Structure and phase behavior of poly(acrylic acid)-ferric ion complex aqueous solutions

In this study, we investigate the conformational evolution and phase behavior of poly(acrylic acid) (PAA) solution upon the introduction of ferric ions through a combination of small angle X-ray scattering (SAXS), turbidity, zeta-potential and pH measurements. Salt-free PAA aqueous solution is a weak polyelectrolyte solution. The introduced ferric ion can coordinate with the carboxylic acid groups, yielding H+ ions to lower the pH value. We find two transitions with increasing concentration of the ferric ions: a polyelectrolyte to apparent good solution transition characterized by the disappearance of the polyelectrolyte peak in the X-ray scattering, and a phase separation characterized by a sharp increase of the turbidity. Detailed analyses of pH and zeta-potential reveal the molecular details of the three regions. Namely, (1) the polyelectrolyte region locates at log[H+] (= -pH) ≫ log(3[Fe3+]), where the H+ ions are mainly contributed from the dissociation of carboxylic acid, and the polymer chains are negatively charged, (2) the good solution region locates at log[H+] ∼ log(3[Fe3+]), where the H+ ions are mainly yielded from coordination between COO- and Fe3+, and polymer chains are nearly neutralized, and (3) the phase separation locates at log[H+] ≪ log(3[Fe3+]), where the Fe3+ ions are not fully coordinated, and charge inversion occurs. The phase separation occurs when the chains are densely and tightly coordinated with Fe3+ ions.