Abstract Understanding hydrogen dissolution mechanisms in bridgmanite (Bgm), the most abundant mineral in the lower mantle, is essential for understanding water storage and rheological and transport properties in the region. However, interpretations of O‐H bands in Fourier transform infrared spectroscopy (FTIR) spectra of Bgm crystals remain uncertain. We conducted density functional theory (DFT) calculations on vibrational characteristics of O‐H dipoles and performed polarized FTIR measurements to address this issue. DFT calculations for four substitution models—Mg vacancies, Si vacancies, Al3+ + H+substitution for Si4+, and Al substitution with Mg vacancies—reveal distinct O‐H bands with different polarizations. Deconvolution of polarized FTIR spectra on Mg0.88Fe2+0.035Fe3+0.065Al0.14Si0.90O3and Mg0.95Fe2+0.033Fe3+0.027Al0.04Si0.96O3crystals shows five major O‐H bands with distinct polarizations along principal crystallographic axes. These experimental and calculated results attribute O‐H bands centered at 3,463–3,480, 2,913–2,924, and 2,452–2,470 cm−1to Mg vacancies, Si vacancies, and Al3+ + H+substitution for Si4+, respectively. The total absorbance coefficient of bridgmanite was calculated to be 82,702(6,217) L/mol/cm2. Mg and Si vacancies account for 43%–74% of the total water content, making them dominant hydrogen dissolution mechanisms in Bgm. The band frequencies for the Mg and Si vacancies in Bgm are drastically different from those in olivine and ringwoodite, corresponding to the significant changes in O‐H bond strengths and in the Si and Mg coordination environments from upper‐mantle to lower‐mantle minerals. These results highlight the need to incorporate hydrogen dissolution mechanisms in Bgm for understanding electrical conductivity and rheology of the lower mantle.
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Dissolution kinetics of cementitious magnesium silicate hydrate in air‐equilibrated water
Abstract Magnesium silicate hydrate (M‐S‐H) represents a promising alternative to traditional cement, particularly for low‐pH construction applications such as nuclear waste encapsulation and carbon dioxide injection. The durability of construction materials, a critical aspect of their suitability for various purposes, is primarily governed by the kinetics of dissolution of the binder phase under service conditions. In this study, we employed in situ atomic force microscopy to assess the dissolution rates of M‐S‐H in water equilibrated with air. Quantitative analysis based on changes in volume and height revealed dissolution rates ranging from 0.18 to 3.09 × 10−12 mol/cm2/s depending on the precipitate Mg/Si ratio and morphology. This rate surpasses its crystalline analogs, talc (Mg3Si4O10(OH)2) and serpentine (Mg3(Si2O5)(OH)4), by about three to five orders of magnitude. Interestingly, oriented M‐S‐H dissolved faster than non‐oriented M‐S‐H. Spatially resolved assessments of dissolution rates facilitated a direct correlation between rates and morphology, showing that edges and smaller crystallites dissolve at a faster pace compared to facets and larger crystallites. The outcomes of this study provide insights into the mechanisms governing the dissolution of M‐S‐H and the factors dictating its durability. These findings hold implications for the strategic design and optimization of M‐S‐H for various applications.
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- Award ID(s):
- 2342381
- PAR ID:
- 10535205
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- Volume:
- 107
- Issue:
- 12
- ISSN:
- 0002-7820
- Format(s):
- Medium: X Size: p. 8547-8555
- Size(s):
- p. 8547-8555
- Sponsoring Org:
- National Science Foundation
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