O processo tradicional de recuperação de metais de resíduos de equipamentos eletroeletrônicos (REEE) geralmente envolve processamento pirometalúrgico. Entretanto, o uso desta tecnologia para processar placas de circuito impresso (PCI) obsoletas pode levar à liberação de dioxinas e furanos, devido à decomposição térmica de retardantes de chama e resinas poliméricas presentes no substrato das placas. Portanto, este trabalho propõe uma rota hidrometalúrgica para recuperação de metais. O comportamento dos metais, com destaque para cobre, zinco e níquel, durante a lixiviação ácida, foi estudado em três temperaturas diferentes (35ºC, 65ºC e 75ºC), com e sem adição de um agente oxidante (peróxido de hidrogênio H2O2). A cinética de dissolução ácida desses metais foi estudada baseada na análise química por ICP-OES (Espectrometria de emissão ótica por plasma acoplado indutivamente) e EDX (Espectroscopia de fluorescência de raios-X por energia dispersiva). O balanço de massa e a análise química indicaram que a etapa de lixiviação sem adição de oxidante é pouco eficaz na extração dos metais, sendo responsável pela dissolução de menos do que 6% do total extraído. A 65ºC e H2SO4 1 mol/L, com adição de 5 mL de H2O2 (30%) a cada quinze minutos e densidade de polpa de 1 g / 10 mL, 98,1% do cobre, 99,9% do zinco e 99,0% do níquel foram extraídos após 4 horas. A cinética de dissolução desses metais é controlada pela etapa da reação química, seguindo, dependendo da temperatura, a equação 1 (1 XB)1/3 = k1.t ou a equação ln (1 XB) = k4.t. / The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flameretardants and polymeric resins present in the board substrate. Therefore, this work proposes a hydrometallurgical route for the recovery of metals. The acid leaching behavior of metals, especially copper, zinc and nickel, has been investigated at three different temperatures (35ºC, 65ºC e 75ºC) with and without the addition of an oxidizing agent (hydrogen peroxide H2O2). The dissolution kinetics for acid leaching of these metals was studied based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry) and EDX (Energy Dispersive X-ray Spectroscopy). The mass balance and chemical analysis showed that the acid leaching without the addition of an oxidizing agent is inefficient at extracting the metals, being responsible for less than 6% of the total mass leached during the hydrometallurgical route proposed. At 65ºC with 1 mol/L H2SO4 added 5 mL H2O2 (30%) each fifteen minutes under pulp density of 1 g / 10 mL, 98,1% of copper, 99,9% of zinc and 99,0% of nickel were extracted after 4 hours. The dissolution kinetics of these metals, depending on the temperature, followed 1 (1 XB)1/3 = k1.t or ln (1 XB) = k4.t, i.e. chemically controlled reaction model.

O consumo de produtos eletroeletrônicos, em especial de computadores pessoais, aliado ao avanço tecnológico, diminui a vida útil dos equipamentos a cada geração e o intenso marketing gera um rápido processo de substituição. As placas de circuito impresso são encontradas em praticamente todos os equipamentos eletroeletrônicos e são particularmente problemáticas para reciclar devido à mistura heterogênea de material orgânico, metais e fibra de vidro. As placas de circuito impresso são industrialmente recicladas através de processos hidrometalúrgicos e pirometalúrgicos. A biolixiviação, que é baseada na capacidade de microrganismos solubilizarem metais, pode ser usada para recuperar metais de placas de circuito impresso de computadores. O presente trabalho investigou a recuperação de metais de placas de circuito impresso de computadores obsoletos através de processo biohidrometalúrgico. Para isto, as placas de circuito impresso foram processadas através de cominuição seguida de separações magnética e eletrostática. A bactéria Acidithiobacillus ferrooxidans-LR foi cultivada e adaptada na presença de placas de circuito impresso. Um estudo de frascos agitados foi realizado com amostras do material não-magnético das placas de circuito impresso para avaliar a influência da adaptação bacteriana, densidade de polpa, velocidade de rotação e concentração inicial de Fe+2 sobre o processo de biolixiviação. Lixiviação com sulfato férrico também foi estudada para efeitos de comparação. Os parâmetros analisados foram: pH, Eh, concentração de Fe+2, extração de metais, análises por EDS e MEV. Os resultados da caracterização mostraram que através da separação magnética é possível obter duas frações: material magnético, na qual ficou concentrado o ferro, permitindo sua posterior recuperação, e material não-magnético, na qual ficou concentrado cobre, zinco, alumínio, estanho e ouro. Para a extração de cobre, zinco e alumínio, os resultados do estudo de frascos agitados permitiram a definição das condições: densidade de polpa de 15gL-1, volume de inóculo (bactérias adaptadas) de 10% (v/v), velocidade de rotação de 170rpm, e concentração inicial de Fe+2 de 6,75gL-1. A lixiviação com sulfato férrico extraiu menos de 35% do cobre do que a biolixiviação, porém é um fator contribuinte assim como a lixiviação promovida pelo ácido sulfúrico. Imagens obtidas no MEV mostraram diferenças entre as superfícies das amostras do material não-magnético antes e depois da biolixiviação, evidenciando os pits de corrosão formados pelo contato da bactéria. / Consumption of electric and electronic devices, especially personal computers, coupled with technological advances, decreases equipments lifespan in each generation and intense marketing generates a rapid replacement process. Printed circuit boards are found in all electric and electronic equipment and are particularly problematic to recycle because of the heterogeneous mix of organic material, metals, and fiberglass. Printed circuit boards are industrially recycled by hydrometallurgical and/or pyrometallurgical processes. Bioleaching, which is based on microorganisms capacity to dissolve metals into soluble elements, can be used to metal recovery from printed circuit boards of computers. This study investigated metal recovery from printed circuit boards of obsolete computers by biohydrometallurgical process. Printed circuit boards from obsolete computers were processed by size reduction followed by magnetic and electrostatic separation. Bacteria Acidithiobacillus ferrooxidans-LR were grown and adapted in presence of printed circuit board. A shake-flask study was carried out with printed circuit board samples (non-magnetic material). Influence of bacterial adaptation, pulp density, rotation speed and initial Fe+2 concentrations on bioleaching were evaluated. Leaching in acidic ferric sulphate was also performed for comparison purposes. Analyzed parameters were: pH, Eh, ferrous iron concentration, metals extraction, EDS and SEM analysis. Characterization results shown that through magnetic separation, it is possible to obtain two fractions: magnetic material, which concentrated iron; and non-magnetic material, which concentrated copper, zinc, aluminum, tin and gold. Results obtained in the extraction of copper, zinc and aluminum allowed to define optimal conditions of bioleaching: pulp density of 15gL-1, inoculums volume (adapted bacteria) of 10% (v/v), rotation speed of 170rpm, and Fe+2 initial concentration of 6.75gL-1. Ferric iron leaching extracted less copper (35%) than bioleaching, but its a contribute factor as leaching promoted by diluted sulfuric acid. SEM analysis shown surface differences between non-magnetic material before and after bioleaching, showing corrosion pits formed by bacteria contact.

A geração global de resíduo eletrônico (REEE) cresce a uma taxa de cerca de 40 milhões de toneladas por ano. Este constante incremento na geração dos REEEs somado às recentes legislações tem impulsionado pesquisas focadas no desenvolvimento de processos para recuperação de materiais e sustentabilidade da indústria eletroeletrônica. Dentro destes resíduos encontram-se as placas de circuito impresso (PCIs) que estão presentes na maioria dos EEEs, têm composição heterogênea que varia conforme a fonte, país de proveniência e época, e tecnologia de fabricação. Assim, este trabalho teve por objetivo a realização de rota hidrometalúrgica (extração sólido/líquido) e biohidrometalúrgica para reciclagem de placas de circuito impresso provenientes de impressoras visando a recuperação de cobre. Para tanto fez-se inicialmente a caracterização da PCI e o desenvolvimento de uma rota combinada de processamento físico seguida por processo hidrometalúrgico ou biohidrometalúrgico. O processamento físico e de caracterização foi composto por etapas de cominuição, separação magnética, classificação granulométrica, visualização em lupa binocular, microscópio eletrônico de varredura acoplado com detector de energia dispersiva de raios X (MEV/EDS), digestão ácida, perda ao fogo e análise química por AAS e ICP. Já, o processamento hidrometalúrgico foi composto por duas etapas de extração sólido/líquido: a primeira em meio sulfúrico e a segunda em meio sulfúrico oxidante. Para os ensaios de biolixiviação utilizou-se uma cepa bacteriana composta por 3 espécies microbianas: Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans e Leptospirillum ferrooxidans. Verificou-se que a placa possui 4 camadas de Cu intercaladas por fibra de vidro, é lead free e seus componentes representam 53,3 % do seu peso. A porcentagem em massa correspondente ao material não magnético é de 74,6 % e do magnético 25,4 %. Os materiais moído e não magnético apresentaram tendência em se acumular nas frações mais grossas. Já na fração magnética, o acúmulo do material ocorreu na fração mais fina (0,053 mm). A separação dos metais através de classificação granulométrica não foi possível. A PCI estudada é composta por: 44% de metais, 28,5 % de polímeros e 27,5 % de cerâmicas. Sendo: Ag-0,31 %; Al3,73 %; Au0,004 %; Cu 32,5 %; Fe1,42 %; Ni0,34 %; Sn0,96 % e Zn0,64 %. A extração de Cu no processamento hidrometalúrgico foi de 100 % e o fator de recuperação 98,46 %, o que corresponde a uma recuperação de 32 kg de Cu em 100 kg de PCI. Já no processamento biohidrometalúrgico, a extração de Cu alcança 100 % quando utilizados 2 % de densidade de polpa e 100 % de inóculo. O fator de recuperação é de 100 % e a recuperação de Cu em 100 kg de PCI é de 32,5 kg. O processamento hidrometalúrgico apresenta como vantagens quando comparado ao biohidrometalúrgico: menor tempo de extração (8 h versus 4 dias); seletividade de Cu; maior densidade de polpa (10 % versus 2 %). Já a biolixiviação utiliza menor temperatura de trabalho (36 ºC versus 75 ºC) e dispensa a etapa de separação magnética. / The increase in the generation of waste electrical and electronic equipment (WEEE), 40 tons per year, allied with the enactment of new laws encouraged researches focused on the developing of processes to reclaim materials and on the sustainability of the electrical and electronics industry. Whithin the WEEEs, printed circuit boards (PCB) composition is heterogeneous and varies according to several factors, including: kind of EEE, when and where it was produced and fabrication technology. The goal of this work is to perfom a hydrometallurgical route (solid/liquid extraction) and a biohydrometallurgical route to recycle PCB from discarded printers aiming the recovery of copper. To do so, the first step is to characterize the PCB and the development of a combined fisical processing followed by hydrometallurgical and biohydrometallurgical routes. The fisical and the characterization processes, in that order, consisted on griding, magnetic separation, granulometric screening, visual assessement by binocular magnifier, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), acid digestion, loss on fire, and chemical analyzes by AAS and ACP-OES. The hydrometallurgical stage consisted on two steps: solid/liquid extraction by sulfuric acid leaching and solid/liquid extraction by sulfuric acid leaching with an oxidizing agent. The bioleaching tests used a mixed bacterial strain: Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans. The results showed that PCB consisted on 4 layers of copper and fiber glass, not possesing lead (leadfree) on its composition and its components constitute 53.3 % weight percentage. The non-magnetic fraction (NMA) weight percentage represents 74.6 %, the magnetc fraction (MA) represents 25.4 %. The grinded material and the non-magnetic fraction presented an inclination to build up on thickest fractions. On the magnetic fraction this behavior occurred on the thinnest fraction (0.053 mm). The metal separation using granulometric screening was not possible and the visual assessement by binocular magnifier was conclusive for this research. The composition of the studied PCB is: 44 % metal, 28.5 % polymer and 27.5 % ceramics. Beeing: Ag-0.31 %, Al-3.73 %, Au-0.004 %, Cu-32.5 %, Fe-1.42 %, Ni-0.34 %, Sn-0.96 %, Zn-0.64 % and other metals-4.10 %. Copper extraction in the hydrometallurgical process achieved 100 % and the recuperation factor 98.46 %, which means a recovery of 32 kg of copper in 100 kg of PCB. However in biohydrometallurgical process, the copper extraction reached 100 % on the forth day using a 2 % pulp density and 100 % inoculum. The recuperation factor achieved 100 % and, therefore, copper recovery in 100 kg of PCB is equivalent to 32.5 kg. The hydrometallurgical processing has many advantages compared to the biohydrometallurgical processing: a smaller extraction time (8 h versus 4 days); Cu selectivity; higher pulp density (10 % versus 2 %). However, bioleaching uses an inferior working temperature (36 ºC versus 75 ºC) and dont require magnetic separation.

In resource recovery from end-of-life printed circuit board (PCB), the physical processing route is considered most environmentally friendly. The −75 µm fraction generated during the comminution assays well above many precious and base metal deposits, but contributes overall drop in value recovery. This investigation was aimed at exploiting the versatility of froth flotation for beneficiation of the PCB comminution fines. Chemical composition characterisation work shows wet assay of constituents in the sample vary with digestion condition. Absolute assays as for hazardous constituents thus require comparison of data from more than one digestion condition. Comparative assaying of samples from beneficiation treatments can use aqua regia digestion which gives a less hazardous procedure compared to hydrogen fluoride combined with microwave and nitric acid treatments. It also gives leach liquor from which all constituent elements can be analysed, compared to that from total digestion via sodium peroxide fusion. For this sample total digestion will therefore not always give better results compared to partial digestion. Findings also show that thermogravimetric analysis may not be recommended in PCB characterisation. It gave no distinct inflexion point to characterize any constituent. This is due to the very diverse material constituents of the sample. Further on characterisation, the sample gave a loose bulk density lighter than water, and true sample density of 3 g/cm3. This coupled with surface hydrophobicity observed necessitates that pulping the sample must be done under water. Light optical and scanning electron microscopy showed particle liberation was very high, but not total. Morphology of the metallic particles was very diverse, with average circularity shape factor of 0.63. This coupled with the material diversity is a major constraint in sub-sieve size analysis of the sample. As shown by scanning electron microscopy energy dispersive X-ray spectroscopy, the liberated particles themselves contain more than one chemical element, being alloys. Beneficiation operation therefore cannot attempt to separate such particles into constituent elements but some bulk collection of metallic values into a concentrate. Reverse flotation of metallic values based on a scheme described as natural hydrophobic response (NHR) was found successful. Favorable kinetics under the scheme gave about 500 rpm and 500 ml/min aeration rate, at 300 g sample in a 3.5 l Leeds cell. Without the use of a collector, natural hydrophobic response was observed. The system also gave a stable froth without the aid of a frother. Investigations (surface tension and dynamic froth stability height measurements, combined with general literature) show the NHR froth is a fine particle stabilised froth, and not surfactant stabilised. Au and Pd, were among the elements best enriched into the sink; 64 % recovery for Au at enrichment ratio of three. Flotation over narrower and coarser fraction (+106 – 75 µm) shows the NHR scheme can be successfully applied at this size. Chemical conditioning schemes investigated shows very minimal responses to reagents. Potassium amyl xanthate (PAX) did not condition the metallic particles for flotation remarkably as it does with native metals. Sulfidation with sodium hydrogen sulfide shows a little improvement in response to PAX. Sodium mercaptobenzothiazole – a very selective collector for tarnished copper and lead minerals – did not show such selectivity in the PCB comminution fines pulp. Some cationic pull with tetrabutyl ammonium chloride towards selective pull of non-metallic values after NHR pull has subsided was observed, although very little also. Macromolecular depression with carboxyl methyl cellulose did not subdue the natural hydrophobic response up to profuse percentage dosages. Depression by lowering surface tension, described as gamma depression, using Betamin 127A (active constituent: ethoxy nonyl phenol) was effective to wet hydrophobic particles, but still not helpful for selective pull after chemical conditioning. At the lowered surface tension, frothing sets in coupled with entrainment. Probable causatives for the poor response to reagents are surface oxidation of the metallic particles and depression by calcium ions in pulp. Surface studies with field emission scanning electron microscope and auger electron spectroscopy composition depth profiling, show presence of organic layers on the surface of the metallic particles. The surfaces were also found to be oxidised down to about 340 nm depth profiled. None of the surfaces is a pure alloy, but occurring in forms that will be relatively inert to reagents. Beside these, from aqua regia wet assaying, the sample contains about 7 % calcium by mass, and ICP-MS trace element analysis of the process water confirms calcium presence up to 7 ppm equilibrium concentration in the pulp. Judging from the responses, the natural hydrophobic response scheme can be well recommended for PCB comminution fines flotation. Optimisation of the performance of the scheme responds remarkably well to kinetic parameters variation. With the generally low impeller energy and aeration rate found favourable for PCB CF flotation, and the zero reagent cost (no collector, no frother) of the NHR scheme, PCB comminution fines flotation shows good prospects. / Thesis (PhD)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

Orientador: Yuzo Iano / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-27T18:51:43Z (GMT). No. of bitstreams: 1 Camilo_Edson_M.pdf: 3518346 bytes, checksum: 0264cd60aaed512cef0dacda58a43540 (MD5) Previous issue date: 2015 / Resumo: Este trabalho de Mestrado tem como objetivo contribuir para a área de placa de circuito impresso no que se refere ao projeto de layout focado não só em satisfazer as conexões das trilhas, mas nas regras de projeto com foco na redução de curto circuito de solda para o processo de solda por onda. Projetos de PCB (Printed Circuit Board) ou PCI (Placa de Circuito Impresso) envolvem uma série de conhecimentos no que se refere ao entendimento das funcionalidades dos circuitos e para tanto é importante que se faça o correto posicionamento dos componentes em grupos de circuitos pela funcionalidade; além disso, é importante que se conheça as regras de capacidade de corrente, de distâncias de isolação em função das tensões aplicadas, características de impedância, áreas de restrição mecânica entre outras. O que será visto neste trabalho está focado na aplicação de conceitos e considerações ligadas ao processo de montagem da placa eletrônica por solda a onda. Muitos dos defeitos que ocorrem num processo de montagem da PCB são atribuídos ao processo de montagem da PCB como, por exemplo, a temperatura da solda, o tempo de solda, quantidade de fluxo aplicado na placa, altura da onda de solda, etc. Recomendações sobre posicionamento de componentes PTH (Pin Through Hole) e SMD (Surface Mounting Devise) em relação ao sentido em que a PCB entra em direção à solda a onda, recursos de aplicação de serigrafia, tipos de laminados, de formato das ilhas de solda, adição de técnica de ladrão de solda e as recomendações da IPC (Association Connecting Electronics Industries) serão descritos neste trabalho. O correto entendimento dos defeitos que ocorrem durante o processo de montagem da PCB reflete na constante melhoria e aperfeiçoamento do projeto do layout da placa, que por sua vez resulta num processo de montagem de placa com menos ocorrência de defeitos de fabricação e consequentemente melhor qualidade do produto. Menos retrabalho nas PCBs significa menos custo de produção que reflete em maior lucro para as empresas. As propostas apresentadas neste trabalho são fruto de resultados práticos vivenciados na indústria e de pesquisa em literatura dos assuntos relacionados a defeitos em PCB e processos de solda por onda. O conjunto destas recomendações e seus resultados estão aqui descritos e ilustrados para servirem de referência aos futuros pesquisadores e leitores / Abstract: This work aims to contribute to the area of the printed circuit board in regard to layout design focused not only on satisfying the connections of the tracks but the design rules focused on reducing short- circuit solder for wave solder process . Projects PCB (Printed Circuit Board) involve a lot of knowledge when it comes to understanding the features of both circuit and is important to make the correct positioning of components into groups of circuits for feature addition is important to know the rules of current capacity, isolation distances depending on the applied voltage, impedance characteristics, areas of mechanical restrictions among others. What will be seen in this work is focused on application of concepts and considerations involved in the process of mounting the electronic board by solder wave. Many of the defects which occur in the process of assembling the PCB are assigned to the PCB assembly process such as the temperature of the solder, weld time , amount of flux applied to the board, solder wave height, etc. Recommendations on positioning components PTH( Pin Through Hole) and SMD( Surface Mounting Devise) relative to the direction in which the PCB goes toward the wave solder , screen printing application features , format type of solder lands , techniques of solder thief and the IPC ( Association Connecting Electronics Industries) recommendations will be described on this work . The correct understanding of the defects that occur during the assembly process of the PCB reflects on constant improvement and refinement of the board layout design, which in turn results in a process of mounting plate with fewer occurrences of defects in workmanship and consequently better quality product. Less rework means less PCBs in production cost which reflects in higher profits for companies. The proposals presented in this paper are the result of practical results experienced in industry and research literature on the subjects related to defects in PCB and wave solder processes. All these recommendations and their results are described and illustrated to better serve as reference for future researchers and readers / Mestrado / Telecomunicações e Telemática / Mestre em Engenharia Elétrica

Aim of this Diploma thesis was to create a device capable of receiving navigational data from GPS. These data are subsequently stored in fixed memory and after connection with the PC are displayed it on the satellite map. The device was realized by using FPGA and GPS module LEA-5s. Description was created in the VHDL language, which was implemented into the circuit. The part of VHDL design was description of PICOBLAZE processor that controls whole system. For displaying and archiving data stored in device was created PC application GPS TRACER. It is able to display stored trace on the satellite map by using Google maps server. For created device were designed and manufactured PCBs, which were manually fitted.

This work deals with the design scheme and printed circuit boards for drives teaching laboratory Stand, for teaching at the Department of Power Electrical and Electronic VUT Brno.

The project idea was created from the demand of a renewal for a Power Distributor Unit also known as a PDU. The current product had successively turned in to a cable mess because of short term solutions. This made the product non user friendly, inconvenient and non-agile to handle troubleshooting. To develop this project, a PCB design was created by simplifying and improving circuit diagrams until satisfied. Once the final circuit diagram was obtained, a PCB layout design was created. The result of the project, due to limited time, was only theoretical. The finished product was not tested as there was no time allowing this.

Microfluidic flow devices coupled with quantitative Raman spectroscopy are able to provide a deep insight into the reaction mechanism and kinetics of electrocatalytic reactions. With a microfluidic flow device made with glass microscope slides and polymer building blocks, the feasibility of this technique was examined by methanol electrooxidation reaction with a Pt working electrode. Pre-calibration of the Raman peak area was done with solutions of known concentrations of methanol and its major oxidation product, i.e., formate, which enabled the time-dependent Raman spectra taken during the reaction to be converted to time-dependent concentrations. These were interpreted in terms of a model with one-dimensional convection and the reaction kinetics. An improved version of this technique was then applied to a comparative study of different alcohols with Ni-based electrodes. This showed the production of formate as the major product from the oxidation of alcohols with vicinal OH groups, leading to the discovery that C-C bond dissociation is a major reaction pathway for vicinal diols and triols if Ni electrocatalysts are used. It is also suggested that the cleavage of C-C bonds is the rate-determining step. The potential use of printed circuit boards (PCB) in the next generation of a novel microfluidic device was explored, as PCB have advantages over regular electrochemical microfluidic substrates, such as simpler electrode fabrication strategies, more wiring layers, and customization of size and shape of electrodes. Pretreatments and electrodeposition protocols of nickel, silver, palladium and platinum on PCB were successfully developed, together with four types of PCB-based microfluidic devices designed with an open-source PCB design software. This work establishes a new electrochemical microfluidic platform for online and in-situ monitoring of electrocatalytic reactions, which can quickly determine the reaction mechanism and kinetics. / Graduate

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第17966号 / エネ博第291号 / 新制||エネ||60(附属図書館) / 30796 / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 石原 慶一, 教授 東野 達, 教授 酒井 伸一 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM