The optimal conditions for deposition of nickel coating and Ni-layered double hydroxide metal matrix composite coatings onto stainless steel discs in a modified all-sulfate solutions have been examined. Nickel films provide good general corrosion resistance and mechanical properties as a protective layer on many metallic substrates. In recent years, there has been interest in incorporation nano-dimensional ceramic materials, such as montemorillonite, into the metal matrices to improve upon the corrosion and mechanical properties. Layered double hydroxides have been used as corrosion enhancer in polymer coatings by increasing mechanical strength and lowering the corrosion rate but until now, have not been incorporated in a metal matrix by any means. Layered double hydroxides can be easily synthesized in a variety of elemental compositions and sizes but typically require the use of non-polar solvents to delaminate into nanodimensional colloidal suspensions. The synthesis of a Zn-Al LDH has been studied and characterized. The effects of the non-polar solvents dimethylformamide and n-butanol on the deposition and corrosion resistance of nickel coatings from a borate electrolyte bath have been studied, a nickel-LDH nanocomposite coating has been synthesized by electrochemical deposition and the corrosion resistance has been studied. Results indicate an improvement in corrosion resistance for the coatings with minimal change in the nickel matrix's internal strain and crystallite size.

The hybridization of direct write (DW) and additive manufacturing (AM) technologies to create additively manufactured electronics (AME) has enabled the integration of electrical functionality to form multifunctional AM components. Current work in AME has demonstrated the integration of conductive traces into and onto geometries and form factors that are not possible through traditional electronics packaging processes. This has largely been accomplished by using AM and DW technology to deposit conductive inks to form interconnects on the surface of AM substrates or within multimaterial AM geometries. However, the requisite thermal post-processing and high resistivity of the conductive inks and the limitations in thermal and dielectric performance of printable substrates commonly used in AME restrict the capabilities of these parts. This thesis proposes an alternative process for the conformal deposition of low resistivity traces on additively manufactured all-aromatic polyimides (AM-PI) without the use of conductive inks. This is accomplished through the selective patterning of laser induced graphene (LIG), a porous 3D graphene fabricated via laser irradiation, onto the AM-PI. While the resultant LIG is conductive, its resistivity is further reduced by the electrodeposition of copper (Cu-LIG). In this thesis, the synthesis of LIG on AM-PI, thermally post processed to 240℃, 300℃, and 450℃, is demonstrated and characterized through sheet resistance measurements and Raman spectroscopy. AM-PI post-processed to 300℃ demonstrated the lowest resistivity LIG formation (13.8 Ω/square). The resistivity of Cu-LIG is compared to an industry standard silver ink (Micromax CB028) used in direct write hybrid manufacturing applications. Cu-LIG was found to have a measured resistivity (1.39e-7 Ω·m), two orders of magnitude lower than the measured resistivity of the CB028 silver ink (1.62e-5 Ω·m). Additionally, the current capacity of the Cu-LIG was demonstrated and Joule heating of the material was observed via IR thermography. Cu-LIG demonstrated no failure of conductive trace or substrate under 5A of current for 2 minutes, heating to a maximum recorded temperature of 76.3℃. Several multifunctional components were fabricated as case studies to further validate the process. Several small passive electronic devices (e.g., a heater and an interdigitated capacitor) are fabricated to demonstrate selective deposition of complex copper traces. The fabrication of an Archimedes spiral on a hemispherical substrate via Cu-LIG is completed to demonstrate the ability to use the process to fabricate conformal conductive traces. An LED circuit is fabricated on a face-center cubic AM-PI lattice which demonstrates multi-planar fabrication on geometrically complex 3D printed substrates. / Master of Science / The hybridization of direct write (DW) and additive manufacturing (AM) technologies to create additively manufactured electronics (AME) has enabled the fabrication of AM components which have electronic functionality. Current work in AME has demonstrated the integration of conductive traces into and onto geometries and form factors that are not possible through traditional electronics packaging processes. This has largely been accomplished through the deposition of conductive inks to form interconnects on the surface of AM substrates or within multimaterial AM geometries. However, these conductive inks require thermal post-processing temperatures which exceed the thermal performance of common AM substrates. The dielectric performance of AM substrates is also restrictive to the capabilities of these parts. This thesis proposes an alternative process for the conformal deposition of low resistivity traces on high performance additively manufactured all-aromatic polyimides (AM-PI) without the use of conductive inks. This is accomplished through the selective patterning of laser induced graphene (LIG), a porous 3D graphene fabricated via laser irradiation, onto the AM-PI. While the resultant LIG is conductive, its resistivity is further reduced by the electrodeposition of copper (Cu-LIG). In this thesis, the synthesis of LIG on AM-PI, thermally post processed to 240℃, 300℃, and 450℃, is demonstrated and characterized through sheet resistance measurements and Raman spectroscopy. AM-PI post-processed to 300℃ demonstrated the lowest sheet resistance LIG formation (13.8 Ω/square). The resistivity of Cu-LIG is compared to an industry standard silver ink (Micromax CB028) used in direct write hybrid manufacturing applications. Cu-LIG was found to have a measured resistivity (1.39e-7 Ω·m), two orders of magnitude lower than the measured resistivity of the CB028 silver ink (1.62e-5 Ω·m). Additionally, the thermal performance and current capacity of the Cu-LIG was demonstrated by observing resistive heating of the material under current load via IR thermography. Cu-LIG demonstrated no failure of conductive trace or substrate under 5A of current for 2 minutes, heating to a maximum recorded temperature of 76.3℃. Several multifunctional components were fabricated as case studies to further validate the process. A heater and an interdigitated capacitor are fabricated to demonstrate selective deposition of complex copper traces. The fabrication of an Archimedes spiral on a dome via Cu-LIG is completed to demonstrate the ability to use the process to fabricate conformal conductive traces. An LED circuit is fabricated on an AM-PI lattice which demonstrates multi-planar fabrication on geometrically complex 3D printed substrates.

Com a Revolução Industrial e a adoção do modelo econômico urbano e industrial, baseado no consumo, ocorreu o aumento da geração de resíduos, frutos das diferentes atividades humanas. A galvanoplastia é um processo que embeleza e protege mecanicamente peças metálicas e está presente nas indústrias do setor metal-mecânico de Nova Friburgo. Neste processo, dois resíduos importantes são gerados: um oriundo do pré-tratamento das peças metálicas e outro das estações de tratamento de efluentes industriais. Neste trabalho, tais resíduos, denominados de (RGs), foram incorporados à borracha natural (NR) em substituição total ou parcial ao óxido de zinco (ZnO). O possível efeito ativador dos RGs sobre a vulcanização e as propriedades da borracha natural foi investigado. As misturas foram realizadas em um misturador de calandras, utilizando-se um sistema convencional (CV). A cinética de vulcanização foi estudada nas temperaturas de 150C, 160C e 170C, através de ensaios reométricos e a determinação de parâmetros tais como: tempo de pré-cura (ts1); tempo ótimo de vulcanização (t90); torques mínimo (Ml) e máximo (Mh); constantes de velocidade; e, energias de ativação. Com relação às propriedades mecânicas, a resistência à tração e a resistência ao rasgamento foram determinadas. As composições de NR contendo RGs apresentaram diminuição do tempo ts1, aumento das constantes de velocidade e diminuição das energias de ativação. No entanto, a resistência ao rasgamento foi mantida em um nível satisfatório apenas nas composições em que o ZnO foi substituído parcialmente em 25%. / With the Industrial Revolution and the adoption of urban and industrial economic model, based on consumption, there was an increased in the generation of wastes, as a result of different human activities. Electroplating is a process that embellishes and mechanically protects metallic parts and it is present in the industries of metalmechanical segment of Nova Friburgo. In this process, two important wastes are generated: one from pre-treatment of metal parts, other from industrial sewage station. In this investigation, these wastes, named RGs, were incorporated in the natural rubber (NR) in partial or total replacement to zinc oxide (ZnO). A possible activator effect of RGs upon vulcanization and properties of natural rubber was investigated. Mixes are prepared in a two-roll mixer using a conventional system (CV). Vulcanization kinetics was studied at 150, 160 and 170C through of rheometric tests and the determination of parameters such as: scorch time (ts1); optimum cure time (t90); minimum torque (Ml); maximum torque (Mh); constants rates (k); and, activation energies. In relation to mechanical properties, tensile and tear strength were determined. NR compositions with RGs presented a diminution in ts1 values, increase in the constants rates and diminution of activation energies. However, tear strength is maintained in a satisfactory level only in the compositions where ZnO was partially replaced in 25%.

Com a Revolução Industrial e a adoção do modelo econômico urbano e industrial, baseado no consumo, ocorreu o aumento da geração de resíduos, frutos das diferentes atividades humanas. A galvanoplastia é um processo que embeleza e protege mecanicamente peças metálicas e está presente nas indústrias do setor metal-mecânico de Nova Friburgo. Neste processo, dois resíduos importantes são gerados: um oriundo do pré-tratamento das peças metálicas e outro das estações de tratamento de efluentes industriais. Neste trabalho, tais resíduos, denominados de (RGs), foram incorporados à borracha natural (NR) em substituição total ou parcial ao óxido de zinco (ZnO). O possível efeito ativador dos RGs sobre a vulcanização e as propriedades da borracha natural foi investigado. As misturas foram realizadas em um misturador de calandras, utilizando-se um sistema convencional (CV). A cinética de vulcanização foi estudada nas temperaturas de 150C, 160C e 170C, através de ensaios reométricos e a determinação de parâmetros tais como: tempo de pré-cura (ts1); tempo ótimo de vulcanização (t90); torques mínimo (Ml) e máximo (Mh); constantes de velocidade; e, energias de ativação. Com relação às propriedades mecânicas, a resistência à tração e a resistência ao rasgamento foram determinadas. As composições de NR contendo RGs apresentaram diminuição do tempo ts1, aumento das constantes de velocidade e diminuição das energias de ativação. No entanto, a resistência ao rasgamento foi mantida em um nível satisfatório apenas nas composições em que o ZnO foi substituído parcialmente em 25%. / With the Industrial Revolution and the adoption of urban and industrial economic model, based on consumption, there was an increased in the generation of wastes, as a result of different human activities. Electroplating is a process that embellishes and mechanically protects metallic parts and it is present in the industries of metalmechanical segment of Nova Friburgo. In this process, two important wastes are generated: one from pre-treatment of metal parts, other from industrial sewage station. In this investigation, these wastes, named RGs, were incorporated in the natural rubber (NR) in partial or total replacement to zinc oxide (ZnO). A possible activator effect of RGs upon vulcanization and properties of natural rubber was investigated. Mixes are prepared in a two-roll mixer using a conventional system (CV). Vulcanization kinetics was studied at 150, 160 and 170C through of rheometric tests and the determination of parameters such as: scorch time (ts1); optimum cure time (t90); minimum torque (Ml); maximum torque (Mh); constants rates (k); and, activation energies. In relation to mechanical properties, tensile and tear strength were determined. NR compositions with RGs presented a diminution in ts1 values, increase in the constants rates and diminution of activation energies. However, tear strength is maintained in a satisfactory level only in the compositions where ZnO was partially replaced in 25%.

Low profile, conformal antennas have considerable advantages for Aerospace and Military platforms where conventional antenna system add weight and drag. Direct Write (DW) technology has been earmarked as a potential method for fabricating low profile antennas directly onto structural components. This thesis determines the key design rules and requirements for DW fabrication of planar antennas. From this, three key areas were investigated: the characterisation of DW ink materials for functionality and durability in harsh environments, localised processing of DW inks and the optimisation of DW conductive ink material properties for antenna fabrication. This study mainly focused on established DW technologies such as micro-nozzle and inkjet printing due to their ability to print on conformal surfaces. From initial characterisation studies it was found that silver based micro-nozzle PTF inks had greater adhesion then silver nano-particle inkjet inks but had lower conductivity (2% bulk conductivity of silver as opposed to 8% bulk conductivity). At higher curing temperatures (>300??C) inkjet inks were able to achieve conductivities of 33% bulk conductivity of silver. However, these temperatures were not suitable for processing on temperature sensitive surfaces such as carbon fibre. Durability tests showed that silver PTF inks were able to withstand standard aerospace environments apart from Skydrol immersion. It was found that DW inks should achieve a minimum conductivity of 30% bulk silver to reduce antenna and transmission line losses. Using a localised electroplating process (known as brush plating) it was shown that a copper layer could be deposited onto silver inkjet inks and thermoplastic PTF inks with a copper layer exhibiting a bulk conductivity of 66% bulk copper and 57% bulk copper respectively. This was an improvement on previous electroless plating techniques which reported bulk copper conductivities of 50% whilst also enabling DW inks to be plated without the need for a chemical bath. One of the limitations of many DW ink materials is they require curing or sintering before they become functional. Conventional heat treatment is performed using an oven which is not suitable when processing DW materials onto large structural component. Previous literature has investigated laser curing as means of overcoming this problem. However, lasers are monochromatic and can therefore be inefficient when curing materials that have absorption bands that differ from the laser wavelength. To investigate this, a laser diode system was compared to a broadband spot curing system. In the curing trials it was found that silver inks could be cured with much lower energy density (by a factor of 10) using the broadband white light source. Spectroscopy also revealed that broadband curing could be more advantageous when curing DW dielectric ink materials as these inks absorb at multiple wavelengths but have low heat conductivity. Themodynamical modelling of the curing process with the broadband heat source was also performed. Using this model it was shown that the parameters required to cure the ink with the broadband heat source only caused heat penetration by a few hundred micro-metres into the top surface of the substrate at very short exposure times (~1s). This suggested that this curing method could be used to process the DW inks on temperature sensitive materials without causing any significant damage. Using a combination of the developments made in this thesis the RF properties of the DW inks were measured after broadband curing and copper plating. It was found that the copper plated DW ink tracks gave an equivalent transmission line loss to a copper etched line. To test this further a number of GPS patch antennas were fabricated out of the DW ink materials. Again the copper plated antenna gave similar properties to the copper etched antenna. To demonstrate the printing capabilities of the micro-nozzle system a mock wireless telecommunications antenna was fabricated on to a GRP UAV wing. In this demonstrator a dielectric and conductive antenna pattern was fabricated on to the leading edge of the wing component using a combination of convection curing and laser curing (using an 808nm diode laser).

published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

Copper (Cu) electrodeposition on ruthenium (Ru) oxides was studied due to important implications in semiconductor industry. Ruthenium, proposed as the copper diffusion barrier/liner material, has higher oxygen affinity to form different oxides. Three different oxides (the native oxide, reversible oxide, and irreversible oxide) were studied. Native oxide can be formed on exposing Ru in atmosphere. The reversible and irreversible oxides can be formed by applying electrochemical potential. Investigation of Cu under potential deposition on these oxides indicates the similarity between native and reversible oxides by its nature of inhibiting Cu deposition. Irreversible oxide formed on Ru surface is rather conductive and interfacial binding between Cu and Ru is greatly enhanced. After deposition, bimetallic corrosion of Cu/Ru in different polyphenols was studied. Polyphenols are widely used as antioxidants in post chemical mechanical planarization (CMP). For this purpose, different trihydroxyl substituted benzenes were used as antioxidants. Ru, with its noble nature enhances bimetallic corrosion of Cu. Gallic acid (3,4,5 - trihydroxybenzoic acid) was chosen as model compound. A mechanism has been proposed and validity of the mechanism was checked with other antioxidants. Results show that understanding the chemical structure of antioxidants is necessary during its course of reaction with Cu.

The optimal conditions for deposition of zinc-nickel alloys onto stainless steel discs in alkaline solutions have been examined. In the past cadmium has been used because it shows good corrosion protection, but other methods are being examined due to the high toxicity and environmental threats posed by its use. Zinc has been found to provide good corrosion resistance, but the corrosion resistance is greatly increased when alloyed with nickel. The concentration of nickel in the deposit has long been a debated issue, but for basic solutions a nickel concentration of 8-15% appears optimal. However, deposition of zinc-nickel alloys from acidic solutions has average nickel concentrations of 12-15%. Alkaline conditions give a more uniform deposition layer, or better metal distribution, thereby a better corrosion resistance. Although TEA (triethanolamine) is most commonly used to complex the metals in solution, in this work I examined TEA along with other complexing agents. Although alkaline solutions have been examined, most research has been done in pH ≥ 12 solutions. However, there has been some work performed in the pH 9.3-9.5 range. This work examines different ligands in a pH 9.3-9.4 range. Direct potential plating and pulse potential plating methods are examined for optimal platings. The deposits were examined and characterized by XRD.

Aiming at applications in space exploration as well as for monitoring natural hazards, this thesis focuses on understanding and overcoming the challenges of extending the applicability of microsystems to temperatures above 600°C as well as chemically harsh environments. Alumina and zirconia high-temperature co-fired ceramics (HTCC) with platinum as the conductor material, have in this thesis, been used to manufacture a wide range of high-temperature tolerant miniaturized sensors and actuators, including pressure and flow sensors, valves, a combustor, and liquid monopropellant microthrusters. Interfacing for high temperatures is challenging. One solution is to transfer the signal wirelessly. Here, therefor, wireless pressure sensors have been developed and characterized up to 1000°C. It is usually unwanted that material properties change with temperature, but by using smart designs, such changes can be exploited to sense physical properties as in the gas flow sensor presented, where the temperature-dependent electrical conductivity of zirconia has been utilized. In the same manner, various properties of platinum have been exploited to make temperature sensors, heaters and catalytic beds. By in-situ electroplating metals after sintering, even more capabilities were added, since many metals that do not tolerate HTCC processing can be added for additional functionality. An electroplated copper layer that was oxidized and used as an oxygen source in an alumina combustor intended for burning organic samples prior to sample analysis in a lab on a chip system, and a silver layer used as a catalyst in order to decompose hydrogen peroxide in a microthuster for spacecraft attitude control, are both examples that have been explored here. Ceramics are both high-temperature tolerant and chemically resistant, making them suitable for both thrusters and combustors. The corresponding applications benefit from miniaturization of them in terms of decreased mass, power consumption, integration potential, and reduced sample waste. Integrating many functions using as few materials as possible, is important when it comes to microsystems for harsh environments. This thesis has shown the high potential of co-fired ceramics in manufacturing microsystems for aggressive environments. However, interfacing is yet a major challenge to overcome.

Cette thèse présente divers aspects du polissage des eaux usées de galvanoplastie par des zones humides artificielles : analyse de la performance, étude de la configuration et de la mise en œuvre, influence de différentes sources de carbone, évolution du substrat, l'analyse des plantes et des problèmes de conception.Les objectifs de ce travail sont triples: (i) étudier la faisabilité du polissage des effluents de la galvanoplastie, (ii) étudier l'influence des systèmes opérationnels, des plantes, du substrat et de la charge des eaux usées, (iii) comprendre les mécanismes conduisant à une diminution de la charge métallique dans des microcosmes de zones humides construites.Ce travail a fourni de nouvelles informations et élargi les connaissances actuelles sur le traitement des eaux usées industrielles dans les zones humides artificielles. En fait, il s'agit, à notre connaissance, de la première étude concernant l'élimination des métaux et du cyanure d'eaux usées par des zones humides artificielles en écoulement de sub-surface. / This thesis presents various aspects of polishing the electroplating wastewater in constructed wetlands: analysis of the performance, study on the operation and configuration effects, effects of various carbon sources, analysis of the substrate (bed media), analysis of plants, and design issues.The goals of the experiment were to: (i) study the feasibility of polishing electroplating effluent, (ii) study the effect of operating schemes, plants, bed media and wastewater strength, (iii) to elucidate metal removal mechanisms in the CW microcosms.This study furnished new information and expanded the existing knowledge on industrial wastewater treatment in constructed wetlands. In fact, this is, to the best knowledge, the first publication studying the removal of metals and cyanide from electroplating wastewater in subsurface flow constructed wetlands. The aim of this study was to study the polishing of the electroplating wastewater pretreated using physical-chemical methods.