Nanomechanics with the atomic force microscope on polymer surfaces, interfaces and nano-materials

Nysten, Bernard [UCL]

Methods based on the atomic force microscope (AFM) were implemented or developed to measure and map at the nanoscale the mechanical properties of polymer surfaces and of nanomaterials: force spectroscopy, force modulation, phase detection in intermittent-contact mode. Especially, a technique, referred as resonant contact-AFM, was developed. It is based on the electrostatic excitation of the cantilever vibration and on the measurement of its resonance frequency when the tip contacts the probed sample. A theoretical model was developed to determine the tip-sample contact stiffness from the measurement of the frequency shift. These methods were used to study several questions raised in the fields of polymer surfaces and interfaces and of nanomaterials. Surfaces of toughened polypropylene (PP) with ethylene-propylene copolymer (EP) were studied by force spectroscopy and force modulation microscopy (FMM) to characterise the effect of the blending and the moulding processes and the PP/EP viscosity ratio on the surface distribution of the EP rubber nodules. The contribution of the EP rubber to paint adhesion was also demonstrated. Surfaces of atactic polypropylene photo-grafted with acrylic acid monomers were analysed by intermittent-contact AFM (IC-AFM) with phase detection. The combination of these methods with other analytical techniques allowed characterising the chemical composition of the heterogeneous surface morphology obtained after photo-grafting. The tensile elastic modulus of polymer nanotubes and metallic nanowires was measured with force spectroscopy and resonant contact-AFM. These measurements confirmed the ability of resonant contact-AFM to quantitatively measure the mechanical properties of nanomaterials. Moreover, they showed that the measured modulus increased when the nanowires or nanotubes diameter decreases. This behaviour was explained by taking into account the effect of the surface deformation that added a surface stiffness proportional to the surface tension, or surface stress, of the material. Resonant contact-AFM was also used to characterise the variation of the mechanical properties at the interfaces in polymer blends. It was demonstrated that this technique allows the determination of the interfacial width in incompatible polymer blends. It also allowed characterising the mechanical property gradient that can appear in reactive polymer blends.