Studies on dielectric behavior of insulator‐conductor composites

This paper describes the dielectric behavior of an insulator‐conductor composite, namely, the wax‐graphite composite. The variation of specific capacitance of these composites with parameters such as volume fraction and grain size of the conducting particles and temperature has been studied. These observed variations have been explained using the same model [C. Rajagopal and M. Satyam, J. Appl. Phys. 49, 5536 (1978)] which explains electrical conduction in composites. The specific capacitance of these materials appears to be governed by the contact capacitance between the conducting particles and the number of contacts each particle has with its neighbors. The variation of specific capacitance with temperature is attributed to the change in contact area.

Griffiths phase-like behavior and spin-phonon coupling in double perovskite Tb(2)NiMnO(6)

The Griffiths phase-like features and the spin-phonon coupling effects observed in Tb(2)NiMnO(6) are reported. The double perovskite compound crystallizes in monoclinic P2(1)/n space group and exhibits a magnetic phase transition at T(c) similar to 111 K as an abrupt change in magnetization. A negative deviation from ideal Curie-Weiss law exhibited by 1/chi(T) curves and less-than-unity susceptibility exponents from the power-law analysis of inverse susceptibility are reminiscent of Griffiths phase-like features. Arrott plots derived from magnetization isotherms support the inhomogeneous nature of magnetism in this material. The observed effects originate from antiferromagnetic interactions that arise from inherent disorder in the system. Raman scattering experiments display no magnetic-order-induced phonon renormalization below Tc in Tb(2)NiMnO(6), which is different from the results observed in other double perovskites and is correlated to the smaller size of the rare earth. The temperature evolution of full-width-at-half-maximum for the stretching mode at 645 cm(-1) presents an anomaly that coincides with the magnetic transition temperature and signals a close connection between magnetism and lattice in this material. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3671674]

Dependence of Protein Adsorption on Wetting Behavior of UHMWPE-HA-Al2O3-CNT Hybrid Biocomposites

Ultrahigh-molecular-weight polyethylene (UHMWPE) is used as an articulating surface in total hip and knee joint replacement. In order to enhance long-term durability/wear resistance properties, UHMWPE-based polymer-ceramic hybrid composites are being developed. Surface properties such as wettability and protein adsorption alter with reinforcement or with change in surface chemistry. From this perspective, the wettability and protein adsorption behavior of compression-molded UHMWPE-hydroxyapatite (HA)-aluminum oxide (Al2O3)-carbon nanotube (CNT) composites were analyzed in conjunction with surface roughness. The combined effect of Al2O3 and CNT shows enhancement of the contact angle by similar to 37A degrees compared with the surface of the UHMWPE matrix reinforced with HA. In reference to unreinforced UHMWPE, protein adsorption density also increased by similar to 230% for 2 wt.%HA-5 wt.%Al2O3-2 wt.%CNT addition to UHMWPE. An important conclusion is that the polar and dispersion components of the surface free energy play a significant role in wetting and protein adsorption than do the total free energy or chemistry of the surface. The results of this study have major implications for the biocompatibility of these newly developed biocomposites.

Structural-modulation-driven low-temperature glassy behavior in SrRuO3

We present a critical investigation on the structural, magnetic, and magnetotransport properties of two sets of polycrystalline SrRuO3 samples with uniquely defined ferromagnetic transition temperatures. The ac magnetic susceptibility study exhibits the remarkable memory effect, a distinct characteristic of glassy behavior, at low temperatures. The transport study suggests a crossover from Fermi-liquid to non-Fermi-liquid behavior. Most strikingly, the temperature-dependent magnetoresistance exhibits two distinct dips (one around ferromagnetic ordering temperature and the other around 50 K), resembling a double-well potential in appearance. In addition, the temperature-dependent coercive field shows a plateau around 50 K. An attempt has been made to employ neutron diffraction to understand the genesis of such unusual low-temperature magnetic features. From the neutron-diffraction study, we find the evidence for changes in the unit-cell lattice parameters around 60 K and, thus, believe that the low-temperature anomalous magnetic response is closely intertwined to lattice-parameter change.

Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/RGO composite fabricated by a facile one pot synthesis and its lithium storage behavior

In this work, Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/reduced graphene oxide (RGO) composites have been prepared through a facile hydrothermal route in acidic medium at 200 degrees C for 2 days. The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, UV-Visible spectroscopy, Thermogravimetric analysis (TGA), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and electrochemical discharge-charge cycling in lithium ion battery. XRD pattern exhibits the layered structure of Na0.33V2O5 center dot 1.5H(2)O and the composite shows the presence of RGO at 2 theta = 25.8 degrees. FTIR spectrum shows that the band at 760 cm(-1) could be assigned to a V-OH2 stretching mode due to coordinated water. Raman spectrum shows that the band at 264 cm(-1) is due to the presence of water molecules between the layers. FESEM/TEM micrographs reveal that the products consist of nanorings of inner diameter 5 mu m and thickness of the ring is found to be 200-300 nm. Addition of exfoliated graphene oxide (EGO) destroys the formation of rings. The reduction of EGO sheets into RGO is also evidenced by the red shift of the absorbance peak from 228 nm to 264 nm. In this composite Na0.33V2O5 center dot 1.5H(2)O nanorods may adhere to the surface of RGO and/or embedded in the RGO nanosheets. As a result, an effective three-dimensional conducting network was formed by bridging RGO nanosheets, which can facilitate electron transport effectively and thus improve the kinetics and rate performance of Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods. The Na0.33V2O5 center dot 1.5H(2)O/RGO composites exhibited a discharge capacity of 340 mAh g(-1) at a current density of 0.1 mA g(-1) and also an improved cyclic stability. RGO plays a `flexible confinement' function to enwrap Na0.33V2O5 center dot 1.5H(2)O nanorods, which can compensate for the volume change and prevent the detachment and agglomeration of pulverized Na0.33V2O5 center dot 1.5H(2)O, thus extending the cycling life of the electrode. A probable reaction mechanism for the formation of Na0.33V2O5 center dot 1.5H(2)O nanorings is also discussed. (C) 2012 Elsevier B.V. All rights reserved.

Tensile behavior of a free-standing Pt-aluminide (PtAl) bond coat

The tensile behavior of a high activity stand-alone Pt-aluminide (PtAl) bond coat was evaluated by the micro-tensile test method at various temperatures (room temperature to 1100 degrees C) and strain rates (10(-5) s(-1)-10(-1) s(-1).) At all strain rates, the stress strain behavior of the stand-alone coating was significantly affected by the variation in temperature. The stress strain response was linear, indicating brittle behavior, at temperatures below the brittle ductile transition temperature (BDTT). The coating exhibited appreciable ductility (up to 2%) above the BDTT. The strength (both yield stress and ultimate tensile strength) of the coating decreased and its ductility increased with increasing temperature above the BDTT. The tensile behavior of the coating was sensitive to strain rate in the ductile regime, with its strength increasing with increasing strain rate at any given temperature. The BDTT of the coating was found to increase with increasing with increasing strain rate. The coating exhibited two distinct mechanisms of deformation above the BDTT. The transition temperature for the change of deformation mechanism also increased with increasing strain rate. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photophysical behavior of poly(propyl ether imine) dendrimer in the presence of nitroaromatic compounds

This paper deals with a study of the photophysical property of poly(ether imine) (PETIM) dendritic macromolecule in the presence of aromatic compounds. The inherent photoluminescence property of the dendrimer undergoes quenching in the presence of guest aromatic nitro-compounds. From life-time measurements study, it is inferred that the lifetimes of luminescent species of the dendrimer are not affected with nitrophenols as guest molecules, whereas nitrobenzenes show a marginal change in the lifetimes of the species. Raman spectral characteristic of the macromolecular host-guest complex is conducted in order to identify conformational change of the dendrimer and a significant change in the stretching frequencies of methylene moieties of the dendrimer is observed for the complex with 1,3,5-trinitrobenzene, when compared to other complexes, free host and guest molecules. The photophysical behavior of electron-rich, aliphatic, neutral dendritic macromolecule in the presence of electron-deficient aromatic molecules is illustrated in the present study. (C) 2012 Elsevier B.V. All rights reserved.

Effect of Layered MoS2 Nanoparticles on the Frictional Behavior and Microstructure of Lubricating Greases

Lithium stearate soap and layered MoS2 nanoparticles encapsulated in lithium stearate soap are prepared in the laboratory, and their lubricating properties are compared with respect to the particle and particle concentration. The tribotracks after friction test was investigated with Raman Spectroscopy, scanning electron microscopy (SEM) and 3D optical profilometry to understand the action mechanism. The status of the soap particles on a tribotrack changes with time, contact pressure and sliding speed. At low pressure and speed, individual solid undeformed soap particle stand proud of the surface and the topography shows marginal difference with sliding time. In these conditions, no frictional difference between the performance of grease with and without the nanoparticles is observed. Increasing the contact pressure and temperature (low speed and high speed) has a dramatic effect as the soap particles melt and the liquid soap flows over the track releasing the hitherto encapsulated nanoparticles. Consequently, the soap smears the track like a liquid, and the nanoparticles now come directly into the interface and are sheared to generate a low-friction tribofilm. At high particle concentration, the sliding time required for melting of the soap and release of MoS2 is reduced, and the tribofilm is more substantial and uniform consisting of smeared MoS2 and carboxylate soap as observed by SEM and 3D optical profilometry. A change in the Raman Spectra is observed with particle concentration, and this is related to morphology and microstructure of the tribofilm generated.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Acoustic phonon behavior of PbWO4 and BaWO4 probed by low temperature Brillouin spectroscopy

Temperature dependent acoustic phonon behavior of PbWO4 and BaWO4 using Brillouin spectroscopy has been explained for the first time. Low temperature Brillouin studies on PbWO4 and BaWO4 have been carried out from 320-20 K. In PbWO4, we observe a change in acoustic phonon mode behavior around 180 K. But in the case of BaWO4, we have observed two types of change in acoustic phonon mode behavior at 240 K and 130 K. The change in Brillouin shift omega and the slope d omega/dT are the order parameter for all kinds of phase transitions. Since we do not see hysteresis on acoustic phonon mode behavior in the reverse temperature experiments, these second order phase transitions are no related to structural phase change and could be related to acoustic phonon coupled electronic transitions. In PbWO4 he temperature driven phase transition at 180 K could be due to changes in he environment around he lead vacancy (V-pb(2-)) changes the electronic states. In the case of BaWO4, the phase transition at 240 K shows he decrease in penetration depth of WO3 impurity. So it becomes more metallic. The transition at 130 K could be he same electronic transitions as that of PbWO4 as function of temperature. The sound velocity and elastic moduli of BaWO4 shows that it could be the prominent material for acousto-optic device applications. (C) 2014 Elsevier Ltd. All rights reserved.

Model and parameter uncertainty in IDF relationships under climate change

Quantifying distributional behavior of extreme events is crucial in hydrologic designs. Intensity Duration Frequency (IDF) relationships are used extensively in engineering especially in urban hydrology, to obtain return level of extreme rainfall event for a specified return period and duration. Major sources of uncertainty in the IDF relationships are due to insufficient quantity and quality of data leading to parameter uncertainty due to the distribution fitted to the data and uncertainty as a result of using multiple GCMs. It is important to study these uncertainties and propagate them to future for accurate assessment of return levels for future. The objective of this study is to quantify the uncertainties arising from parameters of the distribution fitted to data and the multiple GCM models using Bayesian approach. Posterior distribution of parameters is obtained from Bayes rule and the parameters are transformed to obtain return levels for a specified return period. Markov Chain Monte Carlo (MCMC) method using Metropolis Hastings algorithm is used to obtain the posterior distribution of parameters. Twenty six CMIP5 GCMs along with four RCP scenarios are considered for studying the effects of climate change and to obtain projected IDF relationships for the case study of Bangalore city in India. GCM uncertainty due to the use of multiple GCMs is treated using Reliability Ensemble Averaging (REA) technique along with the parameter uncertainty. Scale invariance theory is employed for obtaining short duration return levels from daily data. It is observed that the uncertainty in short duration rainfall return levels is high when compared to the longer durations. Further it is observed that parameter uncertainty is large compared to the model uncertainty. (C) 2015 Elsevier Ltd. All rights reserved.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.