Size matters: asphaltenes with enlarged aromatic cores promote heat transfer in organic phase-change materials

Recent experiments and atomistic computer simulations have shown that asphaltene byproducts of oil refineries can serve as thermal conductivity enhancers for organic phase-change materials such as paraffin and therefore have the potential to improve the performance of paraffin-based heat storage devices. In this work, we explore how the size of the polycyclic aromatic cores of asphaltenes affects the properties of paraffin-asphaltene systems by means of atomistic molecular dynamics simulations. We show that increasing the size of the asphaltene core from 7-8 aromatic rings to ∼20 rings drastically changes the aggregation behavior of asphaltenes. Instead of relatively small, compact aggregates formed by small-core asphaltene molecules, enlarged cores promote the formation of extended single-column structures stabilized in paraffin by asphaltene's aliphatic periphery. Chemical modification of the asphaltenes by removing the periphery leads to the formation of bundles of columns. In contrast to small-core molecules, asphaltenes with enlarged cores do not suppress paraffin crystallization even at high filler concentrations. Remarkably, asphaltenes with enlarged aromatic cores are able to increase the thermal conductivity of liquid paraffin to a greater extent compared to their small-core counterparts. This effect becomes even more pronounced for modified asphaltenes without the aliphatic side groups. Overall, our computational findings suggest that asphaltenes with enlarged aromatic cores can significantly improve the performance of heat storage devices based on organic phase change materials.