Modulating the mechanical properties of supercrystalline nanocomposite materials via solvent-ligand interactions
Supercrystalline nanocomposite materials with micromechanical properties approaching those of nacre or similar structural biomaterials can be produced by self-assembly of organically modified nanoparticles and further strengthened by cross-linking. The strengthening of these nanocomposites is controlled via thermal treatment, which promotes the formation of covalent bonds between interdigitated ligands on the nanoparticle surface. In this work, it is shown how the extent of the mechanical properties enhancement can be controlled by the solvent used during the self-assembly step. We find that the resulting mechanical properties correlate with the Hansen solubility parameters of the solvents and ligands used for the supercrystal assembly: the hardness and elastic modulus decrease as the Hansen solubility parameter of the solvent approaches the Hansen solubility parameter of the ligands that stabilize the nanoparticles. Moreover, it is shown that self-assembled supercrystals that are subsequently uniaxially pressed can deform up to 6 %. The extent of this deformation is also closely related to the solvent used during the self-assembly step. These results indicate that the conformation and arrangement of the organic ligands on the nanoparticle surface not only control the self-assembly itself but also influence the mechanical properties of the resulting supercrystalline material. The Hansen solubility parameters may therefore serve as a tool to predict what solvents and ligands should be used to obtain supercrystalline materials with good mechanical properties.
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The authors gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)-Projektnummer 192346071-SFB 986.