Shear‐sensitive chain extension of dissolved poly(ethylene oxide) by aluminate ions

The phase behavior of poly(ethylene oxide) (PEO) in aqueous salt solutions has been studied many times but rarely for solution conditions relevant to the hydration process of cement, where PEO's interactions with surrounding ions modulate its application as both plasticizer and strength‐building additive. Here, the conformation, that is, coil size, of PEO was examined in aqueous solutions in the presence of sodium‐, calcium‐ and aluminum‐containing salts. Ion‐induced conformational changes for a model linear PEO were mostly unremarkable and consistent with past reports. However, trends for aluminum‐containing ions, which predominantly occur in water at neutral and basic pH as the monovalent hydroxo‐aluminate anion Al(OH)4−, were different: either present as the sodium or calcium salt, PEO's hydrodynamic radius determined by dynamic light scattering was approximately 30% larger than determined by intrinsic viscosity. The intrinsic viscosity was similar to that measured in the presence of simpler monovalent anions. We hypothesize that aluminum containing ions weakly couple the model polymer's hydroxyl end groups (present at just one chain end), creating polymeric aggregates sensitive to disruption by shearing. Supporting our argument, the hydrodynamic radius determined by dynamic light scattering dropped to the intrinsic viscosity value after hydroxyl groups were converted to methoxy groups. Weak coupling between the complex aluminum ions and the hydroxyl end group of the PEO chain results in a significant difference between the radii measured by the intrinsic viscosity and dynamic light scattering (DLS). The coupling is stable in the DLS's quiescent conditions but broken by the shear forces exerted during the intrinsic viscosity measurement.