We prepared pure and mixed monolayers of methoxy-terminated poly(ethylene glycol)s (m-PEG's) chemically attached to silica surfaces by using m-PEG silane coupling agents of three different molecular weights. These films were subsequently characterized in water by atomic force microscopy (AFM). Images of pure m-PEG monolayers showed the formation of polymer brushes on silica. Force curves between two modified surfaces suggested that an increase in the number of oxyethylene (OE) groups from 6 (PEG6 surface) to 43 (PEG43 surface) to 113 (PEG113 surface) decreased the flexibility of the m-PEG chains in the m-PEG brushes. Frictional force measurements also showed that the friction increased in the order PEG6 < PEG43 < PEG113. Because PEG113 had a molecular weight that was greater than the critical molecular weight for entanglement in a PEG melt and displayed the least stretching of its chain, a chain in the PEG113 brush was thought to participate in entanglements or interchain hydrogen bonding. Mixed monolayers of PEG6 and PEG113 were prepared using various fractions of PEG6 and PEG113. Images of mixed PEG6 and PEG113 monolayers showed that the size of the PEG113 islands in the film decreased as the fraction of PEG113 decreased. The force curves between two modified surfaces suggested that the flexibility of the mixed monolayers decreased as the fraction of PEG113 increased. Frictional force measurements also showed that the friction decreased as the fraction of PEG6 in the PEG6-PEG113 mixed film increased. Entanglements were therefore thought to decrease as the fraction of PEG113 in the mixed monolayer decreased.
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