Barbara Pacewska

The aim of this paper is to discuss the usefulness of thermal analysis methods at various stages of cement composite development, based on a literature review and the authors’ many years of research experience. Current research areas in the cement and construction industries, in which thermal analysis is particularly applicable, are highlighted. The influence of selected factors on the thermal analysis curves is also demonstrated. The following issues are examined in terms of the potential applications of thermal analysis and the information that can be obtained from this method: research on raw materials for cement clinker production; studies on processes occurring in the cement kiln; investigations of cements and hydration/hardening processes. Particular emphasis is placed on the potential applications of thermal analysis in research aimed at reducing the negative environmental impact of cement production, especially the possibilities for using various waste materials as components for cement clinker production or as supplementary cementitious materials. The final part of the paper provides a summary and outlines the main directions for further research.

In this work, the hydration of calcium aluminate cement (CAC, Al₂O₃ ≥ 70%) paste with nano admixtures (0, 0.05%, 0.1% and 0.2%) of nano-silica (NS) and carbon nano-cones (NC) when W/CAC = 0.35 was investigated. The methods of calorimetry, thermal analysis, X-ray diffraction (XRD), IR spectroscopy, and scanning electron microscopy (SEM) were used. In addition, the physical and mechanical properties of hardened cement pastes were determined after 3 days of hardening. NS was found to shorten the induction period of CAC hydration and accelerate the time of the secondary heat release effect, especially in the specimens with the highest NS content. The incorporation of NC (up to 0.2%) slows down the hydration process. After 3 days of hydration, the formation of hydration products, such as C₂AH₈, CAH₁₀, C₃AH₆ and AH₃ hydrates, was observed in CAC pastes, however, the quantitative compositions were different depending on the kind of nano admixture and its amount. SEM results obtained show differences in the effect of NS and NC on the formation of the structure of cement paste during its hardening. Significant changes in CAC paste microstructure were caused by the addition of NS and NC admixtures. Compressive strength was found to increase with the increase of NS and the optimal NS content was found to be 0.10 wt.%. The modification of the cement paste with an NS admixture results in a higher amount of hydrates, lower total porosity, and a higher amount of the smallest pores in the microstructure of the sample. NS and NC influence the hydration behaviour of CAC in different ways, which causes characteristic changes in the microstructure and properties of hardened samples.

Results of research on hydration of four-component binders containing very high amounts of supplementary cementitious materials were presented. The samples were composed of blended pozzolana (a mix of conventional fly ash and spent aluminosilicate catalyst), cement (about 20 wt.% in the binder) and Ca(OH)₂. Spent aluminosilicate catalyst was proposed as activating component which can improve properties of low-cement blends, while the role of Ca(OH)₂ was to enhance pozzolanic reaction. Early and later hydration periods of such blends were investigated by calorimetry, TG/DTG, FTIR and X-ray diffraction. Initial setting time as well as compressive strength were also determined. It was concluded that enhancement of reactivity and improvement of properties of fly ash–cement binders are possible by replacing a part of fly ash with more active fine-grained pozzolana and introducing additional amounts of Ca(OH)₂. The spent catalyst is mainly responsible for accelerating action during the first hours of hydration and for progress of early pozzolanic reaction. Fly ash develops its activity over time, thus synergic effect influences the later properties of composites. Samples containing blended pozzolana exhibit shorter initial setting times and higher compressive strength, as well as faster consumption of Ca(OH)₂ compared to the reference. Investigated mixtures seem to be promising as “green” binders, alternatives to cement, after optimizing their compositions or additional activating procedure.