Swelling of star polymer thin films exposed to supercritical carbon dioxide

Author:

Caglayan Ayse1ORCID,Satija Sushil K.2,Uhrig David3,Hong Kunlun3,Koga Tadanori4,Akgun Bulent1ORCID

Affiliation:

1. Department of Chemistry Bogazici University Istanbul Turkey

2. Center for Neutron Research National Institute of Standards and Technology Gaithersburg Maryland USA

3. Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge Tennessee USA

4. Department of Materials Science and Chemical Engineering Stony Brook University, Stony Brook New York New York USA

Abstract

AbstractImpact of polymer chain architecture on the swelling of supported single‐layer polymer thin films with thicknesses below 80 nm in the presence of supercritical CO2 (scCO2) is investigated using in‐situ neutron reflectivity (NR) and ex‐situ x‐ray reflectivity (XR). 4‐arm star and 8‐arm star deuterated polystyrene (dPS) having similar total molecular weights are used. NR results revealed that the magnitude of the swelling for star polymers increases proportionally with decreasing dry film thicknesses similar to linear polymers. For film thicknesses above 5Rg, architectural differences have no impact on the swelling behavior. However, below 5Rg as the branching increases from linear to 4‐arm star and to 8‐arm star, swelling decreases due to the presence of a relatively thicker adsorbed layer formed by more branched architectures. Ex‐situ XR measurements verified that star architectures swell less than linear architecture and provided new information about the vitrification of the films through rapid quenching and its relation to the amount of CO2 retention.

Publisher

Wiley

Subject

Materials Chemistry,Polymers and Plastics,Physical and Theoretical Chemistry

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