Understanding suspension rheology of anisotropically-charged platy minerals from direct interaction force measurement using AFM

Based on the classical DLVO (Derjaguin–Landau–Verwey–Overbeek) theory, the maximum coagulation of fine particle suspensions would be predicated to occur at the point of zero charge (pzc) of the particles. Although this prediction has been fairly accurate for isotropic particles, the mismatch has been frequently reported for suspensions of anisotropically-charged or charge-mosaic particles, such as talc. Followed by successful preparation of sufficiently smooth talc edge surfaces using the ultramicrotome method for the colloidal force measurements using atomic force microscope (AFM), the anisotropic surface charge properties, i.e., surface charge characteristics of basal planes and edge surfaces of talc at different pH values were determined by fitting the measured force profiles between the AFM tip and both basal plane and edge surfaces to the DLVO theory. The talc basal planes were found to carry a permanent negative charge, while the charge on its edge surfaces was highly pH-dependent. The AFM-derived surface (Stern) potential values of talc basal planes and edge surfaces enable us to calculate the interaction energy for various associations between different charge-mosaic surfaces. The attractive interaction between talc basal planes and edge surfaces was found to dominate the rheological behavior. This study clearly demonstrates the necessity of determining anisotropic surface charge characteristics to improve the understanding of rheological properties and hence to better control their process performance.     

Modelling colloid transport in groundwater; the prediction of colloid stability and retention behaviour

The association of contaminants with mobile colloidal particles present in groundwaters has been recognised as a potentially important mass transfer mechanism for contaminant migration in the environment. To predict the fate of environmental contaminants there is a need to develop numerical models which include colloid-mediated transport. The mobility of groundwater colloids is controlled by their stability towards aggregation and attachment to rock surfaces. For inorganic particles, the conceptual framework for predicting their stability and deposition behaviour is provided by the DLVO theory. However, under conditions unfavourable to coagulation or surface attachment (ie. when particles and surfaces are of like charge) there are significant discrepancies between theory and experimentally measured coagulation and deposition rates.Predictive shortcomings of the DLVO theory arise from the simplicity of the original model, which was formulated for smooth bodies with ideal geometries and uniform surface properties. However, surfaces are by nature rough, non-uniform and heterogeneous in composition. In addition, the theory does not consider the dynamics of particle interactions. Furthermore, the presence of additional forces, which may be either attractive or repulsive, acting at short range, which arise from interactions between surfaces and water, are not accounted for. Significant developments have been made to extend and modify the DLVO model to account for the discrepancies between theory and experiment. In this paper the prediction of colloid stability and deposition behaviour under unfavourable conditions is reviewed. Emphasis is placed on the phenomenological behaviour of inorganic colloids in aqueous systems that may need to be accounted for in a transport model.     

Probing surface charge potentials of clay basal planes and edges by direct force measurements

The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8.     

Determination of anisotropic surface characteristics of different phyllosilicates by direct force measurements

To fundamentally understand the electrokinetic behavior of clay minerals, it is necessary to study the anisotropic surface charge properties of clay surfaces. In this study, two 2:1 layer natural minerals, talc and muscovite, were chosen as representatives of magnesium and aluminum phyllosilicate minerals, respectively. The molecularly smooth basal planes of both platy minerals were obtained by cleavage along the basal planes, while suitable edge surfaces were prepared by an ultramicrotome cutting technique. Silicon nitride atomic force microscopy tip was used as a probe to study the interaction forces between the tip and clay basal/edge surfaces in aqueous solutions of various pH values. The measured interaction force profiles between the tip and clay basal/edge surfaces were fitted with the classical DLVO (Derjaguin-Landau-Verwey-Overbeek) theory, which allows direct determination of electrical surface potential of talc and muscovite surfaces. The surface potential of muscovite basal planes was found to be significantly more negative than the basal plane of talc, both being pH insensitive. In contrast, the surface potential of edge surfaces was highly pH-dependent, exhibiting a point of zero charge (PZC) at pH 7.5 and 8.1 for edges of muscovite and talc, respectively. The observed differences in surface potential of basal planes and edge surfaces for both talc and muscovite are closely related to their crystal structure and ionization characteristics. The protonation reactivity and the contribution of each surface group to the surface charging behavior are modeled using their protonation constants.     

Internal and free energy in a pair of like-charged colloids: Monte Carlo simulations

The effective interaction between two colloidal particles in a bath of monovalent co- and counterions is studied by means of lattice Monte Carlo simulations with the primitive model. The internal electrostatic energy as a function of the colloid distance is studied fixing the position of the colloids. The free energy of the whole system is obtained introducing a bias parabolic potential, that allows us to sample efficiently small separations between the colloidal particles. For small charges, both the internal and free energy increase when the colloids approach each other, resulting in an effective repulsion driven by the electrostatic repulsion. When the colloidal charge is large enough, on the other hand, the colloid-ion coupling is strong enough to form double layers. The internal energy in this case decreases upon approaching the colloids because more ions enter the double layer. This attractive contribution to the interaction between the colloids is stronger for larger charges and larger ionic concentrations. However, the total free energy increases due to the loss of ionic entropy, and resulting finally in a repulsive interaction potential driven by the entropic contributions. The loss of ionic entropy can be almost quantitatively reproduced with the ideal contribution, the same level of approximation as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The overall behavior is captured by the DLVO theory qualitatively, and a comparison is made with the functional form predicted by the theory, showing moderate agreement.     

Temperature effect on the stability of bentonite colloids in water

The stability of natural bentonite suspensions has been investigated as a function of temperature at pH 9 and ionic strength 10(-3) M. The sedimentation rate of the particles is directly related to their stability. The sedimentation kinetics was determined by examining the variation of particle concentration in solution with time. The observed kinetics for sedimentation is discussed quantitatively in terms of the potential energy between particles. The zeta-potential of the particles was measured and the DLVO theory was used to calculate attractive and repulsive potentials. Experimental observations are consistent with DLVO model predictions and show that the stability of bentonite colloids increases with temperature. Differences with other colloidal systems can be attributed to the temperature dependence of the surface charge of bentonite particles.     

Effect of ionic sizes on the stability ratio of a dispersion of particles with a charge-regulated surface

The influence of the ionic sizes on the stability of a dispersion of particles, which have an amphoteric, charged-regulated surface, is discussed. A modified Poisson-Boltzmann equation, which takes into account the sizes of ionic species, is adopted to describe the electrical field. An extended DLVO theory, which takes into account the electrical, the van der Waals, and the hydration energies, is used to estimate the stability of a colloidal dispersion. The effects of the key parameters, including ionic strength, pH, and density of surface sites, on the behavior of problem under consideration are examined. The results obtained are qualitatively consistent with experimental findings in the literature.     

Theoretical and experimental comparison of the colloid stability of two polystyrene latexes with different sign and value of the surface charge

 The purpose of this paper is to apply the classical DLVO theory to explain the colloid stability of two model colloids with similar size and different sign and value of the surface charge. For this comparison the hydrodynamic interaction and the presence of hydration forces (extended DLVO theory) have been taken into account. The experimental stability factor and the experimental doublet rate constant in diffusion conditions were compared with those evaluated theoretically. The mathematical treatment permits an easy evaluation and interpretation of the different adjustable parameters such as the Hamaker constant, diffuse layer potential and the hydration layer thickness. The theoretical and experimental comparison shows that the “extended DLVO theory” only permits to explain the stability curves Log[W]/Log[KBr] in a semiquantitative way by using, for the evaluation of the total interaction potential V _T, a value of the Hamaker constant (A) similar to the classical theoretical one for polystyrene particles dispersed in water. In the case of the anionic latex, it was necessary to admit the presence of a hydration layer of a thickness similar to the radius of the hydrated/dehydrated counterion. On the other hand, by using the experimental doublet rate constant in diffusion conditions, we obtain a lower value of the Hamaker constant (A), but within the range of the A values usually found in previous studies. Received: 8 September 1997 Accepted: 8 January 1998     

Electrostatic interactions between double layers: influence of surface roughness, regulation, and chemical heterogeneities

Electrostatic interactions between two surfaces as measured by atomic force microscopy (AFM) are usually analyzed in terms of DLVO theory. The discrepancies often observed between the experimental and theoretical behavior are usually ascribed to the occurrence of chemical regulation processes and/or to the presence of surface chemical or morphological heterogeneities (roughness). In this paper, a two-gradient mean-field lattice analysis is elaborated to quantifying double layer interactions between nonplanar surfaces. It allows for the implementation of the aforementioned sources of deviation from DLVO predictions. Two types of ion-surface interaction ensure the adjustment of charges and potentials upon double layer overlap, i.e., specific ionic adsorption at the surfaces and/or the presence of charge-determining ions for the surfaces considered. Upon double layer overlap, charges and potentials are adjusted via reequilibrium of the different ion adsorption processes. Roughness is modeled by grafting asperities on supporting planar surfaces, with their respective positions, shapes, and chemical properties being assigned at will. Local potential and charge distributions are derived by numerically solving the nonlinear Poisson-Boltzmann equation under the boundary conditions imposed by the surface profiles and regulation mechanism chosen. Finite size of the ions is taken into account. A number of characteristic situations are briefly discussed. It is shown how the surface irregularities are reflected in the Gibbs energy of interaction.     

Role of Cell Surface Lipopolysaccharides in Escherichia coli K12 adhesion and transport

The influence of bacterial surface lipopolysaccharides (LPS) on cell transport and adhesion has been examined by use of three mutants of Escherichia coli K12 with well-characterized LPS of different lengths and molecular composition. Two experimental techniques, a packed-bed column and a radial stagnation point flow system, were employed to investigate bacterial adhesion kinetics onto quartz surfaces over a wide range of solution ionic strengths. Although the two systems capture distinct deposition (adhesion) mechanisms because of their different hydrodynamics, similar deposition kinetics trends were observed for each bacterial strain. Bacterial deposition rates were directly related to the electrostatic double layer interaction between the bacteria and quartz surfaces, in qualitative agreement with classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. However, DLVO theory does not fully explain the deposition behavior for the bacterial strain with the lengthy, uncharged O-antigen portion of the LPS. Neither the length nor the charge characteristics of the LPS molecule directly correlated to deposition kinetics, suggesting a complex combination of cell surface charge heterogeneity and LPS composition controls the bacterial adhesive characteristics. It is further suggested that bacterial deposition behavior is determined by the combined influence of DLVO interactions, LPS-associated chemical interactions, and the hydrodynamics of the deposition system.     

Influence of monovalent ion size on colloidal forces probed by Monte Carlo simulations

The present work studies the role of ionic size in the interactions between the electrical double layers of colloids immersed into electrolyte solutions of monovalent ions. Such interactions are studied by means of Monte Carlo (MC) simulations and the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Despite the omission of the steric effects and some other features of real electrolyte solutions, DLVO theory is known to work qualitatively well for 1:1 electrolyte solutions. However, this affirmation is based on previous tests where an ionic diameter around 0.4 nm was taken for all ionic species. In contrast, some experimental studies suggest that larger hydrated ions should be considered and even specified for each type of ion. In this work, the importance of ionic size is analyzed by applying the primitive model of electrolyte to the intermediate region between a pair of equally charged infinite planar surfaces. The double layer interactions were calculated from the ionic densities at the distance of closest approach to the charged surfaces, this method constitutes an alternative to the traditional calculations at the midplane. Our MC simulations predict the existence of negative net pressures for monovalent electrolytes in the case of zero charge density. In addition, MC simulations reveal some disagreements with theoretical predictions for ionic diameters larger than 0.4 nm. These discrepancies can become significant if surface charge density is large enough due to the restructuration of the double layer. The physical mechanisms for these deviations are also discussed.     

Colloidal stability of sulfonated polystyrene model colloids. Correlation with electrokinetic data

In this work we describe the colloid stability of functionalized latexes: two sulfonated polystyrene model colloids with the same particle size and different surface charge densities. The critical coagulation concentration (ccc) was determined in the presence of two electrolytes (11 and 22), being around 0.75 M and 0.075 M, respectively. By the DLVO theory the electrokinetic and colloid stability data were correlated to calculate the Hamaker constant at both experimental conditions. By comparing the experimental and theoretical values of the Hamaker constant, it is possible to get more information about the colloidal stabilization mechanism of functionalized latexes. In the case of sulfonated latexes, the electrostatic and seric contributions occur, with different influence for each latex depending of their surface electric charge.     

Resolving the coupled effects of hydrodynamics and DLVO forces on colloid attachment in porous media

Transport of colloidal particles in porous media is governed by the rate at which the colloids strike and stick to collector surfaces. Classic filtration theory has considered the influence of system hydrodynamics on determining the rate at which colloids strike collector surfaces, but has neglected the influence of hydrodynamic forces in the calculation of the collision efficiency. Computational simulations based on the sphere-in-cell model were conducted that considered the influence of hydrodynamic and Derjaguin-Landau-Verwey-Overbeek (DLVO) forces on colloid attachment to collectors of various shape and size. Our analysis indicated that hydrodynamic and DLVO forces and collector shape and size significantly influenced the colloid collision efficiency. Colloid attachment was only possible on regions of the collector where the torque from hydrodynamic shear acting on colloids adjacent to collector surfaces was less than the adhesive (DLVO) torque that resists detachment. The fraction of the collector surface area on which attachment was possible increased with solution ionic strength, collector size, and decreasing flow velocity. Simulations demonstrated that quantitative evaluation of colloid transport through porous media will require nontraditional approaches that account for hydrodynamic and DLVO forces as well as collector shape and size.     

On the restabilization of protein-covered latex colloids at high ionic strengths

Recent experiments on restabilization of protein-covered latex colloids at high ionic strengths reported by Lopez-Leon et al.(1) revealed strong specific anion effects. The same authors also emphasized that a recent polarization model, which involves both hydration and double layer forces, can account only for some of their experimental results but are in disagreement with other experimental results. The aim of the present paper is to show that most experimental results of ref 1 can be described, more than qualitatively, when the association equilibria for all the ions (with both the acidic and basic sites of the protein) are taken into account. As the traditional Poisson-Boltzmann approach, the polarization model neglects additional interactions between ions, and ions and surfaces, not included in the "mean field" electrical potential; therefore, a complete quantitative agreement should not be expected. While many of the discrepancies between calculations and experiment occur at low ionic strengths (10(-)(4)-10(-)(2) M), in the range of validity of the traditional DLVO theory, the latter can neither explain them. It is suggested that the structural modifications of the protein configuration induced by the electrolyte are responsible for some of the disagreements between experiment and calculations.     

Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions

The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-electrolytes with different ion sizes.     

Electrocapillary at contact: potential-dependent adhesion between a gold electrode and a mica surface

Using the electrochemical surface forces apparatus, we investigated adhesion (from pull-off measurements) between gold and mica as the potential of the gold surface was changed externally. Measurements were performed at different concentrations of KClO(4) in a potential window where the gold electrode is ideally polarizable. At applied potentials where the gold-mica interactions are repulsive, we obtain double layer forces that are predictable by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloid stability but deviate from the theory at short range. At applied potentials where the gold-mica interactions are attractive, we observed a very strong dependence of adhesion on the applied potential, a result that cannot be directly related to DLVO theory. We show, however, that an approach based on electrocapillary thermodynamics can be employed to model the potential dependence of adhesion seen in our measurements. This electrocapillary approach presents evidence of charging at the gold-mica interface and stresses the relation between the charge within and outside of the contact area.     

Partitioning of clay colloids at air-water interfaces

Colloid sorption onto air-water interfaces in a variety of natural environments has been previously recognized, but better quantification and understanding is still needed. Affinities of clay colloids for the air-water interface were measured using a bubble-column method and reported as partition coefficients (K). Four types of dilute clay suspensions were measured in NaCl solutions under varying pH and ionic strength conditions: kaolinite KGa-1, illite IMt-2, montmorillonite SWy-2, and bentonite. The K values of three types of polystyrene latex particles with different surface-charge properties were also measured for comparison. Kaolinite exhibited extremely high affinity to the air-water interface at pH values below 7. Illite has lower affinity to air-water interfaces than kaolinite, but has similar pH dependence. Na-montmorillonite and bentonite clay were found excluded from the air-water interface at any given pH and ionic strength. Positively and negatively charged latex particles exhibited sorption and exclusion, respectively, at the air-water interface. These results show the importance of electrostatic interactions between the air-water interface and colloids, especially the influence of pH-dependent edge charges, and influence of particle shape.     

巯基聚乙二醇5000修饰的金溶胶的稳定性: 从DLVO稳定到空间稳定

研究了α-甲氧基-ω-巯基聚乙二醇(mPEG-SH, 5000 MW)修饰的金溶胶的稳定性, 初步探讨了其稳定机制. 将线性mPEG-SH通过巯基化学吸附于金溶胶表面, 可形成高分子层包被的金溶胶. 研究结果表明, PEG修饰的金溶胶可以在pH＝1～13.5或盐浓度高达1.20 mol/L的较苛性条件下保持稳定. 这是由于金溶胶表面吸附的高分子保护层为溶胶提供了新的空间稳定, 取代了溶胶原来的DLVO稳定(实质是电荷稳定). 因而, PEG保护的金溶胶在很大程度上克服了DLVO稳定的溶胶对环境敏感、易聚沉的缺点, 能在复杂的条件(如生理条件)下应用. 鉴于PEG的水溶性、无毒性和生物亲和性, 这种具有较高稳定能力的金纳米粒子/PEG复合体结合了金纳米粒子和PEG的优异性能, 可作为生物纳米探针用于复杂条件下的生物分析.     

Heteroaggregation in binary mixtures of oppositely charged colloidal particles

Heteroaggregation (or heterocoagulation) rate constants have been measured in mixtures of well-characterized colloidal particles of opposite charge with multiangle static and dynamic light scattering. This technique permits routine measurements of absolute heteroaggregation rate constants, also in the presence of homoaggregation. Particularly with multiangle dynamic light scattering, one is able to estimate absolute heteroaggregation rate constants accurately in the fast aggregation regime for the first time. Heteroaggregation rate constants have also been measured over a wide range of parameters, for example, ionic strength and different surface charge densities. Amidine latex particles, sulfate latex particles, and silica particles have been used for these experiments, and they were well characterized with respect to their charging and homoaggregation behavior. It was shown that heteroaggregation rate constants of oppositely charged particles increase slowly with decreasing ionic strength, and provided the surface charge is sufficiently large, the rate constant is largely independent of the surface charge. These trends can be well described with DLVO theory without adjustable parameters.