The colloidal microstructure of concentrated suspensions containing anionic comb-polymer-stabilized magnesium oxide (MgO) particles in water was analyzed by shear rheometry for indications of changes in particle microstructure based on particle size and comb-polymer usage. As the suspensions were sheared at different rates, jamming in the sheared MgO suspensions was observed as shear stress overshoots. The shear-induced evolution of the suspension's microstructure was strongly related to the perceived interactions between neighboring MgO particles in the suspension. In the jammed state, interactions are believed to be enhanced by the formation of entanglements between opposing comb-polymer side-chains. Steric repulsion between side-chains was lessened for large particles on account of their diameters, which further enabled side-chain entanglement during close particle contact under shear. Suspensions with relatively wide particle size distributions (0.5-400 lm) were theorized to form hydrocluster aggregates, while suspensions with narrower particle size distributions (0.5-40 lm) most likely resulted in networked microstructures under the influence of the chain entanglements from the adsorbed comb-polymer.
Lignopolymers are a new class of polymer additives with the capability to be used as dispersants in cementitious pastes. Made with kraft lignin cores and grafted polymer side-chains, the custom-synthesized lignopolymers were examined in terms of the molecular architecture for viscosity reducing potential in inert model suspensions. Lignin-poly(acrylic acid) (LPAA) and lignin-polyacrylamide (LPAm) have been found to vary the rheology of magnesium oxide (MgO) suspensions based on differences in chain architecture and particle-polymer interactions. A commercial comb-polymer polycarboxylate ester was compared to LPAA and LPAm at 2.7 mg/mL, a typical dosage for cement admixtures, as well as 0.25mg/mL. It was found that LPAm was a more effective viscosity reducer than both LPAA and the commercial additive at low concentrations, which was attributed to greater adsorption on the MgO particle surface and increased steric dispersion from PAm side-chain extension. The influence of chain adsorption and grafted side-chain molecular weight on rheology was also tested.
The mechanical response of alginate rafts formed by mixing liquid alginate antacid medication (Gaviscon Extra Strength Liquid Antacid) with acidic solutions was investigated by deforming isolated rafts in a shear rheometer. As rafts were deformed to varying magnitudes of applied strain, rheological parameters were identified and related to the overall strength, durability, and recoverability of rafts formed at different pH (1.1-1.7) and aging conditions (0.5-4 h). Rafts formed in the lowest acidity solutions (pH 1.4, 1.7) were elastically weak ( G'₀ = 60 , 42 Pa for un-aged raft) yet maintained their elasticity during applied shear deformation to large values of strain (γc∼90%, 50%, where G'≈G″), and displayed a low-to-moderate level of elastic recovery following large-strain deformation. Rafts formed in the highest acidity solution had the greatest strength ( G'₀ = 500 Pa for un-aged raft and 21.5 kPa for rafts after 0.5 h of aging), reduced durability (γc∼2.5%, independent of aging), and displayed the greatest recoverability. A trade-off existed between un-aged raft strength and durability while recovery was dependent on durability, solution pH, and age. Rheometry-based evaluations of alginate rafts could be used for the informed design of future gastric retention and antacid products.
Adsorbed polymer additives have been employed to reduce water content and improve cement workability through lowering viscosity, but the influence of over‐dosage and the presence of nonadsorbed chains have yet to be fully understood. Model magnesium oxide (MgO) suspensions were used to investigate the potential processing effect of “free” chain concentration on cementitious mixtures. The rheological impact of the free chains was measured through incorporation of nonadsorbing poly(ethylene glycol) (PEG) to suspensions stabilized with an adsorbed comb‐polymer superplasticizer. Analyses of the rheological data, that showed viscosity‐increases and viscosity‐reduction due to free PEG concentrations revealed a transition from depletion flocculation to depletion stabilization that contributed to the flow properties of the suspensions. The viscosity‐reduction observed for high concentrations of free chains may be useful for improved mixing of cements with free polymer in addition to the adsorbed polycarboxylate ether‐based superplasticizer. Additionally, the influence of free PEG on the macroscale flow behavior was also examined through local velocity measurements under shear. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45696.
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