The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.
Scanning probe microscopy (SPM) techniques have opened the door to nanoscience and nanotechnology by enabling imaging and manipulation of the structure and functionality of matter at nanometer and atomic scales. Here, we analyze the scientific discovery process in SPM by following the information flow from the tip-surface junction, to knowledge adoption by the wider scientific community. We further discuss the challenges and opportunities offered by merging SPM with advanced data mining, visual analytics, and knowledge discovery technologies.
We investigate the nanometer-scale flow of molten polyethylene from a heated atomic force microscope (AFM) cantilever tip during thermal dip-pen nanolithography (tDPN). Polymer nanostructures were written for cantilever tip temperatures and substrate temperatures controlled over the range 100-260 °C and while the tip was either moving with speed 0.5-2.0 µm s(-1) or stationary and heated for 0.1-100 s. We find that polymer flow depends on surface capillary forces and not on shear between tip and substrate. The polymer mass flow rate is sensitive to the temperature-dependent polymer viscosity. The polymer flow is governed by thermal Marangoni forces and non-equilibrium wetting dynamics caused by a solidification front within the feature.
Kelvin probe force microscopy (KPFM) has provided deep insights into the local electronic, ionic and electrochemical functionalities in a broad range of materials and devices. In classical KPFM, which utilizes heterodyne detection and closed loop bias feedback, the cantilever response is down-sampled to a single measurement of the contact potential difference (CPD) per pixel. This level of detail, however, is insufficient for materials and devices involving bias and time dependent electrochemical events; or at solid-liquid interfaces, where non-linear or lossy dielectrics are present. Here, we demonstrate direct recovery of the bias dependence of the electrostatic force at high temporal resolution using General acquisition Mode (G-Mode) KPFM. G-Mode KPFM utilizes high speed detection, compression, and storage of the raw cantilever deflection signal in its entirety at high sampling rates. We show how G-Mode KPFM can be used to capture nanoscale CPD and capacitance information with a temporal resolution much faster than the cantilever bandwidth, determined by the modulation frequency of the AC voltage. In this way, G-Mode KPFM offers a new paradigm to study dynamic electric phenomena in electroactive interfaces as well as a promising route to extend KPFM to the solid-liquid interface.
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