Effect of shear rate on aggregate size and morphology investigated under turbulent conditions in stirred tank

Aggregation and breakage of aggregates produced from fully destabilized polystyrene latex particles in turbulent flow was studied experimentally in both batch and continuous stirred tank. Detailed investigation of the initial kinetics showed that the collision efficiency, alpha, depends on the shear rate according to alpha proportional to G(-b), with a power law exponent, b, equal to 0.18. After steady state was reached the dynamic response of the system on a change in stirring speed and solid volume fraction was investigated. It was found that the steady-state values of two measured moments of the cluster mass distribution (CMD) are fully reversible upon a change in stirring speed. This indicates that although the moments of CMD at steady-state depend on the applied shear rate, the aggregate structure is independent of the shear rate in the given range of stirring speeds. This was proved by independent measurement of the fractal dimension, d(f), using image analysis which provided a d(f) equal to 2.62 +/- 0.18 independent of applied stirring speed. The critical aggregate size, below which breakage is negligible, determined by dilution experiments was consequently used to evaluate the aggregate cohesive force holding the aggregate together, which was found to be independent of the aggregate size and equal to 6.2 +/- 1.0 nN.     

Hydrodynamic forces and critical stresses in low-density aggregates under shear flow

The distribution of stresses in rigid colloidal aggregates under a shear flow was investigated numerically for particle-cluster and cluster-cluster aggregates with fractal dimensions ranging from 1.7 to 2.3. stokesian dynamics was used to calculate the hydrodynamic force on each monomer, while the internal intermonomer interactions were calculated by applying force and torque balances on each primary particle. Although the hydrodynamic forces act mainly on the periphery of the clusters, their filamentous structure propagates and accumulates internal stresses toward the inner region of the aggregates, where consequently the most loaded intermonomer bonds are located. The spatial stress distribution, when scaled by the proper power of the radius of gyration, is independent of aggregate size and fractal dimension. This feature has made it possible to identify the most probable locations of bond failure in the structure and to estimate the relationship between shear rate and particle size for the occurrence of restructuring and of breakage.     

Gold nanoparticles protected with pH and temperature-sensitive diblock copolymers

Aqueous dispersions of gold nanoparticles protected with a stimuli-sensitive diblock copolymer were studied as a function of pH and temperature. Poly(methacrylic acid)-block-poly(N-isopropylacrylamide), PMAA-b-PNIPAM, copolymer was synthesized using the RAFT technique. A one-pot method utilizing the dithiobenzoate functionalized polymer was used to prepare gold nanoparticles protected with PMAA-b-PNIPAM. The gold nanoparticles coated with block copolymers, with the PNIPAM block bound to the particle surface and PMAA as an outer block form stimuli-sensitive aggregates in water. The changes in the absorption maxima of the surface plasmon resonance, SPR, of the gold particles and in the size of the aggregates were investigated as a function of pH and temperature. pH was observed to affect the size of the aggregates, whereas the effect of temperature was moderate. However, a blue shift in the SPR was observed both with decreasing pH and increasing temperature. Whereas the PMAA blocks control the colloidal stability of the particles and their aggregates, the thermo-sensitive PNIPAM blocks have a noticeable effect on the polarity of the immediate surroundings of the particles.     

Temperature-responsive solid-liquid separations with charged block-copolymers of poly(N-isopropyl acryamide)

Temperature responsive charged block-copolymers of poly(N-isopropylacrylamide) (PNIPAM) have been used in the solid-liquid separation of alumina mineral particles from aqueous solution. The effects of temperature, polymer charge-sign and fraction of charged segment have been investigated. Batch settling and adsorption studies showed that rapid sedimentation results for suspensions with polymers of opposite charge-sign to the particle surface-charge (counterionic) at 50 °C. Cooling the suspensions after flocculation at 50 °C was found to increase the final solids volume fraction of the sediment beds formed through a mechanism related to partial desorption of polymer and the reduction of the hydrophobic attraction. Suspension stability results after dosing with polymers of similar charge-sign to the particle surface-charge (co-ionic) at both 25 and 50 °C. Increasing the amount of polymer charge increased the influence of polymer charge-sign on the adsorption and solid-liquid separation behavior. The performance of the charged block copolymers are compared to that of the random charged copolymer and neutral homopolymer PNIPAM structures.     

Dependence of aggregate strength, structure, and light scattering properties on primary particle size under turbulent conditions in stirred tank

The steady-state size and structure of aggregates produced under turbulent conditions in stirred tank, for primary particle diameter, d(p), equal to 420 nm and 120 nm, were studied experimentally for various values of the volume average shear rate, G, and solid volume fraction, phi, and compared with data for d(p) = 810 nm. To exclusively investigate the effect of dp, polystyrene latexes with same type and similar density of surface charge groups (sulfate) were used. The mass fractal dimension, d(f), obtained by image analysis, was found to be invariant of d(p) and G, with a value equal to 2.64 +/- 0.18. Small-angle static light scattering was used to characterize the cluster mass distributions by means of the root-mean-square radius of gyration, R(g), and the zero-angle intensity of scattered light, I(0), whose steady-state values proved to be fully reversible with respect to G. The absolute values of R(g) obtained for similar phi and G proved to be independent of d(p), and for all studied conditions, R(g) was proportional to G-1/2. At very low phi, a critical aggregate size for breakage was obtained and used to evaluate the aggregate cohesive force, as a characteristic for the aggregate strength. The aggregate cohesive force was found to be independent of aggregate size, with similar values for the investigated dp. Due to large d(p) and high d(f), the effect of multiple light scattering within the aggregates was found to be present, and by relating the scaling of R(g) with I(0) to d(f), the corresponding correction factors were evaluated. By combination of the independently measured aggregate size and structure, it is possible to experimentally determine the relation between the maximum stable aggregate mass and the hydrodynamic stresses independent of the multiple light scattering present for large d(p) and compact aggregates.     

CFD simulation of aggregation and breakage processes in laminar Taylor-Couette flow

An experimental and computational investigation of the effects of local fluid shear rate on the aggregation and breakage of approximately 10 microm latex spheres suspended in an aqueous solution undergoing laminar Taylor-Couette flow was carried out according to the following program. First, computational fluid dynamics (CFD) simulations were performed and the flow field predictions were validated with data from particle image velocimetry experiments. Subsequently, the quadrature method of moments (QMOM) was implemented into the CFD code to obtain predictions for mean particle size that account for the effects of local shear rate on the aggregation and breakage. These predictions were then compared with experimental data for latex sphere aggregates (using an in situ optical imaging method) and with predictions using spatial average shear rates. The mean particle size evolution predicted by CFD and QMOM using appropriate kinetic expressions that incorporate information concerning the particle morphology (fractal dimension) and the local fluid viscous effects on aggregation collision efficiency match well with the experimental data.     

Experimental and modeling study of breakage and restructuring of open and dense colloidal aggregates

In this work we present experimental and simulation analysis of the breakage and restructuring of colloidal aggregates in dilute conditions under shear. In order to cover a broad range of hydrodynamic and interparticle forces, aggregates composed of primary particles with two sizes, d(p) = 90 and 810 nm, were generated. Moreover, to understand the dependence of breakage and restructuring on the cluster structure, aggregates grown under stagnant and turbulent conditions, having substantially different initial internal structures with fractal dimension d(f) equal to 1.7 and 2.7, respectively, were used. The aggregates were broken by exposing them to a well-defined elongational flow produced in a nozzle positioned between two syringes. To investigate the evolution of aggregate size and morphology, respectively, the mean radius of gyration, , and d(f) were monitored during the breakup process using light scattering and confocal laser scanning microscopy. It was found that the evolution of aggregates' fractal dimension during breakage is solely controlled by their initial structure and is independent of the primary particles size. Similarly, the scaling of the steady-state vs the applied hydrodynamic stress is independent of primary particle size, however, depends on the history of aggregate structure. To quantitatively explain these observations, the breakage process was modeled using stokesian dynamics simulations incorporating DLVO and contact interactions among particles. The required flow-field for these simulations was obtained from computational fluid dynamics. The complex flow pattern was simplified by considering a characteristic stream line passing through the zone with the highest hydrodynamic stress inside the nozzle, this being the most critical flow condition experienced by the clusters. As the flow-field along this streamline was found to be neither pure simple shear nor pure extensional flow, the real flow was approximated as an elongational flow followed by a simple shear flow, with a stepwise transition between them. Using this approach, very good agreement between the measured and simulated aggregate size values and structure evolution was obtained. The results of this study show that the process of cluster breakup is very complex and strongly depends on the initial aggregate structure and flow-field conditions.     

Destructive aggregation: aggregation with collision-induced breakage

Mean-field population balance equations are used to describe the evolution of particle size distributions in a wide variety of systems undergoing simultaneous aggregation and breakage. In this paper we develop a population balance that includes aggregation combined with collision-induced particle breakage for arbitrary fragment distribution functions, provided that this distribution function depends only on the total mass of the particles undergoing a collision. We then develop a specific distribution function for arbitrary two-body collisions by postulating that each collision produces a transition-state aggregate having the morphology of a linear polymer. The behavior of the resulting equation is then analyzed for the case in which the collision kernel is a constant, and partial analytical solutions are derived and compared to corresponding Monte-Carlo simulation results. The computer simulations are then used to validate a proposed scaling law for the steady-state particle size distribution. Lastly, the behavior of the aggregation with collision-induced-breakage population balance equation is compared and contrasted with the behavior of an analogous aggregation with linear-breakage population balance equation.     

贵阳污灌区菜地土壤团聚体中有机碳和重金属的含量特征及相关性分析

以贵阳某污灌区菜地土壤为研究对象,分别采用微波消解-电感耦合等离子体质谱(ICP-MS)法和水合热重铬酸钾氧化分光光度法分析不同粒径土壤团聚体中重金属和有机碳的含量特征,并对有机碳和重金属的相关性进行分析。结果表明,以2mm粒径团聚体的含量为最高,约占75%。Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中含量最高,Cr在5～8mm粒径团聚体中含量最高,As在不同粒径团聚体中的含量变化不大,重金属含量随土层深度增大而减小。土壤重金属富集因子表现为CuPbCdZnCrAs,Cu、Zn、Cd和Pb在0.25～0.5mm粒径团聚体中分布因子最高,而在5～8mm粒径团聚体中重金属的质量负载因子最大。土壤有机碳含量随团聚体粒径的增大表现为先增大后减小,不同粒径团聚体中Cu、Cd、Pb和As含量与有机碳含量均呈显著正相关(p0.05)。污灌区菜地土壤Cr、As在5～8mm粒径团聚体中富集现象显著,Cu、Zn、Cd、Pb在0.25～0.5mm粒径团聚体中均表现出显著的富集特征。6种重金属在5～8mm粒径团聚体中的质量负载因子均为最高,表明6种重金属在5～8mm粒径团聚体中的贡献最大。     

A modeling approach to describe the adhesion of rough, asymmetric particles to surfaces

A combined theoretical and experimental study of the adhesion of alumina particles and polystyrene latex spheres to silicon dioxide surfaces was performed. A boundary element technique was used to model electrostatic interactions between micron-scale particles and planar surfaces when the particles and surfaces were in contact. This method allows quantitative evaluation of the effects of particle geometry and surface roughness on the electrostatic interaction. The electrostatic interactions are combined with a previously developed model for van der Waals forces in particle adhesion. The combined model accounts for the effects of particle and substrate geometry, surface roughness and asperity deformation on the adhesion force. Predictions from the combined model are compared with experimental measurements made with an atomic force microscope. Measurements are made in aqueous solutions of varying ionic strength and solution pH. While van der Waals forces are generally dominant when particles are in contact with surfaces, results obtained here indicate that electrostatic interactions contribute to the overall adhesion force in certain cases. Specifically, alumina particles with complex geometries were found to adhere to surfaces due to both electrostatic and van der Waals interactions, while polystyrene latex spheres were not affected by electrostatic forces when in contact with various surfaces.     

Salt effects on aggregation of O-carboxymethylchitosan in aqueous solution

The effects of salt with different valences (NaCl, CaCl2 and CrCl3) on the aggregation of O-carboxylmethylchitosan (OCMCS) in dilute aqueous solution were investigated using viscometry, dynamic laser light scattering (DLS) and atomic force microscopy (AFM). With increasing OCMCS concentration beyond a critical aggregation concentration (cac) of approximately 0.045 g/l, the aggregation of OCMCS appears in solution. The driving forces of the OCMCS aggregation are intermolecular hydrogen bond, hydrophobic interaction and electrostatic repulsion. The OCMCS aggregation behavior strongly depends on the valence of salt. When NaCl is added, the aggregate size increases with NaCl concentration. When CaCl2 or CrCl3 is added to a given OCMCS concentration, there exists a critical concentration each of Ca2+ and Cr3+. Before the critical concentration, the aggregates decrease in size with increasing salt concentration due to the intra-aggregate complexation; while after the critical concentration, the size of the aggregates increases with salt concentration due to the inter-aggregate complexation. Moreover, the effect of Cr3+ on the OCMCS aggregation is greater than that of Ca2+. The formation of the intra-aggregate complexation is found to be a kinetic process and the aggregate size decreases with time; the formation of the inter-aggregate complexation is also kinetic where the aggregate size increases with time. The aggregates dominated by the intra-aggregate complexation are small, compact and spherical, while the aggregates dominated by the inter-aggregate complexation show the big, compact and spherical morphology.     

AuNPs/PNIPAM复合颗粒的制备及其温敏性质

将金纳米颗粒(AuNPs)组装到聚N-异丙基丙烯酰胺(PNIPAM)水凝胶微球表面制备出AuNPs/PNIPAM复合颗粒. 将PNIPAM 凝胶的温敏特性与AuNPs的光学性质结合, 通过改变温度调节AuNPs的局部表面等离子共振(LSPR)吸收峰位置. 研究结果表明, 温度升高使AuNPs的LSPR吸收峰发生红移, 并且这种效应是可逆的. 同时发现, AuNPs的光学性质还可以作为表征PNIPAM水凝胶微球温敏行为的一种手段. 利用透射电镜、紫外-可见光谱仪及动态光散射仪对AuNPs/PNIPAM复合颗粒的形貌、光学性质、粒径变化等进行了分析.     

Surface interaction forces mediated by poly(N-isopropylacrylamide) (PNIPAM) polymers: effects of concentration and temperature

Total internal reflection microscopy was used to directly measure the interaction potentials between a micron-sized silica sphere and a flat silica surface in the presence of a linear poly(N-isopropylacrylamide) (PNIPAM) aqueous solution. When the PNIPAM concentration was low, no discernible forces were detected. A further increase in PNIPAM concentration resulted in a long-range attraction which was likely due to a combined of the reduced electrostatic interaction between the silica particle and the flat surface after the polymer adsorption and polymer bridges formation. On the other hand, for a fixed PNIPAM concentration, the interaction potential profiles between the particle and flat surface were once again characterized by attraction as temperature was increased. This attractive force can be explained in terms of the conformational changes of PNIPAM chains at the surfaces, which subsequently affected the polymer adsorption and enhanced the segment–segment interaction among the adsorbed polymer chains.     

Effects of hectorite content on the temperature-sensitivity of PNIPAM microgels

A new method, adopting inorganic clay (synthetic hectorite) as a physical cross-linker, was used to prepare poly(N-isopropylacrylamide) (PNIPAM) microgels via surfactant-free emulsion polymerization. The effect of hectorite content on the temperature-sensitivity of PNIPAM microgels was investigated by means of DLS, UV/Vis and DSC. It was found that, in the absence of surfactant, with increasing hectorite content, the particle size tends to decrease to 300 nm at room temperature, while increases as weight ratio (WR) of hectorite and N-isopropylacrylamide (NIPAM) exceeds 21%. Furthermore, with increasing WR from 7% to 21%, the volume phase transition temperature of PNIPAM microgels has little shift, while decreases slightly when WR increases up to 28%.     

Novel temperature‐ and pH‐responsive graft copolymers composed of poly(L‐glutamic acid) and poly(N‐isopropylacrylamide)

A series of novel temperature‐ and pH‐responsive graft copolymers, poly(L ‐glutamic acid)‐g‐poly(N‐isopropylacrylamide), were synthesized by coupling amino‐semitelechelic poly(N‐isopropylacrylamide) with N‐hydroxysuccinimide‐activated poly(L ‐glutamic acid). The graft copolymers and their precursors were characterized, by ESI‐FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (¹H NMR). The phase‐transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering. The solution behavior of the copolymers showed dependence on both temperature and pH. The cloud point (CP) of the copolymer solution at pH 5.0–7.4 was slightly higher than that of the solution of the PNIPAM homopolymer because of the hydrophilic nature of the poly(glutamic acid) (PGA) backbone. The CP markedly decreased when the pH was lowered from 5 to 4.2, caused by the decrease in hydrophilicity of the PGA backbone. At a temperature above the lower critical solution temperature of the PNIPAM chain, the copolymers formed amphiphilic core‐shell aggregates at pH 4.5–7.4 and the particle size was reduced with decreasing pH. In contrast, larger hydrophobic aggregates were formed at pH 4.2. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4140–4150, 2008     

Investigation of the role of the interplay between water and temperature on the growth of alkylsiloxane submonolayers on silicon

We have investigated the influence of the interplay of the temperature and the water concentration in the adsorption solution on the growth of self-assembled monolayers on silicon using octadecyltrichlorosilane as the precursor. Toluene has been used as the solvent. The morphology of the submonolayer films has been investigated by atomic force microscopy (AFM). The surface coverages have been determined both with ellipsometry and through quantitative evaluation of AFM images. The size distribution of species in the precursor solution has been studied with dynamic light scattering. The influence of water concentrations between 8 and 18 mmol/L has been investigated in the temperature range from 2 to 35 degrees C. Dynamic light scattering revealed a unimodal size distribution of ordered aggregates in solution with a hydrodynamic radius of 200 nm regardless of the temperature and water concentration. However, formation of these features was faster at higher water contents and lower temperatures. Moreover, a characteristic temperature, which was higher for higher water concentrations, was found, above which such aggregates could not be detected anymore. Below this temperature an increase of the aggregate concentration has been observed until a plateau had been reached within a temperature range of approximately 5 degrees C. AFM measurements and ellipsometry on the corresponding submonolayer films showed that this temperature range is also associated with a transition from fast growth via characteristic fractally shaped islands to comparatively slow homogeneous growth via adsorption of individual molecules. The results are discussed in terms of diffusion and adsorption limitations.     

Crystallization kinetics of thermosensitive colloids probed by transmission spectroscopy

The kinetics of crystallization of poly-N-isopropylacrylamide (PNIPAM) particles has been investigated using the UV-visible transmission spectroscopy. Since the particle size decreases with the increase in temperature, microgel dispersions of different volume fractions have been obtained by varying the temperature of a single sample. It is found that the rates of the change in crystallinity, the average crystallite size, and the number density of crystallites at the most rapid stage over a certain time interval at various temperatures can be described by the power-law relations. At 19 degrees C, the PNIPAM system behaves as a hard sphere system under microgravity. The hard sphere theory based on Monte Carlo simulation has been used as a reference point to compare with conventional hard spheres, soft spheres, and PNIPAM spheres.     

Disodium guanosine 5'-monophosphate self-associates into nanoscale cylinders at pH 8: a combined diffusion NMR spectroscopy and dynamic light scattering study

We report a combined NMR and dynamic light scattering (DLS) study on the size of supramolecular structures formed by disodium guanosine 5'-monophosphate, Na(2)(5'-GMP), at pH 8. In general, two distinct types of aggregate species are present in an aqueous solution of Na(2)(5'-GMP). One type consists of stacking 5'-GMP monomers, and the other contains stacking G-quartets. Both types of aggregates can be modeled as rodlike cylinders. The cylinder diameter is 10 and 26 A for monomer aggregates and quartet aggregates, respectively. For Na(2)(5'-GMP) concentrations between 18 and 34 wt %, the cylinders formed by stacking G-quartets have an average length between 8 and 30 nm, corresponding to a stack of approximately 24-87 G-quartets. These nanoscale aggregates are significantly larger than what had previously been believed for Na(2)(5'-GMP) self-association at pH 8. The length of both types of 5'-GMP aggregates was found to increase with Na(2)(5'-GMP) concentration but was insensitive to the added NaCl in solution. While the aggregate size for monomer aggregates increases with a decrease in temperature, the size of G-quartet aggregates is essentially independent of temperature. We found that the size of G-quartet aggregates is slightly larger in D(2)O than in H(2)O, whereas the size of monomer aggregates remains the same in D(2)O and in H(2)O. We observed a linear relationship between the axial ratio of the 5'-GMP cylinders and the Na(2)(5'-GMP) concentration for both types of 5'-GMP aggregates, which suggests a common stacking mechanism for monomers and G-quartets.     

Effects of poly(N‐isopropylacrylamide) on the solution properties of hydrophobically modified acrylamide copolymer

The hydrophobic interaction between hydrophobically modified acrylamide copolymer (HMPAM) and poly(N‐isopropylacrylamide) (PNIPAM) in aqueous solutions was investigated. The results show that the solution properties of HMPAM are significantly influenced by the addition of PNIPAM. In dilute regime, the intrinsic viscosity of HMPAM in 0.025 wt % PNIPAM/0.1 M NaCl mixed solution is 17.52 dL g^?1, about 2 times 8.66 dL g^?1, that in 0.1 M NaCl solution, which is due to the attractive interaction between the hydrophobic parts of PNIPAM and HMPAM molecules. In semidilute regime, below the saturation concentration, the addition of PNIPAM can lead to both the apparent viscosity and the modulus of HMPAM solutions increasing, which is attributed to the number of aggregation junctions increasing, responsible for the increase of the contribution of the reversible network to the viscosity increase, the β value. In addition, a thermothickening behavior for the HMPAM/PNIPAM mixed solution is observed with increasing temperature over 15–30 °C, which is consistent with the large increase of the Huggins coefficient of HMPAM in the presence of PNIPAM from 1.95 to 7.59 as temperature increases from 25 to 30 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 709–715, 2005     

Restructuring and break-up of two-dimensional aggregates in shear flow

We consider single two-dimensional aggregates, containing glass particles, placed at a water/air interface. We have investigated the critical shear rate for break-up of aggregates with different sizes in a simple shear flow. All aggregates break-up nearly at the same shear rate (1.8 +/- 0.2 s(-)(1)) independent of their size. The evolution of the aggregate structure before break-up was also investigated. With increasing shear rate, the aggregates adopt a more circular shape, and the particles order in a more dense, hexagonal structure. A simple theoretical model was developed to explain the experimentally observed break-up. In the model, the aggregate is considered as a solid circular disk that will break near its diameter. The capillary and drag force on the two parts of the aggregate were calculated, and from this force balance, the critical shear rate was found. The model shows a weak size dependence of the critical shear rate for the considered aggregates. This is consistent with the experimental observations.