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Coupling of organic and inorganic chemistry presents a new degree of freedom in nano-engineering of thermo-mechanical properties of cement-based materials. Despite these vast technological benefits, molecular scale cross-linking of calcium-silicate-hydrate (C-S-H) gel with organic molecules still presents a significant challenge. Herein, we report experimental results on sol-gel synthesis, structure and morphology of nanocrystalline C-S-H cross-linked with dipodal organosilanes. These novel organic-inorganic gels have layered turbostratic molecular structure with similarities to C-S-H precipitating in hydrating cement paste. The organic molecules' chain length controls the interlayer spacing, which shows little to no shrinkage upon dehydration up to 105 °C. However, the structure gets distorted in the basal crystallite plane, in which dimer and trimer Si-polyhedra structures condense on a 2D hexagonal Ca-polyhedra layer. Cross-linked C-S-H gels display plate-like morphology with tendency toward stacking into agglomerates at the larger scale. If successfully realized in cement environment, e.g. high concentration seed, such novel organic-inorganic C-S-H gels could potentially provide cement-based matrices with unique properties unmatched by classical inorganic systems.
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Organic cross-linking decreases the thermal conductivity of calcium silicate hydrates
We study the conductive heat transport through calcium silicate hydrate (C-S-H) and organically cross-linked C-S-H via experiments, micromechanical homogenization theory, and molecular simulations. We find that C-S-H's intrinsic thermal conductivity falls below its amorphous limit when cross-linked with short-chain organosilanes. The observed reduction correlates with the alkyl chain length of the bis-organosilane molecule. To understand the underlying fundamental molecular processes accountable for such a reduction, we construct realistic molecular structures of cross-linked C-S-H and validate them against the spectroscopic and pycnometery measurements. The atomistic simulations indicate that the reduction in the contribution of propagons (propagating heat carriers) and diffusons (diffusive heat carriers) to heat transport, and the amplification of locons (localized vibrational modes), are the main driving factors allowing to limit the heat conduction in C-S-H. Presented findings offer new potential directions to nanoengineering novel admixtures for cement composites and resilient lightweight cementitious mesostructures for thermally efficient building envelopes.
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- Award ID(s):
- 1825921
- PAR ID:
- 10477865
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Cement and Concrete Research
- Volume:
- 174
- Issue:
- C
- ISSN:
- 0008-8846
- Page Range / eLocation ID:
- 107324
- Subject(s) / Keyword(s):
- Calcium-silicate-hydrate Organic molecules Cross-linking Thermal conductivity Experiments and simulations
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.cemconres.2023.107324
