ABSTRACT
In general, phosphate cements have a very rapid setting reaction at room temperature. The same holds for copper slag-based phosphate cements. This means that using them as a binder, for instance as mortar, is always possible on a small scale, but very difficult on a large scale. In this paper, the heat treatment of the copper slag was shown to be an effective way to increase the setting time and keep the mix workable for an adequate period. The main objective of this research was to examine the changes in the phase composition of quenched copper slag after exposure to 500 °C and to evaluate the impact of these changes on the reactivity of the material in an acidic environment, as well as on the mechanical properties, microstructure, and structure of the produced phosphate cement materials. Various experimental methods were utilized to characterize the raw materials and the obtained phosphate cementitious materials, including isothermal microcalorimetry (TAM Air), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as the determination of the chemical composition using X-ray fluorescence (XRF) and the particle size distribution. Furthermore, compressive strength tests were conducted to gauge the mechanical resistance of the materials. The main findings of this work revealed that subjecting the copper slag to a thermal treatment of 500 °C induced a partial transformation in its structure. The high temperature caused the oxidation of some of the divalent iron oxide in the slag, leading to the formation of hematite. This treatment increased the setting time and reduced the reactivity of the copper slag with phosphoric acid, ultimately enabling the production of a dense phosphate-based cementitious material with outstanding mechanical properties. The compressive strength of the newly developed cement was recorded to be greater than 78.9 MPa after 7 days, and this strength continued to increase, reaching 82.5 MPa after 28 days.
ABSTRACT
Copper slag (CS) remains a challenging industrial by-product with a relatively small utilization fraction. The present study investigated the development of one-part alkali-activated cements based on CS, ground granulated blast furnace slag (GGBS) and a mixture of the two as a precursor. We investigated 5 to 15 wt% solid sodium metasilicate (Na2SiO3) and disilicate (Na2Si2O5) as alkaline reagents. Isothermal calorimetry showed that the reactivity of the system was higher for the metasilicate based samples, with early reaction and higher cumulative heat released. Metasilicate based samples also presented a more densified microstructure, lower porosity and higher strength. Better performances were observed with 10 wt% metasilicate/disilicate with respect to the 5 and 15 wt%. The 28-day compressive strength and elastic modulus of 10 wt% metasilicate samples reached 75 MPa and 25 GPa, respectively, and, for paste samples, ranged from 100 wt% GGBS to 50/50 wt% CS/GGBS. The microstructure and calorimetry of the pastes showed that GGBS actively participated in the binding process, whereas CS played a smaller role and acted as a filler and catalyst. The substitution of commercial GGBS by CS up to 50 wt% did not affect the overall performance, thus, bringing CS forward as an economically interesting precursor.
