Effect of droplet size on the rheological properties of highly-concentrated w/o emulsions

Rheological properties of highly concentrated emulsions of the water-in-oil type were studied. Water phase (concentration approximately 91%) consists of a supersaturated aqueous solution of nitrate salts; water comprises less than 20% by mass. The average size of droplets, D, in the emulsions was varied. It was found that the emulsions are non-Newtonian liquids and flow curves measured in a sweep regime of shearing have clear low-shear-rate Newtonian domain. The complete flow curves are fitted by the Cross equation. The elastic modulus is practically constant in a very wide frequency range. Hence the viscoelastic relaxation processes might be expected at times >>100 s and in the short-term side of the curve at approximately 0.01 s. The elastic modulus (measured in oscillating testing and in elastic recovery as well) is proportional to D^-2 while the Newtonian viscosity is proportional to D^–1.The time effects were observed: it was found that the emulsions behave as rheopectic materials because prolonged shearing results in an increase of viscosity in the low shear rate domain of several orders of magnitude.Presented in part at the First Annual European Rheological Conference, Guimarães, Portugal, 11–13 September 2003     

Effect of silica particles on stability of highly concentrated water-in-oil emulsions with non-ionic surfactant

Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.     

From dynamic modulus via different relaxation spectra to relaxation and creep functions

The main goal of the paper is to compare predictive power of relaxation spectra found by different methods of calculations. The experimental data were obtained for a new family of propylene random copolymers with 1-pentene as a comonomer. The results of measurements include flow curves, viscoelastic properties, creep curves and rubbery elasticity of copolymer melts. Different relaxation spectra were calculated using independent methods based on different ideas. It lead to various distributions of relaxation times and their “weights”. However, all of them correctly describe the frequency dependencies of dynamic modulus. Besides, calculated spectra were used for finding integral characteristics of viscoelastic behaviour of a material (Newtonian viscosity, the normal stress coefficient, steady-state compliance). In this sense all approaches are equivalent, though it appears impossible to estimate instantaneous modulus. The most crucial arguments in estimating the results of different approaches is calculating the other viscoelastic function and predicting behaviour of a material in various deformation modes. It is the relaxation and creep functions. The results of relaxation curve calculations show that all methods used give rather similar results in the central part of the curves, but the relaxation curves begin to diverge when approaching the high-time (low-frequency) boundary of the relaxation curves. The distributions of retardation times calculated through different approaches also appear very different. Meanwhile, predictions of the creep curves based on these different retardation spectra are rather close to each other and coincide with the experimental points in the wide time range. Relatively slight divergences are observed close to the upper boundary of the experimental window. All these results support the conclusion about a rather free choice of the relaxation time spectrum in fitting experimental data and predicting viscoelastic behaviour of a material in different deformation modes. Received: 15 March 2000 Accepted: 18 September 2000     

Instability of highly concentrated emulsions with oversaturated dispersed phase. Role of a surfactant

Instability of highly concentrated emulsions of the water-in-oil type which were investigated in this work is related to the existence of the internal phase as an oversaturated salt solution in water. The principal features of crystallization of these systems were studied by as earlier. This study is devoted to the development of this investigation and based on involving different surfactants and various concentrations of surfactants. It was shown that the originally proposed mechanism of crystallization, which suggested that growing crystals break through interfacial layers, was valid for all highly concentrated emulsions under investigation. Moreover, the Kholmogorov-Avrami kinetic equation with an unusually high exponent value equal to 6 is also applicable to different systems. It was proven that the general relationship between the growth of the yield stress and the degree of crystallization can be formulated for all surfactants studied in the work. The role of a surfactant consists in varying the characteristic time constant for the rate of crystallization. This time constant is much lower for a low-molecular-weight surfactant compared to oligomeric surfactants. This constant noticeably increases with an increase of concentration and the decrease of the average droplet size.     

The role of interdroplet interaction in the physics of highly concentrated emulsions

The osmotic pressure and shear modulus of highly concentrated emulsions were modelled by considering both interfacial energy and interdroplet interaction. This was performed for two- and three-dimensional cases and by optimization and approximation methods of predicting film thickness. The results show that even a small source of interaction can result in non-superimposition of scaled osmotic pressure and shear modulus by Laplace pressure for different droplet sizes, and also significant deviation from the models which consider interfacial interaction as the sole source of energy. The model was used to explain the reciprocal squared diameter dependency of elastic modulus: an interaction similar to the van der Waals type can be responsible for this observation. The model can also be used to analyze the interdroplet interactions in highly concentrated emulsions.     

Master curves for elastic and plastic properties of highly concentrated emulsions

Critical comparison of dependences of elastic and plastic properties of highly concentrated emulsions (so-called “compressed” emulsions) on the concentration and droplet sizes is performed. The studied emulsions of water-in-oil type are so-called “liquid explosives.” They are characterized by different mean sizes and different droplet size distributions of the dispersed phase. Different average values (D _av, D ₃₂, and D ₄₃) are used as characteristics of droplet sizes. Experiments are carried out with emulsions of two concentrations. Aqueous phase (dispersed droplets) is presented by supercooled solutions of inorganic salt in water in a metastable state. The concentration limit of the existence of highly concentrated emulsions is determined by the condition of the closest packing of liquid droplets, which lies in the φ* = 0.77–0.80 range. In addition, there is a limiting value of the maximal size of droplets. This limiting value depends on the concentration and meets the requirement that droplets should be small enough for the solution to exist in a supercooled state. The elastic modulus and the yield stress of emulsions studied are proportional to the square of the reciprocal linear size of droplets, which contradicts some theoretical models, according to which these parameter should be proportional to the reciprocal size of droplets. Using the obtained experimental data, we constructed generalized dependences of the elastic modulus and the yield stress on the concentration and size of droplets. These characteristics are in good agreement with the experimental data.     

Accelerated diffusion of chain carriers and kinetic features of heterogeneous processes in gas-phase chain reactions

In gas-phase combustion processes, the regeneration of free atoms and radicals in chain propagation reactions enhances the diffusion flux of these species from the flame zone. In flame propagation in tubular reactors and in filtration combustion, this effect facilitates the access of chain carriers to the surface even at atmospheric pressure, increases the role of heterogeneous reactions (primarily chain termination), and enhances heat removal due to heterogeneous recombination.     

Influence of electrolyte on interfacial and rheological properties and shear stability of highly concentrated W/O emulsions

The effect of the electrolyte concentration on the interfacial interactions, rheological properties and emulsion shear stability was investigated. The increase of the electrolyte concentration leads to the growth of storage modulus and the yield stress of emulsions and enhances the emulsion stability to shearing, while interfacial tension decreases. The observed effects were attributed to the interfacial interaction of a surfactant and an electrolyte that was confirmed by the IR-analysis. The interaction between an electrolyte and a surfactant provides a stable interface.     

Effect of the type of the oil phase on stability of highly concentrated water-in-oil emulsions

The water-in-oil high internal phase emulsions were the subject of the study. The emulsions consisted of a super-cooled aqueous solution of inorganic salt as a dispersed phase and industrial grade oil as a continuous phase. The influence of the industrial grade oil type on a water-in-oil high internal phase emulsion stability was investigated. The stability of emulsions was considered in terms of the crystallization of the dispersed phase droplets (that are super-cooled aqueous salt solution) during ageing. The oils were divided into groups: one that highlighted the effect of oil/aqueous phase interfacial tension and another that investigated the effect of oil viscosity on the emulsion rheological properties and shelf-life. For a given set of experimental conditions the influence of oil viscosity for the emulsion stability as well as the oil/aqueous interfacial tension plays an important role. Within the frames of our experiment it was found that there are oil types characterized by optimal parameters: oil/aqueous phase interfacial tension being in the region of 19–24 mN/m and viscosity close to 3 mPa s; such oils produced the most stable high internal phase emulsions. It was assumed that the oil with optimal parameters kept the critical micelle concentration and surfactant diffusion rate at optimal levels allowing the formation of a strong emulsifier layer at the interface and at the same time creating enough emulsifier micelles in the inter-droplet layer to prevent the droplet crystallization.     

Multi-Walled Carbon Nanotubes as a Cosurfactant for Highly Concentrated Emulsions

The role of multi-wall carbon nanotubes (MWCNT) as a solid surfactant in highly concentrated water-in-oil emulsions was investigated. MWCNT were dispersed in the oil phase. These suspensions are viscoplastic fluids with the yield stress increasing by more than 1000 times with addition of 2% MWCNT, which demonstrates intensive “structurizing” ability. After emulsion preparation, MWCNT were concentrated at the interface, stabilizing emulsions. The dependence of the inversion point on MWCNT concentration was found. Emulsions containing up to 94 wt% of the aqueous phase can be prepared only when MWCNT is combined with conventional surfactant. Rheological properties of such compositions were measured. It was established that emulsions stabilized by a combined surfactant were more stable in comparison to conventional surfactant stabilized emulsion.