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The effect of calcium addition on the microstructures of AZ91 magnesium alloy was investigated. It was found that a small amount of calcium in AZ91 alloy produced a large decrease in the a-Mg grain size and the dispersed fine β-Mg17 Al12 phases. In addition, some Al4 Ca particles were found to exist in the AZ91 alloy containing 0.5 wt% Ca. EDS analysis and water-quenched technique revealed that the grain-refining mechanism of calcium for the AZ91 alloys was mainly attributed to the role of restricting growth of calcium in the primary a-Mg crystals.