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Brownian dynamics simulations (BDS) of sedimentation and irreversible adsorption of colloidal particles on a planar surface were carried out at bulk particle volume fractions (φ) in the range 0.05 to 0.25. The sedimentation and adsorption of colloidal particles were simulated as a non-sequential process that allows simultaneous settling and adsorption of particles. A kinetic model for the formation of particle monolayers based on the available surface fraction (θ(A)) is proposed to predict simulation results. The simulations show a value of 0.625 for the maximum fractional surface coverage (θ(∞)) and a monolayer structure insensitive to φ. However, the kinetic order of the monolayer formation process has a strong dependence with φ, changing from a value close to a unit, at low φ, to a value around two at high φ. This change in the kinetic reaction order is associated to differences of particle adsorption mechanism on the surface. At low φ values, the monolayer formation is achieved by independent adsorption of single particles and the reaction order is close to 1. At high φ values, the simultaneous adsorption of two particles on the surface leads to an increase of the reaction order to values close to 2.
Assuntos
Coloides/química , Modelos Moleculares , Movimento (Física) , Adsorção , Algoritmos , Cinética , Propriedades de SuperfícieRESUMO
We report zeta potential and aggregation kinetics data on colloidal latex particles immersed in water-alcohol media. Zeta potential values show absolute maxima for volume fractions of alcohol of 0.10 and 0.05 for ethanol and 1-propanol, respectively. For methanol, no maximum of the absolute value of the zeta potential was found. Aggregation kinetics was studied by means of a single-cluster optical sizing equipment and for alcohol volume fractions ranging from 0 to 0.1. The aggregation processes are induced by adding different potassium bromide concentrations to the samples. We expected to find a slowdown of the overall aggregation kinetics for ethanol and 1-propanol, and no significant effect for methanol, as compared with pure water data. That is, we expected the zeta potential to govern the overall aggregation rate. However, we obtained a general enhancement of the aggregation kinetics for methanol and 1-propanol and a general slowdown of the aggregation rate for ethanol. In addition, aggregation data under ethanol show a slower kinetics for large electrolyte concentration than that obtained for intermediate electrolyte concentration. We think that these anomalous behaviors are linked to layering, changes in hydrophobicity of particle surfaces due to alcohol adsorption, complex ion-water-alcohol-surface structuring, and competition between alcohol-surface adsorption and alcohol-alcohol clustering.
RESUMO
Colloidal aggregation processes arising at different electrolyte concentrations were studied by means of experiments and confronted with theoretical predictions of different kinetic aggregation models. For this purpose, aqueous dispersions of relatively large polystyrene microspheres were chosen as experimental systems. Aggregation was induced by adding KBr electrolyte to the initially stable particle dispersions. During the aggregation processes, the cluster-size distribution was monitored by means of single cluster light scattering. Analyzing the time evolution of the monomer concentration, we found that the processes arising even at moderate electrolyte concentrations cannot be described by pure time-independent irreversible aggregation models. Hence, alternative models such as time-dependent irreversible aggregation and several reversible aggregation models were also tested. The model that considers a time-dependent sticking probability was found to fit the data quite satisfactorily. Nevertheless, the fitted was so slow that it seems not very likely to find such a behavior in real systems. The aggregation-fragmentation models reported in the literature were unable to reproduce the experimental observations. Hence, a more realistic reversible aggregation model was developed. This model accounts also for reenforced or double bonds between the constituent particles. The corresponding fit improved significantly and reached the same quality as the time-dependent model. Moreover, the obtained fitting parameters were in qualitative agreement with the DLVO predictions and so, reversible aggregation seems to be a more reasonable explanation for the experimental data than time-dependent irreversible aggregation. However, no definite statement on the possible secondary bond fragmentation mechanism may be made since both the applied shear stress in the measuring cell and thermal fluctuations can cause weaker bonds to break.
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The influence of the sticking probability P and the drift velocity on kinetics and structure formation arising in coupled aggregation and sedimentation processes was studied by means of simulations. For this purpose, a large prism with no periodical conditions for the sedimentation direction was considered allowing for sediment formation at the prism base. The time evolution of the cluster size distribution (CSD) and weight-average cluster size (n(w)) were determined in three different regions of the prism. The cluster morphology and the sediment structure were also analyzed. We found that the coupled aggregation and sedimentation processes in the bulk are governed by P for short times, and controlled by the Péclet number Pe for long times. In the lower part of the reaction volume, where the sediment grows, the local n(w) grows at sufficiently large times analytically with an exponent of four. This behavior seems to be independent of Pe and P. The obtained results are in good agreement with the experimental data reported by C. Allain, M. Cloitre, and M. Wafra [Phys. Rev. Lett. 74, 1478 (1995)] and support the idea of a possible internal cluster rearrangement for the experiments. Finally, we discuss how the scale dependent fractal character of the sediment is related to the different stages of the aggregation process.
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Reversible aggregation processes were simulated for systems of freely diffusing sticky particles. Reversibility was introduced by allowing that all bonds in the system may break with a given probability per time interval. In order to describe the kinetics of such aggregation-fragmentation processes, a fragmentation kernel was developed and then used together with the Brownian aggregation kernel for solving the corresponding kinetic master equation. The deduced fragmentation kernel considers a single characteristic lifetime for all bonds and accounts for the cluster morphology by averaging over all possible configurations for clusters of a given size. It became evident that the simulated cluster-size distributions could be described only when an additional fragmentation effectiveness was considered. Doing so, the stochastic solutions were in good agreement with the simulated data.
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The stabilization of antibody-latex complexes at high salt concentration is an event that cannot be explained by the widespread DLVO theory. Adsorption of antibodies on polystyrene latex usually leads to a loss in colloidal stability. However, after the expected particle aggregation induced by an increase in ionic strength, an 'anomalous' restabilization occurs when the electrolyte concentration increases even more. This non-DLVO behaviour can be explained taking into account the hydration forces, which become significant in hydrophilic surfaces. This restabilization has already been observed in different protein latex complexes. In the present work, a study on the stability patterns of polystyrene particles covered independently by mammalian and chicken antibodies has been performed. This study reveals that avian antibodies present a more hydrophobic surface than that of mammalian antibodies. In addition, it has been possible to obtain some information about the molecular orientation of the adsorbed antibodies from the stability experiments. This information has been corroborated by an immunoreactivity study.
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The use of egg yolk antibodies (IgY) instead of IgG from mammalian species may present several advantages in the development of routine diagnostic immunoassays. On the one hand, the animal suffering is reduced, as antibodies are obtained directly from the egg. On the other hand, the use of IgY avoids the rheumatoid factor interference. The rheumatoid factor interacts with IgG molecules in many immunoassays causing false positive results. Despite these advantages, IgY antibodies are scarcely used. As part of an aim to develop a diagnostic test based on IgY-latex agglutination, a preliminary study on some characteristics of the IgY-latex complexes is carried out. In this work, protein adsorption and desorption, isoelectric point, electrokinetic mobility, and colloidal stability are analysed. Results are compared to those obtained by IgG. Interesting differences are observed (which mainly arise from the difference in molecular structure between IgY and IgG), suggesting that IgY is a more hydrophobic molecule than IgG. In addition, colloidal dispersions of IgY-covered latex particles are more stable (at pH 8) than those sensitized by IgG.