Effect of floc structure on the rate of shear coagulation

We derived a mathematical expression for the temporal evolution of the number of particles due to shear coagulation, covering the later stage by expanding the initial stage approximation to take into account the formation of floc structure. In the derivation, it is assumed that flocculation proceeds through binary collisions between identical fractal flocs. The capture efficiency between flocs is calculated on the basis of trajectory analysis, which is determined by viscous hydrodynamic interaction between flocs and van der Waals attractive forces between two primary particles located at colliding points of flocs. The validity of the derived equation was tested by a coagulation experiment using polystyrene sulfate latex particles under conditions of rapid coagulation. The experiment was carried out in a laminar Couette flow generated in the gap between two concentric cylinders. Careful and direct observation of flocculation under microscopy provided the data on the fractal dimension as well as the temporal evolution of number concentration of flocs. The measured rate of coagulation gradually increases in accordance with the formation of the fractal structure of flocs. This behavior agreed very well with the prediction based on the derived equation.     

Driven Brownian coagulation of polymers

We present an analysis of the mean-field kinetics of Brownian coagulation of droplets and polymers driven by input of monomers which aims to characterize the long time behavior of the cluster size distribution as a function of the inverse fractal dimension, a, of the aggregates. We find that two types of long time behavior are possible. For 0≤a<1/2 the size distribution reaches a stationary state with a power law distribution of cluster sizes having exponent 3/2. The amplitude of this stationary state is determined exactly as a function of a. For 1/2相似文献   

Brownian coagulation at high concentration

Particle growth by Brownian coagulation at high concentration in the continuum regime is investigated by solving the Langevin dynamics (LD) equations for each particle trajectory of polydisperse suspensions. By monitoring the LD attainment of the self-preserving size distribution (SPSD), it is shown that the classic Smoluchowski collision frequency function is accurate for dilute particle volume fractions, phis, below 0.1%. At higher phis, coagulation is about 4 and 10 times faster than for the classic theory at phis = 10 and 20%, respectively. For complete particle coalescence upon collision, SPSDs develop even in highly concentrated suspensions (up to phis = 35%), as with dilute ones, but are broadened with increasing phis. At high particle concentration, an overall coagulation rate is proposed that reduces to the classic one at low concentration. Detailed collision frequency functions are also obtained at various phis values. Fractal-like agglomerates undergoing coagulation at constant fractal dimension attain an SPSD only temporarily because their effective volume fraction continuously increases, approaching gelation in the absence of restructuring or fragmentation.     

Porosity and interior structure of flocculated activated sludge floc

This work estimated the porosities of activated sludge flocs, cationic polyelectrolyte flocculated, based on free-settling tests, buoyant weight measurements, and confocal laser scanning microscope (CLSM) tests. The extent of advective flow was estimated based on bubble-tracking test. The former two measurements suggested a close-to-unity porosity, that is, an extremely void floc interior. Meanwhile, the latter two tests recommended a dense floc interior with a porosity less than 64%. A discrepancy exists between the porosities estimated by various tests. A floc model was proposed based on the understanding that a vast amount of bound water in the floc was regarded as void in buoyant weight measurement, but was impermeable for advective flow. The distribution rather than the mean value of the porosity controls the advective flow. There existed no simple correlation between the porosities measured by different tests.     

Steady shear rate rheology of suspensions, as described by the giant floc model

The break-down of a particle network by shear is described as the development of shear planes: a region able to withstand low shear stresses may break down under a larger stress; thus with increasing shear stress and shear rate, the mutual distance (A) between successive shear planes decreases until, at very high shear rates, A approaches the particle diameter. The shear planes are idealised as flat planes. Energy dissipation during shear is predominantly due to the energy dissipated through the movement of the particles; the energy dissipation due to breakage and renewed formation of bonds between particles is relatively small. A consideration of the energy dissipated during the encounters of particles during shear, including that dissipated by entrained particles, then leads to a relation between this energy dissipation and the average fraction L, over which a moving particle entrains a neighbour. L includes the effect of parts of the network which are rotating under the influence of the shear. In the limit of large shear rates, L is found to depend only to a small extent on whether the suspension is coagulated or not.     

Role of dipole-dipole interaction on enhancing Brownian coagulation of charge-neutral nanoparticles in the free molecular regime

In contrast to van der Waals (vdW) forces, Coulombic dipolar forces may play a significant role in the coagulation of nanoparticles (NPs) but has received little or no attention. In this work, the effect of dipole-dipole interaction on the enhancement of the coagulation of two spherically shaped charge-neutral TiO(2) NPs, in the free molecular regime, is studied using classical molecular dynamics (MD) simulation. The enhancement factor is evaluated by determining the critical capture radius of two approaching NPs for different cases of initial dipole direction with respect to path (parallel∕perpendicular) and orientation with respect to each other (co-orientated∕counterorientated). As particle diameter decreases, the enhancement of coagulation is augmented as the ratio of dipole-dipole force to vdW force becomes larger. For 2-nm TiO(2) NPs at 273 K, the MD simulation predicts an average enhancement factor of about 8.59, which is much greater than the value of 3.78 when only the vdW force is considered. Nevertheless, as temperature increases, the enhancement factor due to dipole-dipole interaction drops quickly because the time-averaged dipole moment becomes small due to increased thermal fluctuations (in both magnitude and direction) of the instantaneous dipole moment.     

Study on improving the turbidity measurement of the absolute coagulation rate constant

The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.     

Change in particle size distribution of fractal agglomerates during Brownian coagulation in the free-molecule regime

Time evolution of particle size distribution of fractal agglomerates undergoing Brownian coagulation in the free-molecule regime was investigated. A simple analytical solution for the size distribution change was obtained by using the assumption that the size distribution during the coagulation process can be represented by a time-dependent log-normal function. The derived solution consists of three parameters of the log-normal distribution function. This study is believed to provide the first analytical solution for all the parameters of the log-normal distribution of fractal agglomerates undergoing coagulation in the free-molecule regime. To validate the derived solution, numerical computations were performed. The results were compared with the analytical solution and good agreement was obtained.     

Effect of particle size distribution on the collection efficiency of Brownian particles

The main purpose of the present paper is to investigate the effect of the normal Gaussian size distribution on the deposition of Brownian particles onto a spherical collector, by applying the Brownian dynamic simulation method and the Kuwabara flow field model with different types of DLVO interaction energy curves and the shadow effect. The simulation results show that the collection efficiency of Brownian particles always increases with a wider particle size distribution region. The same increased tendencies are also observed for the case of increasing Reynolds number and for the case of increasing the particle size to the collector size ratio. When compared to the available experimental data, the present simulation method fits well with the experimental data when the specific deposit per collector is not large.     

Characterization of floc size and structure under different monomer and polymer coagulants on microfiltration membrane fouling

The characteristic of aggregates pre-coagulated by inorganic monomer alum, polymer aluminium chlorohydrate(ACH) and polyaluminium chloride(PACl) coagulants impose major impact on the removal of humic acids (HAs) and the reduction of microfiltration (MF) membrane fouling. The fractal dimension of flocs formed by ACH and PACl is higher than that by monomer alum, indicating Keggin structure produced by polymer coagulants is much more compact compared with hexameric ring structure of alum hydrolysis species. Correspondingly, cake layer specific resistance is far higher and the MF membrane flux deteriorates much more severely when pre-coagulated by ACH and PACl than by alum. Moreover, the higher basicity contains in PACls, the cake layer fouling is more serious for producing more proportion of dense hydrolysis species Al₁₃. Thus, the polymer coagulant ACH and PACl seems not adapt to the pre-coagulation–MF process for cake layer resistance increase two to three times although they save 60–70% dose in comparison with alum for HAs removal. Additionally, for three Al-based coagulants under sweep coagulation condition, insufficient dose result in lower HAs removal and produce more small particles caused higher cake layer specific resistance according to Carman–Kozeny relationship. On the other hand, coagulant hydrolysis species as direct contaminant loading aggravated cake resistance on the MF membrane when overdosed. The optimum dose should keep the minimum to provide better HAs removal efficiency, and produce lower cake layer specific resistance and higher membrane filterability for pre-coagulation–MF hybrid process.     

Effect of polymerization rate on the polyethylene structure obtained with a high activity catalyst system

The effect of polymerization rate on polyethylene structure, using magnesium reduced titanium tetrachloride catalysts together with the usual aluminium alkyl activator, is described. It is shown that the polymer bulk density and the nascent super-molecular structure formed during ethylene polymerization depends upon the rate of polymerization. The results indicate that, with increasing polymerization rate, the catalyst active sites produce polymer with different densities. One possible explanation for this phenomenon lies in considering the inhibition of crystallization by high polymerization rates. Experimental results on different polymer morphologies are discussed. Finally models for the structure of polymer particles are considered briefly.     

Boundary effect on the drag force on a nonhomogeneous floc

The boundary effect on the drag force acting on a spherical floc having a nonhomogeneous structure is examined by considering a spherical floc at the centerline of a cylindrical tube. The floc is simulated by an entity having a two-layer structure, and its porous nature mimicked by varying the relative magnitude of the permeability of its inner and outer layers. The results of numerical simulation reveal that the tube wall has the effect of compressing the streamlines and vorticity contours. Also, as in the case of a rigid entity, the wake in the rear region of a floc, which arises from the convective motion of the fluid, is depressed. For fixed volume-averaged permeability, the influence of the tube wall on the behavior of a heterogeneous floc is more significant than that on the behavior of a homogeneous floc, and the influence varies with the structure of the former. The heterogeneous structure of a floc leads to a deviation in the modified drag coefficient-Reynolds number relation from a Stokes-law-like correlation. The smaller the average permeability of a floc the greater the deviation, but the presence of the tube wall has the effect of reducing the deviation.     

Effect of the structure of reactants on the reaction rate constants of aromatic nitroso oxides with olefins

The reactivity of phenylnitroso oxide, (p-methylphenyl)nitroso oxide, (p-nitrophenyl)nitroso oxide, (m-nitrophenyl)nitroso oxide, and (p-bromophenyl)nitroso oxide toward a number of olefins in acetonitrile at room temperature was studied using flash photolysis. It was found that the reaction rate constant decreased with decreasing energy of a molecular orbital with a maximum contribution from the atomic orbitals of carbon atoms in the C=C bond of olefins. This, along with a positive slope of the Hammett function for the reactions of substituted phenylnitroso oxides with 1-hexene and styrene, suggest an electrophilic character of these species. The temperature dependence of the rate constant of the reaction of phenylnitroso oxide with 1-hexene was studied: log A = 7.9 ± 0.4 [l mol^-1 s^-1]; E_a = 38 ± 2 kJ/mol.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 842–847.Original Russian Text Copyright © 2004 by Chainikova, Khursan, Safiullin.     

On the use of the Knudsen number and aerosol Knudsen number in the kinetics of Brownian coagulation of aerosols

We consider, on the basis of dimensional analysis, the use of the Knudsen number and aerosol Knudsen number in the kinetics of Brownian coagulation of aerosols. The aerosol Knudsen numberKn _p emerges naturally when one assumes that the aerosol particle motion can be described in terms of Brownian motion. Examples of dimensionless coagulation constants consistent with the use ofKn _p are also discussed.     

Effect of structure on the rate and mechanism of thermolysis of some 4-substituted 3-methylfuroxans

Russian Journal of General Chemistry -     

Absolute rate of turbulent coagulation from turbidity measurement

Turbidity method has been applied to assess colloid stability. While the method is simple and easy, it is not straightforward in evaluating absolute coagulation rates of colloidal particles. That is, the method requires the evaluation of the extinction cross section of doublets. Recently, the turbidity measurement has been successfully utilized to evaluate the absolute Brownian coagulation rate constant with the T-matrix method, which calculates the extinction cross section of doublets at arbitral size range. The present work was performed to extend the applicability of the method to turbulent coagulation. To this end, we measured the turbidity change of coagulating latex suspensions in a turbulent flow. The measurement was performed as a function of particle size. From the turbidity vs. time relationship, we evaluated turbulent coagulation rate constant using the T-matrix method. Obtained values of the constants agreed well with theoretical ones, demonstrating the usefulness of turbidity method for turbulent coagulation.     

Effect of pH and gaseous ammonia flow rate on the composition and structure of ammonium uranate

Ammonium uranate was precipitated from uranyl nitrate solution using gaseous ammonia, then filtered, washed with demineralized water and dried. The influence of pH and ammonia flow rate on their composition and structure were examined by X-ray diffraction analysis, making use of additional information obtained from infrared analysis.     

Brownian force profile reconstruction of interfacial 1-nonanol solvent structure

Using Brownian force profile reconstruction (BFPR), we measured the solvent structure force profile of interfacial 1-nonanol between graphite and methyl terminated alkane thiol SAM surfaces. BFPR harnesses the thermal motion of the cantilever to accurately and precisely reconstruct force profiles that may be stiffer than the intrinsic cantilever stiffness. Novel methods to compensate instrument noise and seamlessly stitch together subsections of the force profile significantly improve upon previous reconstruction techniques using thermal noise. The increased accuracy and precision of BFPR could enable the measurement of stiff or rough energy landscapes such as solvent structure or ligand-protein binding. The force profile for interfacial 1-nonanol solvent structure was well fit by an exponentially decaying sinusoid function with a period of 4.5 A for distances greater than four molecular layers, revealing liquid behavior. Distances shorter than four molecular layers displayed solid behavior with interlayer transitions being 3.9 A and possible crystal orientation rearrangements causing submolecular steps upon subsequent confinement.