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.

Response of shock wave deformation in AA5086 aluminum alloy

The AA5086 aluminum alloy sheets with different starting textures were subjected to shock wave deformation with an input impulse of similar to 0.2 Ns. Microstructural examination indicate no significant change in grain size; however, the evolution of substructure manifesting intra-granular misorientation was evident. The improvement in hardness indicates the absence of recovery and strain hardening during shock deformation. Shock deformed samples show characteristic texture evolution with high Brass {110}< 112 > component. The study demonstrates the viability of high velocity forming of AA5086 aluminum alloy sheet using shock wave. (C) 2014 Elsevier B.V. All rights reserved.

Image-Segmentation Technique to Analyze Deformation Profiles in Different Direct Shear Tests

Results from interface shear tests on sand-geosynthetic interfaces are examined in light of surface roughness of the interacting geosynthetic material. Three different types of interface shear tests carried out in the frame of direct shear-test setup are compared to understand the effect of parameters like box fixity and symmetry on the interface shear characteristics. Formation of shear bands close to the interface is visualized in the tests and the bands are analyzed using image-segmentation techniques in MATLAB. A woven geotextile with moderate roughness and a geomembrane with minimal roughness are used in the tests. The effect of surface roughness of the geosynthetic material on the formation of shear bands, movement of sand particles, and interface shear parameters are studied and compared through visual observations, image analyses, and image-segmentation techniques.

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.

The contribution of grain boundary sliding in tensile deformation of an ultrafine-grained aluminum alloy having high strength and high ductility

An as-cast Al-7 % Si alloy was processed by high-pressure torsion (HPT) for up to 10 turns at temperatures of 298 or 445 K. The HPT-processed samples had ultrafine-grained structures and they were tested in tension at room temperature at various strain rates in the range from 1.0 x 10(-4) to 1.0 x 10(-2) s(-1). The contributions of grain boundary sliding (GBS) to the total strain were measured directly using atomic force microscopy. Samples simultaneously showing both high strength and high ductility contained the highest fractions of high-angle grain boundaries (HAGB) and exhibited the highest contributions from GBS, whereas samples showing high strength but low ductility gave negligible values for the sliding contributions. It is concluded that high strength and high ductility require both an ultrafine grain size and a high fraction of HAGB.

High-Temperature Deformation Processing Map Approach for Obtaining the Desired Microstructure in a Multi-component (Ni-Ti-Cu-Fe) Alloy

An equiatomic NiTiCuFe multi-component alloy with simple body-centered cubic (bcc) and face-centered cubic solid-solution phases in the microstructure was processed by vacuum induction melting furnace under dynamic Ar atmosphere. High-temperature uniaxial compression experiments were conducted on it in the temperature range of 1073 K to 1303 K (800 degrees C to 1030 degrees C) and strain rate range of 10(-3) to 10(-1) s(-1). The data generated were analyzed with the aid of the dynamic materials model through which power dissipation efficiency and instability maps were generated so as to identify the governing deformation mechanisms that are operative in different temperature-strain rate regimes with the aid of complementary microstructural analysis of the deformed specimens. Results indicate that the stable domain for the high temperature deformation of the multi-component alloy occurs in the temperature range of 1173 K to 1303 K (900 degrees C to 1030 degrees C) and (epsilon) over dot range of 10(-3) to 10(-1.2) s(-1), and the deformation is unstable at T = 1073 K to 1153 K (800 degrees C to 880 degrees C) and (epsilon) over dot = 10(-3) to 10(-1.4) s(-1) as well as T = 1223 K to 1293 K (950 degrees C to 1020 degrees C) and (epsilon) over dot = 10(-1.4) to 10(-1) s(-1), with adiabatic shear banding, localized plastic flow, or cracking being the unstable mechanisms. A constitutive equation that describes the flow stress of NiTiCuFe multi-component alloy as a function of strain rate and deformation temperature was also determined. (C) The Minerals, Metals & Materials Society and ASM International 2015

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.

Deformation behaviour of Rheocast A356 Al alloy at microlevel considering approximated RVEs

A micromechanical approach is considered here to predict the deformation behaviour of Rheocast A356 (Al-Si-Mg) alloy. Two representative volume elements (RVEs) are modelled in the finite element (FE) framework. Two dimensional approximated microstructures are generated assuming elliptic grains, based on the grain size, shape factor and area fraction of the primary Al phase of the said alloy at different processing condition. Plastic instability is shown using stress and strain distribution between the Al rich primary and Si rich eutectic phases under different boundary conditions. Boundary conditions are applied on the approximated RVEs in such a manner, so that they represent the real life situation depending on their position on a cylindrical tensile test sample. FE analysis is carried out using commercial finite element code ABAQUS without specifying any damage or failure criteria. Micro-level in-homogeneity leads to incompatible deformation between the constituent phases of the rheocast alloy and steers plastic strain localisation. Plastic stain localised regions within the RVEs are predicted as the favourable sites for void nucleation. Subsequent growth of nucleated voids leads to final failure of the materials under investigation.

Fracture in metallic glasses: mechanics and mechanisms

Significant progress in understanding the mechanical behavior of metallic glasses (MGs) was made over the past decade, particularly on mechanisms of plastic deformation. However, recent research thrust has been on exploring the mechanics and physics of fracture. MGs can be very brittle with K-Ic values similar to silicate glasses and ceramics or very tough with K-Ic akin to high toughness crystalline metals. Even the tough MGs can become brittle with structural relaxation following annealing at temperatures close to glass transition temperature (T-g). Detailed experimental studies coupled with complementary numerical simulations of the recent past have provided insights on the micromechanisms of failure as well as nature of crack tip fields, and established the governing fracture criteria for ductile and brittle glasses. In this paper, the above advances are reviewed and outstanding issues in the context of fracture of amorphous alloys that need to be resolved are identified.

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.

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.

Texture evolution during hot deformation of Moly-TZM

Moly-TZM was deformed at constant strain rate of 1.0 s(-1) to investigate the high strain rate deformation behaviour by microstructural and stress response change within a temperature range of 1400-1700 degrees C. To correlate the deformation behaviour with orientational change, recrystallization and recovery of the material, the microstructural investigation was undertaken using scanning electron microscopy (SEM) of electron back scattered diffraction (EBSD). Depending on the grain size and orientation spread recrystallized grains were identified and texture was calculated. Change in grain boundary characteristics with increasing temperature was determined by the misorientation angle distribution for the deformed and recrystallized grains. Subgrain coalescence and increase in subgrain size with increasing temperature was observed, indicating recrystallization not only occurred from the nucleation of the dislocation free grains in grain boundaries but also from the subgrain rotation and merging of the subgrains by annihilation of the low angle grain boundaries. Detailed studies on the evolution of texture of recrystallized grains showed continuous increase in <001> fiber texture in recrystallised grains, in contrast to a mixed fiber <001> +<111> for the deformed grains.

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.