Structural and microstructural characterizations of nanocrystalline hydroxyapatite synthesized by mechanical alloying

Single phase nanocrystalline hydroxyapatite (HAp) powder has been synthesized by mechanical alloying the stoichiometric mixture of CaCO₃ and CaHPO₄ powders in open air at room temperature, for the first time, within 2 h of milling. Nanocrystalline hexagonal single crystals are obtained by sintering of 2 h milled sample at 500 °C. Structural and microstructural properties of as-milled and sintered powders are revealed from both the X-ray line profile analysis and transmission electron microscopy. Shape and lattice strain of nanocrystalline HAp particles are found to be anisotropic in nature. Particle size of HAp powder remains almost invariant up to 10 h of milling and there is no significant growth of nanocrystalline HAp particles after sintering at 500 °C for 3 h. Changes in lattice volume and some primary bond lengths of as-milled and sintered are critically measured, which indicate that lattice imperfections introduced into the HAp lattice during ball milling have been reduced partially after sintering the powder at elevated temperatures. We could achieve ~ 96.7% of theoretical density of HAp within 3 h by sintering the pellet of nanocrystalline powder at a lower temperature of 1000 °C. Vickers microhardness (VHN) of the uni-axially pressed (6.86 MPa) pellet of nanocrystalline HAp is 4.5 GPa at 100 gm load which is close to the VHN of bulk HAp sintered at higher temperature. The strain-hardening index (n) of the sintered pellet is found to be > 2, indicating a further increase in microhardness value at higher load.     

Structure, dielectric, ferroelectric, and energy density properties of (1 − x)BZT–xBCT ceramic capacitors for energy storage applications

We investigate the dielectric, ferroelectric, and energy density properties of Pb-free (1 ? x)BZT–xBCT ceramic capacitors at higher sintering temperature (1600 °C). A significant increase in the dielectric constant, with relatively low loss was observed for the investigated {Ba(Zr_0.2Ti_0.8)O₃}_(1?x ){(Ba_0.7Ca_0.3)TiO₃} _x (x = 0.10, 0.15, 0.20) ceramics; however, electric breakdown was low (~140, 170, 134 kV/cm), and of which room temperature (300 K) charging curve energy density values are largest ~0.88, 0.94, and 0.87 J/cm³ with maximum high dielectric constant values ~7800, 8400, and 5200, respectively. Bulk ceramic BZT–BCT materials have shown interesting energy densities with good energy storage efficiency (~72 %) at high sintering temperature; they might be one of the strong candidates for high energy density capacitor applications in an environmentally protective atmosphere.     

Structural,microstructural and magneto-electric properties of single-phase BiFeO3 nanoceramics prepared by auto-combustion method

Polycrystalline nano BiFeO₃ powders were synthesized by auto-combustion method using urea as fuel and metal nitrates (Fe(NO₃)₃·9H₂O, Bi(NO₃)₃·5H₂O) as oxidizers. In order to optimize the single-phase synthesis condition of BiFeO₃, different fuel to oxidizer ratios have been investigated. The preliminary structural investigation using X-ray diffraction shows the samples were of single phase and crystallize in rhombohedral structure (R3c). The ferroelectric and antiferromagnetic ordering temperatures of BiFeO₃ were found to be 832 °C and 364 °C respectively, from differential thermal analysis. The temperature dependent dielectric study shows an anomaly around 215 °C which corresponds to magneto-electric coupling in the material. Field-emission scanning electron micrographs show effect of fuel to oxidizer ratio on grain size evolution. The ferroelectric hysteresis loops for all the samples were measured at a frequency of 100 Hz confirming the ferroelectric nature. An evidence of magneto-electric coupling was also observed at room temperature from magneto-capacitance measurements.     

Kinetics of phase transfer catalyzed reduction of nitrochlorobenzenes by aqueous ammonium sulfide: Utilization of hydrotreater off-gas for the production of value-added chemicals

The reduction of nitrochlorobenzenes (NCBs) was carried out in an organic solvent, toluene, under liquid–liquid mode with phase transfer catalyst, tetrabutylammonium bromide (TBAB). The selectivity of chloroanilines (CANs) was found to be 100%. The reaction rate of m-nitrochlorobenzene (MNCB) was found to be highest among the three NCBs followed by o- and p-nitrochlorobenzene (ONCB and PNCB). The reactions were found to be kinetically controlled with apparent activation energies of 22.8, 19.6 and 9.4 kcal/mol for ONCB, PNCB and MNCB, respectively. The effects of different parameters such as TBAB concentration, NCB concentration, sulfide concentration, ammonia concentration, and elemental sulfur loading on the conversion and reaction rate of NCBs were studied to establish the mechanism of the reaction. The rate of reaction of NCBs was found to be proportional to the concentrations of the catalyst and NCBs and to the cube of the concentration of sulfide. A generalized empirical kinetic model was developed to correlate the experimentally obtained conversion versus time data for the three NCBs.     

A comparative study of the bias corrected estimates in logistic regression

Logistic regression is frequently used in many areas of applied statistics. The maximum likelihood estimates (MLE) of the logistic regression parameters are usually computed using the iterative Newton-Raphson method. It is well known that these estimates are biased. Several methods are proposed to correct the bias of these estimates. Among them Firth (1993) and Cordeiro and McCullagh (1991) proposed two promising methods. The conditional exact method (CMLE) is popular for small-sample estimates, and is available in many software packages. In this article we compare these methods in terms of their bias. In general, our extensive simulations show that the methods proposed by Cordeiro and McCullagh and by Firth work well, though Cordeiro and McCullagh is slightly better in our simulations. In case of separation, Firth or CMLE can be used; however, a judicious approach is required when there is a wide variation in results. Two real data analyses are given exhibiting these properties. The data analysis also includes bootstrap results.     

Novel Synthesis of SrBi2Nb2O9 Powders From Hydroxide Precursors

Simple hydroxide precursors were used for the first time for the synthesis of a typical Aurivillius compound (SrBi₂Nb₂O₉ (SBN)) at a low temperature. This method is very advantageous because it circumvents the use of SrCO₃ in the case of conventional ceramics as well in the coprecipitation methods, thereby lowering the formation of the product phase. Commercially purchased strontium hydroxide is mixed thoroughly with freshly precipitated bismuth and niobium hydroxides in a stoichiometric ratio and heated at different temperatures ranging from 100°C to 750°C for 12 h. The sequence of the reaction and evolution of the product phase was monitored by X-ray diffraction (XRD) studies by recording the XRD for samples calcined at different temperatures. The incipient SBN phase begins to form at temperatures as low as 400°C, and phase formation was complete only at 650°C as revealed by the XRD observations. The differential thermal/thermogravimetric analyses) also corroborate this result. The morphology and average particle size of these powders were investigated by transmission electron microscopy studies.     

Effect of electrode configuration and mode of deposition on magnetoresistance in electrodeposited Co/Cu multilayers on n-Si by a fully electrochemical method

Electrodeposition of metallic multilayers on Si is normally preceded by the vapour deposition of a metallic layer. Since vapour deposition produces an additional step in the production process, direct electrodeposition of multilayers on Si is desirable. However, direct electrodeposition on Si has resulted in low magnetoresistance (MR) - of the order of 1% - at room temperature. With the use of (i) electroless plated copper back contact, (ii) composite potentiostatic pulses, (iii) horizontal electrode configuration and (iv) non-continuous mode of deposition, a room temperature MR of 5.8% has been achieved.     

Bio-hydrometallurgical processing of low grade chalcopyrite for the recovery of copper metal

A process flowsheet was developed to recover copper metal from the lean sulfide ore of copper available at Malanjkhand, Hindustan Copper Limited (HCL), India. Copper pregnant leach solution (PLS) obtained from bio-heap leaching of chalcopyrite containing 0.3% copper was purified through solvent extraction (SX) and the copper recovered by electrowinning (EW). The copper-free raffinate obtained from SX stripping unit was returned back to the bioleaching circuit. The purity of the electrolytic copper produced at pilot scale was found to be 99.96%. During electrowinning, the effect of flow rate of electrolyte on current efficiency and energy consumption was also studied.