4-Picoline-N-oxide complexes of rare-earth bromides

In continuation of our work on the effect of the anion on the coordination chemistry of the rare-earth metal ions, we have now extended our studies to 4-picoline-N-oxide (4-Pie NO) complexes of rare-earth bromides. By ohangi~ the method of preparation Harrison and Watsom (1) have prepared two types of Sm(IIl) complexes and three types of Eu(III) complexes of 4-pioollne-N-Oxide in the presence of perchlorate ions. We have isolated two types of pyridine-N-Oxide complexes of rare-earth bromides, also by changing the method of preparation (2). The effect of the change of the preparative method on the composition of the lanthanide complexes is exhibited in the case of other complexes also (3-6). But our attempts to prepare 4-picoline-N-Oxide of rare-earth bromides having different stoichiometries were unsucessful . The composition of the complexes is the same for all the complexes prepared. The results of the physico-chemical studies on these 4-Pic NO complexes of rare-earth bromides are discussed in the present paper.

Earth pressures on retaining walls due to Anisotropic and nonhomogeneous backfills

In this paper an attempt is made to study the lateral earth pressures on retaining walls as affected by anisotropy and non-homogeneity with respect to cohesion, of the backfill. Both the passive and active conditions are studied and the method of characteristics is used in the analysis. Numerical results show that, as the coeficient of anisotropy, k, defined as the ratio of vertical strength to horizontal strength, changes from 0-8 to 2, the pressure at the top of the wall decreases considerably.Also, as k changes fvom 0.8 to 2, the mod$ed passive and active earth pressure coeficients decrease when cohesion increases with depth and are unaffected by k when cohesion is constant with depth. On the other hand, when the rate of increase of cohesion with depth increares, the mod@ed earth pressure coefficients are found to increase considerably.

Heat transfer to power-law fluids in thermal entrance region with viscous dissipation for constant heat flux conditions

An analytical solution of the heat transfer problem with viscous dissipation for non-Newtonian fluids with power-law model in the thermal entrance region of a circular pipe and two parallel plates under constant heat flux conditions is obtained using eigenvalue approach by suitably replacing one of the boundary conditions by total energy balance equation. Analytical expressions for the wall and the bulk temperatures and the local Nusselt number are presented. The results are in close agreement with those obtained by implicit finite-difference scheme. It is found that the role of viscous dissipation on heat transfer is completely different for heating and cooling conditions at the wall. The results for the case of cooling at the wall are of interest in the design of the oil pipe line.

Cooling of a composite slab

A mixed boundary value problem associated with the diffusion equation, that involves the physical problem of cooling of an infinite parallel-sided composite slab, is solved completely by using the Wiener-Hopf technique. An analytical expression is derived for the sputtering temperature at the quench front being created by a cold fluid moving on the upper surface of the slab at a constant speed v. The dependence of the various configurational parameters of the problem under consideration, on the sputtering temperature, is rather complicated and representative tables of numerical values of this important physical quantity are prepared for certain typical values of these parameters. Asymptotic results in their most simplified forms are also obtained when (i) the ratio of the thicknesses of the two materials comprising the slab is very much smaller than unity, and (ii) the quench-front speed v is very large, keeping the other parameters fixed, in both the cases.

On plane-wave propagation in a uniform pipe in the presence of a mean flow and a temperature gradient

A theoretical study on the propagation of plane waves in the presence of a hot mean flow in a uniform pipe is presented. The temperature variation in the pipe is taken to be a linear temperature gradient along the axis. The theoretical studies include the formulation of a wave equation based on continuity, momentum, and state equation, and derivation of a general four-pole matrix, which is shown to yield the well-known transfer matrices for several other simpler cases.

Metal-Nucleotide Interactions: Crystal Structures of Alkali (Li+, Na+, K+) and Alkaline Earth (Ca2+, Mg2+) Metal Complexes of Adenosine 2'-Monophosphate

Crystal structures of lithium, sodium, potassium, calcium and magnesium salts of adenosine 2'-monophosphate (2'-AMP) have been obtained at atomic resolution by X-ray crystallographic methods. 2'-AMP.Li belongs to the monoclinic space group P21 with a = 7.472(3)Å, b = 26.853(6) Å, c = 9.184(1)Å, b = 113.36(1)Å and Z= 4. 2'-AMP.Na and 2'-AMP.K crystallize in the trigonal space groups P31 and P3121 with a = 8.762(1)Å, c = 34.630(5)Å, Z= 6 and a = 8.931(4), Åc = 34.852(9)Å and Z= 6 respectively while 2'-AMP.Ca and 2'-AMP.Mg belong to space groups P6522 and P21 with cell parameters a = 9.487(2), c = 74.622(13), Z = 12 and a = 4.973(1), b = 10.023(2), c = 16.506(2), beta = 91.1(0) and Z = 2 respectively. All the structures were solved by direct methods and refined by full matrix least-squares to final R factors of 0.033, 0.028, 0.075, 0.069 and 0.030 for 2'-AMP.Li, 2'-AMP.Na, 2'- AMP.K, 2'-AMP.Ca and 2'-AMP.Mg, respectively. The neutral adenine bases in all the structures are in syn conformation stabilized by the O5'-N3 intramolecular hydrogen bond as in free acid and ammonium complex reported earlier. In striking contrast, the adenine base is in the anti geometry (cCN = -156.4(2)°) in 2'-AMP.Mg. Ribose moieties adopt C2'-endo puckering in 2'-AMP.Li and 2'-AMP.Ca, C2'-endo-C3'-exo twist puckering in 2'-AMP.Na and 2'-AMP.K and a C3'-endo-C2'-exo twist puckering in 2'-AMP.Mg structure. The conformation about the exocyclic C4'-C5' bond is the commonly observed gauche-gauche (g+) in all the structures except the gauche- trans (g-) conformation observed in 2'-AMP.Mg structure. Lithium ions coordinate with water, ribose and phosphate oxygens at distances 1.88 to 1.99Å. Na+ ions and K+ ions interact with phosphate and ribose oxygens directly and with N7 indirectly through a water oxygen. A distinct feature of 2'-AMP.Na and 2'-AMP.K structures is the involvement of ribose O4' in metal coordination. The calcium ion situated on a two-fold axis coordinates directly with three oxygens OW1, OW2 and O2 and their symmetry mates at distances 2.18 to 2.42Å forming an octahedron. A classic example of an exception to the existence of the O5'-N3 intramolecular hydorgen bond is the 2'-AMP.Mg strucure. Magnesium ion forms an octahedral coordination with three water and three phosphate oxygens at distances ranging from 2.02 to 2.11Å. A noteworthy feature of its coordination is the indirect link with N3 through OW3 oxygen resulting in macrochelation between the base and the phosphate group. Greater affnity of metal clays towards 5' compared to 2' and 3' nucleotides (J. Lawless, E. Edelson, and L. Manring, Am. Chem. Soc. Northwest Region Meeting, Seattle. 1978) due to macrochelation infered from solution studies (S. S. Massoud, H. Sigel, Eur. J. Biochem. 179, 451-458 (1989)) and interligand hydrogen bonding induced by metals postulated from metal-nucleotide structures in solid state (V. Swaminathan and M. Sundaralingam, CRC. Crit. Rev. Biochem. 6, 245-336 (1979)) are borne out by our structures also. The stacking patterns of adenine bases of both 2'-AMP.Na and 2'-AMP.K structures resemble the 2'-AMP.NH4 structure reported in the previous article. 2'-AMP.Li, 2'-AMP.Ca and 2'-AMP.Mg structures display base-ribose O4' stacking. An overview of interaction of monovalent and divalent cations with 2' and 5'-nucleotides has been presented.

Transition of turbulent pipe flow

The velocity profile in turbulent pipe flow is usually divided into two regions, a wall or inner region and a core or outer region. For the inner region, the viscosity and wall shear stress are the important parameters governing the velocity distribution whereas for the outer region, the wall reduces the velocity below the maximum velocity independent of viscosity. In the present work, a velocity model is proposed for turbulent flow in the wall region of a pipe covering the entire transition from smooth to rough flows. Coupling this model for the wall region with the power law velocity model for the core region, an equation for the friction factor is obtained. The model constants are evaluated by using Nikuradse's experiments in the fully smooth and rough turbulent flows. The model shows good agreement with the friction factor and the velocity profiles obtained by Nikuradse for the transition region of turbulent flow.

Transition from radiatively inefficient to cooling dominated phase in two temperature accretion disks around black holes

We investigate the transition of a radiatively inefficient phase of a viscous two temperature accreting flow to a cooling dominated phase and vice versa around black holes. Based on a global sub-Keplerian accretion disk model in steady state, including explicit cooling processes self-consistently, we show that general advective accretion flow passes through various phases during its infall towards a black hole. Bremsstrahlung, synchrotron and inverse Comptonization of soft photons are considered as possible cooling mechanisms. Hence the flow governs a much lower electron temperature similar to 10(8) - 10(9.5) K compared to the hot protons of temperature similar to 10(10.2) - 10(11.8) K in the range of the accretion rate in Eddington units 0.01 less than or simiar to (M) over dot less than or similar to 100. Therefore, the solutions may potentially explain the hard X-rays and the gamma-rays emitted from AGNs and X-ray binaries. We finally compare the solutions for two different regimes of viscosity and conclude that a weakly viscous flow is expected to be cooling dominated compared to its highly viscous counterpart which is radiatively inefficient. The flow is successfully able to reproduce the observed minosities of the under-fed AGNs and quasars (e.g. Sgr A*), ultra-luminous X-ray sources (e.g. SS433), as well as the highly luminous AGNs and ultra-luminous quasars (e.g. PKS 0743-67) at different combinations of the mass accretion rate and ratio of specific heats.

Triassic eclogite from northern Vietnam: inferences and geological significance

The first finding of low-temperature eclogites from the Indochina region is reported. The eclogites occur along the Song Ma Suture zone in northern Vietnam, which is widely regarded as the boundary between the South China and Indochina cratons. The major lithology of the area is pelitic schist that contains garnet and phengite with or without biotite, chloritoid, staurolite and kyanite, and which encloses blocks and lenses of eclogite and amphibolite. The eclogites commonly consist of garnet, omphacite, phengite, rutile, quartz and/or epidote with secondary barroisite. Omphacite is commonly surrounded by a symplectite of Na-poor omphacite and Na-rich plagioclase. In highly retrograded domains, diopside + tremolite + plagioclase symplectites replace the primary phases. Estimated peak-pressure metamorphic conditions based on isochemical phase diagrams for the eclogites are 2.1-2.2 GPa and 600-620 degrees C, even though thermobarometric results yield higher pressure and temperature conditions (2.6-2.8 GPa and 620-680 degrees C). The eclogites underwent a clockwise P-T trajectory with a post-peak-pressure increase of temperature to a maximum of > 750 degrees C at 1.7 GPa and a subsequent cooling during decompression to 650 degrees C and 1.3 GPa, which was followed by additional cooling before close-to-isothermal decompression to similar to 530 degrees C at 0.5 GPa. The surrounding pelitic schist (garnet-chloritoid-phengite) records similar metamorphic conditions (580-600 degrees C at 1.9-2.3 GPa) and a monazite chemical age of 243 +/- 4 Ma. A few monazite inclusions within garnet and the cores of some zoned monazite in garnet-phengite schist record an older thermal event (424 +/- 15 Ma). The present results indicate that the Indochina craton was deeply (> 70 km) subducted beneath the South China craton in the Triassic. The Silurian cores of monazite grains may relate to an older non-collisional event in the Indochina craton.

13C nuclear magnetic resonance studies of the binding of alkali and alkaline earth metal salts to amides

3C resonances of carbonyl and methyl groups in amides are shifted down-field on interaction with alkali and alkaline earth metal salts. The magnitude of the shift depends on the ionic potential of the cation. Ions like Li+ bind to the amide carbonyl group both in neat amide solutions as well as in concentrated salt solutions in water.

Two-temperature accretion around rotating black holes: a description of the general advective flow paradigm in the presence of various cooling processes to explain low to high luminous sources

We investigate viscous two-temperature accretion disc flows around rotating black holes. We describe the global solution of accretion flows with a sub-Keplerian angular momentum profile, by solving the underlying conservation equations including explicit cooling processes self-consistently. Bremsstrahlung, synchrotron and inverse Comptonization of soft photons are considered as possible cooling mechanisms. We focus on the set of solutions for sub-Eddington, Eddington and super-Eddington mass accretion rates around Schwarzschild and Kerr black holes with a Kerr parameter of 0.998. It is found that the flow, during its infall from the Keplerian to sub-Kepleria transition region to the black hole event horizon, passes through various phases of advection: the general advective paradigm to the radiatively inefficient phase, and vice versa. Hence, the flow governs a much lower electron temperature similar to 10(8)-10(9.5) K, in the range of accretion rate in Eddington units 0.01 less than or similar to (M) over dot less than or similar to 100, compared to the hot protons of temperature similar to 10(10.2)-10(11.8) K. Therefore, the solution may potentially explain the hard X-rays and gamma-rays emitted from active galactic nuclei (AGNs) and X-ray binaries. We then compare the solutions for two different regimes of viscosity. We conclude that a weakly viscous flow is expected to be cooling dominated, particularly at the inner region of the disc, compared to its highly viscous counterpart, which is radiatively inefficient. With all the solutions in hand, we finally reproduce the observed luminosities of the underfed AGNs and quasars (e. g. Sgr A*) to ultraluminous X-ray sources (e. g. SS433), at different combinations of input parameters, such as the mass accretion rate and the ratio of specific heats. The set of solutions also predicts appropriately the luminosity observed in highly luminous AGNs and ultraluminous quasars (e. g. PKS 0743-67).

Theoretical Studies of Hard Filling in Loop Heat Pipes

Loop heat pipe is a passive two-phase heat transport device that is gaining importance as a part of spacecraft thermal control systems and also in applications (such as in avionic cooling and submarines). Hard fill of a loop heat pipe occurs when the compensation chamber is full of liquid. A theoretical study is undertaken to investigate the issues underlying the loop beat pipe hard-fill phenomenon. The results of the study suggest that the mass of charge and the presence of a bayonet have significant impact on the loop heat pipe operation. With a largern mass of charge, a loop heat pipe hard fills at a lower heat load. As the heat load increases, there is a steep rise in the loop heat pipe operating temperature. In a loop heat pipe with a saturated compensation chamber, and also in a hard-filled loop heat pipe without a bayonet, the temperature of the compensation chamber and that of the liquid core are nearly equal. When a loop heat pipe with a bayonet hard fills, the compensation chamber and the evaporator core temperatures are different.

High P-T granulite relicts from the Imjingang belt, South Korea:Tectonic significance

This study presents a detailed description on crustal metamorphic signatures of garnet-clinopyroxene-quartz-rutile-bearing high P-T granulites, Samgot unit, Imajingang belt, northwestern Korean Peninsula that formed during Permo-Triassic regional metamorphism related to the amalgamation of East Asian continental fragments. Lenses and blocks of high P-T granulites and garnet-bearing leucosomes occur within mafic metamorphic rocks (mainly amphibolites). The mafic blocks comprise relicts of granoblastic garnet and clinopyroxene with medium-grained quartz and rutile. These relict mineral assemblages are confined to local micro-domains and constitute remnants of peak metamorphism. Plagioclase and amphibole form only as retrograde phases in medium ton coarse-grained moats that rim grain boundaries between relict peak mineral assemblages. This microstructure represents the reaction between garnet, clinopyroxene, quartz and rutile in the presence of melt to form amphibole, plagioclase and titanite with minor biotite. The leucosome domains consist of euhedral garnets within the quartz-K feldspar-plagioclase (granitic) matrix, probably representing peritectic garnet growth along with melting. The rare earth element (REE) composition of minerals also support the peritectic garnet growth with a positive Eu/Eu* (positive Eu anomaly), while the relict garnet shows a slight negative anomaly typical for high-grade granulites. The peak-metamorphic conditions calculated from thermodynamic modeling and compositional isopleths indicate a temperature around c. 900 degrees C at a pressure around c. 20 kbar. The present P-T path indicates a clear multi-stage decompression history with initial decompression and cooling followed by a stage of decompression during hydration possibly during Late Triassic exhumation. The results from this study together with the presence of eclogites from the Hongsung area suggest that the Imjingang area and the western Gyeonggi massif likely resided at crustal levels deeper than those of the eastern and southern part of the Gyeonggi massif. (C) 2009 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Embodied energy in cement stabilised rammed earth walls

Rammed earth walls are low carbon emission and energy efficient alternatives to load bearing walls. Large numbers of rammed earth buildings have been constructed in the recent past across the globe. This paper is focused on embodied energy in cement stabilised rammed earth (CSRE) walls. Influence of soil grading, density and cement content on compaction energy input has been monitored. A comparison between energy content of cement and energy in transportation of materials, with that of the actual energy input during rammed earth compaction in the actual field conditions and the laboratory has been made. Major conclusions of the investigations are (a) compaction energy increases with increase in clay fraction of the soil mix and it is sensitive to density of the CSRE wall, (b) compaction energy varies between 0.033 MJ/m(3) and 0.36 MJ/m(3) for the range of densities and cement contents attempted, (c) energy expenditure in the compaction process is negligible when compared to energy content of the cement and (d) total embodied energy in CSRE walls increases linearly with the increase in cement content and is in the range of 0.4-0.5 GJ/m(3) for cement content in the rage of 6-8%. (C) 2009 Elsevier B.V. All rights reserved.

Influence of Cooling Rate on the Enthalpy Relaxation and Fragility of a Metallic Glass

Structural relaxation behavior of a rapidly quenched (RQ) and a slowly cooled Pd40Cu30Ni10P20 metallic glass was investigated and compared. Differential scanning calorimetry was employed to monitor the relaxation enthalpies at the glass transition temperature, T-g , and the Kolrausch-Williams-Watts (KWW) stretched exponential function was used to describe its variation with annealing time. It was found that the rate of enthalpy recovery is higher in the ribbon, implying that the bulk is more resistant to relaxation at low temperatures of annealing. This was attributed to the possibility of cooling rate affecting the locations where the glasses get trapped within the potential energy landscape. The RQ process traps a larger amount of free volume, resulting in higher fragility, and in turn relaxes at the slightest thermal excitation (annealing). The slowly cooled bulk metallic glass (BMG), on the other hand, entraps lower free volume and has more short-range ordering, hence requiring a large amount of perturbation to access lower energy basins.