Complex structural phase transitions in slightly Ca modified Na0.5Bi0.5TiO3

A temperature dependent neutron powder diffraction study, in conjunction with dielectric and ferroelectric characterization, of slightly Ca modified Na0.5Bi0.5TiO3 (NBT) revealed an instability with regard to a non-polar orthorhombic (Pbnm) distortion above room temperature. This intermediate orthorhombic phase has earlier been reported for unmodified NBT by electron diffraction studies, but has never been captured by global (x-ray/neutron) diffraction techniques. Calcium substitution seems to amplify the magnitude of this intermediate orthorhombic distortion thereby making the corresponding superlattice reflections become visible in the neutron diffraction pattern. The study revealed the following sequence of very complex structural evolution with temperature: Cc -> Cc + Pbnm -> Pbnm + P4/mbm -> P4/mbm -> Pm (3) over barm.

Metal cholate hydrogels: versatile supramolecular systems for nanoparticle embedded soft hybrid materials

This work describes the formation of hydrogels from sodium cholate solution in the presence of a variety of metal ions (Ca2+, Cu2+, Co2+, Zn2+, Cd2+, Hg2+ and Ag+). Morphological studies of the xerogels by electron microscopy reveal the presence of helical nanofibres. The rigid helical framework in the calcium cholate hydrogel was utilised to synthesize hybrid materials (AuNPs and AgNPs). Doping of transition metal salts into the calcium cholate hydrogel brings out the possibility of synthesising metal sulphide nano-architectures keeping the hydrogel network intact. These novel gel-nanoparticle hybrid materials have encouraging application potentials.

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.

Preparation and characterization chemistry of nano-crystalline Ni-Cu-Zn ferrite

In submitted research; nanocrystalline powders having elements Ni0.5Cu0.25Zn0.25Fe2 xInxO4 with varied amounts of indium ( x = 0.0, 0.1, 0.2, 0.3 and 0.4) were grown-up by modified citrate to nitrate alchemy. The realism of single phase cubic spinel creation of the synthesized ferrite samples was studied by the DTA-TGA, XRD, SEM, EDX, FT-IR, VSM and dielectric measurements. SEM was applied to inspect the morphological variations and EDX was used to determine the compositional mass ratios. The studies on the dielectric constant (epsilon'), dielectric loss (epsilon `'), loss tangent (tan delta), ac conductivity (sigma(ac)), resistive and reactive parts of the impedance analysis (Z' and Z `') at room temperature were also carried out. The saturation magnetizations (Ms) were determined using the vibrating sample magnetometer (VSM). Ms. decreased with the increase In3+ doping content, as Fe3+ of 5(mu B) ions are replaced by In3+ of 5 mu(B) ions. (C) 2012 Elsevier B. V. All rights reserved.

Electrical transport characteristics of ZnO-Bi2O3-B2O3 glasses

Optically clear glasses in the ZnO-Bi2O3-B2O3 (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz-10 MHz)-independent dielectric characteristics associated with significantly low loss (D = 0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18 +/- 4 ppm A degrees C-1 in the 35-250 A degrees C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi3+ cations in their own and different local environment.

Strategies for the Synthesis of Graphene, Graphene Nanoribbons, Nanoscrolls and Related Materials

Single-layer graphene (SLG), the 3.4 angstrom thick two-dimensional sheet of sp(2) carbon atoms, was first prepared in 2004 by mechanical exfoliation of graphite crystals using the scotch tape technique. Since then, SLG has been prepared by other physical methods such as laser irradiation or ultrasonication of graphite in liquid media. Chemical methods of synthesis of SLG are more commonly used; the most popular involves preparation of single-layer graphene oxide followed by reduction with a stable reagent, often assisted by microwave heating. This method yields single-layer reduced graphene oxide. Other methods for preparing SLG include chemical vapour deposition over surfaces of transition metals such as Ni and Cu. Large-area SLG has also been prepared by epitaxial growth over SIC. Few-layer graphene (FLG) is prepared by several methods; arc discharge of graphite in hydrogen atmosphere being the most convenient. Several other methods for preparing FLG include exfoliation of graphite oxide by rapid heating, ultrasonication or laser irradiation of graphite in liquid media, reduction of few-layer graphene oxide, alkali metal intercalation followed by exfoliation. Graphene nanoribbons, which are rectangular strips of graphene, are best prepared by the unzipping of carbon nanotubes by chemical oxidation or laser irradiation. Many graphene analogues of inorganic materials such as MoS2, MoSe2 and BN have been prepared by mechanical exfoliation, ultrasonication and by chemical methods involving high-temperature or hydrothermal reactions and intercalation of alkali metals followed by exfoliation. Scrolls of graphene are prepared by potassium intercalation in graphite or by microwave irradiation of graphite immersed in liquid nitrogen.

Electrothermal Ageing of Epoxy Nanocomposites

Constant stress accelerated ageing experiments were conducted on unfilled epoxy and epoxy alumina nanocomposites with different filler loadings of 0.1, 1 and 5 wt%. Electrical (6 kV/mm), thermal (60 degrees C) and combined electrothermal (6 kV/mm and 60 degrees C) ageing experiments were performed for a duration of 250 h. The leakage current through the samples were continuously monitored and the variation in the tan delta values with ageing duration was also monitored. It was observed that the increase in the tan delta value with ageing duration was less for the epoxy alumina nanocomposites as compared to the unfilled epoxy. Dielectric spectroscopy measurements were performed on the samples before and after the ageing in the frequency range of 10(-2) to 10(6) Hz. The permittivity and tan delta values were found to increase in the low frequency range. The volume resistivity of unfilled epoxy and epoxy alumina nanocomposites were also measured before and after the ageing. The volume resistivity improved marginally for the thermally aged samples, but reduced for the electrically aged and the electrothermally aged samples. The decrease in the value of volume resistivity was more for the multistress aged unfilled epoxy samples as compared to the multistress aged epoxy alumina nanocomposites. It was also observed that the unfilled epoxy samples having a higher value of tan delta failed first. The time to failure of the samples showed an increasing trend with an increase in the nano filler loading of epoxy alumina nanocomposites.

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.

Studies on lithium L-ascorbate dihydrate: An interesting chiral nonlinear optical crystal

Lithium L-Ascorbate dihydrate (LLA) is a new metal organic nonlinear optical crystal belonging to the saccharide family. Single crystals of LLA were grown from aqueous solution. Solubility of the crystal has a positive temperature coefficient facilitating growth by slow cooling. Rietveld refinement was used to confirm the phase formation. The crystal has prismatic habit with (010), (001) and (10-1) prominent faces. Thermal analysis shows that the crystal is stable up to 102 degrees C. Transmission spectrum of the crystal extends from 302 nm to 1600 nm. Dielectric spectroscopic analysis revealed Cole Cole behaviour and prominent piezoelectric resonance peaks were observed in the range of 100-200 kHz. Second harmonic generation (SHG) conversion efficiency of up to 2.56 times that of a phase matched KDP crystal was achieved when the (010) plate of LLA single crystal was rotated about the +ve c axis, by 9.4 degrees in the clockwise direction. We also observed SHG conical sections which were attributed to noncollinear phase matching. The observation of the third conical section suggests very high birefringence and large nonlinear coefficients. A detailed study of surface laser damage showed that the crystal has high multiple damage thresholds of 9.7 GW cm(-2) and 42 GW cm(-2) at 1064 nm and 532 nm radiation respectively. (C) 2012 Elsevier B.V. All rights reserved.

Effect of Temperature Cycling on Conduction Mechanisms in CdTe Thin Films

CdTe thin films of 500 thickness prepared by thermal evaporation technique were analyzed for leakage current and conduction mechanisms. Metal-insulator-metal (MIM) capacitors were fabricated using these films as a dielectric. These films have many possible applications, such as passivation for infrared diodes that operate at low temperatures (80 K). Direct-current (DC) current-voltage (I-V) and capacitance-voltage (C-V) measurements were performed on these films. Furthermore, the films were subjected to thermal cycling from 300 K to 80 K and back to 300 K. Typical minimum leakage currents near zero bias at room temperature varied between 0.9 nA and 0.1 mu A, while low-temperature leakage currents were in the range of 9.5 pA to 0.5 nA, corresponding to resistivity values on the order of 10(8) a''broken vertical bar-cm and 10(10) a''broken vertical bar-cm, respectively. Well-known conduction mechanisms from the literature were utilized for fitting of measured I-V data. Our analysis indicates that the conduction mechanism in general is Ohmic for low fields < 5 x 10(4) V cm(-1), while the conduction mechanism for fields > 6 x 10(4) V cm(-1) is modified Poole-Frenkel (MPF) and Fowler-Nordheim (FN) tunneling at room temperature. At 80 K, Schottky-type conduction dominates. A significant observation is that the film did not show any appreciable degradation in leakage current characteristics due to the thermal cycling.

Structural and relaxor characteristics of Ca0.18Sr0.226Ba0.594Nb2O6

Polycrystalline Ca0.18Sr0.226Ba0.594Nb2O6 (CSBN18) was synthesized via the solid-state reaction route. X-ray structural studies confirmed it belonged to the tetragonal tungsten bronze family. Rietveld refinement of the X-ray data has been carried out for CSBN18 where the atomic positions and site occupancy factors for A-sites have been determined. The dielectric properties of CSBN18 ceramic were studied as a function of temperature in the 100 Hz - 1 MHz frequency range. The dielectric relaxation followed the Vogel-Fulcher relation wherein E-a = 37.4 meV; T-f = 131.5 degrees C and omega(0) = 4.31 x 10(9) rad s(-1). A high pyroelectric coefficient of similar to 250 mu C m(-2).K was obtained around the transition temperature (similar to 150 degrees C). This is significantly higher than that reported for polycrystalline SrxBa1-xNb2O6 (SBN). However, the piezoelectric coefficient (d(33)) of the title composition was as low as 6 pC N-1.

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.