Comb polymer architecture effects on the rheological property evolution of concentrated cement suspensions

We have studied the rheological behavior of concentrated cement suspensions in the absence and presence of comb polymers comprised of a polyacrylic acid (PAA) backbone and charge-neutral, poly(ethylene oxide) (PEO) teeth. These species possessed a uniform backbone molecular weight and graft density, with varying teeth molecular weight. Both PAA, a linear polyelectrolyte, and PAA/PEO comb polymers imparted initial stability to concentrated cement suspensions above a critical weight fraction, w* of 4 mg/(g of cement). Cement-PAA suspensions, however, set prematurely. Their rapid, irreversible stiffening stemmed from deleterious interactions between PAA and multivalent counterions in solution. Interestingly, the presence of PEO teeth comprised of only a few monomer units in length mitigated such interactions. The rheological property evolution of concentrated cement-PAA/PEO suspensions exhibited complex behavior ranging from the reversible gel-like response observed at short teeth lengths to a remarkable gel-to-fluid transition observed during the deceleratory period for systems comprised of longer PEO teeth. At longer hydration times, all cement-PAA/PEO suspensions exhibited initial elastic modulus values, G(i)' similar to exp(t/tau(c)) before the onset of the acceleratory period, followed by initial set. Their characteristic hydration time, tau(c), and set time depended strongly on the concentration of "free" carboxylic acid groups [COO-] arising from non-adsorbed polyelectrolyte species in solution.