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Admixtures are important constituents to enhance the performance of concrete. They allow for more efficient use of binders which can mitigate negative environmental impacts from producing cement-based materials. Commonly used rheology modifying agents like polycarboxylate ethers or cellulose ethers are synthetic or semi-synthetic, respectively. This requires additional energy consumption for their production and global supply chains particularly for many developing regions, which will be large consumers of concrete in the future. However, many locally available bio-based polysaccharides could be effectively used instead. These polymers are often overlooked by engineers and scientists due to their limited distribution and inherent complexity, yet they represent an underleveraged source of precursors for admixtures. This study investigates the action mechanisms of some bio-based rheology modifying agents, i.e., acacia gum and miscanthus gum, and provides a comparison to a conventionally modified starch. The results show that the mechanism of action of these polymers is closely related to the composition of the mixture, mixing regime, and the composition of the aqueous phase. Depending on the agent, either plasticizing or stabilizing effects on rheology can be revealed.
Binary systems composed of Portland cement (PC) and calcium sulfoaluminate (CSA) cement have stood out for applications requiring high early strengths. Nevertheless, the application of these systems may be limited due to their properties in the fresh state, which requires a better understanding of the rheological behavior of these materials. Thus, this study evaluated the incorporation of different polycarboxylate-based superplasticizer (SP) contents (0.15, 0.20, and 0.25 wt%) on PC and PC-CSA binary cement pastes. Rotational rheometry, isothermal calorimetry, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption and desorption tests to assess the pore size distribution of cement pastes were conducted. While the SP incorporation reduced the dynamic yield stress of PC pastes, it progressively increased the yield stress of PC-CSA systems. The increase in SP content increased the main heat flow peak of PC-CSA pastes, although it did not significantly affect the cumulative heat after 160 h of hydration. FTIR and XRD confirm higher ettringite contents in the binary systems and indicate the presence of carboaluminates phases after 7 d of hydration in both PC and PC-CSA and hemicarboaluminate in PC-CSA pastes. The CSA incorporation reduced the cumulative pore volume by up to 32% compared to PC pastes, while the SP content evaluated did not significantly affect the porosity of PC-CSA pastes.
This study investigated the effect of incorporating three types of nanosilica (NS), two powders, and one colloidal suspension on the hydration, strength, and microstructure of calcium sulfoaluminate (CSA) cement pastes prepared with and without a superplasticizer (SP). X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and compressive strength tests were performed after 2, 5, and 28 days of hydration. The results showed that both NS powders delayed cement hydration at an early age, which was attributed to particle agglomeration (confirmed by dynamic light scattering). Whereas well-dispersed colloidal NS did not significantly affect the hydration of CSA at the investigated ages. SP incorporation improved the dispersion of CSA cement particles, resulting in a 10% increase in the degree of hydration of ye’elimite at 28 days for the system without NS. Conversely, when the SP was incorporated in NS-containing mixtures, it hindered cement hydration of the systems with powdered NS, but did not significantly affect the cement hydration of the system containing colloidal NS. The SEM images suggested that the SP changed the ettringite morphology, thereby negatively affecting the mechanical strength of the CSA pastes.
Pozzolanalime mortars modified with water-repellent admixtures were designed and studied to obtain mortars for restoration application. Powdered silane and calcium stearates were mixed with pozzolana, lime and sand and the chemicalphysical properties of the resulting mortars were evaluated by X-ray diffraction, electron microscopy (SEM-EDX), thermogravimetric analysis and FT-IR spectroscopy. The mechanical behavior, the pore structure and the hygric behavior were measured. The resistance of water-repellent mortars to the salt crystallization was evaluated. Both calcium stearates and powdered silane allowed good water-repellent protection even if the water-repellent agents and their dosage modified some physical properties and the hydration kinetic.
Nonclassical crystallization typically occurs via the attachment of individual nanoparticles. Intuitively, materials synthesized via this route should exhibit pronounced surface roughness and porosity as a hallmark of the formation process via particle accretion. Here, we demonstrate that nonclassical mineralization of calcium carbonate allows synthesis of ultra-smooth and dense surfaces with unprece-dented root-mean-square roughness of 0.285 nm, simply by con-trolling the hydration state of the nanosized building blocks using Mg doping. High fidelity coating of corrugated substrates can even be achieved. Nonclassical crystallization can thus lead to space-filling inorganic solid-state materials transgressing the implicit porosity commonly expected for particle-driven self-organization processes.
Hybrid cements are composites made of Portland cement or Portland clinker and one or more supplementary cementitious materials like slag, fly ash or metakaolin, activated with an alkali salt. To date, their hydration mechanism and the phase formation at various temperatures is insufficiently understood, partly due to the large variability of the raw materials used. In the present study, three hybrid cements based on ground granulated blast furnace slag, fly ash, Portland clinker and sodium sulfate, and an alkali-activated slag/fly ash blend were cured at 10 and 21.5°C, and subsequently analyzed by XRD, 27Al MAS NMR, and TGA. The compressive strength of the hybrid cements was higher by up to 27% after 91-day curing at 10°C, compared to curing at 21.5°C. The experimental results as well as thermodynamic modeling indicate that the differences in compressive strength were related to a different phase assemblage, mainly differing amounts of strätlingite and C-N-A-S-H, and the associated differences of the volume of hydration products. While the strätlingite was amorphous to X-rays, it could be identified by 27Al MAS NMR spectroscopy, TGA and thermodynamic modeling. The microstructural properties of the hybrid cements and the alkali-activated slag/fly ash blend as well as the compatibility between thermodynamic modeling results and experimental data as a function of curing temperature and time are discussed.
Volumetric changes follow Portland cement hydration reactions: aluminates' hydration is generally expansive, whereas silicates' reaction leads to shrinkage. Determining the volumetric variation at very early ages (i.e., first minutes/hours) presents operational challenges; most standards prescribe the measurement on specimens that are already hardened, while measurements from the fresh state are not standardized. This article reports the first attempt to use in-situ X-ray diffraction (XRD) to measure the early-age volumetric variation of a cementitious paste. For this purpose, a C3A + gypsum paste was assessed for 36 h, measuring its vertical displacement over time through XRD. The results showed that the expansion increased in the first ∼13 h, in line with the ettringite formed up to ∼11 h. In addition, the volumetric expansion agreed well with the heat release in calorimetry. It is concluded that the volumetric variation measurement of cementitious pastes through in-situ XRD is a promising technique, but further studies are needed to make this technique consolidated.
Organic admixtures are an indispensable component of modern concrete. Thus, their purposeful application is not only technically and economically viable but in addition an inevitable tool to make concrete more environmentally friendly. In this context, the use of polysaccharides has increasingly gained interest in the built environment as sustainable resource for performance enhancement. However, due to its origin, biopolymers possess a vast variety of molecular structures which can result in incompatibilities with other polymers present in concrete, such as superplasticizers. The present study highlights effects of the joint application of different types of starches and polycarboxylates with respect to their influence on cement hydration and structural build-up of cement pastes.
The increasingly sophisticated nature of modern, more environmentally friendly cementitious binders requires a better understanding and control particularly of the complex, dynamic processes involved in the early phase of cement hydration. In-situ monitoring of properties of a constantly changing system over a defined period of time calls for simple, sensitive, fast, and preferably also non-invasive methods like optical spectroscopy
Superplasticizers (SPs) have been employed in concrete technology for decades to improve the workability of concrete in its fresh state. The addition of SPs in cement-based systems affects the early properties. Although the interaction of the cement particles with various SPs has been extensively researched, there still exists limited research on the interaction of SPs with supplementary cementitious materials such as rice husk ash (RHA). This paper investigates the rheological properties and early hydration kinetics of RHA-blended systems with three types of SPs, a polycarboxylate ether (PCE) and two lignosulphonates (LS-acc and LS-ret). In rheological properties, the addition of SP causes an initial improvement of workability as the yield stress is significantly reduced. The pastes with PCE and LS-acc show a slight increase of yield stress over time whereas pastes with LS-ret tend to lower the yield stress slightly over time, further improving the workability. Without SP, pastes with RHA show a lower yield stress but an increase in plastic viscosity as cement is further replaced with RHA. The addition of the LS SPs is observed to lower the plastic viscosity but remains constant with further replacement of cement with RHA. This indicates that LS SPs further adsorbs on RHA particles and hydration products produced causing dispersion of the particles
within the system. In early hydration kinetics, pastes with PCE retard hydration and the degree of retardation is further increased with LS SPs. In the presence of RHA, the retardation of LS SP systems is significantly reduced. The pastes with PCE show more ettringite in the SEM micrographs, but is observed to be shorter needles. This indicates an initial good workability for PCE. However, C-S-H and CH were observed to be low in quantity, whereby the pastes with LS show more nucleation sites for C-S-H and CH. The ettringite needles in the LS systems were similar in quantity and more elongated in some cases but not abundant as in the PCE systems.