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In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials.

In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials.

In some systems, including copper niobium, it has been found that as the scale of the two phases decreases, there is an anomalous increase in strength. Mechanisms of this strengthening have been postulated, but a general theory has yet to be developed. A model system to study the co-deformation of fine scale materials was developed and characterized. An aluminum 18.5at.% zinc alloy was selected and discontinuously precipitated to produce 100% transformation and an interlamellar spacing of 240nm.The material was tested using strain rate jump tests to determine the temperature sensitivity, tensile tested to determine work hardening and the temperature sensitivity, wire drawn to study the effect of large plastic deformation and finally tension compression tested to determine internal stresses. The bulk properties of the two phases are well known allowing for a detailed analysis of the composite properties when combined with the mechanical results. The material showed increased strength above the rule of mixture prediction from bulk properties due to a fine scale microstructure . Although the lamellar material had a much higher strength than the rule of mixtures would predict, the overall strength of the alloy did not approach that of more conventional high strength aluminum alloys. The material was found to be temperature and rate dependent, with an increased work hardening rate as the temperature was decreased. Temperature was found to play a key role in the stress partitioning between the two phases. Temperature dependent relaxation processes lowered the stress partitioning between the hard and soft phases as the temperature was increased. Therefore, stress relaxation must be minimized to maximize the strengthening found in fine scale materials. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

In this thesis, in investigation of various diffusion couple designs is discussed with the aim of enhancing the interaction between the three diffusive flow. Experimental investigation of the theoretical predictions his been carried out for infinite and finite couple boundary conditions. The four independent diffusion coefficients in the copper-rich copper-zinc-tin system have been measured it two temperatures for the dilute composition range. / Thesis / Master of Science (MS)

Orientador: Celia Marina de Alvarenga Freire / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-13T07:27:48Z (GMT). No. of bitstreams: 1 Santos_MarciaCristinaGoncalvesdos_D.pdf: 5280662 bytes, checksum: 763649a5f0d49aa48853a896ab0335c2 (MD5) Previous issue date: 2009 / Resumo: Aço galvanizado e aço eletrodepositado com liga ZnFe são materiais comuns na indústria de construção civil e automotiva. Esses materiais à base de zinco necessitam, entretanto, serem protegidos de ambientes corrosivos através de um tratamento de superfície que geralmente contém cromo hexavalente ( Cr6+), tóxico para o meio ambiente e cancerígeno para o homem. O presente trabalho apresenta um estudo com filmes contendo diferentes silanos: viniltrietoxissilano (VS), bis-(1,2-[trietoxissilil] etano) (BTSE) ou bis-(3-[trietoxissilil]-propil? tetrassulfeto (BTESPTS) e nitratos de terras raras (Ce ou La), como revestimentos de conversão para a camada de liga ZnFe. Esses sistemas foram avaliados através das análises de Espectroscopia Fotoelétrica de Emissão de Raios-X (XPS), das Curvas de Polarização, da Espectroscopia de Impedância Eletroquímica (EIE), da Microscopia Eletrônica de Varredura (MEV) e Espectrometria de Energia Dispersiva (EDS). Os resultados de EIE e polarização indicaram que os sistemas estudados foram eficientes contra corrosão e que seu desempenho dependia do tipo de silano. Os sistemas ZnFe+Ce+BTSE+BTESPTS e ZnFe+La+BTSE+BTESPTS mostraram o melhor resultado contra corrosão. / Abstract: Galvanized and zinc electroplated steels are very useful materials in automotive and construction industries. These zinc based materials, however, need to be protected against corrosive environments through a surface treatment that generally has hexavalent chromium wich is toxic to the environment and may cause cancer to human being. This thesis shows a study about films containing different silanes: vinyltriethoxysilane (VS), bis-(1,2-[triethoxysilyl]ethane) (BTSE) or is-(3-[triethoxysilyl]-propyl]tetrasulfide (BTESPTS) and rare earth nitrates (Ce, La) as conversion coatings to the zinc-iron alloy electroplated steel. These systems were evaluated using X-Ray Photoelectron Spectroscopy (XPS), Polarization Curves, Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscopy (SEM) and EDS. The EIS and Polarization results have shown that the systems under study were efficient against corrosion and its performance depended upon the type of silane. The inciron+Ce+BTSE+ BTESPT and zinc-iron+La+BTSE+BTESPT systems have shown the best result against corrosion. / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

<p>  </p> <p>Cyclar process was previously developed to convert propane and butane into aromatics using gallium-promoted ZSM-5 zeolites (Ga/ZSM-5). However, it has two major limitations. Firstly, light gases (methane and ethane) limit the yield of higher molecular weight hydrocarbons for propane conversion. Secondly, ethane is unreactive on Ga/ZSM-5 catalysts. Relative rates and selectivity for propane conversion on two components, gallium (Ga/Al2O3) and acid ZSM-5 (H-ZSM-5) were investigated, and the results suggest that light gas was produced by propane monomolecular cracking on ZSM-5 due to the imbalance of alkane dehydrogenation and olefin conversion rates on two catalytic functions. A PtZn alloy catalyst, which has >99% propene selectivity and 30 times higher rate than Ga, was used for the dehydrogenation function. The bifunctional PtZn/SiO2+ZSM-5 catalyst has high yields of aromatics with low methane selectivity (<5%) at ~70% propane conversion. The results suggest methane can be minimized by utilizing the PtZn alloy and lowering the monomolecular cracking rate by ZSM-5. In addition, PtZn alloy increases aromatics selectivity. Aromatics formation pathway was investigated by studying the rate and selectivity of a model intermediate (cyclohexene) on ZSM-5, PtZn/SiO2 and Ga/Al2O3. Benzene is formed at similar rates on Ga/Al2O3 and ZSM-5 but cracking of cyclohexene on the latter is two orders of magnitude higher than the benzene formation rate, indicating cracking of cyclic hydrocarbons leads to low aromatization rate on Ga/ZSM-5. The benzene formation rate on the PtZn/SiO2 is 200 times higher than that on ZSM-5, suggesting aromatics are formed by the metal pathway on PtZn/SiO2+ZSM-5. </p> <p>Unlike Ga/ZSM-5 catalysts, PtZn/SiO2+ZSM-5 catalysts also convert propane to aromatics at low temperature (350 ℃). The temperature effect on propane dehydroaromatization pathways on the PtZn/SiO2+ZSM-5 bifunctional catalysts was investigated to develop strategies for propane conversion to valuable liquid hydrocarbons. At high temperature (550 ℃), high dehydrogenation rates and lower monomolecular cracking rates are required to minimize methane formation, leading to primarily propene and BTX (benzene, toluene, and xylenes). By recycling propene in the propane conversion range of 30-45%, >80% BTX yields is likely achievable at full recycle. At mid temperature (400-450 ℃), the product has high selectivity to gasoline-blending hydrocarbons (butanes, C5+ hydrocarbons, toluene, and xylenes) at 15-25% propane conversions because dehydrogenation rates are moderately high, and oligomerization is more favored than cracking. At low temperature (350℃), ~25% propane conversion is achieved and has high selectivity (~60%) to butanes, but the propane conversion rates are likely too low to be practical. While methane formation by monomolecular cracking limits liquid yields at high reaction temperature, at mid and low temperatures, hydrogen co-produced at high propane conversions saturates light olefins to make undesired ethane, which becomes major yield-loss reaction on the PtZn/SiO2+ZSM-5. </p> <p>Finally, PtZn/SiO2+ZSM-5 catalysts can convert ethane to C3+ and aromatics but the methane selectivity increases rapidly at high ethane conversion. The roles of two catalytic function (Pt-Zn alloy and ZSM-5) in the dehydroaromatization pathways of ethane and propane will be further studied and their product distribution will be compared to have better understandings on the differences in the dominant yield-loss reaction and dehydroaromatization pathways. </p>

The aim of this research proj ect was to produce compositionally modulated zincnickel and zinc-nickel-manganese coatings usi ng a single bath process by variation of the applied electroplating current density. These could then be considered as possible replacements for electroplated cadmium. Zinc-nickel electrodeposits from both a simple bath and one containing the complexant tris(hydroxymethyl)methylamine (TRIS) were produced using either bath or by selective electroplating onto mild steel, 2014-T6 aluminium and 2000 series aluminium alloy connector shells. Zinc-nickelmanganese coatings were electroplated onto mild steel, using both DC and pulse electroplating from sulphate based baths containing either the complexant TRIS or sodium citrate. The coatings and the various electrodeposition processes were evaluated by thickness measurements, cun'ent efficiency calculations, composition detennination using energy dispersive X-ray anal ys is and SEM to examine the morphology. Corrosion characteristics were investigated by neutral salt fog exposure, alternate immersion, atmospheric trials, and electrochemical immersion tests including potential monitoring, galvanic and polarisation measurements. Other properties such as microhardness and surface electrical conductivity were also investigated. Compositionally modulated zinc-nickel and ziJlc-nickel-manganese were successfully deposited from single baths with nickel contents ranging from 5-20% Ni and manganese contents varying from 0-12% Mn. Current efficiency measurements showed the efficiency to be low especially for the zinc-nickel-manganese coatings, which exhibited a distinct morphology when electroplated from the citrate bath. Corrosion testing indicated that both coatings had a lower corrosion resistance than cadmium especially in accelerated tests, with a reduction in corrosion resistance being seen as the nickel content was increased; due to a decrease in density of the electroplate. This, and increasing through-thickness porosity promoted ennoblement of zinc-nickel and zinc-nickel-manganese leading to the coatings becoming nonsacri ficial to the substrate in accelerated tests. Zinc-nickel-manganese showed less white rust than zinc-nickel and exhibited lligher micro-hardness than zinc, cadmium and zinc-nickel. Electrical measurements indicated that both coatings were sufficiently conductive to meet the surface conductivity requirements for use on electrical connector shells.

Orientador: Celia Marina de Alvarenga Freire / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-06T09:54:51Z (GMT). No. of bitstreams: 1 Lumpp_SheilaNatalia_D.pdf: 7607784 bytes, checksum: 0892439e357279a60883fdec8ee11bd8 (MD5) Previous issue date: 2005 / Resumo: Os revestimentos de ligas de zinco obtidos por processo de eletrodeposição apresentam maior resistência à corrosão que o zinco puro, porém necessitam de um tratamento posterior para reduzir a formação dos produtos de corrosão branca. O processo de cromatização, até o presente momento, apresenta os melhores resultados como tratamento de passivação para revestimentos de ligas de zinco, embora seja altamente tóxico. Os primeiros estudos com o objetivo de eliminar o uso do cromo hexavalente utilizaram metais oxianions similares ao cromato, como molibdatos, vanadatos e permanganatos, sendo o molibdato o mais estudado devido a sua natureza não tóxica e habilidade para a formação de filmes que reduzem a corrosão localizada em aços inoxidáveis. Este processo de formação de camadas passivas pode ser realizado por imersão ou por tratamento catódico em soluções de molibdatos de amônio ou de sódio. Um outro processo estudado como alternativo à substituição do cromo hexavalente é baseado em metais terras raras. Recentemente, na literatura têm-se encontrado somente resultados em alumínio e aço inoxidável, porém ainda são poucos os estudos em revestimentos de ligas de zinco. O objetivo deste trabalho é estudar o uso de molibdatos e terras raras como agentes passivantes para revestimentos de ligas ZnNi e ZnCo eletrodepositados. Os revestimentos foram preparados usando banho comercial, sendo analisados em processo de eletrodeposição, o uso da corrente pulsada e contínua. O efeito da densidade de corrente média e os valores de rendimento de ciclo sobre a resistência à corrosão do revestimento, foram investigados. O tratamento catódico em solução de molibdato de amônio, e os tratamentos eletroquímico e de imersão em nitrato de cério foram considerados. A morfologia dos revestimentos de liga ZnNi e ZnCo e também das camadas de passivação foram analisadas utilizando microscópio eletrônico de varredura. A composição dos revestimentos de liga foi determinada pela técnica de EDS e a resistência à corrosão pela técnica de Espectroscopia de Impedância Eletroquímica (ElE) / Abstract: The electroplated zinc alloy coatings present better corrosion resistance than pure zinc, but they need a posterior passive treatment aiming the reduction of the formation of white corrosion products. Chromate conversion process is the process that, until now, presents the best results as passive treatment for zinc alloy coatings, although it presents high toxicity. The first studies with the objective of the elimination of hexavalent chromium made use of oxyanions similar to chromate, such as molybdate, vanadate and permanganate, being molybdate the most studied one, due to its non toxic nature and its ability in reducing stainless steel pit corrosion. In molybdate oxide process, the passive layer can be formed by immersion or by cathodic treatment in ammonium or sodium molybdate solutions. Another passive process, that has been studied for substituting hexavalent chromium process is based on rare earth. However, in literature, it is found only results for aluminium and stainless steel corrosion control, but not for electroplated zinc alloy coatings. The purpose of the present work is to study the use of molybdate and rare earth in passive processes for electroplated ZnNi and ZnCo alloy coatings. The coatings are prepared using commercial bath, being analyzed, in plating process, the use of continuous and pulse current coating electrodeposition. The effect of average current density and duty cycle values on coatings corrosion resistance are investigated. In passive processes, cathodic treatment in ammonium molybdate solution; electrochemical treatment and immersion treatment in cerium nitrate and ammonium molybdate solutions were considered. The morphology of ZnNi and ZnCo coatings and of passive layers are evaluated using Scanning Electronic Microscopy (SEM). Composition of zinc alloy coatings was determined by EDS technique and corrosion resistance was evaluated by Electrochemical Impedance technique / Doutorado / Materiais e Processos / Doutor em Engenharia Mecânica

Electroplated zinc-alloy coatings have been used on fasteners in the automotive industry for many years. The coating often consists of three layers: a zinc-alloy layer, a passivation layer and a sealer or top-coat. The coating layers affect the functional properties of the fastener (mainly the corrosion resistance, friction coefficient and electrical conductivity), and the aim of this thesis has been to increase the understanding of how these functional properties are affected by the properties of the coating. The corrosion resistance, friction coefficient and electrical conductivity of several different fasteners have been tested. Variations in these properties are connected with morphological and chemical properties of the electro-deposited zinc-alloy coating, passivation layer and sealer/top-coat of the fasteners. Measurement methods include scanning electron microscope and energy dispersive x-ray spectroscopy (SEM-EDX), light optical microscope (LOM), x-ray fluorescence (XRF), glow discharge optical emission spectroscopy (GD-OES), broad ion beam (BIB) and Fourier transform infrared spectroscopy (FTIR). From the results it can be concluded that the surface structure of zinc-nickel layers differs significantly from supplier to supplier. Screws with a thicker and rougher zinc-nickel surface structure displays higher friction values, but lower electrical resistance values. Optimisation of both of these properties is thus challenging. The distribution and surface structure of the outmost top-coat layer also differs between suppliers, but no connection between this and the functional properties of the screw has been found. The corners of the screw heads are often lacking a proper zinc-alloy coating, and this is also where corrosion is initiated. In general, the zinc-nickel alloy coating systems are performing better and display less corrosion spreading effects than the zinc-iron or pure zinc systems in terms of corrosion. / Elektropläterade zinklegeringsbeläggningar har använts på fästelement inom bilindustrin under många år. Beläggningen består ofta av tre skikt: ett zinklegeringsskikt, ett passiveringsskikt och en ”top-coat”, eller ”sealer”. Beläggningsskikten påverkar fästelementens funktionella egenskaper (främst korrosionsbeständighet, friktionskoefficient och elektrisk ledningsförmåga) och syftet med denna avhandling har varit att öka förståelsen för hur dessa funktionella egenskaper påverkas av ytbeläggningens egenskaper. Korrosionsmotståndet, friktionskoefficienten och den elektriska ledningsförmågan hos flera olika fästelement har mätts. Variationer i dessa egenskaper kopplas till de morfologiska och kemiska egenskaperna hos den elektropläterade zinklegeringsskiktet, passiveringsskiktet och top-coat-skiktet hos fästelementen. Mätmetoder inkluderar svepelektronmikroskop och röntgenspektroskopi (SEMEDX), ljusoptiskt mikroskop (LOM), röntgenfluorescens (XRF), optisk strålningsspektroskopi (GD-OES), bred jonstråle (BIB) och Fourier-transformerad infraröd spektroskopi (FTIR). Av resultaten kan man dra slutsatsen att ytstrukturen hos zink-nickelskiktet skiljer sig avsevärt från leverantör till leverantör. Skruvar med tjockare och hårdare zink-nickelytstruktur visar högre friktionsvärden, men lägre elektriska resistansvärden. Optimering av båda dessa egenskaper är således utmanande. Distributionen och ytstrukturen hos det yttersta top-coat-skiktet skiljer sig också mellan leverantörer, men ingen samband mellan detta och skruvens funktionella egenskaper har hittats. Skruvhuvudets hörn saknar ofta en lämplig zinklegeringsbeläggning, och det är också där korrosion initieras. I allmänhet fungerar zink-nickellegeringsbeläggningssystemen bättre och visar mindre spridningseffekter i termer av korrosion än zinkjärn eller rena zinksystem.