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

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

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

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]

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

Multiscale understanding of tricalcium silicate hydration reactions

Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates (C-S-H) nanocrystalline gel. This hydration reaction is poorly understood at the nanoscale. The understanding of atomic arrangement in nanocrystalline phases is intrinsically complicated and this challenge is exacerbated by the presence of additional crystalline phase(s). Here, we use calorimetry and synchrotron X-ray powder diffraction to quantitatively follow tricalcium silicate hydration process: i) its dissolution, ii) portlandite crystallization and iii) C-S-H gel precipitation. Chiefly, synchrotron pair distribution function (PDF) allows to identify a defective clinotobermorite, Ca11Si9O28(OH)2.8.5H2O, as the nanocrystalline component of C-S-H. Furthermore, PDF analysis also indicates that C-S-H gel contains monolayer calcium hydroxide which is stretched as recently predicted by first principles calculations. These outcomes, plus additional laboratory characterization, yielded a multiscale picture for C-S-H nanocomposite gel which explains the observed densities and Ca/Si atomic ratios at the nano- and meso- scales.This 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

Functional bold MRI: advantages of the 3 T vs. the 1.5 T

We quantitatively evaluate the benefits of a higher field strength for functional brain MRI (fMRI) based on the blood oxygenation level-dependent contrast. The 3-T fMRI shows a higher sensitivity for the motor and somatosensory stimulation and more specific localization in the grey substance. The 3-T fMRI detects additional areas of activation with the motor paradigm

The impact of silent vascular brain burden in cognitive impairment in Parkinson's disease

White matter hyperintensities (WMHs) detected by magnetic resonance imaging (MRI) of the brain are associated with dementia and cognitive impairment in the general population and in Alzheimer's disease. Their effect in cognitive decline and dementia associated with Parkinson's disease (PD) is still unclear. METHODS: We studied the relationship between WMHs and cognitive state in 111 patients with PD classified as cognitively normal (n = 39), with a mild cognitive impairment (MCI) (n = 46) or dementia (n = 26), in a cross-sectional and follow-up study. Cognitive state was evaluated with a comprehensive neuropsychological battery, and WMHs were identified in FLAIR and T2-weighted MRI. The burden of WMHs was rated using the Scheltens scale. RESULTS: No differences in WMHs were found between the three groups in the cross-sectional study. A negative correlation was observed between semantic fluency and the subscore for WMHs in the frontal lobe. Of the 36 non-demented patients re-evaluated after a mean follow-up of 30 months, three patients converted into MCI and 5 into dementia. Progression of periventricular WMHs was associated with an increased conversion to dementia. A marginal association between the increase in total WMHs burden and worsening in the Mini Mental State Examination was encountered. CONCLUSIONS: White matter hyperintensities do not influence the cognitive status of patients with PD. Frontal WMHs have a negative impact on semantic fluency. Brain vascular burden may have an effect on cognitive impairment in patients with PD as WMHs increase overtime might increase the risk of conversion to dementia. This finding needs further confirmation in larger prospective studies