Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Synthesis and characterization of nano silicon and titanium nitride powders using atmospheric microwave plasma technique

We have demonstrated a simple, scalable and inexpensive method based on microwave plasma for synthesizing 5 to 10 g/h of nanomaterials. Luminescent nano silicon particles were synthesized by homogenous nucleation of silicon vapour produced by the radial injection of silicon tetrachloride vapour and nano titanium nitride was synthesized by using liquid titanium tetrachloride as the precursor. The synthesized nano silicon and titanium nitride powders were characterized by XRD, XPS, TEM, SEM and BET. The characterization techniques indicated that the synthesized powders were indeed crystalline nanomaterials.

Electrochemical phase formation (ECPF): Nucleation growth vis-a-vis adsorption models

The nucleataon growth model of electrochemical phase formation is analysed for the hnear potential sweep input Apart from deducing diagnostic criteria and method~ of estimating model parameters, the predictions of the nucleation growth model are compared and contrasted with those of a sample adsorption model A dastlnCtlOn is made possible between adsorption and phase transition, which seems useful for understanding the nature of ECPF phenomena, especially underpotentlal deposition (UPD).

Atmospheric Noise on the Bispectrum in Optical Speckle Interferometry

Based on a simple picture of speckle phenomena in optical interferometry it is shown that the recent signal-to-noise ratio estimate for the so called bispectrum, due to Wirnitzer (1985), does not possess the right limit when photon statistics is unimportant. In this wave-limit, which is true for bright sources, his calculations over-estimate the signal-to-noise ratio for the bispectrum by a factor of the order of the square root of the number of speckles.

Mesospheric influences on linkages between solar activity and lower atmospheric phenomena

Analyses of rocket data at mid- and high-latitude locations over the American Continent show a solar activity-dependent mesospheric heating effect in the 60 to 90 km altitude region. A study of the altitude dependence of the effect shows that the heating and associated processes propagating downwards through the mesosphere do not cause discernible effects, below the 50 to 60 km layer. At Thumba, a significant short-term heating effect attributable to varying solar ultraviolet fluxes causing variable heating of atmospheric ozone is observed. This effect does not seem to propagate downwards into the upper stratosphere.

Nucleation parameters for polymer crystallization from non-isothermal thermal analysis

Differential scanning calorimetry (DSC) has been used to obtain kinetic and nucleation parameters for polymer crystallization under a non-isothermal mode of operation. The available isothermal nucleation growth-rate equation has been modified for non-isothermal kinetic analysis. The values of the nucleation constant (K g ) and surface free energies (sgr, sgr e ) have been obtained for i-polybutene-1, i-polypropylene, poly(L-lactic acid), and polyoxymethylene and are compared with those obtained from isothermal kinetic analysis; a good agreement in both is seen.

Equatorial modes observed in atmospheric variables

Wavenumber-frequency spectral analysis of different atmospheric variables has been carried Out using 25 years of data. The area considered is the tropical belt 25 degrees S-25 degrees N. A combined FFT wavelet analysis method has been used for this purpose. Variables considered are outgoing long wave radiation (OLR), 850 hPa divergence, zonal and meridional winds at 850, 500 and 200 hPa levels, sea level pressure and 850 hPa geopotential height. It is shown that the spectra of different variables have some common properties, but each variable also has few features diffe:rent from the rest. While Kelvin mode is prominent in OLR, and zonal winds, it is not clearly observed in pressure and geopotential height fields; the latter two have a dominant wavenumber zero mode not seen in other variables except in meridional wind at 200 hPa and 850 hPa divergences. Different dominant modes in the tropics show significant variations on sub-seasonal time scales.

Atmospheric survey of pollen of Parthenium hysterophorus

An aerobiological survey to study the incidence and concentration of the pollen of Parthenium hysterophorus was conducted in Bangalore, India for a period of one year. This study indicated that Parthenium pollen was present in the atmosphere in significant amounts eigher as single pollen grains or in the form of clumps during the months of June to August.

Optical and Physical Properties of Atmospheric Aerosols over the Bay of Bengal during ICARB

Simultaneous and collocated measurements of total and hemispherical backscattering coefficients (σ and β, respectively) at three wavelengths, mass size distributions, and columnar spectral aerosol optical depth (AOD) were made onboard an extensive cruise experiment covering, for the first time, the entire Bay of Bengal (BoB) and northern Indian Ocean. The results are synthesized to understand the optical properties of aerosols in the marine atmospheric boundary layer and their dependence on the size distribution. The observations revealed distinct spatial and spectral variations of all the aerosol parameters over the BoB and the presence of strong latitudinal gradients. The size distributions varied spatially, with the majority of accumulation modes decreasing from north to south. The scattering coefficient decreased from very high values (resembling those reported for continental/urban locations) in the northern BoB to very low values seen over near-pristine environments in the southeastern BoB. The average mass scattering efficiency of BoB aerosols was found to be 2.66 ± 0.1 m2 g−1 at 550 nm. The spectral dependence of columnar AOD deviated significantly from that of the scattering coefficients in the northern BoB, implying vertical heterogeneity in the aerosol type in that region. However, a more homogeneous scenario was observed in the southern BoB. Simultaneous lidar and in situ measurements onboard an aircraft over the ocean revealed the presence of elevated aerosol layers of enhanced extinction at altitudes of 1 to 3 km with an offshore extent of a few hundred kilometers. Back-trajectory analyses showed these layers to be associated with advection from west Asia and western India. The large spatial variations and vertical heterogeneity in aerosol properties, revealed by the present study, need to be included in the regional radiative forcing over the Bay of Bengal.

On the Purity of Atmospheric Glow-Discharge Plasma

Purity of the glow-discharge plasma at atmospheric pressure for surface modification applications is always debatable, since it works at ambient atmosphere. We have demonstrated on the use of optical emission spectroscopy to test the purity of this kind of plasma. The effect of gas flow pattern, nature of gas, and its flow rate on the plasma chemistry was studied. The importance of proper system design in maintaining a uniform flow of heavy and inert gases as carrier gas in atmospheric glow-discharge plasma was confirmed. The surface of a plasma-treated PET sample was analyzed using X-ray photoelectron spectroscopy to verify the studies on plasma purity done using emission spectrum.

Some pulse characteristics of atmospheric radio noise bursts at 3 MHz

An atmospheric radio noise burst represents the radiation received from one complete lightning flash at the frequency to which a receiver is tuned and within the receiver bandwidth. At tropical latitudes, the principal source of interference in the frequency range from 0.1 to 10 MHz is the burst form of atmospheric radio noise. The structure of a burst shows several approximately rectangular pulses of random amplitude, duration and frequency of recurrence. The influence of the noise on data communication can only be examined when the value of the number of pulses crossing a certain amplitude threshold per unit time of the noise burst is known. A pulse rate counter designed for this purpose has been used at Bangalore (12°58′N, 77°35′E) to investigate the pulse characteristics of noise bursts at 3 MHz with a receiver bandwidth of 3.3 kHz/6d B. The results show that the number of pulses lying in the amplitude range between peak and quasi-peak values of the noise bursts and the burst duration corresponding to these pulses follow log normal distributions. The pulse rates deduced therefrom show certain correlation between the number of pulses and the duration of the noise burst. The results are discussed with a view to furnish necessary information for data communication.

Peptide hairpin nucleation with the obligatory Type I' beta-turn Aib-(D)Pro segment

The alpha-aminoisobutyric acid-D-proline (Aib-(D)Pro) dipeptide is an obligatory Type I' beta-turn forming segment that nucleates hairpin formation.

Adsorption-nucleation/growth based model for electrochemical phase formation and Avrami ansatz for a multicomponent competitive growth process

The existing models describing electrochemical phase formation involving both adsorption and a nucleation/growth process are modified. The limiting cases leading to the existing models are discussed. The characteristic features of the potentiostatic transients are presented. A generalization of the Avrami ansatz is given for two or more competitive irreversibly growing phases.