Revealing the co-doping effects of fluorine and copper on the formation and hydration of cement clinker

Fluorine in fluorite mineralizer and copper were easily doped together into cement clinker during cement kiln co-disposing wastes bearing Cu, yet that co-doping effects on the formation and hydration of cement clinker get few attention. The findings in this work revealed that the co-doping CaF2 (fluorine source) and CuO (copper source) into cement clinker showed a synergistic effect on the burnability, the immobilization rates of fluorine and copper in clinker phased were promoted. Compared with doping CaF2 into cement clinker, Co-doping CaF2 and CuO further enhanced the formation of alite and brownmillerite, while hindered the formation of tricalcium aluminate, and also triggered the right shift of characteristic diffraction peaks for C3S polymorphisms. It co-doping not only changed the microstructures, but also induced the visible defects on the surfaces of clinker mineral grains. In addition, most of fluorine would likely enter into the alite structure by replacing O2– of silicate phases, while most of copper would possibly enter into the brownmillerite structure by replacing Fe3+. Compared with the hydration process of cement clinker doped with CaF2, Co-doping CaF2 and CuO further accelerated the initial hydration process, obviously prolonged the induction period, but promoted the later hydration of co-doped clinker. Although the mechanisms about co-doping on the hydration process of co-doped clinker need more investigation, the above findings could extend the value-added utilization of wastes bearing Cu to reduce the large CO2 emission and energy/resource consumption in cement industry.