Rheology of semi-dilute emulsions: viscoelastic effects caused by the interfacial tension

The steady state rheological properties of viscous emulsions are discussed in the dilute and semi-dilute concentration regions. In these systems the first normal stress differences can be measured as well. Such data have been collected over a wide range of ratios of droplet over matrix viscosity. In this manner data became available to evaluate the Choi-Schowalter model. Application of the latter to the normal stresses requires that the droplet diameter be known. At high shear rates the droplet diameter changes nearly inversely proportional to the shear rate. This results in a first normal stress difference proportional to shear rate and hence a ‘normal viscosity’ can be defined. This is used to compare the data with the available theoretical predictions. At low shear rates deviations from a constant normal viscosity can be observed. They are associated with a hysteresis region, where no single steady state droplet size can be defined anymore. Slightly viscoelastic components have been used as well to investigate whether this would result in deviations from the behaviour observed for mixtures of Newtonian fluids.     

Effect of electrolytes and surfactant concentration on the interfacial tension of o/w emulsion

Summary The adsorption studies of proteincationic, anionic and non-ionic surfactants and effect of electrolytes on the adsorption of triton 100 and protein mixture on kerosene oil/water interface have been studied. The lowering of interfacial tension is found to depend upon the emulsifier concentration and valency of the ions.     

Critical behavior and interfacial tension of mixtures of propylene glycol and ethylene glycol oligomers

This investigation presents an analysis of the critical behavior of mixtures of oligomers of propylene glycol, PG₁₇, and ethylene glycol, EG_n, withn=3, 4, 5, 6.4, 8.7, 12.1 and 22.1. The critical coordinates, _c andT _c were determined from the phase diagrams. The critical compositions compare very well with the Huggins-Flory predictions. The interaction parameter _n is around one for EG₃, EG₄ and EG₅ and it increases up to two for the higher oligomers. The break in the interaction parameter also corresponds to a minimum in the critical temperature. The phase diagrams and the interfacial tension were used to get the critical exponents and , respectively. The data were analysed with two approaches. First, from the temperature dependence of the length of the tie-lines and of the interfacial tension up to the upper critical solution temperature, UCST. Second, with the data at 30°C using the critical temperature of the systems as the variable. The first method led to =0.39±0.05 in good agreement with the result of the second method, =0.37±0.04. The exponents for the interfacial tension, , determined with the first method for PG₁₇ with EG_6.4, EG_8.7 and EG_12.1 are =1.66±0.11, 1.46±0.25 and 1.73±0.18, respectively. The second method led to =1.17±0.14. The critical exponents are compared to mean field and ising-3D predictions.     

A novel proton conductor of imidazole-aluminium phosphate hybrids in the solid state

Anhydrous proton transport at temperatures above 100 °C has attracted considerable attention in the development of fuel cells that operate at intermediate temperatures. Liquid-state imidazole (ImH) is known to be a fast anhydrous proton conductor above 100 °C; however, evaporation and severe conductivity drops above and below its melting point (～90 °C), respectively, are major drawbacks to ImH. In this paper, we report a novel solid-state anhydrous ImH-Al(H(2)PO(4))(3) (AlP) hybrid material prepared via a simple synthesis using mechanical milling. This solid-state hybrid exhibits relatively a high ionic conductivity of ～0.1 mS cm(-1) at 100 °C and remarkably a small activation energy of 0.23 eV. In addition, the ImH-AlP hybrid material provides a means of overcoming both temperature-dependent drawbacks to pure ImH: (1) the ImH-AlP hybrid is thermally stable up to 130 °C, and (2) the hybrid material maintains high ionic conductivity below the melting point of ImH.     

Grand canonical Monte Carlo simulation of a model colloid-polymer mixture: coexistence line, critical behavior, and interfacial tension

Grand canonical Monte Carlo simulations are used to study phase separation in a simple colloid-polymer model, the so-called Asakura-Oosawa model. To overcome the problem of small acceptance rates of the grand-canonical moves, cluster moves are introduced. Successive umbrella sampling, recently introduced by Virnau and Muller [J. Chem. Phys. 120, 10925 (2004)], is used to access the phase-separated regime. The unmixing binodal and the interfacial tension are measured and compared to theoretical predictions. By means of finite-size scaling, the behavior close to the critical point is also investigated. Close to criticality, we observe substantial deviations from mean-field behavior.     

Viscous behavior of concentrated emulsions of two immiscible Newtonian fluids with interfacial tension

A new equation for the relative viscosity of infinitely dilute emulsions of noncolloidal droplets is proposed using the analogy between shear modulus and shear viscosity. In the limit of capillary number -->0, the proposed equation reduces to the well-known Taylor viscosity law for infinitely dilute emulsions. Starting from the proposed equation for an infinitely dilute emulsion, new viscosity equations for concentrated emulsions are then developed using a differential scheme. The proposed equations for concentrated emulsions are evaluated in light of a large body of published experimental data on the viscosity of emulsions.     

Effect of interfacial rheology on model emulsion coalescence II. Emulsion coalescence

In Part I, surface pressure isotherms were measured for model interfaces between a dispersed water phase and a continuous phase of asphaltenes, toluene, and heptane. Here, the coalescence rate of model emulsions prepared from the same components is determined from measured drop size distributions at 23 degrees C. A correlation is found between the initial coalescence rate and the interfacial compressibility. It is shown that the change in coalescence rate as the emulsion ages and coalesces can be predicted from surface pressure isotherm data also obtained at 23 degrees C. The stability of the emulsions was further assessed in terms of free water resolved after a treatment of heating at 60 degrees C and centrifugation. The emulsions were aged up to 24 h prior to treatment. The free water resolution appears to correlate to the "capacity for coalescence" of the interfacial film; that is, to the product of the initial film compressibility and (1-CR), where CR is the film ratio at which the film crumples.     

Effect of interfacial rheology on model emulsion coalescence I. Interfacial rheology

Interfacial elasticity and "dynamic" surface pressure isotherms were measured for interfaces between a dispersed water phase and a continuous phase of asphaltenes, toluene, and heptane. The interfacial modulus is a function of asphaltene concentration and in all cases reached a maximum at an asphaltene concentration of approximately 1 kg/m(3). The modulus increased significantly as the interface aged and slightly as the heptane content increased to a practical limit of 50 vol%. The modulus was approximately the same at 23 and 60 degrees C. The modulus correlated with the inverse of the initial compressibility determined from surface pressure isotherms. The surface pressure isotherms also indicated that a phase transition occurred as the interface was compressed leading to the formation of low compressibility films. Crumpling was observed upon further compression. The phase transition shifted to a higher film ratio with an increase in heptane content and interface age. Asphaltene concentration and temperature (23 and 60 degrees C) has little effect on the surface pressure isotherms. The surface pressure and elasticity measurements are consistent with the gradual formation of a cross-linked asphaltene network on the interface.     

Influence of bulk elasticity and interfacial tension on the deformation of gelled water-in-oil emulsion droplets: an AFM study

We used atomic force microscopy (AFM) to study the deformation and wetting behavior of large (50-250 microm) emulsion droplets upon mechanical loading with a colloidal glass probe. Our droplets were obtained from water-in-oil emulsions. By adding gelatin to the water prior to emulsification, also droplets with a bulk elasticity were prepared. Systematic variations of surfactant and gelatin concentrations were made, to investigate their effect on the deformation and wetting behavior of the droplets and to identify the contributions of interfacial tension, bulk elasticity, and expelled water. The AFM experiments were performed in force--distance mode and showed on approach a repulsive regime which in many cases was terminated by a jump-in of the probe. In the case of pure water (i.e. gelatin-free) droplets, the repulsive part of the curve showed a good linearity, thus allowing the extraction of an effective droplet spring constant. This quantity was found to decrease on raising the surfactant concentration from below the critical micelle concentration (cmc) to well above the cmc, and its numerical values were found to correspond remarkably well to literature values for the interfacial tension. Our findings indicate that, on gelatin increase inside the droplets, the bulk elasticity gradually becomes dominant and the droplets' stiffness does not depend anymore on surfactant concentration. Also the stability of the droplet interface against wetting, as measured by the force at which the jump-in instability occurs, was enhanced by gelatin. For gelatin concentrations of > or =15 wt %, the droplets were found to behave like purely elastic bodies. Both gelatin and surfactant contribute positively to the stability against interface breakup.     

Hygrothermal recovery behavior of cellulose-rich gelatinous layer in tension wood studied by viscoelastic vibration measurement

Hygrothermal treatment induces irreversible dimensional changes of green wood i.e. hygrothermal recovery (HTR). To understand what happened to cellulose-rich gelatinous (G-) layer in green tension wood during HTR, changes in vibrational properties of konara oak (Quercus serrata Thunb. ex Murray) tension wood (TW) and normal wood (NW) collected from sapwood after hygrothermal treatment were tested regarding HTR. After this treatment, all specimens were air-dried, and their vibrational properties and dimensions were measured in this dried state. The hygrothermal treatment induced an increase in mechanical loss tangent (tanδ) and a decrease in specific dynamic Young’s modulus (E’/ρ). Changes in vibrational properties due to hygrothermal treatment appeared to depend on treatment time and temperature with higher temperatures and longer treatment durations producing larger increases in tanδ and larger decreases in E’/ρ. In TW with a G-layer, a clear correlation between changes in vibrational properties and HTR strains was identified. Tanδ increased and E’/ρ decreased corresponding to HTR strains. Contraction of the G-layer in TW cell walls due to release of locked-in growth stress by hygrothermal treatment seems to be the most plausible mechanism underlying changes in vibrational properties and generation of HTR. In NW without a G-layer, HTR strain was below the limit of detection, which obscures potential correlations. Differences in the intensities of changes in vibrational properties after 120 min hygrothermal treatments at 60, 80, and 100 °C were not significant after drying; however, the difference in the intensities of HTR strains apparently remained after drying.

     

Effect of interfacial tension on the dynamic behavior of droplet formation during microchannel emulsification

Microchannel (MC) emulsification is a novel technique for producing monodisperse emulsions. In this study, we investigated the effect of interfacial tension on the dynamic behavior of droplet formation with various surfactant concentrations. Interfacial tension did not affect the resultant droplet diameter in lower flow velocity ranges, but it did affect the time-scale parameters. These results were interpreted using the droplet formation mechanism reported in our previous study. At surfactant concentrations below 0.3%, the emulsification behavior was differed from that at higher surfactant concentrations. An analysis of diffusional transfer indicated that dynamic interfacial tension affects the emulsification behavior at lower surfactant concentrations. Dynamic interfacial tension that exceeded the equilibrium value led to a shorter detachment time. This resulted in stable droplet formation of monodispersed emulsions by spontaneous transformation, even at flow velocities above the predicted critical flow velocity. A previous study predicted that the droplet formation would become unstable and polydispersed larger droplets would form over critical flow velocity. Wetting of the MC with the dispersed phase at lower surfactant concentrations induced formation of larger polydispersed droplets at high flow velocities.     

Experimental determination of interfacial tension by different dynamical methods under simple shear flow conditions with a novel computer-controlled parallel band apparatus

We present experimental investigations on droplet deformation under simple shear flow conditions, using a computer-controlled parallel band apparatus and an optical device which allows us to record the time dependence of the droplet shape. Several methods are applied to determine the interfacial tension from the observed shape and relaxation mechanism. Specific software developed in our laboratory allows the droplet to be fixed in a certain position for extended times, in fact, indefinite. This is an advantage over most other work done in this area, where only limited time is available. In our experiments, the transient deformation of sheared droplets can be observed to reach the steady state. The measured systems were Newtonian, both droplet and fluid phase. Droplet deformation, orientation angle and retraction were studied and compared to several models. The interfacial tension of the different systems was calculated using the theories of Taylor, Rallison, and Hinch and Acrivos. The results obtained from the analysis of the droplet deformation were in very good agreement with drop detachment experiments of Feigl and co-workers. The study of orientation angle shows qualitative agreement to the theory of Hinch and Acrivos but reveals larger quantitative discrepancies for several empirical fitting parameters of the used model. Analysis of the relaxation of sheared drops provided estimates of the interfacial tension that were in very good agreement with the steady-state measurements.     

Prediction of solid-fluid interfacial tension and contact angle

Two simple equations have been developed using the lattice theory and the regular solution assumption to predict the solid-vapor and solid-liquid interfacial tension. The required parameters are the liquid critical temperature and volume, the solid melting temperature and the molar volume of liquid and solid compounds. To confirm the models, the predicted solid-fluid interfacial tension values have been used to predict the contact angle of the liquid drop on the solid surface applying Young's equation. Agreement of the predicted contact angle with the experimental data reveals the reliability of the developed models.     

Study of the interfacial tension in model and technical emulsions in the presence of surfactants and inorganic electrolytes

Interfacial tension in the oil/water system in the presence of various ionic surfactants and inorganic electrolytes was studied. Special features of the effect of the surfactant and oil phase natures, of the structure of their molecules, and also of the electrolytes containing ions with various radii, valences, and hydratabilities on the value of the interfacial tension were studied. The criteria and conditions of obtaining model emulsions based on paraffin hydrocarbons and technical emulsions based on vegetable oils were determined.     

Influence of interfacial rheology on foam and emulsion properties

Foams and emulsions are stabilized by surfactant monolayers that adsorb at the air-water and oil-water interfaces, respectively. As a result of monolayer adsorption, the interfaces become viscoelastic. We will describe experiments showing that foaming, emulsification, foam and emulsion stability, are strongly dependent upon the value of compression elasticity and viscosity. This will include excited surface wave devices for the measurement of surface viscoelasticity and thin film videointerferometry for the study of model films between air bubbles and emulsion drops.     

A new mechanistic Parachor model to predict dynamic interfacial tension and miscibility in multicomponent hydrocarbon systems

Widely used traditional Parachor model fails to provide reliable interfacial tension predictions in multicomponent hydrocarbon systems due to the inability of this model to account for mass transfer effects between the fluid phases. In this paper, we therefore proposed a new mass transfer enhanced mechanistic Parachor model to predict interfacial tension and to identify the governing mass transfer mechanism responsible for attaining the thermodynamic fluid phase equilibria in multicomponent hydrocarbon systems. The proposed model has been evaluated against experimental data for two gas-oil systems of Rainbow Keg River and Terra Nova reservoirs. The results from the proposed model indicated good IFT predictions and that the vaporization of light hydrocarbon components from crude oil to gas phase is the governing mass transfer mechanism for the attainment of fluid phase equilibria in both the gas-oil systems used. A multiple linear regression model has also been developed for a priori prediction of exponent in the mechanistic model by using only the reservoir fluid compositions, without the need for experimental measurements. The dynamic nature of interfacial tensions observed in the experiments justifies the use of diffusivities in the mechanistic model, thus enabling the proposed model predictions to determine dynamic gas-oil miscibility conditions in multicomponent hydrocarbon systems.     

Synthesis and fluorescence enhancement behavior of a novel fluorescent aqueous polyurethane emulsion DDAQ-TDI-PU

A novel fluorescent aqueous polyurethane emulsion DDAQ-TDI-PU was synthesized by blocking the anthraquinone moiety of 1,4-diamino-2,3-diphenoxyanthraquinone(DDAQ) into polyurethane chain using 2,4-tolylene diisocyanate(TDI),poly(propylene glycol) and 2,2-dimethylol propionic acid.The chain structure of DDAQ-TDI-PU was confirmed by means of Fourier transform infrared spectroscopy and UV-vis analysis.Comparing to the UV-vis spectrum of DDAQ,DDAQ-TDI-PU showed a hypsochromic shift from the absorption maxima of 518,558,609 nm to 510,548,586 nm,respectively.It was found that the fluorescence intensity of DDAQ-TDI-PU emulsion was enhanced greatly comparing with that of DDAQ.The fluorescence of DDAQ-TDI-PU was very stable not only for the long term storage but also for the fluorescence quencher.     

Anomalous temperature dependence of interfacial tension in water-hydrocarbon mixtures

An experimental study of the interfacial tension (IFT) as a function of temperature for three water-hydrocarbon mixtures is reported. The interfacial tension rises with increasing temperature for all mixtures studied, which contradicts the Antonov rule.