Structural, EPR, photo and thermoluminescence properties of ZnO:Fe nanoparticles

Zn(1-x)Fe(x)O(1+0.5x) (x = 0.5-5 mol%) nanoparticles were synthesized by a low temperature solution combustion route. The structural characterization of these nanoparticles by PXRD, SEM and TEM confirmed the phase purity of the samples and indicated a reduction in the particle size with increase in Fe content. A small increase in micro strain in the Fe doped nanocrystals is observed from W-H plots. EPR spectrum exhibits an intense resonance signal with effective g values at g approximate to 2.0 with a sextet hyperfine structure (hfs) besides a weak signal at g approximate to 4.13. The signal at g approximate to 2.0 with a sextet hyperfine structure might be due to manganese impurity where as the resonance signal at g approximate to 4.13 is due to iron. The optical band gap E-g was found to decrease with increase of Fe content. Raman spectra exhibit two non-polar optical phonon (E-2) modes at low and high frequencies at 100 and 435 cm(-1) in Fe doped samples. These modes broaden and disappear with increase of Fe do pant concentration. TL measurements of gamma-irradiated (1-5 kGy) samples show a main glow peak at 368 degrees C at a warming rate of 6.7 degrees Cs-1. The thermal activation parameters were estimated from Glow peak shape method. The average activation energy was found to be in the range 0.34-2.81 eV. (C) 2012 Elsevier B.V. All rights reserved.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

Dispersed ZrO2 nanoparticles in MCM-48 with high adsorption activity

A new two-step synthesis of ZrO2-MCM nanocomposites using the gel combustion technique was accomplished; the resulting material had a high-surface area and showed very high adsorption activity. The deposition of 25 nm ZrO2 particles over MCM was achieved using gel combustion technique with glycine as a fuel, and the formation of nanocomposites was confirmed using transmission electron microscopy. The composites were also characterized by XRD, SEM, FTIR and N2 adsorption-desorption analysis. The nanocomposites were tested for the adsorption of cationic dyes. High rates of adsorption and large dye uptake were observed over the nanocomposites. The rate of adsorption over the nanocomposites was higher than that observed for physical ZrO2-MCM mixtures and commercial activated carbon. The nanocomposite with 10 wt % ZrO2 showed the highest rate of adsorption owing to the synergistic effects of ZrO2 surface groups, smaller particle size, fine dispersion and high-surface area of the composite. (c) 2012 American Institute of Chemical Engineers AIChE J, 58: 29872996, 2012

Carbonization of solvent and capping agent based enhancement in the stabilization of cobalt nanoparticles and their magnetic study

We describe a hybrid synthetic protocol, the solvated metal atom dispersion (SMAD) method, for the synthesis and stabilization of monodisperse amorphous cobalt nanoparticles. By employing an optimized ratio of a weakly coordinating solvent and a capping agent monodisperse colloidal cobalt nanoparticles (2 +/- 0.5 nm) have been prepared by the SMAD method. However, the as-prepared samples were found to be oxidatively unstable which was elucidated by their magnetic studies. Oxidative stability in our case was achieved via a pyrolysis process that led to the decomposition of the organic solvent and the capping agent resulting in the formation of carbon encapsulated cobalt nanoparticles which was confirmed by Raman spectroscopy. Controlled annealing at different temperatures led to the phase transformation of metallic cobalt from the hcp to fcc phase. The magnetic behaviour varies with the phase and the particle size; especially, the coercivity of nanoparticles exhibited strong dependence on the phase transformation of cobalt. The high saturation magnetization close to that of the bulk value was achieved in the case of the annealed samples. In addition to detailed structural and morphological characterization, the results of thermal and magnetic studies are also presented.

Magnetocaloric effect and nature of magnetic transition in nanoscale Pr0.5Ca0.5MnO3

Systematic measurements pertinent to the magnetocaloric effect and nature of magnetic transition around the transition temperature are performed in the 10 nm Pr0.5Ca0.5MnO3 nanoparticles (PCMO10). Maxwell's relation is employed to estimate the change in magnetic entropy. At Curie temperature (T-C) similar to 83.5 K, the change in magnetic entropy (-Delta S-M) discloses a typical variation with a value 0.57 J/kg K, and is found to be magnetic field dependent. From the area under the curve (Delta S vs T), the refrigeration capacity is calculated at T-C similar to 83.5K and it is found to be 7.01 J/kg. Arrott plots infer that due to the competition between the ferromagnetic and anti-ferromagnetic interactions, the magnetic phase transition in PCMO10 is broadly spread over both in temperature as well as magnetic field coordinates. Upon tuning the particle size, size distribution, morphology, and relative fraction of magnetic phases, it may be possible to enhance the magnetocalorific effect further in PCMO10. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4759372]

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Microstructural Evolution and Some Unusual Effects During Thermo-Mechanical Cycling of Sn-Ag-Cu Alloys

Sn-Ag-Cu (SAC) solders are susceptible to appreciable microstructural coarsening during storage or service. This results in evolution of joint properties over time, and thereby influences the long-term reliability of microelectronic packages. Accurate prediction of this aging behavior is therefore critical for joint reliability predictions. Here, we study the precipitate coarsening behavior in two Sn-Ag-Cu (SAC) alloys, namely Sn-3.0Ag-0.5Cu and Sn-1.0Cu-0.5Cu, under different thermo-mechanical excursions, including isothermal aging at 150 degrees C for various lengths of time and thermo-mechanical cycling between -25 degrees C and 125 degrees C, with an imposed shear strain of similar to 19.6% per cycle, for different number of cycles. During isothermal aging and the thermo-mechanical cycling up to 200 cycles, Ag3Sn precipitates undergo rapid, monotonous coarsening. However, high number of thermo-mechanical cycling, usually between 200 and 600 cycles, causes dissolution and re-precipitation of precipitates, resulting in a fine and even distribution. Also, recrystallization of Sn-grains near precipitate clusters was observed during severe isothermal aging. Such responses are quite unusual for SAC solder alloys. In the regime of usual precipitate coarsening in these SAC alloys, an explicit parameter, which captures the thermo-mechanical history dependence of Ag3Sn particle size, was defined. Brief mechanistic description for the recrystallization of Sn grains during isothermal aging and reprecipitation of the Ag3Sn due to high number of thermo-mechanical cycles are also presented.

Synthesis of a mixed-metal spinel, NiMn2O4, through site-selective substitution in MOF, (NiMn2){C6H3(COO)(3)}(2)]: synthesis, structure and magnetic studies

A mixed-metal metal-organic framework (MOF) compound NiMn2{C6H3(COO)(3)}(2)], I, is prepared hydrothermally by replacing one of the octahedral Mn2+ ions in Mn-3{C6H3(COO)(3)}(2)] by Ni2+ ions. Magnetic studies on I suggest antiferromagnetic interactions with weak canted antiferromagnetism below 8 K. On heating in flowing air I transforms to NiMn2O4 spinel at low temperature (T < 400 degrees C). The thermal decomposition of I at different temperatures results in NiMn2O4 with particle sizes in the nano regime. The nanoparticle nature of NiMn2O4 was confirmed using PXRD and TEM studies. Magnetic studies on the nanoparticles of NiMn2O4 indicate ferrimagnetism. The transition temperature of NiMn2O4 nanoparticles exhibits a direct correlation with the particle size. This study highlights the usefulness of MOF compound as a single-source precursor for the preparation of important ceramic oxides with better control on the stoichiometry and particle size.

Superparamagnetic behaviour and T-1, T-2 relaxivity of ZnFe2O4 nanoparticles for magnetic resonance imaging

In the present study, ZnFe2O4 nanoparticles were synthesized by the chemical co-precipitation followed by calcinations at 473 and 673K for 4h. Particle sizes obtained were 4 and 6nm for the calcination temperatures of 473 and 673K, respectively. To study the origin of system's low temperature spin dynamic behaviour, temperature dependence of susceptibility was investigated as a function of particle size and frequency. Slight increase in the grain size from 4nm at 473K to 6nm at 673K has led to a peak shift of temperature dependence of susceptibility measured at a constant frequency of 400Hz. Temperature dependence of at different frequencies also resulted in peak shift. Relaxation time dependence of peak temperature obeys a power law, which provides the fitting parameters within the range of superparamagnetic nature of the particles. Further, dependence of relaxation time and peak temperature obeys VogelFulcher law rather than NeelBrown equation demonstrating that the particles follow the behaviour of superparamagnetism of slightly interacting system. Spinlattice, T-1 and spinspin, T-2 relaxivity of proton of the water molecule in the presence of chitosan-coated superparamagnetic ZnFe2O4 nanoparticle yields the values of 0.002 and 0.360s(1)perppm.

Processing of enriched elemental boron (B-10 similar to 65 at. %)

Procedures were developed for purification and processing of electrodeposited enriched boron powder for control rod application in India's first commercial Proto Type Fast Breeder Reactor (PFBR). Methodology for removal of anionic (F-, Cl-, BF4-) and cationic (Fe2+, Fe3+, Ni2+) impurities was developed. Parameters for grinding boron flakes obtained after electrodeposition were optimized to obtain the boron powder having particle size less than 100 gm. The rate of removal of impurities was studied with respect to time and concentration of the reagents used for purification. Process parameters for grinding and removal of impurities were optimized. A flowsheet was proposed which helps in minimizing the purification time and concentration of the reagent used for the effective removal of impurities. The purification methodology developed in this work could produce boron that meets the technical specifications for control rod application in a fast reactor.

Effect of TiO2 on electrical and magnetic properties of Ni0.35Cu0.12Zn0.35Fe2O4 synthesized by the microwave-hydrothermal method

The nanocomposites of xTiO(2)+(1-x)Ni0.53Cu0.12Zn0.35Fe2O4 (where 0 <= x >= 1) were prepared using microwave hydrothermal (M H) method at 165 degrees C/45 min. The as-synthesized powders were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The particle size of the powder varies from 18 to 35 nm. The as prepared powders were densified at 500 degrees C/30 min using microwave sintering method. The sintered composites were characterized by XRD and scanning electron microscopy (SEM). The bulk densities of the present composites were increasing with the addition of TiO2. The grain sizes of all the composite vary between 65 nm and 90 nm. The addition of TiO2 to ferrite increased the dielectric properties (epsilon' and epsilon `') also the resonant frequency of all the composites was found to be greater than 1 GHz. The imaginary part of permeability mu `' was found to increase with an increase of TiO2.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Plant latex mediated green synthesis of ZnAl2O4:Dy3+ (1-9 mol%) nanophosphor for white light generation

ZnAl2O4:Dy3+ (1-9 mol%) nanophosphors were synthesized by a simple, cost effective and environmental friendly route using Euphorbia tirucalli plant latex. The structural properties and morphological features of the phosphors were well studied by PXRD, FTIR, SEM and TEM measurements. The luminescent properties of ZnAl2O4:Dy3+ (1-9 mol%) nanophosphors were investigated from the excitation and emission spectra. The phosphor performance was evaluated by color co-ordinates. The values were well located in the near white region as a result it was highly useful for the fabrication of green component in WLEDs. The average particle size was found to be similar to 9-18 nm and same was confirmed by TEM and Scherrer's method. The highest photoluminescence (PL) and thermoluminescence (TL) intensity was obtained to be similar to 7 mol% Dy3+ concentration. A single TL glow peak was recorded at 172 degrees C at a warming rate of 2.5 degrees Cs (1). The intensity at 172 degrees C peak increases linearly up to 1 kGy and after that it diminishes. PL intensity was studied with different plant latex concentration (2-8 ml) and highest PL intensity was recorded for similar to 8 ml. The optimized phosphor showed good reusability, low fading and wide range of linearity with gamma-dose hence the phosphor was quite useful in radiation dosimetry. (C) 2013 Elsevier B.V. All rights reserved.

A promising ketone containing alternating copolymer for organic photovoltaics

An alternating copolymer containing dithienylcyclopentadienone, thiophene and benzothiadiazole was synthesized by palladium (0) catalyzed Stille coupling reaction. Structural characterization of the synthesized alternating copolymer was carried out by NMR and FTIR spectroscopy. This solution processable copolymer shows an excellent thermal stability and has a broad absorption range from 300-800 nm. High LUMO energy level and low band gap of the synthesized copolymers suggest that, this copolymer will be a better donor material for application in organic photovoltaics. Particle size analysis and molecular weight determination of the synthesized copolymer through dynamic light scattering experiment indicates that, high molecular weight copolymer was obtained by this polymerization route. Photovoltaic devices were fabricated from the blend of copolymer and phenyl-C61- butyric acid methyl ester as the active material. Fabricated photovoltaic device results show that this alternating copolymer is a promising candidate for use in organic photovoltaics.

Evaluation of chitosan nanoformulations as potent anti-HIV therapeutic systems

Background: Antiretroviral Therapy (ART) is currently the major therapeutic intervention in the treatment of AIDS. ART, however, is severely limited due to poor availability, high cytotoxicity, and enhanced metabolism and clearance of the drug molecules by the renal system. The use of nanocarriers encapsulating the antiretroviral drugs may provide a solution to the aforementioned problems. Importantly, the application of mildly immunogenic polymeric carrier confers the advantage of making the nanoparticles more visible to the immune system leading to their efficient uptake by the phagocytes. Methods: The saquinavir-loaded chitosan nanopartides were characterized by transmission electron microscopy and differential scanning calorimetry and analyzed for the encapsulation efficiency, swelling characteristics, particle size properties, and the zeta potential. Furthermore, cellular uptake of the chitosan nanocarriers was evaluated using confocal microscopy and Flow cytometry. The antiviral efficacy was quantified using viral infection of the target cells. Results: Using novel chitosan carriers loaded with saquinavir, a protease inhibitor, we demonstrate a drug encapsulation efficiency of 75% and cell targeting efficiency greater than 92%. As compared to the soluble drug control, the saquinavir-loaded chitosan carriers caused superior control of the viral proliferation as measured by using two different viral strains, NL4-3 and Indie-C1, and two different target T-cells, Jurkat and CEM-CCR5. Conclusion: Chitosan nanoparticles loaded with saquinavir were characterized and they demonstrated superior drug loading potential with greater cell targeting efficiency leading to efficient control of the viral proliferation in target T-cells. General significance: Our data ascertain the potential of chitosan nanocarriers as novel vehicles for HIV-1 therapeutics. (C) 2013 Elsevier B.V. All rights reserved.