Review of non-reactive and reactive wetting of liquids on surfaces

Wettability is a tendency for a liquid to spread on a solid substrate and is generally measured in terms of the angle (contact angle) between the tangent drawn at the triple point between the three phases (solid, liquid and vapour) and the substrate surface. A liquid spreading on a substrate with no reaction/absorption of the liquid by substrate material is known as non-reactive or inert wetting whereas the wetting process influenced by reaction between the spreading liquid and substrate material is known as reactive wetting. Young's equation gives the equilibrium contact angle in terms of interfacial tensions existing at the three-phase interface. The derivation of Young's equation is made under the assumptions of spreading of non-reactive liquid on an ideal (physically and chemically inert, smooth, homogeneous and rigid) solid, a condition that is rarely met in practical situations. Nevertheless Young's equation is the most fundamental starting point for understanding of the complex field of wetting. Reliable and reproducible measurements of contact angle from the experiments are important in order to analyze the wetting behaviour. Various methods have been developed over the years to evaluate wettability of a solid by a liquid. Among these, sessile drop and wetting balance techniques are versatile, popular and provide reliable data. Wetting is affected by large number of factors including liquid properties, substrate properties and system conditions. The effect of these factors on wettability is discussed. Thermodynamic treatment of wetting in inert systems is simple and based on free energy minimization where as that in reactive systems is quite complex. Surface energetics has to be considered while determining the driving force for spreading. Similar is the case of spreading kinetics. Inert systems follow definite flow pattern and in most cases a single function is sufficient to describe the whole kinetics. Theoretical models successfully describe the spreading in inert systems. However, it is difficult to determine the exact mechanism that controls the kinetics since reactive wetting is affected by a number of factors like interfacial reactions, diffusion of constituents, dissolution of the substrate, etc. The quantification of the effect of these interrelated factors on wettability would be useful to build a predictive model of wetting kinetics for reactive systems.     

NMR spectra, GIAO and charge density calculations of five-membered aromatic heterocycles

The B3LYP/6-31+G(d) molecular geometry optimized structures of 17 five-membered heterocycles were employed together with the gauge including atomic orbitals (GIAO) density functional theory (DFT) method at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p) and B3LYP/6-311+G(2d,p) levels of theory for the calculation of proton and carbon chemicals shifts and coupling constants. The method of geometry optimization for pyrrole (1), N-methylpyrrole (2) and thiophene (7) using the larger 6-311++G(d,p) basis sets at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p), B3LYP/6-31+G(2d,p) and B3LYP/cc-pVTZ levels of theory gave little difference between calculated and experimental values of coupling constants. In general, the (1)H and 13C chemical shifts for all compounds are in good agreement with theoretical calculations using the smaller 6-31 basis set. The values of nJHH(n=3, 4, 5) and rmnJ(CH)(n=1, 2, 3, 4) were predicted well using the larger 6-31+G(d,p) and 6-311++G(d,p) basis sets and at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p), B3LYP/6-31+G(2d,2p) levels of theory. The computed atomic charges [Mülliken; Natural Bond Orbital Analysis (NBO); Merz-Kollman (MK); CHELP and CHELPG] for the B3LYP/6-311++G(d,p) geometry optimized structures of 1-17 were used to explore correlations with the experimental proton and carbon chemical shifts.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.     

Optical properties and highly efficient laser oscillation of Nd:YAG ceramics

Optical absorption, emission spectra have been measured for polycrystalline Nd-doped Y₃Al₅O₁₂ ceramics. Fluorescence lifetimes of 257.6 μs, 237.6 μs, 184.2 μs and 95.6 μs have been obtained for 0.6%, 1%, 2% and 4% neodymium-doped YAG ceramics, respectively. For the first time, highly efficient laser oscillation at 1064 nm has been obtained with this kind of ceramics. Slope efficiency of 53% has been achieved on a uncoated 4.8-mm thick 1% Nd:YAG ceramics sample. Optical to optical conversion efficiency is 47.6%. Laser oscillation has also been obtained with a 2% Nd:YAG ceramics. The optical properties and laser output results have been compared with that of Nd:YAG single crystal grown by the Czochralski method. Almost identical results have been achieved including laser experiments results. But fabrication of Nd:YAG ceramics is much easier compared to the single-crystal growth method. And also large size (now of about 400 mm diameter×5 mm is available) and high-concentration (>1%) Nd:YAG ceramics can be fabricated. The results show that this kind of Nd:YAG ceramics is a very good alternative to Nd:YAG single crystal. Received: 20 April 2000 / Published online: 16 August 2000     

Carmine and Fast Green as Corrosion Inhibitors for Mild Steel in Hydrochloric Acid Solution

The inhibition action of carmine and fast green dyes on corrosion of mild steel in 0.5 M HCl was investigated using mass loss, polarization and electrochemical impedance (EIS) methods at 300 K. The inhibition efficiency was found to increase with increasing concentration of the inhibitors. The inhibition efficiency of fast green (%η - 98) is higher than that of carmine (%η - 92) and found to be maximum in 1 × 10^-3 M solution. The inhibitors act as mixed type with predominant cathodic effect. The inhibitors were adsorbed on the mild steel surface according to the Temkin adsorption isotherm. The surface morphology of the mild steel specimens was evaluated using SEM images.     

Isolation and Crystal Structure of 6α,7α-Epoxy-5α,17α,27-trihydroxy-1-oxo-22R-witha-2,24-dienolide monohydrate-A Withasteroid from Withania somnifera Leaves

Abstract  

(5R,6S,7S,8S,9S,10R,13S,14S,17S,20R,22R)-6α,7α-epoxy-5α,17α,27-trihydroxy-1-oxo-22R-witha-2,24-dienolide has been isolated from Withania somnifera leaves. Three-dimensional X-ray intensity data were collected at 293 K on Bruker CCD area-detector diffractometer equipped with graphite-monochromated MoKα radiation (λ = 0.71073 ?). The compound crystallizes in monoclinic space group P21 with unit cell parameters: a = 6.4540(2), b = 11.3656(4), c = 17.4982(5) ?, β = 90.730 ^o(2), Z = 2. The crystal structure was refined to a final R-value of 0.0419 for 6122 observed reflections. One water solvent molecule was observed. All the rings of the steroid skeleton are trans connected. Rings A and B exists in a half-chair conformation, ring C a chair, and five membered ring D is intermediate between half-chair and envelope. The δ-lactone ring E adopts a distorted sofa conformation. The characteristic pattern observed in the packing diagram is the appearance of twisted chains of molecules. The packing of the molecules in the crystal is stabilized by intra- and intermolecular O–H···O and C–H···O interactions.     

Redox magnetohydrodynamic enhancement of stripping voltammetry: toward portable analysis using disposable electrodes, permanent magnets, and small volumes

The use of redox magnetohydrodynamics (MHD) to enhance the anodic stripping voltammetry (ASV) response of heavy metals has been investigated, with respect to achieving portability: disposable electrodes consisting of screen-printed carbon (SPC) on a low temperature co-fired ceramic (LTCC) substrate, small volumes, and permanent magnets. The analytes tested (Cd(2+), Cu(2+), and Pb(2+)) were codeposited on SPC with Hg(2+) to form a Hg thin film electrode. High concentrations of Fe(3+) were used to produce a high cathodic current which generates a significant Lorentz force in the presence of a magnetic field. This Lorentz force induces solution convection during the deposition step, enhancing the mass transport of analytes to the electrode and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared to analyses performed without a magnet. The effects on ASV signal of varying Hg(2+) concentration (0.10 and 1.0 mM), deposition time (10-600 s), and electrode surface roughness were investigated. In addition, analyses were performed using a real lake water matrix. By using the disposable LTCC-SPC working electrodes in small volumes (150 microL) and with small permanent magnets (0.78 T), peak areas were increased by 75% when compared to the signal obtained in the absence of a magnetic field. A limit of detection of 25 nM for Cd(2+) was observed with only a 1 min preconcentration time.     

Analysis of natural convective heat transfer of nano coated aluminium fins using Taguchi method

Rectangular aluminium fins were preferred for analysis and coated by carbon nano tubes using PVD to enhance the heat transfer rate of fins. Convective heat transfer rates for coated and non-coated surfaces were calculated and compared. The temperature and heat transfer characteristics were investigated using Nusselt, Grashof, Prandtl and Rayleigh numbers and also optimized by Taguchi method and ANOVA analysis. The average percentage of increase in fin efficiency is 5 %.     

Vortex dynamics of a trapezoidal bluff body placed inside a circular pipe

The influence of Reynolds number and blockage ratio on the vortex dynamics of a trapezoidal bluff body placed inside a circular pipe is studied experimentally and numerically. Low aspect ratio, high blockage ratio, curved end conditions (junction of pipe and bluff body), axisymmetric upstream flow with shear and turbulence are some of the intrinsic features of this class of bluff body flows which have been scarcely addressed in the literature. A large range (200:200,000) of Reynolds number (Re_D) is covered in this study, encompassing all the three pipe flow regimes (laminar, transition and turbulent). Four different flow regimes are defined based on the distinct features of Strouhal number (St)–Re_D relation: steady, laminar irregular, transition and turbulent. The wake in the steady regime is stationary with no oscillations in the shear layer. The laminar regime is termed as irregular owing to irregular vortex shedding. The vortex shedding in this regime is observed to be symmetric. The emergence of separation bubble downstream of the bluff body on either side is another interesting feature of this regime, which is further observed to be symmetric. Two pairs of mean streamwise vortices are noticed in the near-wake regime, which are termed as reverse dipole-type wake topology. Beyond the irregular laminar regime, the Strouhal number falls gradually and vortex shedding becomes more periodic. This regime is named transition and occurs close to the Reynolds number at which transition to turbulence takes place in a fully developed pipe. The turbulent regime is characterised by a nearly constant Strouhal number. Typical Karman-type vortex shedding is noticed in this regime. The convection velocity, wake width formation length and irrecoverable pressure loss are quantified to highlight the influence of blockage ratio. These results will be useful to develop basic understanding of vortex dynamics of confined bluff body flow for several practical applications.