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Water sorption also impacts the thermal expansion behavior of ultrathin PVAc films in the glassy state, especially in the region below ∼290 K. As can be seen in Figure 2 b, the thickness change of a 23 nm thick dry PVAc film as a function of temperature in glassy state becomes almost negligible, indicating the reduction of thermal expansivity toward zero in the glassy state with decreasing temperature. We suspect that this originates from water absorption upon cooling: as already mentioned, the sample environment is not perfectly dry, so PVAc films can absorb small amounts of water upon cooling. Similar behavior was not seen in a detailed study [ Kim, S.; Hewlett, S. A.; Roth, C. B.; Torkelson, J. M. Eur. Phys. J. E 2009, 30, 83 - 92 ] of thermal expansion coefficient in confined PS films, presumably because PS sorbs almost no water from the atmosphere.
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