Mortars and concretes are ubiquitous materials with very complex hierarchical microstructures. To fully understand their main properties and to decrease their CO₂footprint, a sound description of their spatially resolved mineralogy is necessary. Developing this knowledge is very challenging as about half of the volume of hydrated cement is a nanocrystalline component, calcium silicate hydrate (C-S-H) gel. Furthermore, other poorly crystalline phases (e.g.iron siliceous hydrogarnet or silica oxide) may coexist, which are even more difficult to characterize. Traditional spatially resolved techniques such as electron microscopy involve complex sample preparation steps that often lead to artefacts (e.g.dehydration and microstructural changes). Here, synchrotron ptychographic tomography has been used to obtain spatially resolved information on three unaltered representative samples: neat Portland paste, Portland–calcite and Portland–fly-ash blend pastes with a spatial resolution below 100 nm in samples with a volume of up to 5 × 10⁴ µm³. For the neat Portland paste, the ptychotomographic study gave densities of 2.11 and 2.52 g cm⁻³and a content of 41.1 and 6.4 vol% for nanocrystalline C-S-H gel and poorly crystalline iron siliceous hydrogarnet, respectively. Furthermore, the spatially resolved volumetric mass-density information has allowed characterization of inner-product and outer-product C-S-H gels. The average density of the inner-product C-S-H is smaller than that of the outer product and its variability is larger. Full characterization of the pastes, including segmentation of the different components, is reported and the contents are compared with the results obtained by thermodynamic modelling.

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 nm.

Portland cements (PCs) and cement blends are multiphase materials of different fineness, and quantitatively analysing their hydration pathways is very challenging. The dissolution (hydration) of the initial crystalline and amorphous phases must be determined, as well as the formation of labile (such as ettringite), reactive (such as portlandite) and amorphous (such as calcium silicate hydrate gel) components. The microstructural changes with hydration time must also be mapped out. To address this robustly and accurately, an innovative approach is being developed based on in situ measurements of pastes without any sample conditioning. Data are sequentially acquired by Mo K α ₁ laboratory X-ray powder diffraction (LXRPD) and microtomography (µCT), where the same volume is scanned with time to reduce variability. Wide capillaries (2 mm in diameter) are key to avoid artefacts, e.g. self-desiccation, and to have excellent particle averaging. This methodology is tested in three cement paste samples: (i) a commercial PC 52.5 R, (ii) a blend of 80 wt% of this PC and 20 wt% quartz, to simulate an addition of supplementary cementitious materials, and (iii) a blend of 80 wt% PC and 20 wt% limestone, to simulate a limestone Portland cement. LXRPD data are acquired at 3 h and 1, 3, 7 and 28 days, and µCT data are collected at 12 h and 1, 3, 7 and 28 days. Later age data can also be easily acquired. In this methodology, the amounts of the crystalline phases are directly obtained from Rietveld analysis and the amorphous phase contents are obtained from mass-balance calculations. From the µCT study, and within the attained spatial resolution, three components (porosity, hydrated products and unhydrated cement particles) are determined. The analyses quantitatively demonstrate the filler effect of quartz and limestone in the hydration of alite and the calcium aluminate phases. Further hydration details are discussed.

The effect of superplasticiser, borax and the water-to-cement ratio on BYF hydration and mechanical strengths has been studied. Two laboratory-scale BYF cements—st-BYF (with β-C₂S and orthorhombic C₄A₃$\overline{\mathrm{S}}$) and borax-activated B-BYF (with α’_H-C₂S and pseudo-cubic C₄A₃$\overline{\mathrm{S}}$)—have been used, and both show similar particle size distribution. The addition of superplasticiser and externally added borax to BYF pastes has been optimised through rheological measurements. Optimised superplasticiser contents (0.3, 0.4 and 0.1 wt % for st-BYF, B-BYF and st-BYF with externally added 0.25 wt % B₂O₃, respectively) result in low viscosities yielding homogeneous mortars. The calorimetric study revealed that st-BYF is more reactive than B-BYF, as the values of heat released are 300–370 J/g and 190–210 J/g, respectively, after 7 days of hydration; this fact is independent of the water-to-cement ratio. These findings agree with the higher degree of hydration at 28 days of β-C₂S in st-BYF (from 45 to 60%) than α’_H-C₂S in B-BYF (~20 to 30%). The phase assemblage evolution has been determined by LXRPD coupled with the Rietveld method and MAS-NMR. The formation of stratlingite is favoured by increasing the w/c ratio in both systems. Finally, the optimisation of fresh BYF pastes jointly with the reduction of water-to-cement ratio to 0.40 have allowed the achieving of mortars with compressive strengths over 40 MPa at 7 days in all systems. Moreover, the st-BYF mortar, where borax was externally added, achieved more than 70 MPa after 28 days. The main conclusion of this work does not support Lafarge’s approach of adding boron/borax to the raw meal of BYF cements. This procedure stabilises the alpha belite polymorph, but its reactivity, in these systems, is lower and the associated mechanical strengths poorer.