This master thesis report evaluatesthe lubricating effect of graphene (G)and graphene oxide (GO). Thesematerials have been added, in particlecondition, in Ag-based slidingcontacts and lubricating greases. Thework focuses on the tribologicalevaluation of these materials,especially friction, wear and contactresistance analyses. The friction andwear behaviors of Ag-based contactscontaining of a wide concentrationrange of graphene and graphene oxideare tested against pure silver using atest load of 2 and 10 N at a constantspeed of 5 cm/s. It was revealed thatsmall amounts of G and GO are able tosignificantly reduce the frictioncoefficient and wear rate. Contactresistance measurements revealed thatresults similar to pure Ag can beachieved with G content up to 10vol%.Possible mechanisms, which maycontribute to this tribologicalbehavior are the Ag-C interactions andthe lubricating nature of graphene.Friction tests with G and GOcontaining lubricating greases showinconsistent results, and both greasesand corresponding test methods forevaluation require furtheroptimization. The overall, promising,tribological behavior of G and GOholds for the implementation invarious industrial applications. Thereis no doubt that these kinds ofmaterials can play an important rolein ABBs future work. This masterthesis report shows yet anotherapplication area for theseextraordinary materials.

Nanomaterials have been studied extensively in the last decade in the context of many applications such as polymer composites, energy harvesting systems, sensors, ‘transparent’-like materials, field-effect transistors (FETs), spintronic devices, gas sensors and biomedical applications. Graphene, a recently discovered two-dimensional form of carbon has captured the interest of material scientists, and physicists alike due to its excellent electrical, mechanical and thermal properties. Graphene has also kindled a tremendous interest among chemists and cell biologists to create cellular-electronic interface in the context of bio-electronic devices as it can enable fabricating devices with enhanced potential as compared to conventional bio-electronics. Graphene’s unique electronic properties and sizes comparable with biological structures involved in cellular communication makes it a promising nanostructure for establishing active interfaces with biological systems. In the recent past Field effect transistors (FETs) have been successfully fabricated using carbon nanotubes (CNTs) and nanowires (NWs) and electrical characterization of these FETs were done by interfacing them with various cell cultures, tissues and muscle cells. In these cases, exceptionally high surface area to thickness ratio of FETs provides high percentage of collectible signals and the cells that are used for the study are typically placed on the FET. In this thesis, we examine a different approach towards forming bio-electronic interfaces by covering the graphene oxide (reduced) sheets on the yeast cells. Graphene oxide and reduced graphene oxide sheets as two-dimensional electronic materials have very high charge carrier mobility, extremely high surface area to thickness ratio, mechanical modulus and elasticity. We report the synthesis of graphene oxide using wet chemistry method, reduction of graphene oxide using different reducing agents and electrical characterization of graphene oxide’s conductivity. Micro-meter sized graphene sheets are used to encapsulate the yeast cells with the aid of calcium and gold nanoparticle chains. We also demonstrate that graphene sheets form electrically conductive layers on the yeast cells and developing an electromechanical coupling with the cell. The mechanical and electrical characteristics of graphene sheets are highly dependent on the cell volume and structure which are in turn related to the environment around the cell. Furthermore, using the same principle of electromechanical coupling we study the dynamics of cell surface stresses and cell volume modification, which are of importance in processes such as cell growth, division, and response to physiological factors such as osmotic stresses.

Since its isolation in 2004, the research landscape around graphene and other 2D materials has expanded rapidly and now encompasses fields as diverse as electronic engineering and drug delivery. For biomedical applications, one of the most desirable properties of the graphene family of nanomaterials (GFNs) is their 2D geometry; the high surface area to volume ratio that is characteristic of nanomaterials is taken to its extreme in a material that can be viewed as being entirely surface. This particular property alongside the versatility with which they may be functionalised both makes GFNs well positioned to function as the foundation of highly tailored and multifunctional therapeutics platforms. In this project, two GFN types, namely pristine graphene and graphene oxide, were prepared to form suspensions suitable for application to therapeutics delivery. Firstly, experiments using four essential amino acids with pristine graphitic material were undertaken to assess whether graphene flakes could be suitably exfoliated and suspended using sonication in the presence of aqueous solutions of these biocompatible molecules. A positive correlation was found between the hydrophobicity of the amino acid and the presence of one or more aromatic rings in the amino acid, and the efficacy of exfoliation both in terms of concentration achieved in suspension and flake thinness. However, the system itself was found to be highly complex, both with regards to the sonication used to exfoliate the graphitic flakes, and the interactions between the amino acids and the flakes. These considerations limited the wider applicability of this form of graphene preparation for therapeutics delivery applications. Secondly, work was performed on graphene oxide (GO), a GFN far more studied in the literature, but notoriously heterogeneous. Therefore much of the work completed focused on its characterisation. A combination of established and novel fluorescence-based characterisation methods were used to fully characterise three preparations of GO, before preliminary experiments were undertaken to test their interactions with cell components. The work showed that the inherent fluorescence of GO can be exploited to improve suspension characterisation; raster image correlation spectroscopy (RICS) was used to measure the apparent hydrodynamic radii of the flakes and flow cytometry was used to provide insight into the interactions between GO flakes and serum components. Preliminary cellular experiments confirmed that flow cytometry could be also employed to assess particular graphene characteristics in the context of cell culture, demonstrating the relatively low toxicity of PEGylated GO compared to unfunctionalised GO. Finally, as the therapeutics target for this project was leukaemia, a targeting ligand was designed and synthesised that could bind to CXCR4 - a receptor that is overexpressed on CLL B-cells, as well as many other cancer types. The ligand was synthesised such that it could easily be attached to GO, however its molecular structure is flexible enough that it can be attached to a number of different therapeutics materials. It was confirmed using both competition and functional assays that the molecule was antagonistic, and was able to deliver a conjugated fluorescent molecule specifically to the CXCR4 receptors on primary CLL B-cells. The work presented in this thesis illustrates the complexity that affects the use of GFNs in biomedicine, but also confirms the potential for their future development. The field is still young, and therapeutics delivery is likely to benefit from advances in the preparation of pristine graphene, and from methods to minimise the heterogeneity of GO. These steps will support a route towards clinical application. In addition, as the field of 2D materials expands, other materials with enviable surface area to volume ratios may come to the fore. Furthermore, this thesis has shown the value of exploring novel approaches to the characterisation of GFNs, and has identified approaches that may be exploited to improve applications of GFNs in biomedicine. Additionally, the aim of using GFNs as a platform for a multifunctional therapeutics delivery vehicle was developed with regards to the attractive CXCL12/CXCR4 axis, which is relevant in a large number of disease states including over 20 cancers, by demonstrating a flexible targeting ligand that could be used to exploit the CXCR4 receptor as a drug delivery target.

>Magister Scientiae - MSc / Supercapacitors are one of the important subjects concerning energy storage which has proven to be a challenge in this country. Currently, the electrodes of most commercial supercapacitor are made of carbon which is known to be inexpensive and has high resistance to corrosion. These carbon based supercapacitors operate under EDLC. They offer fast charging/discharging rates and have the ability to sustain millions of cycles without degrading. With their high power densities, they bridge the gap between batteries which offer high energy densities but are slow in charging/discharging and conventional dielectric capacitors which are very fast but having very low energy densities. The objective of this work was to develop a high performance supercapacitor using polyanilino-graphene oxide intercalated with platinum group metal nanocomposites. Specific capacitance of each material was investigated with the objective of ascertaining the material that has the best capacitance. In this work, GO was functionalized with aniline and intercalated with Pt, Pd and Pd-Pt nanocomposites. The nanomaterials were characterized with FTIR, Ultravioletvisible (UV-visible) spectroscopy, high resolution scanning electron microscopy (HRSEM), high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray microanalysis (EDS) and X-ray diffraction (XRD) analysis. The composites were tested for possible application as supercapacitor materials using potentiostatic-galvanostatic constant current charge/discharge. The synthesized materials had good electronic, mechanical, optical, physical etc. properties as proven by the various characterization techniques but they proved not to be ideal for application as supercapacitor materials. The materials tested negative when tested for both anodic and cathodic materials therefore we can conclude that the materials are not good supercapacitor materials and therefore cannot be used in application as novel as supercapacitors.

The control of environmental pollution, particularly in wastewater treatment, is one of the major concerns of the 21st century. Among the currently available pollution control technologies, photocatalysis is one of the most promising and efficient approaches to the reduction of pollutants. Graphene, a carbon nanomaterial with specific physical and chemical properties, has been reported as a promising potential new catalyst material in this field. A Bi2WO6 photocatalyst modified with graphene oxide was synthesized in a two-step hydrothermal process. Compared with pure Bi2WO6, the modified photocatalyst with 1.2 wt% graphene oxide improved photoactivity during the degradation of rhodamine-B (RhB) dye pollutant, by facilitating the dissociation of photogenerated excitons, which in turn results in more O2- radicals. XRD characterization showed that the modification of Bi2WO6 with graphene oxide does not affect its structure or morphology. The adsorption properties of graphene also contribute to the improvement of photoactivity. Other parameters such as catalyst dosage, temperature and solution pH are studied, with the aim to improve the efficiency of RhB removal.

The lithium-ion battery is the most preferred choice for energy storage, for example, in electric vehicle batteries and electronic devices. These commonly utilized transition metal-based cathodes and graphite anodes. However, replacing the active materials with organic, redox-active materials is of great interest since these organic batteries are excelling in charging speed and cycling stability. Therefore, in the present thesis, the synthesis and characterization of potential organic electroactive materials, mainly polymers, are investigated. Concerning the structure of the polymers, linear polymers, three-dimensional / crosslinked polymers, as well as dendrimers, were chosen. The electroactive subunits include viologen, imide, triphenylamine, porphyrin, and ferrocene, either as homopolymer or copolymer, as well as active materials like graphene oxide (GO) or electrolytes. The characterization of the structures was performed by means of NMR, FTIR spectroscopy, and elemental analysis. The electrochemical properties of products were investigated by the cyclic voltammetry (CV) technique. Electrodes were prepared by drop-casting a solution of the polymers onto a current collector, and the (dis)charge performance was investigated. To enhance the conductivity of the layers, composites of the polymers with GO were prepared. Since the performance depends on the electrolyte composition, different types of solvents and salts were used and compared. The capacities in a thin film of pure polymers and dendrimers were much smaller than in the composite film with rGO. These performances are based on the molecular self-assembly of polymers and dendrimers on individual GO sheets yielding colloidal polymer/dendrimer@GO and efficient GO/rGO transformation electrocatalyzed by polymers and dendrimers. However, the stability and capacity of some polymers and dendrimers such as P2, P5, P6 and G2 were not optimal in this type of composite film. Moreover, the peak potential in the positive charge range assigned to the nitrogen centre of triphenylamine and porphyrin was found to decrease after the first scan, which is probably due to a dissolution of the film. Therefore different methods were used to composite polymer or dendrimer with GO such as reducing GO before mixing. As noticed that the redox behaviour of amine and ferrocene are reversible, but the stability of radical cation species is not stable in organic solvent after oxidation. Besides the preparation of electrodes by drop-casting, the layer-by-layer process was used by alternate dipping between cationic polymer solution and anionic GO or Poly(sodium p-styerenesulfonate) (PSS) solution. PSS acts as a counter ion for the polymer, which changes the moving species in the electrolyte from anion to cation. As noted that a large cation (TBA+) shows lower capacity compared to small cations (Li+, K+). Apart from the CV, quartz crystal microbalance (QCM) was used to monitor layer growth.

Graphene Oxide (GO) has emerged within the last decade as a next generation material for water treatment. Fabrication of graphene oxide membranes has been limited in scale and application due to repulsive hydration forces causing GO layers to electrostatically separate. In this study, chitosan is utilized to increase GO stability in the wet state through interactions with the negatively charged GO sheets (CSGO). This simple aqueous self-assembly allows scalable fabrication and enhanced stability for membrane applications in crosslow. The CSGO membrane’s performance was tested in a crosslow reactor and challenged with methylene blue at concentrations ranging from 1 to 100 ppm at 345 kPa with fluxes ranging from 1 to 4.5 L/(m2 hr) with 100% removal by physical rejection. This work demonstrates that the CSGO composite matrix is a potential alternative to traditional polymeric membranes for water treatment using a renewable biopolymer and minimal chemical input.

No description available.

The development of a new class of alternative plastics has been encouraged in the past few years due to the serious environmental issues, such as toxicity and carbon dioxide emissions. Hence, the introduction of renewable, biodegradable, and biocompatible materials is becoming critical as substituents of conventional synthetic plastics. To design a new system of novel TEMPO-oxidized cellulose nanofibrils (TOCNs)/graphene oxide (GO) composite, the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation was utilized to disintegrate never-dried wood nanofibrillated cellulose (NFC). GO was incorporated through high intensity homogenization and ultrasonication with varying degree of oxidation (0.5X, 1X, and 2X) of NFC and GO percent loadings: 0.4, 1.2, and 2.0wt %. As a result, despite the presence of carboxylate groups and graphene oxide (GO), X-ray diffraction (XRD) test showed the crystallinity of the bio-nanocomposite was not altered. Scanning electron microscopy (SEM) was used to characterize their morphologies. In addition, the thermal stability of TOCN/GO composite decreased upon oxidation level, and dynamic mechanical analysis (DMA) signified strong intermolecular interactions with the improvement in Young's storage modulus, and tensile strength. Fourier transform infrared spectroscopy (FTIR) was employed to see the hydrogen bonds between GO and cellulosic polymer matrix. The oxygen transmission rate (OTR) of TOCN/GO composite decreased. The water vapor permeability (WVP) was not significantly affected by the reinforcement with GO, but the moderate oxidation enhanced the barrier properties. Ultimately, the newly fabricated TOCN/GO composite can be utilized in a wide range of life science applications, such as food and medical industries. / Master of Science / In recent years, petroleum-based polyolefins have been contributing to severe environmental issues. With this in perspective, the development of a new class of alternative plastics has been encouraged. Hence, the introduction of renewable, biodegradable, and biocompatible materials is becoming critical as a substitute for non-degradable synthetic plastics. In this study, a new system of novel cellulose-based plastic composites was designed by incorporating carbon nanofillers at various percent loadings and different degree of surface modification of the plastics. These treatments are the economical way to achieve the targeted properties for industrial applications, exhibiting the obvious improvement in tensile strength due to the strong interaction between nanofillers and cellulose. In addition, water vapor and oxygen barrier properties play significant roles in food packaging since food decay is vulnerable to these two factors. The barrier performance was enhanced by hindering the permeation of oxygen gases, whereas the water vapor permeability was not significantly affected by the reinforcement with carbon nanofillers. Ultimately, the newly fabricated cellulose plastic can be utilized in various applications, especially, such as the pharmaceutical and biomedical areas, packaging for food and goods, and agriculture due to their high availability, sustainability, and biodegradability.

The solid acid catalyst of the Keggin-type 12-tungstophosphoric acid (H3PW12O40, HPW) is supported on partially reduced graphene oxide (PRGO) nanosheets for acid-catalyzed reactions. HPW is a new class of catalyst with a good thermal stability and high Bronsted acidity in order to replace common mineral acids. However, it has low specific surface area (1-5 m2/g). Therefore, the possibility of PRGO as a catalytic support for HPW is investigated due to its high surface area (2630 m2/g) and good thermal stability. The synthesis of HPW-GO catalyst is prepared using microwave and laser irradiation without using any chemical reducing agents. The HPW-GO catalysts are characterized by Ultraviolet-visible spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FT-IR), Raman Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD) techniques, and Transmission Electron Microscopy (TEM). Also, the surface acidity is measured by a non-aqueous titration of n-butyl amine. Furthermore, the application for catalysts is tested by three acid-catalyzed reactions: Esterification, Friedel-Crafts acylation, and Pechmann condensation. The greatest acidity for the microwave irradiation method is with the loading of 85 wt% HPW-GO and 60wt% HPW-GO for laser irradiation. The results observed provide an excellent opportunity for PRGO as a catalytic support for HPW for acid-catalyzed reactions.