title: Adsorption and aqueous lubricating properties of charged and neutral amphiphilic diblock copolymers at a compliant, hydrophobic interface.
abstract: We have investigated the adsorption and lubricating properties of neutral and charged amphiphilic diblock copolymers at a hydrophobic polydimethylsiloxane (PDMS) interface in an aqueous environment. The diblock copolymers consist of a hydrophilic block of either neutral poly(ethylene glycol) (PEG) or negatively charged poly(acrylic acid) (PAA) and of a hydrophobic block of polystyrene (PS) or poly(2-methoxyethyl acrylate) (PMEA), thus generating PEG-b-X or PAA-b-X, where X block is either PS or PMEA. The molecular weight ratios were roughly 1:1 with each block ca. 5 kDa. Comparing the neutral PEG and charged PAA buoyant blocks with all other conditions identical, the former showed superior adsorption onto nonpolar, hydrophobic PDMS surfaces from a neutral aqueous solution. PEG-based copolymers showed substantial adsorption for both PS and PMEA as the anchoring block, whereas PAA-based copolymers showed effective adsorption only when PMEA was employed as the anchoring block. For PAA-b-PS, the poor adsorption properties are chiefly attributed to micellization due to the high interfacial tension between the PS core and water. The poor lubricating properties of PAA-b-PS diblock copolymer for a PDMS-PDMS sliding contact was well correlated with the poor adsorption properties. PAA-b-PMEA copolymers, despite their sizable amount of adsorbed mass, showed insignificant lubricating effects. When the charges of the PAA-b-PMEA diblock copolymers were screened by either adding NaCl to the aqueous solution or by lowering the pH, both the adsorption and lubricity improved. We ascribe the poor adsorption and inferior aqueous lubricating properties of the PAA-based diblock copolymers compared to their PEG-based counterparts mainly to the electrostatic repulsion between charged PAA blocks, hindering the facile formation of the lubricating layer under cyclic tribological stress at the sliding PDMS-PDMS interface.
authors.affiliation: Department of Mechanical Engineering, Technical University of Denmark, DK-2800, Kgs. Lyngby, Denmark.
authors.forename: Troels
authors.initials: T
authors.lastname: Røn
authors.forename: Irakli
authors.initials: I
authors.lastname: Javakhishvili
authors.forename: Katja
authors.initials: K
authors.lastname: Jankova
authors.forename: Søren
authors.initials: S
authors.lastname: Hvilsted
authors.forename: Seunghwan
authors.initials: S
authors.lastname: Lee
mesh_terms: D000179:Acrylates / Q000737:chemistry; D000327:Adsorption; D000409:Alanine / Q000031:analogs & derivatives / Q000737:chemistry; D057927:Hydrophobic and Hydrophilic Interactions; D008153:Lubrication; D011092:Polyethylene Glycols / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000179:Acrylates; D011108:Polymers; C413485:poly(2-methoxyethylacrylate); C078798:3-(phenylamino)alanine; D011092:Polyethylene Glycols; D000409:Alanine