Phonon and structural changes in deformed Bernal stacked bilayer graphene.

We present the first Raman spectroscopic study of Bernal bilayer graphene flakes under uniaxial tension. Apart from a purely mechanical behavior in flake regions where both layers are strained evenly, certain effects stem from inhomogeneous stress distribution across the layers. These phenomena such as the removal of inversion symmetry in bilayer graphene may have important implications in the band gap engineering, providing an alternative route to induce the formation of a band gap.

Nanostructured heteroarm star block terpolymers via an extension of the "in-out" polymerization route.

In this communication an extended "in-out" polymerization method is presented, which leads to the synthesis of novel heteroarm star block terpolymers of the type A(n)(B-b-C)(n). A four step/one-pot synthetic procedure is pursued using anionic polymerization under an inert atmosphere. The resulted star-shaped terpolymer consists of a divinyl benzene nodule bearing pure polystyrene and poly(hexyl methacrylate)-block-poly(methyl methacrylate) diblock copolymer arms. It is shown that this kind of star terpolymers can self-assemble in the bulk forming lamellae mesophase by arm and block segregation. The mechanical properties of the terpolymer have been examined in detail. Finally, the proposed synthetic procedure can be easily employed in other controlled polymerization methods.

Efficient Mechanical Stress Transfer in Multilayer Graphene with a Ladder-like Architecture.

We report that few graphene flakes embedded into polymer matrices can be mechanically stretched to relatively large deformation (>1%) in an efficient way by adopting a particular ladder-like morphology consisting of consecutive mono-, bi-, tri-, and four-layer graphene units. In this type of flake architecture, all of the layers adhere to the surrounding polymer inducing similar deformation on the individual graphene layers, preventing interlayer sliding and optimizing the strain transfer efficiency. We have exploited Raman spectroscopy to quantify this effect from a mechanical standpoint. The finite element method and molecular dynamics simulations have been used to interpret the above experimental findings. The results suggest that a step pyramid-like architecture of a flake can be ideal for efficient loading of layered materials embedded into a polymer and that there are two prevailing mechanisms that govern axial stress transfer, namely, interfacial shear transfer and axial transmission through the ends. This concept can be easily applied to other two-dimensional materials and related van der Waals heterostructures fabricated either by mechanical exfoliation or chemical vapor deposition by appropriate patterning. This work opens new perspectives in numerous applications, including high volume fraction composites, flexible electronics, and straintronic devices.

Stress transfer mechanisms at the submicron level for graphene/polymer systems.

The stress transfer mechanism from a polymer substrate to a nanoinclusion, such as a graphene flake, is of extreme interest for the production of effective nanocomposites. Previous work conducted mainly at the micron scale has shown that the intrinsic mechanism of stress transfer is shear at the interface. However, since the interfacial shear takes its maximum value at the very edge of the nanoinclusion it is of extreme interest to assess the effect of edge integrity upon axial stress transfer at the submicron scale. Here, we conduct a detailed Raman line mapping near the edges of a monolayer graphene flake that is simply supported onto an epoxy-based photoresist (SU8)/poly(methyl methacrylate) matrix at steps as small as 100 nm. We show for the first time that the distribution of axial strain (stress) along the flake deviates somewhat from the classical shear-lag prediction for a region of ∼ 2 µm from the edge. This behavior is mainly attributed to the presence of residual stresses, unintentional doping, and/or edge effects (deviation from the equilibrium values of bond lengths and angles, as well as different edge chiralities). By considering a simple balance of shear-to-normal stresses at the interface we are able to directly convert the strain (stress) gradient to values of interfacial shear stress for all the applied tensile levels without assuming classical shear-lag behavior. For large flakes a maximum value of interfacial shear stress of 0.4 MPa is obtained prior to flake slipping.

Failure processes in embedded monolayer graphene under axial compression.

Exfoliated monolayer graphene flakes were embedded in a polymer matrix and loaded under axial compression. By monitoring the shifts of the 2D Raman phonons of rectangular flakes of various sizes under load, the critical strain to failure was determined. Prior to loading care was taken for the examined area of the flake to be free of residual stresses. The critical strain values for first failure were found to be independent of flake size at a mean value of -0.60% corresponding to a yield stress up to -6 GPa. By combining Euler mechanics with a Winkler approach, we show that unlike buckling in air, the presence of the polymer constraint results in graphene buckling at a fixed value of strain with an estimated wrinkle wavelength of the order of 1-2 nm. These results were compared with DFT computations performed on analogue coronene/PMMA oligomers and a reasonable agreement was obtained.

Raman 2D-band splitting in graphene: theory and experiment.

We present a systematic experimental and theoretical study of the two-phonon (2D) Raman scattering in graphene under uniaxial tension. The external perturbation unveils that the 2D mode excited with 785 nm has a complex line-shape mainly due to the contribution of two distinct double resonance scattering processes (inner and outer) in the Raman signal. The splitting depends on the direction of the applied strain and the polarization of the incident light. The results give new insight into the nature of the 2D band and have significant implications for the use of graphene as reinforcement in composites since the 2D mode is crucial to assess how effectively graphene uptakes an applied stress or strain.

Compression behavior of single-layer graphenes.

Central to most applications involving monolayer graphenes is its mechanical response under various stress states. To date most of the work reported is of theoretical nature and refers to tension and compression loading of model graphenes. Most of the experimental work is indeed limited to the bending of single flakes in air and the stretching of flakes up to typically approximately 1% using plastic substrates. Recently we have shown that by employing a cantilever beam we can subject single graphenes to various degrees of axial compression. Here we extend this work much further by measuring in detail both stress uptake and compression buckling strain in single flakes of different geometries. In all cases the mechanical response is monitored by simultaneous Raman measurements through the shift of either the G or 2D phonons of graphene. Despite the infinitely small thickness of the monolayers, the results show that graphenes embedded in plastic beams exhibit remarkable compression buckling strains. For large length (l)-to-width (w) ratios (> or =0.2) the buckling strain is of the order of -0.5% to -0.6%. However, for l/w < 0.2 no failure is observed for strains even higher than -1%. Calculations based on classical Euler analysis show that the buckling strain enhancement provided by the polymer lateral support is more than 6 orders of magnitude compared to that of suspended graphene in air.