Heats of reaction and heat capacity changes were measured using scanning nanocalorimetry for a nickel and aluminum bilayer where initial heating rates of 104 K/s were achieved. Multiple exotherms were observed on the initial heating, but the number of intermediate exotherms decreased with increasing heating rate. The final phase was the B2 NiAl intermetallic. Results from the nanocalorimeter were compared with a conventional differential scanning calorimeter (operating at 0.7 K/s) to understand the effect of significant (10 000×) increases in heating rate on the phase transformation sequence. The high heating rate in the nanocalorimeter delays reaction initiation, causes the exothermic peaks to shift to higher temperatures, and appears to suppress the formation of intermediate, metastable phases. Potential explanations for this apparent suppression are discussed. © 2013 American Institute of Physics.