Heterogeneous nucleation of Cu6Sn5 in Sn-Cu-Al solders

Cu6Sn5 is a common intermetallic in Pb-free soldering. We explore the influence of dilute aluminium additions on the heterogeneous nucleation and grain refinement of primary Cu6Sn5 in Sn-4Cu-xAl solders. For cooling rates relevant to soldering, it is found that 0.02 and 0.2 wt%Al cause significant grain refinement of Cu6Sn5 with 0.2 wt%Al increasing the number of Cu6Sn5 grains per unit area by a factor of ∼8. Grain refinement is shown to be due to heterogeneous nucleation of Cu6Sn5 on either delta-Cu33Al17 or gamma1-Cu9Al4, coupled with significant constitutional supercooling ahead of growing Cu6Sn5 crystals. Reproducible orientation relationships are measured between the Cu-Al intermetallics and Cu6Sn5, with a planar lattice mismatch of less than 2.5%. The role of potent nuclei and solutal growth restriction are discussed with reference to the grain refinement of structural casting alloys.