Controlled aggregation of colloidal particles for toner applications

Micrometer‐sized particles were formed by controlled aggregation of carboxylated polystyrene colloidal spheres having a mean diameter of about 200 nm with a commercial cationic coagulant. To identify the parameters governing the size and structure of the aggregates, the aggregate size distribution was studied over a period of time with dynamic light scattering. The effect of the particle concentration, pH, and ionic strength on the aggregation behavior was investigated. The coagulant concentration used for present studies was 5 parts per hundred on the basis of the polystyrene particles and the particle concentrations used were 10–15%. The particle size distribution for the latex suspensions was also investigated with a 10% aluminum sulfate [Al₂(SO4)₃·14H₂O] solution as a model coagulant. With the commercial coagulant, aggregation was found to be slower at lower pH than at neutral pH. At pH 6, the particles started to aggregate within minutes and form aggregates of about 1000 nm. We expected that lowering the pH would reduce interparticle repulsive forces and enhance the collision efficiency. However, at a lower pH of 2, the aggregation process slowed down. Increasing the ionic strength at neutral pH led to a broader aggregate size distribution, and the population of larger aggregates increased. The suspensions with the model coagulant showed similar behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological behaviour of cement and silica suspensions: Particle aggregation modelling

Cement and silica suspension rheological behaviour is modelled by supposing that particle aggregation occurs. With two independent parameters, the variation of the shear viscosity as a function of the shear rate for cement or silica suspensions having different solid volume fractions can be predicted. The model is in good agreement with experimental data. Cement suspensions are initially very similar to unreactive silica suspensions. The values of adhesion forces obtained seem to show that the effective interaction areas are very small. It reflects the fact that in the dormant period the particles are contacting at points, which become progressively higher in surface as C-S-H precipitates at these contacts. The model used is consistent with the observed power law variation of static and dynamic yield stresses with solid volume fraction. The aggregates formed under shear seem to be very compact, which is presumably related to the large solid volume fractions of the studied suspensions.     

Assembly of alumina particles in aqueous suspensions induced by high-frequency AC electric field

The role of high-frequency alternating current (AC) electric field in the assembly of alumina particles in aqueous media was investigated. Field–particle interactions were in situ investigated for coarse and fine powder particles in very dilute suspensions. For both coarse and fine particles, AC field-induced assembly led to the formation of chains of particles within a minute, which were aligned in the field direction. However, a much finer network of particle chains evolved in fine particle suspensions. Threshold field strength for chain formation was also lower for fine particles (28 V/mm) than for coarse particles (50 V/mm), suggesting stronger interactions for finer particles. Chain length increased with both field strength and field duration. Chain formation was attributed to mutual dielectrophoretic (DEP) interaction forces. Increase in DEP forces with field strength resulted in enhanced interactions. For finer particles, decreasing interparticle distance might have favored stronger interactions. Suspension microstructure was disrupted as soon as the field was removed. However, higher field duration was associated with an improved pattern stability and retention following the field removal. Finally, particle motion was studied in deliberately applied spatially nonuniform AC field, which revealed different mechanisms of chain formation for coarse (negative-DEP) and fine (positive-DEP) particles.     

Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles

Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles were investigated. The state of dispersion was evaluated in terms of zeta potential, apparent viscosity and the mean particle size of solid phase in the solution. Zeta potential, apparent viscosity and the mean particle size as a function of pH were performed in absence of dispersant. The result showed that electrostatic stabilization of the aqueous suspension of barite nanoparticles can be accomplished in low acidic and high basic range of pH. In presence of sodium polyacrylate (PAA-Na) dispersant, the isoelectric point (IEP) of the barite nanoparticles was shifted to lower pH and the negative zeta potential was increased in a large range of pH above the (IEP). The optimum amount of PAA-Na dispersant is discussed in the light of zeta potential and viscosity. It is found that the adsorption of PAA is correlated to the net surface charge of the barite nanoparticles and the fraction of dissociated polymer at pH 4, 8.5 and 10. At pH 4, the state of dispersion was achieved at higher amount of electrolyte due to the low fraction of negatively charged dissociated polymer and the positively charge particles. At basic pH, the fraction of dissociated polymer was high and the surface charge of particle was highly negative, therefore, the lowest viscosity was obtained at a small amount of PAA. In addition, the optimum amount of polymer decreased with the increase in pH of the suspension.     

Effect of Volume Fraction on Transient Structural Behavior of Aerosol Particles Using Off-Lattice Kinetic Monte Carlo Simulation

Fractal-like aggregates exhibit interesting properties that determine their physicochemical advantages, and thus, the control and prediction of aggregation is critical for many applications. An off-lattice kinetic Monte Carlo (KMC) simulation was performed to investigate the aggregate evolution from primary particles to three-dimensional fractal aggregates, at three different volume fractions. We have found that at low volume fraction, aggregation kinetics is slow, and aggregate morphology is widely open and stringy, with fractal dimension of (D_f) 1.8, in which the system is constantly preserved in the dilute regime. In denser volume fractions, however, the aggregation kinetics appears to be accelerated and aggregate morphology is more compact and less stringy due to the transition from dilute to dense regimes. Moreover, the volume fractions determine what kind of coagulation mechanism may occur to produce aggregates with different morphologies. At low volume fraction, coagulation is predominated by coagulation between aggregates in which the maximum probability of interpenetration event is only 18%. This suggests that aggregates at low volume fraction can maintain their self-similarity behavior. While at high volume fraction, coagulation is predominated by two subsequent coagulation mechanisms, namely, primary particle–aggregate and aggregate–aggregate interaction. The probability of interpenetration event increases up to 40%. In addition, the interpenetration process as well as the primary particle–aggregate coagulation, particularly in the dense regime, could produce superaggregates with a hybrid structure with a high fractal dimension at large size scales and a low fractal dimension at small scales. A detail mechanism for the formation of superaggregates was discussed.

Copyright © 2015 American Association for Aerosol Research     

Aggregate structure and effect of phthalic anhydride‐modified soy protein on the mechanical properties of styrene‐butadiene copolymer

The aggregate structure of phthalic anhydride (PA) modified soy protein isolate (SPI) was investigated by estimating its fractal dimension from the equilibrated dynamic strain sweep experiments. The estimated fractal dimensions of the filler aggregates were less than 2, indicating that these particle aggregates have a distorted or broken two‐dimensional sheet‐like structure. The results also indicated that the aggregate structure has a greater effect on the composite reinforcement than the overall aggregate size. Tensile strength, elongation, Young's modulus, and toughness of hydrolyzed/modified soy composites are comparable with those of carbon black reinforced composites at 10–15% filler fraction. The moduli of PA‐modified SPI composites were less sensitive to the pH of the composite preparation compared to the unmodified SPI. The composites prepared at acidic pH, with lower filler fraction, or filled with hydrolyzed/modified SPI are more elastic and less fatigue. The composites of PA‐modified SPI had better recovery properties when prepared at acidic instead of alkali pH. PA‐modified hydrolyzed SPI composites prepared at acidic pH showed a similar recovery property to that of carbon black reinforced composites, but with greater shear elastic moduli. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Monte Carlo simulation of the diffusion-limited aggregating process of particle suspension systems

The aggregating process of particle suspension systems is a very universal phenomena and crucial for various processes both in nature and in industry. In this paper, the aggregating process was simulated with offlattice diffusion-limited cluster-cluster aggregation (DLCA) Monte Carlo programs. The self-similar fractal structures of aggregates have been clearly demonstrated by the statistical analysis of gyration radius distribution and the existence of a scaling distribution of the reduced cluster size. The fractal dimension determined from the relationship between mass and gyration radius of aggregates was 1.80 or so. The fractal dimension of the aggregates drawn from the radial distribution function and structure factor of a single aggregate is about 1.90–2.10. It was also showed that, along with the increasing of particle volume fraction, the fractal dimension will increase in a nearly square root manner, and the spatial range of the fractal structure appearing becomes narrower. Also, the gelation transition can only occur in a particle suspension system where the particle volume fraction is greater than a critical value.     

Monte Carlo simulation of the diffusion-limited aggregating process of particle suspension systems

The aggregating process of particle suspension systems is a very universal phenomena and crucial for various processes both in nature and in industry. In this paper, the aggregating process was simulated with off-lattice diffusion-limited cluster-cluster aggregation (DLCA) Monte Carlo programs. The self-similar fractal structures of aggregates have been clearly demonstrated by the statistical analysis of gyration radius distribution and the existence of a scaling distribution of the reduced cluster size. The fractal dimension determined from the relationship between mass and gyration radius of aggregates was 1.80 or so. The fractal dimension of the aggregates drawn from the radial distribution function and structure factor of a single aggregate is about 1.90–2.10. It was also showed that, along with the increasing of particle volume fraction, the fractal dimension will increase in a nearly square root manner, and the spatial range of the fractal structure appearing becomes narrower. Also, the gelation transition can only occur in a particle suspension system where the particle volume fraction is greater than a critical value.     

Effect of volume fraction and particle size on wall slip in flow of polymeric suspensions

For especially highly concentrated suspensions, slip at the wall is the controlling phenomenon of their rheological behavior. Upon correction for slip at the wall, concentrated suspensions were observed to have non‐Newtonian behavior. In this study, to determine the true rheological behavior of model concentrated suspensions, “multiple gap separation method” was applied using a parallel‐disk rheometer. The model suspensions studied were polymethyl methacrylate particles having average particle sizes, in the range of 37–231 μm, in hydroxyl terminated polybutadiene. The effects of particle size and solid particle volume fraction on the wall slip and the true viscosity of model concentrated suspensions were investigated. It is observed that, as the volume fraction of particles increased, the wall slip velocity and the viscosity corrected for slip effects also increased. In addition, for model suspensions in which the solid volume fraction was ≥81% of the maximum packing fraction, non‐Newtonian behavior was observed upon wall slip correction. On the other hand, as the particle size increased, the wall slip velocity was observed to increase and the true viscosity was observed to decrease. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 439–448, 2005     

Continuous particle separation with localized AC-dielectrophoresis using embedded electrodes and an insulating hurdle

This paper reports a microfluidics-based lab-on-a-chip device combining the alternating current (AC) dielectrophoresis (DEP) and pressure-driven flow for separation of particle/cell mixtures. The dielectrophoretic separation is achieved by a hybrid design using a PDMS (poly-dimethylsiloxane) hurdle and a pair of embedded metal electrodes to generate localized non-uniform AC electric field. Since the particles and the cells are transported through the small DEP separation region, the negative effects associated with the Joule heating and exposure to the electric field have been significantly reduced. Mixtures of polystyrene particles of different sizes and yeast cells with polystyrene particles were successfully separated at AC electric field of 200 kHz.     

Preparation of high pure α-Al2O3 nanoparticles at low temperatures using Pechini method

A Pechini process was successfully used to synthesize alpha-alumina (98.95% mass fraction) at relatively low calcination temperature (925 °C). The synthesis of these nanoparticles was carried out using a polymer prepared from citric acid and ethylene glycol by the melt blending method. This polymer worked as a chelating agent for aluminum cations. The final products were produced after a dual-stages thermal treatment. The resulting α-alumina consisted of nanoparticles of 8–16 nm in diameters with a surface area (～8 m² g^?1). The mass fraction of α-alumina was dependent on the concentration of aluminum salt and polymer precursor's solutions, while the surface area of the final product was dependent on the mass fraction of θ-alumina.     

碳酸钙悬浮液混凝处理后的流变性

应用LVDV-Ⅲ+型可编程流变仪测定了微米级碳酸钙悬浮液混凝处理后的流变特性,考察因素包括悬浮液固相质量浓度、pH值、混凝剂种类及添加量、搅拌速度.结果表明,混聚后碳酸钙悬浮液在测定范围内流变曲线符合Herschel-Bulkley模型.表观粘度随颗粒浓度的增大而增大,其中屈服应力随体系浓度的增大而增大,刚性系数随体系...     

Aggregate structures formed via a bridging flocculation mechanism

A high molecular weight cationic polyelectrolyte has been used to flocculate a colloidal dispersion of anionic polystyrene latex particles. The polymer used had a high charge density and the flocculation occurred at a solution pH where both the polymer and the particles were fully charged. Under these conditions, flocculation is expected to occur through a bridging flocculation mechanism. Low angle laser light scattering has been used to follow the flocculation process as a function of time; parameters of interest were the aggregate sizes, size distributions, and aggregate mass fractal dimensions. The light scattering measurements showed that the flocs formed had a mass fractal character. All the systems examined here were overdosed with respect to the optimum flocculation concentration of polymer. Under these conditions, decreasing the polymer concentration was seen to result in an increased flocculation efficiency. A secondary growth process was also observed whereby initially formed fractal aggregates can subsequently aggregate again. These larger aggregates are also expected to be mass fractals although this cannot be determined from the light scattering measurements due to the superposition of Fraunhofer diffraction effects. This type of fractal-in-fractal character is unusual.     

Mechanics and Microstructures of Concentrated Particle Gels

It is often assumed that the viscoelastic properties of dense colloids are determined by the colloid volume fraction, the interaction potential, as well as the particle size distribution and shape. The dependence of the viscoelastic behavior of particle suspensions and gels on these parameters has been widely studied, and is well understood in many cases. In contrast, our knowledge on the influence of microstructure on mechanical and rheological properties, in particular for high solid loading suspensions as used in ceramic processing, is much less developed. This aspect has been the focus of recent experiments, which show that small changes in microstructure can have dramatic effects on the mechanics and dynamics of concentrated colloidal gels. In this article, we attempt to give an overview of the influence of microstructure on the mechanical and rheological properties of colloidal systems. Particular attention is given to colloidal particle gels at high volume fractions.     

On the preparation of organosilanized silicon carbide aqueous suspension

The functionalization of ceramic nanoparticles with organosilanes is commonly employed to improve the surface adhesion mechanism for specific applications, especially in polymer composites. However, this surface modification changes the behavior of the nanoparticles in suspension, which is important for applications that require preparation involving aqueous medium. In the present study the influence of organosilanization on the size and stability of SiC particles in aqueous medium was evaluated. Initially, SiC particles were organofunctionalized using (3-aminopropyl) triethoxysilane through two different reaction routes (SiC_{Sil I} and SiC_{Sil II}). XPS spectroscopy of solid particles showed higher content of nitrogen atoms arising from the organosilanization reaction in the SiC_{Sil II}, prepared in ethanol. Compared to the unmodified SiC aqueous suspension, the organosilanized SiC aqueous suspensions presented much higher particle sizes, with the largest particle size distribution, assigned mainly to the organosilanization of SiC agglomerates. Subsequently, polyethylenimine (PEI) was tested as a dispersant for the aqueous suspensions, aiming to increase the repulsion forces among the particles and induce their de-agglomeration. The addition of PEI to SiC and SiC_{Sil II} particle aqueous suspensions resulted in a drastic reduction in the particle size (up to 40% (D50) at pH 5.5) and narrowest particle size distribution over a wide pH range. This fact was attributed to the PEI electrosteric effect on aqueous suspensions containing SiC or SiC_{Sil II}, which was supported by dynamic laser scattering and zeta potential results.     

Ultrasonic Dispersion of TiO2 Nanoparticles in Aqueous Suspension

Aggregation and dispersion behavior of nanometer and submicrometer scale TiO₂ particles in aqueous suspension were investigated using three kinds of mechanical dispersion methods: ultrasonic irradiation, milling with 5-mm-diameter balls, and milling with 50 μm beads. Polyacrylic acids with molecular weights ranging from 1200 to 30 000 g/mol were used as a dispersant, and the molecular weight for each dispersion condition was optimized. Viscosities and aggregate sizes of the submicrometer powder suspensions were not appreciably changed in the ultrasonic irradiation and 5-mm-ball milling trials. In contrast, in the trials in which nanoparticle suspension was used, ultrasonic irradiation produced better results than 5-mm-ball milling. Use of ultrasonication enabled dispersion of aggregates to primary particle sizes, which was determined based on the specific surface area of the starting TiO₂ powders, even for relatively high solid content suspensions of up to 15 vol%. Fifty-micrometer-bead milling was also able to disperse aggregates to the same sizes as the ultrasonic irradiation method, but 50-μm-bead milling can be used only in relatively low solid content suspensions. It was concluded that the ultrasonic dispersion method was a useful way to prepare concentrated and highly dispersed nanoparticle suspensions.     

Influence of aggregate size and volume fraction on shrinkage induced micro-cracking of concrete and mortar

In this paper, the influence of aggregate size and volume fraction on shrinkage induced micro-cracking and permeability of concrete and mortar was investigated. Nonlinear finite element analyses of model concrete and mortar specimens with regular and random aggregate arrangements were performed. The aggregate diameter was varied between 2 and 16 mm. Furthermore, a range of volume fractions between 0.1 and 0.5 was studied. The nonlinear analyses were based on a 2D lattice approach in which aggregates were simplified as monosized cylindrical inclusions. The analysis results were interpreted by means of crack length, crack width and change of permeability. The results show that increasing aggregate diameter (at equal volume fraction) and decreasing volume fraction (at equal aggregate diameter) increase crack width and consequently greatly increases permeability.     

Effects of aggregate size and angularity on alkali-silica reaction

The effects of reactive aggregate size and aggregate angularity on alkali-silica reaction (ASR) were studied. An all-in natural reactive aggregate was used. The coarse aggregate particles were crushed to obtain crushed fine particles. The angularity of the aggregate was determined using ASTM C1252 and EN 933-6 methods. ASTM C1260 accelerated mortar bar test was conducted to compare the ASR expansion caused by various aggregate size fractions. The effect of the size of the particles on ASR expansion was studied by replacing each size fraction of the non-reactive aggregate with the reactive aggregate of the same size. In spite of similarity of the chemical and mineralogical compositions, the crushed aggregate caused higher ASR expansion than the natural aggregate in all size fractions. The summation of the expansions of individual reactive size fractions of both aggregates was found to be higher than that of corresponding control mixtures.     

Controlled mesoporous film formation from the deposition of electrosprayed nanoparticles

Thin films of controlled morphology were fabricated by electrospray drying a colloidal nanoparticle suspension using a conductive and volatile solvent and impacting the nanoparticles on a substrate. Three parameters were used for control: impact velocity, size of the nanoparticles or nanoparticle agglomerates, and solvent volatility. The impact velocity was controlled by charging nanoparticles through electrospray dispersion and varying the electric field driving the particle impaction. It was found that the structure is governed by the relative importance of charged particle drift imposed by the external electric field and the thermal velocity due to Brownian motion. Peclet number correlates with the morphology of the deposit where columnar structures result from high Pe, corresponding to ballistic deposition and porous, fractal-like structures result from small Pe. These patterns match predictions based on Monte Carlo simulations in the literature. For dispersions with higher nanoparticle concentrations, droplet evaporation causes densification of the particle ensemble to form a spherical aggregate that deposits in a predominantly ballistic manner, with smaller aggregates forming denser films. If the droplet evaporation lifetime is altered for the aggregates to be partially wet upon impacting the substrate, the subsequent rapid evaporation of the remaining solvent on the substrate leads to formation of films with high interconnectivity. Films formed by the electrospray technique have large-scale uniformity and their structure is independent of thickness. The interpretation of the observed morphologies in terms of Peclet number and Damkhöler number provides a conceptual framework for a rational design of film structures as required by many applications.

Copyright © 2017 American Association for Aerosol Research