skip to main content

Title: Dispersing nano- and micro-sized portlandite particulates via electrosteric exclusion at short screening lengths
In spite of their high surface charge (zeta potential ζ = +34 mV), aqueous suspensions of portlandite (calcium hydroxide: Ca(OH) 2 ) exhibit a strong tendency to aggregate, and thereby present unstable suspensions. While a variety of commercial dispersants seek to modify the suspension stability and rheology ( e.g. , yield stress, viscosity), it remains unclear how the performance of electrostatically and/or electrosterically based additives is affected in aqueous environments having either a high ionic strength and/or a pH close to the particle's isoelectric point (IEP). We show that the high native ionic strength (pH ≈ 12.6, IEP: pH ≈ 13) of saturated portlandite suspensions strongly screens electrostatic forces (Debye length: κ −1 = 1.2 nm). As a result, coulombic repulsion alone is insufficient to mitigate particle aggregation and affect rheology. However, a longer-range geometrical particle–particle exclusion that arises from electrosteric hindrance caused by the introduction of comb polyelectrolyte dispersants is very effective at altering the rheological properties and fractal structuring of suspensions. As a result, comb-like dispersants that stretch into the solvent reduce the suspension's yield stress by 5× at similar levels of adsorption as compared to linear dispersants, thus enhancing the critical solid loading ( i.e. , at which jamming occurs) by 1.4×. Significantly, the behavior of diverse dispersants is found to be inherently related to the thickness of the adsorbed polymer layer on particle surfaces. These outcomes inform the design of dispersants for concentrated suspensions that present strong charge screening behavior.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Soft Matter
Page Range / eLocation ID:
3425 to 3435
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. We report a colloid–polymer model system with tunable bridging interactions for microscopic studies of structure and dynamics using confocal imaging. The interactions between trifluoroethyl methacrylate-co-tert-butyl methacrylate copolymer particles and poly(acrylic acid) (PAA) polymers were controllable via polymer concentration and pH. The strength of adsorption of PAA on the particles, driven by pH-dependent interactions with polymer brush stabilizers on the particle surfaces, was tuned via solution pH. Particle–polymer suspensions formulated at low pH, where polymers strongly adsorbed to the particles, contained clusters or weak gels at particle volume fractions of ϕ = 0.15 and ϕ = 0.40. At high pH, where the PAA only weakly adsorbed to the particle surface, particles largely remained dispersed, and the suspensions behaved as a dense fluid. The ability to visualize the suspension structure is likely to provide insight into the role of polymer-driven bridging interactions in the behavior of colloidal suspensions.

    more » « less
  2. We explore the rheology during a startup flow of well-characterized polyelectrolyte microgel suspensions, which form soft glasses above the jamming concentration. We present and discuss results measured using different mechanical histories focusing on the variations of the static yield stress and yield strain. The behavior of the shear stress growth function is affected by long-lived residual stresses and strains that imprint a slowly decaying mechanical memory inside the materials. The startup flow response is not reversible upon flow reversal and the amplitude of the static yield stress increases with the time elapsed after rejuvenation. We propose an experimental protocol that minimizes the directional memory and we analyze the effect of aging. The static yield strain γ p and the reduced static yield stress σ p / σ y , where σ y is the dynamic yield stress measured from steady flow measurements, are in good agreement with our previous simulations [Khabaz et al., “Transient dynamics of soft particle glasses in startup shear flow. Part I: Microstructure and time scales,” J. Rheol. 65, 241 (2021)]. Our results demonstrate the need to consider memory and aging effects in transient measurements on soft particle glasses. 
    more » « less
  3. Weitz, David (Ed.)

    A hallmark of concentrated suspensions is non-Newtonian behavior, whereby the viscosity increases dramatically once a characteristic shear rate or stress is exceeded. Such strong shear thickening is thought to originate from a network of frictional particle–particle contact forces, which forms under sufficiently large stress, evolves dynamically, and adapts to changing loads. While there is much evidence from simulations for the emergence of this network during shear thickening, experimental confirmation has been difficult. Here, we use suspensions of piezoelectric nanoparticles and exploit the strong local stress focusing within the network to activate charge generation. This charging can then be detected in the measured ac conductance and serve as a signature of frictional contact formation. The direct link between stress-activated frictional particle interactions and piezoelectric suspension response is further demonstrated by tracking the emergence of structural memory in the contact network under oscillatory shear and by showing how stress-activated friction can drive mechano-transduction of chemical reactions with nonlinear reaction kinetics. Taken together, this makes the ac conductance of piezoelectric suspensions a sensitive in-situ reporter of the micromechanics associated with frictional interactions.

    more » « less
  4. Debris flows are dense and fast-moving complex suspensions of soil and water that threaten lives and infrastructure. Assessing the hazard potential of debris flows requires predicting yield and flow behavior. Reported measurements of rheology for debris flow slurries are highly variable and sometimes contradictory due to heterogeneity in particle composition and volume fraction ( ϕ ) and also inconsistent measurement methods. Here we examine the composition and flow behavior of source materials that formed the postwildfire debris flows in Montecito, CA, in 2018, for a wide range of ϕ that encapsulates debris flow formation by overland flow. We find that shear viscosity and yield stress are controlled by the distance from jamming, Δ ϕ = ϕ m − ϕ , where the jamming fraction ϕ m is a material parameter that depends on grain size polydispersity and friction. By rescaling shear and viscous stresses to account for these effects, the data collapse onto a simple nondimensional flow curve indicative of a Bingham plastic (viscoplastic) fluid. Given the highly nonlinear dependence of rheology on Δ ϕ , our findings suggest that determining the jamming fraction for natural materials will significantly improve flow models for geophysical suspensions such as hyperconcentrated flows and debris flows. 
    more » « less
  5. Adsorption processes at mineral–water interfaces control the fate and transport of arsenic in soils and aquatic systems. Mechanistic and thermodynamic models to describe this phenomenon only consider inner-sphere complexes but recent observation of the simultaneous adsorption of inner- and outer-sphere arsenate on single crystal surfaces complicates this picture. In this study, we investigate the ionic strength-dependence of the macroscopic adsorption behavior and molecular-scale surface speciation of arsenate bound to gibbsite and bayerite. Arsenate adsorption decreases with increasing ionic strength on both minerals, with a larger effect at pH 4 than pH 7. The observed pH-dependence corresponds with a substantial decrease in surface charge at pH 7, as indicated by zeta-potential measurements. Extended X-ray absorption fine structure (EXAFS) spectroscopy finds that the number of second shell Al neighbors around arsenate is lower than that required for arsenate to occur solely as an inner-sphere surface complex. Together, these observations demonstrate that arsenate displays macroscopic and molecular-scale behavior consistent with the co-occurrence of inner- and outer-sphere surface complexes. This demonstrated that outer-sphere species can be responsible for strong adsorption of ions and suggests that environments experiencing an increase in salt content may induce arsenic release to water, especially under weakly acidic conditions. 
    more » « less