Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Experimental studies on the influence of intermediate principal stress and inclination on the mechanical behaviour of angular sands

A comprehensive experimental study has been made on angular sand to investigate various aspects of mechanical behavior. A hollow cylinder torsion testing apparatus is used in this program to apply a range of stress conditions on this angular quartzitic fine sand under monotonic drained shear. The effect of the magnitude and inclination of the principal stresses on an element of sand is studied through these experiments. This magnitude and inclination of the principal stresses are presented as an ``ensemble measure of fabric in sands''. This ensemble measure of fabric in the sands evolves through the shearing process, and reaches the final state, which indeed has a unique fabric. The sand shows significant variation in strength with changing inclination of the principal stresses. The locus of the final stress state in principal stress space is also mapped from these series of experiments. Additional aspects of non-coaxiality, a benchmarking exercise with a few constitutive models is presented here. This experimental approach albeit indirect shows that a unique state which is dependent on the fabric, density and confining stress exists. This suite of experiments provides a well-controlled data set for a clear understanding on the mechanical behavior of sands.

Tunable mechanical and thermal properties of ZnS/CdS core/shell nanowires

Using all-atom molecular dynamics (MD) simulations, we have studied the mechanical properties of ZnS/CdS core/shell nanowires. Our results show that the coating of a few-atomic-layer CdS shell on the ZnS nanowire leads to a significant change in the stiffness of the core/shell nanowires compared to the stiffness of pure ZnS nanowires. The binding energy between the core and shell region decreases due to the lattice mismatch at the core-shell interface. This reduction in binding energy plays an important role in determining the stiffness of a core/shell nanowire. We have also investigated the effects of the shell on the thermal conductivity and melting behavior of the nanowires.

Compressive and Flexural Properties of Functionally Graded Fly Ash Cenosphere-Epoxy Resin Syntactic Foams

The present study focuses on developing functionally graded syntactic foams (FGSFs) based on a layered co-curing technique. The FGSFs were characterized for compressive and flexural properties and compared with plain syntactic foams. The results showed that the specific compressive modulus was 3-67% higher in FGSFs compared to plain syntactic foams. FGSF exhibited 5-34% and 34-87% higher specific modulus and strength, respectively in flexural mode. The microscopic examinations of comparative responses of the filler and matrix to deformation suggest that the failure is dominated by the matrix. The gradient in the composition of syntactic foams helps in effectively distributing the stress throughout the microstructure and results in improved mechanical performance of syntactic foams. From the microscopy studies, it is evident that, the failure mechanism in the FGSF under flexural loading is governed by a crack that initiated on the tensile side of the specimen and propagated through the thickness to cause complete fracture. The microscopic observations further clearly demonstrate the existence of seamless interfaces between the layers and a clear difference in the cenosphere concentration across the interface, affirming the gradation in the prepared samples. The results show that appropriate compositions of FGSFs can be selected to develop materials with improved mechanical performance. POLYM. COMPOS., 36:685-693, 2015. (c) 2014 Society of Plastics Engineers

Lizards of the Thar Desert - Resource partitioning and community composition

How similar species co-exist in nature is a fundamental question in community ecology. Resource partitioning has been studied in desert lizard communities across four continents, but data from South Asia is lacking. We used area-constrained visual encounter surveys to study community composition and spatial and temporal resource partitioning in a lizard community during summer in the Thar Desert, western India, addressing an important biogeographic gap in knowledge. Twelve one-hectare grids divided into 25 m x 25 m plots were placed across four habitats barren dunes, stabilized dunes, grassland, and rocky hills. We recorded 1039 sightings of 12 species during 84 sampling sessions. Lizard abundance decreased in the order stabilized dunes > grassland > barren dunes > rocky hills; richness was in roughly the opposite order. Resource partitioning was examined for the seven commonest species. Overall spatial overlap was low (<0.6) between species pairs. Overlap was higher within habitats, but species showed finer separation through use of different microhabitat categories and specific spatial resources, as well as by positioning at different distances to vegetation. Diurnal species were also separated by peak time of activity. Space appears to be an important resource dimension facilitating coexistence in this desert lizard community. (C) 2015 Elsevier Ltd. All rights reserved.

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

Temperature Dependence of Mechanical Properties in Molecular Crystals

Quantitative evaluation of the mechanical behavior of molecular materials by a nanoindentation technique has gained prominence recently. However, all the reported data have been on room-temperature properties despite many interesting phenomena observed in them with variations in temperature. In this paper, we report the results of nanoindentation experiments conducted as a function of temperature, T, between 283 and 343 K, on the major faces of three organic crystals: saccharin, sulfathiazole (form 2), and L-alanine, which are distinct in terms of the number and strength of intermolecular interactions in them. Results show that elastic modulus, E, and hardness, H, decrease markedly with increasing T. While E decreases linearly with T, the variations in H with T are not so, and were observed to drop by similar to 50% over the range of T investigated. The slope of the linear fits to E vs T for the organic crystals was found to be around 1, which is considerably higher than the values of 0.3-0.5 reported in the literature for metallic, ionic, and covalently bonded crystalline materials. Possible implications of the observed remarkable changes in H for pharmaceutical manufacturing are highlighted.

Restoration Mechanisms During the Friction Stir Processing of Aluminum Alloys

In the current study, correlation of microstructure evolution with bulk crystallographic texture formation during friction stir processing (FSP) of commercial aluminum alloys has been attempted. Electron back-scattered diffraction and X-ray diffraction techniques were employed for characterizing the nugget zone of optimum friction stir processed samples. Volume fraction of measured texture components revealed that the texture formation in aluminum alloys is similar irrespective of the alloy composition. Recrystallization behavior during FSP was more of a composition dependent phenomenon.

Spatial modulation of the composition of a binary liquid near a repulsive wall

When a binary liquid is confined by a strongly repulsive wall, the local density is depleted near the wall and an interface similar to that between the liquid and its vapor is formed. This analogy suggests that the composition of the binary liquid near this interface should exhibit spatial modulation similar to that near a liquid-vapor interface even if the interactions of the wall with the two components of the liquid are the same. The Guggenheim adsorption relation quantifies the concentrations of two components of a binary mixture near a liquid-vapor interface and qualitatively states that the majority (minority) component enriches the interface for negative (positive) mixing energy if the surface tensions of the two components are not very different. From molecular dynamics simulations of binary mixtures with different compositions and interactions we find that the Guggenheim relation is qualitatively satisfied at wall-induced interfaces for systems with negative mixing energy at all state points considered. For systems with positive mixing energy, this relation is found to be qualitatively valid at low densities, while it is violated at state points with high density where correlations in the liquid are strong. This observation is validated by a calculation of the density profiles of the two components of the mixture using density functional theory with the Ramakrishnan-Yussouff free-energy functional. Possible reasons for the violation of the Guggenheim relation are discussed.

Mechanical properties of CNT-Bisphenol E cyanate ester-based CFRP nanocomposite developed through VARTM process

This paper reports on the effect of multiwall carbon nanotubes (CNTs) without and with chemical functionalization on the mechanical properties of Bisphenol E cyanate ester resin (BECy) based carbon fibre reinforced plastic (CFRP) laminated composites. BECy with its low viscosity, low moisture uptake and superior mechanical properties is selected for its application in CFRP laminates through the cost-effective Vacuum Assisted Resin Transfer Moulding (VARTM) process. However, unlike CNT-epoxy-CFRP composites, processing and performance issues such as dispersion of CNTs, chemical bonding with resin, functionalization effects, effects on mechanical properties, etc. for BECy-CNT-CFRP composite system are not well reported. The objective of this study is to improve the mechanical properties of BECy resin with small additions of CNTs and functionalized CNTs in CFRP laminates. CNTs and fCNTs are infused into BECy using ultrasonication and standard mixing methods. Improvements in Young's modulus and strength in tension, compression, shear, flexure and interlaminar shear strength are analysed. It is observed that addition of 0.5wt% CNTs effected for maximum mechanical properties of the resin and 1wt% CNTs for the mechanical properties of CNT-CFRP nanocomposite. Further, improvements obtained with fCNTs are marginal. Dispersion behaviour and effect of CNTs/fCNTs in load transfer corroborated with SEM pictures are presented. The enhanced mechanical properties realized in VARTM processing of BECy-CFRP laminate indicate clear advantage of CNT based modification of the process.

Simultaneous enhancement in mechanical strength, electrical conductivity, and electromagnetic shielding properties in PVDF-ABS blends containing PMMA wrapped multiwall carbon nanotubes

A unique approach was adopted to drive the multiwall carbon nanotubes (MWNTs) to the interface of immiscible PVDF-ABS blends by wrapping the nanotubes with a mutually miscible homopolymer (PMMA). A tailor made interface with an improved stress transfer was achieved in the blends with PMMA wrapped MWNTs. This manifested in an impressive 108% increment in the tensile strength and 48% increment in the Young's modulus with 3 wt% PMMA wrapped MWNTs in striking contrast to the neat blends. As the PMMA wrapped MWNTs localized at the interface of PVDF-ABS blends, the electrical conductivity could be tuned with respect to only MWNTs, which were selectively localized in the PVDF phase, driven by thermodynamics. The electromagnetic shielding properties were assessed using a vector network analyser in a broad range of frequency, X-band (8-12 GHz) and Ku-band (12-18 GHz). Interestingly, enhanced EM shielding was achieved by this unique approach. The blends with only MWNTs shielded the EM waves mostly by reflection however, the blends with PMMA wrapped MWNTs (3 wt%) shielded mostly by absorption (62%). This study opens new avenues in designing materials, which show simultaneous improvement in mechanical, electrical conductivity and EM shielding properties.

Tailored mechanical behavior of magnetic particles loaded carbon nanotube foam in presence of magnetic field

The compressive behavior of carbon nanotube (CNT) foam with an entangled microstructure has become an important research area due to its excellent energy absorption capability. This report presents a tailored mechanical behavior of CNT foam under an applied magnetic field when all CNTs in the foam are coated with magnetic nanoparticles. The presence of nanoparticles not only enhanced the stiffness of the foam to four times but also revealed a nonlinear variation in both the stress and energy absorption capability with the gradual increase of the magnetic field. Magnetization of both CNT and attached nanoparticles along the magnetic field direction are shown to play a crucial role in determining the dominant deformation mechanism.

Variation of Electrical Resistivity with High Pressure in Ge-Te-Sn Glasses: A Composition Dependent Study

The variation of normalized electrical resistivity in the system of glasses Ge15Te85-xSnx with (1 <= x <= 5) has been studied as a function of high pressure for pressures up to 9.5 GPa. It is found that with the increase in pressure, the resistivity decreases initially and shows an abrupt fall at a particular pressure, indicating the phase transition from semiconductor to near metallic at these pressures, which lie in the range 1.5-2.5 GPa, and then continues being metallic up to 9.5 GPa. This transition pressure is seen to decrease with the increase in the percentage content of tin due to increasing metallicity of tin. The semiconductor to near metallic transition is exactly reversible and may have its origin in a reduction of the band gap due to high pressure.

Composition dependent multiple structural transformations of myoglobin in aqueous ethanol solution: A combined experimental and theoretical study

Experimental studies (circular dichroism and ultra-violet (UV) absorption spectra) and large scale atomistic molecular dynamics simulations (accompanied by order parameter analyses) are combined to establish a number of remarkable (and unforeseen) structural transformations of protein myoglobin in aqueous ethanol mixture at various ethanol concentrations. The following results are particularly striking. (1) Two well-defined structural regimes, one at x(EtOH) similar to 0.05 and the other at x(EtOH) similar to 0.25, characterized by formation of distinct partially folded conformations and separated by a unique partially unfolded intermediate state at x(EtOH) similar to 0.15, are identified. (2) Existence of non-monotonic composition dependence of (i) radius of gyration, (ii) long range contact order, (iii) residue specific solvent accessible surface area of tryptophan, and (iv) circular dichroism spectra and UV-absorption peaks are observed. Interestingly at x(EtOH) similar to 0.15, time averaged value of the contact order parameter of the protein reaches a minimum, implying that this conformational state can be identified as a molten globule state. Multiple structural transformations well known in water-ethanol binary mixture appear to have considerably stronger effects on conformation and dynamics of the protein. We compare the present results with studies in water-dimethyl sulfoxide mixture where also distinct structural transformations are observed along with variation of co-solvent composition. (C) 2015 AIP Publishing LLC.

Dependence of ``critical cloud fraction' on aerosol composition

Recent studies, over regions influenced by biomass burning aerosol, have shown that it is possible to define a critical cloud fraction' (CCF) at which the aerosol direct radiative forcing switch from a cooling to a warming effect. Using 4 years of multi-satellite data analysis, we show that CCF varies with aerosol composition and changed from 0.28 to 0.13 from postmonsoon to winter as a result of shift from less absorbing to moderately absorbing aerosol. Our results indicate that we can estimate aerosol absorption from space using independently measured top of the atmosphere (TOA) fluxes Cloud Aerosol Lidar with Orthogonal Polarization-Moderate resolution Imaging Spectroradiometer-Clouds and the Earth's Radiant Energy System (CALIPSO-MODIS-CERES)] combined algorithms for example.