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.     

The effects of multivalent electrolytes on the gravity-induced flocculation of colloidal particles in binary suspensions

The effects of multivalent electrolytes on gravity-induced heteroflocculation behavior of binary suspensions under different gravity forces are investigated based on the turbidity measurement method. The heteroflocculation behavior of the binary suspensions described by the stability ratio is well analyzed by using the stability diagram and the DLVO theory. It is found that the stability ratios of the binary suspensions decrease with the increase of either the electrolyte concentration and valence or the gravity forces and with the decrease of the size ratio of the latexes components of the binary suspension. Because the theoretical stability ratios obtained by the trajectory analysis method are always higher than the corresponding heteroflocculation experimental values obtained by turbidity measurements, we successfully apply the “regressed” surface potentials determined from the flocculation experiments of monodispersed suspension to predict the stability ratios of the corresponded binary suspension.     

Flocculation performance of different polyacrylamide and the relation between optimal dose and critical concentration

Flocculation performance of four kinds of polyacrylamide (PAM) with different chain end group, namely, PAM, star-PAM, PGS-PAM and Al(OH)₃-PAM hybrids, in Kaolin suspensions have been investigated by Spectrophotometer. It was found that their flocculation efficiency deceases in the order: PGS-PAM > Al(OH)₃-PAM ≈ star-PAM > PAM. It was also found that the optimal dose (C_od) of the polymer flocculant in flocculation process is proportional to the critical concentration (C∗) of polymer flocculant in solution and to the suspension solid content (C_ss) in Kaolin suspensions.     

Microscopic phase behavior of supercritical carbon dioxide + non-ionic surfactant + water systems at elevated pressures

The microscopic phase behavior of the supercritical carbon dioxide (scCO₂) + polyethylene oxide-2,6,8-trimethyl-4-nonyl ether (TMN) + water systems at about 3 wt% of TMN were investigated using a synthetic method with a microscope. The two types of TMN (TMN-3 and TMN-10) used in this work had molecular weight distributions caused by the distribution of the number of ethylene oxide groups. Two different types of phase transition were observed when pressure was decreased gradually at a constant temperature from the high pressure at which the transparent phase was observed to the low pressure at which the separate vapor–liquid phases were observed for the scCO₂ + TMN-3 + water system at 3 wt% of TMN-3. The transparent phase was colorless under all experimental conditions and the phase transition from a transparent phase to a turbidity phase with small, dispersed droplets was observed at the higher side phase transition (higher phase transition pressure). As the pressure continued to decrease, another phase transition was observed from the phase with small droplets to a state with an accelerating aggregation of droplets (lower phase transition pressure). In the turbidity phase between the higher and the lower phase transition, the degree of turbidity became higher with decreasing pressure. On the other hand, in the phase observed below the lower phase transition, a new liquid phase adhered to the sapphire windows and the wall inside the optical cell.     

Synthesis, characterization and flocculation performance of zwitterionic copolymer of acrylamide and 4-vinylpyridine propylsulfobetaine

A novel zwitterionic polyacrylamide AMVPPS copolymer containing sulfobetaine groups was synthesized by copolymerizing acrylamide (AM) and 4-vinylpyridine propylsulfobetaine (4-VPPS) in 0.5 mol/L NaCl solution with potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as initiator. The structure and composition of AMVPPS copolymer were characterized by FT-IR spectroscopy, ¹H NMR and elemental analyses. Thermal stability and solution properties of AMVPPS copolymer were studied by thermogravimetry analysis (TGA) and viscometry. Anti-polyelectrolyte behavior was observed and was found to be enhanced with increasing 4-VPPS content in copolymer. The flocculation performance for 2.5 g/L kaolin suspension and 2.5 g/L hematite suspension was evaluated by transmittance measurement and phase contrast microscopy. The effects of 4-VPPS content in the copolymer, intrinsic viscosity and the added salt on the flocculation performance were investigated. It was found that AMVPPS copolymer was a good flocculant for both anionic kaolin and cationic hematite suspensions and the flocculation performance of copolymer was much better than that of pure polyacrylamide (PAM). A very wide range of the optimum flocculation concentration, named as “flocculation window”, was found for both suspensions. These flocculation characteristics were mainly dependent on the charge neutralization, the intragroup conformation transition from water to NaCl solution and then the interchain bridging of the zwitterionic AMVPPS copolymer.     

Synthesis of cationic guar gum-graft-polyacrylamide at low temperature and its flocculating properties

Acrylamide grafted cationic guar gum (CGG-g-PAM), induced by ceric ammonium sulfate, was synthesized using aqueous polymerization technique at 10 °C and the flocculation property was studied with high-turbidity tobacco wastewater (NTU > 4500). Thus five grades of graft copolymers were obtained through alteration of initiator and monomer concentrations in order to understand the effect of molecular weight on flocculation. The grafted copolymer was characterized by FTIR and SEM. Study of DTG demonstrated that CGG-g-PAM had better heat-resistant performance than guar gum, cationic guar gum (CGG) and polyacrylamide. The dosage of polyaluminium chloride (PAC) and CGG-g-PAM, pH value and molecular weight were considered to be the factors that can influence flocculation efficiency. The result showed best flocculation efficiency occurs at pH 5 when the dosage of CGG-g-PAM and PAC are 3.6 ppm and 120 ppm, respectively. The percentage of turbidity and COD removal are 98% and 24% correspondingly, and its flocculating efficiency prevails over that of CGG and cationic polyacrylamide (CPAM).     

Coagulation and flocculation measurements by photon correlation spectroscopy — colloidal SiO2 bare and covered by polyethylene oxide

With photon correlation spectrometry (PCS) the diffusion coefficients, average diameters and polydispersities of colloidal particles can be determined in dilute aqueous suspensions. In this study PCS is used to follow the coagulation and flocculation of silica particles. Electrolyte solution added to suspensions of bare particles and of particles covered with adsorbed polyethylene oxide layers induces aggregation. The rate constants of aggregation are evaluated by the second-order Smoluchowski theory with the assumptions of spherical aggregated particles and volume proportional light-scattering amplitude. Adsorbed PEO layers of molar mass lower thanM _w=160000 decrease the critical flocculation concentration and the flocculation states and rate constants for bare and covered particles are the same at high electrolyte concentrations. Polymer layers of high molar mass (M _w=325000, 900000) reducved at full coverage the rate constants and stabilize the suspensions even at high electrolyte concentrations. At low coverage adsorption of high molar mass polymers results in the same values as of low molar mass PEO. The correlation between rate constants and hydrodynamic PEO layer thicknesses demonstrates the steric influence of the tails of the adsorbed macromolecules on stability and flocculation.Dedicated to Prof. Dr. Joachim Klein on the occasion of his 60th birthday     

Effects of surfactants and pH of medium on zeta potential and aggregation stability of titanium dioxide suspensions

The effects of benzethonium chloride, sodium dodecylbenzenesulfonate, and 4-(1,1,3,3-(tetramethylbutyl)phenyl poly(ethylene glycol) on the zeta potential and aggregation stability of aqueous rutile-form titanium dioxide suspensions are studied in the pH range of 2–12. It is shown that the nonionic surfactant does not affect significantly the zeta potential and aggregation stability of the suspensions. The influence of ionic surfactants on the aggregation stability of the suspensions considerably depends on the pH of a medium. At pH values above the isoelectric point of titanium dioxide suspensions (pH₀ = 6.2), the suspensions demonstrate a high aggregation stability in the presence of the anionic surfactant, sodium dodecylbenzene-sulfonate (irrespective of its content), while, at pH < pH₀, the aggregation stability of the suspensions markedly increases with the surfactant concentration. In the presence of the cationic surfactant, benzethonium chloride, the aggregation stability of the suspensions is independent of the surfactant concentration at pH < pH₀, whereas, at pH > pH₀, it increases with the surfactant concentration.     

Effect of electrolyte in silicone oil-in-water emulsions stabilised by fumed silica particles

Partially hydrophobised fumed silica particles are used to make silicone oil-in-water emulsions at natural pH of the aqueous phase. The stability and rheological properties of the emulsions and suspensions are studied at NaCl concentrations in the range 0-100 mM. It is found that all emulsions are very stable to coalescence irrespective of the NaCl concentration. However, a strong effect of electrolyte on the creaming and rheological properties is observed and linked to the particle interactions in aqueous suspensions. The creaming rate and extent are large at low electrolyte concentrations but both abruptly decrease at salt concentrations exceeding the critical flocculation concentration of the suspension (approximately 1 mM NaCl). The drastic improvement of the stability to creaming is attributed to the formation of a visco-elastic three-dimensional network of interconnected particles and emulsion droplets.     

FRAGMENTATION OF PRIMARY FLOCS IN EMULSIONS AND THE SUBSEQUENT REDUCTION OF COALESCENCE

In existing theories emulsion desiabilization is considered as the combined processes of irreversible flocculation and coalescence of dispersed droplets. This approach can be justified when the potential pit characterizing the energy of droplet interaction is sufficiently deep, i.e. excluding small droplet dimensions, strong electrosiatic repulsion and low electrolyte concentrations. For smaller droplet dimensions and stronger electrostatic repulsions the emulsion instability must be considered as a combined process of reversible flocculation and coalescence. In this paper a mathematical model that couples the kinetics of flocculation, coalescence and floe fragmentation is developed in order to quantify the kinetic instability of emulsions with charged submicron droplets. The characteristic limes for flocculation (Smoluchowski's time τ_c) for coalescence (coalescence time τ_c) and for disaggregation (doublet lifetimeτ_d) are considered model parameters. The mathematical model applies to the case when and τ_d<< τ_c, which corresponds to a situation with a small multiplet concentration compared to the concentration of doublets and a singlet-doublet quasi-equilibrium. It is established that at singlet-doublet quasi-equilibrium the rate of the decline in the total droplet concentration is described by second order kinetics in distinction to the exponential time dependence valid for coalescence at irreversible flocculation. The double disintegration reduces the entire coalescence rate, expressed as τ_sm/ τ_d. This reduction is very large at small values of Td. The mathematical model presented can hased on the spontaneous disintegration of doublets predict changes in emulsion stability for model systems and also for technologically important emulsions.     

Towards predicting the stability of protein-stabilized emulsions

The protein concentration is known to determine the stability against coalescence during formation of emulsions. Recently, it was observed that the protein concentration also influences the stability of formed emulsions against flocculation as a result of changes in the ionic strength. In both cases, the stability was postulated to be the result of a complete (i.e. saturated) coverage of the interface. By combining the current views on emulsion stability against coalescence and flocculation with new experimental data, an empiric model is established to predict emulsion stability based on protein molecular properties such as exposed hydrophobicity and charge. It was shown that besides protein concentration, the adsorbed layer (i.e. maximum adsorbed amount and interfacial area) dominates emulsion stability against coalescence and flocculation. Surprisingly, the emulsion stability was also affected by the adsorption rate. From these observations, it was concluded that a completely covered interface indeed ensures the stability of an emulsion against coalescence and flocculation. The contribution of adsorption rate and adsorbed amount on the stability of emulsions was combined in a surface coverage model. For this model, the adsorbed amount was predicted from the protein radius, surface charge and ionic strength. Moreover, the adsorption rate, which depends on the protein charge and exposed hydrophobicity, was approximated by the relative exposed hydrophobicity (Q_H). The model in the current state already showed good correspondence with the experimental data, and was furthermore shown to be applicable to describe data obtained from literature.     

Effect of high voltage electrical discharges on filtration properties of Saccharomyces cerevisiae yeast suspensions

In the present work the dead-end filtration of Saccharomyces cerevisiae yeast suspensions disrupted by high voltage electrical discharges (HVED treatment) was investigated. The efficiency of disruption was evaluated using conductivity disintegration index of suspension Z (Z = 0–1) and absorbance spectra of supernatant solutions. The electronic microscopy study, particle sizing and measuring of ζ-potential and turbidity were used to characterize variation of the colloidal properties of a yeast suspension during disruption. The HVED treatment was found to cause an effective disruption of yeast cells and extraction of intracellular proteins and other bio-products. The study of filtration revealed suspension filterability deterioration after disruption. It was shown that filtration behaviour of the HVED-processed suspensions was governed by cake formation, the filtrate volume decreased and the cake resistance increased with increase of Z. For high levels of disruption (Z > 0.99), filtration was governed by membrane fouling. The optimal dosage of polycationic flocculant promoted the formation of flocks and accelerated filtration. However, selected flocculant (poly(diallyldimethylammonium chloride)) provoked binding of bio-product and was inappropriate for using as an agent enhancing extraction from disrupted yeast cells.     

TURBISCAN MA 2000: multiple light scattering measurement for concentrated emulsion and suspension instability analysis

Emulsion or suspension destabilisation often results from coalescence or particle aggregation (flocculation) leading to particle migration (creaming or sedimentation). Creaming and sedimentation are often considered as reversible, while coalescence and flocculation spell disaster for the formulator. Thus, it is of prime importance to detect coalescence or cluster formation at an early stage to shorten the ageing tests and to improve the formulations. This work mainly concerns the independent and anisotropic scattering of light from an emulsion or suspension in a cylindrical glass measurement cell, in relation with the optical analyser TURBISCAN MA 2000. The propagation of light through a concentrated dispersion can be used to characterise the system physico-chemical stability. Indeed, photons undergo many scattering events in an optically thick dispersion before escaping the medium and entering a receiver aperture. Multiple scattering thus contributes significantly to the transmitted and backscattered flux measured by TURBISCAN MA 2000. We present statistical models and numerical simulations for the radiative transfer in a suspension (plane or cylindrical measurement cells) only involving the photon mean path length, the asymmetry factor and the geometry of the light receivers. We further have developed an imaging method with high grey level resolution for the visualisation and the analysis of the surface flux in the backscattered spot light. We compare the results from physical models and numerical simulations with the experiments performed with the imaging method and the optical analyser TURBISCAN MA 2000 for latex beads suspensions (variable size and particle volume fraction). We then present a few examples of concentrated emulsion and suspension instability analysis with TURBISCAN 2000. It is shown that the instrument is able to characterise particle or aggregate size variation and particle/aggregate migration and to detect these phenomena much more earlier than the operator's naked eye, especially for concentrated and optically thick media.     

High-throughput salting-out assisted liquid/liquid extraction with acetonitrile for the simultaneous determination of simvastatin and simvastatin acid in human plasma with liquid chromatography

Simvastatin (SS) is an effective cholesterol-lowering medicine, and is hydrolyzed to simvastatin acid (SSA) after oral administration. Due to SS and SSA inter-conversion and its pH and temperature dependence, SS and SSA quantitation is analytically challenging. Here we report a high-throughput salting-out assisted liquid/liquid extraction (SALLE) method with acetonitrile and mass spectrometry compatible salts for simultaneous LC-MS/MS analysis of SS and SSA. The sample preparation of a 96-well plate using SALLE was completed within 20 min, and the SALLE extract was diluted and injected into an LC-MS/MS system with a cycle time of 2.0 min/sample. The seamless interface of SALLE and LC-MS eliminated drying down step and thus potential sample exposure to room or higher temperature. The stability of SS and SSA in various concentration ratios in plasma was evaluated at room and low (4 °C) temperature and the low temperature (4 °C) was found necessary to maintain sample integrity. The short sample preparation time along with controlled temperature (2-4 °C) and acidity (pH 4.5) throughout sample preparation minimized the conversion of SS → SSA to ≤0.10% and the conversion of SSA → SS to 0.00% The method was validated with a lower limit of quantitation (LLOQ) of 0.094 ng mL⁻¹ for both SS and SSA and a sample volume of 100 μL. The method was used for a bioequivalence study with 4048 samples. Incurred sample reproducibility (ISR) analysis of 362 samples from the study exceeded ISR requirement with 99% re-analysis results within 100 ± 20% of the original analysis results.     

The use of dielectric spectroscopy for the characterization of polymer-induced flocculation of polystyrene particles

The flocculation of colloidal suspensions is an important unit operation in many industries, as it greatly improves the performance of solid separation processes. The number of available techniques for evaluating flocculation processes on line is limited, and most of these are only functional in dilute suspensions. Thus, techniques usable for flocculation characterization in high-solids suspensions are desirable. This study investigates the use of dielectric spectroscopy to monitor the flocculation of polystyrene particles with a cationic polymer. The frequency-dependent permittivity is modeled and the model parameters are used to describe the particle aggregation. The results show a peak in the modeled time constants of the dielectric relaxation at the onset of flocculation. Further, the adsorption of polymeric flocculant onto the particle surface results in a reduction in particle charge, evident as a decrease in the magnitude of the dielectric dispersion. The use of dielectric spectroscopy is found to be valuable for assessing flocculation processes in high-solids suspensions, as changes in parameters such as floc size and charge can be detected.     

Simultaneous determination of Ephedra sinica and Citrus aurantium var. amara alkaloids by ion-pair chromatography

Ephedra sinica (Ma Huang) preparations have recently gained a lot of attention because of serious side effects associated with their prolonged consumption. Citrus aurantium var. amara is now used as an alternative, despite the fact that similar side effects are suspected. We have developed and validated the first analytical procedure for the simultaneous determination of all major alkaloids from both species. Using the ion-pairing reagent SDS, a C-18 stationary phase (3 μm material) and a pH-gradient for elution enabled the baseline separation of six alkaloids ((±)-octopamine, (±)-synephrine, tyramine, (−)-norephedrine, (+)-pseudoephedrine and (−)-ephedrine) within less than 30 min. The method is sensitive (LOD ≤ 4.6 ng and LOQ ≤ 16.2 ng on-column), selective (l-tyrosine and l-phenylalanine, two closely related amino acids did not interfere), accurate (recovery rates of spiked samples were between 97.5 and 102.0%), repeatable (σ_rel ≤ 4.6%) and precise (intra-day variation ≤7.7%, inter-day variation ≤7.0%). Without the need of a special sample treatment different matrices (plant material, commercial products) were successfully analyzed for their alkaloid content. Dominant alkaloids were (−)-ephedrine (0.9-1.6%) and/or (±)-synephrine (0.1-3.0%). Whether a product contained Ephedra-alkaloids or not could be determined in all investigated samples unambiguously.     

Coalescence coupled with either coagulation or flocculation in dilute emulsions

In current theories [R.G.P. Borwankar, L.A. Lobo, D.T.G. Wasan, Colloids Surf. 69 (1992) 35; K.D. Danov, N.D. Denkov, D.N. Petsev, R. Borwankar, Langmuir 9 (1993) 1731; S.S. Dukhin, J. Sjöblom, J. Dispers. Sci. Technol. 19 (1998) 311], emulsion destabilization is considered as the combined processes of droplet coagulation/flocculation and coalescence. Irreversible aggregation is usually called coagulation, and the term flocculation is used for reversible aggregation. These theories have different conditions of applicability which are not specified. An approximate criterion for discrimination between coalescence coupled with either coagulation or flocculation in dilute emulsions is proposed. Such discrimination is made possible by comparing the characteristic time for coagulation (Smoluchowski time) with that for floc fragmentation (droplet doublet lifetime, τ_d). As droplet dimension and electrolyte concentration decrease, and the Stern potential increases, τ_d is reduced and flocculation takes place. The quantity τ_d enables one to specify the conditions for the two separate cases. The important role of retarded van der Waals forces, screening length and hydration forces in emulsion coalescence is demonstrated.     

Coupling between polymer adsorption and colloidal particle aggregation

Studies of the adsorption of high molecular weight polymers on colloidal latex and silica particles and their subsequent flocculation were carried out. Neutral polyethylene oxide samples with both a narrow and a broad molecular weight distribution were used together with low charged cationic copolymers. The influence of the particle concentration and polymer dose on the flocculation were systematically investigated under quiescent conditions.Equilibrium bridging only occurred with polyelectrolyte, even in very dilute suspensions, at high particle coverage. In contrast to this, non-equilibrium bridging occurred with both neutral polymer and polyelectrolytes but only for more concentrated suspensions and small amounts of adsorbed polymer. Polymer adsorption in dilute suspensions, which did not show particle aggregation was measured an electrophoretic technique. In more concentrated suspensions, where flocculation takes place, we found that aggregation prevents further polymer adsorption and induces both an excluded volume and a surface effect. The consequences on the shape of the isotherms differ according to the aggregation mechanism.A significant decrease of the amount, , of adsorbed polymer is observed with non-equilibrium bridging. When both mechanisms simultaneously contribute to the aggregation, the value of depends on their relative importance. In the intermediate range of copolymer dose their respective contributions are critically sensitive to the details of the mixing step and stirring, leading to non reproducible experimental results.     

Thermal and caloric equations of state for stable and metastable Lennard-Jones fluids: I. Molecular-dynamics simulations

The method of molecular dynamics has been used to calculate the pressure, internal energy and isochoric heat capacity of the Lennard–Jones fluid for 208 states in the range of temperatures 0.35 ≤ k_BT/? ≤ 2.0 and densities 0.001 ≤ ρσ³ ≤ 1.2. The array of data obtained, along with stable states, includes homogeneous metastable states (supersaturated vapor, superheated and supercooled liquid). Spinodals of supersaturated vapor and superheated liquid have been approximated. In a stable region the data obtained are compared with the results of previous papers. The behavior of thermodynamic properties of the fluid in the event of homogeneity disturbance and formation of micro-heterogeneous (“two-phase”) states has been considered.     

Determination of total phosphorus and nitrogen in turbid waters by oxidation with alkaline potassium peroxodisulfate and low pressure microwave digestion, autoclave heating or the use of closed vessels in a hot water bath: comparison with Kjeldahl digestion

The evaluation of the use of alkaline peroxodisulfate digestion with low pressure microwave, autoclave or hot water bath heating for the determination of total phosphorus and nitrogen in turbid lake and river waters is described. The efficiency of these digestion procedures were compared to a Kjeldahl digestion procedure with sulphuric acid-potassium sulfate and copper sulfate. The final solution before digestion was 0.045 M in potassium peroxodisulfate and 0.04 M in sodium hydroxide. Procedures were evaluated by the analysis of suspensions of two reference materials, National Institute of Environmental Science, Japan, no. 3 Chlorella and no. 2 pond sediment and natural turbid waters. Best recoveries of phosphorus and nitrogen by microwave heating were obtained when solutions were digested at 95 °C for 40 min. Quantitative recoveries of phosphorus from Chlorella suspensions up to 1000 mg/l were obtained by all three heating procedures, but incomplete recoveries of nitrogen occurred above 20 mg N/l in the digested sample. Good recoveries of phosphorus and nitrogen from suspended sediment suspensions were obtained only from solutions containing <150 mg/l of suspended sediments. Recoveries of phosphorus from phosphorus compounds containing COP and CP bonds added to distilled water were quantitative (94-113%) except for polyphosphates (microwave, 34±8; autoclave, 114±6; water bath, 96±4) and aluminium phosphate (8-23%). Recoveries of nitrogen compounds containing CN bonds added to distilled water were quantitative (94-96%). The analysis of a range of natural turbid water samples by alkaline peroxodisulfate and microwave, autoclave and water bath heating gave similar total phosphorus and nitrogen results. All procedures using alkaline peroxodisulfate underestimate phosphorus concentrations at high suspended sediment concentrations (>150 mg/l) and are only suitable for the analysis of very turbid samples when the turbidity is due to organic matter (algal cells, plant detritus). Underestimation of nitrogen occurs when samples contain more than 20 mg N/l.