Microsized Pore Structure Determination in EPDM Rubbers Using High-Pressure ¹²⁹Xe NMR Techniques

Microsized pore parameters, such as pore size and distance between pores in a series of model EPDM rubbers, were determined in situ under the pressure of 500 psi using ¹²⁹Xe nuclear magnetic resonance (NMR) techniques: spin-lattice (T₁) and spin-spin (T₂) relaxation measurements, pulsed-field gradient (PFG) NMR, and two-dimensional exchange spectroscopy (2D EXSY). The T₁/T₂ (≫1) ratio for the xenon confined in the pores is larger than that for nonconfined free xenon. This suggests that almost the entire pore surface interacts with xenon atoms like a closed pore. While these pores still connect each other through very narrow diffusion/exchange channels, it is possible to observe the echo decay in PFG-NMR and cross-peaks in 2D EXSY. The results show that both diffusion (D_pore ≈ 2.1 × 10^-10 m²/s) and exchange (exchange rate, τ_exch = a few tens of milliseconds) of xenon between a pore within the material and outer surface are prolonged. The exchange distances (l), which correspond to the xenon gas penetration depth, were estimated to be 70-100 μm based on the measured diffusion coefficients and exchange rate (1/τ_exch). NMR diffraction analysis reveals that pore size (a) and pore distance (b) are on the order of magnitude of micrometers and tens of micrometers, while the diffusion coefficients of xenon gas in the diffusion channels (D_eff) are about 10^-8 m²/s. Overall, this study suggests that the pores with a few micrometers connected through very narrow flowing channels with the length of several tens of micrometers are developed 70 to 100 μm below the rubber surface. Furthermore, the overall steady-state diffusion of xenon is slower, approximately 2 orders of magnitudes, than the diffusion in the channel between the pores. The pore and exchange distances correlated with the composition of rubbers showed that the properties of EPDM rubber as a high-pressure gas barrier could be improved by reducing the size of cracks and the depth of gas penetration by the addition of both carbon black and silica fillers.