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Natural pozzolan is a promising supplementary cementitious material for hydraulic concrete due to the pozzolanic effect, especially in the area where fly ash is scarce. In this paper, the physical properties of pozzolan were evaluated. The effects of pozzolan fineness and content on the microstructure, compressive strength, and early-age chemical shrinkage of pozzolan blended cement pastes were investigated. The results showed that the addition of pozzolan decreased the compressive strength of hardened cement pastes. The pozzolanic reactivity was closely related to the fineness of pozzolan, and higher pozzolan content led to lower strength. X-ray diffraction (XRD) and thermogravimetric (TG) analysis proved that Ca(OH)2 was consumed by reacting pozzolan, forming new calcium silicate hydrated (C-S-H). Besides, the addition of pozzolan caused the increase in porosity, which was reflected by the increase in macro-pores content. The chemical shrinkage of cement pastes was mainly determined by the hydration rate of cement, so the early-age chemical shrinkage was notably reduced after adding pozzolan due to its lower reactivity than cement clinker. In addition, finer pozzolan particles resulted in less macro-defects in the cement matrix, which enhanced the deformation resistance of hardened cement paste, and thus the chemical shrinkage was also decreased. [ABSTRACT FROM AUTHOR]