title: Modeling the adsorption behavior of linear end-functionalized poly(ethylene glycol) on an ionic substrate by a coarse-grained Monte Carlo approach.
abstract: The rheology of cement pastes can be controlled by polymeric dispersants such as branched polyelectrolytes that adsorb on the surfaces of silicate particles. In the present work, we analyze the adsorption behavior of ad hoc-prepared end-carboxylated poly(ethylene glycol), or PEG, on CaCO(3) particles as a model of cement in an early hydration stage. The experimental adsorption isotherms form the base of a theoretical study aimed at unraveling polymer conformational aspects of adsorption. The study was carried out with Monte Carlo simulations using a coarse-grained bead-and-spring model of linear end-charged polymer chains adsorbing on a flat, continuous, uniformly charged surface. The adsorption driving force was introduced by a Debye-Hückel electrostatic screened potential to describe the interaction between the negatively charged end group of PEG and the positively charged CaCO(3) surface empirically. With a suitable length-scale conversion between real PEG and the coarse-grained model, the calculated and experimental adsorption isotherms can be semiquantitatively compared. The theoretical results reproduce the fundamental aspects of polymer adsorption, in essential agreement with analytical approaches relating the isotherm shape to the polymer conformational properties. The conformational transition mushroom-brush of the adsorbed polymer is located on the isotherm and is related to the molecular shape. The solvent quality effect and the solution ionic strength are also considered, and their implications on the isotherms are discussed.
authors.affiliation: Institute for Biochemical Research G. Ronzoni, via G. Colombo 81, 20133 Milan, Italy. stefano.elli@gmail.com
authors.forename: Stefano
authors.initials: S
authors.lastname: Elli
authors.forename: Lidia
authors.initials: L
authors.lastname: Eusebio
authors.forename: Paolo
authors.initials: P
authors.lastname: Gronchi
authors.forename: Fabio
authors.initials: F
authors.lastname: Ganazzoli
authors.forename: Marco
authors.initials: M
authors.lastname: Goisis
mesh_terms: D000327:Adsorption; D002119:Calcium Carbonate / Q000737:chemistry*; D008958:Models, Molecular; D009010:Monte Carlo Method; D009994:Osmolar Concentration; D011092:Polyethylene Glycols / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013499:Surface Properties
chemical_list: D012997:Solvents; D011092:Polyethylene Glycols; D002119:Calcium Carbonate