Rheological and hydration characterization of calcium sulfoaluminate cement pastes

Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO₂ than ordinary Portland cement (OPC). However, it is essential to understand all parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt.%) and w/c ratio (0.4 and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured X-ray diffraction patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt.% gypsum but decreases the strengths for mortars containing 10 wt.% gypsum.     

Contribution of limestone to the hydration of calcium sulfoaluminate cement

Calcium sulfoaluminate (CSA) cements can be blended with mineral additions such as limestone for properties and cost optimization. This study investigates the contribution of limestone to the hydration of a commercial CSA clinker regarding the hydration kinetics, hydrate assemblage and compressive strength. Nine formulations were defined at M-values of 0, 1.1 and 2.1 (M = molar ratio of anhydrite to ye’elimite) without and with medium and high limestone contents.Calorimetric results indicate that limestone accelerates the hydration reaction especially at M = 1.1, probably due to the filler effect. The phase assemblages were calculated by thermodynamic modeling using Gibbs Energy Minimization Software (GEMS). With increasing limestone content the formation of ettringite and calcium monocarboaluminate is predicted at the expense of calcium monosulfoaluminate. With increasing M-value more ettringite is predicted at the expense of the monocarbonate and less calcite takes part in the hydration reactions.The modeled results compare well with the experimental data after 90 d of hydration, except that calcium hemicarboaluminate was found instead of monocarbonate, which is assumed to be due to kinetics considerations.The lowest compressive strength occurs in ternary formulations, whereas in the absence of calcium sulfate, strength is significantly higher.The results presented here indicate that in CSA cements, limestone accelerates early hydration kinetics, takes part in the hydration reactions at M < 2, and has a positive effect on strength development in systems without anhydrite.     

The effect of zinc oxide additions on the performance of calcined sodium montmorillonite and illite shale supplementary cementitious materials

The objectives of this study were to use activation treatments on sodium montmorillonite and illite shale, to alter early hydration or later pozzolanic reactivity when used as supplementary cementitious materials (SCMs). For comparison purposes, treatment methods were also applied to the highly reactive pozzolan, metakaolin, and the inert filler, quartz. Activation treatment strategies included the addition of 0.15 wt% zinc oxide and the use of thermal treatments to the SCMs at temperatures of 650 °C, 830 °C and 930 °C. The use of zinc oxide additions increased the early hydration rate of SCM-containing pastes, yet introduced a chemical retardation and negatively impacted early compressive strengths. Moreover, the results suggest that retardation was inversely correlated with the pozzolanic reactivity of the SCM used. Thermal treatment methods were effective at influencing the SCM pozzolanic reactivity, with montmorillonite calcined at 830 °C and illite calcined at 930 °C behaving as late-reacting pozzolans. SCMs calcined at these temperatures resulted in higher 90 day compressive strengths compared to mortars containing the quartz filler. Overall, this study provides insight into different strategies that maybe used to enhance the reactivity of impure calcined clays in order to facilitate their acceptance into the concrete industry.     

Clinkering and hydration of belite-alite-ye´elimite cement

Some belite-ye´elimite-ferrite (BYF) cements present low mechanical strengths mainly due to the slow reactivity of belite. A solution to this problem may be the activation of BYF clinkers by preparing them with a coexistence of alite and ye'elimite, which are known as belite-alite-ye´elimite (BAY) cements.The objective of this work was the preparation of BAY mortars that show higher mechanical strengths than BYF mortars. In order to attain this, the clinkering conditions to prepare BAY-clinker (2 kg) with the following mineralogical composition 60.6 (2) wt% of belite, 14.3 (2) wt% of alite and 10.4 (1) wt% of ye'elimite were optimized (900°C/30 min-1300°C/15 min). The hydration mechanism of cement pastes (with 12 wt% of anhydrite and water-to-cement ratios of 0.4 and 0.5) was studied through laboratory X-ray powder diffraction and thermo-analyses. Finally, BAY mortars with higher compressive strengths than BYF-mortars were obtained (viz. 24.8 and 17.1 MPa for BAY and BYF mortars at 7 days of hydration, respectively).     

Synthesis,characterization and properties of calcium ferroaluminate belite cements produced with electric arc furnace steel slag as raw material

This study investigated the use of 10 (M1), 17 (M2) and 27 wt.% (M3) electric arc furnace steel slag (EAFS) as a raw material in the production of calcium ferroaluminate belite cement clinker, after firing at 1320 °C. The thermal behavior of the raw meals was studied by TG/DSC and XRD whereas for the analysis of the clinkers, XRD/QXRD, SEM/EDS and EPMA were employed. The resulting clinker was co-grinded with 5 and 20 wt.% Flue Gas Desulfurization (FGD) gypsum and the properties were determined by a series of tests in accordance to EN standards. The evolution of hydration was investigated by SEM and the development of compressive strength. The results revealed that the formed phases in the clinkers were C₂S, C₄AF and C₄A₃Ŝ. The main hydration products were ettringite, AFm and hydrogarnet. The leached Cr^VI was below 1 ppm in M3. Compressive strength in cements with 5 wt.% FGD gypsum was (in MPa): 18.3 for M1, 14.3 for M2 and 7.8 for M3 at 28 days, whereas for 20 wt.% FGD gypsum, the values were almost doubled.     

Increasing the reactivity of metakaolin-cement blends using zinc oxide

This study aimed to improve the reactivity of metakaolin-cement mixtures using ZnO additions. Kaolinite samples with 0.1–1 wt% ZnO were calcined at temperature intervals of 50 °C from 500 to 650 °C for 1 h. The resulting metakaolins were examined for structural changes after calcination and for their pozzolanic reactivity, influence on the hydration behavior of cement pastes, and impact on the compressive strength of mortar cubes. ZnO behaved as a delayed accelerator for cement paste. However, when ZnO was combined with highly amorphous metakaolin, chemical retardation was eliminated while acceleration was maintained. Such systems also had increased 28-day compressive strengths. ZnO additions did not affect the degree of dehydroxylation or the pozzolanic reactivity of the metakaolin. These results could facilitate the use of less pure calcined clays as SCM by providing a mechanism for improving reactivity and may also impact the ability to use zinc-contaminated materials in concrete.     

A study on the effect of nano silica on compressive strength of high volume fly ash mortars and concretes

This paper presents the effect of nano silica (NS) on the compressive strength of mortars and concretes containing different high volume fly ash (HVFA) contents ranging from 40% to 70% (by weight) as partial replacement of cement. The compressive strength of mortars is measured at 7 and 28 days and that for concretes is measured at 3, 7, 28, 56 and 90 days. The effects of NS in microstructure development and pozzolanic reaction of pastes containing above HVFA contents are also studied through backscattered electron (BSE) image and X-ray diffraction (XRD) analysis. Results show that among different NS contents ranging from 1% to 6%, cement mortar containing 2% NS exhibited highest 7 and 28 days compressive strength. This NS content (2%) is then added to the HVFA mortars and concretes and the results show that the addition of 2% NS improved the early age (7 days) compressive strength of mortars containing 40% and 50% fly ash by 5% and 7%, respectively. However, this improvement is not observed at high fly ash contents beyond 50%. On the other hand, all HVFA mortars exhibited improvement in 28 days compressive strength due to addition of 2% NS and the most significant improvement is noticed in mortars containing more than 50% fly ash. In HVFA concretes, the improvement of early age (3 days) compressive strength is also noticed due to addition of 2% NS. The BSE and XRD analysis results also support the above findings.     

Jet mill grinding of portland cement,limestone, and fly ash: Impact on particle size,hydration rate,and strength

While the majority of commercial ordinary portland cement (OPC) is ground using a ball mill or a vertical roller mill, other industries have shown that jet mill grinding can be an alternative approach for grinding materials. This paper investigates the potential application of jet mill grinding for two systems. The first system is a blend of OPC and 15% limestone, and the second system is a blend of OPC and 40% fly ash. It was observed that when jet mill grinding is used, the average particle size of the powders is decreased to approximately 4 μm or less with a narrower particle size distribution than that achieved using ball milling. In addition to evaluating the size and shape of the particles obtained from the jet mill grinding process, this paper focuses on evaluating, using isothermal calorimetry, the effect these changes in particle size and distribution have on the extent and rate of hydration as well as their effect on the compressive strength of cement pastes or mortars.This study also investigated differences between inter-grinding and blending separately ground materials to form an OPC/limestone mixture. Both inter-ground and separately ground OPC/limestone mortars demonstrated an accelerated hydration at early ages accompanied by an increase in early age strength. This appears to be primarily due to the increased surface area of the finer particles that provides more available surface for the hydration reaction. The inter-grinding appeared to be more effective than grinding the materials separately because an improved graded particle size distribution was obtained. The inter-ground OPC/limestone mixture shows accelerated initial hydration at water to powder ratios (w/p, where powder = cement + limestone) of 0.50 and 0.35 when compared with the samples before grinding. At the lower w/p of 0.35, the OPC/limestone mixture appears much more efficient. In the OPC/fly ash mixture, jet mill grinding also accelerates the rate of hydration and strength development.     

Durability of very high volume fly ash cement pastes and mortars in aggressive solutions

The resistance of very high volume fly ash cement pastes and mortars activated by Na₂SO₄ has been monitored following immersion for up to 90 d in 0.1 M HCl, 4.4% Na₂SO₄ and ASTM-compliant sea water. Changes in the compressive strengths of mortars and in crystalline phases, bond environments, and the microstructure of pastes following immersion were monitored. Experiments were repeated with a commercially available sulfate resistant cement. Both cements were found to present adequate resistance to both sea water and the Na₂SO₄ solution. However, both were severely degraded by acid immersion. Differences in potential degradation mechanisms based on the chemistry of the fly ash binder and the reference cement are discussed.     

Tailored setting times with high compressive strengths in bassanite calcium sulfoaluminate eco-cements

This work deals with the hydration of a calcium sulfoaluminate (CSA) eco-cement prepared with bassanite and different additives (type and content) at a fixed water/CSA ratio of 0.5. Pastes prepared with bassanite show high water demands, high viscosity values and short initial setting times which are related to the fast dissolution rate of bassanite and the subsequent precipitation of gypsum. These facts have a dramatic effect onto the mechanical strength values, and make necessary the addition of additives.Here, the addition of different amounts of specific retarders (polycarboxylate, tartaric acid and phosphonic acid) not only improved the workability of pastes and mortars, but also delayed the setting time by modifying the dissolution rates of the phase(s), and improved mechanical strengths. Finally, mortars with high compressive strengths (46 and 84 MPa at 1 and 7 days of hydration, respectively) and, chiefly, tailored setting times with high strengths have been prepared.     

Structure and strength of NaOH activated concretes containing fly ash or GGBFS as the sole binder

The influence of the concentration of the activating agent (4, 6, or 8 M sodium hydroxide solution), and activator-to-binder ratio (0.40, 0.50, or 0.60) on the compressive strengths, pore structure features, and microstructure of concretes containing Class F fly ash or ground granulated blast furnace slag (GGBFS) as the sole binder is reported. The starting material contents and the curing parameters (temperature and curing duration) are optimized to provide the highest compressive strengths. Statistical analysis of the compressive strength results show that the activator concentration has a larger influence on the compressive strengths of activated concretes made using fly ash and the activator-to-binder ratio influences the compressive strengths of activated GGBFS concretes to a greater degree. Activated fly ash concretes and pastes are found to be more porous and contains a larger fraction of pores greater than 10 μm in size as compared to activated GGBFS mixtures. The differences in the microstructure and the reaction products between activated fly ash and GGBFS pastes are detailed.     

Formulation of mortars with nano-SiO2 and nano-TiO2 for degradation of pollutants in buildings

This paper reports on the design of cement mortars that use nano-SiO₂ (nS) and nano-TiO₂ (nT) particles, aiming to improve the durability of traditional building materials while giving new functionalities (aerial decontamination of pollutants). Samples with 0–2 wt.% nS, 0–20 wt.% nT, 0.45–7 wt.% superplasticizer (SP) and 0.45–0.58 water/binder weight ratio were prepared. The formulations of mortars were defined according to rheology and flow table measurements, then showing suitable workability. The temperature of hydration, compressive strength, water absorption, and photocatalytic degradation of pollutants (NO_x and Orange II dye) were also evaluated. In general, the rheological behavior and the temperature of hydration changed in distinct levels, depending on the dosage and type of nanoadditives, but nT influenced more significantly the results. However, such differences were not identified on the compressive strength and water absorption. In addition, NO_x photocatalytic degradation up to 1 h under solar light ranged from 65% to 80%, while Orange II degradation after 9 h under visible light changed from 18% to 50%.     

Effects of NaOH concentrations on physical and electrical properties of high calcium fly ash geopolymer paste

The effects of sodium hydroxide (NaOH) concentration on setting time, compressive strength and electrical properties at the frequencies of 100 Hz–10 MHz of high calcium fly ash geopolymer pastes were investigated. Five NaOH concentrations (8, 10, 12, 15 and 18 molar) were studied. The liquid to ash ratio of 0.4, sodium silicate to sodium hydroxide ratio of 0.67 and low temperature curing at 40 °C were selected in making geopolymer pastes. The results showed that NaOH concentration had significant influence on the physical and electrical properties of geopolymer paste. The pastes with high NaOH concentrations showed increased setting time and compressive strength due to a high degree of geopolymerization as a result of the increased leaching of silica and alumina from fly ash. The dielectric constant and conductivity increased with NaOH concentration while tan δ decreased due to an increase in geopolymerization. At the frequency of 10³ Hz, the dielectric constants of all pastes were approximately 10⁴ S/cm and decreased with increased frequency. The relaxation peaks of tan δ reduced with an increase in NaOH concentration and ranged between 2.5 and 4.5. The AC conductivity behavior followed the universal power law and the values were in the range of 3.7 × 10⁻³–1.5 × 10⁻² at 10⁵–10⁶ Hz.     

Statistical analysis for freeze–thaw resistance of cement mortars containing marble dust and glass fiber

This paper investigated the usability of marble dust and glass fiber against the harmful effects of freeze–thaw (FT) cycles on cement mortars as experimentally and statistically. To this end, the cement mortar specimens containing marble dust (0%, 20%, 40% and 50% by volume) and glass fiber (0 kg/m³, 0.25 kg/m³, 0.50 kg/m³, 0.75 kg/m³) were prepared. The compressive and flexural strengths of the specimens were determined after being exposed to FT cycles. In order to reduce the numbers of experiments, an L₁₆ (4² × 2¹) Taguchi orthogonal array was adopted to the study. Amounts of glass fiber, percentages of marble dust and cycles of freeze–thaw, were changed to explore their effects on the compressive and flexural strengths of the mortar specimens. Statistically effects of the factors were also determined by using analysis of variance (ANOVA) method. Finally, experimental findings were compared with statistical results and a good agreement between them was achieved.     

Influence of polyether polyol on the hydration and engineering properties of calcium sulfoaluminate cement

The aim of the present paper was to investigate the efficiency of polyether polyol as shrinkage-reducing admixture on pastes and mortars prepared with calcium sulfoaluminate cement (CSA). CSA was prepared by mixing CSA clinker and re-crystallized gypsum in different proportions. Three types of polyether polyol were added at a dosage of 1.5 wt% of CSA when hydrating pure pastes and standard mortars. The engineering properties of mortars (compressive strength, drying shrinkage) and the microstructure of pastes were investigated. The results show that polyol reduces drying shrinkage of CSA-based mortars without affecting the nature of hydrates formed. The effect of polyol mainly depends on its molecular weight.     

Properties of binary and ternary reactive MgO mortar blends subjected to CO2 curing

Research and development of low CO₂ binders for building material applications is warranted in efforts to reduce the negative environmental impacts associated with the cement and concrete industry. The purpose of this study is to investigate the effect of carbonation curing on the mineralogy, morphology, microstructure and evolution of compressive strength of mortars comprised of general use (GU) cement, ground granulated blast furnace slag (GGBFS), and reactive MgO used as cement replacement. This study investigates binary (GU–MgO) and ternary (GU–GGBFS–MgO) blends exposed to atmosphere curing (0.0038%CO₂) and carbonation curing (99.9%CO₂). Carbonation-cured mortars exhibited greater compressive strengths than atmosphere mortars at all ages (7 d, 28 d, and 56 d). Increasing percentages of reactive MgO decreased the compressive strength markedly less for carbonation-cured mortars than atmosphere-cured mortars particularly due to magnesium calcite formations. Magnesium calcite influenced the morphology of carbonates and promoted the carbonate agglomeration resulting in a dense and interconnected microstructure.     

Microstructure and mechanical performance of modified mortar using hemp fibres and carbon nanotubes

Mechanical performance of modified mortar using hemp fibres is studied following various processing conditions. Hemp fibres combined with carbon nanotubes (CNT) are introduced in mortar and their effect is studied as function of curing time. The cement phase is replaced by different percentages of dry or wet hemp fibres ranging from 1.1 wt% up to 3.1 wt% whereas carbon nanotubes are dispersed in the aqueous solution. Our experimental results show that compressive and flexural strengths of wet fibres modified mortar are higher than those for dry hemp-mortar material. The achieved optimal percentage of wet hemp fibres is 2.1 wt% allowing a flexural strength higher than that of reference mortar. The addition of an optimal CNT concentration (0.01 wt%) combined with wet hemp has a reinforcing effect which turns to be related to an improvement of compressive and flexural strengths by 10% and 24%, respectively, in comparison with reference condition.     

Alkali-activated complex binders from class C fly ash and Ca-containing admixtures

Processes that maximize utilization of industrial solid wastes are greatly needed. Sodium hydroxide and sodium silicate solution were used to create alkali-activated complex binders (AACBs) from class C fly ash (CFA) and other Ca-containing admixtures including Portland cement (PC), flue gas desulfurization gypsum (FGDG), and water treatment residual (WTR). Specimens made only from CFA (CFA100), or the same fly ash mixed with 40 wt% PC (CFA60–PC40), with 10 wt% FGDG (CFA90–FGDG10), or with 10 wt% WTR (CFA90–WTR10) had better mechanical performance compared to binders using other mix ratios. The maximum compressive strength of specimens reached 80.0 MPa. Geopolymeric gel, sodium polysilicate zeolite, and hydrated products coexist when AACB reactions occur. Ca from CFA, PC, and WTR precipitated as Ca(OH)₂, bonded in geopolymers to obtain charge balance, or reacted with dissolved silicate and aluminate species to form calcium silicate hydrate (C-S-H) gel. However, Ca from FGDG probably reacted with dissolved silicate and aluminate species to form ettringite. Utilization of CFA and Ca-containing admixtures in AACB is feasible. These binders may be widely utilized in various applications such as in building materials and for solidification/stabilization of other wastes, thus making the wastes more environmentally benign.     

The effect of heat treatment on the compressive strength of cement-slag mortars

Thirty-eight mix proportions of ordinary Portland cement-slag mortars (OSMs) were used to study the effects of temperature and relative humidity on strength. Three levels of slag (0%, 40%, and 50%) and different temperatures were used; the 50% level and heat curing of 60 °C for duration of 20 h were found to be the optimum. The optimum mortar’s strength at 3 and 7 days for the specimens cured in air were 55.0 and 62.0 MPa, respectively. The results show that for durations of 4–26 h, the strength of specimens cured in air is greater than those cured in water. This is a novelty with major advantages in arid areas. It was proved that more ettringite production at early ages resulted in higher early strengths. Comparison of curing regimes with different temperatures and the same relative humidity or different relative humidity and the same temperatures showed that higher strengths are attributed to higher temperatures and lower relative humidity, respectively.     

A study on the effects of high temperature on mechanical properties of fiber reinforced cementitious composites

The flexural strength and ductility properties of cementitious composites (mortar) under high temperature may be significantly improved by incorporating different types of fibers. In this study, four different types of fibers are added to cement mortars with the aim to investigate their mechanical contributions to mortars under high temperature, comparatively. Polypropylene (PP), carbon (CF), glass (GF) and polyvinyl alcohol (PVA) fibers are chosen for research. These fibers are added into mortars in five different ratios (0.0%, 0.5%, 1.0%, 1.50% and 2.0%) by volume. The mortars are subjected to the following temperatures: 21 °C (normal conditions), 100 °C (oven dry), 450 °C and 650 °C. The mechanical properties investigated are flexural strength, deflection and compressive strength of the cement mortars. In addition, thin sections of mortars are investigated to obtain changes in mortar because of high temperature. It is concluded that all fiber types contribute to the flexural strengths of mortars under high temperature. However, this contribution decreases with an increase in temperature. The samples with PVA show the best flexural performance (75–150%) under high temperature. CF which does not melt under high temperature also gives high flexural strength (11–85%). The compressive strengths of the mortars reduce under high temperature or with fiber addition. The highest increase in flexural strength and the lowest decrease in compressive strength is at 0.5–1.5% for CF if all temperature conditions are taken into consideration. The optimum fiber addition ratios of the samples containing PP and GF are 0.5% by volume. And for PVA, it is between 0.5% and 1.5% by volume.