We probe the role
of surface functionalization and physical properties
of nanoinclusions in thermal conductivity enhancement during liquid–solid
phase transition in a hexadecane-based phase change material (PCM).
Hexadecane-based PCM is loaded with six different nanoinclusions:
carbon black nanopowder (CBNP), nickel nanoparticles (NiNPs), copper
nanoparticles, silver nanowires (AgNWs), multiwalled carbon nanotubes,
and graphene nanoplatelets (GNPs). The nanoinclusions CBNP, NiNP,
AgNW, and GNP are surface-functionalized with oleic acid. Nanoinclusion-loaded
PCM showed a large enhancement in thermal conductivity, which was
more prominent in the solid state. Interestingly, a maximum thermal
conductivity enhancement of ∼122% was observed in the solid
state for the PCM loaded with 0.01 wt % CBNP. Higher thermal conductivity
enhancement in the solid state is attributed to the formation of a
nanocrystalline network structure during freezing of the PCM, consisting
of a needlelike microstructure, which is confirmed by optical phase
contrast microscopy. During solidification, the nanoinclusions are
driven toward the grain boundaries, thereby forming a quasi-two-dimensional
network of percolating structures with high thermal transport efficiency
due to the enhancement of phonon-mediated heat transfer and near-field
radiative heat transfer. Thermal conductivity increases with the increased
loading of the nanoinclusions due to the formation of more interconnecting
aggregates. Among the carbon-based nanoinclusions, the highest thermal
conductivity enhancement is obtained for the PCM loaded with CBNP,
which is attributed to the low fractal dimensions and volume-filling
capability of CBNP aggregates. In the case of metallic nanoinclusions,
the highest thermal conductivity enhancement is obtained for the PCM
loaded with AgNW, which is due to the large aspect ratio of AgNW.
The carboxylic group of oleic acid attached to the nanoinclusions
is found to provide better steric stability with insignificant aggregation
and improved thermal stability, which are beneficial for practical
applications. Our results indicate that the initial thermal conductivity
of carbon-based nanoinclusions has an insignificant role in the thermal
conductivity enhancement of the PCM but the volume-filling capability
of the nanoinclusion has a prominent role. The findings from the present
study will be beneficial for tailoring the properties of nanoinclusion-loaded
organic PCM for thermal energy storage and reversible thermal switching
applications at room temperature.