An EQCM Investigation of Electrochemical Precipitation of Mn(OH)(2) and Its Capacitance Behavior

Electrochemical quartz crystal microbalance (EQCM) has been used to study the electrochemical precipitation of Mn(OH)(2) on a Au crystal and its capacitance properties. From the EQCM data, it is inferred that NO3- ions get adsorbed on the Au crystal and then undergo reduction, resulting in an increase in pH near the electrode surface. Precipitation of Mn2+ occurs as Mn(OH)(2), with an increase in mass of the Au crystal. Mn(OH)(2) undergoes oxidation to MnO2, which exhibits electrochemical supercapacitor behavior on subjecting to electrochemical cycling in a Na2SO4 electrolyte. EQCM data indicate mass variations corresponding to surface insertion/extraction of Na+ ions during discharge/charge cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3479665] All rights reserved.

Nucleation and growth of Al2O3/metal composites by oxidation of aluminum alloys

The nucleation and growth mechanisms during high temperature oxidation of liquid Al-3% Mg and Al-3% Mg-3% Si alloys were studied with the aim of enhancing our understanding of a new composite fabrication process. The typical oxidation sequence consists of an initial event of rapid but brief oxidation, followed by an incubation period of limited oxide growth after which bulk Al2O3/Al composite forms. A duplex oxide layer, MgO (upper) and MgAl2O4 (lower), forms on the alloy surface during initial oxidation and incubation. The spinel layer remains next to the liquid alloy during bulk oxide growth and is the eventual repository for most of the magnesium in the original alloy. Metal microchannels developed during incubation continuously supply alloy through the composite to the reaction interface. During the growth process, a layered structure exists at the upper extremity of the composite, consisting of MgO at the top surface, MgAl2O4 (probably discontinuous), Al alloy, and finally the bulk Al2O3 composite containing microchannels of the alloy. The bulk oxide growth mechanism appears to involve continuous formation and dissolution of the Mg-rich oxides at the surface, diffusion of oxygen through the underlying liquid metal, and epitaxial growth of Al2O3 on the existing composite body. The roles of Mg and Si in the composite growth process are discussed.

Thermodynamics Of Aluminum Strontium Alloys

The activity of strontium in liquid Al-Sr alloys (X(Sr) less-than-or-equal-to 0.17) at 1323 K has been determined using the Knudsen effusion-mass loss technique. At higher concentrations (X(Sr) greater-than-or-equal-to 0.28), the activity of strontium has been determined by the pseudoisopiestic technique. Activity of aluminium has been derived by Gibbs-Duhem integration. The concentration - concentration structure factor of Bhatia and Thornton at zero wave vector has been computed from the thermodynamic data. The behaviour of the mean square thermal fluctuation in composition and the thermodynamic mixing functions suggest association tendencies in the liquid state. The associated solution model with Al2Sr as the predominant complex can account for the properties of the liquid alloy. Thermodynamic data for the intermetallic compunds in the Al-Sr system have been derived using the phase diagram and the Gibbs' energy and enthalpy of mixing of liquid alloys. The data indicate the need for redetermination of the phase diagram near the strontium-rich corner.

Sensitivity of the simulated precipitation to changes in convective relaxation time scale

The paper describes the sensitivity of the simulated precipitation to changes in convective relaxation time scale (TAU) of Zhang and McFarlane (ZM) cumulus parameterization, in NCAR-Community Atmosphere Model version 3 (CAM3). In the default configuration of the model, the prescribed value of TAU, a characteristic time scale with which convective available potential energy (CAPE) is removed at an exponential rate by convection, is assumed to be 1 h. However, some recent observational findings suggest that, it is larger by around one order of magnitude. In order to explore the sensitivity of the model simulation to TAU, two model frameworks have been used, namely, aqua-planet and actual-planet configurations. Numerical integrations have been carried out by using different values of TAU, and its effect on simulated precipitation has been analyzed. The aqua-planet simulations reveal that when TAU increases, rate of deep convective precipitation (DCP) decreases and this leads to an accumulation of convective instability in the atmosphere. Consequently, the moisture content in the lower-and mid-troposphere increases. On the other hand, the shallow convective precipitation (SCP) and large-scale precipitation (LSP) intensify, predominantly the SCP, and thus capping the accumulation of convective instability in the atmosphere. The total precipitation (TP) remains approximately constant, but the proportion of the three components changes significantly, which in turn alters the vertical distribution of total precipitation production. The vertical structure of moist heating changes from a vertically extended profile to a bottom heavy profile, with the increase of TAU. Altitude of the maximum vertical velocity shifts from upper troposphere to lower troposphere. Similar response was seen in the actual-planet simulations. With an increase in TAU from 1 h to 8 h, there was a significant improvement in the simulation of the seasonal mean precipitation. The fraction of deep convective precipitation was in much better agreement with satellite observations.

Vapor-Pressure Of Calcium Corresponding To The Reduction Of Calcia By Aluminum

The equilibrium pressure of calcium corresponding to the reduction reaction 6CaO (s) + 2Al (l) half-arrow-right-over-half-arrow-left 3CaO.Al2O3 (s) + 3Ca (g) has been measured by Knudsen effusion - mass loss analysis in the temperature range 1190 - 1500 K. The measured vapour pressure can be expressed as a function of temperature by the relation: log p(Ca) (Pa) = -10,670/T + 9.267 The calcium generated is partially absorbed by aluminium to form an alloy. The equilibrium composition of the alloy at 1373 K was found to be 22 mol% Ca - 78 mol% Al. The measured vapour pressure is in good agreement with that computed from thermodynamic data.

Directional solidification of aluminum-nickel eutectic alloys using electroslag remelting

Attempts were made to produce directionally solidified, specifically grain aligned Al-6 wt pct Ni eutectic alloy using a laboratory scale ESR unit. For this purpose sand cast alloy electrodes were electroslag remelted under different mold conditions. The grain structure of the ingots obtained from these meltings showed that insulated silica molds gave the best vertical alignment of grains along the length of the ingot. The NiAl3 fibers within the grains tended to fan out and there was only a preferred alignment of fibers along the growth direction under the conditions of our experiments. The ESR parameters most suitable for vertical alignment of eutectic grains have been identified. In some electroslag remelting trials ingots were grown on a seed ingot. This resulted in a fewer vertical grains compared to the case when no seed ingot was used. The sand cast specimen of the eutectic exhibited a maximum tensile strength of around 88.2 MN/m2 (9.0 kg/mm2) whereas conventional ESR using water cooled mold gave strength value of 98.0 MN/m2 (10 kg/mm2). The directionally solidified ESR material showed longitudinal tensile strength as high as 213.7 MN/m2 (21.8 kg/mm2) which could be further increased to 220.6 MN/m2 (22.5 kg/mm2) by using the seed ingot. The average growth rate was varied between 5 to 25 mm/min during electroslag remelting in this study. The flow stresses, tangent modulus and ultimate tensile strength of directionally solidified eutectic increased with increasing growth rates.

Precipitation in small systems-I. stochastic analysis

Precipitation in small droplets involving emulsions, microemulsions or vesicles is important for Producing multicomponent ceramics and nanoparticles. Because of the random nature of nucleation and the small number of particles in a droplet, the use of a deterministic population balance equation for predicting the number density of particles may lead to erroneous results even for evaluating the mean behavior of such systems. A comparison between the predictions made through stochastic simulation and deterministic population balance involving small droplets has been made for two simple systems, one involving crystallization and the other a single-component precipitation. The two approaches have been found to yield quite different results under a variety of conditions. Contrary to expectation, the smallness of the population alone does not cause these deviations. Thus, if fluctuation in supersaturation is negligible, the population balance and simulation predictions concur. However, for large fluctuations in supersaturation, the predictions differ significantly, indicating the need to take the stochastic nature of the phenomenon into account. This paper describes the stochastic treatment of populations, which involves a sequence of so-called product density equations and forms an appropriate framework for handling small systems.

Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?

Recently, it was found that a reduction in atmospheric CO2 concentration leads to a temporary increase in global precipitation. We use the Hadley Center coupled atmosphere-ocean model, HadCM3L, to demonstrate that this precipitation increase is a consequence of precipitation sensitivity to changes in atmospheric CO2 concentrations through fast tropospheric adjustment processes. Slow ocean cooling explains the longer-term decrease in precipitation. Increased CO2 tends to suppress evaporation/precipitation whereas increased temperatures tend to increase evaporation/precipitation. When the enhanced CO2 forcing is removed, global precipitation increases temporarily, but this increase is not observed when a similar negative radiative forcing is applied as a reduction of solar intensity. Therefore, transient precipitation increase following a reduction in CO2-radiative forcing is a consequence of the specific character of CO2 forcing and is not a general feature associated with decreases in radiative forcing. Citation: Cao, L., G. Bala, and K. Caldeira (2011), Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?, Geophys. Res. Lett., 38, L06703, doi:10.1029/2011GL046713.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Modeling of precipitation in reverse micellar systems

A model of the precipitation process in reverse micelles has been developed to calculate the size of fine particles obtained therein. While the method shares several features of particle nucleation and growth common to precipitation in large systems, complexities arise in describing the processes of nucleation, due to the extremely small size of a micelle and of particle growth caused by fusion among the micelles. Occupancy of micelles by solubilized molecules is governed by Poisson statistics, implying most of them are empty and cannot nucleate of its own. The model therefore specifies the minimum number of solubilized molecules required to form a nucleus which is used to calculate the homogeneous nucleation rate. Simultaneously, interaction between micelles is assumed to occur by Brownian collision and instantaneous fusion. Analysis of time scales of various events shows growth of particles to be very fast compared to other phenomena occurring. This implies that nonempty micelles either are supersaturated or contain a single precipitated particle and allows application of deterministic population balance equations to describe the evolution of the system with time. The model successfully predicts the experimental measurements of Kandori ct al.(3) on the size of precipitated CaCO3 particles, obtained by carbonation of reverse micelles containing aqueous Ca(OH)(2) solution.

Study of embedded lead-tin nanoparticles in aluminum matrix

Nanoembedded lead-tin alloys in aluminum matrix were synthesized by rapid solidification processing. These melt-spun aluminum alloys were then investigated using XRD, EDX and TEM. The XRD study reveals that the melt-spun samples contain elemental aluminum, lead and tin. The TEM analysis shows that embedded particles in aluminium matrix have a distinct two-phase contrast of lead and tin. The lead and tin in these nanoalloys exhibit an orientation relationship with the matrix aluminum and with each other. DSC studies were conducted to reveal the melting and solidification characteristics of these embedded nanoalloys. DSC thermograms exhibit features of multiple solidification exotherms on thermal cycling, which can be attributed to sequential melting and solidification of lead and tin in the respective alloys.