Transient Thermal Conductivity Minimum in Phenolic Foam Insulation: Closed-Cell Structural Dependence and Long-Term Aging Behavior

Closed-cell phenolic foam (PF) insulation is widely assumed to exhibit monotonically increasing thermal conductivity after cutting, driven by progressive blowing agent release. This study reports a previously uncharacterized behavior: a consistent decrease–minimum–rebound pattern in the days to weeks after cutting, defined here as the transient thermal conductivity minimum (TTCM). Using n-pentane-blown PF foam, thermal conductivity and mass were tracked under standard (23 °C) and accelerated aging conditions (70 °C, 110 °C; slicing per KS M ISO 11561), complemented by gas chromatography–flame ionization detection (GC-FID), attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FT-IR), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), and scanning electron microscopy (SEM). TTCM reductions of 3.8–16.7% were observed across all closed-cell specimens; a reference PF foam with cell-wall micro-perforations showed no TTCM, establishing intact closed-cell structure as a prerequisite. The mechanism is attributed to redistribution of dissolved n-pentane from the polymer matrix into the cell gas phase, thermodynamically favored by the proximity of n-pentane’s boiling point (36.07 °C) to the heat flow meter (HFM) hot plate temperature (33 °C). In the post-TTCM phase, thermal conductivity rises progressively as n-pentane is displaced by air; the rate of this rise is strongly dependent on diffusion path length. These results establish two mechanistically distinct aging stages and identify their respective governing factors.