Development of a reactor for growth of diamond tubular films

Orientador: Vitor BaranauskasDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de ComputaçãoResumo: Foi projetado e construído um reator para sintetização de filmes diamantíferos tubulares, por processo de deposição química a partir da fase vapor assistido por filamentos quentes (também conhecido como processo HFCVD - "Hot Filament assisted Chemical Vapor Deposition"). Obtiveram-se filmes de alta homogeneidade com a manutenção do substrato em rotação durante o crescimento. O torque para a rotação ocorre por acoplamento magnético de ímãs posicionados no suporte do substrato e ímãs montados em sistema externo ao reator, mantidos em rotação por um pequeno motor elétrico. Os materiais usados como substratos poderão ter secção de corte transversal circular, quadrada, triangular ou outra qualquer. No caso dos substratos serem ocos (caso mais comum) a temperatura é medida no interior do substrato durante o crescimento, sendo útil para determinar o tipo de material diamantífero que se pretende sintetizar: diamante, DLC (Diamond Like Carbon), carbono amorfo, diamante micro e nanocristalino, etc. São apresentados resultados de crescimento de filmes sobre tubos cilíndricos de quartzo e análise dos mesmos por microscopia eletrônica de varredura e espectroscopia Raman.Abstract: A hot-filament chemical vapor deposition system was designed and built to grow diamond thin films. This system fed with ethanol highly diluted in hydrogen was employed to deposited diamond layers onto quartz tubes with diameters of 6 mm and length of 10 cm. High uniformity microcrystalline diamond films were obtained thanks the maintenance of the substrate in rotation during growth process. The rotation of the substrate was carried out by magnetic coupling of magnets positioned into support of the substrate and magnets mounted in the system held in rotation by a small electric motor outside of the reactor. The temperature of the substrates was measured inside of them during the growth process. The control of the temperature is useful to determine the type of material that is intended to synthesize: micro and nanodiamond, Diamond Like Carbon (DLC), amorphous carbon and so on. This work presents the results of these growths and their characterization by scanning electron microscopy and Raman spectroscopy.MestradoEletrônica, Microeletrônica e OptoeletrônicaMestre em Engenharia Elétric

A rational experimental approach to identify correctly the working voltage window of aqueous-based supercapacitors

It is common to find in the literature different values for the working voltage window (WVW) range for aqueous-based supercapacitors. In many cases, even with the best intentions of the widening the operating voltage window, the measured current using the cyclic voltammetry (CV) technique includes a significant contribution from the irreversible Faradaic reactions involved in the water-splitting process, masked by fast scan rates. Sometimes even using low scan rates is hard to determine precisely the correct WVW of the aqueous-based electrochemical capacitor. In this sense, we discuss here the best practices to determine the WVW for capacitive current in an absence of water splitting using complementary techniques such as CV, chronoamperometry (CA), and the electrochemical impedance spectroscopy (EIS). To accomplish this end, we prepare and present a model system composed of multiwalled carbon nanotubes buckypaper electrodes housed in the symmetric coin cell and soaked with an aqueous-based electrolyte. The system electrochemical characteristics are carefully evaluated during the progressive enlargement of the cell voltage window. The presence of residual Faradaic current is verified in the transients from the CA study, as well as the impedance changes revealed by EIS as a function of the applied voltage, is discussed. We verify that an apparent voltage window of 2.0 V determined using the CV technique is drastically decreased to 1.2 V after a close inspection of the CA findings used to discriminate the presence of a parasitic Faradaic process. Some orientations are presented to instigate the establishment in the literature of some good scientific practices concerned with the reliable characterization of supercapacitors10CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP310544/2019-0; 301095/2018-32014/02163-7; 2017/11958-1; 2018/20756-

Effect of conductivity, viscosity, and density of water-in-salt electrolytes on the electrochemical behavior of supercapacitors: Molecular dynamics simulations and: In situ characterization studies

We report here molecular dynamics simulations combined with in situ experimental studies to understand the advantages and disadvantages of replacing conventional (salt-in-water, SiWE) aqueous-based electrolytes with very concentrated (water-in-salt, WiSE) systems in supercapacitors. Atomistic molecular dynamics simulations were employed to investigate the energetic, structural, and transport properties of aqueous electrolytes based on sodium perchlorate (NaClO4). Simulations covered the concentrations range of 1 mol dm-3 (1 mol kg-1) to 8 mol dm-3 (15 mol kg-1), demonstrating a significant increase in viscosity and density and reduction in ionic conductivity as the concentration reaches the WiSE conditions. A carbon-based symmetric supercapacitor filled with WiSE showed a larger electrochemical stability window (ESW), allowing to span the cell voltage and specific energy. Larger ESW values are possible due to the formation of a solvent blocking interface (SBI). The formation of ionic aggregates owing to the increasing cohesive energy in WiSE disturbs the hydrogen-bond network resulting in physicochemical changes in the bulk liquid phase. In addition, the molal ratio between water and ions is decreased, resulting in a low interaction of the water molecules with the electrode at the interface, thus inhibiting the water-splitting considerably.Fil: Da Silva, Débora A. C.. Universidade Estadual de Campinas; BrasilFil: Pinzón, Manuel J.. Universidade Estadual de Campinas; BrasilFil: Messias Da Silva, Andresa. Universidad Federal do Abc; Brasil. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Fileti, Eudes E.. Universidade de Sao Paulo; BrasilFil: Pascon, Aline. Universidade Estadual de Campinas; BrasilFil: Franco, Débora V.. University of Jequitinhonha e Mucuri's Valley; BrasilFil: Da Silva, Leonardo Morais. University of Jequitinhonha e Mucuri's Valley; BrasilFil: Zanin, Hudson G.. Universidade Estadual de Campinas; Brasi

ATLANTIC EPIPHYTES: a data set of vascular and non-vascular epiphyte plants and lichens from the Atlantic Forest

Epiphytes are hyper-diverse and one of the frequently undervalued life forms in plant surveys and biodiversity inventories. Epiphytes of the Atlantic Forest, one of the most endangered ecosystems in the world, have high endemism and radiated recently in the Pliocene. We aimed to (1) compile an extensive Atlantic Forest data set on vascular, non-vascular plants (including hemiepiphytes), and lichen epiphyte species occurrence and abundance; (2) describe the epiphyte distribution in the Atlantic Forest, in order to indicate future sampling efforts. Our work presents the first epiphyte data set with information on abundance and occurrence of epiphyte phorophyte species. All data compiled here come from three main sources provided by the authors: published sources (comprising peer-reviewed articles, books, and theses), unpublished data, and herbarium data. We compiled a data set composed of 2,095 species, from 89,270 holo/hemiepiphyte records, in the Atlantic Forest of Brazil, Argentina, Paraguay, and Uruguay, recorded from 1824 to early 2018. Most of the records were from qualitative data (occurrence only, 88%), well distributed throughout the Atlantic Forest. For quantitative records, the most common sampling method was individual trees (71%), followed by plot sampling (19%), and transect sampling (10%). Angiosperms (81%) were the most frequently registered group, and Bromeliaceae and Orchidaceae were the families with the greatest number of records (27,272 and 21,945, respectively). Ferns and Lycophytes presented fewer records than Angiosperms, and Polypodiaceae were the most recorded family, and more concentrated in the Southern and Southeastern regions. Data on non-vascular plants and lichens were scarce, with a few disjunct records concentrated in the Northeastern region of the Atlantic Forest. For all non-vascular plant records, Lejeuneaceae, a family of liverworts, was the most recorded family. We hope that our effort to organize scattered epiphyte data help advance the knowledge of epiphyte ecology, as well as our understanding of macroecological and biogeographical patterns in the Atlantic Forest. No copyright restrictions are associated with the data set. Please cite this Ecology Data Paper if the data are used in publication and teaching events. © 2019 The Authors. Ecology © 2019 The Ecological Society of Americ

Cylindrical diamond electrodes for wastewater treatment

Orientadores: Vitor Baranauskas, Alfredo Carlos PeterlevitzTese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de ComputaçãoResumo: Eletrodos cilíndricos de diamante foram desenvolvidos com até 75 cm2 de área e aplicados em degradações eletroquímicas de poluentes recalcitrantes em águas. Estudo sistemático foi realizado para a deposição de filmes de diamantes condutores e bem aderentes à superfície de diversos materiais. Estes eletrodos foram caracterizados em termos de suas propriedades físicas e eletroquímicas por microscopia eletrônica de varredura, espectroscopia Raman e de energia dispersiva de Raio-X, voltametria, nanoindentação, quatro pontas de prova e ensaios de aderência. As oxidações de diversos micro-poluentes emergentes em água foram estudadas e monitoradas por absorbância na região do UV/Vis, demanda química de oxigênio (COD) e carbono orgânico total (TOC). Os resultados obtidos nas eletrodegradações, empregando os eletrodos cilíndricos de diamante desenvolvidos, foram plenamente satisfatórios quando comparado com os melhores resultados já apresentados na literatura, utilizando placas de diamante convencionaisAbstract: Cylindrical diamond electrodes are developed with area up to 75 cm2 and were applied in electrochemical degradation of organic pollutants in wastewater. Systematic study was carried out to deposit conductive and well-adherent diamond onto several materials. These electrodes were characterized in term of their material and electrochemical properties by scanning electron microscopy (SEM), Raman and energy dispersive spectroscopy, voltammetry, nanoindentation, four points probe, pull-off test. The oxidation of several micro-pollutants in water were studied and monitored by UV/Vis absorbance, Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC). The electrodegradation results employing cylindrical boron-doped diamond (BDD) electrodes were satisfactory compared with best results obtained with conventional plate-shape BDD electrodesDoutoradoEletrônica, Microeletrônica e OptoeletrônicaDoutor em Engenharia Elétric

A perspective on silicon-based polymer-derived ceramics materials for beyond lithium-ion batteries

Energy storage devices beyond lithium-ion batteries (LIBs), such as sodium-ion, potassium-ion, lithium-sulfur batteries, and supercapacitors are being considered as alternative systems to meet the fast-growing demand for grid-scale storage and large electric vehicles. This perspective highlights the opportunities that Si-based polymer-derived ceramics (PDCs) present for energy storage devices beyond LIBs, the complexities that exist in determining the structure-performance relationships, and the need for in situ and operando characterizations, which can be employed to overcome the complexities, allowing successful integration of PDC-based electrodes in systems beyond LIBs