Estudo da extração de índio a partir de telas de cristal líquido (LCD).

Ao longo dos últimos anos, o crescimento ao acesso a esse tipo de tecnologia pelos consumidores brasileiros tem intensificado o aumento no interesse ambiental e econômico dos LCDs. Os displays de cristal líquido são utilizados em televisores, calculadoras, telefones celulares, computadores (portáteis e tablets), vídeo games entre outros equipamentos eletrônicos. O avanço tecnológico neste campo tem tornado estes aparelhos obsoletos cada vez mais rápido, aumentando o volume de resíduos de LCDs a ser dispostos em aterros o que contribui para a redução da sua vida útil. Neste contexto, os LCDs provenientes de televisores de LED LCD tem se tornado uma fonte importante de resíduos de equipamentos eletroeletrônicos (REEE). Assim, torna-se essencial o desenvolvimento de métodos e processos para tratamento e reciclagem de LCDs. Deste modo, o objetivo do presente trabalho é a caracterização física e química de telas de cristal líquido provenientes de displays de televisores de LED LCDs e o estudo de uma rota hidrometalúrgica para recuperação de índio. Para tanto se utilizou técnicas de tratamento de minérios e análises físicas e químicas (separação granulométrica, perda ao fogo, visualização em lupa binocular, TGA, FRX, FT-IR) para caracterização do material e quantificação do índio antes e, após, a rota hidrometalúrgica que, por sua vez, foi realizada em reatores de bancada utilizando três agentes lixiviantes (ácido nítrico, sulfúrico e clorídrico), três temperaturas (25ºC, 40ºC e 60ºC) e quatro tempos (0,5h; 1h; 2h e 4h). Encontrou-se que a tela de cristal líquido representa cerca de 20% da massa total do display de televisores de LCD e que é composta por aproximadamente 11% em massa de polímeros e 90% de vidro + cristal líquido. Verificou-se também que há seis camadas poliméricas nas telas de cristal líquido, onde: um conjunto com 3 polímeros compõe o analisador e o polarizador, sendo que o polímero da primeira e da terceira camada de cada conjunto é triacetato de celulose e corresponde a 64% da massa de polímeros das telas. Já o polímero da segunda camada é polivinilalcool e representa 36% da massa de polímeros. Os melhores resultados obtidos nos processos de lixiviação foram com o ácido sulfúrico, nas condições de 60°C por 4h, relação sólido-líquido 1/5. Nessas condições, foi extraído em torno de 61% do índio contido tela de LCD.

Electronic structure of gated graphene and graphene ribbons

We study the electronic structure of gated graphene sheets. We consider both infinite graphene and finite width ribbons. The effect of Coulomb interactions between the electrically injected carriers and the coupling to the external gate are computed self-consistently in the Hartree approximation. We compute the average density of extra carriers n2D, the number of occupied subbands, and the density profiles as a function of the gate potential Vg. We discuss quantum corrections to the classical capacitance and we calculate the threshold Vg above which semiconducting armchair ribbons conduct. We find that the ideal conductance of perfectly transmitting wide ribbons is proportional to the square root of the gate voltage.

Vacancy-induced magnetism in graphene and graphene ribbons

We address the electronic structure and magnetic properties of vacancies and voids both in graphene and graphene ribbons. By using a mean-field Hubbard model, we study the appearance of magnetic textures associated with removing a single atom (vacancy) and multiple adjacent atoms (voids) as well as the magnetic interactions between them. A simple set of rules, based on the Lieb theorem, link the atomic structure and the spatial arrangement of the defects to the emerging magnetic order. The total spin S of a given defect depends on its sublattice imbalance, but some defects with S=0 can still have local magnetic moments. The sublattice imbalance also determines whether the defects interact ferromagnetically or antiferromagnetically with one another and the range of these magnetic interactions is studied in some simple cases. We find that in semiconducting armchair ribbons and two-dimensional graphene without global sublattice imbalance, there is a maximum defect density above which local magnetization disappears. Interestingly, the electronic properties of semiconducting graphene ribbons with uncoupled local moments are very similar to those of diluted magnetic semiconductors, presenting giant Zeeman splitting.

Hydrogenated graphene nanoribbons for spintronics

We show how hydrogenation of graphene nanoribbons at small concentrations can open venues toward carbon-based spintronics applications regardless of any specific edge termination or passivation of the nanoribbons. Density-functional theory calculations show that an adsorbed H atom induces a spin density on the surrounding π orbitals whose symmetry and degree of localization depends on the distance to the edges of the nanoribbon. As expected for graphene-based systems, these induced magnetic moments interact ferromagnetically or antiferromagnetically depending on the relative adsorption graphene sublattice, but the magnitude of the interactions are found to strongly vary with the position of the H atoms relative to the edges. We also calculate, with the help of the Hubbard model, the transport properties of hydrogenated armchair semiconducting graphene nanoribbons in the diluted regime and show how the exchange coupling between H atoms can be exploited in the design of novel magnetoresistive devices.

Electronic properties of the MoS2-WS2 heterojunction

We study the electronic structure of a heterojunction made of two monolayers of MoS2 and WS2. Our first-principles density functional calculations show that, unlike in the homogeneous bilayers, the heterojunction has an optically active band gap, smaller than the ones of MoS2 and WS2 single layers. We find that the optically active states of the maximum valence and minimum conduction bands are localized on opposite monolayers, and thus the lowest energy electron-holes pairs are spatially separated. Our findings portray the MoS2-WS2 bilayer as a prototypical example for band-gap engineering of atomically thin two-dimensional semiconducting heterostructures.

Disposable electrochromic polyaniline sensor based on a redox response using a conventional camera: A first approach to handheld analysis

We present a disposable optical sensor for Ascorbic Acid (AA). It uses a polyaniline based electrochromic sensing film that undergoes a color change when exposed to solutions of ascorbic acid at pH 3.0. The color is monitored by a conventional digital camera working with the hue (H) color coordinate. The electrochromic film was deposited on an Indium Tin Oxide (ITO) electrode by cyclic voltammetry and then characterized by atomic force microscopy, electrochemical and spectroscopic techniques. An estimation of the initial rate of H, as ΔH/Δt, is used as the analytical parameter and resulted in the following logarithmic relationship: ΔH/Δt = 0.029 log[AA] + 0.14, with a limit of detection of 17 μM. The relative standard deviation when using the same membrane 5 times was 7.4% for the blank, and 2.6% (for n = 3) on exposure to ascorbic acid in 160 μM concentration. The sensor is disposable and its applicability to pharmaceutical analysis was demonstrated. This configuration can be extended for future handheld configurations.

Singular Temperatures Connected to Charge Transport Mechanism Transitions in Perylene Bisimides from Steady-State Photocurrent Measurements

Perylene bisimides (PBIs) are n-type semiconducting and photogenerating materials widely used in a variety of optoelectronic devices. Particularly interesting are PBIs that are simultaneously water-soluble and liquid-crystalline (PBI-W+LC) and, thus, attractive for the development of high-performing easily processable applications in biology and “green” organic electronics. In this work, singular temperatures connected to charge transport mechanism transitions in a PBI-W+LC derivative are determined with high accuracy by means of temperature-dependent photocurrent studies. These singular temperatures include not only the ones observed at 60 and 110 °C, corresponding to phase transition temperatures from crystalline to liquid-crystalline (LC) and from LC to the isotropic phase, respectively, as confirmed by differential scanning calorimetry (DSC), but also a transition at 45 °C, not observed by DSC. By analyzing the photocurrent dependence simultaneously on temperature and on light intensity, this transition is interpreted as a change from monomolecular to bimolecular recombination. These results might be useful for other semiconducting photogenerating materials, not necessarily PBIs or even organic semiconductors, which also show transport behavior changes at singular temperatures not connected with structural or phase transitions.

Chemical and isotopic compositions of hydrothermal manifestations and minerals from the Broken Spur hydrothermal field

A representative collection of hydrothermal manifestations was sampled practically from all hydrothermal mounds of the Broken Spur hydrothermal vent field with use of the Mir manned submersibles during three cruises of R/V Akademik Mstislav Keldysh. Mineral associations characteristic for different morphological types of sulfide ores from hydrothermal pipes, plates, and diffusers are assessed. Particular attention is paid to distribution of minor elements and their distribution patterns determined by mineralogical zonation. Measured isotopic composition of sulfur in sulfide minerals varies from 0.4 to 5.2 per mil that indicates their similarity with ores from the Snake Pit vent field and is related to dilution of hot ore-bearing solutions by seawater and reduction of water sulfate ions to H2S with heavy isotopic composition.

Controlling Long-Range Ordered Self-assembly of Solid-Binding Peptide Monolayers on Atomically Flat Layered Materials

Thesis (Master's)--University of Washington, 2016-06

Study of optical properties of electropolymerized melanin films by photopyroelectric spectroscopy

Photopyroelectric (PPE) spectroscopy, in the 350-1,075 nm wavelength range, was used to study the optical properties of electropolymerized melanin films on indium tin oxide (ITO) coated glass. The PPE intensity signal as a function of the wavelength lambda, V (n)(lambda) and its phase F (n)(lambda) were independently measured. Using the PPE signal intensity and the thermal and optical properties of the pyroelectric detector, we were able to calculate the optical absorption coefficient beta of melanin in the solid-state. We believe this to be the first such measurement of its kind on this material. Additionally, we found an optical gap in these melanin films at 1.70 eV.

Generic Technique to Generate Large Branched DNA Complexes

The inherent self-recognition properties of DNA have led to its use as a scaffold for various nanotechnology self-assembly applications, with macromolecular complexes, metallic and semiconducting nanoparticles, proteins, inter alia, being assembled onto a designed DNA scaffold. Such structures may typically comprise a number of DNA molecules organized into macromolecules. Many studies have used synthetic methods to produce the constituent DNA molecules, but this typically constrains the molecules to be no longer than around 100 base pairs (30 nm). However, applications that require larger self-assembling DNA complexes, several tens of nanometers or more, need to be generated by other techniques. Here, we present a generic technique to generate large linear, branched, and/or circular DNA macromolecular complexes. The effectiveness of this technique is demonstrated here by the use of Lambda Bacteriophage DNA as a template to generate single- and double-branched DNA structures approximately 120 nm in size.

A study of field emission from semiconductors

In an attempt to clarify the behaviour of semi-conductor field emitters the properties of a narrow band gap material were investigated. A retarding potential analyser was built and tested using a tungsten emitter. The energy distribution of electrons emitted from single crystals of lead telluride (band gap 0.3 eV) and gallium phosphide (band gap 2.26 eV) were measured. The halfwidths of the distributions are discussed with respect to the relevant parameters for the materials. Methods of tip preparation had to be developed. The halfwidth of the energy distribution of electrons field emitted from carbon fibres was measured to be 0.21 ± 0.01 eV. A mechanism explaining the long lifetime of the emitters in poor vacuua is proposed.

Matrix-free mass spectrometric imaging using laser desorption ionisation Fourier transform ion cyclotron resonance mass spectrometry

Mass spectrometry imaging (MSI) is a powerful tool in metabolomics and proteomics for the spatial localization and identification of pharmaceuticals, metabolites, lipids, peptides and proteins in biological tissues. However, sample preparation remains a crucial variable in obtaining the most accurate distributions. Common washing steps used to remove salts, and solvent-based matrix application, allow analyte spreading to occur. Solvent-free matrix applications can reduce this risk, but increase the possibility of ionisation bias due to matrix adhesion to tissue sections. We report here the use of matrix-free MSI using laser desorption ionisation performed on a 12 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. We used unprocessed tissue with no post-processing following thaw-mounting on matrix-assisted laser desorption ionisation (MALDI) indium-tin oxide (ITO) target plates. The identification and distribution of a range of phospholipids in mouse brain and kidney sections are presented and compared with previously published MALDI time-of-flight (TOF) MSI distributions.

The influence of composition on the optical properties of electrodeposited gold

In industry the colour of a gold alloy electrodeposit is checked by visual comparison with standard panels. The aims of the present work have been to access the application of spectrophotmetric techniques to the measurement of the colour of gold alloy electrodeposits and to examine the factors that influence the colour of thin deposits. The minimum thickness of deposit required to produce its final colour and completely hide the underlying substrate was measured and found to depend on the nature of the substrate, the plating solution and the operating conditions. Bright and matt electrodeposits were studied. The influence of alloying gold by adding copper, silver and indium to the plating solution were investigated. CIE chromaticity coordinates were calculated from spectrophotometric data using a computer programme written for the purpose. The addition of silver to a simple gold bath caused the colour of the deposit to change from yellow through green to near white in a smooth progression as the amount of silver in solid solution steadily increased. The colour of deposits formed when additions of copper were made was complicated by the formation of intermediate phases. À colour in the blue region of the spectrum was obtained in a few experiments investigating the influence of indium additions to the gold bath.