C. Galiotis

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.

Subjecting a Graphene Monolayer to Tension and Compression

The mechanical behaviour of graphene flakes under both tension and compression is examined using a cantilever-beam arrangement. Two different sets of samples were employed involving flakes just supported on a plastic bar but also embedded within the plastic substrate. By monitoring the shift of the 2D Raman line with strain, information on the stress transfer efficiency as a function of stress sign and monolayer support were obtained. In tension, the embedded flake seems to sustain strains up to 1.3%, whereas in compression there is an indication of flake buckling at about 0.7% strain. The retainment of such a high critical buckling strain confirms the relative high flexural rigidity of the embedded monolayer.

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.

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.

Development of a universal stress sensor for graphene and carbon fibres

Carbon fibres are a significant volume fraction of modern structural airframes. Embedded into polymer matrices, they provide significant strength and stiffness gains by unit weight compared with competing structural materials. Here we use the Raman G peak to assess the response of carbon fibres to the application of strain, with reference to the response of graphene itself. Our data highlight the predominance of the in-plane graphene properties in all graphitic structures examined. A universal master plot relating the G peak strain sensitivity to tensile modulus of all types of carbon fibres, as well as graphene, is presented. We derive a universal value of—average—phonon shift rate with axial stress of around −5ω0−1 (cm−1 MPa−1), where ω0 is the G peak position at zero stress for both graphene and carbon fibre with annular morphology. The use of this for stress measurements in a variety of applications is discussed.Carbon fibres (CF) represent a significant volume fraction of modern structural airframes. Embedded into polymer matrices, they provide significant strength and stiffness gains over unit weight as compared to other competing structural materials. Nevertheless, no conclusive structural model yet exists to account for their extraordinary properties. In particular, polyacrynonitrile (PAN) derived CF are known to be fully turbostratic: the graphene layers are slipped sideways relative to each other, which leads to an inter-graphene distance much greater than graphite. Here, we demonstrate that CF derive their mechanical properties from those of graphene itself. By monitoring the Raman G peak shift with strain for both CF and graphene, we develop a universal master plot relating the G peak strain sensitivity of all types of CF to graphene over a wide range of tensile moduli. A universal value ofaverageshift rate with axial stress of 1 1 1 0 ~ 5 (cm MPa ) ω − − − − is calculated for both graphene and all CF exhibiting annular (“onion-skin”) morphology.

Interfacial studies on model composites by laser Raman spectroscopy

Abstract A new technique for the determination of fibre strain in composites has been developed over the years. The strain-sensitive property of high-performance fibres is a vibrational frequency which can be measured by laser Raman spectroscopy (LRS). The application of this technique for performing interfacial studies on model short- and long-fibre composites will be reviewed in this paper. By subjecting these composites to various degrees of mechanical deformation a number of parameters, such as the transfer length, the stress transfer efficiency and the initiation of fibre debonding or matrix yielding, can be assessed. Finally, by simply balancing the tensile and the shear forces acting along the interface, the interfacial shear stress distribution at each level of applied load can be obtained.

The study of model polydiacetylene/epoxy composites: Part 1 The axial strain in the fibre

A mode composite system consisting of one polydiacetylene single crystal fibre in an epoxy resin matrix has been subjected to tensile strain parallel to the fibre direction. The strain at all points along the length of the fibre was determined by resonance Raman spectroscopy while that of the matrix was measured by conventional techniques. Comparison of the fibre and matrix strain showed two distinct regions. Below about 0.5% matrix strain the composite followed Reuss-type behaviour with equal stress in the fibre and the matrix. At higher matrix strain the composite followed Voigt-type behaviour with any increase in matrix strain matched by an equal increase in fibre strain. In this region the strain distribution along the length of the fibre could be approximately described by the shear-lag model of Cox. The critical length of the fibre was found to increase linearly with fibre diameter as predicted by that model. Good qualitative agreement was found with the predictions of a calculation based on finite element analysis over the full range of applied stress.

Interfacial Shear Stress Distribution in Model Composites Part 2: Fragmentation Studies on Carbon Fibre/Epoxy Systems

The micromechanics of reinforcement of a model composite system con sisting of a continuous high-modulus (HM) carbon fibre embedded in an epoxy resin have been investigated. The composite was subjected to incremental tensile loading up to full fibre fragmentation, while the strain in the fibre was monitored at each level of load using a laser Raman spectroscopic (LRS) technique. The average strain in the fibre increased linearly with applied matrix strain up to a value of 0.8 %, when the first fibre fracture oc curred. After fracture, the strain in the fibre was found to build from the tips of the fibre breaks, reaching a maximum value in the middle of each fragment. The shape of the load transfer profiles at the locality of the fibre tips indicated that the stress transfer efficiency had been affected by the fracture process. The length of interfacial debonding at the point of fibre fracture was found to be driven by the strain energy of the fractured fragments. The interfacial shear stress (ISS) distributions at various levels of applied load along in dividual fragments, have been derived from the load transfer profiles using a balance of forces analysis. The shape of the ISS profiles confirmed that interfacial debonding initiated from the tips of the fibre breaks, whereas good fibre/matrix adhesion was retained around the mid-length of each fragment. By increasing the applied strain to 1.8%, the maximum ISS values also increased in spite of the presence of debonding at the fibre tips. An upper ISS limit of 42 MPa was calculated at this point. Further increases of the applied strain to 5% resulted in significant reductions in the values of the maximum ISS, as well as an in crease, of the frictional slip towards the middle of each fragment. Finally, by employing the assumptions of the conventional fragmentation test, the calculated value of the nominal interfacial shear strength at the point of full fragmentation was lower by a factor of 2 than the value measured by the LRS method.

Effect of fibre sizing on the stress transfer efficiency in carbon/epoxy model composites

The micromechanics of reinforcement of a model composite consisting of continuous high-modulus fibre embedded in epoxy resin has been investigated as a function of fibre sizing. The composite was subjected to incremental tensile loading up to full fragmentation, while the stress in the fibre was monitored at each level of applied strain with the new technique of remote laser Raman microscopy. The two systems exhibited differences in the residual stress field with the unsized fibre being in compression. The average stress in the fibre increased linearly with applied matrix strain up to first fracture. After fracture, the stress in the fibre was found to build from the tips of the fibre breaks, reaching a maximum value at the middle of each fragment. The shape of the stress transfer profiles indicated minor differences between the two systems at moderate strains. At high strains, the stress transfer profiles of the two systems were distinctly different possibly owing to the presence of two different interfacial failure modes in the two types of model composites. The maximum interfacial shear stress for both systems was of the order of 40 MPa with the sized system exhibiting slightly better adhesion. SEM examination of the fracture surfaces revealed clear interfacial failure for the unsized system whereas the sized system indicated areas of good adhesion.

Characterization of PAN-based carbon fibres with laser Raman spectroscopy

Laser Raman spectroscopy (LRS) has been employed to characterize the structure and morphology of a series of carbon fibres, to assess the combined effects of ultimate firing temperature (UFT) and pre-graphitization drawing during manufacture and, finally, to investigate the influence of oxidative treatment upon the integrity of the fibre surface. Ten types of PAN-based carbon fibres of varying modulus, diameter and manufacturing method, were examined. All their spectral features were recorded and analysed in terms of position, bandwidth and band intensity. Low-modulus fibres, produced at low graphitization temperatures, exhibit weak and broad Raman bands in the 1200–1700 cm−1 frequency region. With the increase of the firing temperature, the spectral features sharpen and new lines appear at higher frequencies. The observed changes in the Raman spectra are discussed in detail and related to alterations in the conditions of manufacture.