Turbulent free convection above a heated plate inclined at a small angle to the horizontal Journal

An investigation has been made of the structure of the motion above a heated plate inclined at a small angle (about 10°) to the horizontal. The turbulence is considered in terms of the similarities to and differences from the motion above an exactly horizontal surface. One effect of inclination is, of course, that there is also a mean motion. Accurate data on the mean temperature field and the intensity of the temperature fluctuations have been obtained with platinum resistance thermometers, the signals being processed electronically. More approximate information on the velocity field has been obtained with quartz fibre anemometers. These results have been supplemented qualitatively by simultaneous observations of the temperature and velocity fluctuations and also by smoke experiments. The principal features of the flow inferred from these observations are as follows. The heat transfer and the mean temperature field are not much altered by the inclination, though small, not very systematic, variations may result from the complexities of the velocity field. This supports the view that the mean temperature field is largely governed by the large-scale motions. The temperature fluctuations show a systematic variation with distance from the lower edge and resemble those above a horizontal plate when this distance is large. The largescale motions of the turbulence start close to the lower edge, but the smaller eddies do not attain full intensity until the air has moved some distance up the plate. The mean velocity receives a sizable contribution from a ‘through-flow’ between the side-walls. Superimposed on this are developments that show that the momentum transfer processes are complex and certainly not capable of representation by any simple theory such as an eddy viscosity. On the lower part of the plate there is surprisingly large acceleration, but further up the mixing action of the small eddies has a decelerating effect.

Kinetic decomposition of Ni2SiO4 in oxygen potential gradients

Nickel orthosilicate (Ni2SiO4) has been found to decompose into its component binary oxides in oxygen potential gradients at 1373 K. Nickel oxide was formed at the high oxygen potential boundary, while silica was detected at the low oxygen potential side. Significant porosity and fissures were observed near the Ni2SiO4/SiO2 interface and the SiO2 layer. The critical oxygen partial pressure ratio required for decomposition varied from 1.63 to 2.15 as the oxygen pressures were altered from 1.01 ⊠ 105 to 2.7X 10−4 Pa, well above the dissociation pressure of Ni2SiO4. Platinum markers placed at the boundaries of the Ni2SiO4 sample indicated growth of NiO at the higher oxygen potential boundary, without any apparent transport of material to the low oxygen potential side. However, significant movement of the bulk Ni2SiO4 crystal with respect to the marker was not observed. The decomposition of the silicate occurs due to the unequal rates of transport of Ni and Si. The critical oxygen partial pressure ratio required for decomposition is related both to the thermodynamic stability of Ni2SiO4 with respect to component oxides and the ratio of diffusivities of nickel and silicon. Kinetic decomposition of multicomponent oxides, first discovered by Schmalzried, Laqua, and co-workers [H. Schmalzried, W. Laqua, and P. L. Lin, Z. Natur Forsch. Teil A 34, 192 (1979); H. Schmalzried and W. Laqua, Oxid. Met. 15, 339 (1981); W. Laqua and H. Schmalzried, Chemical Metallurgy—A Tribute to Carl Wagner (Metallurgical Society of the AIME, New York, 1981), p. 29] has important consequences for their use at high temperatures and in geochemistry.

Growth and study of BaZrO3 thin films by pulsed excimer laser ablation

Thin films of BaZrO3 (BZ) were grown using a pulsed laser deposition technique on platinum coated silicon substrates. Films showed a polycrystalline perovskite structure upon different annealing procedures of in-situ and ex-situ crystallization. The composition analyses were done using Energy dispersive X-ray analysis (EDAX) and Secondary ion mass spectrometry (SIMS). The SIMS analysis revealed that the ZrO2 formation at the right interface of substrate and the film leads the degradation of the device on the electrical properties in the case of ex-situ crystallized films. But the in-situ films exhibited no interfacial formation. The dielectric properties have been studied for the different temperatures in the frequency regime of 40 Hz to 100kHz. The response of the film to external ac stimuli was studied at different temperatures, and it showed that ac conductivity values in the limiting case are correspond to oxygen vacancy motion. The electrical modulus is fitted to a stretched exponential function and the results clearly indicate the presence of the non-Debye type of dielectric relaxation in these materials.

Measurement of Heat Transfer Rate on Backward-Facing Steps at Hypersonic Mach Number

Two backward-facing models with step heights of 2 and 3 mm are used to measure the convective surface heat transfer rates by using platinum thin-film gauges, deposited on Macor inserts. Heat transfer rates have been theoretically calculated along the flat plate portion of a model using the Eckert reference temperature method. The experimentally determined surface heat transfer rate distributions are compared with theoretical and numerical estimations. Experimental heat flux distribution over a flat plate model showed good agreement with the reference temperature method at stagnation enthalpy range of 0.8-2 MJ/kg. Theoretical analysis has been used for downstream of a backward-facing step using Gai's nondimensional analysis. It has been found from the present study that approximately 10 and 8 step heights are required for the flow to reattach for 2 and 3 mm step height backward-facing step models, respectively, at a nominal Mach number of 7.6.

Cyclometalated complexes derived from calix[4] arene bisphosphites and their catalytic applications in cross-coupling reactions

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p-tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p-tert-butyl-or p-H-calix[4]arene are connected to a P(OR) ( R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C-C or C-H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd-P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C-C cross-coupling reactions but, on an average, the yields are only modest. (C) 2011 Elsevier B.V. All rights reserved.

Carbon based materials for low temperature detection

Resistance temperature detectors (RTDs) are being widely used to detect low temperature, while thermocouples (TCs) are being used to detect high temperature. The materials suitable for RTDs are platinum, germanium, carbon, carbon-glass, cernox, etc. Here, we have reported the possible application of another form of carbon i.e. carbon nanotubes in low temperature thermometry. It has been shown the resistance R and the sensitivity of carbon nanotube bundles can be tuned and made suitable for ultralow temperature detection. We report on the R-T measurement of carbon nanotube bundles from room temperature down to 1 K to felicitate the possible application of bundles in low temperature RTDs. ©2008 American Institute of Physics

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

Revision of thermodynamic data on MnO Al2O3 melts

The high temperature region of the MnO-A1203 phase diagram has been redetermined to resolve some discrepancies reported in the literature regarding the melting behaviour of MnA1,04. This spinel was found to melt congruently at 2108 (+ 15) K. Theactivity of MnOin MnO-Al,03 meltsand in the two phase regions, melt + MnAI,04 and MnAI2O4 + A1203, has been determined by measuring the manganese concentration in platinum foils in equilibrium under controlled oxygen potentials. The activity of MnO obtained in this study for M ~ O - A I ,m~el~ts is in fair agreement with the results of Sharma and Richardson.However. the alumina-rich melt is found to be in equilibrium with MnAl,04 rather than AI2O3. as suggested by ~ha rmaan d Richardson. The value for the acthity of MnO in the M~AI ,O,+ A1,03 two phaseregion permits a rigorous application of the Gibbs-Duhem equation for calculating the activity of A1203 and the integral Gibbs' energy of mixing of MnO-A1203 melts, which are significantly different from those reported in the literature.

Synthesis and characterization of silicone polymer/functionalized mesostructured silica composites

A thermally stable and flexible composite has been synthesized by following a consecutive `two-step', solvent free route. Silicone polymer containing internal hydrides was used as a polymer matrix and mesoporous silica functionalized with allytrimethoxysiloxane was used as a filler material. In the second step, the composite preparation was carried out using the hydrosilylation reaction mediated by `Karastedt' platinum catalyst. The results of the studies suggest that the composites are thermally stable, hydrophobic and flexible and can be potentially used for encapsulating flexible electronic devices.

Gibbs energies of formation of intermetallic phases in the systems Pt Mg, Pt Ca and Pt Ba and some applications

The standard Gibbs energies of formation of platinum-rich intermetallic compounds in the systems Pt-Mg, Pt-Ca, and Pt-Ba have been measured in the temperature range of 950 to 1200 K using solid-state galvanic cells based on MgF2, CaF2, and BaF2 as solid electrolytes. The results are summarized by the following equations: ΔG° (MgPt7) = −256,100 + 16.5T (±2000) J/mol ΔG° (MgPt3) = −217,400 + 10.7T (±2000) J/mol ΔG° (CaPt5) = −297,500 + 13.0T (±5000) J/mol ΔG° (Ca2Pt7) = −551,800 + 22.3T (±5000) J/mol ΔG° (CaPt2) = −245,400 + 9.3T (±5000) J/mol ΔG° (BaPt5) = −238,700 + 8.1T (±4000) J/mol ΔG° (BaPt2) = −197,300 + 4.0T (±4000) J/mol where solid platinum and liquid alkaline earth metals are selected as the standard states. The relatively large error estimates reflect the uncertainties in the auxiliary thermodynamic data used in the calculation. Because of the strong interaction between platinum and alkaline earth metals, it is possible to reduce oxides of Group ILA metals by hydrogen at high temperature in the presence of platinum. The alkaline earth metals can be recovered from the resulting intermetallic compounds by distillation, regenerating platinum for recycling. The platinum-slag-gas equilibration technique for the study of the activities of FeO, MnO, or Cr2O3 in slags containing MgO, CaO, or BaO is feasible provided oxygen partial pressure in the gas is maintained above that corresponding to the coexistence of Fe and “FeO.”

Thermodynamic properties of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5Tm intermetallics

The Gibbs’ energies of formation of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5 Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell:Ta,M + MF3 /CaF2 /Pt5 M + Pt + MF3 ,TaTaM+MF3CaF2Pt5M+Pt+MF3Ta.The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt5M compound. The results can be summarized by the equations:DGf° á Pt5 La ñ = - 373,150 + 6 ·60 T( ±300 )J mol - 1 DGf° á Pt5 Ce ñ = - 367,070 + 5 ·79 T( ±300 )J mol - 1 DGf° á Pt5 Pr ñ = - 370,540 + 4 ·69 T( ±300 )J mol - 1 DGf° á Pt5 Tb ñ = - 372,280 + 4 ·11 T( ±300 )J mol - 1 DGf° á Pt5 Tm ñ = - 368,230 + 4 ·89 T( ±300 )J mol - 1 Unknown control sequence '\hfill'relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt5M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt5M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.

The standard molar Gibbs energy of formation of YbPt3 and LuPt3 intermetallics

The standard molar Gibbs energies of formation of YbPt3 and LuPt3 intermetallic compounds have been measured in the temperature range 880 K to 1100 K using the solid-state cells:View the MathML source and View the MathML source The trifluoride of Yb is not stable in equilibrium with Yb or YbPt3. The results can be expressed by the equations: View the MathML source View the MathML source The standard molar Gibbs energy of formation of LuPt3 is −41.1 kJ · mol−1 more negative than that for YbPt3 at 1000 K. Ytterbium is divalent in the pure metal and trivalent in the intermetallic YbPt3. The energy required for the promotion of divalent Yb to the trivalent state is responsible for the less negative ΔfGmo of YbPt3. The enthalpies of formation of the two intermetallics are in reasonable agreement with Miedema's model. Because of the extraordinary stability of these compounds it is possible to reduce oxides of Yb and Lu with hydrogen in the presence of platinum at View the MathML source. The equilibrium chemical potential of oxygen corresponding to the reduction of Yb2O3 and Lu2O3 by hydrogen in the presence of platinum is presented in the form of an Ellingham diagram.

Low oxygen potential boundary for the stability of YBA2Cu3O7−δ

On lowering the oxygen potential, the tetragonal phase of YBa2Cu3O7−δ was found to decompose into a mixture of Y2BaCuO5, BaCuO2 and BaCu2O2 in the temperature range 773–1173 K. The 123 compound was contained in a closed crucible of yttria-stabilized zirconia in the temperature range 773–1073 K. Oxygen was removed in small increments by coulometric titration through the solid electrolyte crucible at constant temperature. The oxygen potential was calculated from the open circuit e.m.f. of the solid state cell after successive titrations. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The decomposition of the 123 compound manifested as a plateau in oxygen potential. The decomposition products were identified by X-ray diffraction. At temperatures above 1073 K there was some evidence of reaction between the 123 compound, solid electrolyte crucible and platinum. For measurements above 1073 K, the 123 compound was contained in a magnesia crucible placed in a closed outer silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid state cell based on yttria-stabilized zirconia which served both as a pump and sensor. The lower oxygen potential limit for the stability of the 123 compound is given by View the MathML source The oxygen non-stoichiometric parameter δ for the 123 compound has a value of 0.98 (View the MathML source) at dissociation.

Effect of gas injection on drag and surface heat transfer rates for a 30 degrees semi-apex angle blunt body flying at Mach 5.75

Effect of coolant gas injection in the stagnation region on the surface heat transfer rates and aerodynamic drag for a large angle blunt body flying at hypersonic Mach number is reported for two stagnation enthalpies. A 60° apex-angle blunt cone model is employed for this purpose with air injection at the nose through a hole of 2mm diameter. The convective surface heating rates and aerodynamic drag are measured simultaneously using surface mounted platinum thin film sensors and internally mounted accelerometer balance system, respectively. About 35–40% reduction in surface heating rates is observed in the vicinity of stagnation region whereas 15–25% reduction in surface heating rates is felt beyond the stagnation region at stagnation enthalpy of 1.6MJ/kg. The aerodynamic drag expressed in terms of drag coefficient is found to increase by 20% due to the air injection.