Compressive Yield Stress of Flocculated Kaolin Suspensions in Seawater.

The mining industry has resorted to using seawater while trying to find a solution to the water shortage, which is severe in some regions. Today, the industry looks to tailings dams to recover more water and, thus, increase recirculation. The migration of interstitial water due to the consolidation of particle networks can give rise to large water mirrors in different dam areas. These pools can contain enough water to be recovered and recirculated if the external stress caused by the weight of the pulp exceeds the compressive yield stress. The density and rheological properties of the discarded pulps determine the feasibility of water expulsion during tailings consolidation. As these conditions are largely established in the thickening stage, it is necessary to revisit operations, looking at the dam as a water source. Thus, a thorough understanding of the compressive properties that determine the level of consolidation of typical pulps and their relationships to aggregate properties, such as size and fractal dimension, is crucial. Here, the effect of two types of water, industrial water and synthetic seawater, on kaolin flocculation, sedimentation rate, yield stress, and compressive yield stress were studied. In addition, the relationship of these properties with the flocculant dose and the resulting aggregate size and fractal dimension was examined. One promising finding to practitioners was that salt and small doses of high molecular weight flocculant improved the consolidation of kaolin slurries under compression. These conditions generated low compressive yield stress compared to fresh water and water with low salt content, favoring the consolidation of the pulps and the release of water.

Species Surface Distribution and Surface Tension of Aqueous Solutions of MIBC and NaCl Using Molecular Dynamics Simulations.

Methyl isobutyl carbinol (MIBC) is a high-performance surfactant with unusual interfacial properties much appreciated in industrial applications, particularly in mineral flotation. In this study, the structure of air-liquid interfaces of aqueous solutions of MIBC-NaCl is determined by using molecular dynamics simulations employing polarizable and nonpolarizable force fields. Density profiles at the interfaces and surface tension for a wide range of MIBC concentrations reveal the key role of polarizability in determining the surface solvation of Cl- ions and the expulsion of non-polarizable Na+ ions from the interface to the liquid bulk, in agreement with spectroscopic experiments. The orientation of MIBC molecules at the water liquid-vapor interface changes as the concentration of MIBC increases, from parallel to the interface to perpendicular, leading to a well-packed monolayer. Surface tension curves of fresh water and aqueous NaCl solutions in the presence of MIBC intersect at a reproducible surfactant concentration for a wide range of salt concentrations. The simulation results for a 1 M NaCl aqueous solution with polarizable water and ions closely capture the MIBC concentration at the intercept. The increase in surface tension of the aqueous MIBC/NaCl mixture below the concentration of MIBC at the intersection seems to originate in a disturbance of the interfacial hydrogen bonding structure of the surface liquid water caused by Na+ ions acting at a distance and not by its presence on the interface.

The Impact of Residual Dispersant on the Flocculation and Sedimentation of Synthetic Tailings in Seawater.

Dispersants under certain conditions favor the flotation of molybdenite in seawater; however, it is not clear if the entrainment of residues to the thickening stage can compromise the quality of the clarified water. In this work, the impact of small concentrations of sodium hexametaphosphate (SHMP) on the flocculation and sedimentation of synthetic tailings containing kaolinite, muscovite, and quartz in seawater is evaluated. The flocculant polymer is a high-molecular-weight polyacrylamide, and the pH is alkaline. The results are auspicious for mineral processing. On the one hand, the impact of SHMP is not entirely negative and can be lessened by limiting entrainment, which is good for copper and molybdenum ore processing. On the other hand, if the small increase in turbidity generated by the SHMP is tolerated, it is possible to expect improved settling speeds. Without SHMP, large but light agglomerates are formed. With SHMP, smaller but denser aggregates are formed, settling faster, and minute aggregates increase turbidity. The underlying mechanism derives from the competition between SHMP and polymer chains for the cations in solution; the result is a greater repulsion between the chains, which leads to greater repulsion and thus dispersion of smaller flocculant coils. The study shows that SHMP in concentrations of 1 to 3 kg/t is perfectly acceptable. The results represent an advance in the understanding of SHMP interactions with polymers and minerals in water clarification, which should be of interest to the industry whose sustainability in some regions depends on closing the water cycle.

Estimating the Shear Resistance of Flocculated Kaolin Aggregates: Effect of Flocculation Time, Flocculant Dose, and Water Quality.

The resistance of kaolin aggregates to shearing in water clarification and recovery operations is a critical input in designing thickener feed wells. A recently formulated but already available criterion is used to determine the shear strength of flocculated kaolin aggregates. The flocculant is a high molecular weight anionic polyelectrolyte. The resistance of the aggregates is evaluated as a function of flocculation time, flocculant dosage, and water quality. The determination is based on a standardized experimental method. First, the time evolution of the average size of kaolin flocs is measured when aggregates are exposed to incremental shear rates from a predetermined base value. Then, the results are fitted to a pseudo-first-order model that allows deriving a characteristic value of the shear rate of rupture associated with the upper limit of the strength of the aggregates. In seawater, at a given dose of flocculant, the strength of the aggregates increases with time up to a maximum; however, at longer times, the resistance decreases until it settles at a stable value corresponding to stable aggregates in size and structure. A higher flocculant dosage leads to stronger aggregates due to more bridges between particles and polymers, leading to a more intricate and resistant particle network. In industrial water with very low salt content, the resistance of the kaolin aggregates is higher than in seawater for the same dose of flocculant. The salt weakens the resistance of the aggregates and works against the efficiency of the flocculant. The study should be of practical interest to concentration plants that use seawater in their operations.

Lime/Sodium Carbonate Treated Seawater to Improve Flocculation and Sedimentation of Clay-Based Tailings.

Seawater treated with lime and sodium carbonate in different proportions to reduce magnesium and calcium contents is used in flocculation and sedimentation tests of artificial quartz and kaolin tailings. Solid complexes were separated from water by vacuum filtration, and factors such as lime/sodium carbonate ratio, kaolin content, flocculation time, and flocculant dose are evaluated. The growth of the aggregates was captured in situ by a focused beam reflectance measurement (FBRM) probe. Solid magnesium and calcium complexes are formed in raw seawater at pH 11, impairing the performance of flocculant polymers based on polyacrylamides. The results show that the settling rate improved when the treatment's lime/sodium carbonate ratio increased. That is, when a greater removal of magnesium is prioritized over calcium. The amount of magnesium required to be removed depends on the mineralogy of the system: more clay will require more significant removal of magnesium. These results respond to the structural changes of the flocs, achieving that the more magnesium is removed, the greater the size and density of the aggregates. In contrast, calcium removal does not significantly influence flocculant performance. The study suggests the necessary conditions for each type of tailing to maximize water recovery, contributing to the effective closure of the water cycle in processes that use seawater with magnesium control.

New route for self-assembly of α-lactalbumin nanotubes and their use as templates to grow silver nanotubes.

Nanotubes are formed by self-assembly of α-lactalbumin milk protein following a different route than established for the hydrolysis which involves V8 enzyme, phosphate buffer and appropriate amounts of calcium at neutral pH. The resulting nanotubes are used as templates for the growth of conductive silver nanotubes. TEM, SEM-EDS, AFM and FTIR are used for characterization.

Direct measurement of interaction forces between bovine serum albumin and poly(ethylene oxide) in water and electrolyte solutions.

The net interaction between a probe tip coated with bovine serum albumin (BSA) protein and a flat substrate coated with poly(ethylene oxide) (PEO) polymer was measured directly on approach in water and electrolyte solutions using AFM. The approach force curve between the two surfaces was monotonically repulsive in water and in electrolyte solutions. At pH ~5, slightly above the isoelectric point (pI) of BSA, and at large distances, the force was dominated by electrostatic repulsion between the oxygen atoms of the incoming protein with those belonging to the ether groups of PEO. Such repulsive force and range decreased in NaCl. Under physiological conditions, pH 6, BSA is definitely charged and the electrostatic repulsion with ether groups in PEO appears at larger separation distances. Interestingly, at pH 4, below the pI of BSA, the repulsion decreased because of an attractive, although weak, electrostatic force that appeared between the ether groups in PEO and the positively charged amino groups of BSA. However, for all solution conditions, once compression of PEO begun, the net repulsion was always dominated by short-range polymeric steric repulsion and repulsive enthalpy penalties for breaking PEO-water bonds. Results suggest that PEO in mushroom conformation may also be effective in reducing biofouling.

Force exerted by a nanoscale capillary water bridge between two planar substrates.

Molecular dynamics simulation of a nanoscale capillary water bridge between two planar substrates is used to determine the resulting force between the substrates without arbitrariness regarding geometry and location of the free surface of the bridge. The substrates are moderately hydrophilic. The force changes continuously as the separation between the substrates changes except for small gaps where it becomes discontinuous because the bridge is unable to adopt stable configurations at any distance apart. Further exploration of the bridge and the force as the substrates approach each other reveals an underlying oscillatory force with an increasing repulsive component at separation distances equivalent to few water molecules. According to the average number of hydrogen bonds per water molecule (HBN), at very small gap sizes, water molecules which are very close to the surfaces are unable to maximize HBN thus contributing to the repulsive force. Our simulation results of force versus gap size agree with calculations based on other methods, some very different, and also reproduce the typical magnitude of the experimental force. Finally, a macroscopic force balance correctly describes the force-distance curve except for bridges constituted of water layers only.

Population balance modelling of particle flocculation with attention to aggregate restructuring and permeability.

A population balance model based on a detailed literature review is used to describe coagulation and flocculation kinetics as well as the time evolution of aggregate size distribution in a turbulent shear flow simultaneously with the breakage and restructuring of aggregates. The fractal nature and permeability of the aggregates and their evolution with time are also part of the model. Restructuring is absent in coagulation with soluble salts, but is present in flocculation caused by large polyelectrolyte molecules; in the latter, aggregates never reach a steady-state size, but a size that decreases gradually through particle and polymer rearrangement. The model is tested against available experimental data for monodisperse polystyrene particles coagulated with hydrated aluminium sulphate at different shear rates, and precipitated calcium carbonate flocculated with a cationic polyelectrolyte of very high molecular weight at different flocculant dosages. The numerical solution of the model requires adjusting three parameters, i.e, maximum collision efficiency (αmax), critical force needed for the breakage of the aggregates (B) and rate of aggregate restructuring (γ), which are obtained from minimising the difference between experimental data and model predictions. The model studied for the two very different systems shows excellent agreement with experimental flocculation kinetics and a reasonably good fit for aggregate size distributions. The model is most sensitive to the fragmentation rate through parameter B, somewhat less to the collision efficiency through parameter αmax and little to γ. When the aggregates undergo restructuring, properties such as permeability, breakage rate and collision rate change considerably over time. When the aggregates are permeable, the collision frequency is significantly smaller than when they are impervious.

A molecular dynamics study of the force between planar substrates due to capillary bridges.

Molecular dynamics simulations are used to study capillary liquid bridges between two planar substrates and the origin, strength and range of the resulting force between them. Pairwise interactions are described by the Lennard-Jones potential. Surface wettability is tuned by varying the fluid-substrate well depth interaction parameter. The force between the substrates due to a bridge of liquid is estimated by different methods including non-equilibrium simulations of moving substrates connected by liquid bridges and macroscopic balance of forces. The latter involves knowledge of liquid-vapor interfacial free energy, curvature radii, radius of wetted area and contact angle at the triple-phase contact line. All these physical quantities are estimated from equilibrium simulations. The force is attractive when the substrates are solvophilic or moderately solvophobic; and thus for cavities surrounded by the same liquid the force is attractive even when the substrates are moderately solvophilic. Two threshold values for the fluid-substrate potential interaction parameter can be identified; one for which the effective interaction between substrates due to liquid bridges changes from repulsive to attractive and another for which the capillary bridge becomes mechanically unstable and breaks into droplets.

Nanoscale adhesive forces between silica surfaces in aqueous solutions.

Nanoscale adhesive forces between a colloidal silica probe and a flat silica substrate were measured with an atomic force microscope (AFM) in a range of aqueous NaCl, CaCl2, and AlCl3 solutions, with concentrations ranging from 10(-)(6) to 10(-)(2) M at pH ∼5.1. Notably, the measured force curves reveal large pull-off forces in water which increase in electrolyte solutions, with jump-off-contact occurring as a gradual detachment of the probe from the flat substrate rather than as a sharp discontinuous jump. The measured force curves also show that the number and size of the steps increase with concentration and notably with electrolyte valence. For the higher concentration and valence the steps become jumps. We propose that these nanoscale adhesive forces between mineral surfaces in aqueous solutions may arise from newly born cavities or persistent subnanometer bubbles. Formation of cavities or nanobubbles cannot be observed directly in our experiments; however, we cannot disregard them as responsible for the discontinuities in the measured force data. A simple model based on several cavities bridging the two surfaces we show that is able to capture all the features in the measured force curves. The silica surfaces used are clean but not intentionally hydroxylated, as contact angle measurements show, and as such may be responsible for the cavities.

AFM forces between mica and polystyrene surfaces in aqueous electrolyte solutions with and without gas bubbles.

Force curves between a flat mica substrate and a polystyrene microsphere were measured with an atomic force microscope (AFM) in carefully degassed water and aqueous NaCl, CaCl2, and AlCl3 solutions. The pH of the water used does not change significantly with degassing treatment, and its value remains close to 6. Electrolyte concentration ranges from 10-4 to 10-2M and pH from 4.7 to 5.1. We have found that the repulsive long-range electrostatic force between mica and polystyrene is attenuated by the presence of electrolytes and counterbalanced by a long-range attractive force, which we referred to as a hydrophobic force, which is longer-ranged than the ever present attractive van der Waals force. This force, which includes the adhesive bridging of residual air bubbles and newborn vapor cavities, and any other unknown forces, is reasonably well represented by a unique exponential law. Prefactor and decaying length are not very sensitive to electrolyte type, concentration, and pH, suggesting that any new force included in the law, in addition to adhesive bridges, should obey a non-classical electrostatic mechanism. However, we also know that liquid/solid contact angle and liquid/vapor surface tension increase with electrolyte concentration and valence increasing the stability of bubbles and cavities which in turn increase the bridging force. Clearly, these effects are hidden in the empirical force law.

Nanoscale repulsive forces between mica and silica surfaces in aqueous solutions.

Nanoscale repulsive forces between mineral surfaces in aqueous solutions were measured for the asymmetric mica-silica system. The force measured with an atomic force microscope (AFM) has universal character in the short range, less than ∼1 nm or about 3-4 water molecules, independent of solution conditions, that is, electrolyte ion (Na, Ca, Al), concentration (10(-6)-10(-2)M), and pH (3.9-8.2). Notably, the force is essentially the same as for the glass-silica system. Single force curves for a mica-silica system in a 10(-4)M aqueous NaCl solution at pH ∼ 5.1 show oscillations with a period of about 0.25 nm, roughly the diameter of a water molecule, a consequence of a layer-by-layer dehydration of the surfaces when pushed together. This result provides additional support to the idea that nanoscale repulsive forces between mineral surfaces in aqueous solutions arise from a surface-induced water effect; the water between two mineral plates that are pushed together becomes structured and increasingly anchored to the surface of the plates by the creation of a hydrogen-bonding network that prevents dehydration of the surfaces.

Short-range forces between glass surfaces in aqueous solutions.

We found that the force between glass surfaces measured with an atomic force microscope (AFM) has universal character in the short range, less than approximately 1 nm or about 3-4 water molecules, independent of solution conditions, that is, electrolyte ion size, charge and concentration and pH. Our results suggest that the excess DLVO force, obtained by subtracting the DLVO theory with a charge regulation model from the AFM force data, essentially does not change with the electrolytes Na, Ca, and Al, in the range of concentration from 10(-6) to 10(-2) M and the range of pH from 3.1 to 7.9. Single force curves for a glass-silica system in a 10-4 M aqueous NaCl solution at pH approximately 5.1 show oscillations with a period of about 0.25 nm, roughly the diameter of a water molecule. We postulate that the excess force between glass surfaces arises from a surface-induced solvent effect, from the creation of a hydrogen-bonding network at the surface level, rather than from a solvent-induced surface steric hindrance.