Nanoparticles, i.e. particles with at least one dimension smaller than 100 nm, are present in large quantities in ambient air and can also be found in an increasing amount of consumer products. It is known that many nanomaterials have physicochemical properties that differ from physicochemical properties of the same material in bulk size. It is therefore important to characterize nanoparticles and to evaluate their toxicity. To understand mechanisms behind nanotoxicity, it is important to study the uptake of nanoparticles, and how they are accumulated. For these purposes model studies of cellular uptake are useful. In this thesis metal oxide and carbon-based nanoparticles have been studied in living cells using Raman spectroscopy. Raman spectroscopy is a method that facilitates a non-destructive analysis without using any fluorescent labels, or any other specific sample preparation. It is possible to collect Raman images, i.e. images where each pixel corresponds to a Raman spectrum, and to use the spectral information to detect nanoparticles, and to identify organelles in cells. In this thesis the question whether or not nanoparticles can enter the cell nucleus of lung epithelial cells has been addressed using hyperspectral analysis. It is shown that titanium dioxide nanoparticles and iron oxide nanoparticles are taken up by cells, and also in the cell nucleus. In contrast, graphene oxide nanoparticles are mainly found attached on the outside of the cell membrane and very few nanoparticles are found in the cell, and none have been detected in the nucleus. It is concluded that graphene oxide nanoparticles are not cytotoxic. However, a comparison of Raman spectra of biomolecules in cells exposed to graphene oxide, unexposed cells and apoptotic cells, shows that the graphene oxide nanoparticles do affect lipid and protein structures. In this thesis, several multivariate data analysis methods have been used to analyze Raman spectra and Raman images. In addition, super-resolution algorithms, which originally have been developed to improve the resolution in photographic images, were optimized and applied to Raman images of cells exposed to submicron polystyrene particles in living cells.

The generation of new nanoscale fabrication techniques is both novel and necessary for the generation of new devices and new materials. Graphene, a heavily studied and versatile material, provides new avenues to generate these techniques. Graphene’s 2-dimensional form remains both robust and uncommonly manipulable. In this project we show that graphene can be combined with the yeast cell, Saccharomyces cerevisiae, arguably the most studied and utilized organism on the planet, to generate these new techniques and devices. Graphene oxide will be used to encapsulate yeast cells and we report on the development of a method to electrically read the behaviour of these yeast cells. The advantage of an encapsulation process for a cell sensor is the ability to create a system that can electrically show both changes in ion flow into and out of the cell and mechanical changes in the cell surface. Since the graphene sheets are mechanically linked to the surface of the cell, stresses imparted to the sheets by changes in the cell wall or cell size would also be detectable. The development process for the encapsulation will be refined to eradicate excess gold on the yeast cells as well as to minimize the amount of stray, unattached graphene in the samples. The graphene oxide encapsulation process will also be shown to generate a robust substrate for material synthesis. With regards to cell sensing applications, sources of noise will be examined and refinements to the device setup and testing apparatus explored in order to magnify the relevant electrical signal. The spherical topography of an encapsulated yeast cell will be shown to be an advantageous substrate for material growth. Zinc oxide, as a sample material being investigated for its own applications for photovoltaics, will be grown on these substrates. The spherical nature of the encapsulated cell allows for radial material growth and a larger photo-active area resulting in a device with increased efficiency over a planar complement. The zinc oxide nanorods are grown via an electrochemical growth process which also reduces the graphene oxide sheets to electrochemically reduced graphene. XRD analysis confirms that the material synthesized is infact zinc oxide. The nanorods synthesized are 200nm to 400nm in width and 1µm in length. The increase efficiency of the non-planar device and the effectiveness of the encapsulated cell as a growth substrate indicate encapsulated cells as a research avenue with significant potential.

Thin films with the ability to impart oxygen and other types of gas barrier are crucial to commercial packaging applications. Commodity polymers, such as polyethylene (PE), polycarbonate (PC) and polyethylene terephthalate (PET), have insufficient barrier for goods requiring long shelf life. Current gas barrier technologies like plasma-enhanced vapor deposition (PECVD) often create high barrier metal oxide films, which are prone to cracking when flexed. Bulk composites composed of polymer and impermeable nanoparticles show improved barrier, but particle aggregation limits their practical utility for applications requiring high barrier and transparency. Layer-by-layer (LbL) assemblies allow polymers and nanoparticles to be mixed with high particle loadings, creating super gas barrier thin films on substrates normally exhibiting high gas permeability. Branched polyethylenimine (PEI) and poly (acrylic acid) (PAA) were deposited using LbL to create gas barrier films with varying pH combinations. Film thickness and mass fraction of each component was controlled by their combined charge. With lower charge density (PEI at pH 10 and PAA at pH 4), PEI/PAA assemblies exhibit the best oxygen barrier relative to other pH combinations. An 8 BL PEI/PAA film, with a thickness of 451 nm, has an oxygen permeability lower than 4.8 x 10^-21 cm^3 * cm/cm^2 * s * Pa, which is comparable to a 100 nm SiOx nanocoating. Crosslinking these films with glutaraldehyde (GA), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDC) or heating forms covalent bonds between PEI and/or PAA. Oxygen transmission rates (OTR) of 8 BL films crosslinked with 0.1M GA or 0.01M EDC show the best oxygen barrier at 100% RH. Graphene oxide (GO) sheets and PEI were deposited via LbL with varying GO concentration. The resulting thin films have an average bilayer thickness from 4.3 to 5.0 nm and a GO mass fraction from 88 to 91wt%. Transmission electron microscopy and atomic force microscopy images reveal a highly-oriented nanobrick wall structure. A 10 BL PEI/GO film that is 91 nm thick, made with a 0.2 wt% GO suspension, exhibits an oxygen permeability of 2.5 x 10^-20 cm^3 * cm/cm^2 * s * Pa. Finally, the influence of deposition time on thin film assembly was examined by depositing montmorillonite (MMT) or laponite (LAP) clays paired with PEI. Film growth and microstructure suggests that smaller aspect ratio LAP clay is more dip-time dependent than MMT and larger aspect ratio MMT has better oxygen barrier. A 30 BL PEI/MMT film made with 10 second dips in PEI has the same undetectable OTR as a film with 5 minute dips (with dips in MMT held at 5 minutes in both cases), indicating LbL gas barrier can be made more quickly than initially thought. These high barrier recipes, with simple and efficient processing conditions, are good candidates for a variety of packaging applications.

>Magister Scientiae - MSc / Pollution of water sources, aquifers and wetland systems caused by industry, agriculture, and municipally treated wastewater is a worldwide problem that contributes to the scarcity of clean and potable water. Rivers, channels, lakes, oceans, and ground water are often contaminated by a variety of organic substances that can affect aquatic life and threaten human health. Organic compounds such as antibiotics that are not effectively removed by modern day water treatment technology are a growing threat to water quality and health. The emergence of antibiotics in the environment particularly aquatics have become a matter of concern as they may result in induction and spread of bacterial resistance which may be harmful to humans or animals. After administration, antibiotics for human use or their metabolites are excreted into the effluent and reach the sewage treatment plant (STP). Not all Antibiotics in sewage treatment plants are eliminated. Consequently they can pass through the sewage system and may end up in environmental and even potable water systems. Antibiotic residues have been reportedly found in places such as hospital wastewaters, wastewater treatment plants and surface waters all over the world with concentrations ranging from approximately 60-120000 ng/, 2-580 ng/L and 5-1300 ng/L respectively. The current methods that are used to detect antibiotics can be quite expensive and time consuming due to sample preparation (necessary for detection of very low concentrations of antibiotics in water) and technology used in the instruments. Electrochemical sensors and biosensors are simple systems, with high selectivity and sensitivity for individual measurements and cost effectiveness. The development of composites based on conductive phases dispersed in polymeric matrices has led to important advances in analytical electrochemistry. Polyamic acid and graphene oxide are both materials with well-defined electrochemistry and are easily processable in the design of various sensor formats. In this study we present a novel polyamic acid - graphene oxide (PAA/GO) electrode which was prepared for electrochemical screening of antibiotic residues in aqueous systems. Polyamic acid (PAA) and graphene oxide (GO) were successfully synthesized independently and characterized using SEM which was used to study the morphology of the PAA, FTIR spectroscopy to confirm chemical structures and functional groups as well as CV and SWV which were used to identify the unique electrochemical behavior of PAA and GO respectively. Polyamic acid-graphene oxide nanocomposite was prepared and characterized by CV, SWV, FTIR and SEM. The novel electrode (PAA/GO/SPCE) was prepared by electrochemically depositing PAA/GO (0.03 mg/mL) onto SPCE electrodes using 5 cycles between −1000 mV and 1000 mV at 50 mVs. The analytical performance of the electrochemical sensor towards detection of neomyxin and norlfoxacin was compared to standard Uv-vis spectroscopy method. The Uv-vis spectroscopy showed LOD of 1.61x10-5 M and 1.41x10-5 M for norfloxacin and neomycin respectively. The PAA/GO electrochemical sensor had a LOD of 3.37x10-7 M for norfloxacin and 1.066x10-6 M for neomycin. Sensitivity of the UV/vis method was comparable to electrochemical sensor sensitivity for neomycin and norfloxacin.

Magister Scientiae - MSc (Chemistry) / Pulmonary Tuberculosis (TB) a disease second to HIV/AIDS is a global health problem that arises in two states; as an active state and as a latent state. Diagnosis of active TB is tedious and requires expensive procedures since there is no recognizable method for the sole detection of active TB. The current diagnosis consists of chest X-rays and multiple sputum cultures used for acid-fast bacilli detection. The TB diagnosis of children is particularly difficult which further complicates the diagnosis. Thus, rapid identification of this pathogen is important for the treatment and control of this infection to allow effective and timely therapy. In an effort to solve this issue, this study reports the development of immunosensors constructed with electroactive layers of amino groups functionalized graphene oxide (GO) doped respectively with green synthesized zinc oxide (ZnO NPs) nanoparticles and silver (Ag NPs) nanoparticles on glassy carbon electrodes. The surface morphology of GO, ZnO NPs, Ag NPs and their composites was revealed by employing High-Resolution Transmission Electron Microscopy (HR-TEM) and High-Resolution Scanning Electron Microscopy (HR-SEM) while the composition and structure of these materials were studied using Fourier Transform Infra-Red Spectroscopy (FTIR). The resultant graphene oxide-metallic composites were covalently attached with CFP-10 and/or ESAT-6 antibodies to achieve the electrochemical detection. The immunosensor was then used for the impedimetric and amperometric detection of anti-CFP-10 and/or anti-ESAT-6 antigens in standard solutions.

O aumento das preocupações com o meio ambiente tem trazido à indústria de tratamento de superfícies novos desafios quanto ao desenvolvimento de revestimentos com maior desempenho quanto à resistência à corrosão e ao desgaste, observando a redução do impacto ambiental. Neste contexto, o objetivo do presente trabalho é obter um filme compósito à base de silano com incorporação de partículas de óxido de grafeno visando o aumento da resistência à corrosão e ao desgaste da liga de alumínio AA 2024-T3. A liga de alumínio AA 2024-T3 é um material bastante usado na indústria aeronáutica devido às propriedades mecânicas e à baixa densidade. Contudo, essa liga não oferece a resistência à corrosão e ao desgaste exigidos para aplicação na indústria aeronáutica, sendo necessário o emprego de revestimentos protetores. Dentre os revestimentos propostos para essa aplicação os revestimentos híbridos têm sido estudados, e mais recentemente a incorporação de partículas à essa matriz tem sido proposta visando melhorar as propriedades desses filmes. Nesse trabalho os revestimentos compósitos de matriz híbrida com incorporação de óxido de grafeno foram obtidos pelo processo de sol-gel a partir de um sol contendo os precursores alcoóxidos tetraetoxisilano (TEOS) e 3-trimetoxisilil-propil-metacrilato (MAP) com dispersão de partículas de óxido de grafeno em diferentes concentrações (1 g.L-1, 0,5 g.L-1, 0,25 g.L-1 e 0 g.L-1). Os filmes foram obtidos empregando-se o método de dip-coating à temperatura ambiente, com velocidade de retirada de 10 cm.min-1. O óxido de grafeno utilizado foi caracterizado quanto à estrutura utilizando as análises de FTIR, Raman, TGA e microscopia eletrônica de varredura de alta resolução. Para avaliar a estrutura do filme compósito obtido foram utilizadas as análises de FTIR, Raman e TGA. Microscopia eletrônica de varredura de alta resolução foi usada a fim de verificar a uniformidade do filme e avaliar a dispersão das partículas no filme. Os ensaios de polarização potenciodinâmica e impedância eletroquímica foram utilizados para analisar o comportamento referente à corrosão. Avaliou-se também a molhabilidade dos filmes, pelo método da gota séssil. As propriedades mecânicas do filme foram avaliadas empregando-se o ensaio de desgaste pela técnica de esfera sobre plano e teste de adesão. Nas condições estudas, a adição das partículas de óxido de grafeno não alterou a resistência à corrosão, contudo evidenciou-se uma contribuição positiva quanto ao aumento da resistência ao desgaste do filme. / The growing concern with the environment has created new challenges to the surface treatment industry, encouraging the development of coatings with a better performance in regards to the mechanical resistance and corrosion properties, observing the reduction of the environmental impact. In this context, this work aims to make a composite coating with graphene oxide charge to improve the corrosion and wear resistance in aluminum alloy AA 2024-T3. The aluminum alloy AA 2024-T3 is a material used in the aeronautics industry due to its low density and good mechanical proprieties. However, this alloy does not have the corrosion and wear resistance required by the aeronautics industry, requiring the use of protective coatings. Among the protective coatings proposed for this application, the hybrid films have been studied and more recently the incorporation of particles has been proposed to improve the proprieties of this film. In this work the hybrid matrix composite coating with incorporation of graphene oxide was obtained by sol-gel process from a sol containing alkoxide precursors Tetraetoxisilano (TEOS) and 3-(trimetoxisililpropil) metacrylate (MAP) with graphene oxide dispersion in different concentrations (1 g.L-1, 0,5 g.L-1, 0,25 g.L-1 e 0 g.L-1). The films were obtained using the dip-coating method in room temperature with 10 cm.min-1 of removal rate. For the characterization of the graphene oxide structure FTIR, Raman, TGA and scanning electron microscope were used. To measure the structure of composite films proprieties FTIR, Raman and TGA were used. In addition, the scanning electron microscope was used on composite film on aluminum alloy in order to verify the uniformity of film and to assess the behavior of the particles on film. The potentiodynamic polarization and the electrochemical impedance were used to analyze the behavior against corrosion. To measure the wettability contact angles measured by the sessile drop method were used. The film was examined for mechanical proprieties with the ball-on-plate and with the adhesion test. In the studied conditions, the adding of the particles of graphene oxide did not change the corrosion resistance, but it showed a positive contribution to the wear resistance.

SILVA, José Júnior Alves da. Microscopia de força elétrica em amostra de óxido de grafeno. 2013. 100 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2013. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-05-13T21:31:02Z No. of bitstreams: 1 2013_tese_jjasilva.pdf: 30925308 bytes, checksum: b2e1379686008553b3699b7736b7335b (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-05-13T21:38:16Z (GMT) No. of bitstreams: 1 2013_tese_jjasilva.pdf: 30925308 bytes, checksum: b2e1379686008553b3699b7736b7335b (MD5) / Made available in DSpace on 2014-05-13T21:38:17Z (GMT). No. of bitstreams: 1 2013_tese_jjasilva.pdf: 30925308 bytes, checksum: b2e1379686008553b3699b7736b7335b (MD5) Previous issue date: 2013 / Carbon-based structures have played a major role in scientific and technological fields. This is due to the versatility of the element carbon, the pillar of organic chemistry, which can form a variety of structures (about 10 million compounds), besides being a basic constituent of all known life forms. Depending on the conditions, this phenomenal element can occur in several allotropic forms: from an extremely brittle material, such as graphite, so incredibly resistant materials such as diamond, carbon nanotubes and graphene. These graphitic materials have been studied extensively, and present unique properties and great potential for technological applications. Among these materials, graphene currently occupies the most prominent position by having special electronic and mechanical properties. The graphene oxide is a class of graphitic structure consisting essentially of a graphene layer decorated with epoxide and hydroxyl groups on the surface and carboxyl and carbonyl groups on the edges. Its stoichiometry depends strongly on the method of production. In addition the graphene oxide is one of the main routes for obtaining large-scale graphene also it has several interesting properties, which allow, for example, biological applications, since their functional groups make it very reactive, besides being easily dispersed in water. Many issues related to graphene oxide are yet unclear, as also its structure, training procedure and mechanisms of interaction. Thus, the electric force microscopy (EFM) was used as the main tool to study electrostatic properties of a graphene oxide sample obtained by a modified Hummer method. By means of a simplified model, it was possible to develop a method for the analysis of the EFM measurements and so determine the presence and the sign of the net charge of the sample. Furthermore it is possible to clarify the origin of the edge phenomenon observed in EFM experiments. / As estruturas a base de carbono tem um papel de grande importância nos campos da ciência e da tecnologia. Isso graças à versatilidade do elemento carbono, pilar da química orgânica, que consegue formar uma diversidade de estruturas (cerca de 10 milhões de compostos), além de ser um constituinte básico de toda forma de vida conhecida. Dependendo das condições de formação, este fenomenal elemento, pode se apresentar em diversas formas alotrópicas: desde um material extremamente frágil, como o grafite, até materiais incrivelmente resistentes como o diamante, nanotubos de carbono e o grafeno. Esses materiais grafíticos têm sido extensivamente estudados, apresentando propriedades únicas e grande potencial em aplicações tecnológicas. Dentre eles, o grafeno ocupa, atualmente, a posição de maior destaque por possuir propriedades mecânicas e eletrônicas diferenciadas. O óxido de grafeno é uma classe de estruturas grafíticas constituída basicamente de uma camada de grafeno decorada com grupos epóxido e hidroxila na superfície e grupos carboxílicos e carbonila nas bordas. A sua estequiometria depende fortemente do método de obtenção. Esse material, além de ser uma das principais rotas para a obtenção em larga escala do grafeno, também apresenta diversas propriedades interessantes, que possibilitam, por exemplo, aplicações biológicas, uma vez que seus grupos funcionais o tornam bastante reativo além de ser facilmente dispersado em água. Muitas questões relacionadas ao óxido de grafeno ainda não estão bem esclarecidas, como sua própria estrutura, processo de formação e mecanismos de interação. Nesse sentido, foi utilizada, como principal ferramenta, a microscopia de força elétrica (EFM) para estudar propriedades eletrostáticas de uma amostra de óxido de grafeno obtida utilizando-se um método de Hummer modificado. Por meio de um modelo simplificado, foi possível desenvolver um método para análise das medições de EFM e assim determinar a presença e o sinal da carga líquida da amostra. Além de ser possível esclarecer a origem do fenómeno de borda observado nos experimentos de EFM.

This thesis provides several nanomaterial systems that can be used as contrast agents in magnetic resonance imaging (MRI) and for optical fluorescence imaging. Nanoparticle systems described in this thesis fall under three categories: (a) graphene oxide-nanoparticle composites for MRI contrast agent application, (b) core-shell nanoparticles for MRI contrast agent application and (c) nanoparticle systems for both MRI and optical fluorescence imaging. In the case of graphene oxide based nano-composites, the following observations were made: (i) in the case of graphene oxide-Fe3O4 nanoparticle composite, it was observed that high extent of oxidation of the graphene oxide and large spacing between the graphene oxide sheets containing Fe3O4 nanoparticles provides the optimum structure for yielding a very high transverse proton relaxivity value, (ii) in the case of graphene oxide-Gd2O3 nanoparticle composite, it was observed that this composite exhibits high value for both longitudinal and transverse relaxivity values making it a potential materials for multi-contrast study of pathologies with a single agent, (iii) in the case of graphene oxide-CoFe2O4 nanoparticle composites, it was observed that an increase in the reflux time of the reaction mixture containing this composite led to appreciable variations in the proton relaxivity values. Transverse relaxivity value of the water protons increased monotonically with increase in the reflux time. Whereas, the longitudinal relaxivity value initially increased and then decreased with increase in the reflux time. In the case of coreshell nanoparticles for MRI contrast agent application two different core-shell systems were investigated. They are MnFe2O3-Fe3O4 core-shell nanoparticles and CoFe2O4-MnFe2O4 coreshell nanoparticles. Investigations of both the core-shell nanoparticle systems revealed that the proton relaxivity value obtained in the dispersion of the core-shell nanoparticles was considerably greater than the proton relaxivity value obtained in the presence of single phase nanoparticles of the core and shell phases. Very high value of transverse relaxivity in the case core-shell nanoparticles was due to the large magnetic inhomogeneity created by the core-shell nanoparticles in the water medium surrounding it. In the case of nanoparticle systems for both MRI and optical fluorescence imaging, two different systems were investigated. They were CoFe2O4-ZnO core-shell nanoparticles and Gd doped ZnS nanoparticles [Zn1-xGdxS, x= 0.1, 0.2 and 0.3] formed on graphene oxide sheets or coated with chitosan. In the case of CoFe2O4-ZnO core-shell nanoparticles it was observed that fluorescent CoFe2O4-ZnO core-shell nanoparticles with the unique geometry in which CoFe2O4 ferrite nanoparticles agglomerates were present within larger sized hollow ZnO capsules yields very high value of transverse proton relaxivity when compared to the proton relaxivity value exhibited by the individual CoFe2O4-ZnO coreshell nanoparticles. In the case of Gd doped ZnS nanoparticles, two different systems were synthesized and the values of the longitudinal and transverse proton relaxivity obtained were compared. These systems were (i) graphene oxide- Zn1-xGdxS (x= 0.1, 0.2 and 0.3) nanoparticle composites and (ii) chitosan coated Zn1-xGdxS (x= 0.1, 0.2 and 0.3) nanoparticles. It was observed that Gd doped ZnS nanoparticles in both cases exhibit both longitudinal and transverse relaxivity values. The relaxivity values showed a clear dependence on the composition of the nanoparticles and the nanoparticle environment (presence and absence of graphene oxide). It was also observed that Gd doped ZnS nanoparticle can be used for florescence imaging.

abstract: Reverse osmosis (RO) membranes are considered the most effective treatment to remove salt from water. Specifically, thin film composite (TFC) membranes are considered the gold standard for RO. Despite TFC membranes good performance, there are drawbacks to consider including: permeability-selectivity tradeoff, chlorine damage, and biofouling potential. In order to counter these drawbacks, polyamide matrixes were embedded with various nanomaterials called mixed matrix membranes (MMMs) or thin film nanocomposites (TFNs). This research investigates the use of graphene oxide (GO) and reduced graphene oxide (RGO) into the polyamide matrix of a TFC membrane. GO and RGO have the potential to alter the permeability-selectivity trade off by offering nanochannels for water molecules to sieve through, protect polyamide from trace amounts of chlorine, as well as increase the hydrophilicity of the membrane thereby reducing biofouling potential. This project focuses on the impacts of GO on the permeability selectivity tradeoff. The hypothesis of this work is that the permeability and selectivity of GO can be tuned by controlling the oxidation level of the material. To test this hypothesis, a range of GO materials were produced in the lab using different graphite oxidation methods. The synthesized GOs were characterized by X-ray diffraction and X-ray photoelectron microscopy to show that the spacing is a function of the GO oxygen content. From these materials, two were selected due to their optimal sheet spacing between 3.4 and 7 angstroms and embedded into desalination MMM. This work reveals that the water permeability coefficient of MMM embedded with GO and RGO increased significantly; however, that the salt permeability coefficient of the membrane also increased. Future research directions are proposed to overcome this limitation. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2017

abstract: Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications. In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance. An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å). / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2018