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The physical performance of an epoxy-based material is largely influenced by the formation of heterogeneous nanostructures (HNSs) in the glassy three-dimensional epoxy network. Thus, understanding the connectivity and local mechanical properties of HNSs formed in cured epoxy networks is of critical importance in the development of advanced epoxy-based materials for innovative adhesion technology. Here, we use bimodal atomic force microscopy (AFM) to map the local mechanical responses of HNSs evolved in an epoxy–amine system during curing. Both modulus and dissipated energy quantities describing the elastic and adhesive responses, respectively, were simultaneously obtained at different harmonic vibrations in each bimodal AFM measurement. HNSs exhibiting different elastic and adhesive responses were clearly visualized for all epoxy networks at different levels of curing. The architecture and local mechanical responses of HNSs were visibly altered with increasing degree of conversion. Soft domains representing network regions with relatively lower elastic moduli and weaker adhesive interactions were dominant and continuously connected at initial stages of curing up to conversion degrees of ∼91%. However, hard domains became increasingly connected upon approaching the fully cured stage. In combination with previously reported results obtained using the particle tracking technique to study the network heterogeneity at lower conversion degrees of the same epoxy system, we were able to provide a full picture describing the generation and development of mechanical heterogeneities in the network during curing in which the length scale of the heterogeneities decreased from several hundred nanometers at the pregelation stage to ∼10 nm at the fully cured stage. [ABSTRACT FROM AUTHOR]

The addition of a small fraction of solid nanoparticles to thermosetting polymers can substantially improve their fracture toughness, while maintaining various intrinsic thermomechanical properties. The underlying mechanism is largely related to the debonding process and subsequent formation of nanovoids at a nanoscale nanoparticle/epoxy interface, which is thought to be associated with a change in the structural and mechanical properties of the formed epoxy network at the interface compared with the matrix region. However, a direct characterization of the local physical properties at this nanoscale interface remains significantly challenging. Here, we employ a recently developed bimodal atomic force microscopy technique for the direct mapping of nanoscale elastic and adhesive responses of an amine-cured epoxy resin filled with ∼50 nm diameter silica nanoparticles. The obtained elastic modulus and dissipated energy maps with high spatial resolution evidence the existence of a ∼20-nm-thick interfacial epoxy layer surrounding the nanoparticles, which exhibits a reduced modulus and weaker adhesive response in comparison with the matrix properties. While the presence of such a soft and weak-adhesive interfacial layer is found not to affect the architecture of structural heterogeneities in the epoxy matrix, it conceivably supports the toughening mechanism related to the debonding and plastic nanovoid growth at the silica/epoxy interface. The incorporation of this soft interfacial layer into the Halpin-Tsai model also provides a good explanation for the effect of the silica fraction on the tensile modulus of cured epoxy nanocomposites.

The nanoscale determination of the mechanical properties of interfaces is of paramount relevance in materials science and cell biology. Bimodal atomic force microscopy (AFM) is arguably the most advanced nanoscale method for mapping the elastic modulus of interfaces. Simulations, theory, and experiments have validated bimodal AFM measurements on thick samples (from micrometer to millimeter). However, the bottom-effect artifact, this is, the influence of the rigid support on the determination of the Young's modulus, questions its accuracy for ultrathin materials and interfaces (1-15 nm). Here we develop a bottom-effect correction method that yields the intrinsic Young's modulus value of a material independent of its thickness. Experiments and numerical simulations validate the accuracy of the method for a wide range of materials (1 MPa to 100 GPa). Otherwise, the Young's modulus of an ultrathin material might be overestimated by a 10-fold factor.

High-speed atomic force microscopy (AFM) enabled the imaging of protein interactions with millisecond time resolutions (10 fps). However, the acquisition of nanomechanical maps of proteins is about 100 times slower. Here, we developed a high-speed bimodal AFM that provided high-spatial resolution maps of the elastic modulus, the loss tangent, and the topography at imaging rates of 5 fps. The microscope was applied to identify the initial stages of the self-assembly of the collagen structures. By following the changes in the physical properties, we identified four stages, nucleation and growth of collagen precursors, formation of tropocollagen molecules, assembly of tropocollagens into microfibrils, and alignment of microfibrils to generate microribbons. Some emerging collagen structures never matured, and after an existence of several seconds, they disappeared into the solution. The elastic modulus of a microfibril (∼4 MPa) implied very small stiffness (∼3 × 10 -6 N/m). Those values amplified the amplitude of the collagen thermal fluctuations on the mica plane, which facilitated microribbon build-up.

The spatial resolution of atomic force microscopy (AFM) needed to resolve material interfaces is limited by the tip-sample separation ( d) dependence of the force used to record an image. Here, we present a new multiscale functional imaging technique that allows for in situ tunable spatial resolution, which can be applied to a wide range of inhomogeneous materials, devices, and interfaces. Our approach uses a multifrequency method to generate a signal whose d-dependence is controlled by mixing harmonics of the cantilever's oscillation with a modulated force. The spatial resolution of the resulting image is determined by the signal's d-dependence. Our measurements using harmonic mixing (HM) show that we can change the d-dependence of a force signal to improve spatial resolution by up to a factor of two compared to conventional methods. We demonstrate the technique with both Kelvin probe force microscopy (KPFM) and bimodal AFM to show its generality. Bimodal AFM with harmonic mixing actuation separates conservative from dissipative forces and is used to identify the regions of adhesive residue on exfoliated graphene. Our electrostatic measurements with open-loop KPFM demonstrate that multiple force modulations may be applied at once. Further, this method can be applied to any tip-sample force that can be modulated, for example, electrostatic, magnetic, and photoinduced forces, showing its universality. Because HM enables in situ switching between high sensitivity and high spatial resolution with any periodic driving force, we foresee this technique as a critical advancement for multiscale functional imaging.

Tapping mode atomic force microscopy (AFM), also known as amplitude modulated (AM) or AC mode, is a proven, reliable, and gentle imaging mode with widespread applications. Over the several decades that tapping mode has been in use, quantification of tip-sample mechanical properties such as stiffness has remained elusive. Bimodal tapping mode keeps the advantages of single-frequency tapping mode while extending the technique by driving and measuring an additional resonant mode of the cantilever. The simultaneously measured observables of this additional resonance provide the additional information necessary to extract quantitative nanomechanical information about the tip-sample mechanics. Specifically, driving the higher cantilever resonance in a frequency modulated (FM) mode allows direct measurement of the tip-sample interaction stiffness and, with appropriate modeling, the set point-independent local elastic modulus. Here we discuss the advantages of bimodal tapping, coined AM-FM imaging, for modulus mapping. Results are presented for samples over a wide modulus range, from a compliant gel (∼100 MPa) to stiff materials (∼100 GPa), with the same type of cantilever. We also show high-resolution (subnanometer) stiffness mapping of individual molecules in semicrystalline polymers and of DNA in fluid. Combined with the ability to remain quantitative even at line scan rates of nearly 40 Hz, the results demonstrate the versatility of AM-FM imaging for nanomechanical characterization in a wide range of applications.

Fast quantitative mapping of mechanical properties with nanoscale spatial resolution represents one of the major goals of force microscopy. This goal becomes more challenging when the characterization needs to be accomplished with subnanometer resolution in a native environment that involves liquid solutions. Here we demonstrate that bimodal atomic force microscopy enables the accurate measurement of the elastic modulus of surfaces in liquid with a spatial resolution of 3 Å. The Young's modulus can be determined with a relative error below 5% over a 5 orders of magnitude range (1 MPa to 100 GPa). This range includes a large variety of materials from proteins to metal-organic frameworks. Numerical simulations validate the accuracy of the method. About 30 s is needed for a Young's modulus map with subnanometer spatial resolution.