Low-temperature polaronic relaxations with variable range hopping conductivity in FeTiMO(6) (M = Ta,Nb,Sb)

Low-temperature dielectric measurements on FeTiMO(6) (M = Ta,Nb,Sb) rutile-type oxides at frequencies from 0.1 Hz to 10 MHz revealed anomalous dielectric relaxations with frequency dispersion. Unlike the high-temperature relaxor response of these materials, the low-temperature relaxations are polaronic in nature. The relationship between frequency and temperature of dielectric loss peak follows T(-1/4) behavior. The frequency dependence of ac conductivity shows the well-known universal dielectric response, while the dc conductivity follows Mott variable range hopping (VRH) behavior, confirming the polaronic origin of the observed dielectric relaxations. The frequency domain analysis of the dielectric spectra shows evidence for two relaxations, with the high-frequency relaxations following Mott VRH behavior more closely. Significantly, the Cr- and Ga-based analogs, CrTiNbO(6) and GaTiMO(6) (M = Ta,Nb), that were also studied, did not show these anomalies.

Optical conductivity of perovskite manganites

We calculate the optical conductivity sigma(omega) for doped rare-earth manganites based on the recently proposed microscopic ``two fluid'' l-b model. We study the temperature dependence of sigma(omega) for La(0.825)Sr(0.175)MnO(3), which has a metallic ground state. At low temperatures, the calculated sigma(omega) shows a ``two-peak'' structure consisting of a far-infrared coherent Drude peak and a broad mid-infrared ``polaron'' peak, as observed in experiments. Upon heating, the Drude peak rapidly loses spectral weight, and sigma(omega) crosses over to having just a single broad mid-infrared peak. The temperature dependence of the mid-infrared peak and the spectral weight transfer between the two peaks are also in agreement with experimental findings. We also study the doping dependence of sigma(omega) for the same compound. The integrated spectral weight under the Drude peak increases rapidly as the doping level is increased from an underdoped, insulating state (x = 0.1) to a highly doped, metallic state (x = 0.3), again in agreement with trends seen experimentally.

Thermally induced phase separation in P alpha MSAN/PMMA blends in presence of functionalized multiwall carbon nanotubes: Rheology, morphology and electrical conductivity

The focus of this work is the evaluation and analysis of the state of dispersion of functionalized multiwall carbon nanotubes (CNTs), within different morphologies formed, in a model LCST blend (poly[(alpha-methylstyrene)-co-(acrylonitrile)]/poly(methyl-methacryla te), P alpha MSAN/PMMA). Blend compositions that are expected to yield droplet-matrix (85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA, wt/wt) and co-continuous morphologies (60/40 P alpha MSAN/PMMA, wt/wt) upon phase separation have been combined with two types of CNTs; carboxylic acid functionalized (CNTCOOH) and polyethylene modified (CNTPE) up to 2 wt%. Thermally induced phase separation in the blends has been studied in-situ by rheology and dielectric (conductivity) spectroscopy in terms of morphological evolution and CNT percolation. The state of dispersion of CNTs has been evaluated by transmission electron microscopy. The experimental results indicate that the final blend morphology and the surface functionalization of CNT are the main factors that govern percolation. In presence of either of the CNTs, 60/40 P alpha MSAN/PMMA blends yield a droplet-matrix morphology rather than co-continuous and do not show any percolation. On the other hand, both 85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA blends containing CNTPEs show percolation in the rheological and electrical properties. Interestingly, the conductivity spectroscopy measurements demonstrate that the 15/85 P alpha MSAN/PMMA blends with CNTPEs that show insulating properties at room temperature for the miscible blends reveal highly conducting properties in the phase separated blends (melt state) as a result of phase separation. By quenching this morphology, the conductivity can be retained in the blends even in the solid state. (C) 2011 Elsevier Ltd. All rights reserved.

Effective thermal conductivity of a heat generating rod bundle dissipating heat by natural convection and radiation

A numerical study of conjugate natural convection and surface radiation in a horizontal hexagonal sheath housing 19 solid heat generating rods with cladding and argon as the fill gas, is performed. The natural convection in the sheath is driven by the volumetric heat generation in the solid rods. The problem is solved using the FLUENT CFD code. A correlation is obtained to predict the maximum temperature in the rod bundle for different pitch-to-diameter ratios and heat generating rates. The effective thermal conductivity is related to the heat generation rate, maximum temperature and the sheath temperature. Results are presented for the dimensionless maximum temperature, Rayleigh number and the contribution of radiation with changing emissivity, total wattage and the pitch-to-diameter ratio. In the simulation of a larger system that contains a rod bundle, the effective thermal conductivity facilitates simplified modelling of the rod bundle by treating it as a solid of effective thermal conductivity. The parametric studies revealed that the contribution of radiation can be 38-65% of the total heat generation, for the parameter ranges chosen. Data for critical Rayleigh number above which natural convection comes into effect is also presented. (C) 2011 Elsevier B.V. All rights reserved.

Crystal Structure, Thermal Expansion and ElectricaH Conductivity of Yo.sCao.2Fel-x Mnx03+o (0 < x < 1.0)

The crystal structure, thennal expansion and electrical conductivity of the solid solutions YOgCao.2Fel-x MnxOJ+c5 (0 ~ x ~ 1.0) were investigated. All compositions had the GdFeOrtype orthorhombic perovskite structure with trace amounts of a second phase present in case of x = 0.8 and 1.0. The lattice parameters were detennined at room tempe'rature by using X-ray powder diffraction (XRPD). The pseudocubic lattice constant decreased with increasing x. The average I inear thermal expansion coefficient (anv) in the temperature range from 673 to 973 K showed negligible change with x up to x = 0.4. The thennal expansion curve for x = I had a slope approaching zero in the temperature range from 648 to 948 K. The calculated activation energy values for electrical conduction indicate that conduction occurs primarily by the small polaron hopping mechanism. The drastic drop in electrical conductivity for a small addition of Mn (0 ~ x ~ 0.2) is caused by the preferential fonnation of Mn4t ion~ (rather than Fe4 +) which act as carrier traps. This continues till the charge compensation for the divalent ions on the A-site is complete. The results indicate that with further increase in manganese content (beyond x =0.4) in the solid solutions, there is an increase in exc :::ss oxygen and consequently, a small increase in Mn'll il>I1~, which are charge compensated by the formation of cation vancancies.

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Structure and temperature dependence of conductivity of Ag2.5Se‐Se composite

Rapid solidification of Ag‐53 at. % Se alloy resulted in the formation of a composite mixture of Ag2.5Se and Se. The microstructure consists of spherical Se grains of 2–20 μm size, randomly distributed in a matrix of Ag2.5 Se. The Se grains were found to be layered hexagonal while the Ag2.5 Se had an orthorhombic crystal structure. The unit cell size of this phase, however, was twice that reported for the equilibrium orthorhombic Ag2 Se compound. The conductivity σ variation with temperature in the range 80–320 K was found to be similar to that observed in degenerate semiconductors. The σ decreased from 295 Ω−1 cm−1 at room temperature to a saturation value of 70 Ω−1 cm−1 for temperatures <80 K. The results are discussed in terms of percolation conduction in the Ag2.5 Se phase.

Effect of pore medium chemistry on hydraulic conductivity of fine grained soils

Hydraulic conductivity of fine-grained soils has assumed greater importance in waste disposal facilities. It is necessary to understand better the factors controlling hydraulic conductivity of fine-grained soils which are used as liners in waste disposal facilities. Hydraulic Conductivity study with ten soils with two fluids having extreme dielectric constants(epsilon) namely water and CCl4 has shown that intrinsic permeability (K) increases drastically with decrease in epsilon. These changes are attributed to the significant reduction in the thickness of diffuse double layer which in turn mainly dependent on the epsilon of the permeant. Hydraulic Conductivity with water of each pair of soils having nearly same liquid limit but different plasticity properties is found to be vastly different, but found to correlate well with shrinkage index, defined as difference between the liquid and the shrinkage limits. Also the ratio Kccl(4)/K-w is found to significantly increase with the increase in the shrinkage index.

Electrical conductivity of Ca-doped YFeO3

Electrical conductivity and Seebeck coefficient of calcium-doped YFeO3, a potential cathode material in solid oxide fuel cells (SOFC), are measured as function of temperature and composition in air to resolve conflicts in the literature both on the nature of conduction (n- or p-type) and the types of defects (majority and the minority) present. Compositions of Y1-xCaxFeO3-delta with x = 0.0, 0.025, 0.05 and 0.1 are studied in the temperature range from 625 to 1250 K. All Y1-xCaxFeO3-delta samples show p-type semiconducting behaviour. Addition of Ca up to 5% dramatically increases the conductivity of YFeO3; increase is more gradual up to 10%. A second phase Ca2Fe2O5 appears in the microstructure for Ca concentrations in excess of 11%.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Effect of cryogenic treatment on thermal conductivity properties of copper

Copper exhibits high thermal conductivity properties and hence it is extensively used in cryogenic applications like cold fingers, heat exchangers, etc. During the realization of such components, copper undergoes various machining operations from the raw material stage to the final component. During these machining processes, stresses are induced within the metal resulting in internal stresses, strains and dislocations. These effects build up resistance paths for the heat carriers which transfer heat from one location to the other. This in turn, results in reduction of thermal conductivity of the conducting metal and as a result the developed component will not perform as per expectations. In the process of cryogenic treatment, the metal samples are exposed to cryogenic temperature for extended duration of time for 24 hours and later tempered. During this process, the internal stresses and strains are reduced with refinement of the atomic structure. These effects are expected to favourably improve thermal conductivity properties of the metal. In this experimental work, OFHC copper samples were cryotreated for 24 hours at 98 K and part of them were tempered at 423K for one hour. Significant enhancement of thermal conductivity values were observed after cryotreating and tempering the copper samples.