Dispersing phase viscometry and zeta potential in alumina dispersions

The stabilities of alumina dispersions were studied as a function of poly- and low molecular weight electrolyte concentration, using viscometry of the dispersing phase, and zeta potential measurements. The relation of polyelectrolyte adsorption to polymer concentration (at different low molecular weight electrolyte concentrations) was found to depend upon the dimensions of the polymer (which were a priori known to decrease with increasing poly- and low molecular weight electrolyte concentration). The occurrence of flocculation and bridging in the destabilization mechanism of the alumina dispersions was also characterized.     

Studies of the Influence of Polyelectrolyte Adsorption on Some Properties of the Electrical Double Layer of ZrO2- Electrolyte Solution Interface

An influence of the molecular weight of the polymer and inorganic contaminations of zirconia on the adsorption and electrokinetic properties on ZrO₂-electrolyte solution interface was studied. Two polymers were used; polyacrylic acid (PAA) and polyacrylamide (PAM). On the basis of the obtained dependencies, main factors responsible for observed changes of zeta potential and surface charge of washed and contaminated ZrO₂ were determined. It was showed, that the change of ionic structure in the Stem layer depends on the number and arrangements of-COOH groups in PAA and PAM macromolecules. These groups are responsible for the conformation of polymer chains near the surface and have direct influence on the amount of the adsorbed polyelectrolyte. The inorganic ions, present on the surface of the oxide, blocking some part of active sites, making them inaccessible for adsorbing by carboxylic groups polymer chains. That makes the adsorption on the contaminated oxide lower than on the washed one. From the comparison of the determined values of the diffuse layer charge and surface charge, the main factor influencing the zeta potential changes at different pH, molecular weight and polymer concentration was determined. Also was demonstrated, that the contaminations of the solid are reason for considerable shift of pH_pzc in relation to pH_icpof the zirconia. Thickness of the adsorption layers and free energies of the adsorption of polyacrylic acid and polyacrylamide on the surface of ZrO₂ were calculated.     

Stabilization of magnetorheological suspensions by polyacrylic acid polymers

This work is devoted to the synthesis and stabilization of magnetorheological suspensions constituted by monodisperse micrometer-sized magnetite spheres in aqueous media. The electrical double-layer characteristics of the solid/liquid interface were studied in the absence and presence of adsorbed layers of high molecular weight polyacrylic acids (PAA; Carbopol). Since the Carbopol-covered particles can be thought of as "soft" colloids, Ohshima's theory was used to gain information of the surface potential and the charge density of the polymer layer. The effect of the pH of the solution on the double-layer characteristics is related to the different conformations of the adsorbed molecules provoked by the dissociation of the acrylic groups present in polymer molecules. The stability of the suspensions was experimentally studied for different pH and polymer concentrations, and in the absence or presence of a weak magnetic field applied. The stability of the suspensions was explained using the classical DLVO theory of colloidal stability extended to account for hydration, steric, and magnetic interactions between particles. Diagrams of potential energy vs interparticle distance show the predominant effect of steric, hydrophilic/hydrophobic, and magnetic interactions on the whole stability of the system. The best conditions to obtain stable suspensions were found when strong steric and hydrophilic repulsions hinder the coagulation between polymer-covered particles, simultaneously avoiding sedimentation by the thickening effect of the polymer solution. When a not too high molecular weight PAA was employed in a low concentration, the task of a long-time antisettling effect compatible with the desired magnetic response of the fluid was achieved.     

CATIONIC POLYMERIC SURFACTANTS

An influence of polyvinyl alcohol molecular weight and acetate groups, present in the macromolecule, on adsorption and electrochemical properties of the TiO₂–polymer solution interface was studied. Calculated thickness of adsorption layers of PVA, on the surface of the oxide, allowed assume that acetate groups may have meaningful influence on the polymer chain conformation at the interface. Structure of macromolecules at titania–polymer solution interface was compared with that of bulk of solution. Obtained data allow determine the changes of the size and shape of polymer coils in the system. The results of experiments let us conclude main factors, responsible for observed zeta potential and surface charge changes of TiO₂. It was proved that change of the ion structure of Stern layer, depends on molecular weight and number of acetate groups (degree of hydrolysis) of PVA macromolecule. Possible mechanism of zeta potential changes was proposed as a function of pH of the solution and molecular weight of the polymer.     

Poly(alkylene oxide) ionomers. XII. Hydrolysis of polymers and copolymers of methyl 10,11-epoxyundecanoate

Ester-substituted oxyethylene polymers and copolymers of methyl 10,11-epoxyundecanoate were prepared with an aluminumalkyl–water coordination initiator system modified with acetylacetone. Poly(ethylene oxide) ionomers, polyelectrolytes, and polycarboxylic acids were obtained by alkaline hydrolysis of the pendant carbomethoxy groups and by neutralizations with acetic acid. The high molecular weight substituted poly(ethylene oxide)s were characterized by spectral, thermal, and dilute solution measurements. The infrared spectra of carboxylate substituted poly(ethylene oxide)s, both homo- and copolymers, show the typical shifts in the carboxyl absorption when going from the ester to the carboxylate group to the free acid. Polymer transitions temperatures, as measured by DSC, changed accordingly. Wide-angle x-ray diffraction measurements strongly suggest the existence of ionic domains in the oxyethylene polymer matrix. Dilute solution properties of the ionomers show typical polyelectrolyte behavior, including a substantial change in viscosity when ionic solute is added.     

Competitive adsorption of polymer and surfactant at a liquid droplet interface and its effect on flocculation of emulsion

We investigate the competitive adsorption of polymer and surfactant at oil-water interface by measuring the hydrodynamic diameter, zeta potential, microstructure and rheology. The polymer used in our experiment is a statistical copolymer of polyvinyl alcohol and vinyl acetate copolymer (PVA-Vac) and the emulsion is oil-in-water system with an average droplet diameter of 200 nm. At low surfactant concentrations, the hydrodynamic diameter remains unchanged but above a critical aggregation concentration, it increases dramatically. The phase contrast optical microscopic images of emulsion droplets preadsorbed with polymers of higher molecular weight show a systematic increase in the floc size on increasing surfactant concentration due to biding of polymer-surfactant complexes on several droplets. The dramatic increase in zeta potential of the droplets on increasing ionic surfactant concentration clearly indicates a preferential adsorption of surfactant at the oil-water interface. The enhanced viscosity upon addition of ionic surfactant into polymers confirms the strong interaction between them. Our studies show that lower molecular weight polymers with suitable ionic surfactants can synergistically enhance the stability of formulations, while longer chain polymers induce bridging flocculation. Our results are useful for preparing oil-in-water formulations with long term stability.     

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.     

Reduced aggregation and sedimentation of zero-valent iron nanoparticles in the presence of guar gum

Injection of nanoscale zero-valent iron (NZVI) is potentially a promising technology for remediation of contaminated groundwaters. However, the efficiency of this process is significantly hindered by the rapid aggregation of the iron nanoparticles. The aim of this study was to enhance the colloidal stability of the nanoparticles through the addition of the "green" polymer guar gum. We evaluated the properties of guar gum and its influence on the surface properties, particle size, aggregation, and sedimentation of iron nanoparticles. Commercial iron nanoparticles were dispersed in guar gum solutions, and their aggregation and sedimentation behaviors were compared to those of bare iron nanoparticles and commercial nanoparticles modified with a biodegradable polymer (polyaspartate). High performance size exclusion chromatography, charge titration, and viscosity assessment showed that guar gum is a high molecular weight polymer which is nearly neutrally charged, rendering it suitable for steric stabilization of the iron nanoparticles. Electrophoretic mobility measurements demonstrated the ability of guar gum to adsorb on the nanoparticles, forming a slightly negatively charged layer. Dynamic light scattering experiments were conducted to estimate the particle size of the different nanoparticle suspensions and to determine the aggregation behavior at different ionic strengths. Guar gum effectively reduced the hydrodynamic radius of the bare nanoparticles from 500 nm to less than 200 nm and prevented aggregation of the nanoparticles even at very high salt concentrations (0.5 M NaCl and 3 mM CaCl(2)). Sedimentation profiles of the different nanoparticle suspensions confirmed the improved stability of the iron nanoparticles in the presence of guar gum. The results strongly suggest that guar gum can be used to effectively deliver stabilized zero-valent iron nanoparticles for remediation of contaminated groundwater aquifers.     

Influence of solution pH on stability of aluminum oxide suspension in presence of polyacrylic acid

The effect of solution pH and molecular weight of polyacrylic acid (PAA) on its adsorption as well as on stabilization-floculation properties of the colloidal Al₂O₃ and electrolyte solution systems was studied. The measurements showed that at pH = 6, the presence of the polymer of molecular weight 2?000 and 240?000 does not change stability of Al₂O₃ suspension. However at pH =3 and 9 the effect of polyacrylic acid is significant. At pH = 3 it creates destabilization of the suspension while at pH = 9 PAA it improves significantly the stability of Al₂O₃. It was shown that the increase in solution pH affects conformation of adsorbed macromolecules which causes the decrease in PAA adsorbed amount and thickness of polymer adsorption layer. By comparing the values of diffusion layer and surface charges, main effects responsible for the decrease in surface charge and ζ potential of the solid in the presence of the polymer as well as suspension stability were determined.     

Effect of pH of aqueous ceramic suspensions on colloidal stability and precision of analytical measurements using slurry nebulization inductively coupled plasma atomic emission spectrometry

Colloidal stability of silicon nitride, silicon carbide and boron carbide aqueous slurries used for slurry nebulization inductively coupled plasma atomic emission spectrometry has been investigated in the pH range 2–10 by electrophoretic mobility and particle size measurements, together with sedimentation tests. The mean particle size of silicon nitride and silicon carbide suspensions change with increasing pH showing a maximum at the isoelectric points (pH 7.5 and 5.5 respectively). The particle size distribution of boron carbide slurries remains practically constant and the zeta potential of suspended boron carbide particles shows a small change in the pH range investigated. The silicon nitride and silicon carbide slurries have good stability at pH below 5 and above 8, respectively. Boron carbide slurries show excellent stability in the whole pH range investigated. The time demand for stabilization of the emission line intensities from the start of nebulization strongly depends on the colloidal stability of slurries. Consequently, it is advantageous to nebulize aqueous suspensions with a pH as far from the isoelectric point of the solid as possible and with the ionic strength of the dispersion medium as low as possible. The RSD values of the line intensity measurements determined after 3 min stabilization time decrease with increasing stability of the aqueous slurries.     

Effect of poly(ethylene oxide)-silane graft molecular weight on the colloidal properties of iron oxide nanoparticles for biomedical applications

The size, charge, and stability of colloidal suspensions of magnetic nanoparticles with narrow size distribution and grafted with poly(ethylene glycol)-silane of different molecular weights were studied in water, biological buffers, and cell culture media. X-ray photoelectron spectroscopy provided information on the chemical nature of the nanoparticle surface, indicating the particle surfaces consisted of a mixture of amine groups and grafted polymer. The results indicate that the exposure of the amine groups on the surface decreased as the molecular weight of the polymer increased. The hydrodynamic diameters correlated with PEG graft molecular weight and were in agreement with a distributed density model for the thickness of a polymer shell end-grafted to a particle core. This indicates that the particles obtained consist of single iron oxide cores coated with a polymer brush. Particle surface charge and hydrodynamic diameter were measured as a function of pH, ionic strength, and in biological buffers and cell culture media. DLVO theory was used to analyze the particle stability considering electrostatic, magnetic, steric, and van der Waals interactions. Experimental results and colloidal stability theory indicated that stability changes from electrostatically mediated for a graft molecular weight of 750 g/mol to sterically mediated at molecular weights of 1000 g/mol and above. These results indicate that a graft molecular weight above 1000 g/mol is needed to produce particles that are stable in a wide range of pH and ionic strength, and in cell culture media.     

Use of polyamino acid analogs of biomineral proteins in dispersion of inorganic particulates important to water treatment

Synthetic polyamino acids (peptides) based on the structure and activity of matrix proteins isolated from oyster shell and other biomineral structures have been identified for use in the prevention of mineral scaling. Matrix proteins are polyanionic and are thought to act as regulators of crystallization during the development of skeletal and other mineral structures. These proteins and their synthetic analogs also contain hydrophobic regions that may enhance their surface-active properties. The dispersion activity of a variety of polyamino acids that are matrix protein analogs has been evaluated in bench-top tests using inorganic mineral particles.

Dispersion activities were measured using particles of iron oxide, kaolin, calcium carbonate, and calcium phosphate (hydroxyapatite). The activity was measured by increases in the spectrophotometric absorbance of test particle suspensions in the presence of dispersants. The increases in absorbance were due to turbidity resulting from the production of smaller particle sizes or slower rates of settling. The results suggest that biopolymers composed of polyanionic polyamino acids may be effective as dispersants. Polyamino acids containing a hydrophobic or phosphorylated domain attached to a polyaspartate backbone demonstrate enhanced activity over polyaspartate. These polyamino acids display comparable activity to commercially available hydrocarbon-based polymeric dispersants.

An economical process for the manufacture of polyamino acids by thermal polycondensation is under development. Clearly, non-toxic and biodegradable polyamino acids present a desirable alternative to toxic non-biodegradable polymers in a number of applications such as detergents and cooling tower additives.     

pH dependent stability of aqueous suspensions of graphene with adsorbed weakly ionisable cationic polyelectrolyte

Stable graphene suspensions were prepared through ultrasonic exfoliation followed by surface modification with the cationic polyelectrolyte poly(ethyleneimine) (PEI). The stability of the suspensions was found to be dependent upon the pH of the solution and the molecular weight of the PEI adsorbed. For the graphene sheets with adsorbed PEI with a molecular weigh of 600 Da, the particles were stabilised through an increased electrostatic repulsion at low pH inferred from in an increase in the measured zeta potential of the particles. However, the graphene with higher molecular weight PEI (70 kDa) was stable over a comparatively larger pH range through a combination of electrostatic repulsion at low pH and steric repulsion at elevated pH. Thus, solution conditions allowing the control of the colloidal sized graphene particles can be easily tuned through judicious management of solution conditions as well as polymer layer properties.     

Studies of the Atrazine Aqueous Suspension Stability in the Presence of an Anionic Polymer—Influences of Polymer Molecular Weight and Solution pH

The influence of the molecular weight of sodium salt of styrene/methacrylic acid (SSMA) copolymers and solution pH value (range of 3–11) on the stability of the atrazine suspension was studied. SSMA with different molecular weights was synthesized by emulsion polymerization. Adsorption, zeta potential measurements, microscopy, and suspension stability measurements were carried out. The obtained results indicate that the adsorption of SSMA on the surfaces of atrazine particles decreases with the increase of the molecular weight, and the hydrogen bonding is the main adsorption force. The presence of SSMA improves the stability of the atrazine suspension. The stability of the atrazine suspension decreases with the increase of the molecular weight of SSMA. On the other hand, the stability of the atrazine suspension with SSMA increases firstly and then decreases with the increase in solution pH in the range of 3–11.     

Evaluation of the Dispersing Properties of Polycarboxylate-Type Superplasticizers with Different Molecular Weight in Cement Systems

In order to evaluate the dispersing properties of polycarboxylate-type superplasticizers (PCs) with different molecular weight in cement pastes, PCs with different molecular weight (low, medium, high) were synthesized, and used as superplasticizer for cement suspensions. The effect of molecular weight of PC on the zeta potential, adsorption, fluidity of the corresponding cement suspensions was investigated systematically, and total interparticle potential energy between particles was calculated. The results show that, the higher molecular weight of PC, the larger adsorption amount of PC. PC with medium molecular weight presents a better dispersing property than PC with high molecular weight, while PC with low molecular weight falls in between. The maintaining dispersing ability of PC for cement particles is weakened gradually with the increasing of molecular weight. The changing rule of total interparticle potential energy produced by PC is in accordance with the changing rule of dispersing property of PC in cement pastes. This indicates that the calculated results of total interparticle potential energy further support the explanation of dispersing property difference of PC in theory. This article uses the sum of electrostatic energy and steric hindrance potential as the total interparticle potential energy to evaluate the dispersing property of PC for the first time, which is meaningful for evaluation of dispersing property of polymer dispersant adsorbed on particle surfaces.     

Dispersion of nanosized aqueous suspensions of barium titanate with ammonium polyacrylate

The colloidal stability of nanosized barium titanate (BaTiO3) aqueous suspensions with ammonium polyacrylate (PAA-NH4) at different pH values has been investigated by means of zeta potential, adsorption isotherm, sedimentation, and rheology characterization. The isoelectric point of BaTiO3 powders is at pH 2.5 and the value of zeta potential is at its maximum near pH 10. The amount of leached barium ion decreases with increasing pH, but the change decreases with increasing initial pH. Adsorption of PAA-NH4 onto the surface of BaTiO3 decreases its zeta potential. Results show that PAA-NH4 adsorption follows Langmuir monolayer adsorption isotherms and the amount of PAA-NH4 required to stabilize nanosized BaTiO3 suspensions decreases as the pH increases. The mechanism of stabilization of BaTiO3 is shown to be electrosteric under the experimental conditions. Good agreement between zeta potential, sedimentation, and rheological tests is found, which identifies an optimum pH value of about 10 and an optimum dispersant concentration of about 2.0 wt%, independent of the solids volume fraction of suspensions.     

Adsorption of polyethyleneimine and polymethacrylic acid onto synthesized hematite

An influence of different functional groups of polymer, its molecular weight, polydispersity ratio (M(w)/M(n)) and presence of impurities on its adsorption in different pH values (3, 6 and 9) onto synthesized hematite (Fe(2)O(3)) was measured. A structure of adsorbed macromolecules of PMA and PEI was obtained according to S-F theory. Two polymers were used: polymethacrylic acid (PMA) of 6500 and 75,100 molecular weight as well as polyethyleneimine (PEI) 25,000 commercial and fractionated. Electrokinetic properties of the interface oxide-polymer solution (surface charge density and zeta potential) were also measured as well as adsorption layer thicknesses (with use of viscosimetric measurements). Obtained data show, that all above-mentioned factors do influence not only the adsorption process itself but also a surface charge, zeta potential and structure of adsorbed polymer layers on polymer/hematite interface.     

Changes of zeta potential and particles size of silica caused by DPPC adsorption and enzyme phospholipase A2 presence

The changes in electrokinetic properties of silica suspensions in the presence of 1,2-dipalmitoyl-sn-glycero-3-phospshocholine (DPPC) were investigated via zeta potential, mean diameter and transmittance determinations. Silica particles were precovered with monolayer (ML) or bilayer (BL) of the phospholopid from chloroform solution (SiO₂/DPPC) or covered by DPPC adsorption from aqueous solution (SiO₂+DPPC). The zeta potential and mean diameter of SiO₂/DPPC suspension were measured as a function of NaCl concentration and due to the phospholipase A₂(PLA₂) action in 10^?3 M NaCl solution and buffer Tris at pH=8 and 9. It was found that the DPPC adsorption onto silica surface decreases its the zeta potential, however the suspensions were stable during the experiment time, probably because of steric stabilization. During PLA₂ enzyme action the changes in zeta potential were observed, which were caused by the hydrolysis products, especially palmitic acid molecules, which also had influence on the stability of these systems.     

Stabilization of superparamagnetic iron oxide nanoclusters in concentrated brine with cross-linked polymer shells

Iron oxide nanoparticles, in the form of sub-100-nm clusters, were synthesized in the presence of poly(acrylic acid) (PAA) or poly(styrene sulfonate-alt-maleic acid) (PSS-alt-MA) to provide electrosteric stabilization. The superparamagnetic nanoclusters were characterized using a superconducting quantum interference device (SQUID), transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA), and zeta potential measurements. To anchor the polymer shell on the nanoparticle surface, the polymer was cross-linked for a range of cross-linking densities. For nanoclusters with only 12% (w/w) PSS-alt-MA, electrosteric stabilization was sufficient even in 8 wt % NaCl. For PAA, the cross-linked polymer shell was essentially permanent and did not desorb even upon dilution of the nanoparticles for iron oxide concentrations down to 0.014 wt %. Without cross-linking, over half of the polymer desorbed from the particle surfaces. This general approach of the adsorption of polymer stabilizers onto nanoparticles followed by cross-linking may be utilized for a wide variety of cross-linkable polymers without the need to form covalent bonds between the nanoparticles and polymer stabilizer. Thus, this cross-linking approach is an efficient and inexpensive method of stabilizing nanoparticles for large-scale applications, including the electromagnetic imaging of subsurface reservoirs, even at high salinity.     

The Dispersion Properties of Precipitated Calcium Carbonate Suspensions Adsorbed with Alkyl Polyglycoside in Aqueous Medium

The zeta potentials and dispersion properties of precipitated calcium carbonate suspensions adsorbed with alkyl polyglycosides in aqueous medium were investigated. Within the investigated pH ranges, the adsorption curves of alkyl polyglycosides on calcium carbonates show sigmoidal shapes, and the zeta potential decreases as the amount of adsorption increases. At positively charged surfaces of low pH, the adsorption amounts were greater than those at negatively charged surfaces, indicating that alkyl polyglycosides were negatively charged in aqueous solutions. At low concentrations of alkyl polyglycosides, the dispersion stabilities of suspensions were very poor and showed no linearity with zeta potentials over the entire range of pHs, which may be attributed to the onset of hydrophobic interaction between particles due to the adsorption of surfactant molecules. This destabilization continued until monolayer coverage by the surfactant layer was complete. Based on the classical DLVO theory, there may be a strong hydrophobic interaction between particles. Beyond monolayer adsorption, the dispersion stability increases, probably by the formation of hemimicelle or admicelle. Therefore, it is believed that ionization of alkyl polyglycosides and admicelles of surfactants on particle surface plays a key role in the stability of dispersions and the abrupt increase in adsorption. Copyright 2000 Academic Press.