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The current reliance of modern society on fossil fuels, and in particular oil and gas, means that industry is forever searching for improved technologies to access and recover crude, from harder to reach and depleting reservoirs. A key innovation in the oil and gas industry is the unbonded flexible riser, a flexible pipeline designed to transfer high pressure crude mixtures from deep sea wells to floating platforms and ships. These risers consist of many concentric layers of barrier polymers, such as polyamide 11, and strengthening steel. Often, high partial pressures of 'sour' fluids, including CO2 and H2S, are found within the crude. Upon permeating through the polyamide 11 barrier layer, along with water, these sour fluids can corrode the steel armouring. Corrosion and subsequent weakening of the steel may lead the riser to fail and, in so doing, risks catastrophic ecological impact, economic challenges and threat to operator life. There is therefore a drive to improve the resistance of polyamide 11 to CO2 and H2S permeation. The impenetrable nature of graphene was used as a starting point for increasing the barrier properties of polyamide 11. This thesis reports the first instance of testing the barrier properties of graphene and its nanocomposites to supercritical fluids of any kind. CO2 and H2S permeability testing was carried out in the gas, liquid and supercritical states at gauge pressures from 2 to 400 bar. In situ polymerisations of the polyamide 11 monomer with graphene nanoplatelets and graphene oxide led to promising materials for improving the barrier properties of the polyamide. Industrially relevant twin-screw extrusion was used to incorporate graphene related materials directly into the polyamide matrix. Extensive voiding limited the efficacy of such materials in CO2 and H2S barrier applications. Chemical vapour deposition was used to synthesise large area graphene that was applied to the polyamide surface. Unavoidable tearing of the graphene led to a porous layer, which allowed unaffected transport of CO2 and H2S through the polyamide. Finally, by laminating a multi-layered graphene paper between two layers of polyamide 11, extraordinary barrier performance was achieved. Compared to pure polyamide, the graphene paper laminates provided up to an order of magnitude reduction in CO2 permeation, and reduced H2S permeation to undetectable levels, even at gauge pressures of up to 400 bar.

This thesis reports research activity on suspended graphene membranes. Scientific results in the form of peer-reviewed publications are presented, along with supporting information to provide context, detailed experimental procedures, and recommendations of future work. The four papers cover a wide variety of topics, but are linked by common experimental sample fabrication techniques. Understanding the mechanical properties of suspended graphene membranes is crucial to the development of graphene nano-electromechanical devices. In the first presented paper, PeakForce QNM (quantitative nanomechanical mapping) atomic force microscopy imaging was used to rapidly map the nanomechanical properties of a range of suspended graphene membranes. The force-displacement behaviour of monolayer graphene extracted from the peak force imaging map was found to be comparable to that taken using standard nanoindentation. By fitting to a simple elastic model, the two-dimensional elastic modulus was measured at around 350Nm-1, corresponding to a Young's modulus of around 1 TPa. The second paper examines the near-IR light-matter interaction for graphene integrated cavity ring resonators based on silicon-on-insulator (SOI) racetrack waveguides. Fitting of the cavity resonances from the predicted transmission spectra reveal the real part of the effective refractive index for graphene, neff = 2.23 ± 0.02 and linear absorption coefficient, alphagTE = 0.11 ±0.01dB micro metre-1. The evanescent nature of the guided mode coupling to graphene at resonance depends strongly on the height of the graphene above the cavity, which places limits on the cavity length for optical sensing applications. Twisted-bilayer graphene (tBLG) exhibits van Hove singularities in the density of states that can be tuned by changing the twisting angle θ. In the third paper, θ-defined tBLG was produced and characterized using optical reflectivity and resonance Raman scattering. This represents the first reported fabrication of a rationally designed (twist engineered) tBLG structure. The θ-engineered optical response is shown to be consistent with persistent saddlepoint excitons. Separate resonances with Stokes and anti-Stokes Raman scattering components can be achieved due to the sharpness of the two-dimensional saddle-point excitons, similar to what has been previously observed for one-dimensional carbon nanotubes. The excitation power dependence for the Stokes and anti-Stokes emissions indicate that the two processes are correlated and that they share the same phonon. Nano-patterned and suspended graphene membranes find applications in electronic devices, filtration and nano-pore DNA sequencing. However, the fabrication of suspended graphene structures with nanoscale features is challenging. In the fourth and final paper, the direct patterning of suspended membranes consisting of a graphene layer on top of a thin layer of hexagonal boron nitride which acts as a mechanical support is demonstrated for the first time, using a highly focused electron beam to fabricate structures with extremely high resolution within the scanning transmission electron microscope. The boron nitride support enables the fabrication of stable graphene geometries which would otherwise be unachievable, by preventing intrinsic strain in graphene membranes from distorting the patterned features after areas are mechanically separated. Line cuts with widths below 2 nm are reported. It is also demonstrated that the cutting can be monitored in-situ utilising electron energy loss spectroscopy (EELS).

Since 2004, graphene attracts intensive attention from scientists and engineers all over the world. During the last decades, the research relates to graphene and other 2 dimensional (2D) materials are rapidly increasing. Approximately, ten thousand journal papers have been published after the discovery of graphene in relative topics widely spread. On the other hand, the simple graphene properties research is nearly completed. Researchers turn their attention to other 2D materials or Van der Waals heterostructures. By increasing the liberty and knowledge of 2D materials, the Van der Waals heterostructures can start to build something on this 2D wander land. In this thesis the Van der Waals heterostructures is based on graphene and some other well known 2D materials such as hexagonal boron nitride (hBN) to study fundamental physics and possible applications in near future. In this thesis, three published papers which are related to Van der Waals heterostructures have been included. The electronic properties of encapsulated graphene on different 2D crystals have been investigated by the capacitance spectroscopy. Several 2D crystals have been tested as a substrate such as MoS2, WS2, mica, LiNbO3…etc. The quality of encapsulated device is correlates the interface self-cleaning. Follow with the fundamental physics study employed by a simple Van der Waals heterostructure. Graphene and hBN is lattice aligned within 2 degrees in difference and creates a new superlattice structure which just like moire pattern happens while two similar patterns overlapped. The basic electronic properties do not vary at near Dirac point. Away from the first generation Dirac point, the superlattice structure affects the band structure in higher carrier concentration. In this paper, aligned graphene-hBN capacitors have been demonstrated to discover more fine details of these many-body interactions in this superlattice structure. The final part is related to twist controlled graphene-graphene resonance tunneling transistors. A Van der Waals heterostructure is constructed by two aligned graphene stripes with a thin layer of hBN as a spacer. The electrons are tunneled from one stripe to another graphene stripe while a bias voltage applied. The resonance tunneling is occurred when two graphene flakes are aligned at certain bias voltage. In this paper, we contribute the resonance tunneling to momentum conservation of tunnelling electrons. Theory simulation is highly agreed with our experiment results.

Intercalation of graphite with alkali metals has previously been shown to, in some cases, produce superconducting compounds from the two non-superconducting components. The use of graphene as a basis to continue this research offers new possibilities as confinement of intercalant species is reduced from bulk graphite. Papers comprised of exfoliated graphene flakes were doped with Li, Cs, K and Ca atoms via vapour transport methods in order to investigate superconducting properties. While Li, Cs and K-doping showed no signs of a superconducting transition as low as 1.8 K, observed through magnetic measurements, Ca-doped graphene became superconducting below 6.4 K – a lower transition temperature than Ca-doped graphite, TC = 11.5 K. The carrier concentration could also be changed using composite papers made from graphene and various proportions of insulating boron nitride flakes, allowing TC to be varied. Optical reflectivity spectra were used to determine the level of doping present in each compound, directly calculated from their estimated plasmon energy. Ca-doped graphene paper exhibited a 20% lower carrier concentration than Ca-intercalated graphite, offering an explanation for the lower value of TC. To allow insight into the partial doping of graphene papers, samples were exposed to air and monitored via dynamic x-ray diffraction techniques and optical analysis during degradation. With prolonged reaction in air, the carrier concentration was found to drop monotonically, while the interlayer separations contracted as intercalant species vacated the structure, leaving an arrangement of flakes similar to that of the initial, un-doped, graphene paper. The range of carrier concentrations observed suggests that doping of graphene flakes is non-discrete, thus implying tunable TC.

Graphene is the first 2D material consisting of carbon atoms densely packed into planar structures. Graphene oxide (GO) is the intermediate derivative of chemically-produced graphene, which retains 2D basal plane structures but is also decorated with functional groups along the basal plane and edges. This functionality allows self-assembly of planar sheets into a paper-like material. However, formations of both intrinsic defects within the sheet structures as well as larger scale extrinsic defects in the paper are expected to significantly degrade mechanical performance. Strength provides the most direct evidence of defect related mechanical behaviour and is therefore targeted for understanding defect effects in GO paper. Such evaluations are crucial both from a technological perspective of realizing designed functions and from a fundamental interest in understanding structure-mechanics in 2D nanomaterials. A complete strategy of performing mechanical testing at different length scales is thus reported to provide a comprehensive description of GO strength. Both conventional larger scale mechanical testing as well as novel smaller length scale evaluations, using in situ atomic force microscopy (AFM) combined with scanning electron microscopy (SEM) and optical microscopy as well as structural probing using synchrotron FT-IR microspectroscopy, were applied to GO materials. Results showed that large structural defects determined mechanical properties of GO papers due to stress concentration effects whereas smaller scale intrinsic effects were defined by interfacial defects and stress concentrations within sheets. Synchrotron FT-IR microspectroscopy provided molecular deformation mechanisms in GO paper, which highlighted the interaction between in-plane C=C and cross-linking C=O bonds. A comprehensive description of macroscopic GO paper using evaluations of strength at the range of length scales studied was attempted, with a good correlation between predictions and experimental observations. This thesis therefore provides a hierarchical understanding of the defects impact on the strength of graphene-based materials from the macroscale to the nanoscale.

Graphene Oxide (GO) is one of the main candidates for the industrial production of graphene-derived materials. Thanks to the oxygen functional groups introduced during its synthesis from Graphite, it is readily processable in polar solvents (among which water stands out for its abundancy and eco-friendliness), while maintaining some of the characteristics attributed to the peculiar hexagonal structure of pristine Graphene. A deep understanding of the chemicophysical properties of graphene-derived materials, and the way those are influenced by the various steps of their fabrication process, is therefore the key to fully exploit such materials in advanced engineering applications. The initial part of this thesis is therefore focused on the background of GO derived materials, from processing methods to characterisation techniques. Two different applications are then approached: light and compact porous absorbers and supercapacitors with active binder. In both the cases GO allows the development of environmentally friendly and scalable fabrication processes, matching with the current transition toward a greener more sustainable industry. More specifically, an ultralight aerogel obtained from a blend of GO and polyvinyl alcohol is proposed as a novel class of acoustic materials with tuneable and broadband sound absorption and sound transmission losses. The same material is then chemically modified to develop multifunctional properties, satisfying the advanced requirements of automotive and aerospace industries. On the other hand, this research work shows also how GO can actively contribute to the electrochemical performance of supercapacitors: as a stand-alone active binder in a first instance and then in a hybrid gel with Starch, a biopolymer processable in water, for a fabrication procedure immediately transferrable to the industry. Additionally, both the approaches share the adoption of a conductive carbon paper derived from the thermal treatment of GO as current collector, for the fabrication of "all-graphene based" devices.

Graphene-based materials (GBM) have recently generated great interest due to their unique two-dimensional (2D) carbon geometry, which confers exceptional physicochemical properties that hold great promise in many fields, including biomedicine. An understanding of how these novel 2D materials interact with the biological milieu is therefore fundamental for their development and use. Graphene oxide (GO) has been proven more biologically friendly than the highly hydrophobic pristine graphene. Therefore, the main aim of this study was to prepare well-characterised GO derivatives and test the hypothesis of their possible use for biomedical applications. GO was prepared reproducibly by a modified Hummers' method and further functionalised by using a radio-metal chelating agent, namely 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) to form GO-DOTA. The constructs were extensively studied using structural, optical and surface characterisation techniques. GO prepared from different forms of graphite demonstrated differences mainly in structure and production yields. However, all GO constructs were found biocompatible, with the mammalian cell cultures tested; furthermore, the biocompatibility of GO prepared as papers was retained when they were used as substrates for cell growth. Radiolabelling of GO-DOTA was further carried out to yield highly stable radio-labelled constructs, both in vitro and in vivo. These constructs were used for in vivo whole-body imaging and biodistribution studies in mice after intravenous administration. Extensive urinary excretion and accumulation mainly in the reticuloendothelial system (RES), including the spleen, liver and lungs, was the main fate of all the GO derivatives used in this thesis. The physicochemical characteristics were determined to play a central role for their preferential fate and accumulation. While the thicker sheets tended to accumulate mainly in the RES, the thinner ones were mostly excreted via the kidneys. Finally, it was crucial to perform safety investigations involving the structure and function of organs at high risk of injury (mainly the kidney and spleen). Our results revealed that no severe structural damage or histopathologic or functional abnormality of these vital organs. However, some preliminary inflammatory responses were detected that require further investigation. In summary, this study helped gain a better understanding of how thin 2D materials interact with biological barriers and the results indicate that these materials could be potential candidates for biological applications. Nevertheless, further investigations are necessary to confirm our findings.

There were three main driving forces behind this thesis: global concern over climate change mainly due to uncontrolled carbon dioxide (CO2) emissions, the excitement over the discovery of graphene and its versatile potential, and the potential to design three-dimensional (3D) or two-dimensional (2D) structures, in our case using unique triptycene molecule. We examined two polymeric materials for CO2 adsorption and suggested simple design of disordered carbons suitable for gas adsorption studies. The approach in each task was to examine structural and adsorption properties of materials using detailed atomistic modelling employing Monte Carlo and Molecular Dynamics techniques and where possible provide experimental measurements to validate the simulations. The thesis is presented as a collection of papers and the work can be divided into three independent projects. The aim of the first project is to utilize graphene as an additive in polymer composites in order to increase separation between the polymer chains increasing available surface area. The matrix used is a polymer of intrinsic microporosity (PIM-1), which possess large surface area and narrow nano-sized ( > 2nm) pore distribution attractive for gas separation membrane applications. Adding a filler can reduce aging of the polymer, and enhance permeability across the membrane, often to the expense of loosing selectivity. Therefore, we investigated the packing of PIM-1 chains in presence of discrete 2D graphene platelets and 3D graphene-derived structures and its effect on composite structure and adsorption properties. We found that additives do not alter structural polymer properties at the molecular level preserving the same adsorption capacity and affinity. Potential permeability increase would benefit from the retention of selectivity in the material. Building on design philosophy of materials with intrinsic microporosity we continued further investigation of 3D graphene-derived structures. The idea is that highly concave molecules or polymer chains pack inefficiently creating microporous materials with sufficient surface area for gas adsorption. 3D propeller-like structures were derived from graphene arms connected through the rigid triptycene and other types of cores. The resulting structures created a large amount of micropores and showed similar CO2/CH4 selectivity to activated carbons reported in the literature. It was shown that rigid triptycene core leads to more open structures. The model was also applied to model commercially available activated carbon to predict n- perfluorohexane adsorption. The fitting to experimental structural information proved to be challenging due to trial and error nature of the approach. Nevertheless, the simple packing procedure and diverse structure design have a great potential to serve as a virtual model for porous carbons that possess pore complexity and does not require any previous experimental data to be build on. The last project concerns CO2 adsorption and selectivity over CH4 and N2 in recently reported triptycene-based polymer. The triptycene shape polymer can form a porous 2D network that can be exfoliated into free-standing sheets and potentially used as a membrane. Sheets stack in the bulk material forming anisotropic channel pores. Additionally it contains fluoro- functional groups, which are known to have a high CO2 affinity. We explored pore structure and chemistry of stacked material for gas adsorption and predicted comparable capacity and CO2 selectivity to other microporous covalent materials such as activated carbons and PIMs. The CH4/N2 selectivity was similar to currently most selective material belonging to MOF family. We showed that fluoro-group have a positive effect on CO2 affinity, however predictions are sensitive to the charges of fluorine atoms assigned by different methods.