the sensitivity of the cavitation stress to the volume fraction of a preexisting void. These results provide plausible explanations for the observations reported in recent atomistic simulations of brittle MGs. An analytical solution for a composite, incompressible elastic-plastic solid with a weak inner core is used to investigate the effect of volume fraction and yield strength of the core on the nature of cavitation bifurcation. It is shown that snap-cavitation may occur, giving rise to sudden formation of voids with finite size, which does not happen in a homogeneous plastic solid. (c) 2012 Elsevier Ltd. All rights reserved.

Photoelectrochemical oxidation of p-nitrophenol on an expanded graphite-TiO2 electrode

In the quest for more efficient photoanodes in the photoelectrochemical oxidation processes for organic pollutant degradation and mineralisation in water treatment, we present the synthesis, characterisation and photoelectrochemical application of expanded graphite-TiO2 composite (EG-TiO2) prepared using the sol-gel method with organically modified silicate. The Brunauer-Emmett-Teller surface area analyser, ultraviolet-visible diffuse reflectance, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry, Raman spectrometry and X-ray photoelectron spectroscopy were employed for the characterisation of the composites. The applicability of the EG-TiO2 as photoanode material was investigated by the photoelectrochemical degradation of p-nitrophenol as a target pollutant in a 0.1 M Na2SO4 (pH 7) solution at a current density of 5 mA cm(-2). After optimising the TiO2 loading, initial p-nitrophenol concentration, pH and current density, a removal efficiency of 62% with an apparent kinetic rate constant of 10.4 x 10(-3) min(-1) was obtained for the photoelectrochemical process as compared to electrochemical oxidation and photolysis, where removal efficiencies of 6% and 24% were obtained respectively after 90 min. Furthermore, the EG-TiO2 electrode was able to withstand high current density due to its high stability. The EG-TiO2 electrode was also used to degrade 0.3 x 10(-4) M methylene blue and 0.1 x 10(-4) M Eosin Yellowish, leading to 94% and 47% removal efficiency within 120 reaction time. This confirms the suitability of the EG-TiO2 electrode to degrade other organic pollutants.

Employing denaturation for rapid electrochemical detection of myoglobin using TiO2 nanotubes

An alternative antibody-free strategy for the rapid electrochemical detection of cardiac myoglobin has been demonstrated here using hydrothermally synthesized TiO2 nanotubes (Ti-NT). The denaturant induced unfolding of myoglobin led to easy access of the deeply buried electroactive heme center and thus the efficient reversible electron transfer from protein to electrode surface. The sensing performance of the Ti-NT modified electrodes were compared vis a vis commercially available titania and GCEs. The tubular morphology of the Ti-NT led to facile transfer of electrons to the electrode surface, which eventually provided a linear current response (obtained from cyclic voltammetry) over a wide range of Mb concentration. The sensitivity of the Ti-NT based sensor was remarkable and was equal to 18 mu A mg(-1) ml (detection limit = 50 nM). This coupled with the rapid analysis time of a few tens of minutes (compared to a few days for ELISA) demonstrates its potential usefulness for the early detection of acute myocardial infarction (AMI).

Gibbs energy of formation of Ca7V4O17

Thermodynamic properties of Ca7V4O17 are measured for the first time using a solid-state electrochemical cell incorporating single crystal of CaF2 as the electrolyte over the temperature range from (900 to 1175) K. An equimolar mixture of CaO and CaF2 is used as the reference electrode and a mixture of Ca3V2O8, Ca7V4O17 and CaF2 as the measuring electrode. Both the electrodes are placed under flowing oxygen gas at ambient pressure. The standard Gibbs energy change for the reaction: 2Ca(3)V(2)O(8) + CaO -> Ca7V4O17; which is related to the chemical potential of CaO in the two-phase region (Ca3V2O8 + Ca7V4O17) of the pseudo-binary system CaO + V2O5, is obtained from the electromotive force of the cell as: Delta(r)G(o) +/- 127/(J . mol(-1)) = Delta mu(CaO) = -11453 + 8.273(T/K). The derived standard enthalpy of formation of Ca7V4O17 from elements in their normal standard states is ( 8208.97 +/- 8) kJ . mol (1) and its standard entropy is (560.05 +/- 7.5) J . K (1) . mol (1), both at T = 298.15 K. The results indicate that Ca7V4O17 decomposes into Ca3V2O8 and CaO at T = (1384 +/- 3) K.

Extraordinary supercapacitor performance of heavily nitrogenated graphene oxide obtained by microwave synthesis

Heavily nitrogenated graphene oxide containing similar to 18 wt% nitrogen, prepared by microwave synthesis with urea as the nitrogen source, shows outstanding performance as a supercapacitor electrode material, with the specific capacitance going up to 461 F g(-1).

Rheometry of dense granular materials: the crucial effects of gravity and confining walls

We describe here the rheological response of dense, slowly deforming granular materials to shear in a cylindrical Couette cell. All components of the stress on the outer cylinder are measured pointwise as a function of the depth, for different methods of construction of the bed that presumably lead to distinct fabrics. The static stress profiles for the different construction protocols are different, but a stress profile that is independent of construction history emerges when the granular column is sheared for sufficient time, in accord with the predictions of plasticity theories. However the qualitative features of the the stress profile under shear differs radically from the predictions of plasticity theories and data reported in earlier studies. We discuss a hypothesis for the anomalous stress profiles that was proposed recently by us, and the ways in which further experiments may to conducted to verify it.

Experimental Studies on the Kinematics of Cutting in Granular Materials

Slow flow in granular materials is characterized by high solid fraction and sustained inter-particle interaction. The kinematics of trawling or cutting is encountered in processes such as locomotion of organisms in sand; trawl gear movement on a soil deposit; plow movement; movement of rovers, earth moving equipment etc. Additionally, this configuration is very akin to shallow drilling configuration encountered in the mining and petroleum industries. An experimental study has been made in order to understand velocity and deformation fields in cutting of a model rounded sand. Under nominal plane strain conditions, sand is subjected to orthogonal cutting at different tool-rake angles. High-resolution optical images of the region of cutting were obtained during the flow of the granular ensemble around the tool. Interesting kinematics underlying the formation of a chip and the evolution of the deformation field is seen in these experiments. These images are also analyzed using a PIV algorithm and detailed information of the deformation parameters such as velocity, strain rate and volume change is obtained.

Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries

Ellagic acid, a naturally occurring polyphenol, extracted from pomegranate husk, is found to be a very good organic electrode material for rechargeable lithium batteries with high reversible capacities of similar to 450 and 200 mA h g(-1) at C/10 and C/2.5 discharge rates, respectively; ex situ NMR studies reveal possible lithiation-delithiation modes at different stages of the charge-discharge process.

Rheometry of granular materials in cylindrical Couette cells: Anomalous stress caused by gravity and shear

The cylindrical Couette device is commonly employed to study the rheology of fluids, but seldom used for dense granular materials. Plasticity theories used for granular flows predict a stress field that is independent of the shear rate, but otherwise similar to that in fluids. In this paper we report detailed measurements of the stress as a function of depth, and show that the stress profile differs fundamentally from that of fluids, from the predictions of plasticity theories, and from intuitive expectation. In the static state, a part of the weight of the material is transferred to the walls by a downward vertical shear stress, bringing about the well-known Janssen saturation of the stress in vertical columns. When the material is sheared, the vertical shear stress changes sign, and the magnitudes of all components of the stress rise rapidly with depth. These qualitative features are preserved over a range of the Couette gap and shear rate, for smooth and rough walls and two model granular materials. To explain the anomalous rheological response, we consider some hypotheses that seem plausibleapriori, but showthat none survive after careful analysis of the experimental observations. We argue that the anomalous stress is due to an anisotropic fabric caused by the combined actions of gravity, shear, and frictional walls, for which we present indirect evidence from our experiments. A general theoretical framework for anisotropic plasticity is then presented. The detailed mechanics of how an anisotropic fabric is brought about by the above-mentioned factors is not clear, and promises to be a challenging problem for future investigations. (C) 2013 AIP Publishing LLC.