Small-angle neutron scattering studies of different mixed micelles composed of dimeric and monomeric cationic surfactants

Measurements of small-angle neutron scattering (SANS) cross sections from different mixed micelles composed of CTAB and Br-, n-C16H33N+Me2-(CH2)(m)N+Me2-n-C16H33, Br- (16-m-16, 2Br(-), where m = 3, 5, and 10), in aqueous media (D2O) are reported. The data have been analyzed using the Hayter and Penfold model for macroion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the micelles. The aggregate composition matches with that predicted from an ideal mixing model. The SANS analysis further indicates that the extent of aggregate growth and the Variations of shapes of the mixed micelles could be modulated by the amount of dimeric surfactant present in these mixtures. With the spacer chain length m less than or equal to 4 in the dimeric surfactant, the propensity of micellar growth is particularly pronounced. The effect of the variation of the temperature for the mixed micellar system (23.1 mol % of 16-3-16, 2Br(-)) was also examined. The systemic microviscosities that the mixed micellar aggregates offer to a solubilized, extrinsic fluorescence probe, 1,6-diphenyl-1,3,5-hexatriene, were determined. The variation of the microviscosities of the mixed micelles as a function of percentages of the dimeric surfactants could be explained in terms of conformational variations and progressive looping of the spacer chain of dimeric surfactants in mixed micellar aggregates with increasing m values.

Isomerization dynamics in viscous liquids: Microscopic investigation of the coupling and decoupling of the rate to and from solvent viscosity and dependence on the intermolecular potential

A detailed investigation of viscosity dependence of the isomerization rate is carried out for continuous potentials by using a fully microscopic, self-consistent mode-coupling theory calculation of both the friction on the reactant and the viscosity of the medium. In this calculation we avoid approximating the short time response by the Enskog limit, which overestimates the friction at high frequencies. The isomerization rate is obtained by using the Grote-Hynes formula. The viscosity dependence of the rate has been investigated for a large number of thermodynamic state points. Since the activated barrier crossing dynamics probes the high-frequency frictional response of the liquid, the barrier crossing rate is found to be sensitive to the nature of the reactant-solvent interaction potential. When the solute-solvent interaction is modeled by a 6-12 Lennard-Jones potential, we find that over a large variation of viscosity (eta), the rate (k) can indeed be fitted very well to a fractional viscosity dependence: (k similar to eta(-alpha)), with the exponent alpha in the range 1 greater than or equal to alpha >0. The calculated values of the exponent appear to be in very good agreement with many experimental results. In particular, the theory, for the first time, explains the experimentally observed high value of alpha even at the barrier frequency, omega(b). similar or equal to 9 X 10(12) s(-1) for the isomerization reaction of 2-(2'-propenyl)anthracene in liquid eta-alkanes. The present study can also explain the reason for the very low value of vb observed in another study for the isomerization reaction of trans-stilbene in liquid n-alkanes. For omega(b) greater than or equal to 2.0 X 10(13) s(-1), we obtain alpha similar or equal to 0, which implies that the barrier crossing rate becomes identical to the transition-state theory predictions. A careful analysis of isomerization reaction dynamics involving large amplitude motion suggests that the barrier crossing dynamics itself may become irrelevant in highly viscous liquids and the rate might again be coupled directly to the viscosity. This crossover is predicted to be strongly temperature dependent and could be studied by changing the solvent viscosity by the application of pressure. (C) 1999 American Institute of Physics. [S0021-9606(9950514-X].

Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 predicted with the two approaches are similar. In general, the deviation between the LMFA and GMFA is greater for smaller n and less sensitive to n for epsilon(aa)(*)> 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Theory of combined AM and high-harmonic FM mode locked laser

Closed form solutions for a simultaneously AM and high-harmonic FM mode locked laser system is presented. Analytical expressions for the pulsewidth and pulsewidth-bandwidth products are derived in terms of the system parameters. The analysis predicts production of 17 ps duration pulses in a Nd:YAG laser mode locked with AM and FM modulators driven at 80 MHz and 1.76 GHz for 1 W modulator input power. The predicted values of the pulsewidth-bandwidth product lie between the values corresponding to the pure AM and FM mode locking values.

Bubble size measurement in a gas-liquid ejector for a sodium chloride-air system

A high speed photographic technique has been employed to measure the Sauter mean diameter of bubbles experimentally in a gas liquid ejector using a sodium chloride-air system. The measured values are compared with the theoretically predicted maximum bubble size diameter using Sprow's correlation. Bubble size as a function of the liquid flow rate and also of its distance from the throat of the ejector has been reported in this paper. The results obtained for this non-reactive system are also compared with those obtained earlier for the air-water system.

Modeling re-ignition and chuffing in solid rocket motors

A nonlinear model is developed to numerically simulate dynamic combustion inside a solid rocket motor chamber. Using this model, the phenomena of re-ignition and chuffing are investigated under low-L* conditions. The model consists of two separate submodels (coupled to each other), one for unsteady burning of propellant and the other for unsteady conservation of mass and energy within the chamber. The latter yields instantaneous pressure and temperature within the chamber. The instantaneous burning rate is calculated using a one-dimensional, nonlinear, transient gas-phase model previously developed by the authors. The results presented in this paper show that the model predicts not only the critical L*, but also the various regimes of L*-instabihty. Specifically, the results exhibit (1) amplifying pressure oscillations leading to extinction, and (2) re-ignition after a dormant period following extinction. The re-ignition could be observed only when a radiation heat flux (from the combustion chamber to the propellant surface) was included. Certain high-frequency oscillations, possibly due to intrinsic instability, are observed when the pressure overshoots during re-ignition. At very low values of initial L*, successive cycles of extinction/reignition displaying typical characteristics of chuffing are predicted. Variations of the chuffing frequency and the thickness of propellant burned off during a chuff with L* are found to be qualitatively the same as that reported from experimental observations.

Propensity of formation of zipper architecture vs. Lincoln log arrangement in solvated molecular complexes of melamine with hydroxybenzoic acids

Molecular complexes of melamine with hydroxy and dihydroxybenzoic acids have been analyzed to assess the collective role of the hydroxyl (OH) and carboxyl (COOH) functionalities in the recognition process. In most cases, solvents of crystallization do play a major role in self-assembly and structure stabilization. Hydrated compounds generate linear chains of melamine molecules with acid molecules pendant resulting in a zipper architecture. However, anhydrous and solvated compounds generate tetrameric units consisting of melamine dimers together with acid molecules. These tetramers in turn interweave to form a Lincoln log arrangement in the crystal. The salt/co-crystal formation in these complexes cannot be predicted apriori on the basis of Delta pK(a) values as there exists a salt-to-co-crystal continuum.

Steady compressible flow of cohesionless granular materials through a wedge-shaped bunker

A continuum model based on the critical-state theory of soil mechanics is used to generate stress, density, and velocity profiles, and to compute discharge rates for the flow of granular material in a mass flow bunker. The bin–hopper transition region is idealized as a shock across which all the variables change discontinuously. Comparison with the work of Michalowski (1987) shows that his experimentally determined rupture layer lies between his prediction and that of the present theory. However, it resembles the former more closely. The conventional condition involving a traction-free surface at the hopper exit is abandoned in favour of an exit shock below which the material falls vertically with zero frictional stress. The basic equations, which are not classifiable under any of the standard types, require excessive computational time. This problem is alleviated by the introduction of the Mohr–Coulomb approximation (MCA). The stress, density, and velocity profiles obtained by integration of the MCA converge to asymptotic fields on moving down the hopper. Expressions for these fields are derived by a perturbation method. Computational difficulties are encountered for bunkers with wall angles θw [gt-or-equal, slanted] 15° these are overcome by altering the initial conditions. Predicted discharge rates lie significantly below the measured values of Nguyen et al. (1980), ranging from 38% at θw = 15° to 59% at θw = 32°. The poor prediction appears to be largely due to the exit condition used here. Paradoxically, incompressible discharge rates lie closer to the measured values. An approximate semi-analytical expression for the discharge rate is obtained, which predicts values within 9% of the exact (numerical) ones in the compressible case, and 11% in the incompressible case. The approximate analysis also suggests that inclusion of density variation decreases the discharge rate. This is borne out by the exact (numerical) results – for the parameter values investigated, the compressible discharge rate is about 10% lower than the incompressible value. A preliminary comparison of the predicted density profiles with the measurements of Fickie et al. (1989) shows that the material within the hopper dilates more strongly than predicted. Surprisingly, just below the exit slot, there is good agreement between theory and experiment.

Capturing higher modes of vibration of micromachined resonators

MEMS resonators have potential applications in the areas of RF-MEMS, clock oscillators, ultrasound transducers, etc. The important characteristics of a resonator are its resonant frequency and Q-factor (a measure of damping). Usually large damping in macro structures makes it difficult to excite and measure their higher modes. In contrast, MEMS resonators seem amenable to excitation in higher modes. In this paper, 28 modes of vibration of an electrothermal actuator are experimentally captured–perhaps the highest number of modes experimentally captured so far. We verify these modes with FEM simulations and report that all the measured frequencies are within 5% of theoretically predicted values.

Study of the CP property of the Higgs boson at a photon collider using gamma gamma -> t(t)over-bar -> lX

We study the possible effects of CP violation in the Higgs sector on t (t) over bar production at a gammagamma collider. These studies are performed in a model-independent way in terms of six form factors {R(S-gamma), J(S-gamma), R(P-gamma), J(P-gamma), S-t, P-t} which parametrize the CP mixing in the Higgs sector, and a strategy for their determination is developed. We observe that the angular distribution of the decay lepton from t/(t) over bar produced in this process is independent of any CP violation in the tbW vertex and hence best suited for studying CP mixing in the Higgs sector. Analytical expressions are obtained for the angular distribution of leptons in the c.m. frame of the two colliding photons for a general polarization state of the incoming photons. We construct combined asymmetries in the initial state lepton (photon) polarization and the final state lepton charge. They involve CP even (x's) and odd (y's) combinations of the mixing parameters. We study limits up to which the values of x and y, with only two of them allowed to vary at a time, can be probed by measurements of these asymmetries, using circularly polarized photons. We use the numerical values of the asymmetries predicted by various models to discriminate among them. We show that this method can be sensitive to the loop-induced CP violation in the Higgs sector in the minimal supersymmetric standard model.

Volume Change behaviour in Calcitic Soil influenced with Sulphuric Acid using Artificial Neural Networks

This paper elucidates the methodology of applying artificial neural network model (ANNM) to predict the percent swell of calcitic soil in sulphuric acid solutions, a complex phenomenon involving many parameters. Swell data required for modelling is experimentally obtained using conventional oedometer tests under nominal surcharge. The phases in ANN include optimal design of architecture, operation and training of architecture. The designed optimal neural model (3-5-1) is a fully connected three layer feed forward network with symmetric sigmoid activation function and trained by the back propagation algorithm to minimize a quadratic error criterion.The used model requires parameters such as duration of interaction, calcite mineral content and acid concentration for prediction of swell. The observed strong correlation coefficient (R2 = 0.9979) between the values determined by the experiment and predicted using the developed model demonstrates that the network can provide answers to complex problems in geotechnical engineering.

A decidable temporal logic with repeating values

Various logical formalisms with the freeze quantifier have been recently considered to model computer systems even though this is a powerful mechanism that often leads to undecidability. In this paper, we study a linear-time temporal logic with past-time operators such that the freeze operator is only used to express that some value from an infinite set is repeated in the future or in the past. Such a restriction has been inspired by a recent work on spatio-temporal logics. We show decidability of finitary and infinitary satisfiability by reduction into the verification of temporal properties in Petri nets. This is a surprising result since the logic is closed under negation, contains future-time and past-time temporal operators and can express the nonce property and its negation. These ingredients are known to lead to undecidability with a more liberal use of the freeze quantifier.

Three-Dimensional Site Characterization Model Using Artificial Neural Networks

This research is designed to develop a new technique for site characterization in a three-dimensional domain. Site characterization is a fundamental task in geotechnical engineering practice, as well as a very challenging process, with the ultimate goal of estimating soil properties based on limited tests at any half-space subsurface point in a site.In this research, the sandy site at the Texas A&M University's National Geotechnical Experimentation Site is selected as an example to develop the new technique for site characterization, which is based on Artificial Neural Networks (ANN) technology. In this study, a sequential approach is used to demonstrate the applicability of ANN to site characterization. To verify its robustness, the proposed new technique is compared with other commonly used approaches for site characterization. In addition, an artificial site is created, wherein soil property values at any half-space point are assumed, and thus the predicted values can compare directly with their corresponding actual values, as a means of validation. Since the three-dimensional model has the capability of estimating the soil property at any location in a site, it could have many potential applications, especially in such case, wherein the soil properties within a zone are of interest rather than at a single point. Examples of soil properties of zonal interest include soil type classification and liquefaction potential evaluation. In this regard, the present study also addresses this type of applications based on a site located in Taiwan, which experienced liquefaction during the 1999 Chi-Chi, Taiwan, Earthquake.

Predictive distribution modeling for rare Himalayan medicinal plant Berberis aristata DC

Predictive distribution modelling of Berberis aristata DC, a rare threatened plant with high medicinal values has been done with an aim to understand its potential distribution zones in Indian Himalayan region. Bioclimatic and topographic variables were used to develop the distribution model with the help of three different algorithms viz. GeneticAlgorithm for Rule-set Production (GARP), Bioclim and Maximum entroys(MaxEnt). Maximum entropy has predicted wider potential distribution (10.36%) compared to GARP (4.63%) and Bioclim (2.44%). Validation confirms that these outputs are comparable to the present distribution pattern of the B. atistata. This exercise highlights that this species favours Western Himalaya. However, GARP and MaxEnt's prediction of Eastern Himalayan states (i.e. Arunachal Pradesh, Nagaland and Manipur) are also identified as potential occurrence places require further exploration.