Journal
LANGMUIR
Volume 26, Issue 2, Pages 838-847Publisher
AMER CHEMICAL SOC
DOI: 10.1021/la902285t
Keywords
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Funding
- Communaute Francaise de Belgique [ARC 06-11/339]
- Belgian Federal Science Policy [IAP-PAI P6/27]
- F.R.S.-FNRS
- Wallonia Region
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We elucidate the sequence of events occurring during the collapse transition of thermoresponsive copolymer brushes based on poly(di(ethyleneglycol) methyl ether methacrylate) chains (PMEO(2)MA) grown by atom-transfer radical polymerization (ATRP). The collapse of the bulk of the brush is followed by quartz crystal microbalance measurements with dissipation monitoring (QCM-D), and the collapse or its outer surface is assessed by measuring equilibrium water contact angles in the captive bubble configuration. The bulk of the brush collapses over a broad temperature interval (similar to 25 degrees C), and the end of this process is signaled by a sharp first-order transition of the surface of the brush. These observations support theoretical predictions regarding the occurrence of a vertical phase separation during collapse, with surface properties of thermoresponsive brushes exhibiting a sharp variation at a temperature of T-br(surf). in contrast, the bulk properties of the brush vary smoothly, with it bulk transition T-br(bulk) occurring oil average similar to 8 degrees C below T-br(surf) and similar to 5 degrees C below the lower critical Solution temperature (LCST) of free chains in solution. These observations should also be valid for planar brushes of other neutral, water-soluble thermoresponsive polymers such as poly(N-isopropylacrylamide) (PNIPAM). We also propose a way to analyze more quantitatively the temperature dependence of the QCM-D response of thermoresponsive brushes and deliver a simple thermodynamic interpretation of equilibrium contact angles, which can be of use for other complex temperature-responsive solvophilic systems.
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