Zheling Li

Sensitive electromechanical sensors using viscoelastic graphene-polymer nanocomposites

Super sensitive, not so silly, putty Many composites blend stiff materials, such as glass or carbon fibers, into a softer elastic polymer matrix to generate a material with better overall mechanical toughness. Boland et al. added graphene to a lightly cross-linked silicone polymer (also known as Silly Putty). The resulting composite has unusual mechanical properties, allowing the manufacture of strain sensors that can detect respiration and the footsteps of spiders. Science, this issue p. 1257 A composite of graphene and a viscoelastic polymer results in a material with unexpected electromechanical properties. Despite its widespread use in nanocomposites, the effect of embedding graphene in highly viscoelastic polymer matrices is not well understood. We added graphene to a lightly cross-linked polysilicone, often encountered as Silly Putty, changing its electromechanical properties substantially. The resulting nanocomposites display unusual electromechanical behavior, such as postdeformation temporal relaxation of electrical resistance and nonmonotonic changes in resistivity with strain. These phenomena are associated with the mobility of the nanosheets in the low-viscosity polymer matrix. By considering both the connectivity and mobility of the nanosheets, we developed a quantitative model that completely describes the electromechanical properties. These nanocomposites are sensitive electromechanical sensors with gauge factors >500 that can measure pulse, blood pressure, and even the impact associated with the footsteps of a small spider.

Deformation of Wrinkled Graphene

The deformation of monolayer graphene, produced by chemical vapor deposition (CVD), on a polyester film substrate has been investigated through the use of Raman spectroscopy. It has been found that the microstructure of the CVD graphene consists of a hexagonal array of islands of flat monolayer graphene separated by wrinkled material. During deformation, it was found that the rate of shift of the Raman 2D band wavenumber per unit strain was less than 25% of that of flat flakes of mechanically exfoliated graphene, whereas the rate of band broadening per unit strain was about 75% of that of the exfoliated material. This unusual deformation behavior has been modeled in terms of mechanically isolated graphene islands separated by the graphene wrinkles, with the strain distribution in each graphene island determined using shear lag analysis. The effect of the size and position of the Raman laser beam spot has also been incorporated in the model. The predictions fit well with the behavior observed experimentally for the Raman band shifts and broadening of the wrinkled CVD graphene. The effect of wrinkles upon the efficiency of graphene to reinforce nanocomposites is also discussed.

Mechanical Stability of Flexible Graphene-Based Displays

The mechanical behavior of a prototype touch panel display, which consists of two layers of CVD graphene embedded into PET films, is investigated in tension and under contact-stress dynamic loading. In both cases, laser Raman spectroscopy was employed to assess the stress transfer efficiency of the embedded graphene layers. The tensile behavior was found to be governed by the “island-like” microstructure of the CVD graphene, and the stress transfer efficiency was dependent on the size of graphene “islands” but also on the yielding behavior of PET at relatively high strains. Finally, the fatigue tests, which simulate real operation conditions, showed that the maximum temperature gradient developed at the point of “finger” contact after 80 000 cycles does not exceed the glass transition temperature of the PET matrix. The effect of these results on future product development and the design of new graphene-based displays are discussed.

Electrochemical exfoliation of graphite in quaternary ammonium-based deep eutectic solvents: a route for the mass production of graphane.

We demonstrate a facile and scalable electrochemical approach to exfoliate graphite, which permits in situ hydrogenation of the resultant graphene via a solvated NR(4+) graphite compound in quaternary ammonium-based deep eutectic solvents. Spectroscopic studies reveal the presence of sp(3) C-H bonds in the hydrogenated graphene. The resulting materials consist of micrometre-sized and predominantly monolayer to few layers thick hydrogenated graphenic flakes. A large band gap (∼4 eV) further establishes the high level of hydrogenation. It is also possible to tune the band gap introduced to the graphene by controlling the level of hydrogenation. The mechanism of the exfoliation and hydrogenation is also discussed.

The Role of Interlayer Adhesion in Graphene Oxide upon Its Reinforcement of Nanocomposites

Graphene oxide (GO) has become a well-established reinforcement for polymer-based nanocomposites. It provides stronger interfacial interaction with the matrix when compared with that of graphene, but its intrinsic stiffness and strength are somewhat compromised because of the presence of functional groups damaging the graphene lattice and increasing its thickness, and its tendency to adopt a crumpled structure. Although the micromechanics of graphene reinforcement in nanocomposites has been studied widely, the corresponding micromechanics investigations on GO have not been undertaken in such detail. In this work, it is shown that the deformation micromechanics of GO can be followed using Raman spectroscopy and the observed behaviour can be analysed with continuum mechanics. Furthermore, it is shown that the reinforcement efficiency of GO is independent of its number of layers and stacking configurations, indicating that it is not necessary to ensure a high degree of exfoliation of GO in the polymer matrix. It also demonstrates the possibility of increasing the concentration of GO in nanocomposites without sacrificing mechanical reinforcement efficiency. This article is part of the themed issue ‘Multiscale modelling of the structural integrity of composite materials’.

Beyond ZnO nanowires for piezotronics and nanogenerators

In the past decade ZnO nanowires have been the key enabling material for demonstrating novel electronics components in the field of piezotronics and in the first realization of a nanogenerator. What are the materials that will be crucial in demonstrating even more novel devices in future years? We propose the use of both core shell nanowires and graphene as key enablers of new functionalities.

Ripples, phonons and bandgap in strained graphene

Using a novel interatomic force field, called MMP, we study the morphology of Graphene layers under a variety of strain conditions. We report that strain induced ripples possess the “right” kind of elastic deformation that is necessary in order to produce appreciable bandgap opening, which we calculate using Tight Binding, even for low enough strain that can be accessed through realistic means. At the same time the vibrational properties, calculated from analytic derivatives of the MMP force field and used within the dynamics matrix method, can be easily linked to strain obtained from Molecular Dynamics, opening the way for accurate modelling of Raman data. We also show that our models have allowed us to realize in practice novel devices based on our predictions.