The Atomic-Level Structure of Cementitious Calcium Aluminate Silicate Hydrate

Despite use of blended cements containing significant amounts of aluminum for over 30 years, the structural nature of aluminum in the main hydration product, calcium aluminate silicate hydrate (C-A-S-H), remains elusive. Using first-principles calculations, we predict that aluminum is incorporated into the bridging sites of the linear silicate chains and that at high Ca:Si and H₂O ratios, the stable coordination number of aluminum is six. Specifically, we predict that silicate-bridging [AlO₂(OH)₄]^5- complexes are favored, stabilized by hydroxyl ligands and charge balancing calcium ions in the interlayer space. This structure is then confirmed experimentally by one- and two-dimensional dynamic nuclear polarization enhanced ²⁷Al and ²⁹Si solid-state NMR experiments. We notably assign a narrow ²⁷Al NMR signal at 5 ppm to the silicate-bridging [AlO₂(OH)₄]^5- sites and show that this signal correlates to ²⁹Si NMR signals from silicates in C-A-S-H, conflicting with its conventional assignment to a "third aluminate hydrate" (TAH) phase. We therefore conclude that TAH does not exist. This resolves a long-standing dilemma about the location and nature of the six-fold-coordinated aluminum observed by ²⁷Al NMR in C-A-S-H samples.