The effect of alloying the Eu element on primary Si refinement in varied purity Al–16Si alloys was studied by scanning electron microscopy (SEM), thermal analysis, micro x–ray diffraction (μ–XRD), electron probe microanalysis (EPMA), and transmission electron microscopy (TEM). The results indicate that the P impurity element in hypereutectic Al–Si alloys has a great influence on the rare earths’ refinement efficiency of primary Si. Coinstantaneous primary Si refinement and eutectic Si modification by Eu was obtained in high purity (HP) Al–16Si and commercial purity (CP) Al–16Si–0.06P alloys, but the primary Si was gradually coarsened in CP Al–16Si alloys. An excellent integration of ultimate tensile strength (144.8 MPa) and elongation (9.8%) of CP hypereutectic Al–16Si–0.06P alloy was obtained by adding 0.15% Eu. The refinement of primary Si in Eu–modified HP Al–16Si alloys was related to the constitutional undercooling of Eu. There was no sufficient Eu element partition into the primary Si particles, and fewer parallel twins, rather than multiple twins, were observed within them. The refinement of primary Si in CP Al–16Si–0.06P alloys was caused by the overlay of two kinds of mechanisms including the heterogeneous nucleation mechanism of AlP and the constitutional supercooling mechanism of Eu. However, in order to refine the primary Si in CP hypereutectic Al–16Si alloys, the Eu:P weight ratio should not exceed 3.33, otherwise the refinement efficiency of primary Si will be reduced due to mutual poisoning between Eu and P. This work can be used to interpret the controversy concerning the influence of rare earths on the primary Si in hypereutectic Al–Si alloys, thereby elucidating the importance of alloy purity to primary Si refinement by rare earths.

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