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1.
The adsorption of poly(vinylamine) (PVA) on poly(styrene sulfate) latex particles is studied, and its consequences on the charging behavior and suspension stability are investigated. The adsorption process is assessed by batch depletion experiments and time-resolved electrophoretic mobility measurements. The adsorption of PVA appears to be basically irreversible. The rate of adsorption decreases with decreasing polymer dose. At low polymer dose, the polymer coverage corresponds to the amount of the polyelectrolyte added, while at high polymer dose, the polymer coverage saturates the surface. Stability ratios are determined by dynamic light scattering, and strongly depend on the polymer dose and salt level. The aggregation is rapid near the isoelectric point (IEP), and it slows down when moving away from it. The charge neutralization is highly nonstoichiometric with charging ratios (CR) larger than unity, meaning that several charges on an adsorbed polyelectrolyte chain are necessary to neutralize a single charge on the particle surface. By comparing the IEP for particles and polyelectrolytes of different charge densities, we find a strong dependence of the CR on the mismatch between the average distances between individual charges on the surface and on the polyelectrolyte. A simple model is proposed to explain this trend.  相似文献   

2.
The pH-dependent adsorption of humic acid (HA) on magnetite and its effect on the surface charging and the aggregation of oxide particles were investigated. HA was extracted from brown coal. Synthetic magnetite was prepared by alkaline hydrolysis of iron(II) and iron(III) salts. The pH-dependent particle charge and aggregation, and coagulation kinetics at pH approximately 4 were measured by laser Doppler electrophoresis and dynamic light scattering. The charge of pure magnetite reverses from positive to negative at pH approximately 8, which may consider as isoelectric point (IEP). Near this pH, large aggregates form, while stable sols exist further from it. In the presence of increasing HA loading, the IEP shifts to lower pH, then at higher loading, magnetite becomes negatively charged even at low pHs, which indicate the neutralization and gradual recharging positive charges on surface. In acidic region, the trace HA amounts are adsorbed on magnetite surface as oppositely charged patches, systems become highly unstable due to heterocoagulation. Above the adsorption saturation, however, the nanoparticles are stabilized in a way of combined steric and electrostatic effects. The HA coated magnetite particles form stable colloidal dispersion, particle aggregation does not occur in a wide range of pH and salt tolerance is enhanced.  相似文献   

3.
Charging properties and colloidal stability of negatively charged polystyrene latex particles were investigated in the presence of linear poly(ethylene imine) (LPEI) of different molecular masses by electrophoresis and dynamic light scattering (DLS). Electrophoretic mobility measurements illustrate that LPEI strongly adsorbs on these particles leading to charge neutralization at isoelectric point (IEP) and charge reversal. Time-resolved DLS experiments indicate that the aggregation of the latex particles is rapid near the IEP and slows down away from this point. Surprisingly, the colloidal stability does not depend on the molecular mass, which indicates that the adsorbed LPEI layer is rather homogeneous.  相似文献   

4.
The aggregation of beta-lactoglobulin (BLG) at ambient temperature was studied using turbidimetry and dynamic light scattering in the range 3.8相似文献   

5.
The effect of anthranilic acid, an aromatic amino acid, on the structural characteristics of nonionic micelles of Triton X-100 at different pH values was investigated by light scattering and small-angle neutron scattering (SANS) measurements. The scattered light intensity decreases as pH is increased or decreased on either side of the isoelectric point (IEP = 3.4) of the amino acid. Analysis of the SANS data using a sticky hard-sphere model shows that the micelles are oblate ellipsoids with an axial ratio of approximately 2.3. No significant change could be observed in the size of the micelles with a change in the pH, while the stickiness parameter (tau), which is related to the interaction potential (u(0)) increases on either side of the IEP. As tau increases, u(o) becomes less negative, indicating a decrease in the attractive interaction between nonionic micelles. This can be explained in terms of the changes in the surface charge of the micelles resulting from a shift in the acid-base equilibrium of the adsorbed amino acid. The variation of the intermicellar interaction as calculated from the stickiness parameter is consistent with the picture of reversal of charge of amino acids with pH. This is further supported by the observed variation of the cloud point of the solutions at different pH values. The change in the interparticle interaction is also reflected in the diffusion coefficient of the micelles measured by dynamic light scattering.  相似文献   

6.
We investigate a series of poly(amidoamine) starburst dendrimers (PAMAM) of different generations in acidic, aqueous solutions using small-angle neutron scattering (SANS). While the overall molecular size is found to be practically unaffected by a pD change, a strong generational dependence of counterion association is revealed. Upon increasing the dendrimer generation, the effective charge obtained from our SANS experiments only shows a small increase in contrast to the nearly exponential increase predicted by a recent atomic simulation. We also find that with the same degree of molecular protonation the specific counterion association, which is defined as the ratio of bound chloride anions to positively charged amines in solutions, is larger for higher-generation PAMAM dendrimer. The associated counterion density also increases upon increasing generation number.  相似文献   

7.
The aggregation rate was determined for the < 0.2 microm size fraction of kaolinite (KGa-2) using simultaneous static and dynamic light scattering at pH 9.5. It was found that method suggested by Holthoff et al. [Langmuir 1996, 12, 5541] is suitable for determination of the absolute aggregation rate constant of a clay dispersion without using the particle optical factors. The determined fast aggregation rate constant is k11,fast = (3.7 +/- 0.2) x 10(-18) m3 s(-1). Stability behavior of kaolinite colloids was studied as a function of concentration of sodium chloride by simultaneous static and dynamic scattering. The critical aggregation concentration was found to be 0.085 +/- 0.005 mol dm(-3). When calculating the relationship between the stability ratio and the electrolyte concentration using the DLVO theory, the best fit to the experimental data was achieved with a Hamaker constant of A = (4.7 +/- 0.2) x 10(-20) J.  相似文献   

8.
We studied systematically aqueous suspensions of amorphous well-characterized silica particles by potentiometric titration, electrophoretic mobility, and time-resolved light scattering. Their charging behavior and aggregation rate constants were measured as a function of pH and ionic strength in KCl electrolytes for three types of particles of approximately 30, 50, and 80 nm in diameter. The charging behavior was consistent with the basic Stern model; the silica particles carry a negative charge, and its magnitude gradually increases with increasing pH and ionic strength. On the other hand, their early-stage aggregation (or coagulation) behavior is complex. The aggregation of the largest particles shows features resembling predictions of the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory. On one hand, the rate constant decreases sharply with increasing pH at low ionic strengths and attains fast aggregation conditions at high ionic strengths. On the other hand, we observe a characteristic slowing down of the aggregation at low pH and high ionic strengths. This feature becomes very pronounced for the medium and the small particles, leading to a complete stabilization at low pH for the latter. Stabilization is also observed at higher pH for the medium and the small particles. From these aggregation measurements we infer the existence of an additional repulsive force. Its origin is tentatively explained by postulating hairy layers of consisting of poly(silicilic acid) chains on the particle surface.  相似文献   

9.
The sizes of soluble polyelectrolyte complexes formed through mixing of solutions of dimethyl sulfate-alkylated rigid pyridine-containing polyphenylene dendrimers of various generations with the solution of sodium polystyrenesulfonate are measured with the use of dynamic light scattering. Effects of the length of the polyanion chain of the dendrimer, the generation number of the dendrimer, and the charge ratio of polymer components on the sizes of the complexes are examined. The results of this study are in agreement with the theoretical analysis of interaction between the charged dendrimer and the polyelectrolyte of the opposite charge sign and suggest the spontaneous formation of nanosized particles of water-soluble complexes.  相似文献   

10.
Charging behavior and colloidal stability of amidine latex particles are studied in the presence of poly(sodium styrene sulfonate) (PSS) and KCl. Detailed measurements of electrophoretic mobility, adsorbed layer thickness, and aggregation (or coagulation) rate constant on varying the polymer dose, molecular mass of the polymer, and ionic strength are reported. Polyelectrolyte adsorption leads to the characteristic charge reversal (or overcharging) of the colloidal particles at the isoelectric point (IEP). In accordance with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, uncharged particles tend to aggregate because of van der Waals attraction, whereas charged particles are stabilized by electrical double layer repulsion. Attractive patch-charge interactions originating from the laterally inhomogeneous structure of the adsorbed polymer substantially decrease the suspension stability or even accelerate the aggregation rate beyond diffusion control. These electrostatic non-DLVO forces become progressively important with increasing molecular mass of the polymer and the ionic strength of the solution. At higher polymer dose of typically 10 times the IEP, one observes the formation of a saturated layer of the adsorbed polymer with a thickness of several nanometers. Its thickness increases with increasing molecular mass, whereby the layer becomes increasingly porous. This layer does not seem to be involved in the suspension stabilization, since at such high polymer doses the double layer repulsion has attained sufficient strength to stabilize the suspension.  相似文献   

11.
The rate of flocculation of cationic polystyrene latex (PSL) particles by smaller, anionic PSL particles has been measured using a low-angle static light scattering technique. The rate of aggregate growth has been investigated as a function of particle size ratio and relative concentration of each particle species (for a constant dose of cationic particles). Contrary to many previous reports, two peaks in the flocculation rate were observed as a function of dose. It is speculated that the peak observed at the lower particle concentration coincides with the dose yielding maximum constant collision efficiency in the steady-state regime, a condition which is attained only after complete adsorption of the smaller particles onto the larger particle species. The peak at the higher particle concentration is believed to be related to the maximum collision rate constant upon reaching the steady-state regime, the value of which corresponds to maximum degree of aggregation and therefore the maximum mean collision efficiency prior to reaching this condition. From classical collision kinetics, the rate of aggregate growth may be represented as being proportional to the product of the collision rate constant and collision efficiency at any given time. Given then that the maximum value of these two variables coincides with different particle concentrations, the product of the response of each to particle dosage can in some cases yield a net bi-modal aggregation rate response to particle dosage.  相似文献   

12.
The diffusion coefficients of hematite particles in polyelectrolyte solution have been investigated using dynamic light scattering. Two apparent diffusion coefficients, a fast and a slow diffusional mode, are observed for the hematite particles in high-molecular-weight sodium polyacrylate solution at pH 10.5. The slow diffusion coefficient (Dslow) shows a decrease with increase in polyelectrolyte concentration. The fast diffusion coefficient (Dfast) shows an increase to a maximum with increasing polyelectrolyte concentration and then a rapid decrease as the polyelectrolyte concentration increases further. With an increase in ionic strength from 10(-4) to 0.1 M NaNO3, the maximum value of Dfast increased in magnitude, while the polyacrylate concentration at which the maximum occurs is seen to increase. The dependence of Dfast on the measurement angle indicates that it is coupled to the fluctuations of the chains. The observed behavior is attributed to the hematite probe particle sensing both macroscopic (viscous) and elastic fluctuations associated with the polyelectrolyte motion.  相似文献   

13.
Three cationic polymers with molecular weights and charge densities of 3.0 x 10(5) g/mol and 10%, 1.1 x 10(5) g/mol and 40%, and 1.2 x 10(5) g/mol and 100% were chosen as flocculants to aggregate silica particles (90 nm), under various conditions, including change in polymer dosage, particle concentration, background electrolyte concentration, and shear rate. The size and structure of flocs produced were determined using the static light scattering technique. On the basis of measurements of polymer adsorption and its effect on the zeta potential and floc properties, it has been found that the polymer charge density plays an important role in determining the flocculation mechanism. Polymers with a 10% charge density facilitate bridging, 40% charged polymers bring about either a combination of charge neutralization and bridging or bridging, depending on the polymer dosage, and polymers with the charge density of 100% induce electrostatic patch flocculation mechanism at the optimum polymer dosage and below but bring about bridging mechanism at the polymer dosage approaching the adsorption plateau value. Bridging aggregation can readily be affected by the particle concentration, and an increase in particle concentration results in the formation of larger but looser aggregates, whereas electrostatic patch aggregation is independent of particle concentration. The addition of a background electrolyte aids in bridging aggregation while it is detrimental to electrostatic patch aggregation. It has also been found that the effect of shear rate on the mass fractal dimension depends on polymer charge density.  相似文献   

14.
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.  相似文献   

15.
气相SiO2在不同pH值介质中的分散特性   总被引:1,自引:0,他引:1  
以激光动态光散射法考察了气相SiO2在不同pH值的H2SO4和NaOH介质中的分散平均水化粒径与表面Zeta电位及二者间的关系。 Zeta电位数据表明,气相SiO2在水中分散的表面硅羟基的等电点(IEP)和滴定终点(TE)的pH值分别为pH(IEP)=2.09和pH(TE)=7.47,利用滴定终点pH (TE)给出了一种简单的气相SiO2表面Si-OH浓度的测定方法。 分散相粒径数据显示,在等电点和滴定终点之间,气相SiO2在水中的分散粒子的粒径能够稳定在230 nm附近;在H2SO4介质中,当pH<pH(IEP)时,随着H2SO4浓度的增大,体系中的分散粒子发生聚结而使表观粒径增大;在NaOH介质中,当pH>pH(TE)时,随着NaOH浓度的增大,分散相的表观水化粒径降低,表明NaOH的加入有利于气相SiO2的分散。  相似文献   

16.
The colloid stability of thymine-coated gold nanoparticles under light irradiation as a function of particle size, surface charge, and exposure time was investigated in alkaline, aqueous solutions as well as in a 0.5 vol % of DMF in H(2)O mixture. With increasing exposure to light irradiation at 280 nm, more and more particles coagulated. Light-induced aggregation of colloidal gold nanoparticles was attributed to reorientation of thymine terminal groups tethered on gold particle surfaces. A smaller particle size and negatively charged surface reduced the rate of photodimerization or even inhibited the photoreaction. UV-vis and FTIR spectroscopy confirmed the photodimerization of terminal thymine molecules under 280 nm light irradiation. The reaction kinetics of thymine photodimerization appears to be a combination of first-order reactions, each having different rates, reflecting the inhomogeneity and high curvature of the gold nanoparticle surfaces.  相似文献   

17.
To elucidate the nature of processes involved in electrically driven particle aggregation in steady fields, flows near a charged spherical colloidal particle next to an electrode were studied. Electrical body forces in diffuse layers near the electrode and the particle surface drive an axisymmetric flow with two components. One is electroosmotic flow (EOF) driven by the action of the applied field on the equilibrium diffuse charge layer near the particle. The other is electrohydrodynamic (EHD) flow arising from the action of the applied field on charge induced in the electrode polarization layer. The EOF component is proportional to the current density and the particle surface (zeta) potential, whereas our scaling analysis shows that the EHD component scales as the product of the current density and applied potential. Under certain conditions, both flows are directed toward the particle, and a superposition of flows from two nearby particles provides a mechanism for aggregation. Analytical calculations of the two flow fields in the limits of infinitesimal double layers and slowly varying current indicate that the EOF and EHD flow are of comparable magnitude near the particle whereas in the far field the EHD flow along the electrode is predominant. Moreover, the dependence of EHD flow on the applied potential provides a possible explanation for the increased variability in aggregation velocities observed at higher field strengths.  相似文献   

18.
The effect of primary particle polydispersity on the structure of fractal aggregates has been investigated through the salt-induced, diffusion-limited aggregation of mixtures of hematite. The fractal dimension was determined experimentally using three independent methods: q dependence of static light scattering, kinetic scaling, and correlation of aggregate mass and linear size both determined from Guinier scattering. The fractal dimensions D(f) obtained were 1.75+/-0.03, 1.76+/-0.03, and 1.70+/-0.05, respectively. The use of a previously derived fractal mean particle size was validated in allowing data collapse to master curves for the aggregation kinetics data. The fractal mean particle size is shown to have general utility by taking a number weighting to describe polydisperse aggregation kinetics and a mass weighting to describe small q scattering behavior. Copyright 2000 Academic Press.  相似文献   

19.
The irreversible thermal aggregation rate and process of bovine serum albumin (BSA) were investigated by means of light scattering technique as a function of temperature. The increasing rate of particle radius was affected by the aggregation temperature, concentration and the presence of fatty acid. The particle radius was larger and the aggregation rate was faster for fatty acid free BSA at higher temperature and concentration. Two thermal aggregation processes were observed at relatively low temperature and concentration, both for fatty acid containing (C-BSA) and fatty acid free BSA (F-BSA). The first process proceeds by an inter-monomer aggregation mechanism, and the second process by inter-aggregates aggregation. The first process is represented by a power law as Rhapp proportional to t(z), which is diffusion limited cluster aggregation (DLCA).  相似文献   

20.
This work investigates the polyanion initiated gelation process in fabricating chitosan-TPP (tripolyphosphate) nanoparticles in the size range of 100-250 nm intended to be used as carriers for the delivery of gene or protein macromolecules. It demonstrates that ionic gelation of cationic chitosan molecules offers a flexible and easily controllable process for systematically and predictably manipulating particle size and surface charge which are important properties in determining gene transfection efficacy if the nanoparticles are used as non-viral vectors for gene delivery, or as delivery carriers for protein molecules. Variations in chitosan molecular weight, chitosan concentration, chitosan to TPP weight ratio and solution pH value were examined systematically for their effects on nanoparticle size, intensity of surface charge, and tendency of particle aggregation so as to enable speedy fabrication of chitosan nanoparticles with predetermined properties. The chitosan-TPP nanoparticles exhibited a high positive surface charge across a wide pH range, and the isoelectric point (IEP) of the nanoparticles was found to be at pH 9.0. Detailed imaging analysis of the particle morphology revealed that the nanoparticles possess typical shapes of polyhedrons (e.g., pentagon and hexagon), indicating a similar crystallisation mechanism during the particle formation and growth process. This study demonstrates that systematic design and modulation of the surface charge and particle size of chitosan-TPP nanoparticles can be readily achieved with the right control of critical processing parameters, especially the chitosan to TPP weight ratio.  相似文献   

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