ABSTRACT
The technique of atomic force microscopy (AFM) bending tests of a suspended nano-object (scroll, tube, rod) makes it possible to calculate the Young's modulus of the material it is made of based on experimental data. However, the calculation results involve a large error due to uncertain conditions (console or bridge) of fixing the test object. One of the ways to reduce this error is based on the theoretical consideration of consoles or bridges as beams with one or two ends resting on Winkler elastic foundations. The beam bending problems have been solved in both cases using Krylov's functions. This has allowed for developing an approach to the analytical identification of fixing conditions and including them in the calculations. The application of the approach is illustrated by AFM measurements of the Young's modulus of MgNi_{2}Si_{2}O_{5}(OH)_{4} nanoscrolls.
ABSTRACT
A group of phyllosilicate nanoscrolls conjoins several hydrosilicate layered compounds with a size mismatch between octahedral and tetrahedral sheets. Among them, synthetic Mg3Si2O5(OH)4 chrysotile nanoscrolls (obtained via the hydrothermal method) possess high thermal stability and mechanical properties, making them prospective composite materials fillers. However, accurate determination of these nano-objects with Young's modulus remains challenging. Here, we report on a study of the mechanical properties evolution of individual synthetic phyllosilicate nanoscrolls after a series of heat treatments, observed with an atomic force microscopy and calculated using the density functional theory. It appears that the Young's modulus, as well as shear deformation's contribution to the nanoscrolls mechanical behavior, can be controlled by heat treatment. The main reason for this is the heat-induced formation of covalent bonding between the adjacent layers, which complicate the shear deformation.
ABSTRACT
Metal-organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M-BTC (M: Fe3+, Co3+, Co2+, Ni2+, and Cu2+; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.
ABSTRACT
Here, we study the stress-induced self-organization of Mg2+ and Ni2+ cations in the crystal structure of multiwalled (Mg1-x ,Nix )3 Si2 O5 (OH)4 phyllosilicate nanoscrolls. The phyllosilicate layer strives to compensate size and surface energy difference between the metal oxide and silica sheets by curling. But as soon as the layer grows, the scrolling mechanism becomes a spent force. An energy model proposes secondary compensation of strain: two cations distribute along the nanoscroll spiral in accordance with preferable radii of curvature. To reveal this, we study synthetic (Mg1-x ,Nix )3 Si2 O5 (OH)4 nanoscrolls by the scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDS) technique. For a number of scrolls, we have found indeed a change of Ni concentration with increase in distance from the nanoscroll central axis. The concentration gradient, according to our estimates, can reach 50â at.% over 25â nm of the wall thickness.
