Discrimination of adhesion and viscoelasticity from nanoscale maps of polymer surfaces using bimodal atomic force microscopy

The simultaneous excitation and measurement of two eigenmodes in bimodal atomic force microscopy (AFM) during sub-micron scale surface imaging augments the number of observables at each pixel of the image compared to the normal tapping mode. However, a comprehensive connection between the bimodal AFM observables and the surface adhesive and viscoelastic properties of polymer samples remains elusive. To address this gap, we first propose an algorithm that systematically accommodates surface forces and linearly viscoelastic three-dimensional deformation computed via Attard's model into the bimodal AFM framework. The proposed algorithm simultaneously satisfies the amplitude reduction formulas for both resonant eigenmodes and enables the rigorous prediction and interpretation of bimodal AFM observables with a first-principles approach. We used the proposed algorithm to predict the dependence of bimodal AFM observables on local adhesion and standard linear solid (SLS) constitutive parameters as well as operating conditions. Secondly, we present an inverse method to quantitatively predict the local adhesion and SLS viscoelastic parameters from bimodal AFM data acquired on a heterogeneous sample. We demonstrate the method experimentally using bimodal AFM on polystyrene-low density polyethylene (PS-LDPE) polymer blend. This inverse method enables the quantitative discrimination of adhesion and viscoelastic properties from bimodal AFM maps of such samples and opens the door for advanced computational interaction models to be used to quantify local nanomechanical properties of adhesive, viscoelastic materials using bimodal AFM.