Characterization of High-Calcium Fly Ashes and Their Potential Influence on Ettringite Formation in Cementitious Systems

Abstract High-calcium Class C fly ashes derived from Powder River Basin coal are currently used in many parts of the U. S. as supplementary cementing materials in portland cement concrete. These fly ashes tend to contain significant amounts of sulfur, calcium, and aluminum, thus they are potential sources of ettringite. Detailed mineralogical characterizations of six high-calcium fly ashes originating from Powder River Basin coal have been carried out. The hydration products formed in pastes made from fly ash and water were investigated. The principal phases produced at room temperature were found to be ettringite (C6AS¯3H32), monosulfate (C4AS¯H12), and strätlingite (C2ASH8). The relative amounts formed varied with the specific fly ash. Three fly ashes were selected for further study. Portland cement /fly ash pastes made with the selected fly ashes were investigated to evaluate ettringite and monosulfate formation. Each of the three fly ashes were mixed with five different Type I portland cements exhibiting a range of C3A and sulfate contents. The pastes had 25% fly ash by total weight of solids and a water: cement + fly ash ratio of 0.45. After mixing, the samples were sealed and placed in a curing room (R.H. = 100%, 23°C) for 28 days and were then analyzed by X-ray diffraction (XRD) and differential scanning calorimetry ( DSC) to determine the principal hydration products. The hydration products identified by XRD were portlandite, ettringite (an AFt phase), monosulfate, and generally smaller amounts of hemicarboaluminate and monocarboaluminate (all AFm phases). Although the amount of ettringite formed varied with the individual cement, only a modest correlation with cement sulfate content and no correlation with cement C3A content was observed. DSC analyses showed that the cement/fly ash pastes generally formed less ettringite than the cement control pastes, but they formed more of the AFm phases (mainly monosulfate). It appears that the addition of high-calcium fly ash reduces the SO4/Al2O3 ratio in the system thus favoring Afm formation.