Influence of calcium aluminate cement (CAC) on alkaline activation of red clay brick waste (RCBW)

In this paper, the effect of calcium aluminate cement (CAC) additions on the alkali activation of red clay brick waste (RCBW) was studied at room temperature and at 65 °C. RCBW was partially replaced with CAC (0–50 wt.%) and blends were activated with NaOH and sodium silicate solutions. The compressive strength evolution was tested on mortars and the nature of the reaction products was analysed by infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, microscopic studies and pH measurements. The results show that the use of CAC accelerates the activation process of RCBW so that 50 MPa were obtained in the blended mortars containing 40 wt.% CAC cured for 3 days at room temperature. CAC did not undergo normal hydration and only the C₃AH₆ phase was identified in the pastes blended with more than 30 wt.% CAC and cured at 65 °C, while the main reaction product was a cementitious gel containing Ca and Al from CAC.     

Pore structure and permeability of hardened calcium aluminate cement pastes of low w/c ratio

The conversion of hydrated calcium aluminate cement (CAC) leads to an increase of its porosity which results in lower strength and higher permeability. Due to particular failures in the past, caused by conversion of CAC concretes, their use is sometimes considered to be not reliable. To evaluate the durability of converted CAC, pastes of two CACs were prepared at low w/c ratios (0.25 and 0.35), heated to 105 °C for 15 days and investigated by means of helium pycnometry, mercury porosimetry and nitrogen adsorption as well as by air permeability measurements. The results were compared to the pore structure properties and permeabilities of hardened Portland cement (OPC) pastes. At identical w/c, CAC pastes and OPC pastes exhibited similar open and total porosities. The threshold radii of the CAC pastes were about one order of magnitude greater while the hydraulic radii of their open pore system were smaller. The CAC pastes possessed somewhat smaller permeabilities than the OPC pastes and can thus be regarded as being as durable as the latter in this respect. From comparison of pore structure parameters and permeabilities it was furthermore concluded that significant pore structure damage occurs in the CAC pastes during mercury porosimetry measurements and therefore the measured threshold radii have to be considered as unreliable.     

Behavior of calcium aluminate cement (CAC) in the presence of hexavalent chromium

Chromium forms part of numerous processes and its unsafe disposal increases the risk of pollution of soils and aquatic systems, especially hexavalent chromium. This paper deals with the behavior of calcium aluminate cement (CAC) in presence of Cr⁶⁺ (0.5, 1.0 and 2.5%) as potassium dichromate (K₂Cr₂O₇). The efficiency of CAC to immobilize Cr⁶⁺ was studied using leaching tests. The hydration temperature, hydration products and compressive strength of CAC in presence of Cr⁶⁺ were also investigated. Analysis of the results showed that the presence of Cr⁶⁺ strongly reduced the rate of reactions, which was related to inhibition of the consumption of anhydrous phases (calcium aluminate). However, leaching tests showed the high efficiency of CAC regarding Cr⁶⁺ immobilization (>90%), better than that presented by Portland cement. CAC also presented both the capacity for hexavalent chromium retention and its reduction.     

Optimization of calcium chloride content on bioactivity and mechanical properties of white Portland cement

This research investigates the optimization of calcium chloride content on the bioactivity and mechanical properties of white Portland cement. Calcium chloride was used as an addition of White Portland cement at 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight. Calcium chloride was dissolved in sterile distilled water and blended with White Portland cement using a water to cement ratio of 0.5. Analysis of the bioactivity and pH of white Portland cement pastes with calcium chloride added at various amounts was carried out in simulated body fluid. Setting time, density, compressive strength and volume of permeable voids were also investigated. The characteristics of cement pastes were examined by X-ray diffractometer and scanning electron microscope linked to an energy-dispersive X-ray analyzer. The result indicated that the addition of calcium chloride could accelerate the hydration of white Portland cement, resulting in a decrease in setting time and an increase in early strength of the pastes. The compressive strength of all cement pastes with added calcium chloride was higher than that of the pure cement paste, and the addition of calcium chloride at 8 wt.% led to achieving the highest strength. Furthermore, white Portland cement pastes both with and without calcium chloride showed well-established bioactivity with respect to the formation of a hydroxyapatite layer on the material within 7 days following immersion in simulated body fluid; white Portland cement paste with added 3%CaCl₂ exhibited the best bioactivity.     

Study of aluminum sulfate and anhydrite on cement hydration process

The influences of aluminum sulfate (AS) introduction and dosage on setting time, hydration heat evolution, hydration product type and pore structure of Portland cement were studied, and the influence of AS on concrete strength was investigated also. The results indicate that AS can effectively accelerate setting time of Portland cement and enhance concrete at early age (1 day) strength. AS can promote hydration process of calcium aluminate but inhibit that of calcium silicate. The effect of AS on hydration process becomes more significant along with the increased dosage; and the introduction of AS can promote the formation of AFt. The research results of this paper favor the opinion of the existence of AFt precursor; and the AFt precursor is amorphous AFm which could not be identified by XRD. With anhydrite as setting regulator, the amorphous AFm retention time is prolonged, and the endothermal peaks produced by amorphous AFm during DSC–MS measurement correspond to 80–160 and 830–910 °C, losing H₂O and SO₂ respectively.     

Styrene–butadiene latex modified calcium aluminate cement mortar

This paper investigates properties of calcium aluminate cement (CAC) mortar modified with the styrene–butadiene-rubber (SBR) latex. This material may be advantageously applied as a rapid repair mortar. Mortar specimens were prepared with constant water-to-cement mass ratio; polymer solid content of latex was varied from 0% to 9%, and Li₂CO₃ was investigated as an accelerator. Specimens were treated at different curing conditions: 1, 7 days and transformation of metastable hydration products at 70 °C. The heat of hydration evolution of mortar specimens was measured by means of a self adopted isoperibol calorimeter.The measurement results indicate that SBR latex improves workability of fresh state mortar and retards nucleation and growth of hydration products. Due to polymer coagulation process and co-matrix formation permeability, stiffness and compressive strength decrease while adhesion strength to old concrete substrate, and flexural strength increase with amount of added latex.     

Chemical activation of calcium aluminate cement composites cured at elevated temperature

The influence of sodium sulfate, as an activator, on the hydration of calcium aluminate cement (CAC)–fly ash (FA)–silica fume (SF) composites was investigated. Different mixes of CAC with 20% pozzolans (20% FA, 20% SF and 10% FA + 10% SF) were prepared and hydrated at 38 °C for up to 28 days. The hydration products were investigated by XRD, DSC and SEM. The results showed that sodium sulfate accelerated the hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH₁₀ and C₂AH₈ to form the strätlingite (C₂ASH₈). The later reactions prevent the strength loss by preventing the conversion of CAH₁₀ and C₂AH₈ to the cubic C₃AH₆ phase. The acceleration effect of Na₂SO₄ on the reactivity of fly ash was more pronounced than on the reactivity of silica fume with respect to reaction with CAH₁₀ and C₂AH₈ phases.     

Chemical activation of calcium aluminate cement composites cured at elevated temperature

The influence of sodium sulfate, as an activator, on the hydration of calcium aluminate cement (CAC)–fly ash (FA)–silica fume (SF) composites was investigated. Different mixes of CAC with 20% pozzolans (20% FA, 20% SF and 10% FA + 10% SF) were prepared and hydrated at 38 °C for up to 28 days. The hydration products were investigated by XRD, DSC and SEM. The results showed that sodium sulfate accelerated the hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH₁₀ and C₂AH₈ to form the strätlingite (C₂ASH₈). The later reactions prevent the strength loss by preventing the conversion of CAH₁₀ and C₂AH₈ to the cubic C₃AH₆ phase. The acceleration effect of Na₂SO₄ on the reactivity of fly ash was more pronounced than on the reactivity of silica fume with respect to reaction with CAH₁₀ and C₂AH₈ phases.     

Effect of calcium sulfate source on the hydration of calcium sulfoaluminate eco-cement

The availability of cements, including eco-cements, with tailored mechanical properties is very important for special applications in the building industry. Here we report a full study of the hydration of calcium sulfoaluminate eco-cements with different sulfate sources (gypsum, bassanite and anhydrite) and two water/cement ratios (0.50 and 0.65). These parameters have been chosen because they are known to strongly modify the mechanical properties of the resulting mortars and concretes. The applied multi-technique characterization includes: phase assemblage by Rietveld method, evolved heat, conductivity, rheology, compressive strength and expansion/retraction measurements. The dissolution rate of the sulfate sources is key to control the hydration reactions. Bassanite dissolves very fast and hence the initial setting time of the pastes and mortars is too short (20 min) to produce homogeneous samples. Anhydrite dissolves slowly so, at 1 hydration-day, the amount of ettringite formed (20 wt%) is lower than that in gypsum pastes (26 wt%) (w/c = 0.50), producing mortars with lower compressive strengths. After 3 hydration-days, anhydrite pastes showed slightly larger ettringite contents and hence, mortars with slightly higher compressive strengths. Ettringite content is the chief parameter to explain the strength development in these eco-cements.     

Flexural strength reduction of cement pastes exposed to CaCl2 solutions

Calcium chloride (CaCl₂) can react with calcium hydroxide (Ca(OH)₂) to form calcium oxychloride which can reduce flexural strength and damage concrete. This paper aims to characterize the reduction in flexural strength of cement pastes exposed to CaCl₂ solutions using the ball-on-three-balls test. The amounts of Ca(OH)₂ and calcium oxychloride in the cement paste are measured using thermogravimetric analysis and low-temperature differential scanning calorimetry, respectively. The volume change that occurs as a result of the reactions between the cement paste and CaCl₂ is also measured. The reduction in flexural strength increases as the concentration of the CaCl₂ solution increases and the exposure temperature decreases. The flexural strength reduction can be mitigated by increasing the amount of supplementary cementitious materials (fly ash) in the cement pastes. Lowering the water-cementitious materials ratio also reduces the flexural strength reduction. The flexural strength reduction is correlated with the amount of calcium oxychloride and the volume change in the cement pastes exposed to the CaCl₂ solution. While the flexural strength reduction is believed to be primarily due to the formation of calcium oxychloride, the formation of Friedel's salt and Kuzel's salt also contributes to the flexural strength reduction.     

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.     

Influence of α-calcium sulfate hemihydrate particle characteristics on the performance of calcium sulfate-based medical materials

This paper presents a systemic study on the effect of α-calcium sulfate hemihydrate (α-hemihydrate) particle characteristics on the performance of calcium sulfate-based materials (CSBM) that widely used in the medical field. The hydration performance and water requirement for normal consistency of α-hemihydrate were investigated. The mechanical strength, microstructure, and pore structure of the hardened CSBM were also examined. The performance of CSBM was greatly affected by the α-hemihydrate crystal properties. α-Hemihydrate crystals with good gradation and a length/diameter ratio of 1–3:1 tended to have perfect fluidity, lower water requirement for normal consistency, and low crystallization velocity. Moreover, in the hardened CSBM hydrated from such α-hemihydrate crystals, the crystal size of the dehydrate was large, and the crystals were interconnected. The strength of the hardened CSBM was sufficient because of low porosity, small pore diameter, and dihydrate crystals firmly in contact. This study serves as a foundation for preparing high performance for CSBM medical applications.     

A hydration study of various calcium sulfoaluminate cements

The present work studies the hydration process and microstructural features of five calcium sulfoaluminate (CSA) cements and a ternary mixture including also ordinary Portland cement (OPC). The pastes were studied with simultaneous differential thermal-thermogravimetric (DTA-TG) analysis, mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), and expansion/shrinkage tests. The DTA-TG analysis confirmed the role of the hydration reactions involving the main CSA clinker constituent, tetracalcium trialuminate sulfate, which produced (i) ettringite when combined with lime and calcium sulfate, (ii) ettringite and aluminum hydroxide in the presence of calcium sulfate alone, and (iii) monosulfate and aluminum hydroxide in the absence of both lime and calcium sulfate. The MIP and SEM were able to discriminate between expansive (ternary mixture and CSA cement containing 50% gypsum) and non-expansive cements. Expansive cement pastes had (i) a nearly unimodal pore size distribution shifted toward higher radii and (ii) ettringite crystals smaller in size during the first day of curing. In a SEM image of a hardened paste of the CSA cement containing 50% gypsum, a stellate ettringite cluster was observed.     

Hydration and properties of nano-TiO2 blended cement composites

Two types of nano-TiO₂ particles were blended into cement pastes and mortars. Their effects on the hydration and properties of the hydrated cement pastes were investigated. The addition of nano-TiO₂ powders significantly accelerated the hydration rate and promoted the hydration degree of the cementitious materials at early ages. It was demonstrated that TiO₂ was inert and stable during the cement hydration process. The total porosity of the cement pastes decreased and the pore size distribution were also altered. The acceleration of hydration rate and the change of microstructure also affected the physical and mechanical properties of the cement-based materials. The initial and final setting time was shortened and more water was required to maintain a standard consistence due to the addition of the nano-TiO₂. The compressive strength of the mortar was enhanced, practically at early ages. It is concluded that the nano-TiO₂ acted as a catalyst in the cement hydration reactions.     

Effects of calcium nitrate and triisopropanolamine on the setting and strength evolution of Portland cement pastes

The purpose of this work is to study the effect of using some admixtures such as calcium nitrate and triisopropanolamine on the setting and hardening process of cement pastes at 20°C temperature. Tests were performed on specimens cast from various mixtures prepared with two types of cements. The results indicate that calcium nitrate alone acts as a setting accelerator, but has relatively little beneficial effect on the long term period development of mechanical resistances. Regardless of the cement type used, triisopropanolamine used alone performed well as a hardening accelerator at all ages. The combined addition of calcium nitrate and triisopropanolamine produced at very early age significant and promising results with respect to both setting and hardening acceleration. Continuous compressive strength increase was observed with time.     

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.     

Carbonation of calcium sulfoaluminate mortars

This study investigated potential physical and chemical parameters that could govern the carbonation rate of calcium sulfoaluminate (CSA) mortars and endeavored to elucidate the microstructural and chemical factors that govern CSA cement's carbonation rate. Experiments included: water absorption, oxygen diffusion, mercury intrusion porosimetry, quantitative X-ray diffraction, thermogravimetric analysis, accelerated carbonation, compression and flexure tests. Additionally, the carbonation process was investigated using thermodynamic modeling. The results show that CSA mortars carbonate much faster than Portland cement mortars and at approximately the same rate as calcium aluminate cement mortars. Additionally, CSA mortars carbonate slower with decreasing w/c, and the anhydrite content of the CSA mortars strongly affects the ye'elimite reaction kinetics which plays an important role in imparting carbonation resistance in CSA mortars. Finally, calcium sulfate additions to CSA clinker to produce CSA cement dilutes the clinker content and reduces the amount of CO₂ that the CSA cement can ultimately bind.     

Performance characteristics of concrete based on a ternary calcium sulfoaluminate–anhydrite–fly ash cement

This paper reports an assessment of the performance of concrete based on a calcium sulfoaluminate–anhydrite–fly ash cement combination. Concretes were prepared at three different w/c ratios and the properties were compared to those of Portland cement and blast-furnace cement concretes. The assessment involved determination of mechanical and durability properties. The results suggest that an advantageous synergistic effect between and ettringite and fly ash (Ioannou et al., 2014) was reflected in the concrete’s low water absorption rates, high sulfate resistance, and low chloride diffusion coefficients. However, carbonation depths, considering the dense ettringite-rich microstructure developed, were higher than those observed in Portland cement concretes at a given w/c ratio. It was concluded that the amount of alkali hydroxides present in the pore solution is as important factor as the w/c ratio when performance of this type of concrete is addressed.     

Calcium sulphate anhydrite based composite binders; effect of Portland cement and four pozzolans on the hydration and strength

The strength, hydration products, microstructure and heat of early hydration were investigated on alternative hydraulic green cements based on calcium sulphate anhydrite partially blended with Portland cement and pozzolans. Four pozzolans of different physical and chemical nature, namely a geothermal waste, silica fume, metakaolin and pulverized fuel ash were characterized. The composite binders showed hydraulic behavior. The use of Portland cement favoured the strength, which was also higher with the incorporation of siliceous nanometric pozzolans compared to the micrometric silicoaluminate pozzolans. The nanoparticles enhanced the early hydration and changed the gypsum morphology promoting denser matrices of hydration products. The geothermal waste pozzolan was the most effective, while one of the composites with metakaolin showed formation of ettringite and strength losses. The heat of hydration of the composites was considerably lower than that of the neat Portland cement.     

Properties of MSW fly ash-calcium sulfoaluminate cement matrix and stabilization/solidification on heavy metals

In this paper, investigations were undertaken to formulate the properties of fly ash-calcium sulfoaluminate (CSA) cement matrix by blending MSW fly ash with CSA cement. The compressive strength, pore structure, hydration phases, and leaching behavior of Zn and Pb doped MSW fly ash-CSA cement matrices were determined by XRD, MIP, DSC, FTIR, EDX, TCLP leaching test and other experiments. The results showed that the addition of MSW fly ash to form fly ash-CSA cement matrix reduced the compressive strengths of matrices and made the pore distribution of matrices coarser, compared to that of pure CSA cement matrix. However, fly ash-CSA cement matrix could effectively immobilize high concentration of heavy metal such as lead and zinc with much lesser leaching of TCLP. Besides ettringite AFt, Friedel phase was a new hydration phase formed in the matrix. The formation of these hydration phases was responsible for huge reservoir of heavy metal stabilization by chemical fixing. Therefore, it could be postulated that MSW fly ash-CSA cement matrix was a potential new constituent of S/S matrix for high concentration of heavy metals such as Zn and Pb ions.