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Influence of continuous phase viscosity on emulsification by ultrasound

Power ultrasound is one means among others of mechanically producing emulsions. In spite of numerous publications on the basic principles of this technique, there is insufficient knowledge of continuous ultrasound emulsification processes and the main parameters of practical relevance. A comparison of this system with other continuous mechanical emulsifying devices is made. The effect of continuous phase viscosity on droplet disruption due to ultrasound is the subject of a more detailed investigation. Continuous phase viscosity is varied by means of water soluble stabilizers (o/w systems) and different oils (w/o systems). At constant energy density, droplet size decreases when adding stabilizers, whereas the viscosity of the oil in w/o emulsions has no effect. Qualitative investigations of the local distribution of cavitation have shown very small penetration depths of cavitation into the liquid. This emphasizes the need for improvement of apparatus design to optimize the emulsification process.

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Unique dual fluorescence of sterically congested hexaalkyl benzenehexacarboxylates: mechanism and application to viscosity probing.

The static and dynamic fluorescence behavior of a series of hexaalkyl benzenehexacarboxylates (R(6)BHC; R = methyl (Me), tert-butyl (tBu), (-)-menthyl (Men), (-)-bornyl (Bor), (-)-1-methylheptyl (MHp), neopentyl (neoPn), and 2-adamantyl (Ad)) was studied by steady-state and time-resolved fluorescence spectroscopy. Dual fluorescence from both the partially relaxed metastable Franck-Condon-like (FC') and the fully relaxed (RX) state was observed for tBu(6)BHC, Men(6)BHC, Bor(6)BHC, MHp(6)BHC, neoPn(6)BHC, and Ad(6)BHC, whereas only single fluorescence from the RX state was observed for Me(6)BHC. Picosecond time-resolved fluorescence spectroscopic measurements clearly demonstrated that the initially formed Franck-Condon (FC) state sequentially converts to the FC' and then to RX state, with the relaxation hindered to such an extent that it shows variation with the steric bulk of the R groups. Thus, the fluorescence lifetimes (tau's) of FC' and RX are critically dependent on the bulkiness of the R groups, varying from 17 to 130 ps and from 0.6 to 1.1 ns, respectively. The relative intensity of FC' and RX fluorescence (I(RX)/I(FC)(')) was found to be dependent on the excitation wavelength, suggesting that the conformational relaxation from the FC' to RX state can compete with the vibrational relaxation of the FC' state. The temperature and pressure dependences were studied by steady-state fluorescence spectroscopy to give the activation energies of 1-3 kcal/mol for the FC'-to-RX relaxation of congested R(6)BHCs, as well as the activation volumes of 2.0, -0.62, and 7.4 mL/mol for tBu(6)BHC, Men(6)BHC, and Bor(6)BHC at room temperature. The fluorescence anisotropy (rho), as a measure of molecular motion, was also determined to be in the ranges of 0.03-0.3 for FC' and 0.003-0.01 for RX. The much larger rho's for the FC' fluorescence by a factor of 2-100 are attributed to the shorter tau's. The I(RX)/I(F' ratio was found to be insensitive to solvent polarity, but critically dependent on solvent viscosity, exhibiting an excellent linear relationship with the reciprocal viscosity. The potential use of these sterically congested R(6)BHCs as microenvironmental viscosity probes is proposed.

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Experimental evidence to support viscosity dependence of rates of Diels-Alder reactions in solvent media.

This note is aimed at ascertaining whether rates of Diels-Alder reactions depend on the viscosity of solvent media in which the reactions are performed. On the basis of the data collected from the literature and in this laboratory, it is seen in general that the rates increase in the solvents with their viscosities ranging up to approximately 1.2 cP. In solvents possessing viscosities above 1.2 cP, a drop in the reaction rates is observed in all cases. The effect of temperature on the above phenomena is also examined.

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Nonionic surfactant and temperature effects on the viscosity of hydrophobically modified hydroxyethyl cellulose solutions.

Nonionic surfactant and temperature effects on the viscosity of hydrophobically modified hydroxyethyl cellulose (HMHEC) solutions are investigated experimentally. Weak shear thickening at intermediate shear rates takes place for HMHEC at moderate concentrations and becomes more significant at lower temperatures. While this amphiphilic polymer in surfactant-free solution does not turn turbid by heating to 95 degrees C, its mixture with nonionic surfactant shows a lower cloud point temperature than does a pure surfactant solution. For some mixture cases, phase separation takes place at temperatures as low as 2 degrees C. The drop of cloud point temperature is attributed to an additional attractive interaction between mixed micelles via chain bridging. With increasing temperature, the viscosity of an HMHEC-surfactant mixture in aqueous solution first decreases but then rises considerably until around the cloud point. The observed viscosity increase can be explained by the interchain association because of micellar aggregation.

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Generalization of the friction theory for viscosity modeling.

The friction theory (FT) approach relates the viscosity of a fluid to its equation of state (EoS), and it is known to give good results for a large number of compounds over wide ranges of temperature and pressure. Previous FT versions were restricted to use EoS of the van der Waals type, i.e., EoS explicitly consisting of a repulsive and an attractive term, which limited the number of usable EoS as well as the accuracy of the viscosity predictions. In this work, the restriction is removed by means of a pragmatic generalized definition of repulsive and attractive terms based on the internal pressure concept. As a result, the FT theory can be extended to practically all types of EoS, from theoretical ones (e.g., EoS based on thermostatistical or renormalization theories) to the highly accurate empirical reference EoS. In combination with the later, the FT is shown to represent experimental viscosity data for several fluids, including water, with an accuracy as high as that required for reference models. Additionally, some relevant phenomena, such as the critical anomaly, appear to follow naturally from the physics already built into the EoS.

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Effect of high-viscosity interphases on drainage between hydrophilic surfaces.

Drainage of water from the region between an advancing probe tip and a flat sample is reconsidered under the assumption that the tip and sample surfaces are both coated by a thin water "interphase" (of width approximately a few nanometers) whose viscosity is much higher than that of the bulk liquid. A formula derived by solving the Navier-Stokes equations allows one to extract an interphase viscosity of approximately 59 kPa x s (or approximately 6.6 x 10(7) times the viscosity of bulk water at 25 degrees C) from interfacial force microscope measurements with both tip and sample functionalized hydrophilic by OH-terminated tri(ethylene glycol) undecylthiol, self-assambled monolayers.

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Photochemical studies as a function of solvent viscosity. A new photochemical pathway in the reaction of (eta5-C5H4Me)2Mo2(CO)6 with CCl4.

This paper reports the results of a study that used systematic changes in the solvent viscosity to probe the photochemical reactivity of the Cp'2Mo2(CO)6 (Cp' = eta5-C5H4CH3) molecule. The quantum yields for photolysis of Cp'2Mo2(CO)6 in the presence of CCl4 were studied as a function of solvent viscosity. The quantum yields did not decrease to zero with increasing solvent viscosity but rather leveled off at a constant, non-zero value. This result cannot be explained by any of the previously reported radical or Mo-CO dissociation photochemical pathways for this molecule, and therefore an additional photochemical pathway is suggested to be operating in the reaction. The new pathway may involve a reactive isomer of Cp'2Mo2(CO)6 or possibly electron transfer between the excited state of Cp'2Mo2(CO)6 and CCl4.

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The macromolecular properties of blood-group substances. Sedimentation-velocity and viscosity measurements.

1. Sedimentation-velocity, intrinsic-viscosity and partial-specific-volume measurements on a typical blood-group-specific glycoprotein are reported for a range of environmental conditions. 2. The sedimentation coefficients, S, are strongly concentration-dependent, and follow the reciprocal law; the limiting values at 2 degrees , 25 degrees and 45 degrees , after correction to 25 degrees , show slight dependence on temperature. 3. The intrinsic viscosities, [eta], at 25 degrees and 45 degrees show more marked temperature-dependence, and correspond to a very asymmetric or very expanded molecular conformation. 4. From the value of the ratio K/[eta], where K=S(0).d(1/S)/dc, it is concluded that the molecular conformation is roughly spherical; application of the Einstein viscosity equation then suggests an expansion factor of about 60, compatible with a flexible configuration approaching that of a random coil. 5. The sedimentation coefficient is not affected by variation of ionic strength in the range 0.01-0.50, nor by pH in the range 3-10. 6. Sodium dodecyl sulphate at 1.5% produces a small decrease in S; the effect is greater than would be expected from the observed extent of binding, but is too small to correspond to a significant change in secondary structure; the serological activity is unaffected by sodium dodecyl sulphate. 7. All the properties observed indicate the absence of any secondary structure in blood-group substances.

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Transport coefficients of the Lennard-Jones model fluid. III. Bulk viscosity.

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This third of a series of four papers presents the results for the bulk viscosity. With comprehensive simulation data at over 350 state points, the temperature and density dependences of the bulk viscosity are characterized in this work over a wide range of fluid states. The bulk viscosity exhibits a large critical enhancement similar to that known for the thermal conductivity, but it extends much farther into the supercritical region and can be observed even at 4.5 times the critical temperature. An investigation of the pressure-fluctuation autocorrelation functions shows that the enhancement is caused by extremely slowly decaying pressure fluctuations.

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The shear viscosity of supercritical oxygen at high pressure.

Shear viscosities of supercritical oxygen have been measured up to a pressure of 5.7 GPa at 294 K. A modified free-volume expression fits the data within 6% between the limits of the tenuous gas and 4.8 times the critical density. Nitrogen viscosities were found to correspond to those of oxygen through a simple scaling by critical constants. Viscosities were measured in the high-pressure diamond-anvil cell with a rolling-ball technique. The dynamics of a sphere rolling on an inclined plane were investigated in the context of these experiments. The effect of a second surface, situated above the sphere, was experimentally determined.

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Assessment of phenomenological models for viscosity of liquids based on nonequilibrium atomistic simulations of copper.

The shear viscosity of liquid copper is studied using nonequilibrium molecular-dynamics simulations under planar shear flow conditions. We examined variation of viscosity as function of shear rate at a range of pressures (ca. 0 - 40 GPa). We analyzed these results using eight different phenomenological models and find that the observed non-Newtonian behavior is best described by the Powell-Eyring (PE) model: eta(gamma) = (eta(0)-eta(infinity))sinh(-1)(taugamma)(taugamma) + eta(infinity), where gamma is the shear rate. Here eta(0) (the zero-shear-rate viscosity) extracted from the PE fit is in excellent agreement with available experimental data. The relaxation time tau from the PE fit describes the shear response to an applied stress. This provides the framework for interpreting the shear flow phenomena in complex systems, such as liquid metal and amorphous metal alloys.

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Shear viscosity of molten alkali halides from equilibrium and nonequilibrium molecular-dynamics simulations.

The shear viscosity of molten NaCl and KCl was calculated through equilibrium (EMD) and nonequilibrium molecular-dynamics (NEMD) simulations in the canonical (N,V,T) ensemble. Two rigid-ion potentials were investigated, namely, the Born-Mayer-Huggins-Tosi-Fumi potential and the Michielsen-Woerlee-Graaf-Ketelaar potential with the parameters proposed by Ladd. The NEMD simulations were performed using the SLLOD equations of motion [D. J. Evans and G. P. Morriss, Phys. Rev. A 30, 1528 (1984)] with a Gaussian isokinetic thermostat and the results are compared with those obtained from Green-Kubo EMD (N,V,T) simulations and experimental shear viscosity data. The NEMD zero strain rate shear viscosity, eta(0), was obtained by fitting a simplified Carreau-type equation and by application of mode-coupling theory, i.e., a eta-gamma(1/2) linear relationship. The values obtained from the first method are found to be significantly lower than those predicted by the second. The agreement between the EMD and NEMD results with experimental data is satisfactory for the two potentials investigated. The ion-ion radial distribution functions obtained with the two rigid-ion potentials for both molten salts are discussed in terms of the differences between the two models.

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Molecular simulation of the shear viscosity and the self-diffusion coefficient of mercury along the vapor-liquid coexistence curve.

In earlier work [G. Raabe and R. J. Sadus, J. Chem. Phys. 119, 6691 (2003)] we reported that the combination of an accurate two-body ab initio potential with an empirically determined multibody contribution enables the prediction of the phase coexistence properties, the heats of vaporization, and the pair distribution functions of mercury with reasonable accuracy. In this work we present molecular dynamics simulation results for the shear viscosity and self-diffusion coefficient of mercury along the vapor-liquid coexistence curve using our empirical effective potential. The comparison with experiment and calculations based on a modified Enskog theory shows that our multibody contribution yields reliable predictions of the self-diffusion coefficient at all densities. Good results are also obtained for the shear viscosity of mercury at low to moderate densities. Increasing deviations between the simulation and experimental viscosity data at high densities suggest that not only a temperature-dependent but also a density-dependent multibody contribution is necessary to account for the effect of intermolecular interactions in liquid metals. An analysis of our simulation data near the critical point yields a critical exponent of beta = 0.39, which is identical to the value obtained from the analysis of the experimental saturation densities.

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Monte Carlo calculations for the intrinsic viscosity of several dendrimer molecules.

We have performed Monte Carlo simulations to reproduce the intrinsic viscosity corresponding to different generation of several types of dendrite molecules: polyamidoamine dendrimers with an ethylendiamine core, polypropylene-imine with a diaminobutane core, and monodendrons and tridendrons of polybenzylether. With this end, we have employed coarse-grained idealizations of the molecules constituted by only two beads in each repeat unit (one in a branching or end unit and one intermediate along the repeat unit) and a simple hard-sphere potential between non-neighboring beads. Our goal is to investigate if this simple model is able to provide a reasonable description of some differences between these systems that have been observed experimentally, in particular, the location of the maximum in the intrinsic viscosity as a function of the generation number. Experimental radii of gyration in a given solvent are reproduced by a fit of the hard-sphere potential diameter. Subsequently, intrinsic viscosities are calculated by the variational approach of Fixman, which yields an accurate lower-bound value with an additional hydrodynamic interaction parameter (the friction radius of the beads). The results show a pronounced variation of the maximum location with the value of the friction radius and the structural details that cannot be mimicked with simpler models. The initial conformations for the Monte Carlo procedure are taken from atomistic configurations thermalized by means of a molecular dynamics.

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Scaling law of shear viscosity in atomic liquid and liquid mixtures.

A scaling law relating the shear viscosity of one and two component liquid mixtures to their excess thermodynamic entropies defined through pair correlation functions is derived by approximating the mode coupling theory expressions of frictions and then combining with the Stokes-Einstein relation. Molecular dynamics simulation has been performed to generate the data of shear viscosity for one and two component liquid mixtures to test the derived scaling law. The derived scaling laws yield numerical results of shear viscosity for one component and two component liquid mixtures, which are in excellent agreement with the molecular dynamics simulation results for a wide range of density and interaction potential.

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Thermodynamic scaling of the viscosity of van der Waals, H-bonded, and ionic liquids.

Viscosities eta and their temperature T and volume V dependences are reported for seven molecular liquids and polymers. In combination with literature viscosity data for five other liquids, we show that the superpositioning of relaxation times for various glass-forming materials when expressed as a function of TV(gamma), where the exponent gamma is a material constant, can be extended to the viscosity. The latter is usually measured to higher temperatures than the corresponding relaxation times, demonstrating the validity of the thermodynamic scaling throughout the supercooled and higher T regimes. The value of gamma for a given liquid principally reflects the magnitude of the intermolecular forces (e.g., steepness of the repulsive potential); thus, we find decreasing gamma in going from van der Waals fluids to ionic liquids. For some strongly H-bonded materials, such as low molecular weight polypropylene glycol and water, the superpositioning fails, due to the nontrivial change of chemical structure (degree of H bonding) with thermodynamic conditions.

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Kinetic theory of viscosity of compressed fluids.

THE VISCOSITY OF A COMPRESSED GAS IS A FUNCTION OF THREE VARIABLES: (1) the degree of crowding of the molecules; (2) their capacity, by reason of softness, flexibility, or rotational inertia, to absorb the vector momentum applied to cause flow; (3) the resistance to this vector momentum offered by the randomly oriented thermal momenta, which becomes significant when the liquid expands sufficiently to permit molecular mean free paths between binary collisions to be long enough for thermal momenta to acquire fractions of their thermal momentum in free space.The fluidity varphi of simple liquids obeys the linear equation varphi = B(V - V(0))/V(0) and its viscosity is, therefore, eta(a) = V(0)/B(V - V(0)); this accounts for components 1 and 2. The contribution of random thermal momenta, 3, obeys the equation, eta(b) = eta(0)(1 - V(t)/V). eta(0) is the viscosity of the dilute gas; V(t) is the molal volume at which the thermal contribution begins. The total momentum, eta = eta(a) + eta(b).Values of eta(0) vary linearly with T(1/2). Values of V(t) are related to heat capacities.

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Temperature and pressure dependence of viscosity of quantum liquid He according to significant structure theory.

Both solid-like and gas-like flow structures are considered in the calculation of viscosity of liquid (4)He using the significant structure theory of liquids. The predominance of quantum mechanical zero-point motion over that arising from thermal excitation is taken into account for the solid-like motion of molecules. The viscosity of liquid (4)He under its own vapor pressure calculated over its whole temperature range is in reasonably good agreement with experimental data. The pressure dependence of viscosity also was obtained. The calculation does not yield good results at high densities where the free jumping of molecules into the nearest neighboring vacancies through the kinetic zero-point motion is no longer plausible.

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