Effects of convection and solid wall on the diffusion in microscale convection flows

The diffusive transport properties in microscale convection flows are studied by using the direct simulation Monte Carlo method. The effective diffusion coefficient D is computed from the mean square displacements of simulated molecules based on the Einstein diffusion equation D = x2 t /2t. Two typical convection flows, namely, thermal creep convection and Rayleigh– Bénard convection, are investigated. The thermal creep convection in our simulation is in the noncontinuum regime, with the characteristic scale of the vortex varying from 1 to 100 molecular mean free paths. The diffusion is shown to be enhanced only when the vortex scale exceeds a certain critical value, while the diffusion is reduced when the vortex scale is less than the critical value. The reason for phenomenon of diffusion reduction in the noncontinuum regime is that the reduction effect due to solid wall is dominant while the enhancement effect due to convection is negligible. A molecule will lose its memory of macroscopic velocity when it collides with the walls, and thus molecules are hard to diffuse away if they are confined between very close walls. The Rayleigh– Bénard convection in our simulation is in the continuum regime, with the characteristic length of 1000 molecular mean free paths. Under such condition, the effect of solid wall on diffusion is negligible. The diffusion enhancement due to convection is shown to scale as the square root of the Péclet number in the steady convection regime, which is in agreement with previous theoretical and experimental results. In the oscillation convection regime, the diffusion is more strongly enhanced because the molecules can easily advect from one roll to its neighbor due to an oscillation mechanism. © 2010 American Institute of Physics. doi:10.1063/1.3528310

Study of turbulent heat transfer of aviation kerosene flows in a curved pipe at supercritical pressure

The now and heat transfer characteristics of China No. 3 aviation kerosene in a heated curved tube under supercritical pressure are numerically investigated by a finite volume method. A two-layer turbulence model, consisting of the RNG k-epsilon two-equation model and the Wolfstein one-equation model, is used for the simulation of turbulence. A 10-species kerosene surrogate model and the NIST Supertrapp software are applied to obtain the thermophysical and transport properties of the kerosene at various temperature under a supercritical pressure of 4 MPa. The large variation of thermophysical properties of the kerosene at the supercritical pressure make the flow and heat transfer more complicated, especially under the effects of buoyancy and centrifugal force. The centrifugal force enhances the heat transfer, but also increases the friction factors. The rise of the velocity caused by the variation of the density does not enhance the effects of the centrifugal force when the curvature ratios are less than 0.05. On the contrary, the variation of the density increases the effects of the buoyancy. (C) 2010 Elsevier Ltd. All rights reserved.

The characteristics of land cover and macroscopical ecology changes in the source region of three rivers in Qinghai-Tibet plateau during last 30 years

We obtained four phases of land cover spatial data sets by interpreting MSS images of middle and late 1970s and three phases of TM images of late 1980s, 2004 and 2008 based on field investigation in Three Rivers' Source Region. We analyzed the temporal and spatial characteristics of land cover and macro ecological changes in Three Rivers' Source Region in Qinghai-Tibet plateau since middle and late 1970s. Indicated by land cover condition index change rate and land cover change index, land cover and macroscopical ecological condition degenerated (7090 period Zc -0.63, LCCI -0.58)-obviously degenerated (9004 period, Zc -0.94, LCCI -1.76)-slightly meliorated (0408 period, Zc 0.06, LCCI 0.33). This course was jointly driven by climate change, grassland stocking pressure and implement of ecological construction project.

Synthesis and characterisation of novel functional polyolefin containing sulfonic acid groups

The strong polar group, sulfonic acid, has successfully been introduced into ethylene/allylbenzene copolymers without degradation or crosslinking via chlorosulfonation reaction with chlorosulfonic acid as a chlorosulforiating agent in 1, 1,2,2-tetrachloroethane followed by hydrolysis. The degree of sulforiation (DS) can be easily controlled by changing the ratio of chlorosulfonic acid to the pendant phenyls of the copolymer. The microstructure of sulfonated copolymers were unambiguously revealed by H-1 NMR and H-1-H-1 COSY spectral analyses, which indicates that all the sulforiation reactions exclusively took place at the para-position of the aromatic rings.

Spectroscopic Study on Water Diffusion in Poly(ester urethane) Block Copolymer Matrix

The diffusion of water in a phase-separated biodegradable poly(ester urethane) shape-memory polymer with poly(E-caprolactone) (PCL) as the soft segment was investigated using time-resolved FTIR-ATR. On the basis of the band fitting and water ordering in drawn films, the broad water band in the 3800-2800 cm(-1) region was decomposed into four bands located at 3620, 3510, 3400, and 3260 cm(-1), and the first two components at 3620 and 35 10 cm(-1) were assigned to the vibrations of antisymmetric and symmetric stretching of water hydrogen bonded with the C=O group of the soft segment. The other two were associated with water bonded to the urethane hard segments in the forms of N-H:O-H:O=C bridge hydrogen bond and double hydrogen bonds with two C=O groups, respectively. Furthermore, band fitting and two-dimensional correlation analyses revealed that in the diffusion process, water first diffuses into the continuous soft-rich PCL phase and then into the hard-rich urethane domains, forming double hydrogen bonds with two C=O groups prior to the bridge hydrogen bond in the form of N-H:O-H:O=C.

New carbazole-based copolymers as amorphous hole-transporting materials for multilayer light-emitting diodes

New carbazole-based copolymers, which contain various concentrations of 9-alkyl-3, 6-carbazole fragments in the main chain connected via alkylene spacers, have been synthesized by Ni(0)-catalyzed Yamamoto-type aryl-aryl coupling reactions. Full characterization of the copolymer structure by NMR spectroscopy and elemental analysis is presented. These compounds represent amorphous materials of high thermal stability with glass transition temperatures of 151-162 degrees C and thermal decomposition starting at temperatures > 390 degrees C. UV-Vis absorption and photoluminescence emission of the copolymers confirmed that the effectively conjugated segment in the 3,6-linked carbazole-type copolymers is limited to dyads (dimeric units). However, copolymers with varying concentrations of the oligocarbazole chromophores demonstrate different charge injection and transport properties in multilayer light-emitting diodes with the copolymers as the hole transport and Alq(3) as the electroluminescent/electron transport layer. The device based on a copolymer composed of oligocarbazole blocks with an average length of around four carbazoles exhibited the best overall performance with a turn-on voltage of 3.5 V, a maximal photometric efficiency of 4.1 cd center dot A(-1) and maximum brightness of about 4 200 cd center dot m(-2).

Synthesis and gas permeability of novel fluorinated poly(phenylene-co-naphthalimide)s

A new class of high-performance polymers [poly(phenylene-co-naphthalimide)s] was prepared through the Ni(0) catalytic coupling of N-(4-chloro-2-trifluromethylphenyl)-5-chloro-1,8-naphthalimide and 2,5-dichlorobenzophenone. The resulting copolymers exhibited high molecular weights (high inherent viscosities) and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and mechanical properties. The glass-transition temperatures of the copolymers ranged from 320 to 403 degrees C and increased as the content of the naphthalimide moiety increased. Tough polymer films, obtained via casting from N-methylpyrrolidone solutions, had tensile strengths of 64-107 MPa and tensile moduli of 3.4-4.7 GPa. The gas permeability coefficients of the copolymers were measured for H-2, CO2, O-2, CH4, and N-2. They showed oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen (permeability coefficient for O-2/permeability coefficient for N-2) in the ranges of 1.39-4.31 and 4.92-5.38 barrer, respectively.

High-efficiency blue light-emitting diodes based on a polyphenylphenyl compound with strong electron-accepting groups

The synthesis and characterization of two new polyphenylphenyl compounds is reported. One compound (CPP) acts as a blue light-emitting material, but contains strong electron-accepting groups that form exciplexes with electron-donating arylamines that are widely used as hole-transporting materials. Inserting a layer of the other compound into the organic light-emitting diodes (see figure) suppresses the formation of exciplexes, and gives high-efficiency blue-light emission from the CPP layer.

Fast densification and electrical conductivity of yttria-stabilized zirconia nanoceramics

Nanocrystalline 8YSZ (8 mol% yttria stabilized zirconia) bulk samples with grain sizes of 20-30 nm were synthesized by Sol-Gel method and then densified under a high pressure of 4.5 GPa at 1273 K for 10 min. The method led to the densification of 8YSZ to a relative density higher than 92% without grain growth. Fourier transmission Raman spectroscopy suggested that 8YSZ underwent a phase transition from the cubic phase to a phase mixture (tetragonal plus a trace of monoclinic) after the densification, which decreased the electrical conductivity to a certain degree as concluded from the impedance spectroscopy.

Isomeric polyimides

This review deals with polyimides based on isomeric dianhydrides and diamines, and with chiral polyimides. First, however, a summary is presented of recent work on the synthesis of isomeric dianhydrides, the reaction of mellophanic dianhydride with diamines, and the tendency toward cyclization in reactions of some dianhydrides and diamines. Then turning to polymers, the discussion covers solubility, thermal and dielectric properties, permeability and permselectivity for gas separation, and rheology of isomeric polyimides. Several useful general rules have been found: i.e. the glass transition temperature of polyimides based on isomeric dianhydrides with a given diamine decreases in the order 3,3'- > 3,4'- > 4,4-dianhydride if the polymers are of comparable molecular weight, whereas the thermal stability and the T-beta/T-g ratio (in absolute temperatures) increase in the order of 3,3'- < 3,4'- < 4,4'-dianhydride. Polyimides from 3,3'- or 3,4'-dianhydride have higher solubility than those from 4,4'-dianhydride. Polyimides from 3,4'-dianhydrides exhibit much lower melt viscosity than those from the other isomeric anhydrides. The dielectric constants of polyimides derived from m,m'-diamines are lower than those from p,p'-diamines. Polyimides based on 3,3'- or 3,4'-dianhydrides have higher permeability and slightly lower permselectivity than polyimides based on 4,4'-dianhydrides.

Grain boundary conductivity of high purity neodymium-doped ceria nanosystem with and without the doping of molybdenum oxide

Solid solutions of Ce1-xNdxO2-x/2 (0.05 <= x <= 0.2) and (Ce1-xNdx)(0.95)MO0.05O2-delta (0.05 <= x <= 0.2) have been synthesized by a modified sol-gel method. Both materials have very low content of SiO2 (similar to 27 ppm). Their structures and ionic conductivities were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and electrochemical impedance spectroscopy (M). The XRD patterns indicate that these materials are single phases with a cubic fluorite structure. The powders calcined at 300 degrees C with a crystal size of 5.7 nm have good sinterability, and the relative density could reach above 96% after being sintered at 1450 degrees C. With the addition Of MoO3, the sintering temperature could be decreased to 1250 degrees C. Impedance spectroscopy measurement in the temperature range of 250-800 degrees C indicates that a sharp increase of conductivity is observed when a small amount of Nd2O3 is added into ceria, of which Ce0.85Nd0.15O1.925 (15NDC) shows the highest conductivity. With the addition of a small amount Of MoO3, the grain boundary conductivity of 15NDC at 600 degrees C increases from 2.56 S m(-1) to 5.62 S m(-1).

Novel hole-transporting materials based on 1,4-bis(carbazolyl)benzene for organic light-emitting devices

Novel hole-transporting molecules containing 1,4-bis(carbazolyl)benzene as a central unit and different numbers of diphenylamine moieties as the peripheral groups have been synthesized and characterized. These compounds are thermally stable with high glass transition temperatures of 141-157 degreesC and exhibit chemically reversible redox processes. Their amorphous state stability and hole transport properties can be significantly improved by increasing the number of diphenylamine moieties in the outer part and by controlling the symmetry of the carbazole-based molecules. These compounds can be used as good hole-tran sporting materials for organic electroluminescent (EL) devices. The device performance based on tri- and tetra-substituted carbazole derivatives is comparable to that of a typical 4,4'-bis[N-(1-naphthyl)-N-phenylamino] biphenyl (NPB)-based device.

An investigation of low-field magnetoresistance in the double perovskites Sr2Fe1-xZnxMoO6, x=0, 0.05, 0.15 and 0.25

The electrical, magnetic and transport properties of Zn doped polycrystalline samples of Sr2Fe1-xZnxMoO6 ( x = 0, 0.05, 0.15 and 0.25) with the double perovskite structure have been investigated. The subtle replacement of Fe3+ ions by Zn2+ ions facilitates the formation of a more ordered structure, while further substitution leads to disordered structure because of the presence of a striped phase. Analysis of the x-ray powder diffraction patterns based on Rietveld analysis indicates that the replacement of Fe3+ by Zn2+ ions favours the formation of Mo6+ ions. The spin-glass behaviour can be explained on the basis of the competition between the antiferromagnetic superexchange and the ferromagnetic double-exchange interaction. The low-field magnetoresistance was moderately enhanced at x = 0.05, and its origin was found to be the competition between the decrease of the concentration of the itinerant electrons and the weaker antiferromagnetic superexchange in the antiphase boundaries. An almost linear negative magnetoresistance in moderate field has been observed for x = 0.25. A possible double-exchange mechanism is proposed for elucidating the observations; it also suggests a coexistence of (Fe3+, Mo5+) and (Zn2+, Mo6+) valence pairs.

Synthesis, structural characterization and electrical property of new oxide ion conductors: La3MMo2O12 (M = In, Ga and Al)

New series of oxides, La3MMo2O12 (M = In, Ga and Al), have been prepared by the solid-state reaction. The composition and elemental distribution were analyzed by the energy-dispersive X-ray (EDX) analysis. As determined by the X-ray diffraction (XRD), these compounds have similar crystal structures that can be indexed on a monoclinic cell at room temperature. AC impedance spectra and the DC electrical conductivity measurements in various atmospheres indicate that they are oxide ion conductors with ionic conductivities between 10(-2) and 10(-3) S/cm at 800 degrees C. The conductivity decreases in the order of La3GaMo2O12 > La3AlMo2O12 > La3InMo2O12, implying that the effect of cell volume and polarization associated with In3+, Ga3+ and Al3+ play an important role in the anion transport of these materials. The reversible phase transition was observed in all these compounds as confirmed by the differential thermal analysis (DTA) and dilatometric measurements.

Synthesis, structural and electrical characterizations of Sr2Fe1-xMxNbO6 (M = Zn and Cu) with double perovskite structure

Sr2Fe1-xZnxNbO6-x/2 (0 <= x <= 0.5) and Sr2Fe1-xCuxNbO6-x/2 (0.01 <= x <= 0.05) with the double perovskite structure have been synthesized. The crystal structures at room temperature were determined from Rietveld refinements of X-ray powder diffraction data. The plots of the imaginary parts of the impedance spectrum, Z '', and the electric modulus, M '', versus log (frequency), possess maxima for both curves separated by less than a half decade in frequency with associated capacities of 2 nF. The enhancement of the overall conductivity Of Sr2Fe1-xMxNbO6-x/2 (M = Cu and Zn) is observed, as increases from 2.48 (3) x 10(-4) S/cm for Sr2FeNbO6 to 3.82 (5) x 10(-3) S/cm for Sr2Fe0.8Zn0.2NbO5.9 at 673 K. Sr2Fe0.8Zn0.2NbO5.9 is chemically stable under the oxygen partial pressure from 1 atm to 10(-22) atm at 873 K. The p and n-type electronic conductions are dominant under oxidizing and reducing conditions, respectively, suggesting a small-polaron hopping mechanism of electronic conduction.