Water-in-oil Pickering high internal phase emulsion (Pickering-HIPE) of dicylopentadiene (DCPD) was prepared by using block copolymer surface-modified calcite (mCalcite) particles. To evaluate the contribution of mCalcite particles comparatively, a neat polyHIPE was first synthesized from a conventional DCPD-based water-in-oil HIPE. SEM analysis demonstrated that polymerization of DCPD-based HIPE and Pickering-HIPE yielded open-porous supporting materials. Mechanical tests showed that mCalcite incorporation significantly improved the compressive modulus of the obtained material compared to the neat support. Tetradecanoic acid (TDA) was used as phase change material (PCM) and was successfully incorporated into the synthesized supporting foams via a solvent-assisted vacuum process. TDA presence in the composite PCM foams, named polyDCPD/TDA and polyDCPD/mCalcite/TDA, was examined based on Brunauer–Emmett–Teller-specific surface area measurement and SEM imaging. The latent heat storage properties and thermal stabilities of the resulting composite PCMs were evaluated by DSC and TGA measurements. The melting temperature and latent heat of melting of the composite PCMs were respectively detected as 52.4 °C and 68.2 J g−1 for polyDCPD/mCalcite/TDA and 52.6 °C and 50.1 J g−1 for polyDCPD/TDA, from DSC thermograms. It was demonstrated that the leak-resistive polyDCPD/mCalcite/TDA exhibited higher thermal stability in comparison with polyDCPD/TDA. Finally, it was concluded that Pickering-polyHIPE supported composite PCM can be efficiently used for low-temperature passive thermal management applications such as solar energy storage, thermal protection of electronic devices etc. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
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