Cooling effects on a model rennet casein gel system: part I. Rheological characterization

The gelation of a model rennet casein system was studied during cooling at different rates. During cooling, casein network structure development was proposed to evolve over a few steps at different length scales: molecules, particles, flocs, or network. Rennet casein flocs are fractal in nature, and fractal dimension and floc size are two variables affecting the rheology and microstructure of a rennet casein gel. Casein structure formation during cooling from 80 to 5 degrees C at four different rates (0.5, 0.1, 0.05, and 0.025 degrees C/min) was monitored by dynamic rheological tests, and a stronger gel developed at a slower cooling rate. During different cooling schedules, similar fractal dimensions were observed due to a lack of difference in the colloidal interactions. Differences among rheological data were possibly caused by variability in floc size, as observed in the second part of this paper. A larger number of smaller-sized flocs enabled gelation at a higher temperature and created a stronger network at a slower cooling rate. Controlling cooling schemes thus provides an approach for manipulating casein gelation and the microstructure for a system of fixed chemical compositions.     

Hierarchical structure of carbon nanotube networks

The hierarchical structure of semidilute suspensions of single-walled carbon nanotubes in polymeric matrices, studied by the use of ultrasmall and small angle neutron scattering, indicates an aggregate size that is independent on both nanotube concentration and polymer matrix and a mesh within the floc that becomes slightly denser with increasing nanotube concentration. The number of clusters grows linearly with concentration of nanotubes. These structural parameters suggest that the interactions between the flocs dictate the concentration-dependent elastic strength scaling of the network, with the absolute values of the specific elastic strength being inversely related to the percolation threshold.     

Fractal structure of asphaltene aggregates

A photographic technique coupled with image analysis was used to measure the size and fractal dimension of asphaltene aggregates formed in toluene-heptane solvent mixtures. First, asphaltene aggregates were examined in a Couette device and the fractal-like aggregate structures were quantified using boundary fractal dimension. The evolution of the floc structure with time was monitored. The relative rates of shear-induced aggregation and fragmentation/restructuring determine the steady-state floc structure. The average floc structure became more compact or more organized as the floc size distribution attained steady state. Moreover, the higher the shear rate is, the more compact the floc structure is at steady state. Second, the fractal dimensions of asphaltene aggregates were also determined in a free-settling test. The experimentally determined terminal settling velocities and characteristic lengths of the aggregates were utilized to estimate the 2D and 3D fractal dimensions. The size-density fractal dimension (D(3)) of the asphaltene aggregates was estimated to be in the range from 1.06 to 1.41. This relatively low fractal dimension suggests that the asphaltene aggregates are highly porous and very tenuous. The aggregates have a structure with extremely low space-filling capacity.     

Flocculated flow of microfibrillated cellulose water suspensions: an imaging approach for characterisation of rheological behaviour

Our aim was to characterise the suspension rheology of microfibrillated cellulose (MFC) in relation to flocculation of the cellulose fibrils. Measurements were carried out using a rotational rheometer and a transparent cylindrical measuring system that allows combining visual information to rheological parameters. The photographs were analyzed for their floc size distribution. Conclusions were drawn by comparing the photographs and data obtained from measurements. Variables selected for examination of MFC suspensions were degree of disintegration of fibres into microfibrils, the gap between the cylinders, sodium chloride concentration, and the effects of changing shear rate during the measurement. We studied changes in floc size under different conditions and during network structure decomposition. At rest, the suspension consisted of flocs sintered together into a network. With shearing, the network separated first into chain-like floc formations and, upon further shear rate increase, into individual spherical flocs. The size of these spherical flocs was inversely proportional to the shear rate. Investigations also confirmed that floc size depends on the geometry gap, and it affects the measured shear stress. Furthermore, suspension photographs revealed an increasing tendency to aggregation and wall depletion with sodium chloride concentration of 10⁻³ M and higher.     

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.     

Shear-thickening flow of nanoparticle suspensions flocculated by polymer bridging

The steady-shear viscosity, dynamic viscoelasticity, and stress relaxation behavior were measured for suspensions of silica nanoparticles dispersed in aqueous solutions of poly(ethylene oxide) (PEO). The suspensions of silica with diameters of 8-25 nm show striking shear-thickening profiles in steady shear and highly elastic responses under large strains in oscillatory shear. Since the silica particles are much smaller than the polymer coils, one molecule can extend through several particles by intrachain bridging. Each polymer coil may remain isolated as a floc unit and the silica particles hardly connect two flocs. Therefore, the flow of suspensions is Newtonian with low viscosity at low shear rates. When the polymer coils containing several nanoparticles are subjected to high shear fields, three-dimensional network is developed over the system. The shear-thickening flow may arise from the elastic forces of extended bridges. But, the polymer chain is easily detached from particle surface by thermal energy because of large curvature of particles. As a result, the network structures are reversibly broken down in a quiescent state and the suspensions behaves as viscoelastic fluids with the zero-shear viscosity.     

Improved dewatering behavior of clay minerals dispersions via interfacial chemistry and particle interactions optimization

Orthokinetic flocculation of clay dispersions at pH 7.5 and 22 degrees C has been investigated to determine the influence of interfacial chemistry and shear on dewatering and particle interactions behavior. Modification of pulp chemistry and behavior was achieved by using kaolinite and Na-exchanged (swelling) smectite clay minerals, divalent metal ions (Ca(II), Mn(II)) as coagulants and anionic polyacrylamide copolymer (PAM A) and non-ionic polyacrylamide homopolymer (PAM N) as flocculants. The pivotal role of shear, provided by a two-blade paddle impeller, was probed as a function of agitation rate (100-500 rpm) and time (15/60 s). Particle zeta potential and adsorption isotherms were measured to quantify the interfacial chemistry, whilst rheology and cryogenic SEM were used to investigate particle interactions and floc structure and aggregate network, respectively. Osmotic swelling, accompanied by the formation of "honeycomb" particle network structure and high yield stress, was produced by the Na-exchanged smectite, but not kaolinite, dispersions. Dispersion of the clay particles in 0.05 M Ca(II) or Mn(II) solution led to a marked reduction in particle zeta potential, complete suppression of swelling, honeycomb network structure collapse and a concomitant reduction in shear yield stress of smectite pulps. Optimum conditions for improved, orthokinetic flocculation performance of negatively charged clay particles, reflecting faster settling flocs comprised (i) coagulation, (ii) moderate agitation rate, (iii) shorter agitation time, and (iv) anionic rather than non-ionic PAM. The optimum dewatering rates were significantly higher than those produced by standard, manual-mixing flocculation techniques (plunging and cylinder inversion) commonly used in industry for flocculant trials. The optimum flocculation conditions did not, however, have a significant impact on the final sediment solid content of 20-22 wt%. Further application of shear to pre-sedimented pulps improved consolidation by 5-7 wt% solid. Higher shear yield stresses and greater settling rates were displayed by PAM A based than PAM N based pulps and this is attributed to the former's more expanded interfacial conformation and greater clay particles bridging ability. It appears that the intrinsic clay particles' physico-chemical properties and interactions limit compact pulp consolidation.     

Rheology and particle interaction of thickened latex

The pseudoplastic rheological properties of concentrated monodisperse polystyrene latexes with known sodium lauryl sulfate and methylcellulose surface coverages have been studied. It was assumed that the flow units of a concentrated thickened latex subjected to mechanical shear are “flocs” which comprise many particles with immobilized medium in the interstices. During shearing, the particle-particle bonds within the flocs undergo compression and stretching, sometimes breaking and reforming, causing the energy dissipation measured as the yield stress. A model was developed to calculate the average number of bonds per floc and this model was applied to an empirical modification of Firth and Hunter's elastic floc model to correlate the yield stress with the particle-particle separation pressure (defined as a measure of the interaction strength). It was found that the yield stress of a thickened latex is affected by the particle-particle interaction and the morphology of the particle flocs. The particle-particle interaction is affected by the surface coverage of thickener and emulsifier, and their concentrations in the aqueous phase, as well as other factors. The morphology of the particle flocs is affected by the particle interaction and the mechanical treatment. The adsorption of emulsifier and thickener, the rheology of the thickened latexes, the morphology of the particle flocs, and the particle-particle interactions, as well as their interrelationships, are described.     

Viscosity effect on the structural compactness of latex flocs formed under weak depletion attractions

Dilute aqueous dispersions of colloidal polystyrene latex spheres were flocculated by adding a nonadsorbing polymer sample, poly(acrylic acid). The structural compactness of the flocs thus formed was characterized in terms of their mass fractal dimension using the small-angle static light scattering technique. It was found that with low poly(acrylic acid) concentrations and thus weak depletion attraction forces, the dispersion medium viscosity had a marked effect on the floc structure. An increase in the viscosity led to formation of denser flocs. This was revealed in three sets of depletion flocculation experiments: (a) adjusting the background electrolyte concentration at a fixed level of poly(acrylic acid), (b) using water and 30% (w/w) glycerol as the respective solvents, and (c) inducing latex flocculation with two poly(acrylic acids) of different molecular weights at the respective critical polyacid concentrations. Direct force measurements were made with atomic force microscopy to isolate the influence of viscosity on floc structure from that of interparticle interaction energies. We conclude that the formation of denser flocs with increasing medium viscosity can be attributed to the reduced diffusivity of particles in the solution. The latter resulted in an enhanced rate of floc restructuring (through relaxation of attached particles) relative to floc growth.     

Filtration characteristics of a mineral mud with regard to turbulent shearing

The constant 1-MPa pressure filtration characteristics of a flocculated polydisperse phosphate slime slurry were examined in relation to the hydrodynamic conditions of the material's conditioning and its granulometric and textural properties. The dynamic character of the flocculation was studied by laser diffractometry. The aggregation, fragmentation and erosion of the flocs were well differentiated. The effect on the specific filtration resistance of the velocity gradient, size distribution, and porosity of the flocs was defined. With shearing at 120–2050 s⁻¹, the inter-floc porosity increases with decreasing granulometric spreading and increasing intra-floc porosity. A fairly high inter-floc porosity inevitably results in an increased permeability. The best filtration performances were obtained after a conditioning favouring the formation of a small distribution spreading index of floc size distribution and a high porosity cake.     

Structure of Hydrous Ferric Oxide Aggregates

The small angle light scattering behavior of hydrous ferric oxide flocs is examined here and found to provide useful insights into the nature of the aggregates formed despite the large size of these aggregates at later times. The flocs appear to exhibit fractal properties over a significant size range though the aggregates appear to be easily disrupted through mixing effects resulting in breakup and/or restructuring to denser assemblages. Background electrolyte concentrations also have some impact on floc structure but mixing effects and apparent destabilization by ferric ions limit the effect of added electrolytes on the stability and structure of ferric oxyhydroxides. Similar estimates of fractal dimensions of these hydrous ferric oxide flocs are obtained both by static light scattering analysis and by a cluster mass scaling approach. The choice of density distribution cutoff function has some impact on derived size and structure parameters and further refinement in this area is needed. Copyright 2000 Academic Press.     

Flocculation of hematite particles by a comparatively large rigid polysaccharide: schizophyllan

We studied the flocculation kinetics and structure of hematite aggregates induced by a large rigid extracellular polysaccharide, schizophyllan. Transmission electron microscopy (TEM), atomic force microscopy (AFM), photon correlation spectroscopy (PCS), and static light scattering (SLS) were used to characterize hematite particles, schizophyllan chains, and their flocs, to follow the time evolution of floc sizes, and to determine floc fractal dimensions. A maximum flocculation rate was found at a certain schizophyllan/hematite ratio. The maximum rate was considerably smaller than the rate of diffusion-limited aggregation (DLA) of hematite particles induced by simple electrolytes. To interpret the experimental results and to reveal various factors affecting the optimal dosage, Monte Carlo simulations were performed on the flocculation of small colloidal particles by relatively long, monodisperse linear polymers. The existence of the maximum flocculation rate was confirmed by computer simulation. However, a higher optimal dosage of schizophyllan was obtained in the experiments. The difference in the optimal dosage can be attributed mostly to the higher adsorption affinity of the hematite on schizophyllan aggregates present in the initial solution and the presence of a large fraction of free polymer chains which do not participate in the flocculation process. Both experiments and computer simulations demonstrated the fractal nature of the schizophyllan-hematite flocs. The fractal dimensions of the flocs at the optimal dosage were determined. A higher fractal dimension was obtained from experiments than from computer simulations, suggesting a reconstruction of the floc structure. Finally, a two-stage flocculation mechanism for hematite particles in the presence of a relatively long schizophyllan polymer was proposed. In the first flocculation stage, the hematite particles are preferentially adsorbed onto the schizophyllan aggregates in solution. The second stage consists of the association of these reactive entities with each other and also with naked chains to form fractal flocs by a bridging mechanism, where the hematite particles play the role of ligands.     

Flocculation of kaolin particles by two typical polyelectrolytes: A comparative study on the kinetics and floc structures

The flocculation kinetics of kaolin particles induced by two polyelectrolytes is studied by using small-angle laser light scattering (SALLS). Two different methods, image analysis and SALLS, are used to calculated the fractal dimensions of flocs formed under different flocculation mechanisms. For a high charge density of polydiallyldimethylammonium chloride (PDADMAC), the initially flocculation rates are slow due to the quite low molecular weight. Smaller and more compact flocs are in the particle–particle connections, and restructuring of the flocs occurs in the flocculation process. With cationic polyacrylamide C498 of very high molecular weight and low charge density, however, the initially flocculation rates are much higher due to its rapid adsorption on kaolin particles, but it will take the adsorbed polymer a much longer time to reach equilibrium due to re-conformation. High potentialities of adsorption prevent the particles from entering the interior of the floc structure or rearrangement, which results in a more open floc structure. Different underlying flocculation mechanisms are evident for these two kinds of polyelectrolytes, in which charge neutralization is mainly involved for the low molecular weight and high charge density polymer of PDADMAC while polymer bridging is suggested to be the dominant mechanism for the high molecular weight polyelectrolyte of C498.     

Hydrodynamic drag force exerted on activated sludge floc at intermediate Reynolds number

We hung the activated sludge flocs on an elastic nylon stick and then subjected it to a uniform water flow and measured its displacement. The hydrodynamic drag force exerted on the floc was subsequently estimated, both for cationic flocculated flocs and for flocculated and then frozen/thawed flocs. A confocal laser scanning microscope (CLSM) was employed to probe the interior structure of flocs. Polyelectrolyte flocculation leads to a compact global structure, and hence high drag force exerted on the floc by water. The corresponding C(D)Omega value at Re=12-27 for flocs ranges from 1.58 to 3.61. Fast freezing would little affect the hydrodynamic drag force. Slow freezing, in contrast, considerably consolidated the floc structure and hence presented impermeable sphere-like behavior of the slowly frozen/thawed flocs.     

Kinetics of rennet casein gelation at different cooling rates

A mathematical model was developed to quantitatively analyze the rheological data of rennet casein gelation at different cooling rates. Kinetic parameters were estimated and correlated with the microstructure development of the protein network. The kinetic model identified structure development upon cooling to be first order, and the network forming energies were estimated for four protein concentrations cooled at four rates. A lower energy for network formation was observed for a slower cooling rate and a higher protein concentration. This observation resulted from the availability of more flocs at a slower cooling rate and a higher casein concentration, simplifying floc cross-linking. By analyzing the kinetics during the aging process of casein gels, no difference in the reaction mechanism was observed. This study illustrated that structure formation resulted from the addition of flocs into the protein network: not all flocs were part of the network at a defined gel point. The incubation period following cooling integrated idle flocs into the network, thereby strengthening the gel. By understanding the gelation mechanism during cooling of rennet casein gels, the structure and thus quality of dairy products, such as processed cheese, may be better controlled.     

Surface analysis of cryofixation-vacuum-freeze-dried polyaluminum chloride-humic acid (PACl-HA) flocs

The powder of polyaluminum chloride-humic acid (PACl-HA) flocs was prepared by cryofixation-vacuum-freeze-drying method. The FTIR spectra show that some characteristic functional groups in polyaluminum chloride (PACl), humic acid (HA), and kaolin still existed in the dried flocs. X-ray diffractometry (XRD) patterns indicate that these flocs are amorphous. Nitrogen adsorption-desorption isotherms were obtained for different samples of the dried PACl-HA flocs. The BET specific surface area, BJH cumulative absorbed volume and BJH desorption average pore diameter of them were determined. The peak values of 8.4-11.2 nm (pore diameter) for pore size distribution (PSD) curves indicate that the pores of the dried flocs are mostly mesopores. The surface fractal dimensions D(s) and the corresponding fractal scales determined from both SEM images and nitrogen adsorption-desorption data sets reveal the multi-scale surface fractal properties of the dried PACl-HA flocs, which exhibited two distinct fractal regimes: a regime of low fractal dimensions (2.07-2.26) at higher scales (23-387 nm), mainly belonging to exterior surface scales, and a higher fractal dimensions (2.24-2.37) at lower scales (0.80-7.81 nm), falling in pore surface scales. Both HA addition and kaolin reduction in dried floc can decrease the irregularity and roughness of external surface. However, for the irregularity and roughness of pore surface, the addition of HA or kaolin in dried floc can increase them. Furthermore, some difference was found between the pore surface fractal dimensions D(s) calculated from nitrogen adsorption and desorption data. The pore surface D(s) values calculated through thermodynamic model were much greater than three.     

Flocculation mechanism induced by cationic polymers investigated by light scattering

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.     

Multilevel structure of sludge flocs

In this work, the structure of two kaolin sludges and a waste activated sludge are investigated using both light-scattering and free-settling methods. Fractal dimensions estimated by the light-scattering and free-settling techniques (D(S) and D(F) respectively) differ significantly and support the hypothesis that naturally occurring aggregates possess a multilevel structure. A two-level floc structural model comprised of (i) a primary floc (of fractal dimension D(S)) consisting of primary particles and (ii) a secondary floc (of fractal dimension D(F)) consisting of the microflocs is proposed to interpret the experimental findings. The structural changes of sludge flocs before and after cationic flocculation are interpreted using the proposed two-level model.     

The effect of molecular weight of nonadsorbing polymer on the structure of depletion-induced flocs

This work explores the structural compactness of depletion-induced particle flocs with respect to the molecular weight of nonadsorbing polymer flocculants. Small-angle static light scattering was used to monitor the structural characteristics of the flocs, which were formed by the addition of nonadsorbing poly(acrylic acids) to a stable colloidal polystyrene latex dispersion. It was found that the floc mass fractal dimension, considered to be a measure of structural compactness, was dependent upon both the molecular weight and the concentration of the polyacid. In particular, reducing the molecular weight of the polymer at a fixed polyacid concentration resulted in higher mass fractal dimensions, despite the highly polydisperse nature of the polymer samples. This structural behavior was attributed to the lower particle sticking efficiencies upon collision. This reduced sticking ability is the result of the shallowing in the secondary potential energy well with decreasing polymer chain length, which was directly supported by atomic force microscopy data. Our results suggest that the formation of a shallower attraction well with a lower molecular weight nonadsorbing polymer is the result of the insufficiency of the increased osmotic pressure to counter-balance the short-ranged nature of the depletion interaction.