Size and pH effect on electrical and conformational behavior of poly(acrylic acid): Simulation and experiment

• Published in: European polymer journal Vol. 42; no. 5; pp. 1135 - 1144
• Main Authors: Laguecir, Abohachem, Ulrich, Serge, Labille, Jérôme, Fatin-Rouge, Nicolas, Stoll, Serge, Buffle, Jacques
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 01-05-2006; Elsevier
• Subjects: Applied sciences; Continental interfaces, environment; Diffusion coefficient; Environment and Society; Environmental Sciences; Exact sciences and technology; Fluorescence correlation spectroscopy; Monte Carlo simulations; Organic polymers; Physicochemistry of polymers; Poly(acrylic acid) ionization; Properties and characterization; Sciences of the Universe; Solution and gel properties; Titration curves; Poly(acrylic acid) ionization; Monte Carlo simulations; Titration curves; Diffusion coefficient; Fluorescence correlation spectroscopy; Monte Carlo method; Computer simulation; Radius of gyration; Experimental study; Polyelectrolyte; Ionic strength; Acrylic acid polymer; pH; Aqueous solution; Acid base titration; Conformation
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/j.eurpolymj.2005.11.023

Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations.