Spinodal decomposition in fine grained materials

We have used a phase field model to study spinodal decomposition in polycrystalline materials in which the grain size is of the same order of magnitude as the characteristic decomposition wavelength (Xsu). In the spirit of phase field models, each grain (i) in our model has an order parameter (η _i) associated with it;η _i has a value of unity inside the ith grain, decreases smoothly through the grain boundary region to zero outside the grain. For a symmetric alloy of composition,c = 0–5, our results show that microstructural evolution depends largely on the difference in the grain boundary energies, y_gb, of A-rich (a) and B-rich (β) phases. If Y _gb ^α is lower, we find that the decomposition process is initiated with an a layer being formed at the grain boundary. If the grain size is sufficiently small (about the same as λ_sd), the interior of the grain is filled with the β phase. If the grain size is large (say, about 10λ_SD or greater), the early stage microstructure exhibits an A-rich grain boundary layer followed by a B-rich layer; the grain interior exhibits a spinodally decomposed microstructure, evolving slowly. Further, grain growth is suppressed completely during the decomposition process.     

Microstructure and electrical conductivity of Al-SiCp composites produced by spray forming process

Al- SiC_p composites have been synthesized by spray forming process with variation in particle flow rate, size of reinforcement particles and their volume fraction. The microstructure of composites and their electrical conductivity have been investigated. The results showed a uniform dispersion of large size particulate phase in the matrix of the primary α- phase with its equiaxed grain morphology. However, clustering of small size particles was observed at the grain boundary and grain junctions. The grain size of the composite materials was observed to be lower than that of the base Al- alloy. The composite materials invariably indicated their lower electrical conductivity compared to that of the monolithic Al- alloy. The electrical conductivity of composites decreased with increase in the volume fraction and decrease in size of the reinforcement particles. A high flow rate of particles during spray deposition resulted in a decrease in its conductivity. These results are explained in the light of thermal mismatch between the matrix and the reinforcement phases resulting in generation of high dislocation density. The droplet- particle interaction and resulting microstructure evolution during the spray deposition of the composites are discussed.     

Anisotropic behaviour of semiconducting tin monosulphoselenide single crystals

Single crystals of ternary mixed compounds of group IV-VI in the form of a series, SnS_xSe_1-x (wherex = 0, 0.25, 0.50, 0.75 and 1), have been grown using direct vapour transport technique. The grown crystals were characterized by the X-ray diffraction analysis for their structural parameter determination. All the grown crystals were found to be orthorhombic. The microstructure analysis of the grown crystals reveals their layered type growth mechanism. From the Hall effect measurements Hall mobility, Hall coefficient and carrier concentration were calculated with all crystals showingp-type nature. The d.c. electrical resistivity measurements perpendicular toc-axis (i.e. along the basal plane) in the temperature range 303–453 K were carried out for grown crystals using four-probe method. The d.c. electrical resistivity measurements parallel to c-axis (i.e. perpendicular to basal plane) in the temperature range 303–453 K were carried out for the same crystals. The electrical resistivity measurements showed an anisotropic behaviour of electrical resistivity for the grown crystals. The anisotropic behaviour and the effect of change in stoichiometric proportion of S and Se content on the electrical properties of single crystals of the series, SnS_xSe_1-x (wherex = 0, 0.25, 0.50, 0.75 and 1), is presented systematically.     

Synthesis and magnetic study of Co-Al substituted calcium hexaferrite

A series of calcium substituted polycrystalline ferrite ceramics with magnetoplumbite structures were synthesized using perfect stoichiometric mixtures of oxides with chemical composition, CaAl_xCo_xFe_12−2xO₁₉ (x = 2−5), by standard ceramic technique. The variation in the values ofH _candM _s,which depends on the additive content and the temperature, was studied by means of a vibration magnetometer. The strong variation observed in coercivity, saturation magnetization and Curie temperature with chemical composition give rise to the possibility of controlling these properties and hence applying these compounds in the millimeter— microwave range.     

Theoretical study of superconductivity in MgB2 and its alloys

Using density-functional-based methods, we have studied the fully-relaxed, fulltronic structure of the newly discovered superconductor, MgB ₂, and BeB₂, NaB₂ and AlB₂. Our results, described in terms of (i) total density of states (DOS) and (ii) the partial DOS around the Fermi energy, E_F, clearly show the importance of B p-electrons for superconductivity. For BeB₂ and NaB₂, our results indicate qualitative similarities but significant quantitative differences in their electronic structure due to differences in the number of valence electrons and the lattice constantsa andc. We have also studied Mg _1-xM_xB₂ (M = Al, Li or Zn) alloys using coherent-potential to describe disorder, Gaspari-Gyorffy approach to evaluate electron-phonon coupling, and Allen-Dynes equation to calculate the superconducting transition temperature, T_c. We find that in Mg_1-xM_xB₂ alloys (i) the way Tc changes depends on the location of the added/modified k-resolved states on the Fermi surface and (ii) the variation of Tc as a function of concentration is dictated by the Bp DOS.     

Preparation and characterization of Ag-added Bi1.84Pb0.4Sr2Ca2.2Cu3O10+x bulk tube conductors for cryogen free superconducting magnet

Bulk tube conductors of Bi _1.84 Pb _0.4 Sr ₂ Ca _2.2 Cu ₃ O _10+x with addition of silver varying from 0 to 25 wt% (not reported earlier) were systematically studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical transport and a.c. susceptibility techniques. The tube conductors formed by cold isostatic pressing (CIP) of the powders obtained from spray drying method have been made successfully. It was found that Ag addition has not only affected the formation of the desired Bi-2223 phase and the microstructure of these large bulk tube samples thereby influencing on the critical current ( I _c ),it also reduces the contact resistance to minimize the cryogen losses. These variations have been found to be Ag content dependent. An optimized value of 10 wt% Ag has been found to produce the best quality tubes showing reproducible I _c value > 120 Amp at 77 K which is in general a requirement to energies of the cryogen free conventional/HTSC superconducting magnets below 20 K.     

Many electron effects in semiconductor quantum dots

Semiconductor quantum dots (QDs) exhibit shell structures, very similar to atoms. Termed as ’artificial atoms’ by some, they are much larger (1 100 nm) than real atoms. One can study a variety of manyelectron effects in them, which are otherwise difficult to observe in a real atom. We have treated these effects within the local density approximation (LDA) and the Harbola-Sahni (HS) scheme. HS is free of the self-interaction error of the LDA. Our calculations have been performed in a three-dimensional quantum dot. We have carried out a study of the size and shape dependence of the level spacing. Scaling laws for the Hubbard ‘U’ are established.     

Optical properties of lead-bismuth cuprous glasses

The optical transmission and absorption spectra in UV- VIS were recorded in the wavelength range 350–800 nm for different glass compositions in the system (CuO) _x (PbO) ₅₀−x(Bi₂O₃)₅₀ (x = 2.5, 5.0, 7.5, 10.0, 12.5, 15.0, 20.0). Absorption coefficient (α), optical energy gap (E_opt), refractive index (n_D), optical dielectric constant (ε′_∞), measure of extent of band tailing (ΔE), constant (β) and ratio of carrier concentration to the effective mass (N/m*) have been reported. The effects of compositions of glasses on these parameters have been discussed. It has been indicated that a small compositional modification of the glasses lead to an important change in all the optical properties including non-linear behaviour. The optical parameters were found to be almost the same for different glasses in the same family.     

Optical absorption and electron spin resonance studies of Cu2+ in Li2O-Na2O-B2O3-As2O3 glasses

The local structure around Cu²⁺ ion has been examined by means of electron spin resonance and optical absorption measurements in xLi₂O-(40-x)Na₂O-50B₂O₃-10As₂O₃ glasses. The site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The ground state of Cu²⁺ isd _x ²−y ².The glass exhibited broad absorption band near infrared region and small absorption band around 548 nm, which was assigned to the ²B_1g →²E_g transition.     

Spectroscopic investigations of Cu2+ in Li2O-Na2O-B2O3-Bi2O3 glasses

Pure and copper doped glasses with composition,x Li ₂ O-(40-x)Na ₂ O-50B ₂ O ₃-10Bi ₂ O ₃,have been prepared over the range 0 ≤ x ≤ 40. The electron paramagnetic resonance (EPR) spectra of Cu²⁺ ions of these glasses have been recorded in the X-band at room temperature. Spin Hamiltonian parameters have been calculated. The molecular bonding coefficients, α² and β², have been calculated by recording the optical absorption spectra in the wavelength range 200–1200 nm. It has been observed that the site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The density and glass transition temperature variation with alkali content shows non-linear behaviour. The IR studies show that the glassy system contains BO₃ and BO₄ units in the disordered manner.     

Fine structure at the diffusion welded interface of Fe3Al/Q235 dissimilar materials

The interface of Fe ₃ Al/Q235 dissimilar materials joint, which was made by vacuum diffusion welding, combines excellently. There are Fe ₃ Al, FeAl phases and α-Fe (Al) solid solution at the interface of Fe ₃ Al/Q235. Aluminum content decreases from 28% to 1.5% and corresponding phase changes from Fe ₃ Al with DO ₃ type body centred cubic bcc structure to α-Fe (Al) solid solution with B2 type bcc structure. All phases are present in sub-grain structure level and there is no obvious brittle phases or micro-defects such as pores and cracks at the interface of Fe ₃ Al/Q235 diffusion joint.     

Versatile preparation method for mesoporous TiO2 electrodes suitable for solid-state dye sensitized photocells

Nano-structured TiO₂ electrodes, suitable for dye sensitized solid-state solar cells were prepared by a new simple spraying technique (SPT). Physical properties of these electrodes were compared with the electrodes prepared by the ‘doctor blade’ technique (typical sliding method, DB). Dye sensitized solid-state solar cells, comprising of CuI as the hole conductor, were fabricated with these electrodes and enhanced photo responses were obtained with SPT electrodes. The effects of additives, either to the spray solution or to the hole conductor on the photoresponses of the above devices were also studied. The cells fabricated with SPT electrodes containing Al(BuⁱO)₃ showed ∼ 2.4% efficiency and addition of 1-ethyl-3-methyl imidazolium thiocyanate into CuI layer further enhanced the efficiency up to 2.75% under the irradiance of 100 mW cm⁻² (AM 1.5).     

Effect of zirconium addition on the recrystallization behaviour of a commercial Al-Cu-Mg alloy

It is well known that the second phase particles have an effect on recrystallization and grain growth behaviour of an alloy. Particularly the bimodal distribution of second phase particles has an effect which is opposite in sense where coarse second phase particles (> 1 μm) stimulate nucleation while fine particles exhibit Zener drag. In the literature, the effect of zirconium addition to aluminium alloys has been well documented in order to produce superplasticity by giving ultra fine grain size to the alloy. Addition of zirconium produces Al ₃ Zr particles which pin the grain boundaries during recrystallization and grain growth. In the present work, zirconium was added to a commercial Al-Cu-Mg alloy and by heat treatment Al ₃ Zr particles were precipitated and after forging, the grain size was an order of magnitude lower than the alloy without zirconium. Transmission electron microscopy was employed to characterize the second phase particles, i.e. Al ₃ Zr particles and found to be rod shaped and identified to be cubic ordered L 1 ₂ phase with a lattice parameter of 0.408 nm. Further, it was observed that fine (100 nm) Al ₃ Zr particles promote only continuous recrystallization which is polygonization of subgrains and subgrain growth. It was found that the fine dispersion of Al ₃ Zr particles inhibits both recrystallization and grain growth in the commercial Al-Cu-Mg alloy.     

Effect of heat treatment on martensitic transformation in Fe-12.5%Mn-5.5%Si-9%Cr-3.5% Ni alloy

In this study, thermally-induced martensitic transformation (γ(fcc) → ε(hcp)) in Fe-12.5%Mn-5.5% Si-9%Cr-3.5% Ni (weight) alloy was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effect of cooling rate was investigated. It was observed that fast cooled sample exhibited regular overlapping of stacking faults and ε martensite plates were formed parallel to each other. TEM investigations showed that the orientation relationship between γ-ε phases corresponds to Shoji-Nishiyama type orientation relationship.     

A study of ultrasonic velocity and attenuation on polycrystalline Ni-Zn ferrites

Polycrystalline NiZn ferrites with different grain sizes (1.2 (Am to 10.2 (Am) were prepared by the usual ceramic method. The magnetic properties were measured at room temperature. The ultrasonic velocity and attenuation were measured on Ni-Zn ferrite by using the pulse transmission method at 1 MHz, in the temperature range 300–600 K. The velocity was found to be slightly sample dependent at room temperature and decreased with increasing temperature, except near the Curie temperature, T _c ,where a small anomaly was observed. The longitudinal attenuation (α ₁ )at room temperature was found to be more sample dependent. The temperature variation of ultrasonic longitudinal attenuation exhibited a broad maximum around 400 K and a sharp maximum just below Curie temperature ( T _c ).The above observations were carried out in the demagnetized state. The application of a 380 mT magnetic field allowed us to reach the saturated state of the sample at all the measuring temperatures. The anomaly observed in the thermal variation of velocities (longitudinal and transverse) and attenuation has been qualitatively explained with the help of the temperature variation of the magneto-crystalline anisotropy constant.     

A new combustion route to γ-Fe2O3 synthesis

A new combustion route for the synthesis of γ-Fe ₂ O ₃ is reported by employing purified a-Fe ₂ O ₃ as a precursor in the present investigation. This synthesis which is similar to a self propagation combustion reaction, involves fewer steps, a shorter overall processing time, is a low energy reaction without the need of any explosives, and also the reaction is completed in a single step yielding magnetic iron oxide i.e. γ-Fe ₂ O ₃ .The as synthesized γ-Fe ₂ O ₃ is characterized employing thermal, XRD, SEM, magnetic hysteresis, and density measurements. The effect of ball-milling on magnetic properties is also presented.     

Effect of Co on the magnetism and phase stability of lithiated manganese oxides

We present first-principles calculations of the relative energies of various phases of lithiated manganese oxides with and without Co. We use the ultrasoft pseudopotential method as implemented in the Vienna ab initio simulation package (VASP). The calculations employ the local spin density approximation (LSDA) as well as the generalized gradient approximation (GGA). We consider monoclinic and rhombohedral structures in paramagnetic, ferromagnetic and antiferromagnetic (AF3) spin configurations. Spin-polarization significantly lowers the total energy in all cases. The effect of Co on the stability of these phases is discussed.     

Significance of structure-property relationship in alumina based porcelain insulators to achieve quality

The catastrophic failures of porcelain insulators in power lines can be minimized by understanding the structure-property relationship that governs the performance. A study addressing the materials aspects has been conducted on alumina based porcelain insulators used in 25 kV railway traction lines. This article asserts the controls exercised by chemical composition, crystalline structural phases and microstructure on the functional reliability and durability of the insulators. Influences of the total alumina, α-Al₂O₃ (corundum) and α-quartz contents, microstructural features including morphologies of mullite needles, quartz and corundum grains in the alumino silicate glassy matrix, large inhomogeneities in matrix constituents and composition have been highlighted.     

Obtaining Kohn-Sham potential without taking the functional derivative

Over the past decade and a half, many new accurate density functionals, based on the generalized gradient approximation, have been proposed, and they give energies close to chemical accuracy. However, accuracy of the energy functional does not guarantee that its functional derivative, which gives the corresponding potential, is also accurate all over space. For example, although the Becke88 exchange-energy functional gives very good exchange energies, its functional derivative goes as —1/2 m comparison to the correct —1 for r ⇇ where ris the distance of the electron from a finite system. On the other hand, accuracy of the potential is of prime importance if one is interested in properties other than the total energy; properties such as optical response depend crucially on the potential in the outer regions of a system. In this paper we present a different approach, based on the ideas of Harbola and Sahni, to obtain the potential directly from the energy density of a given approximation, without taking recourse to the functional derivative route. This leads to a potential that is as accurate as the functional itself. We demonstrate the accuracy of our approach by presenting some results obtained from the Becke88 functional.