Design and optimisation of new formulations of Belite-Alite Calcium Sulfoaluminate (BACSA) eco-cements

Belite Calcium SulfoAluminate (BCSA) eco-cements were developed as OPC substitutes since in their production release 22% less CO2 than OPC. BCSA eco-cements contain belite as main phase (>50 wt%) and ye'elimite as secondary main phase (~30 wt%). However, these materials develop low mechanical strengths at intermediate hydration ages (3, 7 and 28 days). A solution to this problem may involve the design and preparation of clinker/cement with the highest percentage of coexisting alite and ye'elimite. These materials are known as Belite-Alite Calcium SulfoAluminate (BACSA) clinkers/cements. Their manufacture may produce 15% less CO2 than OPC. Alite is the main component of OPC and is responsible for early mechanical strengths. The reaction of alite and ye´elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. This work is focused on the design and optimisation of all the parameters evolved in the preparation of BACSA eco-clinkers that develop mechanical strengths comparable to those of OPC with a reduction in CO2 emissions of at least 15% when compared to OPC production. These parameters include the selection of the raw materials (lime, gypsum, kaolin and sand), milling conditions of the crude, clinkering temperature (from 1280 to 1300ºC) and holding time at every temperature, and final composition. The clinker with the targeted composition (belite ~ 60 wt%, alite ~ 13 wt% and ye'elimite ~ 10 wt%) was chosen to perform the scaling-up (2 kg). BACSA eco-clinkers were chemically and mineralogically characterised through X-ray fluorescence and laboratory X-ray powder diffraction (LXRPD), the latter in combination with the Rietveld methodology to obtain the full phase assemblage including Amorphous and Crystalline non-quantified, ACn, contents. Finally, the hydration of the selected BACSA cement paste (prepared with the scaled-up clinker and anhydrite) was studied mainly through rheological measurements (at very early hydration time) and LXRPD in combination with the Rietveld methodology and G-factor method. The compressive strengths were also measured at different hydration times and were compared with OPC.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech.Societ

Hydration study of Belite-Alite Calcium Sulfoaluminate (BACSA) cement blended with fly ash

The main objective of this work is to understand the effect of the addition of fly ash (0, 15 and 30 wt%) in the hydration of a BACSA cement paste (water/cement=0.4) prepared with 12 wt% of anhydrite. The pastes were characterized, at different hydration ages, through laboratory X-ray powder diffraction (LXRPD) (using an internal standard) combined with the Rietveld methodology and thermal analyses. Details about the phase developments including pozzolanic reactivity will be reported and discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Water-to-cement ratio influence on low-carbon cements performances

Portland Cement (PC) is the most important active ingredient in most of the construction concrete. However, the PC production is associated with a high carbon dioxide release (around 1 ton of CO2 per ton of PC). One approach to reduce CO2 emissions consists on the reformulation of the clinker with less calcite demanding phases, such as, belite rich clinkers. The drawback of this kind of clinkers is the low reactivity of belite (beta-belite). In order to compensate this problem, belite rich clinkers can be prepared with ye’elimite and ferrite or with alite [known as belite-ye’elimite-ferrite (BYF) and belite-alite-ye’elimite (BAY), respectively]. In addition, it can be improved by using a high reactive belite polymorph, such as alpha-belite. In this work, the hydration and mechanical behaviour of BYF and BAY cements (with beta and/or alpha-belite) with different water-to-cement ratios have been studied. The clinkers were produced using natural raw materials, and were mixed with anhydrite (CaSO4) to prepare the corresponding cements. At early ages, the main hydration products of these cements were ettringite, calcium monosulfoaluminate and amorphous aluminium hydroxide. At later ages, stratlingite, katoite and amorphous C-S-H were found. The compressive strength values of the corresponding mortars were correlated with the mineralogy evolution of the pastes (mainly obtained by XRD and TGA).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. I3-Ramón y Cajal Universidad de Malag

Synchrotron x-ray pair distribution function: A tool to characterize cement gels

Cement matrices contain large amounts of crystalline phases jointly with amorphous and/or nanocrystalline phases. Consequently, their analyses are very challenging. Synchrotron powder diffraction in combination with the pair distribution function (PDF) methodology is very useful to characterize such complex cement pastes. This work is focused on the study of the short and medium range atomic arrangement(s) in the different nanocrystalline gels which are present in the cement pastes through total scattering Pair Distribution Function quantitative phase analyses.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Acknowledgments: We thank CELLS-ALBA (Barcelona, Spain) for providing synchrotron beam time and the financial support by BIA2014-57658-C2-1-R and BIA2014-57658-C2-2-R, which is co-funded by FEDER. We also thank Dr. Monica Dapiaggi for her contribution with the PDF study of Ca(OH)2 monolayer

In-situ Molibdenum X-ray powder diffraction study of the early hydration of cementitious systems on a humidity chamber

The durability of cement-based construction materials depends on the environmental conditions during their service life. A further factor is the microstructure of the cement bulk, established by formation of cement hydrates. The development of the phases and microstructure under given conditions is responsible of the high strength of cementitious materials. The investigation on the early hydration behavior of cements and cementing systems has been for a long time a very important area of research: understanding the chemical reactions that lead to hardening is fundamental for the prediction of performances and durability of the materials. The production of 1 ton of Ordinary Portland Cement, OPC, releases into the atmosphere ~0.97 tons of CO2. This implies that the overall CO2 emissions from the cement industry are 6% of all anthropogenic carbon dioxide. An alternative to reduce the CO2 footprint consists on the development of eco-cements composed by less calcite demanding phases, such as belite and ye'elimite. That is the case of Belite-Ye’elimite cements (BY). Since the reactivity of belite is not quick enough, these materials develop low mechanical strengths at intermediate hydration ages. A possible solution to this problem goes through the production of cements which jointly contain alite with the two previously mentioned phases, named as Belite-Alite-Ye’elimite (BAY) cements. The reaction of alite and ye'elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later values. The final goal is to understand the hydration mechanisms of a variety of cementing systems (OPC, BAY and pure phases) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, in-situ laboratory humidity chambers with Molybdenum X-ray Powder diffraction are employed. In the first 2h of hydration, reaction degree (α) of ye'elimite had been decreased for superplasticizer.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Clinkering and early age hydration characterization of Belite-Alite Calcium Sulfoaluminate (BACSA) cements

In this work, four BACSA clinkers with different compositions (belite ~ 70-55 wt %, alite ~ 10-15 wt % and ye’elimite ~ 10-15 wt %) were synthesized (at laboratory scale). Lime, gypsum, kaolin and sand were used as raw materials and clinkering temperatures from 1280 to 1300 ºC were studied. Every BACSA clinker was chemically and mineralogically characterized through X-ray fluorescence and laboratory X-ray powder diffraction (LXRPD), the latter in combination with the Rietveld methodology to obtain the full phase assemblage including amorphous contents. The clinker with the targeted composition (belite ~ wt 60 %, alite ~ 13 wt % and ye’elimite ~ 10 wt %) was chosen to perform the scaling-up (5 kg). To do so, the processing parameters (milling time and clinkering conditions) have been optimized. Finally, the hydration of the corresponding BACSA cement pastes (prepared with the scaled-up clinker and gypsum) was studied through rheological measurements (at very early hydration time), calorimetry and impedance spectroscopy (first 24 h), and LXRPD in combination with the Rietveld methodology and G-factor method, at 1 and 7 hydration days to determine degree of hydration.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Synchrotron Radiation Pair Distribution Function Analysis of Gels in Cements

The analysis of atomic ordering in a nanocrystalline phase with small particle sizes, below 5 nm, is intrinsically complicated because of the lack of long-range order. Furthermore, the presence of additional crystalline phase(s) may exacerbate the problem, as is the case in cement pastes. Here, we use the synchrotron pair distribution function (PDF) chiefly to characterize the local atomic order of the nanocrystalline phases, gels, in cement pastes. We have used a multi r-range analysis approach, where the ~4–7 nm r-range allows determining the crystalline phase contents; the ~1–2.5 nm r-range is used to characterize the atomic ordering in the nanocrystalline component; and the ~0.2–1.0 nm r-range gives insights about additional amorphous components. Specifically, we have prepared four alite pastes with variable water contents, and the analyses showed that a defective tobermorite, Ca11Si9O28(OH)2 8.5H2O, gave the best fit. Furthermore, the PDF analyses suggest that the calcium silicate hydrate gel is composed of this tobermorite and amorphous calcium hydroxide. Finally, this approach has been used to study alternative cements. The hydration of monocalcium aluminate and ye’elimite pastes yield aluminum hydroxide gels. PDF analyses show that these gels are constituted of nanocrystalline gibbsite, and the particle size can be as small as 2.5 nmThis work has been supported by Spanish MINECO through BIA2014-57658-C2-2-R, which is co-funded by FEDER, BIA2014-57658-C2-1-R and I3 (IEDI-2016-0079) grants. We also thank CELLS-ALBA (Barcelona, Spain) for providing synchrotron beam time at BL04-MSPD beamline. Finally, we thank Prof. Simon Billinge, Long Yang and Monica Dapiaggi for their help with the PDF script and simulations for Ca(OH)2 scattering dat

Pair distribution function studies in cementitious systems

The analysis of amorphous/nanocrystalline phase(s) within cement matrices that contain high amounts of crystalline phase(s) is very challenging. Synchrotron techniques can be very useful to characterize such complex samples.1 This work is focused on total scattering Pair Distribution Function (PDF) quantitative phase analyses in selected real-space ranges for a better understanding of the binding gel(s). Powder diffraction data collected in BL04-MSPD beamline have been analyzed by PDF and Rietveld methodologies to determine nanocrystalline and microcrystalline phase contents. The comparison between both methodologies allows us to have a better insight about the nanocrystalline/microcrystalline components which coexist in cement pastes. Three sets of hydrated model samples have been studied: i) monocalcium aluminate, CaAl2O4, the main component of calcium aluminate cements, ii) ye’elimite, Ca4Al6SO16, the main component of calcium sulfoaluminate cements, and iii) tricalcium silicate, Ca3SiO5, the main component of Portland cements. For the CaAl2O4 paste, the PDF fit shows that the aluminum hydroxide gel has a gibbsite local structure with an average particle size close to 5 nm.2 Figure 1 shows the final fit for CaAl2O4 paste in two different real-space regions. On the contrary, for Ca4Al6SO16 paste, it has been found that the particle size of the aluminum hydroxide gel is below 3 nm. Moreover, the Ca3SiO5 paste contains a different nanocrystalline gel, C-S-H, which has also been thoroughly studied. Different crystal structures (including Tobermorite, Clinotobermorite and Jennite) have been tested to find the structural model that fits better the experimental data. The results from this ongoing investigation will be reported and discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. This work has been supported by Spanish MINECO through BIA2014-57658-C2-1-R and BIA2014-57658-C2-2-R, which is co-funded by FEDER, research grants. We also thank CELLS-ALBA for providing synchrotron beam time at BL04-MSPD

Clinkering of calcium sulfoaluminate clinkers: polymorphism of ye'elimite

The manufacture of CSA cements is more environmentally friendly than that of OPC as it releases less CO2. This reduction depends on CSA composition and is due to three factors: i) less emissions from decarbonation in the kilns; ii) lower clinkering temperature, consequently less fuel is needed, and iii) it is easier to grind, implying a depletion in indirect emissions. CSA cements are prepared by mixing the clinker with different amounts of calcium sulfate as a set regulator. Their main performances are fast setting time (followed by a rapid hardening), good chemical resistance and, depending on the amount of the added sulfate source they can work as shrinkage controllers. CSA cements present a wide range of phase assemblages, but all of them contain over 50 wt% of ye'elimite (C4A3s) jointly with belite (C2S), tetracalcium aluminoferrite (C4AF) and other minor components such as CA, Cs, CsH2 and so on [1]. Ye'elimite is also included (~25 wt%) in BYF (Belite- Ye'elimite-Ferrite) or BAY (Belite-Alite-Ye'elimite) clinkers. Ye'elimite has a sodalite type structure with general composition, M4[T6O12]X. Stoichiometric ye'elimite crystal structure at room temperature will be described in detailed. The role of different amounts of minor elements on the synthetic procedure and crystal structures will be also presented [2,3]. This keynote will be also focused on a revision of the effect of raw materials on the mineralogical composition of CSA, BYF and BAY. Specifically, the role of main elements contents in the ye'elimite formation in these systems will be described. Moreover, the effect of minor elements on the polymorphism of both ye'elimite and belite, especially on BYF and BAY clinkers, will be presented [4,5,6].Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Spanish MINECO and FEDER [BIA2017-82391-R] research project and I3 [IEDI-2016-0079] program