Four-component united-atom model of bitumen

TL;DR

This paper introduces a four-component molecular model of bitumen, enabling molecular dynamics simulations that reveal detailed high-temperature dynamics, relaxation processes, and nano-aggregate formation, with results aligning reasonably with experimental data.

Contribution

A novel four-component coarse-grained molecular model of bitumen that captures its dynamic heterogeneity and nano-aggregate formation, facilitating microsecond-scale simulations.

Findings

Molecular diffusivity varies little with temperature.

Distinct dynamical time scales for different constituents.

Nano-aggregates of asphaltene, resin, and resinous oil observed.

Abstract

We propose a four-component molecular model of bitumen. The model includes realistic chemical constituents and introduces a coarse-graining level that suppresses the highest frequency modes. Molecular dynamics simulations of the model are being carried out using Graphic-Processor-Units based software in time spans in order of microseconds, and this enables the study of slow relaxation processes characterizing bitumen. This paper focuses on the high-temperature dynamics as expressed through the mean-square displacement, the stress autocorrelation function, and rotational relaxation. The diffusivity of the individual molecules changes little as a function of temperature and reveals distinct dynamical time scales as a result of the different constituents in the system. Different time scales are also observed for the rotational relaxation. The stress autocorrelation function features a slow non-exponential decay for all temperatures studied. From the stress autocorrelation function, the shear viscosity and shear modulus are evaluated at the highest temperature, showing a viscous response at frequencies below 100 MHz. The model predictions of viscosity and diffusivities are compared to experimental data, giving reasonable agreement. The model shows that the asphaltene, resin and resinous oil tend to form nano-aggregates. The characteristic dynamical relaxation time of these aggregates is different from the homogeneously distributed parts of the system, leading to strong dynamical heterogeneity.