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Creaming and Flocculation of Oil-in-Water Emulsions Containing Sodium Caseinate

The influence of protein content on the stability of concentrated oil-in-water emulsions (35 or 45 vol% oil, droplet diameter approximately 0.5 &mgr;m, pH 6.8) containing sodium caseinate as the sole emulsifying agent has been investigated. Time-dependent creaming profiles were determined at 30°C using an ultrasound velocity scanning technique with data analysis based on a Urick equation renormalization technique. The results indicate that creaming kinetics has a complex dependence on caseinate content. At low protein content (1 wt%), corresponding to less than half that required for saturation monolayer coverage, the emulsion is destabilized by bridging flocculation (accompanied by some coalescence). At higher protein content (2 wt%), where individual droplets are fully protected against protein bridging or coalescence by the thick adsorbed protein layer, the unflocculated emulsion has good stability over a period of several weeks. With further increase of protein content (>/=3 wt%), the observed creaming stability is reduced again, with the rate of serum separation at the bottom of the sample now greatly increased. This is attributed here to depletion flocculation by unadsorbed caseinate, probably in the form of small particles called "casein submicelles." Light microscopy has confirmed that the visually observable extent of reversible depletion flocculation in concentrated emulsions of this type is very sensitive to overall protein content. Once the caseinate concentration reaches a high value (6 wt%), the strength of the depletion interaction is such that it produces a very strong emulsion droplet network which can reorganize only slowly, and is hence much more stable to creaming and serum separation.

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Flocculation of Hematite with Polyacrylic Acid: Fractal Structures in the Reaction- and Diffusion-Limited Aggregation Regimes.

The structure of hematite aggregates in the presence of fairly monodisperse polyacrylic acid (PAA) with two different molecular weights (Mw = 1.36 x 10(6), Mw/Mn = 1.53; Mw = 3.69 x 10(4), Mw/Mn = 1.60) was studied using static light scattering (SLS). The fractal dimensions were calculated from the scattering exponents, after taking into account the finite size of aggregates, using exponential and Gaussian cutoff functions. Three flocculation regimes, namely, pre-DLA, DLA (diffusion-limited aggregation), and post-DLA, were defined based on the polymer concentration. In the DLA regime, fractal dimension values, Df = 1.84 +/- 0.02 and 1.73 +/- 0.02, were obtained using exponential and Gaussian cutoff functions, respectively. A fractal dimension of approximately 2.0 was found, as expected, in the pre-DLA regime (at PAA concentrations lower than the optimal dosage for a DLA regime) where the flocculation rate was reaction limited. In contrast, in the post-DLA regime, the flocculation was slow but the structure of aggregates was as tenuous as in the DLA regime with a fractal dimension Df approximately 1.8. Moreover, for all three regimes, the Df values were independent of the molecular weights of PAA. The lower fractal dimension in post-DLA was probably due to the increased concentration of polymer chains between adjacent particles in aggregates. The steric hindrance favored tip-to-tip aggregation, leading to a more tenuous structure. Copyright 1998 Academic Press.

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Creaming Stability of Flocculated Monodisperse Oil-in-Water Emulsions.

The influence of droplet flocculation on the creaming stability of monodisperse n-hexadecane oil-in-water emulsions was studied. The creaming velocity of emulsions with different droplet radii (0.43 and 0.86 µm), droplet concentrations (1-67 vol%), and sodium dodecyl sulfate (SDS) concentrations (7-80 mM) were measured. Depletion flocculation was observed in the emulsions when the aqueous phase SDS concentration exceeded a particular level ( approximately 40 mM for 0.43-µm droplets and approximately 15 mM for 0.86-µm droplets). Creaming was monitored by measuring the back-scattered light from an emulsion as a function of its height. The creaming velocity increased with increasing flocculation and decreased with increasing droplet concentration. These results have important implications for the formulation of emulsion-based materials. Copyright 2000 Academic Press.

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Hydrophobic Flocculation of Galena Fines in Aqueous Suspensions.

The hydrophobic flocculation of galena fines induced by potassium amyl xanthate (PAX) in aqueous suspensions has been studied using laser diffraction, electrophoretic light scattering, contact angle, and microflotation measurements. The measurements were performed on <2 µm, 2-5 µm, 5-10 µm, and <30 µm size galena by varying several parameters, including PAX concentration, pH, original particle size, kerosene concentration, and suspension stirring. The experimental results have demonstrated that the hydrophobic flocculation was closely correlated with the particle hydrophobicity, but was not lowered upon increasing the particle surface charges due to PAX adsorption, which is contrary to the DLVO theory. This flocculation has been observed to increase with a reduction of the original particle size and an increase in kerosene concentration, and to require sufficient stirring strength and magnitudes of kinetic energy input to achieve the maximum aggregation degree. From the microflotation results, it has been found that the flotation response of galena fines is markedly improved due to the formation of hydrophobic flocs, suggesting that floc flotation is a promising means to recover galena in the fine size range. Copyright 2000 Academic Press.

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Flocculation and Coalescence of Oil-in-Water Poly(dimethylsiloxane) Emulsions.

The stability of poly(dimethylsiloxane) (PDMS) oil-in-water emulsions has been investigated in the presence of added NaCl as well as in the presence of added surfactant. The emulsions were prepared using a combination of nonionic (C(x)E(y), x and y represent the number of methylene (C) and ethylene oxide (E) groups, respectively) and cationic (quarternary alkylammonium) surfactants. The droplets were observed to exhibit weak flocculation in the presence of high NaCl concentration (1 M). Phase separation and optical microscopic observations revealed that the principal mechanism for emulsion destabilization at high salt concentration was coalescence, which was accelerated at elevated temperature (50 degrees C). The effective coalescence rate for diluted emulsions was investigated using photon correlation spectroscopy. The small effective Hamaker constant for PDMS is the primary reason for the slow rate of coalescence observed for the emulsions at neutral pH in the presence of NaCl. The stability of PDMS emulsions to flocculation is qualitatively similar to that reported for low Hamaker constant dispersions (e.g., microgel particles). Addition of cationic surfactants (cetyltrimethylammonium chloride and dodecyl dimethylbenzylammonium chloride) to the negatively charged droplets after preparation was shown to decrease the emulsion stability once the surfactant concentration exceeded the CMC. Electrophoretic mobility measurements showed that added cationic surfactant changed the sign of the droplet charge from negative to positive at concentrations well below the CMC. Charged micelles of the same sign as the droplets are electrostatically excluded from close approach to the droplet surface within a distance (varepsilon) which results in depletion flocculation. Copyright 2000 Academic Press.

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PEO flocculation with phenolic microparticles.

Polystyrene latex and precipitated calcium carbonate (PCC) with and without dextran sulfate pretreatment were flocculated by the consecutive addition of high-molecular-weight poly(ethylene oxide) and a novel composite latex microparticle consisting of a polystyrene core and a poly(p-vinylphenol) shell. Good flocculation of polystyrene latex and PCC was obtained, whereas the PCC coated with dextran sulfate was not flocculated. The interaction of the composite microparticle with the target colloids was governed by electrostatic forces, whereas hydrogen bonding and hydrophobic interactions drove the PEO adsorption onto the composite particles.

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The effects of the thermal prephase transition and salts on the coagulation and flocculation of phosphatidylcholine bilayer vesicles.

Absorbance measurements of sonicated dipalmitoyl phosphatidylcholine vesicles reveal two aggregation processes: flocculation and coagulation. Flocculation is only observed for samples in monovalent cationic salt solutions or in salt-free suspensions. This process is abolished in the presence of di- or trivalent cations. It is also found to be strongly temperature dependent, occurring only below the thermal prephase transition of the lipid. Dispersal of the flocculates is rapid but they re-form at a rate dictated by the hysteresis in the prephase transition. In contrast, coagulation is slow. The extent of coagulation does not seem to be strongly dependent on the temperature, the nature of the electrolyte or its concentration. The relation of the coagulated state to vesicle-vesicle fusion is briefly discussed.

Mathematics↗

The influence of temperature on the flocculation rate of renneted casein micelles.

The flocculation rate constant of completely renneted casein micelles in milk ultrafiltrate was measured by Rayleigh light scattering between 20 and 35 degrees C. In this temperature range an apparent energy of activation of 103 kJ mol (+/-11 kJ mol : n = 50) was measured. At 15 degrees C clotting was not longer perceptible. The activation of the flocculation between 20 and 35 degrees C is explained not so much by the height of the energy barrier separating the clotting micelles, as by the very negative temperature coefficient of that barrier. In line with this conclusion it is suggested that renneted micelles adhere through hydrophobic bonding. The flocculation rate constant of renneted casein micelles is independent of micelle size at the four temperature levels studied.

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Isolation and characterization of a flocculating protein from Moringa oleifera Lam.

A flocculating protein from the seeds of Moringa oleifera Lam. was isolated by extraction with phosphate buffer followed by cation exchange chromatography. The molecular mass of the protein determined by SDS-PAGE was about 6.5 kDa, the isoelectric point was above pH 10. Amino acid analysis and sequencing showed high contents of glutamine, arginine and proline, and a total of 60 residues. The amino terminus is blocked by pyroglutamate. The flocculant capacity, determined in glass powder suspension, is comparable to that of a cationic polymer on polyacrylamide basis. Flocculation activity may be explained by the patch charge mechanism due to low molecular weight and high charge density.

Amino Acids↗

Characterization of flocculent Saccharomyces interspecific hybrids for the production of sparkling wines.

Interspecific hybrids obtained from flocculent Saccharomyces cerevisiae and non-flocculent Saccharomyces uvarum (S. bayanus var. uvarum) are flocculent to a higher degree and have the capacity to ferment well at both low and high temperatures, from 6 to 36 degrees C. These interspecific hybrids generate minor compounds of fermentation in intermediate quantities with respect to the parent strains and produce high-quality sparkling wines, which are not inferior to those of the parent strains. For these reasons, interspecific strains are particularly adapted to production of sparkling wines that are re-fermented in bottles.

Fermentation↗

Can colloidal particles flocculate at two energy minima simultaneously in a quiescent medium?

The effect of electrostatic repulsion forces on the gravity-induced flocculation of non-Brownian particles in a quiescent medium is analyzed, and the phenomenon that colloidal particles can simultaneously flocculate at both the primary minimum and the secondary minimum of the total interaction curve of DLVO theory is proved. A narrow strip region describing this "combined" flocculation behavior exists on the stability diagram, and the concept of a limiting trajectory can be applied to explain this interesting result.

Letter↗

A novel flocculant of Al(OH)3-polyacrylamide ionic hybrid.

A novel flocculant based on hybrid Al(OH)(3)-polyacrylamide (HAPAM) has been synthesized using a redox initiation system ((NH(4))(2)S(2)O(8)-NaHSO(3)) at 40 degrees C in aqueous medium. The HAPAM was characterized by viscometry, IR spectroscopy, TEM, conductivity, and TGA. The flocculation behavior for 0.25 wt% kaolin suspension was evaluated by spectrophotometry and phase contrast microscopy. It was found that an ionic bond exists between Al(OH)(3) colloid and polyacrylamide (PAM) chains in the HAPAM and the flocculation efficiency of HAPAM is much better than that of commercial polyacrylamide (PAM) and PAM/AlCl(3) blend.

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Stimulant sensitive flocculation and consolidation for improved solid/liquid separation.

A novel method of flocculation resulting in both rapid sedimentation and low sediment moisture is described. It relies on changing the inter-particle forces from repulsive to attractive (aggregation and fast settling results) and then back to repulsive (densification of sediment then occurs). The change in inter-particle force is controlled by a stimulus such as pH or temperature. The technique is demonstrated without polymer using the isoelectric point and pH as the stimulus. The polyelectrolyte chitosan produces faster sedimentation and clearer supernatants as a pH sensitive flocculant. Methylcellulose is an effective temperature sensitive flocculant. The sediment bed volumes can be reduced by between 10 and 45% depending upon the conditions which, as yet, have not been fully optimized.

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Gravity-induced flocculation of Brownian particles in quiescent media under weak gravity.

The main scope of the present paper is to study the rigorous problem of coupled gravity-induced/Brownian flocculation for the strong Brownian/weak gravity case, by solving the coupled Langevin type equations on determining the Brownian particles' collision trajectories. When comparing with the previous results, our numerical calculated flocculation rates are as good as those solutions obtained from using the singular perturbation expansion method to solve the steady state governing convective diffusion equation. Our solutions also confirm that the effect of Brownian diffusion can decrease the flocculation rates of colloidal particles under the condition of strong Brownian/weak gravity.

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Interaction between anionic dyes and cationic flocculant P(AM-DMC) in synthetic solutions.

Copolymer of acrylamide and 2-[(methacryloyloxy)ethyl]trimethylammonium chloride [P(AM-DMC)] is found to be effective to combine anionic dyes with strong aqueous solubility. This work aims mainly at revealing the interaction between anionic dyes and [P(AM-DMC)] by running jar test, spectra analysis and equilibrium dialysis experiments. The results show that P(AM-DMC) effectively decolorizes the tested strong water soluble anionic dyes, such as acidic, reactive and direct dyes, from their aqueous solutions under mild acidic and neutral conditions. Higher cationicity and optimal dose of flocculant P(AM-DMC) have to be used to achieve satisfactory and effective decolorization. Comparison of IR spectra of dye, flocculant P(AM-DMC) and the floc formed indicates chemical interaction occurred between sulfonic groups of dye and quaternary ammonium of flocculant. Plots of r-logC suggest cooperative interaction exists evidently for some dyes tested. Addition of KCl or urea reduces binding extent evidently, which shows the importance of electrostatic and hydrophobic interaction. Therefore the interaction between dyes tested and P(AM-DMC) might be controlled by hydrophobic, cooperative interaction and energetic interaction which includes chemical and electrostatic interactions.

Acrylamides↗

Thermal pyrolysis characteristics of polymer flocculated waste activated sludge.

Polyelectrolyte conditioning is a common practice in wastewater management. This paper experimentally elucidated the thermal pyrolysis characteristics of waste activated sludge at a temperature range of 300-900 K (27-627 degrees C) using thermogravimetric analysis (TGA) in inert atmosphere, with especial attention on the effect of polyelectrolyte flocculation (using cationic polyacrylamide). On the pyrolysis rate vs temperature plot two maxima were noted. At the heating rate of 8 degrees C/min, polyelectrolyte does not influence the pyrolysis process. As higher heating rates (14 and 20 degrees C/min), on the other hand, flocculation to charge neutralization point would enhance the rate of thermal pyrolysis. A simple two parallel-reaction kinetic model is applied to interpret the experimental data. Possible roles of flocculant on sludge pyrolysis are discussed on the basis of change in sludge structures and the hindrance of surface reactions of sludge particles.

Electrolytes↗

Role of the secondary minimum on the flocculation rate of nondeformable droplets.

The kinetic stability of suspensions is usually associated with a decrease in the flux of flocculating particles due to the action of a repulsive potential. However, previous calculations on bitumen drops suggest the possible occurrence of relatively fast aggregation rates in systems with large electrostatic barriers for primary minimum flocculation. This indicates a strong effect of the secondary minimum in the process of aggregation. Here, emulsion stability simulations (ESS) are used to study the aggregation behavior of 11 systems showing different depths of the secondary minimum and three particle sizes. Micron size drops (as those of Bitumen emulsions) usually exhibit deep secondary minima, which rarely occur between nanometer size particles. At high surfactant concentrations, these drops do not coalesce but can still show fast aggregation rates caused by irreversible secondary-minimum flocculation. On the other hand, the extent of coalescence in nanometer-size systems markedly depends on the height of the repulsive barrier. Furthermore, the secondary minimum of these smaller particles is usually shallow, causing reversible aggregation or no aggregation at all. In this article, the consequences of the referred behaviors on the magnitude of the stability ratio are discussed.

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Reversible flocculation of silica across the phase boundary of poly(vinyl caprolactam) in aqueous solution.

The colloid stability of silica dispersions in water in the presence of poly(vinyl caprolactam) (PVCAP) has been studied below and above the lower consolute temperature (LCT) of its solutions. The dispersion sediments slowly without PVCAP in the temperature range studied (26-40 degrees C) or with PVCAP below the LCT ( approximately 30 degrees C). In contrast, with PVCAP above the LCT, rapid flocculation occurs at acid pH, with re-dispersal on cooling. Reversible flocculation is also obtained above the LCT by cycling the pH from alkaline to acid and back. The flocculation observed above the LCT may also be regarded as heterocoagulation between the silica particles and the aggregates of the polymer.

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