Synthesis, structure and ionic conductivity in scheelite type Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x=0 and 0.25, Ln = Pr, Sm)

Scheelite type solid electrolytes, Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) have been synthesized using a solid state method. Their structure and ionic conductivity (a) were obtained by single crystal X-ray diffraction and ac-impedance spectroscopy, respectively. X-ray diffraction studies reveal a space group of I4(1)/a for Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) scheelite compounds. The unsubstituted Li0.5Ce0.5MoO4 showed lithium ion conductivity similar to 10(-5)-10(-3) Omega(-1)cm(-1) in the temperature range of 300-700 degrees C (sigma = 2.5 x 10(-3) Omega(-1) cm(-1) at 700 degrees C). The substituted compounds show lower conductivity compared to the unsubstituted compound, with the magnitude of ionic conductivity being two (in the high temperature regime) to one order (in the low temperature regime) lower than the unsubstituted compound. Since these scheelite type structures show significant conductivity, the series of compounds could serve in high temperature lithium battery operations.

Perturbative growth of cosmological clustering. I: Formalism

Here we rederive the hierarchy of equations for the evolution of distribution functions of various orders using a convenient parameterization. We use this to obtain equations for two- and three-point correlation functions in powers of a small parameter, viz., the initial density contrast. The correspondence of the lowest order solutions of these equations to the results from the linear theory of density perturbations is shown for an OMEGA = 1 universe. These equations are then used to calculate, to the lowest order, the induced three-point correlation function that arises from Gaussian initial conditions in an OMEGA = 1 universe. We obtain an expression which explicitly exhibits the spatial structure of the induced three-point correlation function. It is seen that the spatial structure of this quantity is independent of the value of OMEGA. We also calculate the triplet momentum. We find that the induced three-point correlation function does not have the ''hierarchical'' form often assumed. We discuss possibilities of using the induced three-point correlation to interpret observational data. The formalism developed here can also be used to test a validity of different schemes to close the

A lower bound for the hitting set size for combinatorial rectangles and an application

We prove a lower bound of Omega(1/epsilon (m + log(d - a)) where a = [log(m) (1/4epsilon)] for the hitting set size for combinatorial rectangles of volume at least epsilon in [m](d) space, for epsilon is an element of [m(-(d-2)), 2/9] and d > 2. (C) 2002 Elsevier Science B.V. All rights reserved.

Dynamic matrix rank with partial lookahead

We consider the problem of maintaining information about the rank of a matrix $M$ under changes to its entries. For an $n \times n$ matrix $M$, we show an amortized upper bound of $O(n^{\omega-1})$ arithmetic operations per change for this problem, where $\omega < 2.376$ is the exponent for matrix multiplication, under the assumption that there is a {\em lookahead} of up to $\Theta(n)$ locations. That is, we know up to the next $\Theta(n)$ locations $(i_1,j_1),(i_2,j_2),\ldots,$ whose entries are going to change, in advance; however we do not know the new entries in these locations in advance. We get the new entries in these locations in a dynamic manner.

Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

Excess dissipation in dense emulsions

A new model for the structure, elastic properties and dynamics of foams and concentrated emulsions is presented, based on the idea of local regions lacking shear-rigidity in one or more directions which vary randomly through the medium. It is shown to lead naturally to slow (t(-1/2)) stress-relaxation, implying a piece of the dynamic modulus scaling with frequency omega as omega(1/2). Striking experimental confirmation of this prediction using a novel experimental technique is reported, and challenges for the theoretician are offered. This work was done in collaboration with Andrea Liu, Tom Mason, Hu Gang, and David Weitz [1].

Organization of Mn-Clusters in pcu and bcu Networks: Synthesis, Structure, and Properties

Two new anionic inorganic-organic hybrid compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5), I, and H3O](2)Mn-7(mu(3)-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8), II have been prepared by employing mild solvothennal methods. Both the compounds have three-dimensionally extended structures formed by Mn-6 and Mn-7 clusters, respectively. The connectivity between Mn-6 and Mn-7 clusters and 4,4'-sulfonyldibenzoic acid anions (SDBA(2-)) results in a six connected pcu network in I and an eight connected bcu network in II. The presence of hydronium ion (H-3(O+)) along with the solvent molecules in the channels of both the compounds suggested proton conduction in the solids. Proton conductivity studies gave values of similar to 3 x 10(-4) Omega(-1) cm(-1) 98% relative humidity in both the compounds. The high activation energies indicate a vehicle mechanism in the compounds I and II. Magnetic studies indicate antiferromagnetic behavior in both the compounds.

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Effect of Molecular Flexibility on the Nematic-to-Isotropic Phase Transition for Highly Biaxial Molecular Non-Symmetric Liquid Crystal Dimers

In this work, a study of the nematic (N)-isotropic (I) phase transition has been made in a series of odd non-symmetric liquid crystal dimers, the alpha-(4-cyanobiphenyl-4'-yloxy)-omega-(1-pyrenimine-benzylidene-4'-oxy) alkanes, by means of accurate calorimetric and dielectric measurements. These materials are potential candidates to present the elusive biaxial nematic (N-B) phase, as they exhibit both molecular biaxiality and flexibility. According to the theory, the uniaxial nematic (N-U)-isotropic (I) phase transition is first-order in nature, whereas the N-B-I phase transition is second-order. Thus, a fine analysis of the critical behavior of the N-I phase transition would allow us to determine the presence or not of the biaxial nematic phase and understand how the molecular biaxiality and flexibility of these compounds influences the critical behavior of the N-I phase transition.

Effect of network modifiers on spectroscopic properties of erbium-doped phosphate glasses

The integrated absorption cross section Sigma(abs), I peak emission cross section sigma(cmi), Judd-Ofeld intensity parameters Omega(iota) ( t = 2,4,6), and spontaneous emission probability A(R) of Er3+ ions were determined for Erbium doped alkali and alkaline earth phosphate glasses. It is found the compositional dependence of sigma(emi) 5 almost similar to that of Sigma(abs), which is determined by the sum, of Omega(1) (3 Omega(2) + 10 Omega(4) + 21 Omega(6)). In addition, the compositional dependence of Omega(1) was studied in these glass systems. As a result, compared with. Omega(4) and Omega(6) the Omega(2) has a stronger compositional dependence on the ionic radius and content of modifers. The covalency of Er-O bonds in phosphate glass is weaker than that in silicate glass, germanate glass, aluminate glass, and tellurate glass, since Omega(6) of phosphate glass is relatively large. A(R) is affected by the covalency of the Er3+ ion sites and corresponds to the Omega(6) value.

钕离子掺杂和钕铝共掺高硅氧玻璃的光谱性质研究

Nd-doped and Nd-Al-codoped high silica glasses were obtained by sintering porous glass impregnated with Nd3+ and Al3+ ions. The absorption, fluorescence spectra and fluorescence lifetime of Nd-doped and Nd-Al-codoped high silica glasses were measured. The intensity parameters Omega(1), ( t = 2, 4, 6), fluorescence lifetime, radiative quantum efficiency and stimulated emission cross section were calculated by Judd-Ofelt theory. The effect of aluminum codoping on the fluorescence and structural properties of Nd-doped silica glass has been discussed. By comparing the spectroscopic properties with other Nd-doped oxide glasses and commercial silicate glasses, this Nd-doped high silica glass is likely to be a promising laser material for use in high power and high repetition rate lasers.

Efficient frequency upconversion emission in Er3+-doped novel strontium lead bismuth glass

Er3+ -doped strontium lead bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(1) (t = 2,4,6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 2.95 x 10(-20), Omega(4) = 0-91 X 10(-20), and Omega(6) = 0.36 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) --> I-4(15/2), S-4(3/2) I-4(15/2), and F-4(9/2) --> I-4(15/2) respectively were observed. The upconversion mechanisms are discussed based oil the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (C) 2004 Published by Elsevier B.V.

Nanocrystalline silicon films with high conductivity and the application for PIN solar cells

Intrinsic nanocrystalline silicon films (nc-Si:H) were prepared by plasma enhanced chemical vapor deposition (PECVD) method. Films' microstructures and characteristics were studied with Raman spectroscopy and Atom Force Microscope (AFM). The electronic conductivity of nc-Si:H films was found to be 4.9 x 10(0)Omega(-1) cm(-1), which was one order of magnitude higher than the reported 10(-3)-10(-1)Omega(-1)cm(-1). And PIN solar cells with nc-Si:H film as intrinsic thin-layer (ITO/n(+)-nc-Si:H/i-nc-Si:H/p-c-Si/Ag) were researched. The cell's performances were measured, the open-circuit voltage V-oc was 534.7 mV, short-circuit current I-sc was 49.24 mA (3 cm(2)) and fill factor FF was 0.4228. (c) 2006 Elsevier Ltd. All rights reserved.

Structual and optoelectronic properties of polycrystalline silicon thin films prepared by hot-wire chemical vapor deposition at low temperatures

Polycrystalline silicon thin films were prepared by hot-wire chemical vapor deposition ( HWCVD) on glass at 250 degreesC with W or Ta wire as the catalyzers. The structual and optoelectronic properties as functions of the filament temperature, deposition pressure and the filament-substrate distance were studied, and the optimized polycrystalline silicon thin films were obtained with X-c > 90 % ( X-c denotes the crystalline ratio of the film), crystal grain size about 30-40nm, R-d approximate to 0.8nm/s, sigma(d) about 10(-7) - 10(-6) Omega(-1) cm(-1), Ea(a) approximate to 0.5eV and E-opt less than or equal to 1.3eV.

Characteristics of the conductive polyimide film surfaces induced by ultraviolet laser beam

A conducting layer with the conductivity of 1.2 Omega(-1)cm(-1) stripped in a solvent from KrF-laser-irradiated polyimide thin film is taken as a sample to determine the microstructure of the conducting layer. Fourier-transform infrared and X-ray photoelectron spectroscopies show the formation of the carbon-rich clusters after irradiation. The element analysis gives the atomic ratio of C:H:N:O for the carbon-rich cluster as 60:20:3:1. Wide-angle X-ray diffraction indicates that the conducting layer is mainly amorphous carbon with a small amount of the short-range ordered carbon-rich clusters. This study suggests a structural model with three-layer carbon sheets linked together in a random fashion for the short-range ordered carbon-rich clusters. The interplanar spacing is 3.87 Angstrom and the layer diameter 25 Angstrom. The transport model of variable-range hopping in three dimensions is used to explain the conducting behavior of the conducting layer. In our case, the short-range ordered carbon-rich clusters are assumed to be conducting islands dispersed in the amorphous carbon-rich cluster matrix.