How clay particulates affect flow cessation and the coiling stability of yield stress-matched cementing suspensions.

The remarkable increase in the flow resistance of dense suspensions can hinder 3D-printing processes on account of flow cessation in the extruder, and filament fragility/rupture following deposition. Understanding the nature of rheological changes that occur is critical to manipulate flow conditions or to dose flow modifiers for 3D-printing. Therefore, this paper elucidates the influences of clay particulates on controlling flow cessation and the shape stability of dense cementing suspensions that typically feature poor printability. A rope coiling method was implemented with varying stand-off distances to probe the buckling stability and tendency to fracture of dense suspensions that undergo stretching and bending during deposition. The contributions of flocculation and short-term percolation due to the kinetics of structure formation to deformation rate were deconvoluted using a stepped isostress method. It is shown that the shear stress indicates a divergence with a power-law scaling when the particle volume fraction approaches the jamming limit; φ → φj ≈ φmax. Such a power-law divergence of the shear stress decreases by a factor of 10 with increasing clay dosage. Such behavior in clay-containing suspensions arises from a decrease in the relative packing fraction (φ/φmax) and the formation of fractally-architected aggregates with stronger interparticle interactions, whose uniform arrangement controls flow cessation in the extruder and suspension homogeneity, thereby imparting greater buckling stability. The outcomes offer new insights for assessing/improving the extrudability and printability behavior during slurry-based 3D-printing process.

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.