Clinkering and hydration study of non-active and active Belite-Alite-Ye'elimite (BAY) cements

The aim of AIM is to promote industry-driven, interdisciplinary research in material science and engineering in order to provide leading-edge, sustainable solutions to the challenges facing engineers in today’s changing society and environment. http://www.ucl.ac.uk/aim/conference-info/37ccsThe manufacturing process of ye'elimite rich cements emit about 15-37% less CO2 to the atmosphere than OPC. Cements that contain belite, ye’elimite and ferrite, known as BYF cements, are promising eco-friendly binders. However, belite, their main phase, shows a slow hydrating behaviour; therefore the corresponding mortars present lower mechanical strengths than OPC at early ages. To solve this problem, BYF clinkers can be activated by: i) forming alite jointly with belite and ye’elimite during clinkering, known as BAY clinkers. The alite and ye’elimite reaction with water should develop high mechanical strengths at early ages, besides, belite contributes to later curing times. ii) A second activation is based on the stabilisation of alpha forms of belite by dopants. The objective of this work is to obtain two types of BAY clinkers (standard and active BAY) using CaF2 as mineraliser and borax as dopant agent to stabilize alpha forms of belite phase. After that, anhydrite was added as sulphate source to obtain the corresponding cements. The hydration behaviour of these cements has been studied through rheological and x-ray diffraction measurements, the latter combined with Rietveld quantitative phase analysis. In addition, mechanical and dimensional properties of BAY mortars are also presented and discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Nanocrystalline cathodes for PC-SOFCs based on BCZY

Perovskites based on BaCeO3-δ exhibit the highest proton conductivity among this class of materials, however, they are susceptible to hydration and carbonation in presence of water vapor and CO2 [1]. In contrast, the chemical stability of BaZrO3-based protonic conductors is better, but they require sintering temperatures as high as 1700 ºC and suffer from high intrinsic grain boundary resistance, limiting the final performance. Partial substitution of Zr for Ce in Ba(Ce0.9-xZrx)Y0.2O3-δ allows obtaining electrolytes with both high proton conductivity and good chemical stability. The performance of a PC-SOFC at low temperatures depends significantly on the ohmic resistance of the electrolyte, although it can be lowered by reducing the electrolyte thickness. Another important limiting factor is the increase of the cathode polarization resistance due to the thermally activated nature of the oxygen reduction reaction. For this reason, it is essential to obtain high efficiency cathodes operating at reduced temperatures. In this work, BaCe0.6Zr0.2Y0.2O3-δ (BCZY) powders were prepared by freeze-drying precursor method. These powders were mixed with a Zn-containing solution as sintering additive in order to obtain dense pellets with submicrometric grain size at only 1200 ºC. After that, La0.6Sr0.4Co0.8Fe0.2O3 nanocrystalline electrodes were deposited symmetrically onto dense pellets BCZY by conventional spray-pyrolysis [3]. The structure, microstructure and electrochemical properties of these electrodes have been examined by XRD, FE-SEM and impedance spectroscopy. The stability of these electrodes at intermediate temperatures was evaluated as a function of time. These nanocrystalline cathodes exhibit a substantial improvement of the electrode polarization resistance with respect to the same materials prepared by screen-printing method at high sintering temperatures, e.g. 0.7 and 3.2 cm2 at 600 ºC for LSCF cathodes prepared by spray-pyrolysis and screen-printing method respectively (Figure). An anode supported cell with composition LSCF/BCZY/NiO-BCZY was also prepared to test the electrochemical performance.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Rietveld Quantitative Phase Analysis of Oil Well Cement: in Situ Hydration Study at 150 Bars and 150 °C

Oil and gas well cements are multimineral materials that hydrate under high pressure and temperature. Their overall reactivity at early ages is studied by a number of techniques including through the use of the consistometer. However, for a proper understanding of the performance of these cements in the field, the reactivity of every component, in real‐world conditions, must be analysed. To date, in situ high energy synchrotron powder diffraction studies of hydrating oil well cement pastes have been carried out, but the quality of the data was not appropriated for Rietveld quantitative phase analyses. Therefore, the phase reactivities were followed by the inspection of the evolution of non‐overlapped diffraction peaks. Very recently, we have developed a new cell specially designed to rotate under high pressure and temperature. Here, this spinning capillary cell is used for in situ studies of the hydration of a commercial oil well cement paste at 150 bars and 150 °C. The powder diffraction data were analysed by the Rietveld method to quantitatively determine the reactivities of each component phase. The reaction degree of alite was 90% after 7 hours, and that of belite was 42% at 14 hours. These analyses are accurate, as the in situ measured crystalline portlandite content at the end of the experiment, 12.9 wt%, compares relatively well with the value determined ex situ by thermal analysis, i.e., 14.0 wt%. The crystalline calcium silicates forming at 150 bars and 150 °C are also discussed.This research was funded by Spanish MINECO, grant number BIA2017‐82391‐R which is co‐funded by FEDER. We thank Marc Malfois for his help during the experiment performed at NCD‐SWEET beamline at ALBA synchrotron. We also thank Marcus Paul (Dyckerhoff GmbH) for providing the OWC sample with its characterization and helpful discussions

Early hydration study of standard and doped Alite-Belite-Ye’elimite (ABY) cements through Synchrotron Radiation

The manufacturing of ye'elimite-rich cements releases from 15 to 37%, depending on their composition, less CO2 to the atmosphere than ordinary Portland cement (OPC). BYF cements containing belite, ye’elimite and ferrite as main crystalline phases, are promising eco-friendly binders. Nevertheless, belite, its main phase, shows a slow hydrating behaviour and the mechanical strengths are lower than OPC at early ages. Some alternatives to solve this problem are: i) forming alite jointly with belite and ye’elimite during clinkering, Alite Belite Ye’elimite (ABY) clinkers. The hydration of alite and ye’elimite would develop high mechanical strengths at early ages, and belite contributes to later curing times; ii) a second alternative is the stabilisation of alpha forms of belite using dopants such as boron named here after dABY. In this work, two different types of ABY clinkers (standard and doped) have been prepared and characterized to understand their different hydration mechanisms at the same water-to-cement (w/c) ratio. The clinkers have been prepared using CaF2 and ZnO as mineralizers, and borax as dopant agent to stabilize alpha forms of belite (’H-C2S). Afterwards, 14 wt% of anhydrite (as soluble sulphate source) was added to prepare the corresponding cements. Finally, the hydration study was performed at w/c ratio of 0.5. Here, an in-situ hydration study using synchrotron X-ray powder diffraction (SXRPD) for the first 14 hours of hydration is reported. Moreover, these results will be combined with the ex-situ laboratory X-ray powder diffraction study (LXRPD) at 1 day of hydration and calorimetric results. Rietveld quantitative phase analysis has been used to establish the phase evolution across the time.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. MINECO ( BIA2017-82391-R), co-funded by FEDER, and I3 [IEDI-2016-0079]

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

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

A comparative study of experimental configurations in synchrotron pair distribution function

The identification and quantification of amorphous components and nanocrystalline phases with very small crystal sizes, smaller than ~3 nm, within samples containing crystalline phases is very challenging. However, this is important as there are several types of systems that contain these matrices: building materials, glass-ceramics, some alloys, etc. The total scattering synchrotron pair distribution function (PDF) can be used to characterize the local atomic order of the nanocrystalline components and to carry out quantitative analyses in complex mixtures. Although the resolution in momentum transfer space has been widely discussed, the resolution in the interatomic distance space has not been discussed to the best of our knowledge. Here, we report synchrotron PDF data collected at three beamlines in different experimental configurations and X-ray detectors. We not only discuss the effect of the resolution in Q-space, Qmax ins of the recorded data and Qmax of the processed data, but we also discuss the resolution in the interatomic distance (real) space. A thorough study of single-phase crystalline nickel used as standard was carried out. Then, selected cement-related samples including anhydrous tricalcium and dicalcium silicates, and pastes derived from the hydration of tricalcium silicate and ye’elimite with bassanite were analyzed.This work is part of the PhD of Mr. Jesus D. Zea-Garcia. This work was supported by Spanish MINECO and FEDER [BIA2017-82391-R research project and I3 [IEDI-2016-0079] program]

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

Synchrotron pair distribution function approach applied to cement samples

The characterization of the nanocrystalline/amorphous materials is very challenging but the presence of these materials mixed with large amounts of crystalline phases makes the analysis even more complicated. This is the case of cement hydrated samples, since they contain high amounts of crystalline phases jointly with nanocrystalline and amorphous components, making challenging their full characterization. High-energy synchrotron X-ray scattering jointly with the pair distribution function (PDF) methodology is very useful to deeply study complex cement pastes. PDF data give information about the local structure (bonding environments) of the nanocrystalline and amorphous component phases such as cement gels. The main aim of this work is to characterize amorphous/nanocrystalline gels which are present in different cementitious pastes by the PDF approach. Moreover, the PDF technique also gives us quantitatively information about the nanocrystalline and microcrystalline contents. Firstly, the C-S-H gel obtained from the hydration of alite, Ca3SiO5, the main phase of Portland cement, is found to contain two components: a nanocrystalline defective clinotobermorite and an amorphous component which seemed to be monolayers of calcium hydroxide1. Figure below shows the PDF fit of a C-S-H gel formed from the hydration of alite in two selected r-ranges. Secondly, some ye’elimite Ca4Al6O12(SO4) -containing pastes with different sulfate contents have been also studied. The nanocrystalline hydrated phases, such as A-H gel and monosulfoaluminate (AFm) phases have been thoroughly analyzed in the different pastes and the diameters of these nanoparticles have also been reported2. Finally, we will also show here, PDF data for different cement samples (including the Ni sample as standard) that have been collected in two different experimental configurations, i.e., in ID15A beamline at ESRF and in MSPD beamline at ALBA synchrotron3Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. This work has been supported by Spanish MinCIU through BIA2014-57658-C2 and BIA2017-82391-R, which are co-funded by FEDER. We also thank CELLS-ALBA (Barcelona, Spain) and ESRF (Grenoble) for providing synchrotron beam time at BL04-MSPD and ID15A, respectively