Calcium Sulfoaluminate Belite Research Articles

Preparation and Performance of Ternesite-Ye'elimite Cement.

Ternesite–ye’elimite (TCSA) cement is a new type of environmentally advantageous binder prepared by introducing ternesite, a reactive phase, into belite calcium sulfoaluminate cement clinker. This paper reports the laboratory production of TCSA cement by the addition of minor elements to achieve the coexistence of ternesite and ye’elimite. The influence of dopants on the mineralogical composition of clinkers and the clinkering conditions for the preparation of TCSA cement clinkers were investigated by X-ray powder diffraction and scanning electron microscopy. The mechanical properties and hydration products of the cement pastes were also studied. The results indicated that the addition of CaF2, P2O5 and Na2O can promote the coexistence of ternesite and ye’elimite, and that Na2O is the most effective candidate. TCSA cement clinkers could be successfully prepared at 1150 °C for 30 min by doping 0.3% Na2O. The TCSA cement clinkers exhibited shorter setting times than the BCSA cement clinkers. The later strength of TCSA cement showed a significant increase compared with BCSA cement. The effect of Na2O was different on the strength development for TCSA and BCSA cement. The dissolution of ternesite could promote the formation of ettringite. The reactivity of belite was higher in TCSA cement due to the formation of strätlingite.

Mitigating early age cracking in 3D printed concrete using fibres, superabsorbent polymers, shrinkage reducing admixtures, B-CSA cement and curing measures

3D printed concrete is vulnerable to severe early age shrinkage-related cracking due to the absence of formwork and coarse aggregates. To address this, several potential mitigation measures are compared based on their ability to reduce free shrinkage and cracking severity at dosages which do not adversely affect the printability or buildability of a well-developed 3DPC mixture. The results show that a low dosage of short polypropylene microfibres eliminates early age cracking. The external application of a curing agent and multiple applications of misting water are less effective. Calcium sulfoaluminate–belite cement is used to accelerate structuration and proves beneficial in crack mitigation while enhancing buildability. Internal curing, with superabsorbent polymers, is less effective in mitigating plastic cracks but reduces autogenous shrinkage and increases the rate of stiffening. At the dosage used in this study, the shrinkage reducing admixture is relatively ineffective in crack mitigation, with higher dosages adversely affecting the buildability.

Water-to-cement ratio of calcium sulfoaluminate belite cements: Hydration, setting time, and strength development

Little published data is available to guide engineers in designing calcium sulfoaluminate belite (CSAB) cement mixtures with adequate workability, strength, and durability. This lack of understanding of design factors, especially the effect of varying w/c, represents a significant barrier to widespread CSAB use. In this study hydration, setting time, and strength development of two CSAB cements with w/c from 0.3 – 0.6 were evaluated. CSAB reaction kinetics varied with increased w/c depending on CSAB composition, specifically calcium sulfate content – with higher w/c increasing retardation in higher anhydrite/ye'elimite content cement, but reduced retardation in lower anhydrite/ye'elimite cement. For both cements, greater w/c led to greater total hydration, increased setting times, and reduced compressive strengths in the pastes and mortar samples. Setting time was linked more closely to anhydrite content than w/c, with greater sulfate volumes shortening setting times.

Blending eco-efficient calcium sulfoaluminate belite ferrite cement to enhance the physico–mechanical properties of Portland cement paste cured in refrigerated and natural winter conditions

The acceleration impacts of calcium sulfoaluminate belite ferrite (CSABF)—a cement produced from industrial side streams—on the hydration and strength development of Portland cement (PC) paste cured at −5 °C with and without pre-curing at room temperature were investigated. The impacts of eco-friendly CSABF cement content and pre-curing on the setting time and hardened properties of pastes were investigated. Freezing point of the paste and the amount of freezable water (FW) decreased with CSABF cement content and pre-curing. Hydration rate increased with CSABF cement content. By adding an optimal CSABF cement content, the compressive strength of paste cured at −5 °C increased by 500%. The effects of pre-curing on the compressive strength of the subzero-cured pastes were highly dependent on CSABF cement content and curing period. After 6 months, the outdoor-cured 70%PC/30%CSABF paste gained compressive strength comparable to that in the 90-day-old pair cured at −5 °C and continuous strength gain was detected up to one-year. The microstructural observations and porosity results are consistent with compressive strength measurements.

Influence of calcium hydroxide and calcium sulfate on early-age properties of non-expansive calcium sulfoaluminate belite cement

Calcium sulfoaluminate belite (CSAB) cements are currently being promoted as alternative low CO2 cements. CSAB cements have ye'elimite as their primary phase. Ye'elimite hydrates rapidly to form ettringite which contributes towards high early-age strength. The hydration characteristics of ye'elimite are influenced by the presence of calcium sulfate and calcium hydroxide, which can also extend to the mechanical properties. Further, this change in phase composition can modify a non-expansive binder into an expansive binder. In this study, the influence of phase composition on hydration characteristics, expansion, pore structure, and mechanical properties was investigated using CSAB binders with varying gypsum and calcium hydroxide levels. The expansion was directly affected by the amount of calcium sulfate and calcium hydroxide. The differentiating factor between expansive and non-expansive systems was the critical pore size of CSAB binders. Expansive CSAB binders exhibited lower critical pore size than non-expansive binders, highlighting the role of supersaturation. The addition of calcium hydroxide accelerated the kinetics of ye'elimite hydration and increased the expansion. Moreover, the change from a non-expansive to expansive system did not lead to the deterioration of the CSAB binder matrix.

Ferritic calcium sulfoaluminate belite cement from metallurgical industry residues and phosphogypsum: Clinker production, scale-up, and microstructural characterisation

The production of ferrite-rich calcium sulfoaluminate belite (CSABF) cement clinker, also containing MgO, from ladle slag, Fe-slag, and phosphogypsum was translated from a lab-scale to a pilot demonstration in a 7-metre kiln at 1260 °C. An account of the pilot trials/manufacturing is presented, and the process was robust. Laboratory tests prior to scale-up showed that gehlenite formation can be inhibited in the CSABF clinker by adding excess CaO in the raw meal; however, this reduces the amount of iron (Fe) that can be incorporated into ye'elimite and leads to higher ferrite (C6AF2) content. Detailed microstructural analyses were performed on the clinker to reveal the clinker composition as well as the partition of the minor elements. Different ferrite phases with varying amounts of titanium and iron are distinguished. Eighty-five percent of the clinker raw meal was comprised of side-stream materials and the clinker produced in the kiln had chemical raw-material CO2 emissions 90% lower than that of Portland cement made from virgin raw materials. These results can have a significant impact in regions with a prospering metallurgical industry, enabling industrial decarbonisation and resource efficiency.

Synthesis of MgO-Belite calcium sulfoaluminate cement from phosphate mine waste rock and phosphogypsum

MgO-Belite calcium sulfoaluminate low carbon clinker (BCSAC) was successfully synthetized from a raw meal containing more than 77 wt% of phosphate by-products: 67 wt% of phosphate mining waste rocks and 10 wt% of phosphogypsum (PG: CaSO4·2H2O), while the remaining portion was Kaolin clay. The obtained clinker could be considered as an environmental friendly material. In fact, it can be synthetized at lower temperature (1250 °C) and it is physically softer than Portland cement. Ye’elimite and belite were the major cement phases in the obtained clinker. The hydration of the synthesized cements was assessed by microcalorimetry, compressive strength tests, X-ray diffraction and thermogravimetric analysis. Ettringite was identified as the main crystalline hydrate phase, which is in accordance with thermodynamic modelling results. The presence of P2O5 and the residual acidity in PG negatively influenced the strength development. However, the compressive strengths of the obtained belite calcium sulfoaluminate clinkers was higher than Portland cement at 3 and 7 days. It was explained by the high quantity of ettringite in sulfate-rich cement pastes.

Local Al network and material characterization of belite-calcium sulfoaluminate (CSA) cements

Local Al network and material characterization of belite-calcium sulfoaluminate (CSA) cements

The influence of calcium sulfate content on the hydration of belite-calcium sulfoaluminate cements with different clinker phase compositions

The influence of different amounts of gypsum on the hydration of a belite-rich and a ye'elimite-rich belite-calcium sulfoaluminate clinker (BCSA) was investigated. The hydration kinetics, phase assemblages and compressive strength development of cements prepared using ye’elimite/ calcium sulfate molar ratios of 1, 1.5 and 2 were studied. Besides ettringite and monosulfate, aluminium hydroxide, strätlingite, C−S−H, iron-containing siliceous hydrogarnet and hydrotalcite were present as hydration products. Increasing the amount of gypsum increased the ratio of ettringite to monosulfate formed in the cement paste, lowered the amount of pore solution, delayed the dissolution of belite and ferrite, decreased the formation of strätlingite and, in the case of the ye’elimite-rich BCSA, led to an increase in compressive strength. Increased amounts of belite in the clinker led to the formation of higher quantities of C–S–H, at the expense of strätlingite and a lower compressive strength, as belite has a lower degree of reaction than ye’elimite and due to the formation of more C–S–H and strätlingite compared to the more space-filling ettringite. The thermodynamic model established for BCSA cement hydration agrees well with the experimental data. Compressive strength directly correlated with bound water from thermogravimetric analyses and inversely correlated with the porosity calculated from thermodynamic modelling.

Effects of sodium gluconate on hydration reaction, setting, workability, and strength development of calcium sulfoaluminate belite cement mixtures

Fast setting is an important reason restricting the applications of eco-friendly calcium sulfoaluminate belite (CSAB) cement. To help spread the application of CSAB cement, this study investigated the influence of sodium gluconate (SG) as a setting retarder on the setting, workability, and strength development of CSAB cement mixtures. Quantitative X-ray diffraction (QXRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were performed to understand the effects of SG on the hydration and microstructure of CSAB cement mixtures. The results showed that SG effectively extended the setting time and improved the workability of CSAB cement pastes since it retarded ye’elimite hydration and impeded the loss of workability caused by ettringite formation. Low dosages (≤0.5%) of SG increased the unconfined compressive strength (UCS) of CSAB cement mortars at all ages (from 2 h to 90 days) due to the reduction in void content, fast diminishment of the retarding effect at early ages, and slight acceleration on belite hydration at later ages. However, high dosages (≥1%) significantly degraded the UCS of CSAB cement mortars at all ages since high dosages of SG strongly retarded ye’elimite hydration at early ages and caused a looser microstructure at later ages.

Early assessment of hydration and microstructure evolution of belite-calcium sulfoaluminate cement pastes by electrical impedance spectroscopy

In this paper, the interconnectedness among the electrical resistivity, the calorimetric heat and the chemical shrinkage of high Belite calcium sulfoaluminate (BCSA) cement are discussed. Microstructure analyses by using XRD, NMR, ICP-MS and SEM are applied to further demonstrate the relationship among the microstructure, the compositional variation and the electrical resistivity of the hydrated cement paste. Two distinctive hydration stages can be differentiated from the BCSA cementitious materials. First stage is mainly controlled by hydration process of both the ye’elimite and the gypsum, and the second stage is mostly controlled by the formation of AFm and amorphous phases as a secondary hydration process. According to the classic equation depicted the hydration degree of cementitious materials, a specific mathematical equation combining not only traditional parameters but also the electrical resistivity is proposed for the BCSA.

Using alumina-rich sludge and phosphogypsum manufactures low-CO2 cement

Calcium sulfoaluminate-belite (CŜAB) cement has been proposed as a low-CO2 cement for substituting ordinary Portland cement (OPC). The aim of this work was to study synthesis of CŜAB cement from two industrial wastes, namely Alumina-rich sludge (AS) and phosphogypsum (PG). The main phases of the synthesized cement were ye'elimite, larnite, ternesite and anhydrite. The properties of CŜAB cement were investigated through the test of compressive strength, setting time and hydration products. We found that the optimal procedure was burning at 1150 °C for 1 h which needs much lower energy than traditional production. CŜAB cement could reach 39.4 MPa at 28 d hydration, when basicity factor, the ratio of aluminum to sulfur and aluminum to silicon ratio were 0.8, 2.5 and 3 respectively. Blending phosphogypsum into clinker, made paste get a much higher compressive strength (53.2 MPa at 28 d). Adding phosphogypsum to CŜAB cement hindered hydration process of cement and decreased hydration products except for ettringite. Production of this cement is beneficial to recycle industrial wastes and reduce CO2 emission. This is meaningful for further development of cement industry.

Quantitative in Situ X-ray Diffraction Analysis of Early Hydration of Belite-Calcium Sulfoaluminate Cement at Various Defined Temperatures

The influence of temperature on the early hydration of belite-calcium sulfoaluminate cements with two different calcium sulfate to calcium sulfoaluminate molar ratios was investigated. The phase composition and phase assemblage development of cements prepared using molar ratios of 1 and 2.5 were studied at 25, 40 and 60 °C by in situ X-ray powder diffraction. The Rietveld refinement method was used for quantification. The degree of hydration after 24 h was highest at ambient temperatures, but early hydration was significantly accelerated at elevated temperatures. These differences were more noticeable when we increased the temperature from 25 °C to 40 °C, than it was increased from 40 °C to 60 °C. The amount of calcium sulfate added controls the amount of the precipitated ettringite, namely, the amount of ettringite increased in the cement with a higher molar ratio. The results showed that temperature also affects full width at half maximum of ettringite peaks, which indicates a decrease in crystallite size of ettringite at elevated temperatures due to faster precipitation of ettringite. When using a calcium sulfate to calcium sulfoaluminate molar ratio of 1, higher d-values of ettringite peaks were observed at elevated temperatures, suggesting that more ions were released from the cement clinker at elevated temperatures, allowing a higher ion uptake in the ettringite structure. At a molar ratio of 2.5, less clinker is available in the cement, therefore these differences were not observed.

Influence of exposure conditions on expansion characteristics of lime-rich calcium sulfoaluminate-belite blended cement

Expansive characteristics of calcium sulfoaluminate-belite (CSAB) cement can be harnessed for making shrinkage-compensating concrete. The level of expansion is dependent on several factors, such as the amounts of ye'elimite and calcium sulfate available in CSAB cement. Moreover, calcium sulfate from an external source can also influence the expansion characteristics by increasing the supersaturation with respect to ettringite. In this study, the influence of externally available calcium sulfate was investigated by curing a blend of Portland cement (PC) and CSAB cement to different concentrations (1 g/l and 5 g/l) of gypsum solutions. Expansion of the PC-CSAB blended cement was found to be directly affected by the ye'elimite content (CSAB dosage) and the gypsum concentration in exposure solution. The presence of external calcium sulfate during the hydration of ye'elimite was found to affect the hydrate phase assemblage, the pore structure, and the morphology of ettringite. Furthermore, the level of expansion depended on the age at which the specimens were exposed to the gypsum solution, indicating the influence of matrix stiffness on resultant expansion.

Study of Eco-Friendly Belite-Calcium Sulfoaluminate Cements Obtained from Special Wastes

Belite-calcium sulfoaluminate (BCSA) cements are special binders obtained from non-Portland clinkers; they have become increasingly more important due to their environmental impact during the manufacturing process compared to Portland cements, such as lower energy consumption and CO2 emissions. The aim of this paper was to assess the possible use of titanogypsum (T) and water potabilization sludge (W) to reduce the amount of natural raw materials (natural gypsum and clay, respectively) used in the production of BCSA cements. Three BCSA clinker generating raw mixes, containing T and/or W, and a reference mix based only on natural materials (limestone, clay, bauxite and natural gypsum) were heated in an electric furnace at temperatures ranging from 1200 to 1350 °C. Quantitative X-ray diffraction (XRD) analysis of the burnt products showed high conversion of reactants towards the main hydraulically active BCSA clinkers components (C2S and C4A3$), particularly at temperatures of 1300 and 1350 °C. Isothermal calorimetric measurements, differential thermal–thermogravimetric and XRD analyses as well as porosimetric measurements showed that all BCSA cements, from mixing the clinkers (at optimum temperatures) with commercial anhydrite, exhibited similar hydration behavior.

Phase development and hydration kinetics of belite-calcium sulfoaluminate cements at different curing temperatures

The influence of different curing temperatures on the hydration of belite-calcium sulfoaluminate cement was investigated at 20, 40 and 60 °C. The hydration kinetics and the hydrated phase assemblages were studied by isothermal calorimetry, X-ray powder diffraction, differential thermal analysis and thermogravimetric analysis, as well as field emission scanning electron microscopy. The compressive strength development of the cement pastes was also determined. Results showed that, at early ages, hydration was faster and early compressive strength was higher at elevated temperatures than at ambient temperature. On the other hand, at late ages in cement pastes cured at 60 °C, the amount of ettringite decreased, leading to lower compressive strength, indicating that the degree of hydration was lower at higher temperatures. Moreover, at elevated temperatures prismatic ettringite crystals became smaller due to faster hydration. Other hydration products present were aluminium hydroxide, which is formed together with ettringite from the hydration of calcium sulfoaluminate and gypsum, and C–S–H which precipitates as a main hydration product of belite. Belite hydrated in a lesser amount, especially at 60 °C, when the lowest amount of C–S–H was observed.

Immobilization of heavy metals, selenate, and sulfate from a hazardous industrial side stream by using calcium sulfoaluminate-belite cement

Release of heavy metals from different industries and industrial waste is a major global threat for as well humans as ecosystems. In this study, immobilization of an industrial filter sludge (FS) with an extremely high content of several heavy metals (24.6 wt% Pb, 21.7 wt% Hg, and 9.00 wt% Se) and sulfate via calcium sulfoaluminate-belite (CSAB) cement was tested. The ratios of 25%, 50% and 75% of CSAB addition were tested, and the target was to achieve immobilization of the hazardous components. The leaching of Pb, Hg, SeO4, SO4, Ni, Cd, Cu, and As was monitored, and the structure of the immobilized materials was examined via X-ray powder diffraction (XRD) and field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS) analysis. It was observed that Hg, Cu, As, Cd, and Ni were immobilized completely and leaching of Pb was reduced by 69% from the theoretical release. On the other hand, the leaching of SeO4 and SO4 experienced major increase when CSAB was added. XRD indicated significant ettringite formation as the amount of added CSAB increased, and the formation of gypsum as the amount was decreased. FESEM-EDS indicated that the immobilization was largely based on encapsulation into the CSAB binder, but chemical immobilization into the ettringite binder was also observed. It was concluded that the increased release of SO4 and SeO4 might have resulted from an excess amount of sulfates (added gypsum) during hydration.

Production and properties of ferrite-rich CSAB cement from metallurgical industry residues

Blast furnace slag from the steel industry is commercially utilized as a cement replacement material without major processing requirements; however, there are many unutilized steel production slags which differ considerably from the blast furnace slag in chemical and physical properties. In this study, calcium sulfoaluminate belite (CSAB) cement clinkers were produced using generally unutilized metallurgical industry residues: AOD (Argon Oxygen Decarburisation) slag from stainless steel production, Fe slag from zinc production, and fayalitic slag from nickel production. CSAB clinker with a target composition of ye'elimite-belite-ferrite was produced by firing raw materials at 1300 °C. The phase composition of the produced clinkers was identified using quantitative XRD analyses, and the chemical composition of the clinker phases produced was established using FESEM-EDS and mechanical properties were tested through compressive strength test. It is demonstrated that these metallurgical residues can be used successfully as alternative raw materials for the production of CSAB cement that can be used for special applications. In addition, it is shown that the available quantities of these side-streams are enough for significant replacement of virgin raw materials used in cement production.

Effects of comb-like PCE and linear copolymers on workability and early hydration of a calcium sulfoaluminate belite cement

Fluidity control and setting adjustment are two critical issues for practical applications of calcium sulfoaluminate cement because of rapid hydration. A commonly used comb-like polycarboxylate superplasticizer (PCE) and linear copolymers (PAS) of acrylic acid (AA) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with varied monomer ratio were synthesized to study their impacts on fluidity and early hydration of calcium sulfoaluminate belite cement (CSAB). Results show that the linear PAS polymers are very effective in dispersing fresh cement pastes (fcps) and effectively inhibit early hydration of the cement. More AA unit in the PAS molecules leads to stronger inhibition effect on cement hydration. Compared with the PAS polymers, PCE exhibits almost no inhibition effect on cement hydration despite the high initial dispersibility. Thus, cement pastes containing PAS polymers exhibits excellent fluidity retention compared with the PCE containing fcp due to strong retardation effect of the PAS polymers on early formation of AFt crystals.

Self-Cleaning of Photocatalytic Mortar with Glass Aggregate and Calcium Sulfoaluminate-Belite Cement

The self-cleaning performance and mechanism of photocatalytic mortars with different cementitious materials and aggregates was evaluated through a rhodamine B (RhB) degradation test. The self-cleaning property of photocatalytic concrete helps to preserve its aesthetics, NOx removal potential, and surface reflectance. In this study, the addition of TiO2 to calcium sulfoaluminate-belite cement (CSAB) demonstrated a self-cleaning potential like ordinary Portland cement (OPC). Photocatalytic mortar mixes with OPC demonstrated increased self-cleaning efficiency with glass fine aggregate and with higher TiO2 content. However, glass addition was not effective in improving the self-cleaning efficiency of CSAB mortar with TiO2. Replacement of OPC with class F fly ash significantly decreased self-cleaning efficiency. The decrease in pore solution pH with fly ash replacement of OPC or CSAB cement instead of OPC was hypothesized as the cause for the decline in self-cleaning efficiency. An experiment to study the photocatalytic degradation rate of RhB revealed that it increased with higher pH. RhB photocatalytically degrades through N-de-ethylation and cleavage of the chromophore structure depending on the reaction surface characteristics with the first path investigated in this paper. It was shown that some of the RhB on the photocatalytic mortar surface was degraded by the N-de-ethylation path regardless of the cement and aggregate constituents and increasing TiO2 (anatase) content increased RhB degradation through N-de-ethylation.