Mapping positron annihilation lifetime spectroscopy data of a polymer to classical molecular dynamics simulations without shifting the glass transition temperature.
J Chem Phys
; 159(8)2023 Aug 28.
Article
in En
| MEDLINE
| ID: mdl-37606328
ABSTRACT
Positron annihilation lifetime spectroscopy (PALS) enables the nondestructive measurement of nanoscale cavities in materials. In this study, a strategy was proposed for mapping PALS measurement data of isotactic polypropylene to classical molecular dynamics (CMD) simulations. The discrepancy between simulated and experimental glass transition temperatures was resolved by shortening the polymer chains, rather than adjusting for the temperature, using the Williams-Landel-Ferry (WLF) equation. The effective probe radii of ortho-positronium (o-Ps), determined by comparing PALS data with CMD simulations, were â¼0.8 nm, which was consistent with the o-Ps size given by the solution of the Schrödinger equation. The free-volume fraction corresponding to the effective probe radius was 12.3% at the glass transition temperature, close to the value estimated using Simha-Boyer theory. The cavity number density was proportional to the effective probe radius and decreased with temperature. The o-Ps effective probe radius was proportional to both the critical probe radius and the -1/3 power of the monomer number density, and increased with increasing temperature. These findings suggest that combining PALS measurements with CMD simulations may provide insight into cavities in polymeric materials without relying on the WLF equation.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Chem Phys
Year:
2023
Document type:
Article
Affiliation country:
Japan