This article describes and interprets data drawn from a thorough characterisation of a series of cementitious materials. The materials addressed can be divided into three major groups: 1) cements/concretes from well-known and historically documented Roman constructions in Italy; 2) cements recently prepared in the laboratory simulating the compositions of Roman cements, stored for 6 months in environmental conditions similar to those to which the Roman materials have been exposed for 2000 years; 3) concretes prepared from an industrial cement manufactured 6 years ago applying today's knowledge of hybrid cements. An analysis of all the data presented in this article has led its authors to conclude that, conceptually speaking, ancient Roman cements can be identified with modern hybrid 'portland-alkaline' materials. That conceptual identity is based on the detection of the same cementitious phases in the two types of cements (Roman and Hybrid) and naturally of the inclusion of alkalis in the structures of some of the phases observed.
Significant drying shrinkage is one of the main limitations for the wider utilization of alkali-activated slag (AAS). Few previous works revealed that it is possible to reduce AAS drying shrinkage by the use of shrinkage-reducing admixtures (SRAs). However, these studies were mainly focused on SRA based on polypropylene glycol, while as it is shown in this paper, the behavior of SRA based on 2-methyl-2,4-pentanediol can be significantly different. While 0.25% and 0.50% had only a minor effect on the AAS properties, 1.0% of this SRA reduced the drying shrinkage of waterglass-activated slag mortar by more than 80%, but it greatly reduced early strengths simultaneously. This feature was further studied by isothermal calorimetry, mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Calorimetric experiments showed that 1% of SRA modified the second peak of the pre-induction period and delayed the maximum of the main hydration peak by several days, which corresponds well with observed strength development as well as with the MIP and SEM results. These observations proved the certain incompatibility of SRA with the studied AAS system, because the drying shrinkage reduction was induced by the strong retardation of hydration, resulting in a coarsening of the pore structure rather than the proper function of the SRA.
In recent years, the utilization of different non-traditional cements and composites has been increasing. Alkali-activated cementitious materials, especially those based on the alkali activation of blast furnace slag, have considerable potential for utilization in the building industry. However, alkali-slag cements exhibit very rapid setting times, which are too short in some circumstances, and these materials cannot be used for some applications. Therefore, it is necessary to find a suitable retarding admixture. It was shown that the sodium phosphate additive has a strong effect on the heat evolution during alkali activation and effectively retards the hydration reaction of alkali-activated blast furnace slag. The aim of the work is the suggestion of a reaction mechanism of retardation mainly based on Raman and X‑ray photoelectron spectroscopy.
The very early stages of alkaline activation of slag control its rheology and setting, but also affect its hydration, which occurs later. Simultaneously, these parameters are dictated by the nature and dose of the alkaline activator. Therefore, we investigated and compared the changes in slag particles (SEM, BET, laser diffraction), as well as in the pore solution composition (ICP–OES), pH, and conductivity, of alkali-activated slag (AAS) pastes containing the three most common sodium activators (waterglass, hydroxide, and carbonate) and water during the first 24 h of its activation. To ensure the best possible comparability of the pastes, a fairly nontraditional mixture design was adopted, based on the same concentration of Na+ (4 mol/dm3) and the same volume fraction of slag in the paste (0.50). The results were correlated with the pastes’ hydration kinetics (isothermal calorimetry), structural build-up (oscillatory rheology), and setting times (Vicat). Great differences were observed in most of these properties, in the formation of hydration products, and in the composition of the pore solution for each activator. The results emphasize the role of the anionic groups in the activators and of the pH, which help predict the sample’s behavior based on its calorimetric curve, and offer data for further comparisons and for the modelling of AAS hydration for specific activators.
Cement kiln by-pass dust (CKD) is a fine-grained by-product of Portland clinker manufacturing. Its chemical composition is not suitable for returning back into feedstock and, therefore, it has to be discharged. Such an increasing waste production contributes to the high environmental impact of the cement industry. A possible solution for the ecological processing of CKD is its incorporation into alkali-activated blast furnace slag binders. Thanks to high alkaline content, CKD serves as an effective accelerator for latent hydraulic substances which positively affect their mechanical properties. It was found out that CKD in combination with sodium carbonate creates sodium hydroxide in situ which together with sodium water glass content increases the dissolution of blast furnace slag particles and subsequently binder phase formation resulting in better flexural and compressive strength development compared to the sample without it. At the same time, the addition of CKD compensates the autogenous shrinkage of alkali-activated materials reducing the risk of material cracking. On the other hand, this type of inorganic admixture accelerates the hydration process causing rapid loss of workability.
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