Influence of humic acid on the aggregation kinetics of fullerene (C60) nanoparticles in monovalent and divalent electrolyte solutions

The early stage aggregation kinetics of fullerene C60 nanoparticles were investigated in the presence of Suwannee River humic acid and common monovalent and divalent electrolytes through time-resolved dynamic light scattering (DLS). In the absence of humic acid, the aggregation behavior of the fullerene nanoparticles in the presence of NaCl, MgCl2, and CaCl2 was found to be consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability. In the presence of humic acid and NaCl or MgCl2 electrolytes, the adsorbed humic acid on the fullerene nanoparticles led to steric repulsion, which effectively stabilized the nanoparticle suspension. This behavior manifested in a dramatic drop in the rate of aggregation, an increase in the critical coagulation concentration (CCC), and an attained value of less than unity for the inverse stability ratio (or attachment efficiency) at high MgCl2 concentrations. While the increase in the nanoparticle stability was similarly observed in the presence of humic acid at low CaCl2 concentrations, enhanced aggregation occurred at higher CaCl2 concentrations. Measurement of scattered light intensities over time indicated significant aggregation of the humic acid macromolecules in solutions of high CaCl2 concentrations. Transmission electron microscopy (TEM) imaging of the fullerene aggregate structures in the presence of humic acid revealed that bridging of the fullerene nanoparticles and aggregates by the humic acid aggregates is the likely mechanism for the enhanced aggregation at high CaCl2 concentrations.     

Kinetic determination of critical coagulation concentrations for sodium- and calcium-montmorillonite colloids in NaCl and CaCl2 aqueous solutions

The stability of the sodium and calcium forms of montmorillonite was studied at different NaCl and CaCl2 concentrations. The aggregation kinetics was determined from the decrease in particle concentration with time at different electrolyte concentrations. The DLVO theory defines the critical coagulation concentration (CCC) value as the electrolyte concentration that balances the attractive and repulsive potential energies between the particles, making aggregation diffusion-controlled. Therefore CCC values were obtained by extrapolation of the aggregation rate constants measured as a function of ionic strength to conditions where the rate constant value is determined by diffusion only. When the electrolyte was CaCl2, the CCC value was found to be approximately two orders of magnitude lower than the CCC values obtained using NaCl as electrolyte.     

Aggregation kinetics and dissolution of coated silver nanoparticles

Determining the fate of manufactured nanomaterials in the environment is contingent upon understanding how stabilizing agents influence the stability of nanoparticles in aqueous systems. In this study, the aggregation and dissolution tendencies of uncoated silver nanoparticles and the same particles coated with three common coating agents, trisodium citrate, sodium dodecyl sulfate (SDS), and Tween 80 (Tween), were evaluated. Early stage aggregation kinetics of the uncoated and coated silver nanoparticles were assessed by dynamic light scattering over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations that span those observed in natural waters. Although particle dissolution was observed, aggregation of all particle types was still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The aggregation of citrate-coated particles and SDS-coated particles were very similar to that for the uncoated particles, as the critical coagulation concentrations (CCC) of the particles in different electrolytes were all approximately the same (40 mM NaCl, 30 mM NaNO(3), and 2 mM CaCl(2)). The Tween-stabilized particles were significantly more stable than the other particles, however, and in NaNO(3) aggregation was not observed up to an electrolyte concentration of 1 M. Differences in the rate of aggregation under diffusion-limited aggregation conditions at high electrolyte concentrations for the SDS and Tween-coated particles, in combination with the moderation of their electrophoretic mobilities, suggest SDS and Tween imparted steric interactions to the particles. The dissolution of the silver nanoparticles was inhibited by the SDS and Tween coatings, but not by the citrate coating, and in chloride-containing electrolytes a secondary precipitate of AgCl was observed bridging the individual particles. These results indicate that coating agents could significant influence the fate of silver nanoparticles in aquatic systems, and in some cases these stabilizers may completely prevent particle aggregation.     

Aggregation and deposition behavior of boron nanoparticles in porous media

New kinds of solid fuels and propellants comprised of nanomaterials are making their way into civilian and military applications yet the impact of their release on the environment remains largely unknown. One such material is nano boron, a promising solid fuel and propellant. The fate and transport of nano boron under various aquatic systems was investigated in aggregation and deposition experiments. Column experiments were performed to examine the effects of electrolyte concentration and flow velocity on the transport of boron nanoparticles under saturated conditions, whereas aggregation tests were conducted to assess the effects of electrolytes on the aggregation of the boron nanoparticles. Aggregation tests indicated the presence of different reaction-controlled and diffusion-controlled regimes and yielded critical coagulation concentrations (CCC) of 200 mM, 0.7 mM and 1.5 mM for NaCl, CaCl(2), and MgCl(2), respectively. Aggregation and deposition experimental data corresponded with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) model and the constant attachment efficiency filtration model, respectively. Theoretical calculations indicated that both the primary and secondary energy minima play important roles in the deposition of nano boron in sand columns.     

Enhanced aggregation of alginate-coated iron oxide (hematite) nanoparticles in the presence of calcium, strontium, and barium cations

Early-stage aggregation kinetics studies of alginate-coated hematite nanoparticles in solutions containing alkaline-earth metal cations revealed enhanced aggregation rates in the presence of Ca2+, Sr2+, and Ba2+, but not with Mg2+. Transmission electron microscopy (TEM) imaging of the aggregates provided evidence that alginate gel formation was essential for enhanced aggregation to occur. Dynamic light scattering (DLS) aggregation results clearly indicated that a much lower concentration of Ba2+ compared to Ca2+ and Sr2+ was required to achieve a similar degree of enhanced aggregation in each system. To elucidate the relationship between the alginate's affinities for divalent cations and the enhanced aggregation of the alginate-coated hematite nanoparticles, atomic force microscopy (AFM) was employed to probe the interaction forces between alginate-coated hematite surfaces under the solution chemistries used for the aggregation study. Maximum adhesion forces, maximum pull-off distances, and the work of adhesion were used as indicators to gauge the alginate's affinity for the divalent cations and the resulting attractive interactions between alginate-coated hematite nanoparticles. The results showed that alginate had higher affinity for Ba2+ than either Sr2+ or Ca2+. This same trend was consistent with the cation concentrations required for comparable enhanced aggregation kinetics, suggesting that the rate of alginate gel formation controls the enhanced aggregation kinetics. An aggregation mechanism incorporating the gelation of alginate is proposed to explain the accelerated aggregate growth in the presence of Ca2+, Sr2+, and Ba2+.     

Effect of natural organic matter on aggregation behavior of C60 fullerene in water

The stability of C(60) fullerene particles in water affects its mobility, bioavailability, and toxicity to organisms. Natural organic matters (NOMs) have pronounced effects on the aggregation behavior of C(60) fullerene. This study was to examine the effects of NOM structural properties on the aggregation behavior of fullerene water suspension (FWS). Fulvic acid (FA), tannic acid (TA), and two structurally different humic acids (HA1 and HA7) were studied. HA1 and HA7 were sequentially extracted HAs, where HA7 was more hydrophobic than HA1 and had a higher molecular weight. Aggregation was induced by addition of varying amounts of Ca(2+) to the FWS with 2 mg/L of each NOM. The absolute value of zeta potential |ζ| of pure FWS increased after addition of any type of NOM. Addition of Ca(2+) to the FWS+NOM system decreased |ζ| of fullerene almost uniformly for all types of NOM. FWS critical coagulation concentration (CCC) was equal to 14.5, 6.5, 5.4, and 3.7 mM Ca(2+) for HA7, HA1, FA, and TA, respectively. The order of increasing CCCs was positively correlated to the NOMs molecular weight and negatively to their polarity. A nearly constant ζ for FWS+NOM system at a wide range of Ca(2+) concentrations suggested the steric stability rather than electrostatic one. This study highlighted the role of NOM in the fate of manufactured nanoparticles in the environment and linked the structural properties of NOM to their interaction with manufactured nanoparticles.     

Dissolution-accompanied aggregation kinetics of silver nanoparticles

Bare silver nanoparticles with diameters of 82 ± 1.3 nm were synthesized by the reduction of the Ag(NH(3))(2)(+) complex with D-maltose, and their morphology, crystalline structure, UV-vis spectrum, and electrophoretic mobilities were determined. Dynamic light scattering was employed to assess early stage aggregation kinetics by measuring the change in the average hydrodynamic diameter of the nanoparticles with time over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations. From this the critical coagulation concentration values were identified as 30, 40, and 2 mM for NaNO(3), NaCl, and CaCl(2), respectively. Although the silver nanoparticles were observed to dissolve in all three electrolyte solutions, the aggregation results were still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The dissolution of the silver nanoparticles, which were coated with a layer of Ag(2)O, was highly dependent on the electrolyte type and concentration. In systems with Cl(-) a secondary precipitate, likely AgCl, also formed and produced a coating layer that incorporated the silver nanoparticles. Aggregation of the silver nanoparticles was also examined in the presence of Nordic aquatic fulvic acid and was little changed compared to that evaluated under identical fulvic acid-free conditions. These results provide a fundamental basis for further studies evaluating the environmental fate of silver nanoparticles in natural aquatic systems.     

Influence of solution chemistry on the deposition and detachment kinetics of RNA on silica surfaces

The deposition kinetics of RNA extracted from both virus and bacteria on silica surfaces were examined in both monovalent (NaCl) and divalent (CaCl(2)) solutions under a wide range of environmentally relevant ionic strength and pH conditions by utilizing a quartz crystal microbalance with dissipation (QCM-D). To better understand the RNA deposition mechanisms, QCM-D data were complemented by diffusion coefficients and zeta potentials of RNA as a function of examined solution chemistry conditions. Favorable deposition of RNA on poly-l-lysine-coated (positively charged) silica surfaces was governed by the convective-diffusive transport of RNA to the surfaces. The deposition kinetics of RNA on bare silica surfaces were controlled by classic Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions. The presence of divalent cations (Ca(2+)) in solutions greatly enhanced the deposition kinetics of RNA on silica surfaces. Solution pH also affected the deposition behavior of RNA on silica surfaces. Release experiments showed that detachment of RNA from silica surfaces was significant in NaCl solutions, whereas, the deposited RNA on silica surfaces in CaCl(2) solutions was more likely to be irreversible.     

An insight into aggregation kinetics of polystyrene nanoplastics interaction with metal cations

Once inevitably released into the aquatic environment, polystyrene nanoplastics (PS-NPs) will present complicated environmental behaviors, of which the aggregation is a key process determining their environmental fate and impact. In this study, the aggregation kinetics of different sizes (30 nm and 100 nm) of PS-NPs with metal cations (Na⁺, K⁺, Ca²⁺, Mg²⁺ and Pb²⁺) at different solution pH (3, 6 and 8) were investigated. The results showed that the aggregation of PS-NPs increased with cation concentration. Taking Pb²⁺ as an example, the adsorption behavior of cations onto PS-NPs was determined by transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) spectroscopy, which demonstrated Pb²⁺ could be adhered onto the surface of PS-NPs with the effect of charge neutralization. The critical coagulation concentrations (CCC) of smaller PS-NPs were higher than that of larger PS-NPs for monovalent cations, whereas a different pattern is observed for divalent cations. It was suggested that there were other factors that DLVO theory does not consider affect the stability of NPs with different particle sizes. In addition, it should be noted that PS-NPs had the capacity of adsorbing large amounts of heavy metal cations and carried them transport to a long distance, and the corresponding ecological risks need to further elucidate.     

Influence of surface oxidation on the aggregation and deposition kinetics of multiwalled carbon nanotubes in monovalent and divalent electrolytes

The aggregation and deposition kinetics of two multiwalled carbon nanotubes (MWNTs) with different degrees of surface oxidation are investigated using time-resolved dynamic light scattering (DLS) and quartz crystal microbalance with dissipation monitoring (QCM-D), respectively. Carboxyl groups are determined to be the predominant oxygen-containing surface functional groups for both MWNTs through X-ray photoelectron spectroscopy (XPS). The aggregation and deposition behavior of both MWNTs is in qualitative agreement with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical coagulation concentration (CCC) of the highly oxidized MWNTs (HO-MWNTs) is significantly higher than the lowly oxidized MWNTs (LO-MWNTs) in the presence of NaCl (210 and 53 mM, respectively) since HO-MWNTs have a higher surface charge density. In contrast, the aggregation inverse stability profiles of HO-MWNTs and LO-MWNTs are identical and yield comparable CCCs (0.9 and 1.0 mM, respectively) in the presence of CaCl(2). Similar to the results obtained from the aggregation study, HO-MWNTs are considerably more stable to deposition on silica surfaces compared to LO-MWNTs in the presence of NaCl. However, both MWNTs have the same propensity to undergo deposition in the presence of CaCl(2). The remarkable similarity in the aggregation and deposition kinetics of HO-MWNTs and LO-MWNTs in CaCl(2) may be due to Ca(2+) cations having a higher affinity to form complexes with adjacent carboxyl groups on HO-MWNTs than with isolated carboxyl groups on LO-MWNTs.     

Cation-induced collapse of low-molecular-weight polyacrylic acid in the dispersion of barium titanate

Observations on the steric layers formed by the adsorption of low-molecular-weight polyacrylic acid (PAA) were taken using the colloidal probe method in an atomic force microscope. The effects of divalent barium ions and of monovalent potassium ions at varying concentrations were observed on the repulsive interaction profiles. High ionic concentrations screened double-layer forces to small distances, whereby the acting forces were reduced to steric interactions. De Gennes scaling theory was used to model the effect of electrolyte on an aqueous barium titanate system, which was stabilized with PAA. The brush model was found to represent the force curves better than the mushroom model. The collapse of PAA layers with increasing salt approximated a grafted polymer brush in monovalent electrolyte, but the addition of barium ions caused markedly less steric collapse. It is suggested that the formation of a Ba(2+)-PAA complex in the adsorbed layer increases its compressibility parameter.     

Aggregation kinetics of latex microspheres in alcohol-water media

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.     

Specific ion effects on nanoparticle stability and organocation-particle interactions in tetraalkylammonium-silica mixtures

Tetramethylammonium (TMA)- and tetrapropylammonium (TPA)-silica mixtures containing monovalent salts were studied to determine how salt impacts nanoparticle stability and organocation-silica interactions. Dynamic light scattering (DLS) results show that salt concentrations as low as 5 mM can induce nanoparticle aggregation. The extent of aggregation increases with the ionic size of the alkali-metal cations, consistent with the Hoffmeister series. Thus specific ion effects are observed in these mixtures. Pulsed-field gradient (PFG) NMR shows a more obvious increase in the self-diffusion coefficient of TPA than TMA in the presence of salt, indicating TPA is more easily displaced from the nanoparticle surface due to the background electrolyte. A two-site model is used to describe the exchange between tetraalkylammonuim (TAA) adsorbed on the nanoparticles and TAA in solution, from which the binding isotherms of the organocations at low electrolyte concentration was obtained and analyzed using the Langmuir formalism. This analysis also shows specific-ion effects, with the amount of TPA adsorbed to be much smaller than TMA and also much more sensitive to the presence of salt. In the context of the oriented aggregation mechanism proposed previously in the literature, the current work suggests one route for tuning the organocation-particle interaction and thus a route to controlling the rates of some steps in the mechanism.     

Interface tension of silica hydroxylated nanoparticle with brine: a combined experimental and molecular dynamics study

We have used molecular dynamics simulations to calculate the interfacial tension of hydroxylated SiO(2) nanoparticles under different temperatures and solutions (helium and brine with monovalent and divalent salts). In order to benchmark the atomistic model, quartz SiO(2) interfacial tension was measured based on inverse gas chromatography under He atmosphere. The experimental interfacial tension values for quartz were found between 0.512 and 0.617 N/m. Our calculated results for the interfacial tension of silica nanoparticles within helium atmosphere was 0.676 N/m, which is higher than the value found for the system containing He∕α-quartz (0.478 N/m), but it is similar to the one found for amorphous silica surface. We have also studied the interfacial tension of the nanoparticles in electrolyte aqueous solution for different types and salts concentrations (NaCl, CaCl(2), and MgCl(2)). Our calculations indicate that adsorption properties and salt solutions greatly influence the interfacial tension in an order of CaCl(2) > MgCl(2) > NaCl. This effect is due to the difference in distribution of ions in solution, which modifies the hydration and electrostatic potential of those ions near the nanoparticle.     

Fabrication and characteristics of self‐aggregation nanoparticles used for conformance control treatment

In order to alleviate the contradiction between injectability of the profile control agent and its profile control performance, a novel core‐shell heterogeneous structure colloidal particles (CSA) were synthesized, and the mechanism of self‐aggregation plugging was proposed. Cross‐linking inside the nanoparticles and chain‐growth polymerization via capturing acrylamide in the aqueous phase result in the formation of core‐shell heterogeneous structures as proved by TEM observation and XPS analysis. Moreover, CSA nanoparticles exhibit good hydrophilic properties, outstanding thermal stability and limited expansion capacity. Effects of different metal cations and surface group on the self‐aggregation time of CSA nanoparticles were systematically studied. Results showed that divalent cations contributed to more significant aggregation of CSA nanoparticles in comparison to monovalent cations. The increasing cations concentration and valency decreased the thickness of electric double layer, which lead to a decrease in the zeta potential. Core flooding test shows that the injection of nanoparticles which diameter is much smaller that of pore‐throats into the target reservoir can not only successfully enter the depth of porous media, but also effectively block the high permeability areas by the formation of self‐aggregation particle clusters. This study provides a new method for the equilibrium between nanoparticles injectivity and in‐depth profile control of nanoparticles.     

Deposition of nanosized latex particles onto silica and cellulose surfaces studied by optical reflectometry

Deposition of positively charged nanosized latex particles onto planar silica and cellulose substrates was studied in monovalent electrolyte solutions at pH 9.5. The deposition was probed in situ with optical reflectometry in a stagnation point flow cell. The surface coverage can be estimated reliably with island film theory as well as with a homogeneous film model, as confirmed with atomic force microscopy (AFM). The deposition kinetics on the bare surface was of first order with respect to the particle concentration, whereby the deposition rate was close to the value expected for a perfect collector. The efficiency coefficient, which was defined as the ratio of the experimental and theoretical deposition rate constants, was in the range from 0.3 to 0.7. Subsequently, the surface saturated and a limiting maximum coverage was attained (i.e., blocking). These trends were in qualitative agreement with predictions of the random sequential absorption (RSA) model, where electrostatic interactions between the particles were included. It was observed, however, that the substrate strongly influenced the maximum coverage, which was substantially higher for silica than for cellulose. The major conclusion of this work was that the nature of the substrate played an important role in a saturated layer of deposited colloidal particles.     

不同电解质体系中土壤胶体凝聚动力学的动态光散射研究

利用动态光散射技术研究在不同浓度的KNO3和Mg(NO3)2中土壤胶体颗粒的凝聚过程动力学. 通过分析凝聚过程中光强和有效粒径随时间的变化得到: (1)根据凝聚过程中光强的稳定与否, 可以判断土壤胶体凝聚过程中碰撞的发生是由布朗运动支配还是由重力作用支配; (2)在不同的电解质体系下土壤胶体凝聚表现为快速凝聚特征或不同的慢速凝聚特征, 并且在慢速凝聚中存在一个对重力敏感的电解质浓度; (3)两种电解质作用下的土壤胶体凝聚特征相似, 但对Mg(NO3)2体系浓度变化的敏感性远远大于KNO3体系. 此外, 通过分析凝聚平均速率随电解质浓度的变化, 找到慢速凝聚与快速凝聚的电解质浓度转折点, 即临界絮凝浓度(CFC), 提供了一个实验测定CFC的可能方法.     

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.     

Effect of soil parameters on the kinetics of the displacement of Fe from FeEDDHA chelates by Cu

In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact of Cu competition is codetermined by the kinetics of the displacement reaction. In this study, the influence of soil parameters on the displacement kinetics has been examined in goethite suspensions. The displacement reaction predominantly takes place on the reactive surface rather than in solution. The rate at which the o,o-FeEDDHA concentration declined depended on the available reactive surface area, the Cu loading, and the FeEDDHA loading. Soil factors reducing FeEDDHA adsorption (high ionic strength, humic acid adsorption onto the goethite surface, and monovalent instead of divalent cations in the electrolyte) decreased the displacement rate. For meso o,o-FeEDDHA, the displacement rate equation was derived, which is first order in FeEDDHA loading and half order in Cu loading. For soil conditions, the equation can be simplified to an exponential decay function in meso o,o-FeEDDHA solution concentration.     

Solution ionic strength effect on gold nanoparticle solution color transition

Unmodified and modified gold nanoparticles are proposed as sensors using the red to blue transition as an indicator. This work indicates that ionic content is an important variable to track in analytical samples and during the sensor fabrication processes. Mono and multivalent salts where the titrants for a standard gold nanoparticle solution. Multivalent cation salt titrants exhibited a greater sensitivity to color change than monovalent cation salts. The data suggest that specific surface adsorption is the predominant mechanism for the red to blue color change not aggregation. The 3-7 nm Debye length for divalent cations versus the 0.5-1.5 nm for monovalent cations indicates surface electrodynamic resonance effects are an important factor in the observed color changes.