A computational study on the superionic behaviour of ThO2.

This study reports the density functional theory (DFT) and classical molecular dynamics (MD) study of the lattice dynamical, mechanical and anionic transport behaviours of ThO2 in the superionic state. DFT calculations of phonon frequencies were performed at different levels of approximation as a function of isotropic dilation (ε) in the lattice parameter. With the expansion of the lattice parameter, there is a softening of B1u and Eu phonon modes at the X symmetry point of the Brillouin zone. As a result of the nonlinear decrease at the X point, the B1u and Eu phonon modes cross each other at ε = 0.03, which is associated with a sharp increase in the narrow peak of the phonon density of states, signifying a higher occupation and hence a higher coupling of these modes at high temperatures. The mode crossing also indicates anionic conductivity in the 〈001〉 direction leading to occupation of interstitial sites. Moreover, MD and nudged elastic band calculated diffusion barriers indicate that 〈001〉 is the easy direction for anion migration in the normal and superionic states. With a further increase in the lattice parameter, the B1u mode continues to soften and becomes imaginary at a strain (ε) of 0.036 corresponding to a temperature of 3430 K. The calculated temperature variation of single crystal elastic constants shows that the fluorite phase of ThO2 remains elastically stable up to the superionic regime, though the B1u phonon mode is imaginary in that state. This leads to anionic disorder at elevated temperatures. Tracking of anion positions in the superionic state as a function of time in MD simulations suggests a hopping model in which the oxygen ions migrate from one tetrahedral site to another via octahedral interstitial sites.

Perovskite-Ni composite: a potential route for management of radioactive metallic waste.

Management of nickel - based radioactive metallic wastes is a difficult issue. To arrest the release of hazardous material to the environment it is proposed to develop perovskite coating for the metallic wastes. Polycrystalline BaCe0.8Y0.2O3-δ perovskite with orthorhombic structure has been synthesized by sol-gel route. Crystallographic analyses show, the perovskite belong to orthorhombic Pmcn space group at room temperature, and gets converted to orthorhombic Incn space group at 623K, cubic Pm3m space group (with a=4.434Å) at 1173K and again orthorhombic Pmcn space group at room temperature after cooling. Similar observations have been made from micro-Raman study as well. Microstructural studies of BaCe0.8Y0.2O3-δ-NiO/Ni composites showed absence of any reaction product at the interface. This suggests that both the components (i.e. perovskite and NiO/Ni) of the composite are compatible to each other. Interaction of BaCe0.8Y0.2O3-δ-NiO/Ni composites with simulated barium borosilicate waste glass melt also did not reveal any reaction product at the interfaces. Importantly, uranium from the waste glass melt was found to be partitioned within BaCe0.8Y0.2O3-δ perovskite structure. It is therefore concluded that BaCe0.8Y0.2O3-δ can be considered as a good coating material for management of radioactive Ni based metallic wastes.

Investigation of short-range structural order in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 glasses, using X-ray absorption spectroscopy and ab initio molecular dynamics simulations.

Short-range order has been investigated in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 metallic glasses using X-ray absorption spectroscopy and ab initio molecular dynamics simulations. While both of these alloys are good glass formers, there is a difference in their glass-forming abilities (Zr41.5Ti41.5Ni17 > Zr69.5Cu12Ni11Al7.5). This difference is explained by inciting the relative importance of strong chemical order, icosahedral content, cluster symmetry and configuration diversity.

Uptake of hazardous radionuclides within layered chalcogenide for environmental protection.

Ensuring environmental protection in and around nuclear facilities is a matter of deep concern. Toward this, layered chalcogenide with CdI2 crystal structure has been prepared. Structural characterizations of layered chalcogenide suggest 'topotactic ionic substitution' as the dominant mechanism behind uptake of different cations within its lattice structure. An equilibration time of 45 min and volume to mass ratio of 30:1 are found to absorb (233)U, (239)Pu, (106)Ru, (85+89)Sr, (137)Cs and (241)Am radionuclides to the maximum extents.

In situ formation of stable gold nanoparticles in polymer inclusion membranes.

Gold nanoparticles (Au nps) were synthesized in the matrix of a plasticized anion-exchange membrane. The membrane was prepared by solvent casting of the solution containing a liquid anion exchanger trioctylmethylammonium chloride (Aliquat-336), a matrix-forming polymer cellulose triacetate (CTA), and a plasticizer dioctyl phthalate (DOP) dissolved in CH(2)Cl(2). For in situ synthesis of Au nps, the membrane samples were equilibrated with a well-stirred solution containing 0.01 mol L(-1)HAuCl(4). AuCl(4)(-) ions were transferred to membrane matrix as an ion pair with Aliquat-336 by an ion-exchange mechanism. In a second step, AuCl(4)(-) ion-loaded membrane samples were placed in a well-stirred 0.1 mol L(-1) aqueous solution of NaBH(4) for reduction. It was observed that 80% of the anion-exchange sites were readily available for the exchange process after formation of the Au nps. The content of Au nps in the membrane was increased either by increasing the concentration of the Aliquat-336 in membrane or by repeating sequential cycles of loading of AuCl(4)(-) ions followed by reduction with BH(4)(-) in the membrane matrix. TEM images of a cross section of the membrane showed that Au nps were dispersed throughout the matrix of the membrane but excluded from the surface. The size distribution of the nps was found to be dependent on Au content in the membrane. For example, 7- to 16-nm Au nps with average size 10 nm were observed in the membrane after the first cycle of synthesis. On increasing the Au content in the membrane by repeating the cycle of synthesis, the size dispersion of nps broadened from 5 to 20 nm without affecting the average size. The lambda(max) (530 nm) and intensity of the surface plasmon band of Au nps embedded in the matrix of membrane were found to remain unaltered over a testing period of a month in the samples kept in water as well as in air under ambient conditions. This indicated that Au nps were quite stable in the membrane matrix. The experimental information obtained by the radiotracers and energy-dispersive X-ray fluorescence (EDXRF) analyses has been used to understand the process of Au nps formation in the membrane matrix.

Excess enthalpy and luminescence studies of SnO2 nanoparticles.

The extra reactivity of nano materials is attributed to the excess surface energy stored in the sample. The excess enthalpy of SnO2 nano-particles were measured as a function of particle size using a calvet calorimeter. SnO2 with particle size 11, 27, 47 nm and bulk samples (1 microm) were dropped from room temperature to 987, 936 and 885 K and their H(T)-H298 values were determined. The excess enthalpies for SnO2 samples with particle sizes 11, 27 and 47 nm compared to the bulk sample calculated from the difference between H(T)-H298 values of the nano and the bulk samples were found to be 15.06, 3.05, 2.21 kJ x mol(-1) respectively. Luminescence experiments reveal that the surface trap electron density decreases with increase of particle size. The excess enthalpy is related to the surface trap intensity.

Luminescence study on Eu(3+) doped Y(2)O(3) nanoparticles: particle size, concentration and core-shell formation effects.

Nanoparticles of Eu(3+) doped Y(2)O(3) (core) and Eu(3+) doped Y(2)O(3) covered with Y(2)O(3) shell (core-shell) are prepared by urea hydrolysis for 3 h in ethylene glycol medium at a relatively low temperature of 140 °C, followed by heating at 500 and 900 °C. Particle sizes determined from x-ray diffraction and transmission electron microscopic studies are 11 and 18 nm for 500 and 900 °C heated samples respectively. Based on the luminescence studies of 500 and 900 °C heated samples, it is confirmed that there is no particle size effect on the peak positions of Eu(3+) emission, and optimum luminescence intensity is observed from the nanoparticles with a Eu(3+) concentration of 4-5 at.%. A luminescence study establishes that the Eu(3+) environment in amorphous Y (OH)(3) is different from that in crystalline Y(2)O(3). For a fixed concentration of Eu(3+) doping, there is a reduction in Eu(3+) emission intensity for core-shell nanoparticles compared to that of core nanoparticles, and this has been attributed to the concentration dilution effect. Energy transfer from the host to Eu(3+) increases with increase of crystallinity.

Green synthesis of highly stabilized nanocrystalline silver particles by a non-pathogenic and agriculturally important fungus T. asperellum.

A controlled and up-scalable biosynthetic route to nanocrystalline silver particles with well-defined morphology using cell-free aqueous filtrate of a non-pathogenic and commercially viable biocontrol agent Trichoderma asperellum is being reported for the first time. A transparent solution of the cell-free filtrate of Trichoderma asperellum containing 1 mM AgNO(3) turns progressively dark brown within 5 d of incubation at 25 °C. The kinetics of the reaction was studied using UV-vis spectroscopy. An intense surface plasmon resonance band at ∼410 nm in the UV-vis spectrum clearly reveals the formation of silver nanoparticles. The size of the silver particles using TEM and XRD studies is found to be in the range 13-18 nm. These nanoparticles are found to be highly stable and even after prolonged storage for over 6 months they do not show significant aggregation. A plausible mechanism behind the formation of silver nanoparticles and their stabilization via capping has been investigated using FTIR and surface-enhanced resonance Raman spectroscopy.

Vapor-phase photo-oxidation of methanol over nanosize titanium dioxide clusters dispersed in MCM-41 host material part 1: synthesis and characterization.

Nanosize clusters of titania were dispersed in mesoporous MCM-41 silica matrix with the help of the incipient wet-impregnation route, using an isopropanol solution of titanium isopropoxide as precursor. The clusters thus formed were of pure anatase phase and their size depended upon the titania loading. In the case of low (< 15 wt %) loadings, the TiO2 particles were X-ray and laser-Raman amorphous, confirming very high dispersion. These particles were mostly of < or = 2 nm size. On the other hand, larger size clusters (2-15 nm) were present in a sample with a higher loading of approximately 21 wt %. These particles of titania, irrespective of their size, exhibited an absorbance behavior similar to that of bulk TiO2. Powder X-ray diffraction, N2-adsorption and transmission electron microscopy results showed that while smaller size particles were confined mostly inside the pore system, the larger size particles occupied the external surface of the host matrix. At the same time, the structural integrity of the host was maintained even though some deformation in the pore system was noticed in the case of the sample having highest loading. The core level X-ray photoelectron spectroscopy results revealed a + 4 valence state of Ti in all the samples. A positive binding energy shift and the increase of the width of Ti 2p peaks were observed, however, with the decrease in the particle size of supported titania crystallites, indicative of a microenvironment for surface sites that is different from that of the bulk.