Abstract
The test particle insertion method is used to study the solubility of oxygen in two commonly used polymers: polyethylene (PE) and isotactic polypropylene (iPP). Amorphous samples for both polymers were prepared by means of Monte Carlo and molecular dynamics simulations, and the oxygen solubility was measured across different temperatures. The solubility-temperature dependence for iPP proved to be nonmonotonic due to the interplay between binding and reorganizational enthalpy, while for PE, it appeared to be monotonic based on the available data in the studied temperature range. A broad comparison to experiments and simulations is included. Further oxygen insertions were also performed in semicrystalline PE and iPP samples at ambient temperature, and the obtained values were compared to a linear relationship which correlates the solubility in the purely amorphous phase with the solubility in the crystalline phase. The solubility of PE closely follows the linear relationship, while iPP exhibits some divergence. All the semicrystalline samples were previously annealed at elevated temperatures for long periods (a few μs), and a strong effect of annealing was observed on the structure and the solubility of iPP. A well-developed iPP lamellar structure emerged at longer annealing times, while PE develops that structure already in the early crystallization stages. The solubility of semicrystalline iPP samples with lamellar morphology exhibited better agreement with extrapolated solubility values of the amorphous state─the extrapolation was made using a linear relationship connecting solubility in the purely amorphous phase and solubility in mixed phases (amorphous and crystalline). Results on the correlation of the solubility with the local structural ordering are also present.
| Original language | English |
|---|---|
| Pages (from-to) | 9284-9296 |
| Number of pages | 13 |
| Journal | Journal of Physical Chemistry B |
| Volume | 128 |
| Issue number | 38 |
| Early online date | 18 Sept 2024 |
| DOIs | |
| Publication status | Published - 26 Sept 2024 |
Funding
This research forms part of the research program of DPI project nr. 831., and we thank the DPI industrial partners for the helpful discussions. The research work of Fotis Venetsanos was supported by the Hellenic Foundation for Research and Innovation (HFRI) under the fourth Call for HFRI PhD Fellowships (Fellowship Number: 10646). Additionally, this work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. This work was also supported by computational time granted by the National Infrastructures for Research and Technology S.A. (GRNET S.A.) on the National HPC facility-ARIS-under project IDs pr013009_thin and pr015005_thin. Scienomics SARL is gratefully acknowledged for making their software available to us through the Scienomics Group of Scientific Excellence program. Finally, we are also thankful to Prof. Dr. N. van der Vegt and Prof. F. Mu\u0308ller-Plathe for their insightful discussions on gaseous particles solubility in polymeric matrices.