Master of Science / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / 3D-printing is a popular manufacturing technique for making complex parts or small quantity batches. Currently, the applications of 3D-printing are limited by the material properties of the printed material. The processing parameters of commonly available 3D printing processes constrain the materials used to a small set of primarily plastic materials, which have relatively low strength and electrical conductivity. Adding filler materials has the potential to improve these properties and expand the applications of 3D printed material. Carbon nanomaterials show promise as filler materials due to their extremely high conductivity, strength, and surface area. In this work, Graphite, Carbon Nanotubes, and Carbon Black (CB) were mixed with raw Acrylonitrile Butadiene Styrene (ABS) pellets. The resulting mixture was extruded to form a composite filament. Tensile test specimens and electrical conductivity specimens were manufactured by Fused Deposition Method (FDM) 3D-printing using this composite filament as the feedstock material. Weight percentages of filler materials were varied from 0-20 wt% to see the effect of increasing filler loading on the composite materials. Additional tensile test specimens were fabricated and post-processed with heat and microwave irradiation in attempt to improve adhesion between layers of the 3D-printed materials. Electrical Impedance Spectroscopy tests on 15 wt% Multiwalled Carbon Nanotube (MWCNT) composite specimens showed an increase in DC electrical conductivity of over 6 orders of magnitude compared to neat ABS samples. This 15 wt% specimen had DC electrical conductivity of 8.74x10−6 S/cm, indicating semi-conducting behavior. MWCNT specimens with under 5 wt% filler loading and Graphite specimens with under 1 wt% filler loading showed strong insulating behavior similar to neat ABS. Tensile tests showed increases in tensile strength at 5 wt% CB and 0.5 wt% MWCNT. Placing the specimens in the oven at 135 °C for an hour caused increased the stiffness of the composite specimens.

Carbon quantum dots (CQDs) are the latest generation of carbon nanomaterials in applications where fullerenes, carbon nanotubes, and graphene are abundantly used. With several attractive properties such as tunable optical property, edge-functionalization, and defect-rich chemical structure, CQDs have the potential to revolutionize optoelectronics, electro- and photocatalysis, and biomedical applications. Chemical modifications through the addition of heteroatoms, chemical reduction, and surface passivation are found to alter the band gap, spectral position, and emission pathways of CQDs. Despite extensive studies, fundamental understanding of structure-property relationship remains unclear due to the inhomogeneity in chemical structure and a complex emission mechanism for CQDs. This dissertation outlines a series of works that investigate the structure-property relationship of CQDs and its impact in a variety of applications. First, this relationship was explored by modifying specific chemical functionalities of CQDs and relating them to differences observed in optical, catalytic, and pharmacological performance. While a number of scientific articles reported that top-down or bottom-up synthesized CQDs yielded similar properties, the results herein present dissimilar chemical structures as well as photoluminescent and metal sensing properties. Second, the role of nitrogen heteroatoms in top-down synthesized CQD was studied. The effect of nitrogen atoms on spectral position and fluorescence quantum yield was considerably studied in past reports; however, thorough investigation to differentiate various nitrogen related chemical states was rarely reported. By finely tuning both the quantity of nitrogen doping and the distribution of nitrogen-related chemical states, we found that primary amine and pyridine induce a red-shift in emission while pyrrolic and graphitic nitrogen produced a blue-shift in emission. The investigation of nitrogen chemical states was extended to bottom-up synthesized CQDs with similar results. Finally, top-down, bottom-up, nitrogen-doped and chemically reduced CQDs were separately tested for their ability to act as photodynamic anti-cancer agents. This series of experiments uncovered the distribution of reactive oxygen species produced during light exposure which elucidated the photodynamic mechanisms of cancer cytotoxicity. The results presented in this dissertation provide key insight into engineering finely-tailored CQDs as the ideal nanomaterial for a broad range of applications.

In this work, the use of theoretical tools of molecular modeling for tailoring 1D novel nanomaterials is demonstrated. There are four selected nano-structures as examples, each tailored for a specic demand of nano-technology that is yet to be fullled. For the purpose of modeling/calculating the electronic and structural properties, various methods of dening the interatomic interaction, such as empirical potential energy functions, semi-empirical methods and density functional theory, are used. Each of these methods have a dierent level of approximations leading to limitations in their use. Furthermore, each method needs to be calibrated carefully in order to obtain physically meaningful results. Examples being novel nano-structures, there does not exist any experimental observations directly studying the material at hand. Thus, in order to obtain a parameter set that best describes the system, a series of pre-existing structures that are physically and/or chemically related are used. Among the methods employed, the density functional theory (DFT) is certainly the most popular one, due to its accuracy and more importantly the framework it provides for perturbative extensions otherwise nearly impossible to calculate in Hartree-Fock level.

Dans le cadre d’une thèse en cotutelle qui a démarré en Janvier 2013, j'ai développé des biopuces ultra-sensibles pour la détection de maladies infectieuses (Tuberculose et Hepatite C). Ce sujet, qui combine recherche fondamentale et recherche appliquée dans pour le diagnostic précoce de maladies, avait pour but la détection rapide d’espèces chimiques fortement diluées dans un liquide biologique. Cette détection se fait de manière électrochimique, grâce à l’utilisation des nanomatériaux carbonés innovants (feuillets de graphène, nanotubes de carbone (NTCS)) qui sont dotés d’une conductivité électronique élevée. J’intègre ces nanomatériaux par des procédés de micro/nanofabrication sur des électrodes de travail dans des cellules microfluidiques. J'ai démontré qu'en combinant un haut flux et un transducteur en NTCs qu'il est possible d'augmenter de 3 ordres de grandeur la sensibilité de détection dans la chambre fluidique (article soumis à LoC). J'ai aussi étudié par spectroscopîe d'impédance la nature du transfert des charges entre l'électrolyte et la graphène (2ème article en cours de rédaction). Mon doctorat a donc validé une technologie innovante pour les biocapteurs miniaturisés à ADN, avec un fort potentiel de valorisation, dans le domaine de la santé et de l’environnement. / As part of my thesis under joint supervision between UPS and Sfax Universities which started in January 2013, I developed ultra-sensitive biochips for the detection of infectious diseases (Tuberculosis and Hepatitis C). This subject, which combines basic and applied research for the early detection of diseases, aimed rapid detection of highly diluted chemical species such as DNA in a biological fluid. This detection is done electrochemically, through the use of innovative carbon nanomaterials (graphene layers, carbon nanotubes (NTCS)) which are provided with a high electron conductivity. I have integrated these nanomaterials by micro / nano-fabrication processes on working electrodes in microfluidic cells. I demonstrated that by combining a high flow and a that CNTs as transducer, the sensitivity of detection in the fluid chamber can be increased by 3 orders of magnitude (Article submitted to Lab on Chip journal). I also studied by impedance spectroscopy the nature of the charge transfer between the electrolyte and the graphene (2nd article being drafted). My PhD has validated an innovative technology for miniaturized biosensors DNA, with a strong development potential in the field of health and the environment.

Yes / In 1985, the serendipitous discovery of fullerene triggered the research of carbon structures into the world of symmetric nanomaterials. Consequently, Robert F. Curl, Harold W. Kroto and Richard E. Smalley were awarded the Noble prize in chemistry for their discovery of the buckminsterfullerene (C60 with a cage-like fused-ring structure). Fullerene, as the first symmetric nanostructure in carbon nanomaterials family, opened up new perspectives in nanomaterials field leading to discovery and research on other symmetric carbon nanomaterials like carbon nanotubes and two-dimensional graphene which put fullerenes in the shade, while fullerene as the most symmetrical molecule in the world with incredible properties deserves more attention in nanomaterials studies. Buckyball with its unique structure consisting of sp2 carbons which form a high symmetric cage with different sizes (C60, C70 and so on); however, the most abundant among them is C60 which possesses 60 carbon atoms. The combination of unique properties of this molecule extends its applications in divergent areas of science, especially those related to biomedical engineering. This review aims to be a comprehensive review with a broad interest to the biomedical engineering community, being a substantial overview of the most recent advances on fullerenes in biomedical applications that have not been exhaustively and critically reviewed in the past few years.

This thesis focuses on the development of carbohydrate coupling chemistry on nanomaterials and their biological activity studies. It is divided into two parts: In part one, two carbohydrate immobilization approaches, based on perfluorophenyl azide (PFPA)-functionalized silica nanoparticles (SNPs), are presented, where the binding affinity of the glyconanoparticles was evaluated through carbohydrate-lectin interaction. In the first approach, PFPAfunctionalized SNPs were treated with propargylated glycosides and functionalized under copper-catalyzed azide-alkyne cycloaddition (CuAAC) conditions to give glyconanoparticles. For the second approach, a metal-free coupling chemistry based on perfluorophenyl azide-aldehyde-amine cycloaddition (AAAC) was developed for carbohydrate immobilization on PFPA-functionalized SNPs using glycosyl amine and phenylacetaldehyde. Subsequently, a quantitative fluorine nuclear magnetic resonance (19F qNMR) technique was developed to determine the carbohydrate density on the glyconanoparticles. The addition of an internal standard allowed the accurate determination of carbohydrate density, which was then used to calculate the apparent dissociation constant (Kd ) of the glyconanoparticles with lectin by a ligand competition assay. The developed approaches proved general and versatile, and the carbohydrate-presenting nanoplatforms showed high binding specificity in lectin binding. In part two, microwave irradiation was used to functionalize carbon nanomaterials with PFPA followed by carbohydrate conjugation. The microwave-assisted method proved efficient for a number of carbon nanomaterials including carbon nanotubes (CNTs), graphene and fullerene. The carbohydrates on the glyconanomaterials retained their binding patterns towards cognate lectins. / <p>QC 20150907</p>

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In this research the possible utilization of carbon nanomaterials in gas sensing applications are investigated. These materials include the 2-dimensional honeycomb-lattice carbon structure called graphene, and the 1-dimensional structures referred to as carbon nanotubes (CNTs). The extraordinary properties and unique morphology of these nanomaterials, make them excellent candidates for sensory applications. This research thus entails the investigation and development of gas sensors with these carbon nanomaterials. This includes the synthesis of CNTs via a chemical vapour deposition (CVD) technique and the fabrication of resistive thin film sensors with the various materials. The functionalization of carbon nanomaterials is also explored, which delivers promising results for sensing gases at room temperature, especially acetylene (C2H2). Furthermore, a unique method is developed to fabricate ultra thin aluminium microstructures. These metallic electrodes are found to be ideal for nanomaterial integration. An experiment is performed to manufacture an integrated sensor with MWCNTs and following the results, a refinement of the procedure and the investigation of FET-based devices are recommended. The results obtained during this work, indicate that engineered carbon nanostructures, such as CNTs and graphene, can potentially be applied in future sensing technologies. / AFRIKAANSE OPSOMMING: Hierdie navorsing ondersoek die moontlike toepassing van koolstof nano-materiale as gas-sensor tegnologie. Hierdie materiale sluit die 2-dimensionele koolstof struktuur, grafeen, asook die sogenaamde 1-dimensionele koolstof nano-buise in. Die buitengewone eienskappe en unieke morfologie van hierdie nano-materiale, maak hul uitstekende kandidate vir sensor toepassings. Hierdie navorsing ondersoek dus die ontwikkeling van gas-sensors met koolstof nano-materiale, insluitend die sintese van koolstof nano-buise deur middel van ’n chemiese damp-neerslag proses, asook die fabrikasie van resistiewe dun film sensors. Die funksionalisering van koolstof nano-materiale is ook ondersoek en belowende resultate is opgelewer met betrekking tot die deteksie van gasse by kamertemperatuur, veral vir asetileen (C2H2) gas. Verder is ’n unieke metode ontwikkel om ultra dun aluminium mikrostrukture te vervaardig en hierdie metaal elektrodes word as ideaal beskou vir die integrasie van nano-materiale. ’n Eksperiment is uitgevoer om ’n geïntegreerde sensor te vervaardig met multi-wand koolstof nano-buise, waarvan die resultate aandui dat die proses verfyn moet word en dat die moontlike toepassing van veld-effek-transistor toestelle ondersoek moet word. Die resultate wat opgelewer is gedurende hierdie navorsing dui daarop dat ontwikkelde nanostrukture, soos koolstof nano-buise en grafeen, as toekomstige sensor tegnologie geïmplementeer kan word.

Thesis. (M.Tech. (Chemistry)) -- Vaal University of Technology, 2011. / Bis(acetylacetonato)oxovanadium(IV), Manganese(III) acetylacetonate, Co-Zn and Co-Al were prepared as catalyst precursors for the synthesis of carbon materials in a catalytic chemical vapor deposition (CCVD) reactor. The carbon materials produced were characterized with Raman spectroscopy, Scanning electron microscope (SEM), Energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), High resolution transmission electron microscopy (TEM) and Thermogravimetric analysis, (TGA). Carbon material prepared from bis(acetylacetonato)oxovanadium(IV) catalyst precursor showed the presence of carbon spheres with average diameter of 104μm together with small traces of carbon nanotubes or amorphous carbon. Synthesis of bis(acetylacetonato)oxovanadium(IV) catalyst precursor yielded approximately 92% of carbon material. Carbon material prepared from Manganese(III) acetylacetonate catalyst precursor showed the presence of carbon spheres with diameter of 87.5μm. Synthesis of Manganese(III) acetylacetonate catalyst precursor yielded approximately 97% of carbon material. Carbon material produced from Co-Zn and Co-Al catalyst precursors showed the presence of carbon nanotubes with small amounts of amorphous carbon. The use of Co-Zn catalyst precursor yielded approximately 80% of carbon nanotubes, whereas Co-Al catalyst precursor yielded approximately 98% of carbon nanotubes. / Vaal University of Technology; NRF; SASOL

The exceptional properties of carbon nanomaterials make them ideal reinforcements for polymers. However, the main challenges in utilizing their unique properties are their tendency to form agglomerates, their non-controlled orientation, non-homogeneous distribution and finally the change in their shape/size due to processing. All the above are the result of the nanomaterial/polymer interfacial interactions which dictate the overall performance of the composites including the mechanical properties. The aforementioned uncertainties are the reason for the deviation observed between the experimentally determined properties and the theoretically expected ones. The focus of this study is to understand the reinforcing efficiency of carbon nanomaterials in polymers through finite element modeling that captures the effect of the interfacial interactions on the tensile modulus of polymer nanocomposites (PNCs). The novelty of this work is that the probability distribution functions of nanomaterials dispersion, distribution, orientation and waviness, determined through image analysis by extracting 3-D information from 2-D scanning electron micrographs, are incorporated into the finite element model allowing thus for fundamental understanding of how the nanostructure parameters affect the tensile modulus of the PNCs. The nanocomposites are made using melt mixing followed by either injections molding or melt spinning of fibers. Polypropylene (PP) is used as the polymer and carbon nanotubes (CNT) or exfoliated graphite nanoplatelets (xGnP) are used as nanoreinforcements. The presence of interphase, confirmed and characterized in terms of stiffness and width using atomic force microscopy, is also accounted for in the model. The dispersion and distribution of CNT within the polymer is experimentally altered by using a surfactant and by forcing the molten material to flow through a narrow orifice (melt spinning) that promotes alignment of CNT and even of the polymer chains along the flow/drawing direction. The effect of nanomaterials' geometry on the mechanical behavior of PNCs is also studied by comparing the properties of CNT/PP to those of xGnP/PP composites. Finally the reinforcing efficiency of CNT is determined independently of the viscoelastic behavior of the polymer by conducting tensile testing at temperatures below the glass transition temperature of PP. The finite element model with the incorporated image analysis subroutine has sufficient resolution to distinguish among the different cases (dispersion, distribution, geometry and alignment of nanomaterials) and the predicted tensile modulus is in agreement with the experimentally determined one. In conclusion, this study provides a tool, that integrates finite element modeling and thorough experiments that enables design of polymer nanocomposites with engineered mechanical properties.

<p>Detection and control of humidity is very important in our everyday life.<br />Humidity sensors are used in many areas, such as meteorology,<br />environmental protection, medicine, food industry, agriculture, etc.<br />Various transduction techniques, such as capacitive, resistive, acoustic,<br />optical and mechanical, have been adopted for the design of humidity<br />sensors.In the last two decades, carbon nanomaterials materials,<br />especially graphene, are taking their place in the production of humidity<br />sensors. In addition to graphene, graphene oxide (Graphene-oxide-GO)<br />is involved in many areas from electronics to sensors. Printed electronics<br />increasingly becomes the leading technology in the fabrication of<br />sensors. In addition to inexpensive manufacturing and additive processes<br />with reduced infrastructure, the benefits of printed technology are lowpower<br />components, flexible, transparent, thin, components that can be<br />embedded in/on clothes, as well as the production of a large number of<br />components. In the last few years, robots are more involved in human&rsquo;s<br />life, which has led to the need for advanced research in the field of<br />robotics. People communicate with the environment using four senses:<br />touch, hearing, sight and taste. The sense of touch allows people to grab<br />various objects, lift them, perform various tasks, etc. For this reason, it is<br />very important to develop touch sensors, that is, the sensors that will be<br />incorporated into robotic fingers. As one type of such sensor, Force<br />Sensing Resistors (FSR) are used. In these sensors, there is a change in<br />resistance if the sensor is affected by a certain force.</p> / <p>Детекција и контрола влажности су од суштинског значаја у нашем<br />свакодневном животу. Сензори влаге се користе у многим областима,<br />као што су метеорологија, заштита животне средине, медицина,<br />прехрамбена индустрија, пољопривреда, итд. За дизајн сензора влаге<br />углавном се користе капацитивне, резистивне, акустичне, механичке<br />или оптичке структуре. У посљедње двије деценије све више се користе<br />наноструктурни угљенични материјали, посебно графен. Поред графена<br />велику пажњу у многим областима од електронике до сензора је<br />привукао графен-оксид (Graphene-oxide - GO). Штампана електроника<br />све више постаје водећа технологија у изради сензора. Поред јефтине<br />израде и адитивних процеса са смањеном инфраструктуром, предности<br />штампане технологије су компоненте мале масе, савитљиве,<br />транспарентне, танке, компоненте које се могу уградити у/на гардеробу<br />и носити, као и производња великог броја компоненти. У последњих<br />неколико година роботи се све више укључују у људски живот, што је<br />довело до потребе за усавршавањем у области роботике. Људи са<br />окружењем комуницирају помоћу четири чула: додира, слуха, вида и<br />укуса. Чуло додира људима омогућава да дохвате различите предмете,<br />подигну их, обављају различите задатке, итд. Из тог разлога је развој<br />сензора додира, односно сензора који би се уградили у роботске прсте,<br />од веома великог значаја. Као једна врста таквих сензора су отпорнички<br />сензори силе (Force Sensing Resistors - FSR). Код ових сензора долази<br />до промјене отпорности уколико се на сенсор дјелује одређеном силом.</p> / <p>Detekcija i kontrola vlažnosti su od suštinskog značaja u našem<br />svakodnevnom životu. Senzori vlage se koriste u mnogim oblastima,<br />kao što su meteorologija, zaštita životne sredine, medicina,<br />prehrambena industrija, poljoprivreda, itd. Za dizajn senzora vlage<br />uglavnom se koriste kapacitivne, rezistivne, akustične, mehaničke<br />ili optičke strukture. U posljednje dvije decenije sve više se koriste<br />nanostrukturni ugljenični materijali, posebno grafen. Pored grafena<br />veliku pažnju u mnogim oblastima od elektronike do senzora je<br />privukao grafen-oksid (Graphene-oxide - GO). Štampana elektronika<br />sve više postaje vodeća tehnologija u izradi senzora. Pored jeftine<br />izrade i aditivnih procesa sa smanjenom infrastrukturom, prednosti<br />štampane tehnologije su komponente male mase, savitljive,<br />transparentne, tanke, komponente koje se mogu ugraditi u/na garderobu<br />i nositi, kao i proizvodnja velikog broja komponenti. U poslednjih<br />nekoliko godina roboti se sve više uključuju u ljudski život, što je<br />dovelo do potrebe za usavršavanjem u oblasti robotike. LJudi sa<br />okruženjem komuniciraju pomoću četiri čula: dodira, sluha, vida i<br />ukusa. Čulo dodira ljudima omogućava da dohvate različite predmete,<br />podignu ih, obavljaju različite zadatke, itd. Iz tog razloga je razvoj<br />senzora dodira, odnosno senzora koji bi se ugradili u robotske prste,<br />od veoma velikog značaja. Kao jedna vrsta takvih senzora su otpornički<br />senzori sile (Force Sensing Resistors - FSR). Kod ovih senzora dolazi<br />do promjene otpornosti ukoliko se na sensor djeluje određenom silom.</p>