Mohammad Naraghi

Novel method for mechanical characterization of polymeric nanofibers

A novel method to perform nanoscale mechanical characterization of highly deformable nanofibers has been developed. A microelectromechanical system (MEMS) test platform with an on-chip leaf-spring load cell that was tuned with the aid of a focused ion beam was built for fiber gripping and force measurement and it was actuated with an external piezoelectric transducer. Submicron scale tensile tests were performed in ambient conditions under an optical microscope. Engineering stresses and strains were obtained directly from images of the MEMS platform, by extracting the relative rigid body displacements of the device components by digital image correlation. The accuracy in determining displacements by this optical method was shown to be better than 50 nm. In the application of this method, the mechanical behavior of electrospun polyacrylonitrite nanofibers with diameters ranging from 300 to 600 nm was investigated. The stress-strain curves demonstrated an apparent elastic-perfectly plastic behavior with elastic modulus of 7.6+/-1.5 GPa and large irreversible strains that exceeded 220%. The large fiber stretch ratios were the result of a cascade of periodic necks that formed during cold drawing of the nanofibers.

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.

Optimal length scales emerging from shear load transfer in natural materials: application to carbon-based nanocomposite design.

Numerous theoretical and experimental studies on various species of natural composites, such as nacre in abalone shells, collagen fibrils in tendon, and spider silk fibers, have been pursued to provide insight into the synthesis of novel bioinspired high-performance composites. However, a direct link between the mechanical properties of the constituents and the various geometric features and hierarchies remains to be fully established. In this paper, we explore a common denominator leading to the outstanding balance between strength and toughness in natural composite materials. We present an analytical model to link the mechanical properties of constituents, their geometric arrangement, and the chemistries used in their lateral interactions. Key critical overlap length scales between adjacent reinforcement constituents, which directly control strength and toughness of composite materials, emerge from the analysis. When these length scales are computed for three natural materials-nacre, collagen molecules, and spider silk fibers-very good agreement is found as compared with experimental measurements. The model was then used to interpret load transfer capabilities in synthetic carbon-based materials through parametrization of in situ SEM shear experiments on overlapping multiwall carbon nanotubes.

Mechanical deformation and failure of electrospun polyacrylonitrile nanofibers as a function of strain rate

The mechanical deformation of 12μm long electrospun polyacrylonitrile (PAN) nanofibers with diameters of 300–600nm was investigated. The nanofibers were subjected to cold drawing in atmospheric conditions and at strain rates between 10−2 and 10−4s−1. The ultimate strain of the PAN nanofibers was 60%–130% varying monotonically with the strain rate. On the contrary, the fiber tensile strength, ranging between 30 and 130MPa, varied nonmonotonically with the slowest drawing rate resulting in the largest ductilities and fiber strengths. At the two faster rates, the large fiber ductilities originated in the formation of a cascade of ripples (necks), while at the slowest strain rate, the nanofibers deformed homogeneously allowing for the largest engineering strengths and extension ratios.

Bio-Inspired Carbon Nanotube–Polymer Composite Yarns with Hydrogen Bond-Mediated Lateral Interactions

Polymer composite yarns containing a high loading of double-walled carbon nanotubes (DWNTs) have been developed in which the inherent acrylate-based organic coating on the surface of the DWNT bundles interacts strongly with poly(vinyl alcohol) (PVA) through an extensive hydrogen-bond network. This design takes advantage of a toughening mechanism seen in spider silk and collagen, which contain an abundance of hydrogen bonds that can break and reform, allowing for large deformation while maintaining structural stability. Similar to that observed in natural materials, unfolding of the polymeric matrix at large deformations increases ductility without sacrificing stiffness. As the PVA content in the composite increases, the stiffness and energy to failure of the composite also increases up to an optimal point, beyond which mechanical performance in tension decreases. Molecular dynamics (MD) simulations confirm this trend, showing the dominance of nonproductive hydrogen bonding between PVA molecules at high PVA contents, which lubricates the interface between DWNTs.

Extraordinary Improvement of the Graphitic Structure of Continuous Carbon Nanofibers Templated with Double Wall Carbon Nanotubes

Carbon nanotubes are being widely studied as a reinforcing element in high-performance composites and fibers at high volume fractions. However, problems with nanotube processing, alignment, and non-optimal stress transfer between the nanotubes and surrounding matrix have so far prevented full utilization of their superb mechanical properties in composites. Here, we present an alternative use of carbon nanotubes, at a very small concentration, as a templating agent for the formation of graphitic structure in fibers. Continuous carbon nanofibers (CNF) were manufactured by electrospinning from polyacrylonitrile (PAN) with 1.2% of double wall nanotubes (DWNT). Nanofibers were oxidized and carbonized at temperatures from 600 °C to 1850 °C. Structural analyses revealed significant improvements in graphitic structure and crystal orientation in the templated CNFs, with the largest improvements observed at lower carbonization temperatures. In situ pull-out experiments showed good interfacial bonding between the DWNT bundles and the surrounding templated carbon matrix. Molecular Dynamics (MD) simulations of templated carbonization confirmed oriented graphitic growth and provided insight into mechanisms of carbonization initiation. The obtained results indicate that global templating of the graphitic structure in fine CNFs can be achieved at very small concentrations of well-dispersed DWNTs. The outcomes reveal a simple and inexpensive route to manufacture continuous CNFs with improved structure and properties for a variety of mechanical and functional applications. The demonstrated improvement of graphitic order at low carbonization temperatures in the absence of stretch shows potential as a promising new manufacturing technology for next generation carbon fibers.

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.

High-Performance Coils and Yarns of Polymeric Piezoelectric Nanofibers

We report on highly stretchable piezoelectric structures of electrospun PVDF-TrFE nanofibers. We fabricated nanofibrous PVDF-TrFE yarns via twisting their electrospun ribbons. Our results show that the twisting process not only increases the failure strain but also increases overall strength and toughness. The nanofibrous yarns achieved a remarkable energy to failure of up to 98 J/g. Through overtwisting process, we fabricated polymeric coils out of twisted yarns that stretched up to ∼740% strain. This enhancement in mechanical properties is likely induced by increased interactions between nanofibers, contributed by friction and van der Waals interactions, as well as favorable surface charge (Columbic) interactions as a result of piezoelectric effect, for which we present a theoretical model. The fabricated yarns and coils show great promise for applications in high-performance lightweight structural materials and superstretchable piezoelectric devices and flexible energy harvesting applications.

Energy Dissipation Due to Interfacial Slip in Nanocomposites Reinforced with Aligned Carbon Nanotubes

Interfacial slip mechanisms of strain energy dissipation and vibration damping of highly aligned carbon nanotube (CNT) reinforced polymer composites were studied through experimentation and complementary micromechanics modeling. Experimentally, we have developed CNT-polystyrene (PS) composites with a high degree of CNT alignment via a combination of twin-screw extrusion and hot-drawing. The aligned nanocomposites enabled a focused study of the interfacial slip mechanics associated with shear stress concentrations along the CNT-PS interface induced by the elastic mismatch between the filler and matrix. The variation of storage and loss modulus suggests the initiation of the interfacial slip occurs at axial strains as low as 0.028%, primarily due to shear stress concentration along the CNT-PS interface. Through micromechanics modeling and by matching the model with the experimental results at the onset of slip, the interfacial shear strength was evaluated. The model was then used to provide additional insight into the experimental observations by showing that the nonlinear variation of damping with dynamic strain can be attributed to slip-stick behavior. The dependence of the interfacial load-transfer reversibility on the dynamic strain history and characteristic time scale was experimentally investigated to demonstrate the relative contribution of van der Waals (vdW) interactions, mechanical interlocking, and covalent bonding to shear interactions.