Effect of hydrophilic comonomer and surfactant type on the colloidal stability and size distribution of carboxyl- and amino-functionalized polystyrene particles prepared by miniemulsion polymerization

Carboxyl and amino-functionalized polystyrene latex particles were synthesized by the miniemulsion copolymerization of styrene and acrylic acid or 2-aminoethyl methacrylate hydrochloride (AEMH). The reaction was started by using an oil-soluble initiator, such as 2,2'-azobis(2-methylbutyronitrile) (V-59). The effect of the functional monomer content and type of surfactant (non-ionic versus ionic) on the particle size and particle size distribution was investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). A bimodal particle size distribution was observed for functionalized latex particles prepared in the presence of the non-ionic surfactant (i.e., Lutensol AT-50) when 1 wt % of acrylic acid or 3 wt % of AEMH as a comonomer was employed. The copolymer particle nucleation was studied by using a highly hydrophobic fluorescent dye. From the obtained results, the formation of bimodal particle size distribution may be attributed to a budding-like effect, which takes place during the earlier stage of polymerization and is caused by the additional stabilizing energy originated from the ionic groups of a functional polymer. The reaction mechanism of particle formation in the presence of non-ionic and ionic surfactants has been proposed. The amount of the surface functional groups was determined from polyelectrolyte titration data.     

Preparations of polystyrene/aluminum hydroxide and polystyrene/alumina composite particles in an ionic liquid

Polystyrene (PS)/aluminum hydroxide (Al(OH)(3)) composite particles were successfully prepared by the sol-gel process of aluminum isopropoxide (Al(OPr(i))(3)) in a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) using ammonium hydroxide (NH(4)OH) as a catalyst in the presence of PS seed. Transmission electron microscopy observation of ultrathin cross-sections of the composite particles revealed that the composite particles had a core-shell morphology consisting of a PS core and a Al(OH)(3) shell having high crystallinity. The amount of secondary nucleated Al(OH)(3) could be reduced by dropwise addition of NH(4)OH. Moreover, PS/η-Al(2)O(3) composite particles were successfully prepared by heat treatment of PS/Al(OH)(3) at 300 °C in N(2) atmosphere, which is below the decomposition temperature of PS.     

Effect of ionic strength and protein concentration on the transport of proteins through chitosan/polystyrene sulfonate multilayer membrane

The influence of ionic strength and protein concentration on the transport of bovine serum albumin (BSA), ovalbumin and lysozyme through chitosan (CHI)/polystyrenesulfonate (PSS) multilayers on polyether sulfone supports are investigated under ultrafiltration conditions. The percentage transmission and flux of BSA, ovalbumin and lysozyme were found to increase with increase in salt concentration in the protein. The percentage transmission of BSA through 9 bilayer membrane was found to increase from 5.3 to 115.6 when the salt concentration was varied from 0 to 1 M. It was observed that 0.1 M NaCl in BSA solution is capable of permeating all the BSA. When the salt concentration in BSA was further increased, a negative solute rejection (solute enrichment in permeate) was found to take place. With 9 bilayer membrane, the percentage transmission of ovalbumin was found to increase from 23.3 to 125.8 when the salt concentration in protein was increased from 0 to 0.05 M. The effect of protein concentration on protein transport is studied taking BSA as a model protein. BSA was rejected by the multilayer membrane at all the studied concentrations (0.25, 0.5, 1 and 2 mg/ml). With increase in feed concentration, maximum rejection of protein occurred at higher number of CHI/PSS bilayers. BSA solution flux was found to decrease with an increase in BSA concentration. This study indicates that it is possible to fine tune the transport properties of proteins through multilayer membranes by varying the concentration and ionic strength of protein solutions.     

Electrostatic interactions of colloidal particles at vanishing ionic strength

Electrostatic interactions of colloidal particles are typically screened by mobile ions in the solvent. We measure the forces between isolated pairs of colloidal polymer microspheres as the density of bulk ions vanishes. The ionic strength is controlled by varying the concentration of surfactant (NaAOT) in a nonpolar solvent (hexadecane). While interactions are well-described by the familiar screened-Coulomb form at high surfactant concentrations, they are experimentally indistinguishable from bare Coulomb interactions at low surfactant concentration. Interactions are strongest just above the critical micelle concentration, where particles can obtain high surface potentials without significant screening, kappaa < 1. Exploiting the absence of significant charge renormalization, we are able to construct a simple thermodynamic model capturing the role of reverse micelles in charging the particle surface. These measurements provide novel access to electrostatic forces in the limit where the particle size is much less than the screening length, which is relevant not just to the nonpolar suspensions described here, but also to aqueous suspensions of nanoparticles.     

Effect of salt and surfactant concentration on the structure of polyacrylate gel/surfactant complexes

Small-angle X-ray scattering was used to elucidate the structure of crosslinked polyacrylate gel/dodecyltrimethylammonium bromide complexes equilibrated in solutions of varying concentrations of surfactant and sodium bromide (NaBr). Samples were swollen with no ordering (micelle free), or they were collapsed with either several distinct peaks (cubic Pm3n) or one broad correlation peak (disordered micellar). The main factor determining the structure of the collapsed complexes was found to be the NaBr concentration, with the cubic structure existing up to approximately 150 mM NaBr and above which only the disordered micellar structure was found. Increasing the salt concentration decreases the polyion mediated attractive forces holding the micelles together causing swelling of the gel. At sufficiently high salt concentration the micelle-micelle distance in the gel becomes too large for the cubic structure to be retained, and it melts into a disordered micellar structure. As most samples were above the critical micelle concentration, the bulk of the surfactant was in the form of micelles in the solution and the surfactant concentration thereby had only a minor influence on the structure. However, in the region around 150 mM NaBr, increasing the surfactant concentration, at constant NaBr concentration, was found to change the structure from disordered micellar to ordered cubic and back to disordered again.     

Electrokinetic behavior and colloidal stability of polystyrene latex coated with ionic surfactants

This work is focused on analyzing the electrokinetic behavior and colloidal stability of latex dispersions having different amounts of adsorbed ionic surfactants. The effects of the surface charge sign and value, and the type of ionic surfactant were examined. The analysis of the electrophoretic mobility (mu(e)) versus the electrolyte concentration up to really high amounts of salt, much higher than in usual studies, supports the colloidal stability results. In addition, useful information to understand the adsorption isotherms was obtained by studying mu(e) versus the amount of the adsorbed surfactant. Aggregation studies were carried out using a low-angle light scattering technique. The critical coagulation concentrations (ccc) of the particles were obtained for different surfactant coverage. For latex particles covered by ionic surfactants, the electrostatic repulsion was, in general, the main contribution to the colloidal stability of the system; however, steric effects played an important role in some cases. For latices with not very high colloidal stability, the adsorption of ionic surfactants always improved the colloidal stability of the dispersion above certain coverage, independently of the sign of both, latex and surfactant charge. This was in agreement with higher mobility values. Several theoretical models have been applied to the electrophoretic mobility data in order to obtain different interfacial properties of the complexes (i.e., zeta potential and density charge of the surface charged layer).     

Steric stabilization of spherical colloidal particles: Implicit and explicit solvent

We present the results of Monte Carlo simulations and density functional theory treatment of interactions between spherical colloidal brushes both in implicit (good) solvent and in an explicit polymeric solution. Overall, theory is seen to be in good agreement with simulations. We find that interactions between hard-sphere particles grafted with hard-sphere chains are always repulsive in implicit solvent. The range and steepness of the repulsive interaction is sensitive to the grafting density and the length of the grafted chains. When the brushes are immersed in an explicit solvent of hard-sphere chains, a weak mid-range attraction arises, provided the length of the free chains exceeds that of the grafted chains.     

Effect of colloidal stabilizer on the shape of polystyrene/poly(methyl methacrylate) composite particles prepared in aqueous medium by the solvent evaporation method

Effects of the kind and concentration of stabilizers on the nonspherical shape of polystyrene (PS)/poly(methyl methacrylate) (PMMA) composite particles prepared by release of toluene from PS/PMMA/toluene droplets dispersed in stabilizer aqueous solution were examined. In the case of poly(vinyl alcohol), the surfaces of the obtained particles always had a single dimple. In the case of sodium dodecyl sulfate (SDS), the shapes of the composite particles changed from the dimple, via acorn, to spherical with increasing SDS concentration. It was clarified that the dimple and acorn shapes of the PS/PMMA composite particles were caused by contraction of the PS phase after hardening of the PMMA phase in excentered core-shell and hemisphere morphologies, respectively, which were formed by phase separation during toluene evaporation.     

Effects of substrate constraint on crack pattern formation in thin films of colloidal polystyrene particles

Crack formation and the evolution of stress in drying films of colloidal particles were studied using optical microscopy and a modified cantilever deflection technique, respectively. Drying experiments were performed using polystyrene particles with diameters of 47 ± 10 nm, 100 ± 16 nm, and 274 ± 44 nm that were suspended in water. As the films dried, cracks with a well-defined spacing were observed to form. The crack spacing was found to be independent of the particle size used, but to increase with the film thickness. The characteristic crack spacing was found to vary between 20 and 300 μm for films with thickness values in the range 3-70 μm. Cantilever deflection measurements revealed that the stresses that develop in the film increase with decreasing film thickness (increasing surface-to-volume ratio). The latter observation was interpreted in terms of the effects of a substrate constraint which causes the build up of stresses in the films. This interpretation was confirmed by crack formation experiments that were performed on liquid mercury surfaces in which removal of the substrate constraint prevented crack formation. Experiments were also performed on compliant elastomer surfaces in which the level of constraint was varied by changing the substrate modulus. The cracking length scale was found to increase with decreasing substrate modulus. A simple theory was also developed to describe the substrate modulus dependence of the cracking length scale. These combined experiments and theory provide convincing evidence that substrate constraints are an important factor in driving crack formation in thin colloidal films.     

A facile strategy for controlling the self-assembly of nanocomposite particles based on colloidal steric stabilization theory

A heterocoagulation strategy based on colloidal steric stabilization theory has been developed, through which polystyrene (PS) and silica (SiO(2)) particles without any surface modification or functionalization self-assembled rapidly via solution to afford nanocomposite particles with raspberry-like morphology. The formation mechanism is fully studied on the basis of a thermodynamic analysis. The soluble stabilizer and the solvent quality are the main determining factors, which have a significant influence on this self-assembly process and the silica coverage of resultant composites. The relative size of PS to SiO(2) candidates also has the effect of control on the extent of self-assembly. Furthermore, this strategy can be applied to fabricate a broad range of composite materials, including PS/TiO(2), PS/AgI, as well as PS/PS composites.     

Effect of surfactant on retention behaviors of polystyrene latex particles in sedimentation field-flow fractionation: effective boundary slip model approach

A retention theory in sedimentation field-flow fractionation (SdFFF) was developed by exploiting the effective slip boundary condition (BC) that allows a finite velocity for particles to have at the wall, thereby alleviating the limitations set by the no-slip BC constraint bound to the standard retention theory (SRT). This led to an expression for the retention ratio R as R = (R(o) + v*(b))/(R(o) + v*(b)), where R(o) is the sterically corrected SRT retention ratio and v*(b) is the reduced boundary velocity. Then, v*(b) was modeled as v*(b) = v*(b,o)/[1 + (7K*S(o))(1/2)], where S(o) is the surfactant (FL-70) concentration and K* is the distribution coefficient associated with the langmuirian isotherm of the apparent effective mass against S(o). We applied this to study the surfactant effect on the retention behaviors of polystyrene (PS) latex beads of 170-500 nm in diameter. As a result, an empirical relation was found to hold between v*(b,o) and d(o) (estimated from R(o) at S(o) = 0) as v*(b,o) - v*(o,o)[1 - (d(c)/d(o))], where v*(o,o) is the asymptotic value of v*(b,o) in the vanishing d(c)/d(o) limit and d(c) is the cutoff value at which v*(b,o) would vanish. According to the present approach, the no-slip BC (v*(b,o) = 0) was predicted to recover when d(o) ～ d(c), and the boundary slip effect could be significant for S(o) ≤ 0.05%, particularly for large latex beads.     

Effect of pH on monolayer properties of colloidal silica particles at the air/water interface

Monodisperse colloidal silica particles were prepared by the St?ber method and hydrophobized by grafting a silane coupling agent, octadecyltrimethoxysilane. Two different types of silica particles, i.e., hydrophilic and hydrophobic silica particles were spread at the air/water interface to form the Langmuir monolayers. Monolayer properties of those particles were investigated by measuring surface pressure–area (π–A) isotherms at different subphase pH. At pH above the isoelectric point (IEP) of silica, as pH increased the π–A isotherms for the hydrophobic particles slightly shifted to larger surface area whereas those for the hydrophilic particles showed a reverse trend. At pH below the IEP, the π–A isotherms for both types of particles shifted to much larger surface area with different shapes. In order to analyze the π–A isotherm results further, the time dependence of π was examined. When pH is above the IEP, the π for the hydrophilic particles significantly decreased with increasing time and it did more at higher pH. On the other hand, the decrease in π for the hydrophobic particles was insignificant regardless of pH. For both types of silica particles, the decrease in π was minimal at pH below the IEP. These results were discussed in terms of particle desorption into the water subphase and interparticle electrostatic repulsion which is directly influenced by zeta potential.     

Effects of concentration of nonionic surfactant and molecular weight of polymers on the morphology of anisotropic polystyrene/poly(methyl methacrylate) composite particles prepared by solvent evaporation method

The effects of the concentration of polyoxyethylene octylphenyl ether (OP-10) as a nonionic surfactant and the molecular weight of polymers (polystyrene (PS) and poly(methyl methacrylate) (PMMA)) on the morphology of anisotropic PS/PMMA composite particles were investigated. In the case of polymers with lower molecular weight (M _w ≈ 6.0 × 10⁴ g/mol), the PS/PMMA composite particles have dimple, via acorn, to hemispherical shapes along with the increase of the OP-10 concentration. On the other hand, when the polymers have higher molecular weight (M _w ≈ 3.3 × 10⁵ g/mol), the morphology of PS/PMMA composite particles changed from dimple, via hemispherical, to snowman-like structure while the concentration of OP-10 was increased. Furthermore, thermodynamic analysis was first simply made by spreading coefficients, and the results indicated that both the concentration of OP-10 aqueous solution and the molecular weight of polymers were very important to the final morphology of anisotropic composite particles.     

Effect of electrolytes and surfactant concentration on the interfacial tension of o/w emulsion

Summary The adsorption studies of proteincationic, anionic and non-ionic surfactants and effect of electrolytes on the adsorption of triton 100 and protein mixture on kerosene oil/water interface have been studied. The lowering of interfacial tension is found to depend upon the emulsifier concentration and valency of the ions.     

Effect of pressure on electrophoretic mobility of polystyrene latex particles

A capillary electrophoresis system that can apply arbitrary helium gas pressures at both inlet and outlet reservoirs was constructed. The system was used to investigate the effect of pressure on electrophoretic behavior of polystyrene latex particles. The electrophoretic mobility of latex particles was increased with the application of pressure (< 3.0 kgf/cm2). The shrinkage of particle diameter under pressurization was observed using a microscope, however, the magnitude of shrinkage was not enough to explain the increase in electrophoretic mobility. Therefore, the application of pressure might increase the electric charge of the latex particle. Since methanol inhibited the enhancement in the electrophoretic mobility of the latex particles, water might play an important role in increasing mobility.     

Effect of surfactant concentration on the critical thicknesses of liquid films

Summary It is shown that an increase in surfactant concentration at first causes the critical thicknesses of rupture on microscopic films to decrease but gradually a nearly constant value is reached. With films of aqueous solutions of fatty acids (valeric, caproic, caprylic and capric acids), this dependence correlates well with the effect of the surfactant concentration on the damping of capillary waves. With surfactants of the detergent type (OPE-7, OPE-20) in addition to the change of the critical thickness, the transition from rupture to formation of black spots is described, as the surfactant concentration exceedsC _bl. The remarkable fact in the latter case is the independence of the critical thickness of the final state, be it rupture or formation of first or second black films.On the basis of the experimental data the assumption is put forward that the critical thickness of rupture or the critical thickness of formation of black spots is substantially affected by macroscopic non-uniformities in the film thickness. Thus the conclusion is reached that the critical thickness of an ideally plane parallel film which is the object of the theory, must be obtained by extrapolation of the measured value toward extremely small radii.

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Zusammenfassung Es wird gezeigt, daß die kritischen Zerreißdicken mikroskopischer Schaumfilme, die mit der Zunahme der Tensidkonzentration zunächst abnehmen, dann aber ungefähr konstante Werte erreichen. Diese Abhängigkeit ist in guter Übereinstimmungmitdem Einfluß des Tensides auf die Kapillarwellendämpfung in wäßrigen Lösungen von vier Fettsäuren. Bei Tensiden, die gute Schäumer sind (OPE-7, OPE-2) zerreißt der Film mit der Zunahme der Konzentration überC _bl nicht, sondern es bilden sich schwarze Flecke. Es ist sehr interessant, daß die kritische Dicke unabhängig von dem Endzustand (Zerreißen oder Bildung schwarzer Flecke) ist.Aufgrund dieser Experimente wird angenommen, daß die kritische Dicke bei dem Zerreißen oder bei der schwarzen Fleckebildung mikroskopischer Schaumfilme wesentlich von den makroskopischen Ungleichheiten der Filmdicke beeinflußt wird. Daraus wird gefolgert, daß die kritische Dicke eines idealen planparallelen Films durcheine Extrapolation der Meßwerte aufeinen unendlich dünnen Film ermittelt werden kann.

     

Direct measurements of the effects of salt and surfactant on interaction forces between colloidal particles at water-oil interfaces

The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and the surfactant sodium dodecyl sulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain a reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover, the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of three-body interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.     

Fabrication of large scale two-dimensional colloidal crystal of polystyrene particles by an interfacial self-ordering process

Monolayer films of hexagonal close-packed polystyrene (PS) spheres were formed at the air-water interface through a self-ordering process without using Langmuir trough. The contact angle of PS particles on the surface of water was determined by an interfacial swelling method. It was found that the concentration and the nature of surfactant had an obvious influence on the arrangement of PS particles. PS suspension containing Triton X 100 (TX 100) of an appropriate concentration self-assembled into a closely packed monolayer on the surface of water. Sodium dodecyl sulfonate, an anionic surfactant, had a relative weak influence on the arrangement of pre-dried PS particles, in contrast, had an obvious effect on newly synthesized PS particles. Quantitative ultraviolet-visible (UV-vis) absorption spectrometry indicated that about 3% of the added TX 100 was adsorbed on the PS particle surface. Laser diffraction patterns on the monolayer film were used to investigate the lattice orientation. Ultraviolet-visible-near infrared (UV-vis-NIR) spectra of monolayer films of different sized PS particles displayed that the method presented here was universal for preparation of two-dimensional (2D) colloidal crystals.