Thermal transformations occurring during firing of recyclable concrete and hydrated Portland cement paste were monitored quantitatively by in situ and ex situ X‐ray diffraction, thermal analysis, and clinker microscopy. Reactions below 1150°C
were dominated by either the decarbonation of calcium carbonates of the limestone aggregate fraction in the recyclable concrete or the low temperature decomposition of cement hydrates of the cement paste. Continued heating of the cement paste showed a rapid and extensive reaction of the free
lime to form intermediate calcium silicate and aluminate phases such as belite, gehlenite, mayenite, and ye'elimite. The combination of free lime was less rapid in the dominantly limestone‐rich recyclable concrete. Similarly, subsequent melt and clinker phase formation (1250°C and
higher) occurred more rapidly in the hydrated cement paste, indicating a positive contribution of cement hydrates to raw meal burnability. Reactions below typical cement clinkering temperatures were enhanced (1) by the intimate mixing of lime, silicate, and aluminate components in the hydrated
cement and (2) by the elevated sulfate content that acted as flux and belite mineralizer. Lime formed in the thermal decomposition of portlandite (±450°C) was partially carbonated to calcite at temperatures below the onset of calcite decarbonation (±650°C).