Since rocks will generate voltage under load, studying their voltage characteristics is of prime importance for the prevention and control of mine dynamic disasters and the corresponding secondary disasters. In this study, a pressure stimulated voltage (PSV) test system for rock materials under uniaxial compression was constructed to explore the law of PSV variations of rocks. Meanwhile, a nuclear magnetic resonance test system was employed for investigating the influence mechanism of pore structure changes on PSV variations. The following beneficial results were obtained. A “double-peak” phenomenon is observed on the PSV curves of granite and sandstone, whereas, for marble, the phenomenon only appears under high loading rates. The T2 spectra of different types of rock differ greatly. After granite fractures under load, some primary micro-pores are converted into meso-pores and macro-pores, accompanied by the generation of substantial new micro-pores. These micro-pores activate more rock defects (dislocation and grain boundary), resulting in a higher average PSV and peak PSV. After marble fractures, numerous primary micro-pores are transformed into meso-pores and macro-pores, and the proportion of new micro-pores falls. Consequently, its electricity generation capacity weakens. In contrast, sandstone contains a higher proportion of micro-pores. After it fractures, despite the conversion of some micro-pores into meso-pores and macro-pores, abundant micro-pores are generated again, bringing about a relatively high voltage. In short, the changes in overall porosity cannot represent the electricity generation capacity of rock, and the changes in bound cracks exert a profoundly influence on it. The key to the electricity generation capacity of rock lies in the increase and connection of micro-cracks.
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