Equilibrium Swelling of Hydrophilic Polyacrylates in Humid Environments

The hydrophilicity of polymers, as indicated by their swelling characteristics in water, is an important parameter with regard to their use as coatings which are able to modify the wettability and adhesive properties of a material. We have investigated the swelling behavior of a series of hydrophilic random copolymer coatings in controlled humidity environments and in water. Swelling data were obtained from a quartz crystal microbalance (QCM) and from spectroscopic ellipsometry. The hydrophilic polymers are based on polyacrylates with low molecular weight side chains of poly(ethylene glycol) (PEG). These polymers also contain a random distribution of acrylic acid. Triblock copolymers with these random copolymers as the midblock and poly(methyl methacrylate) (PMMA) as the end blocks have also been investigated. At low and intermediate humidities, the swelling behavior of appropriately chosen block copolymers is similar to the swelling behavior of the corresponding polymers that do not have the PMMA end blocks. Substantial differences between the two types of polymers are observed at very high humidities and in water. The PMMA end blocks stabilize the structure of the copolymer layer so that it does not dissolve in water. Swelling curves obtained from the quartz crystal microbalance and from ellipsometry are in agreement with one another when the shape of the quartz crystal resonance (as determined by impedance spectroscopy) is not affected by humidity. We also find evidence for a reversible, humidity-induced phase transition which is readily detectable by the quartz crystal microbalance.