Mechanical Properties and Nanostructure of Monolithic Zeolitic Imidazolate Frameworks: A Nanoindentation, Nanospectroscopy and Finite-Element Study

TL;DR

This study investigates the mechanical properties and nanostructure of monolithic zeolitic imidazolate frameworks (ZIFs) using nanoindentation, nanospectroscopy, and finite-element modeling to understand deformation mechanisms and fracture resistance.

Contribution

It combines experimental nanoindentation, TFM, nanoFTIR, and FE simulations to elucidate the deformation mechanisms and mechanical behavior of ZIF monoliths, advancing understanding for practical applications.

Findings

Grain boundary sliding dominates at low stresses.

Bond breakage and framework failure occur at higher stresses.

Densification of the porous framework happens at the contact zone.

Abstract

The synthesis of metal-organic frameworks (MOFs) in a monolithic morphology is a promising way to achieve the transition of this class of materials from academia to industrial applications. The sol-gel process has been widely employed to produce MOF monoliths. It is relatively cheap and simple compared to other techniques (e.g., mechanical densification) and moreover it allows to produce "pure" monoliths, i.e., without the need of using binders or templates that could affect the functional properties of the MOF. Understanding the mechanical properties of these monoliths is crucial for their transit to practical applications. We studied the mechanical behavior of two zeolitic imidazolate frameworks (ZIF-8 and ZIF-71) by means of instrumented nanoindentation and atomic force microscopy (AFM). Tip Force Microscopy (TFM), an extension of AFM, was used to reveal the surface nanostructure of the monoliths. We employed finite-element (FE) simulations alongside the experiments, to establish a suitable constitutive model and determine an improved estimate of the yield stress of ZIF monoliths. NanoFTIR was subsequently used to pinpoint local structural alteration of the framework in the contact area. The combination of TFM, FE simulations, and nanoFTIR enabled us to identify the mechanical deformation mechanisms in monolithic ZIF materials: grain boundaries sliding is dominating at low stresses, then breakage of chemical bonds and a partial failure of the framework occurs, eventually leading to a densification of porous framework at the contact zone. Finally, we measured the fracture toughness using a cube corner indenter to study the resistance of monoliths against cracking failure.