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.

Antioxidant activity and electrochemical elucidation of the enigmatic redox behavior of curcumin and its structurally modified analogues

Here, we report studies on the antioxidant activity and redox behavior of curcumin and its structurally modified synthetic analogues. We have synthesized a number of analogues of curcumin which abrogate its keto-enol tautomerism or substitute the methylene group at the centre of its heptadione moiety implicated in the hydride transfer and studied their redox property. From cyclic voltammetric studies, it is demonstrated that H-atom transfer from CH2 group at the center of the heptadione link also plays an important role in the antioxidant properties of curcumin along with that of its phenolic -OH group. In addition, we also show that the conversion of 1, 3-dicarbonyl moiety of curcumin to an isosteric heterocycle as in pyrazole curcumin, which decreases its rotational freedom, leads to an improvement of its redox properties as well as its antioxidant activity. (C) 2014 Elsevier Ltd. All rights reserved.

Microstructural Dependence of Work Hardening Behavior in Martensite-Ferrite Microalloyed Steels

Martensite-ferrite microstructures were produced in four microalloyed steels A (Fe-0.44C-Cr-V), B (Fe-0.26C-Cr-V), C (Fe-0.34C-Cr-Ti-V), and D (Fe-0.23C-Cr-V) by intercritical annealing. SEM analysis reveals that steels A and C contained higher martensite fraction and finer ferrite when compared to steels B and D which contained coarser ferrite grains and lower martensite fraction. A network of martensite phase surrounding the ferrite grains was found in all the steels. Crystallographic texture was very weak in these steels as indicated by EBSD analysis. The steels contained negligible volume fraction of retained austenite (approx. 3-6%). TEM analysis revealed the presence of twinned and lath martensite in these steels along with ferrite. Precipitates (carbides and nitrides) of Ti and V of various shapes with few nanometers size were found, particularly in the microstructures of steel B. Work hardening behavior of these steels at ambient temperature was evaluated through modified Jaoul-Crussard analysis, and it was characterized by two stages due to presence of martensite and ferrite phases in their microstructure. Steel A displayed large work hardening among other steel compositions. Work hardening behavior of the steels at a warm working temperature of 540 A degrees C was characterized by a single stage due to the decomposition of martensite into ferrite and carbides at this temperature as indicated by SEM images of the steels after warm deformation.

Synergistic Effect of Mo plus Cu Codoping on the Photocatalytic Behavior of Metastable TiO2 Solid Solutions

Codoping with Cu and Mo is shown to have a synergistic effect on the photocatalytic activity of TiO2. The enhancement in activity is observed only if the synthesis route results in TiO2 in which (Cu, Mo) codopants are forced into the TiO2 lattice. Using X-ray photoelectron spectroscopy, Cu and Mo are shown to be present in the +2 and +6 oxidation states, respectively. A systematic study of the ternary system shows that TiO2 containing 6 mol % CuO and 1.5 mol % MoO3 is the most active ternary composition. Ab initio calculations show that codoping of TiO2 using (Mo, Cu) introduces levels above the valence band, and below the conduction band, resulting in a significant reduction in the band gap (similar to 0.8 eV). However, codoping also introduces deep defect states, which can have a deleterious impact on photoactivity. This helps rationalize the narrow compositional window over which the enhancement in photocatalytic activity is observed.

Optimal control analysis of the dynamic growth behavior of microorganisms

Understanding the growth behavior of microorganisms using modeling and optimization techniques is an active area of research in the fields of biochemical engineering and systems biology. In this paper, we propose a general modeling framework, based on Monad model, to model the growth of microorganisms. Utilizing the general framework, we formulate an optimal control problem with the objective of maximizing a long-term cellular goal and solve it analytically under various constraints for the growth of microorganisms in a two substrate batch environment. We investigate the relation between long term and short term cellular goals and show that the objective of maximizing cellular concentration at a fixed final time is equivalent to maximization of instantaneous growth rate. We then establish the mathematical connection between the generalized framework and optimal and cybernetic modeling frameworks and derive generalized governing dynamic equations for optimal and cybernetic models. We finally illustrate the influence of various constraints in the cybernetic modeling framework on the optimal growth behavior of microorganisms by solving several dynamic optimization problems using genetic algorithms. (C) 2014 Published by Elsevier Inc.

Differential Cocrystallization Behavior of Isomeric Pyridine Carboxamides toward Antitubercular Drug Pyrazinoic Acid

Pyrazinoic acid, the active form of the antitubercular pro-drug Pyrazinamide, is an amphiprotic molecule containing carboxylic acid and pyridine groups and therefore can form both salts and cocrystals with relevant partner molecules. Cocrystallization of pyrazinoic acid with isomeric pyridine carboxamide series resulted in a dimorphic mixed-ionic complex with isonicotinamide and in eutectics with nicotinamide and picolinamide, respectively. It is observed that with alteration of the carboxamide position, steric and electrostatic compatibility issues between molecules of the combination emerge and affect intermolecular interactions and supramolecular growth, thus leading to either cocrystal or eutectic for different pyrazinoic acid-pyridine carboxamide combinations. Intermolecular interaction energy calculations have been performed to understand the role of underlying energetics on the formation of cocrystal/eutectic in different combinations. On the other hand, two molecular salts with piperazine and cytosine and a gallic acid cocrystal of the drug were obtained, and their X-ray crystal structures were also determined in this work.

Low-Wear High-Friction Behavior of Copper Matrix Composites Dispersed With an In Situ Polymer Derived Ceramic

We show that copper-matrix composites that contain 20 vol. % of an in situ processed, polymer-derived, ceramic phase constituted from Si-C-N have unusual friction-and-wear properties. They show negligible wear despite a coefficient of friction (COF) that approaches 0.7. This behavior is ascribed to the lamellar structure of the composite such that the interlamellar regions are infused with nanoscale dispersion of ceramic particles. There is significant hardening of the composite just adjacent to the wear surface by severe plastic deformation.

Compressive flow behavior of Al-Si based alloy: Role of heat treatment

The flow characteristics of a near eutectic Al-Si based cast alloy have been examined in compression at strain rates varying from 3 x 10(-4) to 10(2) s(-1) and at three different temperatures, i.e., room temperature (RT), 100 degrees C and 200 degrees C. The dependence of the flow behavior on heat treatment is studied by testing the alloy in non-heat treated (NHT) and heat treated (HT) conditions. The heat treatment has strong influence on strain rate sensitivity (SRS), strength and work hardening behavior of the alloy. It is observed that the strength of the alloy increases with increase in strain rate and it increases more rapidly above the strain rate of 10(-1) s(-1) in HT condition at all the temperatures, and at 100 degrees C and 200 degrees C in NHT condition. The thermally dependent process taking place in the HT matrix is responsible for the observed greater SRS in HT condition. The alloy in HT condition exhibits a larger work hardening rate than in NHT condition during initial stages of straining. However, the hardening rate decreases more sharply at higher strains in HT condition due to precipitate shearing and higher rate of Si particle fracture. Thermal hardening is observed at 200 degrees C in NHT condition due to precipitate formation, which results in increased SRS at higher temperatures. Thermal softening is observed in HT condition at 200 C due to precipitate coarsening, which leads to a decrease in SRS at higher temperatures. Stress simulations by a finite element method support the experimentally observed particle and matrix fracture behavior. A negative SRS and serrated flow are observed in the lower strain rate regime (3 x 10(-4)-10(-2) s(-1)) at RT and 100 degrees C, in both NHT and HT conditions. The observations show that both dynamic strain aging (DSA) and precipitate shearing play a role in serrated flow. (C) 2015 Elsevier B.V. All rights reserved.

Electrochemical behavior of Zn-graphene composite coatings

A Zn-graphene composite coating was electrodeposited on mild steel. The graphene was synthesized by electrochemical exfoliation of graphite. Electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction techniques were used to characterize the coatings. Compared to a pure Zn coating, the Zn-graphene coating exhibited reduced grain size, reduced surface defects, hillock structures over the coating surface and an altered texture. The corrosion behavior of the coatings was examined by Tafel polarization and electrochemical impedance spectroscopic methods. A significant improvement in the corrosion resistance in terms of reduction in corrosion current and corrosion rate and increase in polarization resistance was noted in the case of the Zn coating containing graphene.

Orotic acid as a useful supramolecular synthon for the fabrication of an OPV based hydrogel: stoichiometry dependent injectable behavior

A facile hydrogelation of a p-pyridylenevinylene derivative (PV) bearing oxyethylene chains in the presence of orotic acid (OA) occurs via various non-covalent interactions. Depending on the PV: OA molar ratio, the hydrogel shows vesicle to either cluster-type aggregate or fiber transformation. Visual color tuning, stimuli-responsiveness and injectable properties of the hydrogel are also observed.

COMPUTATIONAL MODELING OF A MULTI-LAYERED PIEZO-COMPOSITE BEAM MADE UP OF MFC

The Variational Asymptotic Method (VAM) is used for modeling a coupled non-linear electromechanical problem finding applications in aircrafts and Micro Aerial Vehicle (MAV) development. VAM coupled with geometrically exact kinematics forms a powerful tool for analyzing a complex nonlinear phenomena as shown previously by many in the literature 3 - 7] for various challenging problems like modeling of an initially twisted helicopter rotor blades, matrix crack propagation in a composite, modeling of hyper elastic plates and various multi-physics problems. The problem consists of design and analysis of a piezocomposite laminate applied with electrical voltage(s) which can induce direct and planar distributed shear stresses and strains in the structure. The deformations are large and conventional beam theories are inappropriate for the analysis. The behavior of an elastic body is completely understood by its energy. This energy must be integrated over the cross-sectional area to obtain the 1-D behavior as is typical in a beam analysis. VAM can be used efficiently to approximate 3-D strain energy as closely as possible. To perform this simplification, VAM makes use of thickness to width, width to length, width multiplied by initial twist and strain as small parameters embedded in the problem definition and provides a way to approach the exact solution asymptotically. In this work, above mentioned electromechanical problem is modeled using VAM which breaks down the 3-D elasticity problem into two parts, namely a 2-D non-linear cross-sectional analysis and a 1-D non-linear analysis, along the reference curve. The recovery relations obtained as a by-product in the cross-sectional analysis earlier are used to obtain 3-D stresses, displacements and velocity contours. The piezo-composite laminate which is chosen for an initial phase of computational modeling is made up of commercially available Macro Fiber Composites (MFCs) stacked together in an arbitrary lay-up and applied with electrical voltages for actuation. The expressions of sectional forces and moments as obtained from cross-sectional analysis in closed-form show the electro-mechanical coupling and relative contribution of electric field in individual layers of the piezo-composite laminate. The spatial and temporal constitutive law as obtained from the cross-sectional analysis are substituted into 1-D fully intrinsic, geometrically exact equilibrium equations of motion and 1-D intrinsic kinematical equations to solve for all 1-D generalized variables as function of time and an along the reference curve co-ordinate, x(1).

Rheological Behavior of Al-7Si-0.3Mg Alloy at Mushy State

In recent years, semisolid manufacturing has emerged as an attractive option for near net shape forming of components with aluminum alloys. In this class of processes, the key to success lies mainly in the understanding of rheological behavior of the semi-solid slurry in the temperature range between liquidus and solidus. The present study focuses on the non-Newtonian flow behavior of the pseudo plastic slurry of Al-7Si-0.3Mg alloy for a wide shear range using a high-temperature Searle-type rheometer. The rheological behavior of the slurry is studied with respect to relevant process variables and microstructural features such as shear rate, shear duration, temperature history, primary particle size, shape, and their distribution. The experiments performed are isothermal tests, continuous cooling tests, shear jump tests, and shear time tests. The continuous cooling experiments are aimed toward studying the viscosity and shear stress evolution within the slurry matrix with increasing solid fraction at a constant shear rate. Three different cooling rates are considered and their effect on flow behavior of the slurry was studied under iso-shear condition. Descending shear jump experiments are performed to understand the viscous instability of the slurry.

Conceptualization of a Behavior Modification Tool for University Systems and Doctoral Students

This paper describes a university based system relevant to doctoral students who have problems with themselves, their peers and research supervisors. Doctoral students have various challenges to solve and these challenges contribute to delays in their thesis submission. This tool aims at helping them think through their problem in a pre-counseling stage. The tool uses narratives and hypothetical stories to walk a doctoral student through options of responses he or she can make given the situation in the narrative. Narratives were developed after a preliminary survey (n=57) of doctoral students. The survey indicated that problems they experienced were: busy supervisors, negative competition from peers and laziness with self. The narrative scenarios in the tool prompt self-reflection and provide for options to chose from leading to the next scenario that will ensue. The different stages of the stimulus-response cycles are designed based on Thomas-Kilmann conflict resolution techniques (collaboration and avoidance). Each stimulus-response cycle has a score attached that reflects the student's ability to judge a collaborative approach. At the end of all the stages a scorecard is generated indicating either a progressive or regressive outcome of thesis submission.

Effects of Interface Treatment on the Fatigue Behavior of Shape Memory Alloy Reinforced Polymer Composites

Interfacial properties of Shape Memory Alloy (SMA) reinforced polymer matrix composites can be enhanced by improving the interfacial bonding. This paper focuses on studying the interfacial stresses developed in the SMA-epoxy interface due to various laser shot penning conditions. Fiber-pull test-setup is designed to understand the role of mechanical bias stress cycling and thermal actuation cycling. Phase transformation is tracked over mechanical and thermal fatigue cycles. A micromechanics based model developed earlier based on shear lag in SMA and energy based consistent homogenization is extended here to incorporate the stress-temperature phase diagram parameters for modeling fatigue.

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.