Sodium aluminosilicate hydrate (NASH) gel is the primary adhesive constituent in environmentally friendly geopolymer. In this study, to understand the thermal behavior of the material, molecular dynamics was utilized to investigate the molecular structure, dynamic property, and mechanical behavior of NASH gel subjected to temperature elevation from 300 K to 1500 K. The aluminosilicate skeleton in NASH gel provides plenty of oxygen sites to accept H-bond from the invading water molecules. Upon heating, around 18.2% of water molecules are decomposed and produce silicate and aluminate hydroxyls. About 87% of hydroxyls are associated with the aluminate skeleton, which weakens the Al-O bonds and disturbs the O-Al-O angle and the local structure, transforming it from an aluminate tetrahedron to a pentahedron and octahedron. With increasing temperature, both Al-O-Si and Si-O-Si bonds are stretched to be broken and the network structure of the NASH gel is gradually transformed into a branch and chain structure. Furthermore, the self-diffusivity of water molecules and sodium dramatically increases with the elevation of temperature, because the decrease in connectivity of the aluminosilicate network reduces the chemical and geometric restriction on the water and ions in NASH gel under higher temperatures. The high temperature also contributes to around 63% of the water molecules further dissociating and hydroxyl groups forming; meanwhile proton exchange between the water molecules and aluminosilicate network frequently takes place. In addition, a uniaxial tensile test was utilized to study the mechanical behavior of the NASH gel at different temperatures. During the tensile test, the aluminosilicate network was found to depolymerize into a branch or chain structure which plays a critical role in resisting the tensile loading. In this process, the breakage of the aluminosilicate skeleton is accompanied with hydrolytic reactions that further deteriorate the structure. Due to the reduction of the chemical bond stability at elevated temperature, both the tensile strength and stiffness of the NASH gel are weakened significantly. However, the ductility of the NASH gel is improved because of the higher extent of structural arrangement at the yield stage and partly due to the lower water attack. Hopefully, the present study can provide valuable molecular insights on the design of alkali-activated materials with high sustainability and durability.

For GO related nanocomposite design, it is of great importance to understand the behavior of water molecules ultra-confined in the interlayer region of graphene oxide (GO) sheets. In this research, to gain molecular insights into the influence of water on the properties of GO sheets, reactive force field molecular dynamics was employed to model a GO sheet with a water content of 1.3 wt%, 11.5 wt%, 18 wt% and 23.5 wt%. The epoxy and hydroxyl groups in the GO sheet exhibit high reactivity: the proton transferred from hydroxyl to dissociated epoxy contributes to carbonyl formation, which enhances the polarity of the GO sheet and strengthens the H-bond network between the functional groups. The epoxy, hydroxyl and newly formed carbonyl groups contribute to the structural hydrogen bonding with high stability. With increasing water content, the interlayer structural H-bonds between functional groups are gradually substituted by those contributed by water molecules, which weakens the interlayer stiffness and cohesive strength for GO sheets. Furthermore, the reactive force field allows coupling between the mechanical response and chemical reactions during uniaxial tensile deformation in the intra-layer direction. On the one hand, the relative epoxy bond is stretched until it is broken and transformed into a carbonyl group to resist tensile loading. On the other hand, interlayer water molecules, attacking the deformed GO sheets, are dissociated into carboxyl groups in the broken region.

Graphene oxide (GO) reinforced cement nanocomposites open up a new path for sustainable concrete design. In this paper, reactive force-field molecular dynamics was utilized to investigate the structure, reactivity and interfacial bonding of calcium silicate hydrate (C-S-H)/GO nanocomposite functionalized by hydroxyl (C-OH), epoxy (C-O-C), carboxyl (COOH) and sulfonic (SO3H) groups with a coverage of 10%. The silicate chains in the hydrophilic C-S-H substrate provided numerous non-bridging oxygen sites and counter ions (Ca ions) with high reactivity, which allowed interlayer water molecules to dissociate into Si-OH and Ca-OH. On the other hand, protons dissociated from the functional groups and transferred to non-bridging sites in C-S-H, producing carbonyl (C[double bond, length as m-dash]O) and Si-OH. The de-protonation degree of the different groups in the vicinity of the C-S-H surface was in the following order: COOH (SO3H) > C-OH > C-O-C. In the GO-COOH sheet, most COOH groups were de-protonated to COO- groups, which enhanced the polarity and hydrophilicity of the GO sheets and formed stable COOCa bonds with neighboring Ca ions. The de-protonated COO- could also accept H bonds from Si-OH in the C-S-H gel, which further strengthened the interfacial connection. On the contrary, in the GO-Oo sheet, only 8% of the epoxy group was stretched open by the Ca ions and transformed to carbonyl group, showing weak polarity and connection with the C-S-H sheet. Furthermore, uniaxial tensile test on different C-S-H/GO models revealed that C-S-H reinforced with GO-COOH and GO-OH had better interfacial cohesive strength and ductility than that observed under tensile loading. Under the reaction force field, the dissociation of water, the proton exchange between the C-S-H and GO structure, and Oc-Ca-Os bond breakage occurred to resist tensile loading. The weakest mechanical behavior observed in the G/C-S-H, GO-Oo/C-S-H and GO-SO3H/C-S-H composites was attributed to the poor bonding, dissociation of functional groups and instability of atoms in the interface region. Hopefully, the molecular-scale strengthening mechanisms could provide a scientific guide for sustainable design of cement composites.

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