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Influence of PVAc/PVA Hydrolysis on Additive Surface Activity

Squillace, Ophélie; Fong, Rebecca; Shepherd, Oliver; Hind, Jasmine; Tellam, James; Steinke, Nina-Juliane; Thompson, Richard L.

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Ophélie Squillace

Rebecca Fong

Oliver Shepherd

Jasmine Hind

James Tellam

Nina-Juliane Steinke


This aims to establish design rules for the influence of complex polymer matrices on the surface properties of small molecules. Here, we consider the dependence of the surface behaviour of some model additives on polymer matrix hydrophobicity. With stoichiometric control over hydrolysis, we generate systematic changes in matrix chemistry from non-polar, hydrophobic PVAc to its hydrolysed and hydrophilic analogue, PVA. With the changing degree of hydrolysis (DH), the behaviour of additives can be switched in terms of compatibility and surface activity. Sorbitol, a polar sugar-alcohol of inherently high surface energy, blooms to the surface of PVAc, forming patchy domains on surfaces. With the increasing DH of the polymer matrix, its surface segregation decreases to the point where sorbitol acts as a homogeneously distributed plasticiser in PVA. Conversely, and despite its low surface energy, octanoic acid (OA) surprisingly causes the increased wettability of PVAc. We attribute these observations to the high compatibility of OA with PVAc and its ability to reorient upon exposure to water, presenting a hydrophilic COOH-rich surface. The surfactant sodium dodecyl sulfate (SDS) does not show such a clear dependence on the matrix and formed wetting layers over a wide range of DH. Interestingly, SDS appears to be most compatible with PVAc at intermediate DH, which is consistent with the amphiphilic nature of both species under these conditions. Thus, we show that the prediction of the segregation is not simple and depends on multiple factors including hydrophobicity, compatibility, blockiness, surface energy, and the mobility of the components.


Squillace, O., Fong, R., Shepherd, O., Hind, J., Tellam, J., Steinke, N., & Thompson, R. L. (2020). Influence of PVAc/PVA Hydrolysis on Additive Surface Activity. Polymers, 12(1), Article 205.

Journal Article Type Article
Acceptance Date Jan 8, 2020
Online Publication Date Jan 14, 2020
Publication Date Jan 31, 2020
Deposit Date Jan 15, 2020
Publicly Available Date Jan 15, 2020
Journal Polymers
Publisher MDPI
Peer Reviewed Peer Reviewed
Volume 12
Issue 1
Article Number 205
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Published Journal Article (875 Kb)

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Copyright Statement
© This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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