When surface-active molecules or particles assemble at fluid–fluid interfaces, these interfaces acquire complex rheological properties that are of importance in processes that involve flow and deformation of interfaces. Although much progress has been made, interfacial rheology measurements and, in particular, the measurement of interfacial rheological properties of polymers at the air-water interface remain challenging. These are due to weak interactions with the water subphase, the polymer backbone conformation, the glass transition of the interfacial layer, and memory effects. In the present work, we describe systematic rheological measurements of polymer-laden interfaces. The measurements were performed with four different interfacial shear rheometers that can be classified into two types: rheometers in which the surface pressure can be controlled independently, and devices based on fixtures mounted on standard rotational rheometers and lacking control of the surface pressure. We use poly(tert-butyl methacrylate) and poly(methyl methacrylate), two high glass transition temperature, hydrophobic polymers anchored to the water subphase by means of the acrylate group. Using a Langmuir–Pockels (LP) trough, we identify the transition of the polymer monolayer from a viscous to a solid elastic or soft-glassy interface as the polymer surface concentration increases by compression. Then, we compare the linear viscoelastic properties of the interface as obtained by each rheometer. Our results show poor reproducibility and comparability of the rheological data as obtained by different rheometers for the same polymer. This is mainly due to differences in the method used to prepare the layers. For LP-based devices, spreading under dilute conditions and subsequent compression yields layers of compressed glassy blobs with reproducible results. On the other hand, for devices without surface pressure control, deposition of the amount needed to reach a desired concentration may lead to the formation of ill-defined layers resulting in irreproducible data. Furthermore, we find that only when spreading the polymer to form a dilute layer and then controlling the surface pressure by compression, we can clearly distinguish the fluidlike from solidlike interfaces, and a clear correlation is observed between the surface pressure (or interfacial polymer concentration) and the rheological properties of the interface.
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Interfacial shear rheology of glassy polymers at liquid interfacesa)
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September 2023
Research Article|
August 21 2023
Interfacial shear rheology of glassy polymers at liquid interfacesa)
Stelios Alexandris
;
Stelios Alexandris
1
Institute of Electronic Structure and Laser, FORTH
, Heraklion 71110, Crete, Greece
2
Department of Materials Science and Technology, University of Crete
, Heraklion 71003, Crete, Greece
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Daniel Ashkenazi;
Daniel Ashkenazi
3
Department of Chemical Engineering, Ben Gurion University
of the Negev, Beer Sheva 8410501, Israel
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Jan Vermant
;
Jan Vermant
4
Department of Materials, ETH Zurich
CH-8093, Zurich, Switzerland
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Dimitris Vlassopoulos
;
Dimitris Vlassopoulos
1
Institute of Electronic Structure and Laser, FORTH
, Heraklion 71110, Crete, Greece
2
Department of Materials Science and Technology, University of Crete
, Heraklion 71003, Crete, Greece
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Moshe Gottlieb
Moshe Gottlieb
b)
3
Department of Chemical Engineering, Ben Gurion University
of the Negev, Beer Sheva 8410501, Israel
b)Author to whom correspondence should be addressed; electronic mail: mosheg@bgu.ac.il
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b)Author to whom correspondence should be addressed; electronic mail: mosheg@bgu.ac.il
a)
This paper was handled by Editorial Board member G. G. Fuller.
J. Rheol. 67, 1047–1060 (2023)
Article history
Received:
May 06 2023
Accepted:
July 31 2023
Citation
Stelios Alexandris, Daniel Ashkenazi, Jan Vermant, Dimitris Vlassopoulos, Moshe Gottlieb; Interfacial shear rheology of glassy polymers at liquid interfaces. J. Rheol. 1 September 2023; 67 (5): 1047–1060. https://doi.org/10.1122/8.0000685
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