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Market demands and legislation are driving the electronics-manufacturing sector to move rapidly toward a lead-free future, with Pb-containing electronics products to be banned in Europe after 2006. Although the related scientific research has been undertaken for a decade, a number of technical complications still exist, which are further exacerbated due to the concurrent developments in miniaturization and multifunctionality of microelectronic products. As the packaging joint geometry shrinks toward a microscopic scale, the joint fabrication and reliability become extremely sensitive to the composition and resulting microstructure generated from the chosen joining process and materials. The current level of understanding of such issues is still in its infancy and therefore requires further fundamental study. Thermodynamic modeling is employed in this work as a computational tool to study the sensitivity of processing ranges (e.g., reflow temperature) and the resultant reliability of the microjoints by changing the alloying elements and their content in Sn-based lead-free systems. The work is implemented using the MTDATA program developed by the National Physical Laboratory. With a newly developed database containing critically assessed thermodynamic data appropriate for lead-free solder systems, MTDATA allows the prediction of the liquid-solid transformation and phase formation, for example, as a function of chemical composition and temperature. The paper emphasizes the formation and mass fraction of intermetallic precipitates of different phases in the bulk solder joints and the modeling is also validated through experimental work and recent literature. The results are expected to assist the optimization of processing parameters and cost-effective production using lead-free solders.