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Studies of solids by NMR relaxation experiments are special issues based on the following general statements. The experimental decay of macroscopic transverse or longitudinal magnetization follows the exponential law for complete domination of the spin-diffusion mechanism and a single relaxation time characterizes all of the nuclei in rigid solids, even those that are not chemically or structurally equivalent. The spin-diffusion mechanism is typical of systems with nuclei experiencing strong dipolar interactions (protons, fluorine or phosphorus nuclei at relatively small concentrations of paramagnetic centers). For other nuclei with weak dipolar coupling and/or at high concentration of paramagnetic centers, relaxation can be non-exponential following a stretched exponential function, exp(–(τ/T1) β ) or exp(–(τ/T2) β ). For paramagnetic solids, the β value of corresponds to relaxation via direct electron–nucleus dipolar interactions without spin diffusion, while intermediate values between and can be attributed to a diffusion-limited mechanism.