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.     

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).     

Micro-mechanical properties of calcium sulfoaluminate cement and the correlation with microstructures

To investigate the micro-mechanical properties of calcium sulfoaluminate cement and the correlation with the microstructures, we apply a variety of advanced techniques of microstructural and micro-mechanical characterization, including scanning electron microscopy with backscattered electron and energy-dispersive X-ray spectroscopy detectors, X-ray fluorescence, X-ray diffraction and nanoindentation. For the first time, the micro-mechanical properties of material microstructures present in a calcium sulfoaluminate cement are estimated. In the calcium sulfoaluminate cement used in this research, two type of hydration product microstructures with the differentiable microstructural morphologies, compositions and micro-mechanical properties are identified and investigated. The correlation of the micro-mechanical properties with the microstructures shows that the hydration product microstructure containing more ettringite has lower indentation modulus and hardness than that containing more aluminum hydroxide.     

Influence of limestone and anhydrite on the hydration of Portland cements

The addition of CaCO₃ and CaSO₄ to Portland cement clinker influences the hydration and the strength development. An increase of the CaSO₄ content accelerates alite reaction during the first days and results in the formation of more ettringite, thus in a higher early compressive strength. The late compressive strength is decreased in Portland cements containing higher quantities of CaSO₄. The reduced late compressive strength seems to be related to an increase of the S/Si and Ca/Si content in the C–S–H.The presence of calcite leads to the formation of hemicarbonate and monocarbonate thus indirectly to more ettringite. Only a relatively small quantity of calcite reacts to form monocarbonate or hemicarbonate in Portland cement. Although hemicarbonate is thermodynamically less stable than monocarbonate, hemicarbonate formation is kinetically favored. Monocarbonate is present only after 1 week and longer independent of the quantity of calcite available and the content of sulphate in the cement.     

Development of self-leveling screed based on calcium sulfoaluminate cement: Modelling of curling due to drying

The development of cement-based screed unbound to its support is still limited because of the curling that occurs at the corners and perimeter of the screed. This phenomenon is mainly due to the moisture gradient that appears within the thickness of the screed: the upper surface dries and shrinks, whereas lower regions dry less and stay wetter. This paper demonstrates this phenomenon can be mitigated through the use of calcium sulfoaluminate cement instead of ordinary Portland cement. Experiments utilizing an original, specially designed device, show that curling is 3.5 times lower when calcium sulfoaluminate cement is used compared to ordinary Portland cement. The moisture gradient within the thickness of the screed is also lower.A model based on simplified poroelasticity theory describes both fluid transfer and hydro-mechanical coupling. The comparison between experimental and calculated results shows that the model gives a good estimation of the kinetics of the mass loss, and that the numerical simulation is an effective tool to predict curling due to drying.     

Influence of curing temperatures on the hydration of calcium aluminate cement/Portland cement/calcium sulfate blends

In this paper, the effects of curing temperature on the hydration of calcium aluminate cement (CAC) dominated ternary binders (studied CAC: Portland cement: calcium sulfate mass ratio were 22.5: 51.7: 25.8) were estimated at 0, 10, 20 and 40 °C, respectively. Both α-hemihydrate and natural anhydrite were employed as the main source of sulfate. The impacts of temperature on the phase assemblages, morphology and pore structure of pastes hydrated up to 3 days were determined by using X-ray diffraction (XRD), backscattered electron imaging (BEI) and mercury intrusion porosimetry (MIP). Results reveal that the main hydration products are firmly related to calcium sulphoaluminate based phases. Increasing temperature would result in a faster conversion from ettringite to plate-like monosulfate for both calcium sulfate doped systems. When the temperature increases to 40 °C, an extraordinary formation of strätlingite (C₂ASH₈) and aluminium hydroxide is observed in anhydrite doped pastes. Additionally, increased temperature exerts different effects on the pore structure, i.e. the critical pore diameter shifts to finer one for pastes prepared with α-hemihydrate, but changes to coarser one for those made with anhydrite. From the mechanical point of view, increased temperature accelerates the 1-day strength development prominently, while exerts marginal influence on the development of 3-day strength.     

Effect of cement type and limestone particle size on the durability of steam cured self-consolidating concrete

This paper describes a laboratory program to investigate the influence of cement and limestone filler (LF) particle size on the hardened properties and durability performance of steam cured self-consolidating concrete. In addition, the interplay between cement type and LF particle size was investigated. CSA (Canadian Standards Association) Type GU (General Use) and HE (High Early-strength) cements were used with 5% silica fume (SF) [1]. The water-to-cement ratio was 0.34. LF with two nominal particle sizes of 17 μm and 3 μm, which correspond to Blaine fineness of 475 and 1125 m²/kg, respectively, were used. In addition to fresh concrete properties, hardened properties including compressive strength, elastic modulus, ultrasonic pulse velocity and density were measured at 12 h and 16 h, and at 3, 7 and 28 days. Indicators of durability performance including rapid chloride permeability testing (RCPT), sulfate resistance, linear shrinkage, salt scaling resistance and freeze-thaw resistance were evaluated. The results showed that LF improved the 12 and 16-h strength with no influence on later age strength (i.e., 3–28 days). The linear shrinkage and RCPT decreased with the addition of LF. This reduction was linked to the production of calcium mono-carboaluminate. LF did not impact the sulfate resistance, salt scaling resistance or freeze-thaw resistance of concrete.     

Influence of limestone content,fineness, and composition on the properties and microstructure of alkali-activated slag cement

The influence of the fineness, concentration, and chemico-mineralogical composition of limestone on the workability, reaction kinetics, compressive strength, microstructure, and binder gel characteristics of sodium carbonate–based waste-activated waste slag cement pastes was investigated in this work. Alkali-activated slag cements incorporated with limestone, containing 33–100% of calcite, at a content of up to 60% with a 28-day compressive strength of 26.2–48.8 MPa were proposed. The main reaction products of hardened alkali-activated cement pastes and those incorporated with limestone are CSH, CaCO₃, Na₂Ca(CO₃)₂·5H₂O, and Na₂CaSiO₄. “Physically active” limestone does not chemically react with the binder gel but it can improve the physical structure. The higher packing density of mixed cement, without an increase in the water demand, the satisfactory binding strength of limestone with the binder gel lead to the improvement in the physical structure and compressive strength of alkali-activated slag paste.     

Use of sulfoaluminate cement and bottom ash in the solidification/stabilization of galvanic sludge

Solidification/stabilization (S/S) process can improve the physical characteristics of wastes, reduce their leaching and limit the solubility of their heavy metals. The identification of binders able to assume the fixation of contaminants is essential for the success of the technique. In this study, calcium sulfoaluminate cement was added to another waste, bottom ash, in order to treat galvanic sludge. The properties of the resultant solid matrix (MS) were determined: setting time, compressive strength and products of hydration. Solid matrix composed of 77% waste and only 23% cement presented initial setting time lower than 4 h and 28 day-strength of 6 MPa. SEM investigations showed that contaminants present in the galvanic sludge (Cr) were encapsulated in the hydrated phases and particles of bottom ash.     

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.     

Synthesis of belite sulfoaluminate-ternesite cements with phosphogypsum

Phosphogypsum (PG) is an industrial byproduct from phosphoric acid production. In order to facilitate the use of PG, belite sulfoaluminate-ternesite cements were produced with high amounts of PG. This work regards the laboratory production of belite sulfoaluminate-ternesite cements by using a new synthesis method. Using a secondary heat treatment step, the method achieves the coexistence of ye'elimite and ternesite. Quantitative X-ray powder diffraction and electron microscopy were used to analyze the phase composition of clinkers. The secondary heat treatment between 1100 and 1200 °C can significantly facilitate the formation of ternesite in the clinkers. The presence of large amount of ternesite results in a decrease in early strength, but the hydration of ternesite at later ages can increase the strength after 56 days of hardening. The hydration products of pure ternesite and the clinker containing ternesite were also investigated. The results show that pure ternesite can hydrate at a slow rate, and the addition of ye'elimite promotes the hydration of ternesite and the formation of ettringite. The ettringite formation for the clinker containing ternesite mainly depends on the dissolution of gypsum originating from the hydration of ternesite.     

Influence of various amounts of limestone powder on performance of Portland limestone cement concretes

The benefits of limestone as a partial replacement for Portland Cement (PC) are well established. Economic and environmental advantages by reducing CO₂ emissions are well known. The paper describes the effect of various amounts of limestone on compressive strength, water penetration, sorptivity, electrical resistivity and rapid chloride permeability on concretes produced by using a combination of PC and limestone at 28, 90 and 180 days. The percentages of limestone that replace PC in this research are 0%, 5%, 10%, 15% and 20% by mass. The water/(clinker + limestone) or (w/b) ratios are 0.37, 0.45 and 0.55 having a constant total binder content of 350 kg/m³. Generally, results show that the Portland limestone cement (PLC) concretes having up to 10% limestone provide competitive properties with PC concretes.     

Hydration of quaternary Portland cement blends containing blast-furnace slag,siliceous fly ash and limestone powder

In this study the hydration of quaternary Portland cements containing blast-furnace slag, type V fly ash and limestone and the relationship between the types and contents of supplementary cementitious materials and the hydrate assemblage were investigated at ages of up to 182 days using X-ray diffraction and thermogravimetric analysis. In addition thermodynamic modeling was used to calculate the total volume of hydrates. Two blast-furnace slag contents of 20 and 30 wt.% were studied in blends containing fly ash and/or limestone at a cement replacement of 50 wt.%. In all cases the experiments showed the presence of C–S–H, portlandite and ettringite. In samples without limestone, monosulfate was formed; in the presence of limestone monocarbonate was present instead. The addition of 5 wt.% of limestone resulted in a higher compressive strength after 28 days than observed for cements with lower or higher limestone content. Overall the presence of fly ash exerts little influence on the hydrate assemblage. The strength development reveals that amounts of up to 30 wt.% fly ash can be used in quaternary cements without significant loss in compressive strength.     

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.     

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.     

Effect of cement substitution by limestone on the hydration and microstructural development of ultra-high performance concrete (UHPC)

The effect of limestone on the hydration and microstructural development of ultra high performance concrete (UHPC) with different levels of replacement (34%, 54% and 74% by volume) was investigated. Up to 54% replacement of cement by limestone the mixes showed better workability and higher compressive strength (170 MPa at 56 days for 54% addition) compared to a classical mix (155 MPa) with no limestone replacement. The kinetics of hydration were compared for different replacement levels using isothermal calorimetry. The phase development was quantified by X-ray diffraction with Rietveld method combined with thermal gravimetric analysis. The pore structure was examined by mercury intrusion porosimetry. The composition of hydration products was determined by scanning electron microscopy with energy dispersive X-ray analysis. The results showed that the hydration degree of the cement is increased from 39% for classical UHPC to 66% for the UHPC with 54% of limestone.     

Effects of portland cement replacement with limestone on the properties of hardened concrete

Limestone portland cement has a lower environmental impact during the production phase in comparison with portland cement. However, the environmental advantages initially gained should be correlated to the long-term performance of concrete structures. Hence, the knowledge of the long-term properties, and in particular durability performance, is essential to assess the actual environmental impact of limestone replacement. In the literature, there is disagreement on durability behaviour and the contribution of limestone to the resistance to chloride and carbonation penetration is controversial. In this paper, the effect of the percentage of replacement of portland cement with ground limestone, water/binder ratio and cement content on compressive strength, electrical resistivity, sorptivity and resistance to carbonation and chloride penetration was evaluated. Results showed that both mechanical properties and resistance to penetration of aggressive agents decreased by replacing 15% of portland cement with limestone; a further decrease occurred with 30% limestone.     

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.     

A study on hydration,compressive strength,and porosity of Portland-limestone cement mixes containing SCMs

In this study, the hydration of Portland-limestone cement (PLC) pastes and the relationship between compressive strength and porosity of PLC mortar samples containing various levels of supplementary cementitious materials were examined using XRD and MIP techniques. The results revealed that part of the limestone portion of Portland-limestone cements reacts with the alumina phases and produces carboaluminates, which increases compressive strength and reduces porosity. There is an optimum level of limestone corresponding to the available amount of alumina in the binder. Addition of slag or metakaolin provided more alumina, causing more limestone to participate in the hydration reaction and increasing the optimum level of limestone.     

石灰石粉对泵送混凝土性能影响的试验研究

本文主要研究了单掺石灰石粉、石灰石粉与粉煤灰复掺对泵送混凝土拌合物工作性和抗压强度的影响,研究表明：掺加石灰石粉可以改善泵送混凝土的工作性能,与单掺石灰石粉相比,石灰石粉与粉煤灰复掺,具有复合叠加效应,不仅可以改善泵送混凝土的工作性能,同时可提高泵送混凝土的抗压强度。