Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes

The effects of pressure and temperature on the energy (E-op) of the metal-to-metal charge transfer (MMCT, Fe-II --> Co-III) transition of the cyano-bridged complexes trans - [(LCoNCFe)-Co-14(CN)(5)](-) and cis-[(LCoNCFe)-Co-14(CN)(5)](-) (where L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in E-op due to both pressure and temperature were found to be less than the shifts in the energy difference (E degrees) between the Co-III-Fe-II and Co-II-Fe-III redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of Co-II, are discussed in order to account for this trend. To study the effect of pressure on Co-III electronic absorption bands, a new cyano-bridged complex, trans - [(LCoNCCo)-Co-14(CN)(5)], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans -[(LCoNCFe)-Co-14(CN)(5)] center dot 5H(2)O.

Direct numerical simulation of turbulent flow and mass transfer around a rotating circular cylinder

Turbulent flow around a rotating circular cylinder has numerous applications including wall shear stress and mass-transfer measurement related to the corrosion studies. It is also of interest in the context of flow over convex surfaces where standard turbulence models perform poorly. The main purpose of this paper is to elucidate the basic turbulence mechanism around a rotating cylinder at low Reynolds numbers to provide a better understanding of flow fundamentals. Direct numerical simulation (DNS) has been performed in a reference frame rotating at constant angular velocity with the cylinder. The governing equations are discretized by using a finite-volume method. As for fully developed channel, pipe, and boundary layer flows, a laminar sublayer, buffer layer, and logarithmic outer region were observed. The level of mean velocity is lower in the buffer and outer regions but the logarithmic region still has a slope equal to the inverse of the von Karman constant. Instantaneous flow visualization revealed that the turbulence length scale typically decreases as the Reynolds number increases. Wavelet analysis provided some insight into the dependence of structural characteristics on wave number. The budget of the turbulent kinetic energy was computed and found to be similar to that in plane channel flow as well as in pipe and zero pressure gradient boundary layer flows. Coriolis effects show as an equivalent production for the azimuthal and radial velocity fluctuations leading to their ratio being lowered relative to similar nonrotating boundary layer flows.

Field observations of instantaneous water slopes and horizontal pressure gradients in the swash-zone

Field observations of instantaneous water surface slopes in the swash zone are presented. For free-surface flows with a hydrostatic pressure distribution the surface slope is equivalent to the horizontal pressure gradient. Observations were made using a novel technique which in its simplest form consists of a horizontal stringline extending seaward from the beach face. Visual observation, still photography or video photography is then sufficient to determine the surface slope where the free-surface cuts the line or between reference points in the image. The method resolves the mean surface gradient over a cross-shore distance of 5 m or more to within +/- 0.001, or 1/20th -1/100th of typical beach gradients. In addition, at selected points and at any instant in time during the swash cycle, the water surface slope can be determined exactly to be dipping either seaward or landward. Close to the location of bore collapse landward dipping water surface slopes of order 0.05-0.1 occur over a very small region (order 0.5 m) at the blunt or convex leading edge of the swash. In the middle and upper swash the water surface slope at this leading edge is usually very close to horizontal or slightly seaward. Behind the leading edge, the water surface slope was observed to be very close to horizontal or dipping seaward at all times throughout the swash uprush. During the backwash the water surface slope was observed to be always dipping seaward, approaching the beach slope, and remained seaward until a new uprush edge or incident bore passed any particular cross-shore location of interest. The observations strongly Suggest that the swash boundary layer is subject to an adverse pressure gradient during uprush and a favourable pressure gradient during the backwash. Furthermore, assuming Euler's equations are a good approximation in the swash, the observations also show that the total fluid acceleration is negative (offshore) for almost the whole of the uprush and for the entire backwash. The observations are contrary to recent work suggesting significant shoreward directed accelerations and pressure gradients occur in the swash (i.e., delta u/delta t > 0 similar to delta p/delta x < 0), but consistent with analytical and numerical solutions for swash uprush and backwash. The results have important implications for sediment transport modelling in the swash zone.

Erosion-corrosion of mild steel in hot caustic. Part I: NaOH solution

A novel apparatus, high-pressure/high-temperature nickel flow loop, was constructed to study the effect of the flow on the rate of erosion-corrosion of mild steel in hot caustic. It has been successfully used to measure the corrosion rate of 1020 steel in 2.75 M NaOH solution at a temperature of 160 degrees C and velocities of 0.32 and 2.5 m/s. In situ electrochemical methods were used to measure the corrosion rate such as the potentiodynamic sweep, the polarization resistance method, and electrochemical impedance spectroscopy (EIS). Also used were the weight-loss method and scanning electron microscopy (SEM). Eight electrodes/coupons were used to monitor the metal loss rate, four were placed at the low velocity section, while the other four were placed in the high velocity section. The first three coupons in each section were placed within the disturbed flow region, while the fourth was placed in a fully developed flow region. The corrosion rate of the coupons in the high velocity section was generally higher than that of the coupons in the low velocity section. One coupon in the disturbed flow region had a significantly higher corrosion rate than the others. (c) 2005 Elsevier Ltd. All rights reserved.

Erosion-corrosion of mild steel in hot caustic. Part II: The effect of acid cleaning

Corrosion rates of 1020 steel in 2.75 M NaOH solution at a temperature of 160 degrees C and velocities of 0.32 and 2.5 m/s were studied. The focus was on the effect of the acid cleaning which was performed by using strong, inhibited sulphuric acid in between the exposures to caustic. In situ electrochemical methods were used to measure the corrosion rate such as the potentiodynamic sweep and the polarization resistance method. Also used were the weight-loss method and scanning electron microscopy (SEM). Eight electrodes/coupons were used to monitor the metal loss rate, four were placed at the low velocity section, while the other four were placed in the high velocity section of a high temperature flow. The first three coupons in each section were placed within the disturbed flow region, while the fourth was placed in a fully developed flow region. During the exposure of mild steel to the inhibited acid, following the first caustic period, the corrosion rate increased significantly to between 3 and 10mm/y with a few electrodes experiencing as high as 50 mm/y. The second caustic period following the acidic period typically started with very high corrosion rates (20-80 mm/y). The length of this corrosion period was typically 2-3 h with a few exceptions when the high corrosion period lasted 7-10 h. Following the very high corrosion rates experienced at the beginning of the second caustic period, the corrosion rates were reduced sharply (as the corrosion potential increased) to nearly the same levels as those observed during the passive part of the first caustic period. (c) 2005 Elsevier Ltd. All rights reserved.

Measuring and predicting the dynamics of linear monodisperse entangled polymers in rapid flow through an abrupt contraction. A small angle neutron scattering study

Small-angle neutron scattering measurements on a series of monodisperse linear entangled polystyrene melts in nonlinear flow through an abrupt 4:1 contraction have been made. Clear signatures of melt deformation and subsequent relaxation can be observed in the scattering patterns, which were taken along the centerline. These data are compared with the predictions of a recently derived molecular theory. Two levels of molecular theory are used: a detailed equation describing the evolution of molecular structure over all length scales relevant to the scattering data and a simplified version of the model, which is suitable for finite element computations. The velocity field for the complex melt flow is computed using the simplified model and scattering predictions are made by feeding these flow histories into the detailed model. The modeling quantitatively captures the full scattering intensity patterns over a broad range of data with independent variation of position within the contraction geometry, bulk flow rate and melt molecular weight. The study provides a strong, quantitative validation of current theoretical ideas concerning the microscopic dynamics of entangled polymers which builds upon existing comparisons with nonlinear mechanical stress data. Furthermore, we are able to confirm the appreciable length scale dependence of relaxation in polymer melts and highlight some wider implications of this phenomenon.

Quantitative assessment of aortic sclerosis using ultrasonic backscatter

Background. The development of therapeutic interventions to prevent progressive valve damage is more likely to limit the progression of structural damage to the aortic valve with normal function (aortic sclerosis [ASC]) than clinically apparent aortic stenosis. Currently, the ability to appreciate the progression of ASC is compromised by the subjective and qualitative evaluation of sclerosis severity. Methods: We sought to reveal whether the intensity of ultrasonic backscatter could be used to quantify sclerosis severity in 26 patients with ASC and 23 healthy young adults. images of the aortic valve were obtained in the parasternal long-axis view and saved in raw data format. Six square-shaped 11 X 11 pixel regions of interest were placed on the anterior and posterior leaflets, and calibrated backscatter values were obtained by subtracting the regions of interest in the blood pool from the averaged backscatter values obtained from the leaflets. Results. Mean ultrasonic backscatter values for sclerotic valves exceeded the results in normal valve tissue (16.3 +/- 4.4 dB vs 9.8 +/- 3.3 dB, P < .0001). Backscatter values were greater (22.0 +/- 3.5 dB) in a group of 6 patients with aortic stenosis. Within the sclerosis group, the magnitude of backscatter was directly correlated (P < .05) with a subjective sclerosis score, and with transvalvular pressure gradient. mean reproducibility was 2.4 +/- 1.8 dB (SD) between observers, and 2.3 +/- 1.7 dB (SD) between examinations. Conclusion: Measurement of backscatter from the valve leaflets of patients with ASC may be a feasible means of following the progression and treatment response of aortic sclerosis.

OH concentration and temperature measurements by use of near-resonant holographic interferometry

Near-resonant holographic interferometry is demonstrated to measure temperature and species concentration in a two-dimensional steady premixed air-acetylene flame. A peak temperature of (2600 +/- 100) K and a peak OH number density of (9.6 +/- 0.3) X 10(22) m(-3) are obtained, consistent with the expected values for such a flame. These values are determined by recording interferograms with a laser assumed sufficiently detuned from line center so that pressure and temperature broadening can be ignored. The results are thus obtained without making prior assumptions on the temperature or pressure of the flame beyond the existence of thermal equilibrium. (C) 2004 Optical Society of America.

Hydrodynamic evaluation of kangaroo aortic valve matrices for tissue valve engineering

We evaluated the hydrodynamic performance of kangaroo aortic valve matrices (KMs) (19, 21, and 23 mm), as potential scaffolds in tissue valve engineering using a pulsatile left heart model at low and high cardiac outputs (COs) and heart rates (HRs) of 60 and 90 beats/min. Data were measured in two samples of each type, pooled in two CO levels (2.1 +/- 0.7 and 4.2 +/- 0.6 L/min; mean +/- standard errors on the mean), and analyzed using analysis of variance with CO level, HR, and valve type as fixed factors and compared to similar porcine matrices (PMs). Transvalvular pressure gradient (Delta P) was a function of HR (P < 0.001) and CO (P < 0.001) but not of valve type (P = 0.39). Delta P was consistently lower in KMs but not significantly different from PMs. The effective orifice area and performance index of kangaroo matrices was statistically larger for all sizes at both COs and HRs.