Jesus D. Zea-Garcia

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 h, and that of belite was 42% at 14 h. 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.

In situ research of materials under moderate pressures (hundreds of bar) is essential in many scientific fields. These range from gas sorption to chemical and biological processes. One industrially important discipline is the hydration of oil well cements. Existing capillary cells in this pressure range are static as they are easy to design and operate. This is convenient for the study of single-phase materials; however, powder diffraction quantitative analyses for multiphase systems cannot be performed accurately as a good powder average cannot be attained. Here, the design, construction and commissioning of a cost-effective spinning capillary cell for in situ powder X-ray diffraction is reported, for pressures currently up to 200 bar. The design addresses the importance of reducing the stress on the capillary by mechanically synchronizing the applied rotation power and alignment on both sides of the capillary while allowing the displacement of the supports needed to accommodate different capillaries sizes and to insert the sample within the tube. This cell can be utilized for multiple purposes allowing the introduction of gas or liquid from both ends of the capillary. The commissioning is reported for the hydration of a commercial oil well cement at 150 bar and 150°C. The quality of the resulting powder diffraction data has allowed in situ Rietveld quantitative phase analyses for a hydrating cement containing seven crystalline phases.

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, Q_{max ins} of the recorded data and Q_max 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.

The study of nanocrystalline phase atomic ordering is intrinsically complicated. The presence of additional crystalline phase(s) exacerbates this challenge. Here, a synchrotron pair distribution function (PDF) is used to characterise the local atomic order of the nanocrystalline phases in ye'elimite-containing pastes. A multi r-range analysis approach has been used, where the 3–5 nm r-range allows the crystalline phase contents to be determined and the 0·16–3·5 nm is used to characterise the atomic ordering in the nanocrystalline components. Quantitative phase contents have been also derived from these analyses. Specifically, five stoichiometric ye'elimite pastes with variable anhydrite and water contents have been prepared. For the pastes without anhydrite addition, ettringite was not present and two calcium aluminium monosulfate phases were required for good PDF fits. In addition to crystalline calcium aluminium monosulfate (AFm) (c ≈ 2·86 nm), a nanocrystalline AFm phase with a significantly smaller c-unit cell parameter value, c ≈ 2·68 nm, was required, having about a 6 nm particle size. For a paste obtained with 31 wt% of anhydrite addition, the main crystalline phase was ettringite with the aluminium hydroxide having a nano-gibbsite local structure with quite a small average particle size, ≈3·5 nm.

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.

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.