Surface interaction between phyllosilicate particles and sustainable polymers in flotation and flocculation.

Non-renewable chemical reagents are commonly used as dispersants or flocculants of phyllosilicate clay particles in several industrial fields such as water/wastewater treatment, food production, papermaking, and mineral processing. However, environmentally benign reagents are highly desired due to the non-biodegradability and negative impacts of synthetic reagents on aquatic life. In this work, the dispersion and flocculation behavior of sustainable polymers (anionic and cationic biopolymers) sourced from proteins and polysaccharides were studied in serpentine phyllosilicate suspensions using the following bench-scale tests: zeta potential, microflotation, settling and turbidity, and isotherm adsorption using total organic carbon. The anionic polysaccharide-based biopolymer pectin acted as a switchable biopolymer for serpentine. That is, it could switch from being an efficient flocculant at pH 7 to an effective dispersant at pH 10.

A comparative study of biopolymer adsorption on model anisotropic clay surfaces using quartz crystal microbalance with dissipation (QCM-D).

Mitigation of colloid clay particles is critical during flotation and flocculation processes in mineral processing. Most organic and inorganic mitigation reagents have negative impacts on the environment and human health; therefore, biologically derived substances have been attracting attention as alternative reagents. Given the anisotropic nature of clay surfaces, it is imperative to understand reagent adsorption on the individual edge and basal plane surfaces of clays. Quartz crystal microbalance with dissipation (QCM-D) was used in this study to determine the adsorption characteristics of three biopolymers (the protein-based biopolymer, lysozyme, and protein and polysaccharide-based oligomers; protamine and pectin) on model surfaces of the anisotropic edge and basal planes of the clays (e.g., kaolinite and serpentine). SiO2 sensor representing the tetrahedral basal plane, Al2O3 and Mg(OH)2 representing the octahedral basal planes, AlSiO and MgSiO representing the edge faces of clays were used as model surfaces of clay minerals. For kaolinite, protamine adsorbed preferentially on the silica (SiO2) tetrahedral surface at pH 7 and on the alumina (Al2O3) surface at pH 10. Protamine adsorbed primarily on magnesium hydroxide (Mg(OH)2), representative of serpentine, at pH 7 and 10. Lysozyme adsorbed preferentially and irreversibly on the edge basal plane surfaces of both clays at pH 10, while it showed a higher affinity for octahedral surfaces (alumina and magnesium hydroxide) at pH 7. In contrast, pectin adsorbed strongly on the magnesium hydroxide, representative of the basal plane surface of serpentine. An adsorption study revealed that electrostatic attraction and/or hydrogen bonding mechanisms contributed to the adsorption of biopolymers on clay surfaces. This investigation provides a fundamental and practical understanding of biopolymer interactions with clay surfaces during selective flotation and flocculation.

Modulation of soft glassy dynamics in aqueous suspensions of an anisotropic charged swelling clay through pH adjustment.

HYPOTHESIS: Sodium-montmorillonite (Na-Mt) particles are geometrically anisometric that carry a pH dependent anisotropic surface charge. Therefore, it should be possible to manipulate the particle-particle interaction of colloidal range Na-Mt suspensions through pH changes which in turn should alter the soft glassy dynamics of Na-Mt suspensions. EXPERIMENTS: Rheological experiments were used to probe the impact of pH mediated colloidal particle-particle interaction on the physical aging, linear viscoelastic response, and yield stress behavior of Na-Mt suspension. FINDINGS: The temporal evolution of the storage modulus (G') was stronger in the acid regime (pH < 9.5) than the base (pH ≥ 9.5) pH regime. Horizontal shifting of the aging curves in the acid and base regimes led to aging time-H+ concentration and aging time-OH- concentration superposition. An aging time-Na-Mt concentration superposition was also observed in both pH regimes. The critical stress associated with the viscosity bifurcation behavior increased linearly with G' but with different slopes for acid and base regime. We propose that positively charged patches on the Na-Mt particle edge merge with the characteristic surface as a function of H+ ions in the system. This leads to a strongly associated microstructure at low pH and a relatively weak but associated microstructure at natural pH, hence confirming the hypothesis.

Physical aging in aqueous nematic gels of a swelling nanoclay: sol (phase) to gel (state) transition.

Aqueous dispersions of geometrically anisometric, nano-sized sodium-montmorillonite (Na-Mt) display a sol-gel transition at very low solids concentrations. The microstructure of the gel formed at very low ionic strengths is considered electrostatically repulsive with a nematic character, and the gel state at ionic strengths where Debye length is of the order of particle size is conjectured to be free of physical aging. We investigated the nature of osmotically prepared Na-Mt dispersions at low ionic strength (∼10-5 M), below and above the gel point. The sol phase exhibited very low yield stress compared to the gel state, without any sign of physical aging, thus behaving as an equilibrium state. In contrast, the gel exhibited signatures of physical aging, that is, an evolving microstructure that consolidated with time when left undisturbed thus behaving as out of equilibrium state. The physical aging behaviour became more pronounced at Na-Mt concentrations far above the gel point. A critical shear rate existed, below which no stable flows were possible in the gel state representing the microstructural reorganization timescale. Overall, Na-Mt dispersions in the gel state behave like systems that were out of equilibrium with an ever-evolving microstructure, in opposition to the assumption that low ionic strength Na-Mt gels are in an equilibrium phase. The possible origin of physical aging, such as the reversible orientation of Brownian anisotropic particles, stiffening of an existing microstructure, or reorganization of microstructure towards minimal energy configuration is discussed in detail.

Rheological implications of pH induced particle-particle association in aqueous suspension of an anisotropic charged clay.

Kaolinite particles are geometrically anisometric and electrostatically anisotropic. Until recently, the charge of both basal faces of kaolinite was assumed to be independent of pH, and the isoelectric point (IEP) of the edge surface was thought to occur at pH 4-6. Therefore, kaolinite suspensions were expected to have an edge-face association at low pH. However, recent atomic force microscopy (AFM) studies have shown that the kaolinite alumina basal face and edge surface carry a pH-dependent surface charge with an IEP at pH 5-6 and ∼ 3, respectively. Here, we revisit the modes of particle association in kaolinite suspensions and apply Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to study the rheological implications of surface charges of various kaolinite faces from recent AFM-based studies. Specifically, aging within the linear viscoelastic region, small amplitude oscillatory shear behavior (strain amplitude and frequency response), and critical stress behavior were studied as a function of pH. Kaolinite suspensions (40 wt%) exhibited two-step structure recovery after shear rejuvenation and two-step yielding at pH less than the IEP of the alumina basal face. In addition, the storage modulus (G') and critical stress required to stabilize the flow followed non-monotonic behavior as a function of pH. At low pH, the silica face-alumina face mode of association was expected to be dominant rather than the edge-face microstructure. A peak in the G'vs. pH curve at pH 4.5-5 was correlated with the silica face-alumina face attraction estimated from DLVO theory, which passes through a maximum at approximately the same pH. Based on these observations, we propose a qualitative state diagram for kaolinite suspensions in the pH-concentration space.

Mineral carbonation for serpentine mitigation in nickel processing: a step towards industrial carbon capture and storage.

A proof-of-concept for the carbonation-assisted processing of ultramafic nickel ores is presented. Carbonation converts serpentine, the primary gangue or undesirable mineral, to magnesite. It prevents slime coating of fine gangue minerals on pentlandite, the main nickel-bearing mineral, during froth flotation, and improves nickel recovery and concentrate grade. Additionally, CO2 is captured and stored in the form of solid carbonates, thus removing it from the atmosphere. Microflotation experiments demonstrated improved nickel recovery (61.2 to 87.4 wt%) and concentrate grade (20.6 to 24.7 wt%) in carbonated vs. uncarbonated systems. The mechanism behind the improved nickel flotation was investigated by zeta potential measurements, optical imaging microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. These analyses confirmed the absence of slime coating in the carbonated system under the flotation conditions tested. Finally, a preliminary techno-economic analysis was performed to evaluate the cost metrics of incorporating carbonation into nickel mineral processing.

Adsorption of enhanced oil recovery polymer, schizophyllan, over carbonate minerals.

Schizophyllan is a natural polysaccharide that has shown great potential as enhanced oil recovery (EOR) polymer for high-temperature, high-salinity reservoirs. Nevertheless, the adsorption behavior of schizophyllan over carbonate minerals remains ambiguous element towards its EOR applications. Here, we investigate the adsorption of schizophyllan on different carbonate minerals. The effect of mineral type, salinity, and background ions on adsorption is analyzed. Our results indicate the adsorption capacity is higher on calcite and dolomite compared to silica and kaolin and the adsorption capacity decreases with salinity. Moreover, the adsorption kinetics follows pseudo-second order mechanism regardless of the mineral type. Adsorption over calcite is diminished in presence of water structure making ions and enhanced in presence of structure breaking ion and in presence of urea. Gel permeation chromatography results reveal the preferential adsorption of longer chains. The adsorption over carbonate minerals proceed via complex formation between polymer molecule and mineral surface.

3D Printing of Vascular Tubes Using Bioelastomer Prepolymers by Freeform Reversible Embedding.

Bioelastomers have been extensively used in tissue engineering applications because of favorable mechanical stability, tunable properties, and chemical versatility. As these materials generally possess low elastic modulus and relatively long gelation time, it is challenging to 3D print them using traditional techniques. Instead, the field of 3D printing has focused preferentially on hydrogels and rigid polyester materials. To develop a versatile approach for 3D printing of elastomers, we used freeform reversible embedding of suspended prepolymers. A family of novel fast photocrosslinakble bioelastomer prepolymers were synthesized from dimethyl itaconate, 1,8-octanediol, and triethyl citrate. Tensile testing confirmed their elastic properties with Young's moduli in the range of 11-53 kPa. These materials supported cultivation of viable cells and enabled adhesion and proliferation of human umbilical vein endothelial cells. Tubular structures were created by embedding the 3D printed microtubes within a secondary hydrogel that served as a temporary support. Upon photocrosslinking and porogen leaching, the polymers were permeable to small molecules (TRITC-dextran). The polymer microtubes were assembled on the 96-well plates custom made by hot-embossing, as a tool to connect multiple organs-on-a-chip. The endothelialization of the tubes was performed to confirm that these microtubes can be utilized as vascular tubes to support parenchymal tissues seeded on them.

One-Pot Synthesis of Unsaturated Polyester Bioelastomer with Controllable Material Curing for Microscale Designs.

Synthetic polyester elastomeric constructs have become increasingly important for a range of healthcare applications, due to tunable soft elastic properties that mimic those of human tissues. A number of these constructs require intricate mechanical design to achieve a tunable material with controllable curing. Here, the synthesis and characterization of poly(itaconate-co-citrate-co-octanediol) (PICO) is presented, which exhibits tunable formation of elastomeric networks through radical crosslinking of itaconate in the polymer backbone of viscous polyester gels. Through variation of reaction times and monomer molar composition, materials with modulation of a wide range of elasticity (36-1476 kPa) are generated, indicating the tunability of materials to specific elastomeric constructs. This correlated with measured rapid and controllable gelation times. As a proof of principle, scaffold support for cardiac tissue patches is developed, which presents visible tissue organization and viability with appropriate elastomeric support from PICO materials. These formulations present potential application in a range of healthcare applications with requirement for elastomeric support with controllable, rapid gelation under mild conditions.

Probing anisotropic surface properties and interaction forces of chrysotile rods by atomic force microscopy and rheology.

Understanding the surface properties and interactions of nonspherical particles is of both fundamental and practical importance in the rheology of complex fluids in various engineering applications. In this work, natural chrysotile, a phyllosilicate composed of 1:1 stacked silica and brucite layers which coil into cylindrical structure, was chosen as a model rod-shaped particle. The interactions of chrysotile brucite-like basal or bilayered edge planes and a silicon nitride tip were measured using an atomic force microscope (AFM). The force-distance profiles were fitted using the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, which demonstrates anisotropic and pH-dependent surface charge properties of brucite-like basal plane and bilayered edge surface. The points of zero charge (PZC) of the basal and edge planes were estimated to be around pH 10-11 and 6-7, respectively. Rheology measurements of 7 vol % chrysotile (with an aspect ratio of 14.5) in 10 mM NaCl solution showed pH-dependent yield stress with a local maximum around pH 7-9, which falls between the two PZC values of the edge and basal planes of the rod particles. On the basis of the surface potentials of the edge and basal planes obtained from AFM measurements, theoretical analysis of the surface interactions of edge-edge, basal-edge, and basal-basal planes of the chrysotile rods suggests the yield stress maximum observed could be mainly attributed to the basal-edge attractions. Our results indicate that the anisotropic surface properties (e.g., charges) of chrysotile rods play an important role in the particle-particle interaction and rheological behavior, which also provides insight into the basic understanding of the colloidal interactions and rheology of nonspherical particles.