Asphaltenes as novel thermal conductivity enhancers for liquid paraffin: Insight from in silico modeling

The practical use of paraffin and other organic phase-change materials for heat storage is largely limited by their low thermal conductivity. In this paper we employed 60 microsecond-long atomic-scale computer simulations to explore for the first time whether the asphaltenes, natural polycyclic aromatic hydrocarbons, can be used as thermal conductivity enhancers for paraffin. We focused on a simple model molecule of asphaltene (a polycyclic aromatic core decorated with the peripheral alkane chains) and showed that the asphaltenes of such molecular architecture are not able to improve the thermal conductivity of paraffin. This is most likely due to the steric constraints imposed by the peripheral alkane groups, which prevent formation of the extended ordered asphaltene aggregates. To overcome this, we proposed a possible chemical modification of the asphaltene molecules through removing the peripheral alkane groups from their aromatic cores; this could be achieved e.g. by thermal cracking (dealkylation) of asphaltenes. It turns out that such a chemical modification drastically changes the situation: the modified asphaltenes form extended columnar aggregates which can serve as thermal conduction paths, considerably enhancing the thermal conductivity of a liquid composite sample. This effect, however, vanishes upon cooling because the columnar extended stacks of chemically modified asphaltenes transform into the helical twisted structures, which reduces the overlap of adjacent asphaltenes in aggregates. Importantly, all the simulations have been carried out with two different all-atom force fields. We have demonstrated that both computational models give qualitatively similar results. Overall, our findings clearly show that chemically modified asphaltene molecules can be considered as promising carbon-based thermal conductivity enhancers for liquid paraffin; this result can be used for optimizing the paraffin-based thermal energy storage systems.