Nicola Pugno

Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems

We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.

The shear mode of multilayer graphene

The quest for materials capable of realizing the next generation of electronic and photonic devices continues to fuel research on the electronic, optical and vibrational properties of graphene. Few-layer graphene (FLG) flakes with less than ten layers each show a distinctive band structure. Thus, there is an increasing interest in the physics and applications of FLGs. Raman spectroscopy is one of the most useful and versatile tools to probe graphene samples. Here, we uncover the interlayer shear mode of FLGs, ranging from bilayer graphene (BLG) to bulk graphite, and suggest that the corresponding Raman peak measures the interlayer coupling. This peak scales from ~43 cm(-1) in bulk graphite to ~31 cm(-1) in BLG. Its low energy makes it sensitive to near-Dirac point quasiparticles. Similar shear modes are expected in all layered materials, providing a direct probe of interlayer interactions.

Nonlinear material behaviour of spider silk yields robust webs

Natural materials are renowned for exquisite designs that optimize function, as illustrated by the elasticity of blood vessels, the toughness of bone and the protection offered by nacre. Particularly intriguing are spider silks, with studies having explored properties ranging from their protein sequence to the geometry of a web. This material system, highly adapted to meet a spider’s many needs, has superior mechanical properties. In spite of much research into the molecular design underpinning the outstanding performance of silk fibres, and into the mechanical characteristics of web-like structures, it remains unknown how the mechanical characteristics of spider silk contribute to the integrity and performance of a spider web. Here we report web deformation experiments and simulations that identify the nonlinear response of silk threads to stress—involving softening at a yield point and substantial stiffening at large strain until failure—as being crucial to localize load-induced deformation and resulting in mechanically robust spider webs. Control simulations confirmed that a nonlinear stress response results in superior resistance to structural defects in the web compared to linear elastic or elastic–plastic (softening) material behaviour. We also show that under distributed loads, such as those exerted by wind, the stiff behaviour of silk under small deformation, before the yield point, is essential in maintaining the web’s structural integrity. The superior performance of silk in webs is therefore not due merely to its exceptional ultimate strength and strain, but arises from the nonlinear response of silk threads to strain and their geometrical arrangement in a web.

Quantized fracture mechanics

A new energy-based theory, quantized fracture mechanics (QFM), is presented that modifies continuum-based fracture mechanics; stress- and strain-based QFM analogs are also proposed. The differentials in Griffiths criterion are substituted with finite differences; the implications are remarkable. Fracture of tiny systems with a given geometry and type of loading occurs at ‘quantized’ stresses that are well predicted by QFM: strengths predicted by QFM are compared with experimental results on carbon nanotubes, β-SiC nanorods, α-Si3N4 whiskers, and polysilicon thin films; and also with molecular mechanics/dynamics simulation of fracture of carbon nanotubes and graphene with cracks and holes, and statistical mechanics-based simulations on fracture of two-dimensional spring networks. QFM is self-consistent, agreeing to first-order with linear elastic fracture mechanics (LEFM), and to second-order with non-linear fracture mechanics (NLFM). For vanishing crack length QFM predicts a finite ideal strength in agre...

Molecular and nanostructural mechanisms of deformation, strength and toughness of spider silk fibrils.

Spider dragline silk is one of the strongest, most extensible and toughest biological materials known, exceeding the properties of many engineered materials including steel. Silk features a hierarchical architecture where highly organized, densely H-bonded beta-sheet nanocrystals are arranged within a semiamorphous protein matrix consisting of 3(1)-helices and beta-turn protein structures. By using a bottom-up molecular-based approach, here we develop the first spider silk mesoscale model, bridging the scales from Angstroms to tens to potentially hundreds of nanometers. We demonstrate that the specific nanoscale combination of a crystalline phase and a semiamorphous matrix is crucial to achieve the unique properties of silks. Our results reveal that the superior mechanical properties of spider silk can be explained solely by structural effects, where the geometric confinement of beta-sheet nanocrystals, combined with highly extensible semiamorphous domains, is the key to reach great strength and great toughness, despite the dominance of mechanically inferior chemical interactions such as H-bonding. Our model directly shows that semiamorphous regions govern the silk behavior at small deformation, unraveling first when silk is being stretched and leading to the large extensibility of the material. Conversely, beta-sheet nanocrystals play a significant role in defining the mechanical behavior of silk at large-deformation. In particular, the ultimate tensile strength of silk is controlled by the strength of beta-sheet nanocrystals, which is directly related to their size, where small beta-sheet nanocrystals are crucial to reach outstanding levels of strength and toughness. Our results and mechanistic insight directly explain recent experimental results, where it was shown that a significant change in the strength and toughness of silk can be achieved solely by tuning the size of beta-sheet nanocrystals. Our findings help to unveil the material design strategy that enables silk to achieve superior material performance despite simple and inferior material constituents. This concept could lead to a new materials design paradigm, where enhanced functionality is not achieved using complex building blocks but rather through the utilization of simple repetitive constitutive elements arranged in hierarchical structures from nano to macro.

Nanoconfinement of spider silk fibrils begets superior strength, extensibility, and toughness.

Silk is an exceptionally strong, extensible, and tough material made from simple protein building blocks. The molecular structure of dragline spider silk repeat units consists of semiamorphous and nanocrystalline β-sheet protein domains. Here we show by a series of computational experiments how the nanoscale properties of silk repeat units are scaled up to create macroscopic silk fibers with outstanding mechanical properties despite the presence of cavities, tears, and cracks. We demonstrate that the geometric confinement of silk fibrils to diameters of 50 ± 30 nm is critical to facilitate a powerful mechanism by which hundreds of thousands of protein domains synergistically resist deformation and failure to provide enhanced strength, extensibility, and toughness at the macroscale, closely matching experimentally measured mechanical properties. Through this mechanism silk fibers exploit the full potential of the nanoscale building blocks, regardless of the details of microscopic loading conditions and despite the presence of large defects. Experimental results confirm that silk fibers are composed of silk fibril bundles with diameters in the range of 20-150 nm, in agreement with our predicted length scale. Our study reveals a general mechanism to map nanoscale properties to the macroscale and provides a potent design strategy toward novel fiber and bulk nanomaterials through hierarchical structures.

Spatulate structures in biological fibrillar adhesion

To provide an explanation of why most biological hairy adhesive systems involved in locomotion rely on spatulate structures, we have studied the contact formed between a smooth substrate and individual thin-film terminal elements of attachment pads evolved in insects, arachnids and reptiles. The data obtained were analyzed using the Kendall peeling model, which demonstrated that an animal’s attachment ability grows with an overall length of the peeling line, which is the sum of widths of all thin-film elements participating in contact. This robust principle is found to manifest itself across 8 orders of magnitude in an overall peeling line ranging from 64 micrometres for a red spider mite to 1.8 kilometres for a Tokay gecko, generalizing the critical role of terminal elements in biological fibrillar adhesion.

Tunable Water Channels with Carbon Nanoscrolls

Molecular dynamics simulations and theoretical analyses are performed to show that the flow rate of water through the core of carbon nanoscrolls (CNSs) can be adjusted over a broad range through the effective surface energy, which in turn can be tuned by an applied DC or AC electric field. The results suggest that the CNSs hold great promise for applications such as tunable water and ion channels, nanofluidic devices, and nanofilters, as well as tunable gene- and drug-delivery systems.

A translational nanoactuator based on carbon nanoscrolls on substrates

Inspired by recent experimental studies on the fabrication of carbon nanoscrolls (CNSs) on solid substrates, we perform theoretical study and molecular dynamics simulations to investigate the translational rolling/unrolling of a CNS on rigid substrate. We show that a substrate-supported CNS can be controlled to roll forward and backward by tuning its interlayer interaction energy via an external field. The typical energy release rate per unit area of rolling for such controllable and reversible linear motion is estimated to be in the range of (−0.06)–0.08 nN/nm, indicating promising applications as actuators and motors in nanomechanical systems.

Numerical Analysis of Nanotube Based NEMS Devices — Part II: Role of Finite Kinematics, Stretching and Charge Concentrations

In this paper ci nonlinear analysis of nanotuhe based nano-electromechanical systems is reported. Assuming continuum mechanics, the complete nonlinear equation of the elastic line of the nanotube is derived and then numerically solved. In particular, we study singly and doubly clamped nanotubes under electrostatic actuation. The analysis emphasizes the importance of nonlinear kinematics effects in the prediction of the pull-in voltage of the device, a key design parameter. Moreover, the nonlinear behavior associated with finite kinematics (i.e., large deformations), neglected in previous studies, as well as charge concentrations at the tip of singly clamped nanotuhes, are investigated in detail. We show that nonlinear kinematics results in an important increase in the pull-in voltage of doubly clamped nanotube devices, but that it is negligible in the case of singly damped devices. Likewise, we demonstrate that charge concentration at the tip of singly clamped devices results in a significant reduction in pull-in voltage. By comparing numerical results to analytical predictions, closed form formulas are verified. These formulas provide a guide on the effect of the various geometrical variables and insight into the design of novel devices.