In this Feature Article, we discussed the experimental and modeling methods and analyzed the limitations of the surface probing of nanomechanical properties of polymeric and biological materials in static and dynamic regimes with atomic force microscopy (AFM), which are widely utilized currently. To facilitate such measurements with minimized ambiguities, in this study we present a combined method to evaluate the viscoelastic properties of compliant polymeric materials. We collected force-distance data in the static regime for a benchmark polymer material (poly(n-butyl methacrylate)) with an easily accessible glass-transition temperature (about 25 °C) at different loading rates and different temperatures across the glassy state, glass-transition region, and rubbery state. For this analysis, we exploited a Johnson-modified Sneddon's approach in a combination with the standard linear solid model. Critical experimental steps suggested for robust probing are (i) the use of a tip with a well-characterized parabolic shape, (ii) probing in a liquid environment in order to reduce jump-in phenomenon, and (iii) minute indentations to ensure the absence of plastic deformation. Whereas the standard Sneddon's model generates quantitatively adequate elastic modulus values below and above the glass transition, this traditional approach can significantly underestimate actual modulus values in the vicinity of the glass-transition region (15 °C above or below Tg), with major deviations occurring at the loss tangent peak. The analysis of the experimental data with Sneddon's model for the elastic region (glassy and rubbery states) and Johnson's model for the viscoelastic region allowed for the restoration of the universal master curve and the evaluation of the storage modulus, loss modulus, loss tangent, relaxation times, and activation energies of the polymer surface across the glass-transition region and at relevant loading rates.

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We demonstrate the facile fabrication of high aspect ratio nanotubes from responsive block copolymer, polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP), and in situ grown gold nanoparticles. PS-b-P2VP nanotubes are fabricated by template-assisted assembly by utilizing cylindrical pores of porous alumina membranes followed by its dissolution. Solvent annealing was employed to facilitate ordered phase separation of the block copolymer with in the nanotube structure, followed by in situ formation of gold nanoparticles in the P2VP domains occupying the inner and outer shell of the nanotubes. Owing to the pH-sensitive nature of P2VP block, which exhibits a coil to globule transition above pH 3.6, the PS-b-P2VP-gold nanoparticles hybrid nanotubes show reversible changes in topology, size (up to 25%), and collective plasmon resonance appearance. We suggest that PS-b-P2VP-gold nanoparticles hybrid nanotubes with their pH-responsive properties, large surface-to-volume ratio, and through open pore can find intriguing applications in sensing and microfluidic systems.

The transformation of periodic microporous structures fabricated by interference lithography followed by their freezing below glass transition is described. Periodic porous microstructures subjected to internal compressive stresses can undergo sudden structural transformation at a critical strain. The pattern transformation of collapsed pores is caused by the stresses originated during the polymerization of acrylic acid (rubbery component) inside of cylindrical pores and the subsequent solvent evaporation in the organized microporous structure. By confining the polymerization of acrylic acid to localized porous areas complex microscopic periodic structures can be obtained. The control over the mechanical instabilities in periodic porous solids at a sub‐micron scale demonstrated here suggests the potential mechanical tunability of photonic, transport, adhesive, and phononic properties of such periodic porous solids.

Probing of micro- and nanoscale mechanical properties of soft materials with atomic force microscopy (AFM) gives essential information about the performance of the nanostructured polymer systems, natural nanocomposites, ultrathin coatings, and cell functioning. AFM provides efficient and is some cases the exclusive way to study these properties nondestructively in controlled environment. Precise force control in AFM methods allows its application to variety of soft materials and can be used to go beyond elastic properties and examine temperature and rate dependent materials response. In this review, we discuss experimental AFM methods currently used in the field of soft nanostructured composites and biomaterials. We discuss advantages and disadvantages of common AFM probing techniques, which allow for both qualitative and quantitative mappings of the elastic modulus of soft materials with nanosacle resolution. We also discuss several advanced techniques for more elaborate measurements of viscoelastic properties of soft materials and experiments on single cells.