Due to the health and environmental concerns associated with lead usage, the research on alternative lead-free alloys for replacing lead-based solders is a global demand. Despite numerous studies on Sn-based lead-free solders in recent years, there is not yet a standard solder alloy able to cover the spectrum of properties furnished by the classic Sn-Pb alloy. In this sense, particular lead-free alloys compositions have been suited for specific needs and the options have been broadening when elements other than tin are used as the base component, such as indium, gold and bismuth. The later element is well known in the hall of lead-free alloys as an alloying option rather than as a base component. This study aims to establish interrelations of solidification thermal parameters (growth and cooling rates), microstructure features (primary and secondary dendrite arm spacings – λ1 and λ2; eutectic spacing – λE and interphase spacing – λint) and hardness of Bi-Zn alloys (1.5wt% Zn-hypoeutectic, 2.7wt% Zn-eutectic, and 5wt% Zn-hypereutectic alloys) samples, which were directionally solidified in unsteady-state conditions under cooling rates similar to those of found in industrial soldering practice. Examination of the resulting microstructures by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) permitted the different phases morphologies to be characterized: Bi-rich trigonal dendrites and long Zn fibers, as primary phases of, hypoeutectic and hypereutectic alloys, respectively, immersed in a fiber-like eutectic mixture. The combined effects of macrosegregation, Zn alloying and representative scales of the phases forming the microstructure (λint, λ2 and λE) on hardness of the Bi-Zn alloys are evaluated and Hall–Petch type equations relating λint, λ2 and λE to hardness are proposed.
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