Dynamics of zeolite cage and its effect on the diffusion properties of sorbate: persistence of diffusion anomaly in NaA zeolite

Recent computer simulations on zeolites Y and A have found that the diffusion coefficient and the rate of intercage diffusion exhibit, apart from a linear dependence on the reciprocal of the square of the sorbate diameter, an anomalous peak as sorbate diameter approaches the window diameter. Here we report molecular dynamics simulations of zeolite NaA incorporating framework flexibility as a function of sorbate diameter in order to verify the existence of anomalous diffusion. Results suggest persistence of anomalous diffusion or ring effect. This suggests that the anomalous behavior is a general effect characteristic of zeolites Y and A. The barrier for diffusion across the eight-ring window is seen to be negative and is found to decrease with sorbate size. The effect of sorbate on the cage motion has also been investigated. Results suggest that the window expands during intercage migration only if the sorbate size is comparable to the window diameter. Flexible cage simulations yield a higher value for the diffusion coefficient and also the rate of intercage diffusion. This increase has been shown to be due to an increase in the intercage diffusions via the centralized diffusion mode rather than the surface-mediated mode. It is shown that this increase arises from an increase in the single particle density distribution in the region near the cage center.

Effect of strain rate on the high-temperature low-cycle fatigue properties of a nimonic PE-16 superalloy

Strain-rate effects on the low-cycle fatigue (LCF) behavior of a NIMONIC PE-16 superalloy have been evaluated in the temperature range of 523 to 923 K. Total-strain-controlled fatigue tests were per-formed at a strain amplitude of +/-0.6 pct on samples possessing two different prior microstructures: microstructure A, in the solution-annealed condition (free of gamma' and carbides); and microstructure B, in a double-aged condition with gamma' of 18-nm diameter and M23C6 carbides. The cyclic stress response behavior of the alloy was found to depend on the prior microstructure, testing temperature, and strain rate. A softening regime was found to be associated with shearing of ordered gamma' that were either formed during testing or present in the prior microstructure. Various manifestations of dynamic strain aging (DSA) included negative strain rate-stress response, serrations on the stress-strain hysteresis loops, and increased work-hardening rate. The calculated activation energy matched well with that for self-diffusion of Al and Ti in the matrix. Fatigue life increased with an increase in strain rate from 3 x 10(-5) to 3 x 10(-3) s-1, but decreased with further increases in strain rate. At 723 and 823 K and low strain rates, DSA influenced the deformation and fracture behavior of the alloy. Dynamic strain aging increased the strain localization in planar slip bands, and impingement of these bands caused internal grain-boundary cracks and reduced fatigue life. However, at 923 K and low strain rates, fatigue crack initiation and propagation were accelerated by high-temperature oxidation, and the reduced fatigue life was attributed to oxidation-fatigue interaction. Fatigue life was maximum at the intermediate strain rates, where strain localization was lower. Strain localization as a function of strain rate and temperature was quantified by optical and scanning electron microscopy and correlated with fatigue life.

Glasslike elastic properties in the omega-beta alloys

We have measured the internal friction and speed of sound in several polycrystalline alloys, using compound torsional oscillators at frequencies between 60 kHz and 100 kHz and temperatures between 50 mK and 100 K. By combining these data with existing elastic and thermal data on similar alloys, we find that those alloys which can undergo diffusionsless phase transitions, such as Ti:Nb, Ti:V, or Zr:Nb in certain ranges of composition have glasslike excitations, since they have elastic properties which agree in magnitude and temperature dependence with those of amorphous solids. By contrast, crystalline continuous solution alloys, such as Nb:Ta, or alloys with diffusive phase transitions, such as high-pressure quenched Al94Si6, have the same elastic properties as are known for crystals.

Investigation on the Magnetic Anomaly and the Role of Orbital Moment on the Magnetic Properties of LaMn0.5Co0.5O3

Two distinct ferromagnetic phases are present in LaMn0.5Co0.5O3 for which the spin-only magnetic moment calculated from the high temperature dc susceptibility is found to be unusually high. Such a high moment can only be accounted for by assigning the valence state of the cations to Mn2+-Co4+. This is unrealistic as the earlier report based on X-ray absorption spectroscopy (XAS) has suggested the valence state to be mainly Mn4+-Co2+ with traces of Co3+. Also from our studies using XAS, it is found that the valence state is mainly Mn4+-Co2+. In addition, no notable difference is observed in the minor Co3+ present in both phases. Our results based on X-ray magnetic circular dichroism studies (XMCD) reveal the presence of ``distinct'' high orbital moment associated with Co2+ for both phases. Thus it is found that the distinctness of the orbital moment also plays a vital role in determining the magnetic moment and T-c of both phases of LaMn0.5Co0.5O3. By considering the orbital moment obtained from XMCD, the anomaly in the paramagnetic susceptibility is resolved and thus we are able to assign the valence state to Mn4+-Co2+ configuration. The difference in the magnitude of orbital moment in both phases is believed to be due to the crystal field effects.

DNA Photocleavage and Cytotoxic Properties of Ferrocene Conjugates

Ferrocenyl conjugates 2-ferrocenylimidazophenanthroline (1) and 2-ferrocenylimidazophenanthrene (2) were prepared, characterized, and their photoinduced DNA cleavage and photocytotoxic activity were studied. 2-Phenylimidazophenanthroline (3) was used as a control species. Compound 2 was characterized by X-ray crystallography. The interaction of the compounds with double-stranded calf thymus DNA (CT DNA) was studied. The compounds show good binding affinity to CT DNA with K-b values of approximately 10(5) M-1. Thermal denaturation data suggest the groove binding nature of the compounds. The redox-active compounds show poor chemical nuclease activity in the presence of hydrogen peroxide and glutathione (GSH). Compound 1 exhibits significant DNA photocleavage activity in visible light of 476 and 532 nm. Compound 3 shows only moderate DNA cleavage activity. The positive effect of the ferrocenyl moiety is demonstrated by the DNA photocleavage data. Mechanistic investigations reveal the formation of superoxide as well as hydroxyl radicals as the active species. The photocytotoxicity of the compounds in HeLa cells was studied upon irradiation with visible light (400-700 nm). Compound 1 shows efficient photocytotoxic activity with an IC50 value of 13 mu M, while compounds 2 and 3 are less active with IC50 values of > 50 and 22 mu M, respectively.

Substrate-dependent structure, microstructure, composition and properties of nanostructured TiN films

Titanium nitride films of a thickness of similar to 1.5 mu m were deposited on amorphous and crystalline substrates by DC reactive magnetron sputtering at ambient temperature with 100% nitrogen in the sputter gas. The growth of nanostructured, i.e. crystalline nano-grain sized, films at ambient temperature is demonstrated. The microstructure of the films grown on crystalline substrates reveals a larger grain size/crystallite size than that of the films deposited on amorphous substrates. Specular reflectance measurements on films deposited on different substrates indicate that the position of the Ti-N 2s band at 2.33 eV is substrate-dependent, indicating substrate-mediated stoichiometry. This clearly demonstrates that not only structure and microstructure, but also chemical composition of the films is substrate-influenced. The films deposited on amorphous substrates display lower hardness and modulus values than the films deposited on crystalline substrates, with the highest value of hardness being 19 GPa on a lanthanum aluminate substrate. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of substitution of Y on the structural, magnetic, and thermal properties of hexagonal DyMnO3 single crystals

We investigate the structural, magnetic, and specific heat behavior of the hexagonal manganite Dy0.5Y0.5MnO3 in order to understand the effect of dilution of Dy magnetism with nonmagnetic yttrium. In this compound, the triangular Mn lattice orders antiferromagnetic at T-N(Mn) approximate to 68 K observed experimentally in the derivative of magnetic susceptibility as well as in specific heat. In addition, a low-temperature peak at T-N(Dy) similar to 3 K is observed in specific heat which is attributed to rare earth order. The T-N(Mn) increases by 9 K compared to that of hexagonal (h) DyMnO3 while T-N(Dy) is unchanged. A change in slope of thermal evolution of lattice parameters is observed to occur at temperature close to T-N(Mn). This hints at strong magnetoelastic coupling in this geometric multiferroic. In magnetization measurements, steplike features are observed when the magnetic field is applied along the c axis which shift to higher fields with temperature and vanish completely above 40 K. The presence of different magnetic phases at low temperature and strong magnetoelastic effects can lead to such field-induced transitions which resemble metamagnetic transitions. This indicates the possibility of strong field-induced effects in dielectric properties of this material, which is unexplored to date.

Role of lattice defects and crystallite morphology in the UV and visible-light-induced photo-catalytic properties of combustion-prepared TiO2

The physico-chemical, photo-physical and micro-structural properties responsible for the strikingly different photocatalytic behavior of combustion-prepared TiO2 (c.TiO2) and Degussa P25 (d.TiO2) samples are elucidated in this study. Electron microscopy and selected area electron diffraction micrographs revealed that the two samples exhibited different morphologies. The grains of c.TiO2 were spherical and comprised of 5-6 nm size primary particle. On the other hand, d.TiO2 consisted of large (0.5-3.0 mu m) size and irregular shape aggregates having primary particles of 15-40 nm cross-sectional diameter. The ESR study revealed that the presence of certain defect states in c.TiO2 helped in stabilization of O-. and Ti3+-OH type species during room-temperature UV-irradiation. No such paramagnetic species were however formed over d.TiO2 under similar conditions. C1s and Ti 2p XPS spectra provide evidence for the presence of some lattice vacancies in c.TiO2 and also for the bulk Ti4+ -> Ti3+ conversion during its UV-irradiation. Compared to d.TiO2, c.TiO2 displayed considerably higher activity for discoloration of methyl orange but very poor activity for splitting of water, both under UV and visible light radiations. This is attributed to enhanced surface adsorption of dye molecules over c.TiO2, because of its textural features and also the presence of photo-active ion-radicals. On the other hand, the poor activity of c.TiO2 for water splitting is related to certain defect-induced inter-band charge trapping states in the close vicinity of valence and conduction bands of c.TiO2, as revealed by thermoluminescence spectroscopy. Further, the dispersion of nanosize gold particles gave rise to augmented activity of both the catalysts, particularly for water splitting. This is explained by the promotional role of Au-0 or Au-0/TiO2 interfacial sites in the adsorption and charge-adsorbate interaction processes. (C) 2011 Elsevier B.V. All rights reserved.

Electrical transport properties of 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) glasses

Transparent glasses in the system 0.5Li(2)O-0.5M(2)O-2B(2)O(3) (M = Li, Na and K) were fabricated via the conventional melt quenching technique. The amorphous and glassy nature of the samples was confirmed via the X-ray powder diffraction and the differential scanning calorimetry, respectively. The frequency and temperature dependent characteristics of the dielectric relaxation and the electrical conductivity were investigated in the 100 Hz-10 MHz frequency range. The imaginary part of the electric modulus spectra was modeled using an approximate solution of Kohrausch-Williams-Watts relation. The stretching exponent, (3, was found to be temperature independent for 0.5Li(2)O-0.5Na(2)O-2B(2)O(3) (LNBO) glasses. The activation energy associated with DC conduction was found to be higher (1.25 eV) for 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) glasses than that of the other glass systems under study. This is attributed to the mixed cation effect. (C) 2011 Elsevier By. All rights reserved.

Linear optical properties of BaNaB9O15, BaLiB9O15 and SrLiB9O15 glasses

Transparent BaNaB9O15 (BNBO), BaLiB9O15 (BLBO) and SrLiB9O15 (SLBO) glasses were fabricated via the conventional melt-quenching technique. X-ray diffraction (XRD) and Differential thermal analysis (DTA) studies carried out on the as-quenched glasses confirmed their amorphous and glassy nature, respectively. The optical properties for these as-quenched glasses were investigated. The refractive index, optical band gap. Urbach energy and Fermi energy were determined. The average electronic polarizability calculated from the refractive index expression. (C) 2011 Elsevier B.V. All rights reserved.

Sorbate properties of xenon in cloverite: A molecular dynamics study

Molecular dynamics calculations on xenon adsorbed in the cubic cavity of cloverite, a gallophosphate, is presented. Guest-host radial distribution functions, guest-host energy distribution functions, power spectra, and diffusion coefficients for xenon are reported at 397, 494, and 716 K. Results suggest that xenon is highly mobile at 700 K. A shift in the peak position of the power spectra toward lower frequency is observed with increase in temperature. (C) 1994 Academic Press, Inc.

Study of electrical properties of pulsed excimer laser deposited strontium titanate films

Polycrystalline SrTiO3 films were prepared by pulsed excimer laser ablation on Si and Pt coated Si substrates. Several growth parameters were varied including ablation fluence, pressure, and substrate temperature. The structural studies indicated the presence of [100] and [110] oriented growth after annealing by rapid thermal annealing at 600-degrees-C for 60 s. Deposition at either lower pressures or at higher energy densities encouraged film growth with slightly preferred orientation. The scanning electron microscopy studies showed the absence of any significant particulates on the film surface. Dielectric studies indicated a dielectric constant of 225, a capacitance density of 3.2 fF/mum2, and a charge density of 40 fC/mum for films of 1000 nm thick. The dc conductivity studies on these films suggested a bulk limited space charge conduction in the high field regime, while the low electric fields induced an ohmic conduction. Brief time dependent dielectric breakdown studies on these films, under a field of 250 kV/cm for 2 h, did not exhibit any breakdown, indicating good dielectric strength.