Proprietà di conduzione elettrica in campioni di grafene poroso

Il grafene, allotropo del carbonio costituito da un reticolo bidimensionale, è uno dei nanomateriali più promettenti allo stato attuale della ricerca nei campi della Fisica e della Chimica, ma anche dell'Ingegneria e della Biologia. Isolato e caratterizzato per la prima volta nel 2004 dai ricercatori russi Andre Geim e Konstantin Novoselov presso l'Università di Manchester, ha aperto la via sia a studi teorici per comprendere con gli strumenti della Meccanica Quantistica gli effetti di confinamento in due dimensioni (2D), sia ad un vastissimo panorama di ricerca applicativa che ha l'obiettivo di sfruttare al meglio le straordinarie proprietà meccaniche, elettriche, termiche ed ottiche mostrate da questo materiale. Nella preparazione di questa tesi ho personalmente seguito presso l'Istituto per la Microelettronica e i Microsistemi (IMM) del CNR di Bologna la sintesi mediante Deposizione Chimica da Fase Vapore (CVD) di grafene "tridimensionale" (3D) o "poroso" (denominato anche "schiuma di grafene", in inglese "graphene foam"), ossia depositato su una schiuma metallica dalla struttura non planare. In particolare l'obiettivo del lavoro è stato quello di misurare le proprietà di conduttività elettrica dei campioni sintetizzati e di confrontarle con i risultati dei modelli che le descrivono teoricamente per il grafene planare. Dopo un primo capitolo in cui descriverò la struttura cristallina, i livelli energetici e la conduzione dei portatori di carica nel reticolo ideale di grafene 2D (utilizzando la teoria delle bande e l'approssimazione "tight-binding"), illustrerò le differenti tecniche di sintesi, in particolare la CVD per la produzione di grafene poroso che ho seguito in laboratorio (cap.2). Infine, nel capitolo 3, presenterò la teoria di van der Pauw su cui è basato il procedimento per eseguire misure elettriche su film sottili, riporterò i risultati di conduttività delle schiume e farò alcuni confronti con le previsioni della teoria.

Influência da utilização do fluido de corte com adição de grafeno na temperatura de usinagem e formação de rebarba no processo de micro fresamento

As time passed, humanity needed the development of new materials used in various activities. High strength materials such as titanium and Inconel for example, had been studied because they are widely used for implants in biomedicine, as well as their use in aerospace and automotive industries. Because of its thermal and mechanical properties, these materials are considered difficult to machine, promoting a rapid wear of cutting tools, primarily caused by the high temperatures in machining. With the development of new materials has emerged the need of developing new manufacturing processes. One of today’s innovative processes is the micro-manufacturing. Being a process with a defined cutting tool geometry, burr formation is a constant and undesirable phenomenon formed during the machininig process. Being detrimental to the manufacturing process, overspending deburring operations are constantly employed leading to increase the aggregate cost to the manufactured material. Assembly components are also impaired if there is no control of the burr, with consequences including the disposal of components due to the occurence of this phenomenon. This paper presents the study of micro-milling Inconel 718, investigating influential parameters in the formation of burrs in order to minimize the occurrence of this phenome non. Different feed rates per tooth and cutting speed are evaluated, and different cutting fluids with different methods of applying the fluid. Adding graphene to cutting fluids was considered as a variable to be investigated, which is considered an excellent solid lubricant, in addition to increasing the thermal conductivity of the cooling solution (AZIMI; MOZAF FARI, 2015). The micro-milling temperature was evaluated in the present work. It was observed a new phenomenon that causes the machined surface temperature decreases below room temperature when using the solution water + oil. This phenomenon is explained in further chapters. In order to unravel this phenomenon, a new test was proposed and, from this test, it can be concluded, comparatively, which cutting fluid has a better cooling property.Using cutting fluid with different thermal properties has shown influence when analy zing burr formation and reducing machining temperature.

Simulação computacional de materiais bidimensionais: funcionalização de defeitos extensos no grafeno e retenção de contaminantes por argilominerais

In this work are considered two bidimensional systems, with distints chacacteristcs and applicabilitys. Is studied the adsorption of transition metals (MT) Fe, Co, Mn and Ru in extended defects, formed by graphene grain boundaries. First in pristine graphene The hollow site of carbon hexagon, in pristine graphene, are the most stable for MT adsorption. The Dirac cone in eletronic structure of graphene was manteined with the presence of MT. For the considered grain boundaries the MT has a greater stability for absorption in the grain boundaries sites in comparison with pristine graphene. Through the energy barrier values, are observed diffusion chanels for MT localized on the grain boundaries. This diffusion chanels indicate a possible formation of nanolines of MT in graphene. For the first stage of the nanolines, ate observed a better stability for the system with greater MT concentration, due to MT-MT interactions. Also, due to the magnetic moment of the MT, the nanolines show a magnetization. For the most stable configurations the system are metallics, particularly for Fe the band structure indicates an anisotropic spin current. In a second study, are considereted the retention capacity for metallic contaminants Cd and Hg in clayminerals, kaolinite (KAO) and montmorillonite (MMT). Through the adsorption energies of contaminantes in the clayminerals, was observed a increase in stability with the increase of contaminants concentration, due to the interaction Cd-Cd and Hg-Hg. Also, was observed that KAO has a strong interaction beteween monolayers than MMT. In this sence, for the adsoption process of contaminantes in the natural form of KAO and MMT, the latter has a better retention capacity, due to the small net work for contaminant intercalation. However, when the modification of clayminerals, with molecules that increase the spacing between monolayers, exist a optimal condition, which the contaminant absorption are more stable in KAO system than in MMT. In the Langmuir adsorption model for the clayminerals in the optimal monolayer spacing, the retention capacity for Cd and Hg in KAO system are 21% greater than in MMT system. Also, for the X-ray Absorption Near Edge Spectroscopy (XANES) for the K edge of Cd and Hg, are found a positive shift of absorption edge with the decreasing of monolayer spacing. This result indicates a possible way to determine the concentration of adsorbed contaminats in relation to unabsorbed ones, from the decomposition of experimental XANES in the obteined spectras.

Investigação experimental das propriedades termofísicas e da convecção forçada de nanofluido de grafeno

This work presents an experimental investigation of thermal hydraulic performance of the nanofluid composed by graphene nanoparticles dispersed in a mixture of water and ethylene glycol at a ratio of 70:30% by volume. The tests were carried out under forced convection inside a circular tube with uniform heat flux on the wall for the laminar-turbulent transition regime. The mass flow rate ranged from 40 to 70 g/s corresponding to Reynolds numbers between 3000 and 7500. The heat flux was maintained constant at values of 11, 16 and 21 kW/m², as well as the inlet temperature of 15, 20 and 25°C. Three samples were produced with the nanofluid volumetric concentration of 0.05%, 0.10% and 0.15%. Thermophysical properties were experimentaly measured for all samples that were critically compared and discussed with theoretical models most commonly used in the literature. Initially, experiments with distilled water confirmed the validity of the experimental equipment for the thermo-hydraulic tests. Therefore, nanofluid samples that showed the highest thermal conductivity, corresponding to the volumetric concentrations of 0.15% and 0.10%, were subjected to the tests. The thermal-hydraulic performance for both samples was unsatisfactory. The heat transfer coefficients for convection of nanofluids reduced 21% in average, for the sample with = 0.15% and 26% and for =0.10%. The pressure drop of the samples was higher than the base fluid. Finally, the pressure drop and heat transfer coefficient by convection of both samples were also compared to theoretical models. The models used for pressure drop showed an excellent agreement with experimental results, which is remarkable considering the transitional flow.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Structure, Morphology, and Electrochemical Properties of Transition Metal Oxide, Hydroxide, and Phosphate Nanomaterials for Energy Storage

Energy storage technologies are crucial for efficient utilization of electricity. Supercapacitors and rechargeable batteries are of currently available energy storage systems. Transition metal oxides, hydroxides, and phosphates are the most intensely investigated electrode materials for supercapacitors and rechargeable batteries due to their high theoretical charge storage capacities resulted from reversible electrochemical reactions. Their insulating nature, however, causes sluggish electron transport kinetics within these electrode materials, hindering them from reaching the theoretical maximum. The conductivity of these transition metal based-electrode materials can be improved through three main approaches; nanostructuring, chemical substitution, and introducing carbon matrices. These approaches often lead to unique electrochemical properties when combined and balanced.

Ethanol-mediated solvothermal synthesis we developed is found to be highly effective for controlling size and morphology of transition metal-based electrode materials for both pseudocapacitors and batteries. The morphology and the degree of crystallinity of nickel hydroxide are systematically changed by adding various amounts glucose to the solvothermal synthesis. Nickel hydroxide produced in this manner exhibited increased pseudocapacitance, which is partially attributed to the increased surface area. Interestingly, this morphology effect on cobalt doped-nickel hydroxide is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance.

Moreover, a thin layer of densely packed nickel oxide flakes on carbon paper substrate was successfully prepared via the glucose-assisted solvothermal synthesis, resulting in the improved electrode conductivity. When reduced graphene oxide was used for conductive coating on as-prepared nickel oxide electrode, the electrode conductivity was only slightly improved. This finding reveals that the influence of reduced graphene oxide coating, increasing the electrode conductivity, is not that obvious when the electrode is already highly conductive to begin with.

We were able to successfully control the interlayer spacing and reduce the particle size of layered titanium hydrogeno phosphate material using our ethanol-mediated solvothermal reaction. In layered structure, interlayer spacing is the key parameter for fast ion diffusion kinetics. The nanosized layered structure prepared via our method, however, exhibited high sodium-ion storage capacity regardless of the interlayer spacing, implying that interlayer space may not be the primary factor for sodium-ion diffusion in nanostructured materials, where many interstitials are available for sodium-ion diffusion.

Our ethanol-mediated solvothermal reaction was also effective for synthesis of NaTi2(PO4)3 nanoparticles with uniform size and morphology, well connected by a carbon nanotube network. This composite electrode exhibited high capacity, which is comparable to that in aqueous electrolyte, probably due to the uniform morphology and size where the preferable surface for sodium-ion diffusion is always available in all individual particles.

Fundamental understandings of the relationship between electrode microstructures and electrochemical properties discussed in this dissertation will be important to design high performance energy storage system applications.

Synthesis and characterization of nanocomposites based on PANI and carbon nanostructures prepared by electropolymerization

Nanocomposites based on polyaniline (PANI) and carbon nanostructures (CNSs) (graphene (G) and multiwall carbon nanotubes (MWCNTs)) were prepared by in situ electrochemical polymerization. CNSs were inserted into the PANI matrix by dispersing them into the electrolyte before the electropolymerization. Electrochemical characterization by means of cyclic voltammetry and steady state polarization were performed in order to determine conditions for electro- polymerization. Electro-polymerization of the PANI based nanocomposites was carried out at 0.75 V vs. saturated calomel electrode (SCE) for 40 and 60 minutes. The morphology and structural characteristics of the obtained nanocomposites were studied by scanning electron microscopy (SEM) and Raman spectroscopy, while thermal stability was determined using thermal gravimetric analysis (TGA). According to the morphological and structural study, fibrous and porous structure of PANI based nanocomposites was detected well embedding both G and MWCNTs. Also, strong interaction between quinoidal structure of PANI with carbon nanostructures via π–π stacking was detected by Raman spectroscopy. TGA showed the increased thermal stability of composites reinforced with CNSs, especially those reinforced with graphene.

Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.

C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.

Reconfigurable Matching Networks for RF Amplifiers

This article presents applications of reconfigurable matching networks for RF amplifier design. Two possible solutions are given, one where the switching element is a PIN diode, and the other is based on graphene. Due to the fact that its conductivity depends on applied bias voltage, the graphene-based circuits can be used in microwave circuits as controllable elements. The structure of the proposed switch is very simple and it is particularly convenient for microstrip-based circuits. Because of that, a design of reconfigurable amplifier with the graphene-based switch is presented together with the one which has the PIN diode switch. Both amplifiers have the same specifications, and the one with the PIN diode switch is fabricated. The amplifier utilizing the PIN switch was used as a reference to make a comparison the two types of switches. Results of both amplifiers are very similar which indicates possible future applications of the graphene-based switch.

Highly linear reconfigurable UWB filters with independently controlled dual bandnotch

This letter proposes a high-linearity reconfigurable lower ultra-wideband (3.1–5.25 GHz) filter with independently controlled dual bandnotch at WiMAX 3.5 GHz band and satellite communication systems 4.2 GHz band. Reconfigurability has been achieved by the implementation of Graphene based switches (simulation only) and PIN diodes (measurements). The simulation and measurement results in OFF state show an entire bandpass response from 3.1 GHz to 5.25 GHz and with a very low insertion loss. In ON state, the results show that sharp rejections at 3.5 GHz and 4.2 GHz are achieved, with a low passband insertion loss. The two bandnotch operate independently of each other; thus allowing to control the behaviour of the required bandnotch. The third order intermodulation products were also measured in OFF and ON states and the linearity results have been presented. The filter is able to achieve a high performance with good linearity and no significant loss.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Efficient simulations with electronic open boundaries

We present a reformulation of the hairy-probe method for introducing electronic open boundaries that is appropriate for steady-state calculations involving nonorthogonal atomic basis sets. As a check on the correctness of the method we investigate a perfect atomic wire of Cu atoms and a perfect nonorthogonal chain of H atoms. For both atom chains we find that the conductance has a value of exactly one quantum unit and that this is rather insensitive to the strength of coupling of the probes to the system, provided values of the coupling are of the same order as the mean interlevel spacing of the system without probes. For the Cu atom chain we find in addition that away from the regions with probes attached, the potential in the wire is uniform, while within them it follows a predicted exponential variation with position. We then apply the method to an initial investigation of the suitability of graphene as a contact material for molecular electronics. We perform calculations on a carbon nanoribbon to determine the correct coupling strength of the probes to the graphene and obtain a conductance of about two quantum units corresponding to two bands crossing the Fermi surface. We then compute the current through a benzene molecule attached to two graphene contacts and find only a very weak current because of the disruption of the π conjugation by the covalent bond between the benzene and the graphene. In all cases we find that very strong or weak probe couplings suppress the current.

Toward controlled growth of helicity-specific carbon nanotubes

The underlying mechanisms for the nucleation of carbon nanotubes as well as their helicity, remain elusive. Here, using van der Waals dispersion force calculations implemented within density functional theory, we study the cap formation, believed to be responsible for the chirality of surface-catalyzed carbon nanotubes. We find the energetics associated with growth along different facets to be independent of the surface orientation and that the growth across an edge along the axis of the metal particle leads to a perfect honeycomb lattice in a curved geometry. The formation of defects in the graphene matrix, which bend the carbon plane, requires that two or more graphene embryos with significantly different growth axis merge. Such scenario is only possible at the front- or back-end of the metal particle where growth symmetry is broken. The graphene embryos reconstruct their hexagonal structure into pentagons, heptagons, and octagons counterpart to accommodate the tube curvature.

High-Performance WSe2 CMOS Technology and Integrated Circuits.

Because of their extraordinary structural and electrical properties, two dimensional materials are currently being pursued for applications such as thin-film transistors and integrated circuit. One of the main challenges that still needs to be overcome for these applications is the fabrication of air-stable transistors with industry-compatible complementary metal oxide semiconductor (CMOS) technology. In this work, we experimentally demonstrate a novel high performance air-stable WSe2 CMOS technology with almost ideal voltage transfer characteristic, full logic swing and high noise margin with different supply voltages. More importantly, the inverter shows large voltage gain (~38) and small static power (Pico-Watts), paving the way for low power electronic system in 2D materials.