Molecular dynamics study on phase change properties and their nano-mechanism of sugar alcohols: Melting and latent heat

•Investigate melting and latent heat of sugar alcohol phase change materials (PCMs).•Microscopic melting point determination via non-equilibrium molecular dynamics.•Anisotropic melting tendency under 1D heat conductions relates to molecular order.•Latent heat of sugar alcohol PCMs mostly comes from the hydroxy groups.•Number and lifetime of hydrogen bonds connect to the latent heat of sugar alcohols. Sugar alcohol phase change materials have gained considerable attention for heat storage in recent years owing to their higher thermal conductivity and larger latent heat compared to traditional paraffin materials. However, knowledge about the reason of large latent heat and latent heat difference among diverse sugar alcohols as well as the mechanism of melting process remains elusive. In this study, molecular dynamics simulation was employed to investigate the melting process and latent heat of four sugar alcohols (glycerol, erythritol, arabinitol, and mannitol). Melting points and latent heat of fusion were determined first, different melting temperatures were observed under different one-dimensional heat conduction directions in several sugar alcohols. It was found that the strength of intermolecular interactions within molecular crystal layers has a positive correlation with the anisotropic melting tendencies, which can be more intuitively reflected by the difference in the number of hydrogen bonds within the molecular layers. In addition, the decomposition of the latent heat of fusion revealed that the latent heat is mainly composed of van der Waals and Coulombic contributions, where the interaction between hydroxyl groups accounts for a major part. Hydrogen bond analysis demonstrated that the latent heat of fusion is partly due to the breakage of hydrogen bonds during the phase transition of melting. It was also noted that the differences in the hydrogen bonding lifetimes between different sugar alcohols may be related to the magnitude of latent heat of fusion. Erythritol and mannitol which coincidentally happened to have an even number of carbon atoms can fulfill the properties of better PCMs compared to glycerol and arabinitol, which have an odd number of carbons. Those results will pave the way for better design optimization and performance evaluation of sugar alcohols as phase change materials.