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  1. To promote the sustainable development of eco-efficient calcium sulfoaluminate (CSA) cements through the partial replacement of the CSA clinker with supplementary cementitious waste products, the effects of coal fly ashes on the early-age and mature-age properties of a calcium sulfoaluminate (CSA)-based cement paste were investigated. The impacts of both Class C and Class F fly ashes on the rheological properties, hydration kinetics, and compressive strength development of CSA cement paste were studied. Rheology-based workability parameters, representing the rate of loss of flowability, the rate of hardening, and the placement limit, were characterized for the pastes prepared with fixed water-to-cement (w/c) and fixed water-to-binder (w/b) ratios. The results indicate a slight improvement in the workability of the CSA paste by fly ash addition at a fixed w/b ratio. The isothermal calorimetry studies show a higher heat of hydration for the Class C fly ash-modified systems compared to the Class F-modified systems. The results show that fly ash accelerates the hydration of the calcium sulfoaluminate cement pastes, chiefly due to the filler effects, rather than the pozzolanic effects. In general, ettringite is stabilized more by the addition of Class F fly ash than Class C fly ash. Both fly ashes reduced the 1-day compressive strength, but increased the 28-day strength of the CSA cement paste; meanwhile, the Class C modified pastes show a higher strength than Class F, which is attributed to the higher degree of reaction and potentially more cohesive binding C-S-H-based gels formed in the Class C fly ash modified systems. The results provide insights that support that fly ash can be employed to improve the performance of calcium sulfoaluminate cement pastes, while also enhancing cost effectiveness and sustainability. 
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  2. Poor workability is a common feature of calcium sulfoaluminate (CSA) cement paste. Multiple chemical admixtures, such as set retarders and dispersants, are frequently employed to improve the workability and delay the setting of CSA cement paste. A quantitative assessment of the compatibility, efficiency, and the effects of the admixtures on cement paste workability is critical for the design of an appropriate paste formulation and admixture proportioning. Very limited studies are available on the quantitative rheology-based method for evaluating the workability of calcium sulfoaluminate cement pastes. This study presents a novel and robust time-dependent rheological method for quantifying the workability of CSA cement pastes modified with the incorporation of citric acid as a set retarder and a polycarboxylate ether (PCE)-based superplasticizer as a dispersant. The yield stress is measured as a function of time, and the resulting curve is applied to quantify three specific workability parameters: (i) the rate at which the paste loses flowability, (ii) the time limit for paste placement or pumping, marking the onset of acceleration to initial setting, and (iii) the rate at which the paste accelerates to final setting. The results of the tested CSA systems show that the rate of the loss of flowability and the rate of hardening decrease monotonously, while the time limit for casting decreases linearly with the increase in citric acid concentration. The dosage rate of PCE has a relatively small effect on the quantified workability parameters, partly due to the competitive adsorption of citrate ions. The method demonstrated here can characterize the interaction or co-influence of multiple admixtures on early-age properties of the cement paste, thus providing a quantitative rheological protocol for determining the workability and a novel approach to material selection and mixture design. 
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  4. Abstract

    Microcrystalline zeolites of the gismondine family are often reported in alkali‐activated and blended cement systems. However, little is known about gismondine's compatibility with other cementitious phases to determine stability in long‐term phase assemblage. Experimental studies were conducted to investigate the compositional field of gismondine stability in the lime‐alumina‐silica‐hydrate systems, with a particular focus on understanding the compatibility of gismondine with other cement phases such as C‐S‐H, ettringite, monosulfate, strätlingite, katoite, gypsum, calcite, portlandite, alkali, silica, and aluminosilicate phases. Results show that gismondine‐Ca forms readily at ~85°C in high aluminosilicate compositions; and persists in the presence of calcite, gypsum, ettringite, katoite solid solution, low Ca tobermorite‐like C‐S‐H, silica and aluminosilicate phases, at 20‐85°C. However, gismondine‐Ca reacts with: (a) monosulfate, producing ettringite‐thaumasite solid solution; (b) portlandite, forming tobermorite‐like C‐A‐S‐H gel and siliceous katoite at >55°C; (c) aqueous NaOH, generating gismondine‐(Na,Ca), a garronite‐like zeolite P solid solution; and (d) strätlingite leading to the conversion of strätlingite to gismondine indicating the metastability of strätlingite with respect to gismondine at 55°C. The outcomes are discussed to provide insights into the long‐term phase assemblage of relevant cement systems such as lime‐calcined clay, alkali‐activated materials, and potentially ancient Roman concrete.

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