1H NMR spin-spin relaxation and imaging in porous systems : an application to the morphological study of white Portland cement during hydration in the presence of organics

Proton nuclear magnetic resonance (NMR) spin-spin relaxation and imaging have been applied to investigate white Portland cement pastes during hydration in the absence and in the presence of organic solvents. The main organic solvent investigated was methanol, alone or together with the organic waste 2-chloroaniline (2-CA), an aromatic amine representative of an important class of highly toxic compounds. For all the analysed samples, prepared with a solvent-to-cement ratio of 0.4, the decay of the echo magnetization has been fitted by adopting a model that combines an exponential component with a gaussian one. The calculated independent relaxation parameters have been discussed in terms of morphological and dynamical changes that occur during the cement hardening process and pore formation. Three kinds of water molecules: “solid-like” (chemically and physically bound), “liquid-like” (porous trapped) and “free” water, endowed with anisotropic, near isotropic and isotropic motion, respectively, were identified. Spin-echo images collected on the same samples during the hydration kinetics, allowed the changes of water and solvents spatial distribution in the porous network to be monitored, showing percolation phenomena and confirming the multimodal open channels structure of the hardened cement system. Both T2 relaxation and imaging data indicated that a pronounced delay occurs in the cement hardening when organics are present.