O revestimento de níquel químico é largamente utilizado na proteção contra a corrosão de equipamentos e estruturas utilizados na exploração de petróleo em águas profundas. Apesar de ser considerado um dos revestimentos mais adequados para esta finalidade, são muitos os casos em que se verificam falhas prematuras do revestimento em serviço. Isto tem sido atribuído às diferenças nas características do revestimento decorrentes das diferenças do processo de aplicação e da natureza e preparação da superfície dos substratos a serem protegidos. Estas diferenças decorrem do fato de não existirem especificações abrangentes que definam as características necessárias do revestimento para uma garantia de qualidade. Diante disto, o presente trabalho teve como objetivo estudar a influência dos principais fatores sobre o desempenho dos revestimentos de níquel químico utilizando ferramentas estatísticas como: planejamento fatorial, seleção dos melhores subconjuntos de regressão, regressão múltipla e curvas de nível. Os fatores considerados neste estudo foram: tipo e estado superficial do substrato, idade do banho, teor de fósforo no revestimento, natureza e teor de contaminantes no revestimento, espessura do revestimento e tipo de tratamento térmico. A caracterização dos revestimentos de níquel químico foi realizada conforme sugerida na norma ISO 4527 e o desempenho dos revestimentos foi verificado por meio dos ensaios de exposição à névoa salina (1 536 h), exposição ao dióxido de enxofre (10 ciclos) e imersão em água do mar sintética (120 dias). Ensaios eletroquímicos (polarização linear e espectroscopia de impedância eletroquímica) foram realizados somente com o intuito de compará-los ao ensaio de exposição à névoa salina e,assim, ter um ensaio capaz de verificar revestimentos de bom desempenho em um período de tempo menor. Dentro dos intervalos estudados, verificou-se que o desempenho do revestimento de níquel químico é influenciado pelo tipo de substrato, pela espessura da camada depositada, pelo teor de fósforo, pela idade do banho, pelo tratamento térmico e pelos teores dos seguintes contaminantes: enxofre, chumbo, magnésio, cobre, ferro e manganês. A metodologia estatística adotada permitiu verificar a interação entre os fatores influenciadores, fato não considerado na literatura consultada. Além disto, foi possível constatar que os ensaios adotados nas normas internacionais atuais são adequados para verificar a qualidade dos revestimentos. Verificou-se também que os ensaios eletroquímicos, apesar de adequados para o estudo da resistência intrínseca à corrosão do revestimento de níquel químico, não se mostraram adequados para detectar a presença de porosidade que é o principal indicativo da qualidade de proteção por barreira de revestimentos catódicos como o níquel químico. Com os resultados obtidos, será possível a elaboração de uma especificação para se obter revestimentos de níquel químico com bom desempenho. / The autocatalytic nickel-phosphorus (NiP) or electroless nickel (EN) coatings are widely used to protect equipment and structures against corrosion and erosion, used in the exploitation of petroleum in deep waters. Even though NiP is considered as the most appropriate coating for this purpose, many premature failures are verified in service. This has been attributed to the differences in the characteristics of the coating due to the differences in the application processes and in the nature and preparation of the substrate surfaces. The lack of broad specifications that define the required characteristics of the good quality coating is responsible for those differences. The present work had as its objective to identify the main factors related to the NiP performance using statistical tools as: factorial design, best subset regression, multiple regression and contour diagram. The considered factors were: substrate type, substrate surface finishing, bath age, phosphorus content, thickness, heat treatment and impurities. The NiP coatings were characterized in agreement with the ISO 4527 and their performance was verified through the salt spray test (1 536 h), the Kesternish test (10 cycles) and the synthetic sea water immersion test (120 days). Electrochemical tests (linear polarization and electrochemical impedance spectroscopy) were conducted in order to compare them to the salt spray test and thus reducing the testing time. In the studied range, it was verified that the NiP performance is influenced by the following factors: substrate type, thickness coating, phosphorus content, bath age (MTO), heat treatment and the impurities: sulfur, lead, magnesium, copper, iron and manganese. It was possible to verify that the types of accelerated corrosion tests adopted in the current international standards are appropriate to verify the quality of the coatings. It was also verified that the electrochemical tests, despite being suitable to indicate the NiP intrinsic corrosion resistance, are not appropriate to verify the NiP porosity (which is the main indication of a cathodic coating quality). With the obtained results, it will be possible to establish a better specification in order to obtain NiP with good quality.

This work provides a detailed characterization study on H2S poisoning of Pd and Pd/Au alloy composite membranes to obtain fundamental understandings of sulfur poisoning phenomena and preparation of sulfur tolerant membranes. The enhancement of the sulfur tolerance by alloying Pd with Au has been confirmed by both permeation test and microstructure analysis (SEM and XRD). While pure Pd membranes exhibited the permeance decline in the presence of H2S due to both sulfur adsorption and bulk Pd4S formation, Pd/Au alloy membranes showed the permeance loss merely resulted from the surface sulfur adsorption without bulk sulfide formation up to 55 ppm H2S. The XPS study confirmed that the H2S adsorption on the Pd/Au alloy surfaces was dissociative, and both surface Au and Pd sulfides were formed with the preferential Au-S bonding. The adsorption type of sulfur on the Pd/Au alloy surfaces was monolayer with a limited coverage, which increased with decreasing temperature. The permeance loss of Pd/Au membranes was essentially fully recoverable in H2, and the integrity of the membranes remained unaltered after the poisoning/recovery tests. Increasing Au composition in the Pd/Au membranes increased the sulfur tolerance. A Pd/Au alloy membrane of 16.7 wt% Au exhibited a permeance over 50% of its original value in the presence of 5 ppm H2S at 400°C, while a Pd membrane showed 85% permeance loss. The Pd/Au alloy membranes were fabricated by the Au displacement deposition, which had an empirical reaction order of 3.2 determined by the AAS. The HT-XRD study verified that the formed Pd/Au alloy layers were thermally stable up to 500°C.

ABSTRACT Recent global interests in developing hydrogen economy generate substantial research and development for hydrogen production worldwide. Pd membranes are especially suited for high temperature hydrogen separation and membrane reactor applications. Alloying Pd with Ag not only suppresses hydrogen embrittlement, but also increases the permeability of the alloy membrane. The main objective of this work was to carry out fundamental studies to understand the properties of the porous stainless steel (PSS), morphologies of Pd and Ag deposits on PSS, and the structural changes of the membrane layer upon heat treatment. Both coating and diffusion and co-plating techniques were employed in the study. The Pd-Ag membranes that had sandwiched Ag layers suffered from very low selectivity due to the voids formed because of high diffusion rate of Ag. Alloy membranes with high selectivity can be prepared by applying intermediate annealing after each Ag deposition. On the other hand, the homogeneity of the alloy depended very much on the thickness of the deposited layers and annealing temperature and time. A stable co-plating bath was developed to co-plate Pd and Ag simultaneously. Pd-Ag membranes were prepared from co-plating bath using ultrasound to accelerate the plating rate.

A process for micromachining of micro-mirror devices from silicon-on-insulator wafers was proposed and implemented. Test methods and force applicators for these devices were developed. Following successful fabrication of these devices, a novel process for fabrication of devices out of the plane of the silicon wafer was proposed, so that the devices could be actuated electrostatically. In particular, the process makes use of thick photoresist layers as a sacrificial mold into which an amorphous nickel-phosphorous alloy may be deposited. Ideal design of the electrostatically actuated micro-mirrors was investigated, and a final design was selected and modeled using FEA software, which found that serpentine-hinged devices require approximately 33% of the actuation force of their straight-beamed counterparts. An aqueous electroless plating solution composed of nickel acetate, sodium hypophosphite, citric acid, ammonium acetate, and Triton X-100 in was developed for use with the process, and bath operating parameters of 85°C and 4.5 pH were determined. However, this electroless solution failed to deposit in the presence of the photoresist. Several mechanisms proposed for deposition failure included leaching of organic solvents from the photoresist, oxidation of the nickel-titanium seed layer on which the deposition was intended to occur, and nonlinear diffusion of dissolved oxygen in the solution.

Ce projet de recherche avait pour objectif de répondre à un enjeu industriel: Développer un procédé " propre " de métallisation des polymères sans satinage à l'acide chromique (CrVI). Au cours de ce travail, un procédé alternatif s'appuyant sur une technologie innovante de revêtement de surface (la technologie Graftfast®) a été développé. Ce procédé utilisable dans l'eau et à température ambiante permet de greffer chimiquement des polymères vinyliques sur une large gamme de surfaces de natures différentes. Par cette méthode, une couche d'acide polyacrylique (PAA) a été greffée de manière covalente sur différents substrats polymériques (ABS, ABS-PC, PA, PET, PVC, PVDF...). Les propriétés chélatantes des groupes introduits dans ces films minces de polymères ont été mises à contribution pour l'immobilisation de sels métalliques. Une fois réduites au sein de cette interphase, les particules métalliques ont permis la croissance de la couche métallique par immersion dans un bain Electroless en jouant le rôle de catalyseur. Les couches métalliques résultantes ont montré des propriétés électriques et mécaniques identiques à celles obtenues par les procédés industriels actuels. Combiné à des procédés lithographiques bas coûts et innovants, des motifs métalliques localisés sur substrats flexibles et transparents (PET and PVDF) ont été réalisés à l'échelle micrométrique. Afin de répondre encore plus fortement aux contraintes environnementales et économiques actuelles, le procédé de fonctionnalisation de surface par immersion (Graftfast®) a été remplacé par un procédé par impression jet d'encre photo-assisté. Des motifs métalliques sur substrats flexibles du type papier glacé (PVC) ou transparents (PET) avec une résolution micrométrique ont aussi été réalisés. Ces structures présentent également d'excellentes propriétés électriques et mécaniques et laisse envisager une utilisation de ce procédé pour des applications dans le domaine de la microélectronique.

<p>South Africa s coal and platinum mineral resources are crucial resources towards creating an alternative and environmentally sustainable energy system. The beneficiation of these natural resources can help to enhance a sustainable and effective clean energy base infrastructure and further promote their exploration and exportation for economics gains. By diversification of these resources, coal and the platinum group metals (PGMs) especially palladium market can be further harnessed in the foreseeable future hence SA energy security can be guaranteed from the technological point of view. The South Africa power industry is a critical sector, and has served as a major platform in the South African socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. The South Africa power industry is a critical sector, and has served as a major platform in the SA&rsquo / s socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. Coal gasification is considered as a source of hydrogen gas and the effluent gases released during this process include hydrogen sulphide, oxides of carbon and nitrogen, hydrogen and other particulates. In developing an alternative hydrogen gas separating method, composite membrane based on organic-inorganic system is being considered since the other available methods of hydrogen separation are relatively expensive.<br /> &nbsp / </p>

In this work, Poly (diallyldimethylammonium) chloride - (PDDA) was used as a base layer for developing colloid displacement lithography platforms for sensor applications. Previous work shows that glass coated with PDDA and exposed to gold acts as a good platform for colloid displacement lithography. However, for actual sensor applications, electrical isolation of individual sensor sections must be achieved. This is attempted by laying down a 40 μm stripe of PDDA on a cleaned substrate and coating that stripe with gold colloid. The size of 40 μm or less in width is set as the target to fit within the scan window of the AFM. Stripes wider than about 40 μm would be difficult to efficiently pattern with colloid displacement lithography. While the goal of 40 μm wide stripes was achieved with sufficiently diluted PDDA solution, it was found to be difficult to adsorb sufficient amounts of gold colloid on those stripes before the stripes were lost from the glass substrate. Further, electroless deposition was found to produce only a small amount of gold on the PDDA surface without colloid nucleation sites being present.

Šiame darbe tiriami polihidroksiliai alkoholiai sacharozė bei glicerolis, kaip ligandų alternatyvos cheminio variavimo sistemoms su reduktoriumi formaldehidu. Tai yra ekologiškos, biologiškai lengvai suyrančios medžiagos. Šiame darbe atlikti šių medžiagų kompleksų pusiausvyros skaičiavimai, eksperimentai parodantys sacharozės bei glicerolio praktinį pritaikomumą cheminio variavimo sistemose. Ultragarso poveikio cheminėms sistemoms dėsningumai dar nėra vienareikšmiškai ištirti ir suprasti. Siekiant padaryti cheminį metalų nusodinimą efektyvesniu pastaruoju metu cheminio metalizavimo procesams bandoma taikyti ultragarsą. Atlikti tyrimai parodė, kad naudojant sacharozę ir glicerolį ligandais cheminio variavimo tirpaluose vario nusėdimo greitis optimaliomis sąlygomis siekia atitinkamai 2,2 ir 3,4 m/h, o chemiškai nusodinto vario paviršiaus šiurkštumo faktoriai varijuoja 8,5-25,3 ir 2,3-4,3 ribose. Analizuojant gautus duomenis stebimos koreliacijos tarp vario nusėdimo greičio, viršįtampio, paviršiaus šiurkštumo faktoriaus, formaldehido anodinės oksidacijos srovių maksimumų priklausomybių nuo pH. Ultragarso panaudojimas cheminio variavimo sistemose keičia vario nusėdimo greičius. Priklausomai nuo pasirinktos cheminio variavimo sistemos, ultragarso dažnio ar jo skleidimo būdo vario nusėdimo greitis sumažėja iki visiško proceso sustabdymo arba gali padidėti 2-5 kartus ir pasiekti dideles vertes (10,87 μm/h). Ultragarso aplinkoje dažniausiai susiformuoja kompaktiškesnės, lygesnės... [toliau žr. visą tekstą] / This work investigates polyols – glycerol and sucrose – as an alternative ligand for electroless copper plating systems with reducer formaldehyde. Natural polyols are environmentally friendly, easily bio-degradable materials, but has not been studied enough for suitability for copper plating systems. In order to increase of the efficiency, the electroless copper plating was investigated in ultrasonic milieu to observe how ultrasound impacts the copper plating rate and properties of the obtained coatings. Studies have shown that sucrose and glycerol can be used as ligands in solutions for electroless copper plating. A plating rate of copper under optimum conditions can reach 2.2 m h-1 (sucrose) and 3.4 m h-1 (glycerol) and copper surface roughness factors ranging 8.5 - 25.3 (sucrose) and 2,3 - 4.3 (glycerol). Correlations between dependences on pH observed for copper plating speeds, overpotentials, surface roughness factors, anodic oxidation currents of formaldehyde. A use of ultrasound for electroless copper plating systems change speeds. Depending on the choice of copper plating system and ultrasonic frequency, plating rate can decrease or may increase up to 5 times and can reach high values (10.87 m h-1). The copper surface formed in ultrasound environment more compact, smoother.

This work investigates polyols – glycerol and sucrose – as an alternative ligand for electroless copper plating systems with reducer formaldehyde. Natural polyols are environmentally friendly, easily bio-degradable materials, but has not been studied enough for suitability for copper plating systems. In order to increase of the efficiency, the electroless copper plating was investigated in ultrasonic milieu to observe how ultrasound impacts the copper plating rate and properties of the obtained coatings. Studies have shown that sucrose and glycerol can be used as ligands in solutions for electroless copper plating. A plating rate of copper under optimum conditions can reach 2.2 m h-1 (sucrose) and 3.4 m h-1 (glycerol) and copper surface roughness factors ranging 8.5 - 25.3 (sucrose) and 2,3 - 4.3 (glycerol). Correlations between dependences on pH observed for copper plating speeds, overpotentials, surface roughness factors, anodic oxidation currents of formaldehyde. A use of ultrasound for electroless copper plating systems change speeds. Depending on the choice of copper plating system and ultrasonic frequency, plating rate can decrease or may increase up to 5 times and can reach high values (10.87 m h-1). The copper surface formed in ultrasound environment more compact, smoother. / Šiame darbe tiriami polihidroksiliai alkoholiai sacharozė bei glicerolis, kaip ligandų alternatyvos cheminio variavimo sistemoms su reduktoriumi formaldehidu. Tai yra ekologiškos, biologiškai lengvai suyrančios medžiagos. Šiame darbe atlikti šių medžiagų kompleksų pusiausvyros skaičiavimai, eksperimentai parodantys sacharozės bei glicerolio praktinį pritaikomumą cheminio variavimo sistemose. Ultragarso poveikio cheminėms sistemoms dėsningumai dar nėra vienareikšmiškai ištirti ir suprasti. Siekiant padaryti cheminį metalų nusodinimą efektyvesniu pastaruoju metu cheminio metalizavimo procesams bandoma taikyti ultragarsą. Atlikti tyrimai parodė, kad naudojant sacharozę ir glicerolį ligandais cheminio variavimo tirpaluose vario nusėdimo greitis optimaliomis sąlygomis siekia atitinkamai 2,2 ir 3,4 m/h, o chemiškai nusodinto vario paviršiaus šiurkštumo faktoriai varijuoja 8,5-25,3 ir 2,3-4,3 ribose. Analizuojant gautus duomenis stebimos koreliacijos tarp vario nusėdimo greičio, viršįtampio, paviršiaus šiurkštumo faktoriaus, formaldehido anodinės oksidacijos srovių maksimumų priklausomybių nuo pH. Ultragarso panaudojimas cheminio variavimo sistemose keičia vario nusėdimo greičius. Priklausomai nuo pasirinktos cheminio variavimo sistemos, ultragarso dažnio ar jo skleidimo būdo vario nusėdimo greitis sumažėja iki visiško proceso sustabdymo arba gali padidėti 2-5 kartus ir pasiekti dideles vertes (10,87 μm/h). Ultragarso aplinkoje dažniausiai susiformuoja kompaktiškesnės, lygesnės... [toliau žr. visą tekstą]

<p>South Africa s coal and platinum mineral resources are crucial resources towards creating an alternative and environmentally sustainable energy system. The beneficiation of these natural resources can help to enhance a sustainable and effective clean energy base infrastructure and further promote their exploration and exportation for economics gains. By diversification of these resources, coal and the platinum group metals (PGMs) especially palladium market can be further harnessed in the foreseeable future hence SA energy security can be guaranteed from the technological point of view. The South Africa power industry is a critical sector, and has served as a major platform in the South African socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. The South Africa power industry is a critical sector, and has served as a major platform in the SA&rsquo / s socio-economic development. This sector has also been identified as a route towards an independent energy base, with global relevance through the development of membrane technologies to effectively and economically separate and purify hydrogen from the gas mixtures released during coal gasification. Coal gasification is considered as a source of hydrogen gas and the effluent gases released during this process include hydrogen sulphide, oxides of carbon and nitrogen, hydrogen and other particulates. In developing an alternative hydrogen gas separating method, composite membrane based on organic-inorganic system is being considered since the other available methods of hydrogen separation are relatively expensive.<br /> &nbsp / </p>