Optical and structural properties of highly porous shell structured Fe doped TiO2 thin films

TiO2 thin films with 0.2 wt%, 0.4 wt%, 0.6 wt%, and 0.8 wt% Fe were prepared on glass and silicon substrates using sol-gel spin coating technique. The optical cut-off points are increasingly red-shifted and the absorption edge is shifted over the higher wavelength region with Fe content increasing. As Fe content increases, the optical band gap decreases from 3.03 to 2.48 eV whereas the tail width increases from 0.26 to 1.43 eV. The X-ray diffraction (XRD) patterns for doped films at 0.2 wt% and 0.8 wt% Fe reveal no characteristic peaks, indicating that the film is amorphous whereas undoped TiO2 exhibits (101) orientation with anatase phase. Thin films of higher Fe content exhibit a homogeneous, uniform, and nano-structured highly porous shell morphology.

A bottom-up approach for optimization of friction stir processing parameters; a study on aluminium 2024-T3 alloy

Friction stir processing (FSP) is emerging as one of the most competent severe plastic deformation (SPD) method for producing bulk ultra-fine grained materials with improved properties. Optimizing the process parameters for a defect free process is one of the challenging aspects of FSP to mark its commercial use. For the commercial aluminium alloy 2024-T3 plate of 6 mm thickness, a bottom-up approach has been attempted to optimize major independent parameters of the process such as plunge depth, tool rotation speed and traverse speed. Tensile properties of the optimum friction stir processed sample were correlated with the microstructural characterization done using Scanning Electron Microscope (SEM) and Electron Back-Scattered Diffraction (EBSD). Optimum parameters from the bottom-up approach have led to a defect free FSP having a maximum strength of 93% the base material strength. Micro tensile testing of the samples taken from the center of processed zone has shown an increased strength of 1.3 times the base material. Measured maximum longitudinal residual stress on the processed surface was only 30 MPa which was attributed to the solid state nature of FSP. Microstructural observation reveals significant grain refinement with less variation in the grain size across the thickness and a large amount of grain boundary precipitation compared to the base metal. The proposed experimental bottom-up approach can be applied as an effective method for optimizing parameters during FSP of aluminium alloys, which is otherwise difficult through analytical methods due to the complex interactions between work-piece, tool and process parameters. Precipitation mechanisms during FSP were responsible for the fine grained microstructure in the nugget zone that provided better mechanical properties than the base metal. (C) 2014 Elsevier Ltd. All rights reserved.

Precipitation response of the magnesium alloy WE43 in strained and unstrained conditions

The precipitation behavior of the magnesium alloy WE43 (Mg-4%Y-2.3%Nd-0.5%Zr) has been studied in strained and unstrained conditions using Transmission Electron Microscopy (TEM). Ageing treatments were carried out at three temperatures, namely 210 degrees C, 230 degrees C and 260 degrees C. The precipitation sequence during static aging of solution treated (ST) samples has been identified as ST —> beta'' —> beta' followed by the formation of beta(1) and equilibrium beta precipitates form after very long ageing periods. Dynamic precipitation was observed during high temperature deformation, leading to the formation of beta' and intermediate beta(1) precipitates. The strained samples, when further heat treated, resulted in the transformation of beta(1) into beta equilibrium precipitates. The sequence of dynamic precipitation is ST —> beta(1) —> beta and ST —> beta'. (C) 2014 Elsevier B.V. All rights reserved.

Influence of melt pouring temperature and plate inclination on solidification and microstructure of A356 aluminum alloy produced using oblique plate

The preparation of semisolid slurry of A356 aluminum alloy using an oblique plate was investigated. A356 alloy melt undergoes partial solidification when it flows down on an oblique plate cooled from underneath by counter flowing water. It results in continuous formation of columnar dendrites on plate wall. Due to forced convection, these dendrites are sheared off into equiaxed/fragmented grains and then washed away continuously to produce semisolid slurry at plate exit. Melt pouring temperature provides required condition of solidification whereas plate inclination enables necessary shear for producing semisolid slurry of desired quality. Slurry obtained was solidified in metal mould to produce semisolid-cast billets of desired microstructure. Furthermore, semisolid-cast billets were heat treated to improve surface quality. Microstructures of both semisolid-cast and heat-treated billets were analyzed. Effects of melt pouring temperature and plate inclination on solidification and microstructure of billets produced using oblique plate were described. The investigations involved four different melt pouring temperatures (620, 625, 630 and 635 degrees C) associated with four different plate inclinations (30 degrees, 45 degrees, 60 degrees and 75 degrees). Melt pouring temperature of 625 degrees C with plate inclination of 60 degrees shows fine and globular microstructures and it is the optimum.

Finite Element Analysis of Stress Evolution in Al-Si Alloy

A 2D multi-particle model is carried out to understand the effect of microstructural variations and loading conditions on the stress evolution in Al-Si alloy under compression. A total of six parameters are varied to create 26 idealized microstructures: particle size, shape, orientation, matrix temper, strain rate, and temperature. The effect of these parameters is investigated to understand the fracture of Si particles and the yielding of Al matrix. The Si particles are modeled as a linear elastic solid and the Al matrix is modeled as an elasto-plastic solid. The results of the study demonstrate that the increase in particle size decreases the yield strength of the alloy. The particles with high aspect ratio and oriented at 0A degrees and 90A degrees to the loading axis show higher stress values. This implies that the particle shape and orientation are dominant factors in controlling particle fracture. The heat treatment of the alloy is found to increase the stress levels of both particles and matrix. Stress calculations also show that higher particle fracture and matrix yielding is expected at higher strain rate deformation. Particle fracture decreases with increase in temperature and the Al matrix plays an important role in controlling the properties of the alloy at higher temperatures. Further, this strain rate and temperature dependence is more pronounced in the heat-treated microstructure. These predictions are consistent with the experimentally observed Si particle fracture in real microstructure.

Evolution of deformation texture and magnetic properties in a nanocrystalline nickel-20 wt% cobalt alloy

The evolution of crystallographic texture in a nanocrystalline nickel-20 wt% cobalt alloy has been investigated for deformation up to large strains. The effect of texture on magnetic properties has been evaluated. The material shows characteristic copper-type texture at large strain levels. Microstructural examinations indicate that the evolution of texture is assisted by deformation-induced grain growth. The values of saturation magnetization and coercivity have been correlated with the crystallographic texture and grain size. (C) 2014 Elsevier B.V. All rights reserved.

Stress states in individual Si particles of a cast Al-Si alloy: Micro-Raman analysis and microstructure based modeling

The stress states in Si particles of cast Al-Si based alloys depend on its morphology and the heat treatment given to the alloy. The Si particles fracture less on modification and fracture more in the heat treated condition. An attempt has been made in this work to study the effect of heat treatment and Si modification on the stress states of the particles. Such understanding will be valuable for predicting the ductility of the alloy. The stress states of Si particles are estimated by Raman technique and compared with the microstructure-based FEM simulations. Combination of Electron Back-Scattered Diffraction (EBSD) and frequency shift, polarized micro-Raman technique is applied to determine the stress states in Si particles with (111) orientations. Stress states are measured in the as-received state and under uniaxial compression. The residual stress, the stress in the elastic-plastic regime and the stress which causes fracture of the particles is estimated by Raman technique. FEM study demonstrates that the stress distribution is uniform in modified Si, whereas the unmodified Si shows higher and more complex stress states. The onset of plastic flow is observed at sharp corners of the particles and is followed by localization of strain between particles. Clustering of particles generates more inhomogeneous plastic strain in the matrix. Particle stress estimated by Raman technique is in agreement with FEM calculations. (C) 2014 Elsevier B.V. All rights reserved.

Phase Diagram Study of Succinonitrile-Vanillin Organic Alloy System

Phase diagram studies of succinonitrile-vanillin system show the formation of 2:1 congruent melting type compound. Crystallization velocities of pure components, succinonitrile-vanillin complex, and two eutectics have been determined at different undercoolings. On the basis of heat of fusion measurements, excess thermodynamic functions have been calculated. Microstructural studies revealed that impurities modify the morphology. FTIR spectral studies and computer simulation have shown the existence of hydrogen bonding in the eutectics and the congruent melting compound. On the basis of experimental results, the mechanism of formation of eutectics and its solidification behavior are discussed.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 M = Mn, Fe)

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R (3) over barm) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn3+ and low spin configuration for Ru4+ where the itinerant electrons occupy a pi*-band. The onset of a net maximum in the chi vs. T plot at 9.5 K and the negative value of the Weiss constant (theta) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O2- ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau) while Fe seems to retain its 3+ state.

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.

Study of Microstructure Evolution during Semi-Solid Processing of an In-Situ Al Alloy Composite

In the present work, effect of pouring temperature (650 degrees C, 655 degrees C, and 660 degrees C) on semi-solid microstructure evolution of in-situ magnesium silicide (Mg2Si) reinforced aluminum (Al) alloy composite has been studied. The shear force exerted by the cooling slope during gravity driven flow of the melt facilitates the formation of near spherical primary Mg2Si and primary Al grains. Shear driven melt flow along the cooling slope and grain fragmentation have been identified as the responsible mechanisms for refinement of primary Mg2Si and Al grains with improved sphericity. Results show that, while flowing down the cooling slope, morphology of primary Mg2Si and primary Al transformed gradually from coarse dendritic to mixture of near spherical particles, rosettes, and degenerated dendrites. In terms of minimum grain size and maximum sphericity, 650 degrees C has been identified as the ideal pouring temperature for the cooling slope semi-solid processing of present Al alloy composite. Formation of spheroidal grains with homogeneous distribution of reinforcing phase (Mg2Si) improves the isotropic property of the said composite, which is desirable in most of the engineering applications.

Single-ion magnet behaviour of heptacoordinated Fe(II) complexes: on the importance of supramolecular organization

Supramolecular organization of a metal complex may significantly contribute to the magnetization dynamics of mononuclear SMMs. This is illustrated for a heptacoordinated Fe(II) complex with rather moderate Ising-type anisotropy for which a slow magnetization relaxation with significant energy barrier was reached when this complex was properly organized in the crystal lattice. Incidentally, it is the first example of single-ion magnet behaviour of Fe(II) in a pentagonal bipyramid surrounding.

An alluaudite Na-2+Fe-2x(2-x)(SO4)(3)(x=0.2) derivative phase as insertion host for lithium battery

A new desodiated derivative compound, Na0.89Fe1.8(SO4)(3), was prepared by the chemical oxidation of alluaudite Na2.4Fe1.8(SO4)(3) Phase using NOBF4 as oxidant. The structure and valency of Fe were characterized by X-ray diffraction (XRD) and Fe-57 Mossbauer spectroscopy. Intercalation behavior of lithium ions in the structure of Na0.89Fe1.8(SO4)(3) was gauged by electrochemical analyses and ex-situ X-ray diffraction. A high capacity of 110 mAh g(-1) at 0.1 C was obtained with a good rate kinetics within a range of 0.1-10 C(1 C = 118 mAh g-1) involving a high Fe3+/Fe2+ redox potential of 3.75 V (vs. Li/Li+). These results confirmed that the Na2.4-delta Fe1.8(SO4)(3) framework was stable even after oxidation and forms a new competitive cathode for the reversible intercalation of lithium ions. (C) 2014 Elsevier B.V. All rights reserved.

Influence of plate length and plate cooling rate on solidification and microstructure of A356 alloy produced by oblique plate

A356 alloy melt solidifies partially when it flows down on an oblique plate cooled from bottom by counter flowing water. Columnar dendrites are continuously formed on the plate wall. Because of the forced convection, these dendrites are sheared off into equiaxed/fragmented grains and then washed away continuously by producing semisolid slurry at plate exit. Plate cooling rate provides required extent/amount of solidification whereas plate length enables necessary shear for producing semisolid slurry of desired quality. Slurry obtained is solidified in metal mould to produce semisolid-cast billets of desired microstructure. Furthermore, semisolid-cast billets are also heat-treated to improve surface quality. Microstructures of both semisolid-cast and heat-treated billets are compared. The effects of plate length and plate cooling rate on solidification and microstructure of billets produced by using oblique plate are illustrated. Three different plate lengths (200 mm, 250 mm, 300 mm) associated with three different heat transfer coefficients (1000, 2000 and 2500 W/(m(2).K)) are involved. Plate length of 250 mm with heat transfer coefficient of 2000 W/(m(2).K) gives fine and globular microstructures and is the optimum as there is absolutely no possibility of sticking of slurry to plate wall.

Individual and combined additions of calcium and antimony on microstructure and mechanical properties of squeeze-cast AZ91D magnesium alloy

The effects of combined additions of Ca and Sb on the microstructure and tensile properties of AZ91D alloy fabricated by squeeze-casting have been investigated. For comparison, the same has also been studied with and without individual additions of Ca and Sb. The results indicate that both individual and combined additions refine the grain size and beta-Mg17Al12 phase, which is more pronounced with combined additions. Besides alpha-Mg and beta-Mg17Al12 phases, a new reticular Al2Ca and rod-shaped Mg3Sb2 phases are formed following individual additions of Ca and Sb in the AZ91D alloy. With combined additions, an additional Ca2Sb phase is formed suppressing Mg3Sb2 phase. Additions of both Ca and Sb increase yield strength (YS) at both ambient and elevated temperatures up to 200 degrees C. However, both ductility and ultimate tensile strength (UTS) decrease first up to 150 degrees C and then increase at 200 degrees C. The increase in YS is attributed to the refinement of grain size, whereas, ductility and UTS are deteriorated by the presence of brittle Al2Ca, Mg3Sb2 and Ca2Sb phases. The best tensile properties are obtained in the AZXY9110 alloy owing to the presence of lesser amount of brittle Al2Ca and Ca2Sb phases resulted from the optimum content of 1.0Ca and 0.3Sb (wt%). The fracture surface of the tensile specimen tested at ambient temperature reveals cleavage failure that changes to quasi-cleavage at 200 degrees C. The squeeze-cast alloys exhibited better tensile properties as compared to that of the gravity-cast alloys nullifying the detrimental effects of Ca and/or Sb additions. (C) 2014 Elsevier B.V. All rights reserved.