Latex Thermostimulated Flocculation in Poly(N-Vinylcaprolactam) Solutions

The effect of temperature on the flocculation of dilute polystyrene latex in the presence of poly(N-vinylcaprolactam) (PVC), a thermosensitive polymer interacting with water to form systems characterized by a lower critical mixing temperature, is studied by the nephelometry. It is shown that PVC induces latex flocculation only in the presence of a small amount of an inorganic electrolyte. Dependence of the initial flocculation rate on PVC concentration has an extremal pattern, which is typical of polymer flocculants. At concentrations close to those of optimal flocculation, heating in the range below the phase separation temperature (T _ps) increases the flocculation rate and the sizes of forming aggregates. It is found that, at PVC concentrations that do not induce the flocculation at room temperature, heating in the range above T _ps (in the presence of a sensitizing electrolyte) results in an irreversible latex flocculation. The disclosed thermostimulated flocculation is assumed to be due to the deterioration of the solvent thermodynamic quality.     

Salt concentration influence on the efficiency of two cationic polymeric flocculants

The influence of the increase of the solution ionic strength on the flocculation of charged latex particles in the presence of cationic polymers is reported. Empirical flocculation rate constants are experimentally determined using particle counting and for two cationic polymers, one linear and the second with two branches. Comparisons are made with a solution containing monovalent salt only at different ionic concentrations in the absence of polymers. In all cases, polymer-induced flocculation is significantly more efficient than charge screening effects using salt only. Analysis of zeta potential measurements indicates that the charge neutralization and surface charge variations dictate the stability of the latex suspensions. Moreover, the addition of a small amount of salt in the polymer–particle mixtures results in a dramatic decrease of the polymer efficiency which is more pronounced for the linear polymeric flocculant. By increasing further the ionic strength, the rates of polymer flocculation are found to increase again but remain smaller than in the absence of salt.     

Addition of polysaccharides influences colloidal interactions during latex film formation along with film morphology and permeability

In this paper, the effect of two polysaccharides (chitosan and dextran) on latex film morphology and porosity is investigated with atomic force microscopy, and the water permeability of the films is examined as well. Furthermore, latex films formed with mixtures of dextran and poly(ethylene glycol), PEG, are investigated. The results show that latex films without added polymers have the most homogeneous and dense morphology. In films containing dextran the highest degree of flocculation is observed, while these films do not show the highest water permeability. The highest permeability is observed in films containing chitosan and film porosity and permeability correlate positively to increasing chitosan concentration. The permeability of the latex films containing dextran and PEG accelerates with time. Since addition of these polymers to latex suspensions give rise to different morphologies and film permeabilities, this approach has promising abilities for control of film properties and, thus, has potential within controlled drug release.     

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.     

Adsorption of polyelectrolytes on colloidal latex particles, electrostatic interactions and stability behaviour

The stabilization and flocculation behaviour of colloidal latex particles covered with cationic polyelectrolytes (PE) is studied with photon correlation spectroscopy and zetapotential measurements. Diffusion coefficients, flocculation rate constants and zetapotentials have been determined as a function of adsorbed amount of cationic poly-(diallyl-dimethyl-ammoniumchloride) (PDADMAC) of different molar masses and of statistic copolymers of DADMAC and N-methyl-N-vinyl-acetamide (NMVA) of various compositions in water and at high ionic strength. Flocculation by van der Waals attraction can be observed if the zetapotential is low. This occurs, if the surface charge is screened by the oppositely charged cations. Furthermore, in the case of adsorption of high molecular polycations mosaic flocculation occurs if the adsorbed amount is low. At high ionic strength, flocculation takes place if the adsorbed amount is below the adsorption plateau. If the adsorption plateau is reached the suspensions become stabilized. In water the charge reversal at full coverage leads to electrosteric stabilization both with low and high molar mass polycations. At high ionic strength only polycations with high molar mass are able to stabilize the suspension. If a certain molar mass of the polycation is exceeded, steric stabilization of the suspension occurs due to the formation of long adsorbed PE tails and their osmotic repulsion. The layer thicknesses are determined as a function of the molar mass. Received: 4 July 2000/Accepted: 18 August 2000     

The influence of PEO/poly(vinyl phenol-co-styrene sulfonate) aqueous complex structure on flocculation

Colloidal suspensions were flocculated with complexes formed from high molecular weight polyethylene oxide (PEO) and a cofactor. Poly(vinyl phenol-co-potassium styrene sulfate) (PKS) or poly(styrene-co-styrene sulfonate) (PS-co-SSS) copolymers were used as the cofactors for this work. The larger the PEO/cofactor complex species, the better the initial flocculation. Factors such as increasing temperature or ionic strength that gave smaller complexes also gave poorer flocculation. Cofactor performance was sensitive to the balance of hydrophobic phenolic groups and hydrophilic styrene sulfonates. If there are too few phenolic groups, the PEO/PSK complexes are large but are too weak to give shear-resistant flocs, whereas complexes formed with high phenolic content PSK are relatively small, giving poorer flocculation but more shear-resistant flocs. Both phenyl and phenol groups are effective as the hydrophobic component in the cofactor. The hydrogen-bonding potential of phenolic cofactors does not seem to offer much advantage relative to phenyl groups. A crucial step in the flocculation is the adsorption of PEO/cofactor complex onto the target colloids. Thus, flocculation is sensitive to the target colloid surface chemistry. Positively charged precipitated calcium carbonate and surfactant-free polystyrene latex are particularly easy to flocculate because adsorption is driven by electrostatic and hydrophobic interactions, respectively. By contrast, the latex coated with hydrophilic poly(N-isopropylacrylamide) (PNIPAM) does not flocculate because the PEO/cofactor complex does not bind to PNIPAM. Finally, the flocculation of highly negatively charged, dextran sulfate coated calcium carbonate seems to be stimulated by the presence of soluble calcium ions that make the complex less soluble and more likely to adsorb.     

二氧化硅悬浮体的絮凝

微细颗粒的胶体二氧化硅广泛应用于橡胶工业、日用化学工业、无机材料工业等众多部门,它的专门用途不下千余种[1]．二氧化硅微细悬浮体是一种典型胶体分散体系,在其中加入大分子显的有机或无机絮凝剂,研究其絮凝规律,不但对研究絮凝现象的理论和实践有意义,而且有助于认识二氧化硅颗粒的表面性质和该分散体系的稳定性．1实验1·1材料和试剂二氧化硅（上海电化厂）：以燃烧法制得的）“品（白炭黑）,D＊T法测其比表面为7（）11。’·g‘．聚丙烯酸胺（＊＊M．广州南中塑料厂）：白色粉末状,用乙醇从水溶液中沉淀、提纯,粘度法测其…     

The influence of surfactants on latex flocculation with poly(diallyldimethyl ammonium chloride)

Aqueous latex was flocculated by mixtures of poly(diallyldimethyl ammonium chloride), PDADMAC, and anionic surfactants. Sodium dodecyl sulfate, (SDS), and Aerosol OT influenced flocculation whereas nonionic Tergitol NP-10 did not. The flocculation domains were correlated with properties of the polymer-surfactant complexFlocculation was never observed above the CMC of the corresponding surfactant solution without polymer or latex. At SDS concentrations greater than 10^–3.6 M the flocculation boundary corresponded to the first appearance of insoluble polymer-surfactant complex which was characterized by dynamic light scattering and microelectrophoresis. Under these conditions latex (diameter 570 nm) and dispersed polymer-surfactant complex particles (diameters between 30 and 2 000 nm) displayed simultaneous homo and heteroflocculation. The boundaries of the flocculation domains at low surfactant concentration were determined by the ratio of polymer to latex and by the net electrostatic charge of the soluble polymer-surfactant complex. On the other hand, the mechanisms controlling flocculation boundaries in the dispersed polymer-surfactant domain require further clarification.     

Depletion flocculation of latex dispersion in ionic micellar systems

The flocculation behavior of anionic and cationic latex dispersions induced by addition of ionic surfactants with different polarities (SDS and cetyltrimethylammonium bromide (CTAB)) have been evaluated by rheological measurements. It was found that in identical polar surfactant systems with particle surfaces of SDS + anionic lattices and CTAB + cationic lattices, a weak and reversible flocculation has been observed in a limited concentration region of surfactant, which was analyzed as a repletion flocculation induced by the volume-restriction effect of the surfactant micelles. On the other hand, in oppositely charged surfactant systems (SDS + cationic lattices and CTAB + anionic lattices), the particles were flocculated strongly in a low surfactant concentration region, which will be based on the charge neutralization and hydrophobic effects from the adsorbed surfactant molecules. After the particles stabilized by the electrostatic repulsion of adsorbed surfactant layers, the system viscosity shows a weak maximum again in a limited concentration region. This weak maximum was influenced by the shear rate and has a complete reversible character, which means that this weak flocculation will be due to the depletion effect from the free micelles after saturated adsorption.     

Stability of polydimethylsiloxane-magnetite nanoparticle dispersions against flocculation: interparticle interactions of polydisperse materials

The colloidal stability of dispersions comprised of magnetite nanoparticles coated with polydimethylsiloxane (PDMS) oligomers was investigated theoretically and experimentally. Particle-particle interaction potentials in a theta solvent and in a good solvent for the PDMS were predicted by calculating van der Waals, electrostatic, steric, and magnetic forces as functions of interparticle separation distances. A variety of nanoparticle sizes and size distributions were considered. Calculations of the interparticle potential in dilute suspensions indicated that flocculation was likely for the largest 1% of the population of particles. Finally, the rheology of these complexes over time in the absence of a solvent was measured to probe their stabilities against flocculation as neat fluids. An increase in viscosity was observed upon aging, suggesting that some agglomeration occurs with time. However, the effects of aging could be removed by exposing the sample to high shear, indicating that the magnetic fluids were not irreversibly flocculated.     

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.     

Solvation of calcium ions in methanol-water mixtures: molecular dynamics simulation

Molecular dynamics simulations of CaCl2 solutions in water and methanol-water mixtures, with methanol concentrations of 5, 10, 50, and 90 mol %, at room temperature, have been performed. The methanol and water molecules have been modeled as flexible three-site bodies. Solvation of the calcium ions has been discussed on the basis of the radial and angular distribution functions, the orientation of the solvent molecules, and their geometrical arrangement in the coordination shells. Analysis of the H-bonds of the solvent molecules coordinated by Ca2+ has been done. Residence time of the solvent molecules in the coordination shell has been calculated. The preferential hydration of the calcium ions has been found over the whole range of the mixture composition. The water concentration in the first and second coordination shells of Ca2+ significantly exceeds the water content in the solution, despite the very similar interaction energy of the calcium ion with water and methanol. In aqueous solution and methanol-water mixtures, the first coordination shell of Ca2+ is irregular and long-living. The solvent molecules prefer the anti-dipole arrangement, but, in aqueous solutions and water-rich mixtures, the water molecules in the primary shell have only one H-bonded neighbor.     

钴胺素的溶析结晶研究以及离子杂质对晶体生长的影响

采用激光法研究了钴胺素的结晶热力学,包括在不同温度下,不同溶剂配比下的溶解度和超溶解度,介稳区的测定。研究了四种不同的离子杂质(Na+,Mg2+,Ca2+and Fe3+)对钴胺素结晶诱导期的影响。通过实验结果表明钴胺素在溶析结晶过程中,Fe3+和Mg2+要比Na+和Ca2+具有更明显的影响。     

Flocculating Power of Poly-N,N-dimethyl-N,N-diallylammonium Chloride of Various Molecular Weights

The amount of precipitated rubber in flocculation of SKS-30 ARK butadiene-styrene latex was studied as influenced by the concentration of poly-N,N-dimethyl-N,N-diallylammonium chloride cationic polyelectrolyte at various temperatures and concentrations of the latex dispersed phase.     

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.     

Surfactive water-soluble copolymers for the preparation of controlled surface nanoparticles by double emulsion/solvent evaporation

We have already shown that polylactide (PLA) nanoparticles covered with a hydrophilic polymeric layer can be prepared by simple emulsion/solvent evaporation by using amphiphilic copolymers as surfactants during the procedure. The external layer is then constituted by the hydrophilic part of the macromolecular surfactant. This kind of nanospheres is useful for the encapsulation of lipohilic molecules. The use of amphiphilic copolymers as surfactants in the preparation of PLA nanospheres with controlled surface properties, was then applied to the double emulsion/solvent evaporation procedure. The aim was to allow the encapsulation of water-soluble bioactive molecules in PLA particles with controlled surface properties. In this paper, we describe the results obtained with three different water-soluble monomethoxypolyethylene oxide (MPEO)-b-PLA diblock copolymers used as surfactants in the preparation of nanoparticles by double emulsion/solvent evaporation. After organic solvent evaporation, the obtained nanospheres were proved to be really covered by a MPEO layer whose characteristics were determined. It was firstly shown that the MPEO-covered particles did not flocculate at 25 degrees C, even in 4 M NaCl while suspensions of bare nanospheres were destabilized for a NaCl concentration as low as 0.04 M. On the other hand, the suspensions of MPEO-covered nanoparticles in 0.3 M Na2SO4 were found to be very sensitive to temperature as they flocculated at a temperature lying between 45 and 55 degrees C depending on the MPEO-b-PLA composition. This property was attributed to the fact that MPEO is a polymer with a low critical solution temperature. The concentration of MPEO at the nanoparticle surface was then calculated for the three kinds of particles, from the initial flocculation temperature, and was found to be comparable to the value determined directly.     

Polystyrene and polystyrene-butadiene latexes stabilized by poly(N-isopropylacrylamide)

Latexes stabilized by poly(N-isopropylacrylamide) (polyNIPAM) were prepared by polymerizing NIPAM in the presence of polystyrene and polystyrene-butadiene latex or by styrene emulsion polymerization in the presence of NIPAM. In 0.01 M CaCl₂ polyNIPAM stabilized latexes exhibited critical flocculation temperatures in the range 32–35°C, which is approximately equal to the lower critical solution temperature of polyNIPAM in water. Partial substitution of NIPAM with some acrylamide (AM) gave higher flocculation temperatures. Coagulation studies with cleaned latex indicated that the polyNIPAM or polyNIPAM-co-AM polymer chains were anchored to the latex particle surfaces.     

Coagulation of Butadiene-Styrene Latex with Poly-N,N-dimethyl-2-hydroxypropylenammonium Chloride

The flocculating performance of a cationic polyelectrolyte, poly-N,N-dimethyl-2-hydroxypropylenammonium chloride, in recovery of butadiene-styrene rubber in the presence of sulfuric acid at various temperatures was studied. The kinetic curves of flocculation of SKS-30 ARK latex at various amounts of the flocculant added were obtained.     

Preparation and flocculating properties of highly substituted cationic starches of different vegetable origins

Kinetic regularities of flocculation of model kaolin suspensions by highly substituted cationic flocculants synthesized from different starches (corn, waxy corn, potato, and tapioca starches) have been studied as depending on the doses and vegetable origins of the flocculants. The rate of kaolin suspension flocculation has been found to increase with the dose of the cationic starches of all types. It has been shown that, irrespective of the dose, the highest rate of kaolin sedimentation in the model systems is observed in the presence of cationic potato starch. It has been demonstrated that cationic potato starch flocculates kaolin suspensions with concentrations of 0.1, 0.5, and 1.0% with the same efficiency. In this case, the suspensions are almost completely clarified within 2–5 min. Moreover, the dependence of the flocculating efficiency for a 0.1% model suspension on the dose of cationic starch has been found to pass through a maximum at a starch content of 1.0–5.0 mg/g of kaolin depending on the type of starch.     

Reversible flocculation of silica suspensions by water-soluble polymers

The possibility to concentrate, then redisperse colloidal suspensions is not only of great theoretical interest, but is also relevant to the industrial process of solid-liquid separation, which must often be followed by a redispersion stage. Up to now, these consecutive operations were unrealizable in the presence of polymers, since flocculation and adsorption were generally considered irreversible in this case. Previous studies have pointed out the occurrence of two main flocculation mechanisms: charge neutralization and interparticle bridging. The use of copolymers makes it possible to take into account these two different mechanisms together. Using this fact we prepared new copolymers of acrylamide with N-vinylimidazole via radical polymerization and characterized them by light scattering, viscometry, potentiometric titrations, and UV studies. One peculiarity of the chosen system is its dependence on pH: actually the degree of neutralization of such cationic polyelectrolytes does vary with pH, especially near the pK value. This paper shows that these copolymers may induce reversible flocculation of negatively charged suspensions, e.g., silica suspensions, by simple pH adjustment. Performances of the system were followed by various physico-chemical methods. The observed results are explained in terms of flocculation mechanisms as a function of pH.