Direct Comparison of Three Buckling-Based Methods to Measure the Elastic Modulus of Nanobiocomposite Thin Films

To engineer tunable thin-film materials, the accurate measurement of their mechanical properties is crucial. However, characterizing the elastic modulus with current methods is particularly challenging for sub-micrometer thick films and hygroscopic materials because they are highly sensitive to environmental conditions and most methods require free-standing films which are difficult to prepare. In this work, we directly compared three buckling-based methods to determine the elastic moduli of supported thin films: (1) biaxial thermal shrinking, (2) uniaxial thermal shrinking, and (3) the mechanically compressed, strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) method. Nanobiocomposite model films composed of cellulose nanocrystals (CNCs) and polyethyleneimine (PEI) were assembled using layer-by-layer deposition to control composition and thickness. The three buckling-based methods yielded the same trends and comparable values for the elastic moduli of each CNC–PEI film composition (ranging from 15 to 44 GPa, depending on film composition). This suggests that the methods are similarly effective for the quantification of thin-film mechanical properties. Increasing the CNC content in the films statistically increased the modulus; however, increasing the PEI content did not lead to significant changes. For the CNC–PEI system, the standard deviation of elastic moduli determined from SIEBIMM was 2–4 times larger than that for thermal shrinking, likely due to extensive cracking due to the different stress applied to the film when subjected to compression of a relaxed substrate versus the shrinking of a pre-strained substrate. These results show that biaxial thermal shrinking is a reliable method for the determination of the mechanical properties of thin films with a simple implementation and analysis and low sensitivity to small deviations in the input parameter values, such as film thickness or substrate modulus.