Sequential Diffusion Spectra as a Tool for Studying Time-Dependent Translational Molecular Dynamics: A Cement Hydration Study.

The translational molecular dynamics in porous materials are affected by the presence of the porous structure that presents an obstacle for diffusing molecules in longer time scales, but not as much in shorter time scales. The characteristic time scales have equivalent frequency ranges of molecular dynamics, where longer time scales correspond to lower frequencies while the shorter time scales correspond to higher frequencies of molecular dynamics. In this study, a novel method for direct measurement of diffusion at a given frequency of translational molecular dynamics is exploited to measure the diffusion spectra, i.e., distribution of diffusion in a wide range of frequencies. This method utilizes NMR modulated gradient spin-echo (MGSE) pulse sequence to measure the signal attenuation during the train of spin-echoes formed in the presence of a constant gradient. From attenuation, the diffusion coefficient at the frequency equal to the inverse double inter-echo time is calculated. The method was employed to study the white cement hydration process by the sequential acquisition of the diffusion spectra. The measured spectra were also analyzed by the diffusion spectra model to obtain the time-dependence of the best-fit model parameters. The presented method can also be applied to study other similar systems with the time evolution of porous structure.