Tobin Filleter

Local work function measurements of epitaxial graphene

The work function difference between single layer and bilayer graphene grown epitaxially on 6H-SiC(0001) has been determined to be 135±9 meV by means of the Kelvin probe force microscopy. Bilayer films are found to increase the work function as compared to single layer films. This method allows an unambiguous distinction between interface layer, single layer, and bilayer graphene. In combination with high-resolution topographic imaging, the complex step structure of epitaxial graphene on SiC can be resolved with respect to substrate and graphene layer steps.

Ultrahigh Strength and Stiffness in Cross-Linked Hierarchical Carbon Nanotube Bundles

IO N Utilizing the full mechanical capabilities of individual carbon nanotubes (CNT) – which can exhibit tensile strength and elastic modulus of up to 1TPa and 100 GPa, respectively [ 1–4 ] – has motivated a great deal of interest in CNT based nanocomposite materials. [ 5–10 ] Despite this signifi cant scientifi c effort, the strength, modulus, and toughness of CNT based fi bers and composites are typically dominated by weak shear interactions between adjacent shells, tubes, bundles, and matrix materials, [ 2 , 4 , 10 , 11 ] which has limited their application to hierarchical macroscopic composite materials. Here we demonstrate that the mechanical performance of double-walled nanotube (DWNT) bundles is greatly enhanced through high-energy electron-irradiation-induced shell–shell and tube–tube crosslinking. The effective tensile strength and elastic modulus are found to increase by an order of magnitude as compared to un-crosslinked bundles. This enhancement is attributed to covalent bonds formed between outer and inner DWNT shells as well as adjacent DWNT outer tubes within the bundle. Distinct failure mechanisms were also identifi ed through in situ transmission electron microscopy (TEM) tensile tests of individual DWNT bundles revealing a sword-in-sheath like failure mechanism for low cross-linked bundles and complete fracture of all shells for highly cross-linked bundles. The optimized irradiation-induced cross-linking enhancements of DWNT bundles demonstraed here are predicted to translate to up to order-of-magnitude improvements in the mechanical behavior of advanced composites. Engineering lateral interactions through cross-linking has become an essential tool in the development of advanced hierarchical composite materials, many of which are inspired by natural interfaces. [ 12–15 ] Successful hierarchical designs typically require both cross-linking to strong/stiff reinforcement elements (e.g. mineral crystals in the collagen fi brils in bone [ 14 ] ) coupled with soft-sacrifi cial cross-linking (e.g. hydrogen bonding between beta-sheet crystals in spider silk [ 16 ] ) between elements to enhance toughness. In the case of individual CNTs and CNT bundles, one successful approach has been covalent cross-linking via high energy

A Multiscale Study of High Performance Double-Walled Nanotube−Polymer Fibers

The superior mechanical behavior of carbon nanotubes (CNT) and their electrical and thermal functionalities has motivated researchers to exploit them as building blocks to develop advanced materials. Here, we demonstrate high performance double-walled nanotube (DWNT)-polymer composite yarns formed by twisting and stretching of ribbons of randomly oriented bundles of DWNTs thinly coated with polymeric organic compounds. A multiscale in situ scanning electron microscopy experimental approach was implemented to investigate the mechanical performance of yarns and isolated DWNT bundles with and without polymer coatings. DWNT-polymer yarns exhibited significant ductility of ∼20%, with energy-to-failure of as high as ∼100 J g(-1), superior to previously reported CNT-based yarns. The enhanced ductility is not at the expense of strength, as yarns exhibited strength as high as ∼1.4 GPa. In addition, the significance of twisting on the densification of yarns and corresponding enhancement in the lateral interactions between bundles is identified. Experiments at nanometer and macroscopic length scales on DWNT-polymer yarns and bundles further enabled quantification of energy dissipation/storage mechanisms in the yarns during axial deformations. We demonstrate that while isolated DWNT bundles are capable of storing/dissipating up to ∼500 J g(-1) at failure, unoptimal load transfer between individual bundles prevents the stress build up in the yarns required for considerable energy storage at the bundle level. By contrast, through polymer lateral interactions, a much better performance is obtained with the majority of energy dissipated at failure being contributed by the interactions between the polymer coating and the DWNTs as compared to the direct van der Waals interactions between bundles.

Nucleation-Controlled Distributed Plasticity in Penta-twinned Silver Nanowires

A unique size-dependent strain hardening mechanism, that achieves both high strength and ductility, is demonstrated for penta-twinned Ag nanowires (NWs) through a combined experimental-computational approach. Thin Ag NWs are found to deform via the surface nucleation of stacking fault decahedrons (SFDs) in multiple plastic zones distributed along the NW. Twin boundaries lead to the formation of SFD chains that locally harden the NW and promote subsequent nucleation of SFDs at other locations. Due to surface undulations, chain reactions of SFD arrays are activated at stress concentrations and terminated as local stress decreases, revealing insensitivity to defects imparted by the twin structures. Thick NWs exhibit lower flow stress and number of distributed plastic zones due to the onset of necking accompanied by more complex dislocation structures.

In situ TEM electromechanical testing of nanowires and nanotubes

The emergence of one-dimensional nanostructures as fundamental constituents of advanced materials and next-generation electronic and electromechanical devices has increased the need for their atomic-scale characterization. Given its spatial and temporal resolution, coupled with analytical capabilities, transmission electron microscopy (TEM) has been the technique of choice in performing atomic structure and defect characterization. A number of approaches have been recently developed to combine these capabilities with in-situ mechanical deformation and electrical characterization in the emerging field of in-situ TEM electromechanical testing. This has enabled researchers to establish unambiguous synthesis-structure-property relations for one-dimensional nanostructures. In this article, the development and latest advances of several in-situ TEM techniques to carry out mechanical and electromechanical testing of nanowires and nanotubes are reviewed. Through discussion of specific examples, it is shown how the merging of several microsystems and TEM has led to significant insights into the behavior of nanowires and nanotubes, underscoring the significant role in-situ techniques play in the development of novel nanoscale systems and materials.

Multiscale Experimental Mechanics of Hierarchical Carbon-Based Materials

Investigation of the mechanics of natural materials, such as spider silk, abalone shells, and bone, has provided great insight into the design of materials that can simultaneously achieve high specific strength and toughness. Research has shown that their emergent mechanical properties are owed in part to their specific self-organization in hierarchical molecular structures, from nanoscale to macroscale, as well as their mixing and bonding. To apply these findings to manmade materials, researchers have devoted significant efforts in developing a fundamental understanding of multiscale mechanics of materials and its application to the design of novel materials with superior mechanical performance. These efforts included the utilization of some of the most promising carbon-based nanomaterials, such as carbon nanotubes, carbon nanofibers, and graphene, together with a variety of matrix materials. At the core of these efforts lies the need to characterize material mechanical behavior across multiple length scales starting from nanoscale characterization of constituents and their interactions to emerging micro- and macroscale properties. In this report, progress made in experimental tools and methods currently used for material characterization across multiple length scales is reviewed, as well as a discussion of how they have impacted our current understanding of the mechanics of hierarchical carbon-based materials. In addition, insight is provided into strategies for bridging experiments across length scales, which are essential in establishing a multiscale characterization approach. While the focus of this progress report is in experimental methods, their concerted use with theoretical-computational approaches towards the establishment of a robust material by design methodology is also discussed, which can pave the way for the development of novel materials possessing unprecedented mechanical properties.

Experimental-Computational Study of Shear Interactions within Double-Walled Carbon Nanotube Bundles

The mechanical behavior of carbon nanotube (CNT)-based fibers and nanocomposites depends intimately on the shear interactions between adjacent tubes. We have applied an experimental-computational approach to investigate the shear interactions between adjacent CNTs within individual double-walled nanotube (DWNT) bundles. The force required to pull out an inner bundle of DWNTs from an outer shell of DWNTs was measured using in situ scanning electron microscopy methods. The normalized force per CNT-CNT interaction (1.7 ± 1.0 nN) was found to be considerably higher than molecular mechanics (MM)-based predictions for bare CNTs (0.3 nN). This MM result is similar to the force that results from exposure of newly formed CNT surfaces, indicating that the observed pullout force arises from factors beyond what arise from potential energy effects associated with bare CNTs. Through further theoretical considerations we show that the experimentally measured pullout force may include small contributions from carbonyl functional groups terminating the free ends of the CNTs, corrugation of the CNT-CNT interactions, and polygonization of the nanotubes due to their mutual interactions. In addition, surface functional groups, such as hydroxyl groups, that may exist between the nanotubes are found to play an unimportant role. All of these potential energy effects account for less than half of the ~1.7 nN force. However, partially pulled-out inner bundles are found not to pull back into the outer shell after the outer shell is broken, suggesting that dissipation is responsible for more than half of the pullout force. The sum of force contributions from potential energy and dissipation effects are found to agree with the experimental pullout force within the experimental error.

Interfacial Shear Strength of Multilayer Graphene Oxide Films

Graphene oxide (GO) is considered as one of the most promising layered materials with tunable physical properties and applicability in many important engineering applications. In this work, the interfacial behavior of multilayer GO films was directly investigated via GO-to-GO friction force microscopy, and the interfacial shear strength (ISS) was measured to be 5.3 ± 3.2 MPa. Based on high resolution atomic force microscopy images and the available chemical data, targeted molecular dynamics simulations were performed to evaluate the influence of functional structure, topological defects, and interlayer registry on the shear response of the GO films. Theoretical values for shear strength ranging from 17 to 132 MPa were predicted for the different structures studied, providing upper bounds for the ISS. Computational results also revealed the atomic origins of the stochastic nature of friction measurements. Specifically, the wide scatter in experimental measurements was attributed to variations in functional structure and topological defects within the sliding volume. The findings of this study provide important insight for understanding the significant differences in strength between monolayer and bulk graphene oxide materials and can be useful for engineering topological structures with tunable mechanical properties.

Effect of structure on the tribology of ultrathin graphene and graphene oxide films.

The friction and wear properties of graphene and graphene oxide (GO) with varying C/O ratio were investigated using friction force microscopy. When applied as solid lubricants between a sliding contact of a silicon (Si) tip and a SiO2/Si substrate, graphene and ultrathin GO films (as thin as 1-2 atomic layers) were found to reduce friction by ∼6 times and ∼2 times respectively as compared to the unlubricated contact. The differences in measured friction were attributed to different interfacial shear strengths. Ultrathin films of GO with a low C/O ratio of ∼2 were found to wear easily under small normal load. The onset of wear, and the location of wear initiation, is attributed to differences in the local shear strength of the sliding interface as a result of the non-homogeneous surface structure of GO. While the exhibited low friction of GO as compared to SiO2 makes it an economically viable coating for micro/nano-electro-mechanical systems with the potential to extend the lifetime of devices, its higher propensity for wear may limit its usefulness. To address this limitation, the wear resistance of GO samples with a higher C/O ratio (∼4) was also studied. The higher C/O ratio GO was found to exhibit much improved wear resistance which approached that of the graphene samples. This demonstrates the potential of tailoring the structure of GO to achieve graphene-like tribological properties.

Strengthening in Graphene Oxide Nanosheets: Bridging the Gap between Interplanar and Intraplanar Fracture

Graphene oxide (GO) is a layered material comprised of hierarchical features which possess vastly differing characteristic dimensions. GO nanosheets represent the critical hierarchical structure which bridges the length-scale of monolayer and bulk material architectures. In this study, the strength and fracture behavior of GO nanosheets were examined. Under uniaxial loading, the tensile strength of the nanosheets was measured to be as high as 12 ± 4 GPa, which approaches the intrinsic strength of monolayer GO and is orders of magnitude higher than that of bulk GO materials. During mechanical failure, brittle fracture was observed in a highly localized region through the cross-section of the nanosheets without interlayer pull-out. This transition in the failure behavior from interplanar fracture, common for bulk GO, to intraplanar fracture, which dominates failure in monolayer GO, is responsible for the high strength measured in the nanosheets. Molecular dynamics simulations indicate that the elastic release from the propagation of intraplanar cracks initiates global fracture due to interlayer load transmission through hydrogen bond networks within the gallery space of the GO nanosheets. Furthermore, the GO nanosheet strength and stiffness were found to be strongly correlated to the effective volume and thickness of the samples, respectively. These findings help to bridge the understanding of the mechanical behavior of hierarchical GO materials and will ultimately guide the application of this intermediate scale material.