Viscosity behavior of silica suspensions flocculated by associating polymers

Associating polymers are hydrophilic long-chain molecules containing a small number of hydrophobic groups, and act as flocculants in aqueous suspensions. The effects of associating and nonassociating polymers on viscosity behavior are studied for silica suspensions. Since flocculation is induced by polymer bridging, the viscosity behavior is converted from Newtonian to shear-thinning profiles. The additions of surfactant cause an increase in viscosity for suspensions prepared with associating polymer, whereas the flow behavior of suspensions with nonassociating polymer is not significantly influenced. In adsorption of associating polymers onto silica particles, the chain may adopt a conformation with a water-soluble backbone attached to the particle surfaces. The hydrophobic groups extending from the chains adsorbed onto different particles can form a micelle by association with surfactant. Therefore, the bridging flocculation is enhanced by surfactant. The cooperative micellar formation between associating polymer and surfactant is responsible for viscosity increase in suspensions.     

Solid/liquid separation of flocculated suspensions

Solid-liquid separation operations leading to the concentration and isolation of fine particles dispersed in liquids are important in the chemical and mineral processing industries. In spite of this, the procedures available for the prediction of equipment performance remain crude. Almost all major mineral and chemical processing companies now have a clear priority in R&D budgets to develop new approaches to waste minimization; a major part of the problem faced by these industries relates to the effect of management of waste slurries. The processes that manage final waste slurries are often classical “end-of-pipe” solutions. One of the key aims of the present broad program is to understand how to manipulate the structure of slurries within the process so that finally it is possible to engineer clear liquor and simultaneously manageable or tractable waste solids. The best way to process such wastes relies on understanding how to control the compressibility and viscosity of these materials.A generalized approach to understanding and prediction of solid-liquid separation methods based on the measurement of fundamental material properties is reviewed here. This is of value in designing more efficient methods and ultimately to optimizing the performance of solid-liquid separation methods and the selection of flocculants for any given slurry. The model identifies two key parameters, the compressional yield stress Py(φ) and the hindered settling factor r(φ) and laboratory test procedures for the direct measurement of both have been developed. The application of this model to a variety of thickening and filtration processes is demonstrated and a direct relationship between the model parameters and the conventional cake resistance as utilised by current filtration engineers is provided.     

In situ preparation of weakly flocculated aqueous anatase suspensions by a hydrothermal technique

Weakly flocculated aqueous anatase suspensions were prepared in situ by hydrothermally treating amorphous titania particles peptized with different amounts of tetraethylammonium hydroxide (TENOH). The simultaneous formation of hydrous TiO2 polyanions in the presence of OH- and tetraethylammonium cations are two essential conditions for the peptization process to occur. The absence of either of these conditions will cause reprecipitation. Transmission electron microscopy (TEM) revealed that the morphology of the particles formed at low TENOH concentrations consisted of well-dispersed anatase crystals, changing to asterisk-like structured particles with increasing concentrations of TENOH. Because of the extremely high absolute zeta potential (over -70 mV in all the samples) and ionic strength values, nontouching particle networks may be formed in situ in the mother solution in all samples, as predicted by DLVO theory. A trend to coagulation was observed in the suspensions with increasing concentrations of TENOH due to a more pronounced secondary minimum in the particle pair potential curves. Assuming the particles remained in the secondary minimum throughout the hydrothermal treatment may lead to the formation of the asterisk-like hard agglomerates. This may arise from the condensation of the -OH-rich TiO2 particles or from the deposition of material in the interparticle gap during the particle growth process. The green packing density of slip-cast bodies from a suspension containing 20 wt% solids was around 46%.     

Size effect on the rheological behavior of nanoparticle suspensions in associating polymer solutions

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups and tend to create bonds between chains by reversible associating interactions. The effects of associating polymer on the steady-shear viscosity and dynamic viscoelasticity are studied for suspensions of silica nanoparticles with diameters of 8, 18, and 25 nm. The silica particles of 8 nm are entrapped in the transient network of associating polymer by reversible adsorption. The enhancement of network results in the high viscosity with a Newtonian flow profile in the limit of zero shear rate. In suspensions of 25 nm silica, the hydrophobes extending from the chains adsorbed onto different particles can form a micelle by association interactions. The multichain bridging gave rise to the shear-thinning flow and high storage modulus at low frequencies. The suspensions of 25 nm silica are characterized as flocculated systems. Because of intermediate curvature, the flexible bridges are formed between silica particles of 18 nm. When the flexible bridges are highly extended within the lifetime in shear fields, the suspensions show shear-thickening flow. The shear-thickening flow can be attributed to the elastic effect of flexible bridges.     

Shear field modification of strongly flocculated suspensions — Aggregate morphology

Rheological and microscopical studies have been made to elucidate the effects of shear fields on the morphology of concentrated, aggregated model colloids. The models employed are well-characterised, predominantly chargestabilised polymer latices, coagulated by the addition of excess electrolyte. Continuous shear rheological and viscoelastic measurements indicate a very significant decrease in shear yield stress, apparent viscosity and shear modulus following prolonged shearing.Electron microscopy reveals the source of these changes. Freshly coagulated suspensions form networks that are porous, strong and qualitatively similar to simulated structures for diffusion limited aggregation. Following protracted shearing, the network structure is rearranged to yield discrete, tightly packed aggregates with a characteristic size, which is principally a function of the primary particle size.     

Influence of flocculant charge on the dewaterability of flocculated clay suspensions

The influence of charged components of cationic polyelectrolytes on the dewatering of clay-containing suspensions was investigated with a view to better predicting the efficiency of flocculating agents. In flocculation and dewatering experiments on suspensions of harbour sediment and gravel washings, flocculating agents of the polyacrylamide-co-(trimethylammoniumpropyl chloride) (PTCA) type exhibited different dewatering efficiencies depending on the degree of cationicity, F. For harbour sediment, a dewatering index, I_D, of 80 was achieved with the highly charged PTCA 3 (F=40%) at 30% lower flocculant dose than with the weakly cationic PTCA 1 (F=3%). However, for gravel washings PTCA 1 proved to be more effective: for comparable degrees of dewatering (I_D=80) approximately 40% less flocculant was required than for PTCA 3. In shear experiments on gravel washings and model suspensions with particles of differing size (d₅₀=0.5 und 5.7 µm) weakly cationic PTCA 1 exhibited an increased floc stability at lower concentrations than is necessary to achieve maximum I_D values. For harbour sediments and model suspensions with unimodal particle size distributions this stability did not occur until the doses used were higher than the concentrations needed to achieve maximum I_D values.     

Photochemical construction of nanoporous polymer microspheres in Cu/Cu2O nanoparticle suspensions

Taking the poly(styrene-co-acrylamide) (P(St-AM)) as a model material, a novel two-step photochemical method was introduced to construct nanoporous polymer microspheres at room temperature. Under ultraviolet light irradiation, suspensions composed of Cu/Cu₂O nanoparticles were first prepared in an alcohol solution of acetylacetonate and benzophenone. Subsequently, the monomers were photopolymerized around the nanoparticles in the suspension-added precursor solution to form polymer–nanoparticle composite microspheres. Nanoporous polymer microspheres could then be obtained by removing the particles with acid. The products had been investigated by XRD, SEM, TEM, IR, DSC, and BET. Results showed the typical microspheres had diameters of 200~300?nm, and the specific areas and pore volume regularly varied with the quantity of the suspensions. By the optimum control, porous P(St-AM) microspheres with average pore size of 5.7?nm, pore volume of 0.18?cm³/g, and specific surface area of 123.54?m²/g could be obtained. The method represents a new, easily manipulated, cost-effective, and safe route for preparation of porous polymer microspheres using inorganic porogens.     

Self-assembled magnetic nanowires made irreversible by polymer bridging

In this letter, we investigate the mechanism of formation of a recently discovered new type of colloid, irreversible flexible chains of magnetic particles. The chain formation mechanism is based on magnetically induced bridging by adsorbed polymers, and we investigate here the associated phase diagrams, considering both thermodynamic and kinetic aspects. This phase diagram is the consequence of a balance between entropic repulsion between polymer layers at the particles surfaces, depletion forces pushing the particles together, and a short-range attractive force developing when polymers can bridge two particles. We end up with a very simple protocol allowing the formation of long, extremely regular chains, which can find numerous applications in chemistry and biology. The perspectives for the development of a new field of "macrocolloidal chemistry" are discussed.     

Scaling behavior of delayed demixing, rheology, and microstructure of emulsions flocculated by depletion and bridging

This paper describes an experimental comparison of microstructure, rheology, and demixing of bridging- and depletion-flocculated oil-in-water emulsions. Confocal scanning laser microscopy imaging showed that bridging-flocculated emulsions were heterogeneous over larger length scales than depletion-flocculated emulsions. As a consequence, G' as determined from diffusing wave spectroscopy (DWS) corresponded well with G' as measured macroscopically for the depletion-flocculated emulsions, but this correspondence was not found for the bridging-flocculated emulsions. The heterogeneity of bridging-flocculated emulsions was confirmed by DWS-echo measurements, indicating that their structure breaks up into large fragments upon oscillatory shear deformation larger than 1%. Depletion- and bridging-flocculated emulsions showed a different scaling of the storage modulus with the volume fraction of oil and a difference in percolation threshold volume fraction. These differences will be discussed on the basis of the two types of droplet-droplet interactions studied. Gravity-induced demixing occurred in both emulsions, but the demixing processes differed. After preparation of bridging-flocculated emulsions, serum immediately starts to separate, whereas depletion-flocculated systems at polysaccharide concentrations in the overlap regime usually showed a delay time before demixing. The delay time was found to scale with the network permeability, B; the viscosity, eta, of the aqueous phase; and the density difference between oil and water, Deltarho, as tdelay approximately B(-1)etaDeltarho(-1). The results are in line with the mechanism proposed by Starrs et al. (J. Phys.: Condens. Matter 2002, 14, 2485-2505), where erosion of the droplet network leads to widening of the channels within the droplet networks, facilitating drainage of liquid.     

Correlation of viscoelastic properties of stable and flocculated suspensions with their interparticle interactions

This review starts with a general introduction on the properties of concentrated suspensions. The distinction between “dilute”, “solid” and “concentrated” suspensions is given in terms of the balance between Brownian, hydrodynamic and interparticle interactions. A section is given on interparticle interactions and their combinations. The four different types of interactions, namely hard-sphere, electrostatic, steric and van der Waals are described. The flocculation of both electrostatically and sterically stabilized suspensions is also discussed. The next section covers the principles of rheological measurements. Transient (static), dynamic (oscillatory), shear wave propagation and steady state measurements are described. The last part of the review deals with the viscoelastic properties of concentrated suspensions. Four different systems were described and examples were given: (a) Suspensions with hard-sphere interactions; (b) Stable systems with soft (electrostatic) interaction; (c) Sterically stabilised systems; (d) Flocculated and coagulated systems. Both weakly and strongly flocculated systems were discussed.In the above review, particular emphasis was given to the relationship between the viscoelastic properties of concentrated suspensions and their interparticle interactions. As far as was possible, the results obtained from rheological measurements were quantitatively analysed in terms of such interparticle forces. The review demonstrated that such correlation is generally followed and this illustrated the powerful use of rheology for studying interparticle interactions.     

Pure-silica-zeolite MEL low-k films from nanoparticle suspensions

Following our previous works on pure-silica-zeolite (PSZ) MFI, in this study we explore PSZ MEL as a new option for low-k dielectric films. Our motivation has been to increase the microporosity of the spin-on films by moving to structures with a framework density (FD) lower than MFI. Nanoparticle PSZ MEL suspensions were synthesized by a two-stage method that allowed the yield of nanocrystals to be significantly enhanced, while the zeolite nanocrystals remain small. For the first time zeolite nanocrystals of about 50 nm were synthesized with a yield as high as 57%. Nanoparticle suspensions with different particle sizes and crystallinities were spun on silicon wafers to prepare continuous thin films. An ultralow-k value as low as 1.5 was obtained with MEL nanoparticle suspension of high relative crystallinity. The surface roughness of the PSZ MEL film with high relative crystallinity is greatly improved (R(rms) approximately 5.6 nm) compared to MFI films with high relative crystallinity (R(rms) approximately 12 nm).     

Controlled nanoparticle assembly by dewetting of charged polymer solutions

In this paper, we present an alternative approach for controlled nanoparticle organization on a solid substrate by applying dewetting patterns of charged polymer solutions as a templating system. Thin films of charged polymer solutions dewet a solid substrate to form complex dewetting patterns that depend on the polymer charge density. These patterns, ranging from polygonal networks to elongated structures that are stabilized by viscous forces during dewetting, serve as potential templates for two-dimensional nanoparticle organization on a solid substrate. Thus, while nanoparticles dried in pure water undergo self-assembly to form close-packed arrays, addition of charged polymer in the dispersion leads to the formation of open structures that are directed by the dewetting patterns of the polymer solution. In this study, we focus on the application of elongated structures resulting from dewetting of high-charge-density polymer solutions to align nanoparticles of silica and gold into long chains that are several micrometers in length. The particle ordering process is a two-step mechanism: an initial confinement of the nanoparticles in the dewetting structures and self-assembly of the particles within these structures upon further drying by lateral capillary attractions.     

Haloing, flocculation, and bridging in colloid-nanoparticle suspensions

Integral equation theory with a hybrid closure approximation is employed to study the equilibrium structure of highly size asymmetric mixtures of spherical colloids and nanoparticles. Nonequilibrium contact aggregation and bridging gel formation is also qualitatively discussed. The effect of size asymmetry, nanoparticle volume fraction and charge, and the spatial range, strength, and functional form of colloid-nanoparticle and colloid-colloid attractions in determining the potential-of-mean force (PMF) between the large spheres is systematically explored. For hard, neutral particles with weak colloid-nanoparticle attraction qualitatively distinct forms of the PMF are predicted: (i) a contact depletion attraction, (ii) a repulsive form associated with thermodynamically stable "nanoparticle haloing," and (iii) repulsive at contact but with a strong and tight bridging minimum. As the interfacial cohesion strengthens and becomes shorter range the PMF acquires a deep and tight bridging minimum. At sufficiently high nanoparticle volume fractions, a repulsive barrier then emerges which can provide kinetic stabilization. The charging of nanoparticles can greatly reduce the volume fractions where significant changes of the PMF occur. For direct and interfacial van der Waals attractions, the large qualitative consequences of changing the absolute magnitude of nanoparticle and colloid diameters at fixed size asymmetry ratio are also studied. The theoretical results are compared with recent experimental and simulation studies. Calculations of the real and Fourier space mixture structure at nonzero colloid volume fractions reveal complex spatial reorganization of the nanoparticles due to many body correlations.     

Growth of colloidal aggregates through polymer bridging

The stability of colloidal dispersions can be altered through the addition of adsorbing macromolecules. Adsorption of macromolecules on the particle surfaces results in a stepwise aggregation process. We consider the early destabilization steps for nanometric ceria particles dispersed in water. These steps have been characterized through light scattering; they are: i) finite multiplets involving one macromolecule and a small number of particles; ii) bridging between mul tiplets; iii) formation of three-dimensional network of bridges. Each stage can be obtained as an equilibrium state, provided there is an adequate balance of electrostatic repulsions and polymer-induced attractions. Altering this balance may push the system from one state into another, or it may change the structure within one state. For instance, multiplets may be pushed to bind more particles or spill them out, depending on the equilibrium length of bridge; gels may reject solvent and turn into flocs if the equilibrium length of bridges becomes shorter than the average distance between particles.     

Asymmetrical flow field-flow fractionation analysis of water suspensions of polymer nanofibers synthesized via RAFT-mediated emulsion polymerization

The aim of this work is to present a method based on asymmetric flow-field-flow-fractionation coupled on-line to a static light scattering (AF4-UV-SLS) detector to characterize self-assembled nanofibers (NFs). The method developed herein allows the determination of both the length distribution of the NFs as well as the distribution in terms of aggregation number per unit length (A_gg). Given the remaining synthetic challenges of better controlling the structural homogeneity and particle dimensions, the NF length and aggregation number per unit length are becoming essential for the improvement and control of their chemical processes and a better understanding of their properties. The results obtained with this AF4-UV-SLS method indicate that a well-resolved NF length distribution characterization and A_gg determination were attained. These results provide critical information concerning the physical properties of the investigated NFs and open the door to the characterization of new self-assembled polymers with various asymmetrical architectures.     

Forces between interfaces in concentrated nanoparticle suspensions and polyelectrolyte solutions

This article provides an overview of interactions between charged interfaces across concentrated suspensions of charged nanoparticles or solutions of polyelectrolytes. These systems bear many similarities. We distinguish the like-charged and oppositely charged situations. In the like-charged situation, a layered structure in the proximity of the interface is formed. This structure induces a strongly repulsive energy profile at shorter distances, which originates from a gap that is free of nanoparticles or polyelectrolytes. At larger distances, the profile becomes oscillatory. This energy profile can be quantified with a simple model, which distinguishes the near-field region and the far-field region. The parameters entering the model show characteristic scaling relations. In the oppositely charged situation, a saturated, tightly bound layer at the interface forms. This layer leads to a charge reversal of the interface and induces a similar layered structure as in the like-charged case.     

Shear thickening in polymer stabilized colloidal suspensions

This paper adopts a previously developed activation model of shear thickening, published by the authors to sterically stabilized colloidal suspensions. When particles arranged along the compression axis of a sheared suspension, they may overcome the repulsive interaction and form hydroclusters associated with shear thickening. Taking advantage of the total interaction potential of polymeric brush coating and van der Waals attraction, the applicability of the activation model is shown within the validity range of a continuum theory. For the comparison with an extensive experimental investigation, where some parameters are not available, the onset of shear thickening can be predicted with realistic assumptions of the model parameters.     

Novel tuneable optical elements based on nanoparticle suspensions in microfluidics

This work demonstrates the application of dielectrophoretic (DEP) control of silica nanoparticles to form tuneable optical elements within a microfluidic system. The implementation consisted of a microfluidic channel with an array of curved microelectrodes along its base. Various DEP conditions were investigated at alternating current voltage amplitudes, flow rates and frequencies from 5 to 15 V, 2 to 10 μL/min and 0 to 20 MHz, respectively. The fluid channel was filled with deionized water suspending silica particles with diameters of 230 and 450 nm. Experiments were conducted to demonstrate DEP concentration and deflection of the particles and the impact of these particles distributions on the optical transmission through the fluid channel. Both confinement and scattering of the light were observed depending on the particle dimensions and the parameters of the DEP excitation. The results of this investigation illustrate the feasibility of DEP control in an optofluidic system and represent a significant step toward the dynamic formation of electrically controlled liquid optical waveguides.     

Time and distance dependence of reversible polymer bridging followed by single-molecule force spectroscopy

Polymer bridging between surfaces plays an important role in a range of fundamental processes in the material and life sciences. Bridges formed by main-chain reversible polymers differ from their covalent analogs in that they can dynamically adjust their size and shape in response to external stimuli and have the potential to reform following bond scission. In this work, the time and distance dependence of main-chain reversible polymer bridge formation are studied using an atomic force microscope. The bridging process was studied using single-molecule force spectroscopy, and its dependence on the distance between surfaces and equilibration time was probed. The number of bridges formed decreases as the gap width increases, from approximately 2 bridges per 14 s equilibration at separations of 5-15 nm to approximately 0.5 bridges per 14 s equilibration at separations of 35-45 nm. The kinetics of bridge formation appear to be slightly faster at smaller separations.