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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Conformation of Network Strands in Polymer Gels
Small angle neutron scattering was used to measure single chain radii of gyration of end-linked polymer gels before and after cross-linking to calculate the prestrain, which is the ratio of the average chain size in a cross-linked network to that of a free chain in solution. The prestrain increased from 1.06 ± 0.01 to 1.16 ± 0.02 as gel synthesis concentration decreased near the overlap concentration, indicating that the chains are slightly more stretched in the network than in solution. Dilute gels with higher loop fractions were found to be spatially homogeneous. Form factor and volumetric scaling analyses independently confirmed that elastic strands stretch by 2–23% from Gaussian conformations to create a space-spanning network, with increased stretching as network synthesis concentration decreases. Prestrain measurements reported here serve as a point of reference for network theories that rely on this parameter for the calculation of mechanical properties.
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- Award ID(s):
- 2116298
- NSF-PAR ID:
- 10398028
- Date Published:
- Journal Name:
- ACS Macro Letters
- ISSN:
- 2161-1653
- Page Range / eLocation ID:
- 325 to 330
- 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/10.1021/acsmacrolett.3c00006
