This work deals with fatigue properties and stability of microstructure of ultrafine-grained (UFG) copper prepared by severe plastic deformation by means of equal channel angular pressing (ECAP) method. The effect of different fatigue loading regimes and thermal exposition on microstructural changes was investigated and the fatigue lifetime curves were experimentally determined. The research attention was focussed on localization of cyclic plastic deformation and fatigue crack initiation in UFG structure. Experimental results indicate that after stress-controlled fatigue loading (both symmetrical and asymmetrical) the microstructure remains ultrafine; no grain coarsening was observed. Contrary to this, strain-controlled fatigue loading results in formation of bimodal structure. Grain coarsening was observed also after thermal exposition at 250 °C for 30 minutes. Annealing at lower temperatures does not result in grain coarsening or development of bimodal structure. Fatigue loading results in development of surface relief in form of cyclic slip markings. Their density, distribution and shape differ for particular fatigue loading regimes. Differences in crack initiation mechanism in low- and high-cycle fatigue region were found. Nevertheless, the characteristic feature for all loading regimes was stability of UFG microstructure in the region of cyclic slip bands and fatigue cracks.

Selective laser melting (SLM) is an additive manufacturing technology. In this thesis, a heat-treatable Al-3.5Cu-1.5Mg-1Si alloy and related materials (composites and hybrid materials) have been successfully fabricated by selective laser melting and characterized in terms of densification, microstructure, heat treatment, mechanical properties as well as tribological and corrosion behavior. Firstly, the fully dense SLM Al-Cu-Mg-Si alloy was fabricated by SLM successfully. The alloy shows a higher yield strength than SLM Al-12Si alloy, and lower wear resistance and corrosion rate than commercial 2024 alloy before and after T6 heat treatment. Secondly, with the aim of designing new alloy compositions and to examine the phases and microstructures of SLM Al-Cu alloys and to correlate their microstructures with the observed mechanical properties, Al-xCu (x = 4.5, 6, 20, 33 and 40 wt. %) alloys have been synthesized in-situ by SLM from mixtures of Al-4.5Cu and Cu powders. The results indicate that the insufficient Cu solute diffusion during the layer-by-layer processing results in an inhomogeneous microstructure around the introduced Cu powders. With increasing Cu content, the Al2Cu phase in the alloys increases improving the strength of the material. These results show that powder mixtures can be used for the synthesis of SLM composites but the reaction between the matrix and the second-phase should be considered carefully. Thirdly, the TiB2/Al-Cu-Mg-Si composite was also designed and fabricated successfully by SLM and it shows a higher strength than the unreinforced SLM alloy before and after T6 heat treatment. Finally, an Al-12Si/Al-3.5Cu-1.5Mg-1Si hybrid with a good interface was fabricated successfully. This hybrid alloy shows a good yield strength and elongation at room temperature, indicating an effective potential of selective laser melting in the field of hybrid manufacturing.

As current environmental challenges are gaining increased attention, development of clean energy solutions is becoming one of the essential strategies to keep within the boundaries of established environmental policies. Solid oxide cell (SOC) technology can provide clean energy conversion and storage when hydrogen is the energy carrier. The high total energy conversion efficiency resulting from the high operation temperature of SOCs make the technology promising, but material costs must be reduced to make it commercially viable. Therefore, this thesis aims to study the long- term performance of a novel cost-optimized cell interconnect at 650 and 850 °C. At high temperatures, chromium evaporation from the interconnect result in electrode poisoning, which may be mitigated by application of a protective coating. The studied interconnect is an AISI 441 steel with some different pre-oxidized copper and iron spinel coatings. Sample analysis was made mainly with scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and X-ray diffraction. It was found that the most promising pre-oxidation treatment was 24 h at 750 °C and that chromium migration was restrained at 650 °C long-term treatment but not at 850 °C where it wasfound available for evaporation at the surface. / När samtida milljöutmaningar får ökad uppmärksamhet blir gröna energilösningar en av de viktigaste strategierna för att hålla sig inom satta gränser från etablerade miljöriktlinjer. Teknologin bakom fastoxidceller, eller solid oxide cells (SOCs), kan bidra med grön omvandling och lagring av energi när energibäraren är väte. Den höga totala omvandlingseffektiviteten, som kommer med den höga verkningstemperaturen, gör SOC till en lovande teknologi, men materialkostnaderna måste först reduceras innan den blir komersiellt gångbar. Därför syftar detta examensarbete till att undersöka prestandan av en ny, kostnadsoptimerad cellinterkonnektor på lång sikt i 650 och 850 °C. Vid höga temperaturer förångas krom från interkonnektorn, vilket leder till elektrodförgiftning, men kan mildras genom applicering av en skyddande beläggning. Den undersökta interkonnektorn är ett stål som betäcknas AISI 441 belagt med några olika föroxiderade beläggningar av koppar- och järnspinell. Proverna analyserades i huvudsak genom svepelektronmikroskopi kobinerat med energidispersiv röntgenspektroskopi och röntgendiffraktometri. Det visades att den mest lovande föroxideringsbehandlingen var 24 h i 750 °C och att krom förblev återhållet vid 650 °men inte vid 850 °C då det fanns tillgängligt för förångning vidytan.

[pt] Esta tese investigou a síntese de metanol via hidrogenação do CO2 empregando dois conjuntos de catalisadores. O primeiro é composto pelos tradicionais catalisadores de Cu/ZnO/Al e o segundo aborda os catalisadores de In2O3 e ZrO2. Com relação ao Cu/ZnO/Al, foram preparados quatro amostras via coprecipitação. Os resultados mostraram que há um teor ótimo (3,8 por cento at.) de Al para a qual se observa uma maior taxa de formação de metanol. Os catalisadores foram caracterizados por fisissorção de N2, titulação com N2O,espectroscopia de absorção atômica, ICP, DRX, XPS, TPD-(CO2,NH3 e H2O), TPSR-CO2/H2, TEM/HRTEM/EDS. Uma correlação entre a taxa de formação de metanol e a quantidade de vacâncias de oxigênio superficiais do catalisador foi observada. Foi verificado que o Al atua como um promotor na geração de vacâncias de oxigênio. Com relação aos sistemas de In2O3, foi realizado um screening e selecionado nove catalisadores. Esses sólidos foram caracterizados pelas seguintes técnicas: DRX, TPD-NH3, TPD-CO2, TPR-H2 e TPSR-CO2/H2. Foi realizado um estudo em dinâmica molecular clássica investigando os efeitos da dopagem do In2O3 e da interação entre o In2O3 e o ZrO2 e relacionando os resultados com a performance dos catalisadores. O melhor desempenho catalítico foi obtido para o inédito catalisador de 0,6Pt-In2O3+6ZnZrO2, sendo esse desempenho associado à presença de vacâncias. Além disso, pelos cálculos teóricos de dinâmica molecular foi verificado que tanto a mistura física quanto a dopagem do In2O3 podem promovem a mobilidade de oxigênio da rede dos óxidos, o que facilita a formação de vacâncias de oxigênio. Sendo assim, os dois conjuntos de catalisadores estudados mostram que as vacâncias de oxigênio têm papel central na formação do metanol a partir da hidrogenação do CO2. As informações geradas neste trabalho contribuirão para o desenvolvimento de catalisadores promissores para a futura exploração industrial da geração de metanol a partir de CO2. / [en] This thesis investigated methanol synthesis via CO2 hydrogenation using two sets of catalysts. The first set consists of the traditional Cu/ZnO/Al catalysts and the second set involves In2O3 and ZrO2 catalysts. Concerning Cu/ZnO/Al, four samples were prepared via coprecipitation. The results showed that there is an optimum Al content (3.8 percent at.) for which a higher methanol formation rate is observed. The catalysts were characterized by N2 physisorption, titration with N2O, atomic absorption spectroscopy, ICP, XRD, XPS (CO2,NH3 and H2O)-TPD, CO2/H2-TPSR, TEM/HRTEM/EDS. A correlation was observed between the rate of methanol formation and the amount of surface oxygen vacancies on the catalyst. It was found that Al acts as a promoter in the generation of oxygen vacancies. Regarding the In2O3 systems, a screening was carried out and nine catalysts were selected. These solids were characterized using the following techniques: XRD, NH3- TPD, CO2-TPD, TPR-H2 and CO2/H2-TPSR. A classical molecular dynamics study was carried out investigating the effects of doping In2O3 and the interaction between In2O3 and ZrO2 and relating the results to the performance of the catalysts. The best catalytic performance was obtained for the new 0,6Pt-In2O3+6ZnZrO2 catalyst, and this performance was associated with the presence of vacancies. In addition, molecular dynamics calculations showed that both the physical mixture and the doping of In2O3 can promote the mobility of oxygen in the oxide lattice, facilitating the formation of oxygen vacancies. Thus, the two sets of catalysts studied show that oxygen vacancies play a central role in the formation of methanol from the hydrogenation of CO2. The information generated in this work will contribute to the development of promising catalysts for the future industrial exploitation of methanol generation from CO2.

Sb₂S₃ and CuCl were reacted in the ionic liquid [BMIm]Cl · 4.4AlCl₃ (BMIm=1-n-butyl-3-methylimidazolium) at 200°C. Upon cooling to room temperature, orange-red colored, air-sensitive crystals of Cu(Sb₂S₃)[AlCl₄] precipitated. X-ray diffraction on a single-crystal revealed an orthorhombic crystal structure, in which cationic [Cu(Sb₂S₃)]⁺ layers are separated by tetrahedral [AlCl₄]⁻ anions. The uncharged Sb₂S₃ partial structure consists of one-dimensional strands with covalent Sb-S single bonds. The copper(I) cation is coordinated by three sulfur atoms and by one of chlorine atoms of the [AlCl₄]⁻ anion. An optical band gap of 2.14 eV was deduced from UV/Vis spectra. In very good agreement, a band gap of 2.07 eV results from DFT-based calculations involving a new implementation of the bifunctional formalism for the exchange energy. By treatment with 0.1 molar hydrochloric acid, AlCl₃ was leached from Cu(Sb₂S₃)[AlCl₄] yielding a compound with the presumed composition Cu(Sb₂S₃)Cl. Hydrolysis at higher pH resulted in Cu₂₋ₓS and Sb₄O₅Cl₂.

<p dir="ltr">Phase evolution mechanisms in micro and nanoscale devices present unique challenges due to distinct behaviors at reduced scales due to surface diffusion. In solder microbumps with size less than 100 micron, surface diffusion causes voiding in the solder bump accompanied by intermetallic formation at the copper sidewall. As the scale and pitch of the interconnects in electronic packages decrease, there is a need to fabricate test devices that can accurately characterize the phase evolution. The usual approaches to studying phase evolution either rely on large-scale test devices that overlook the influence of reduced device sizes or require prolonged testing that limits systematic comparisons across materials. Furthermore, modeling the phenomena at scale require simulation frameworks that can handle physics such as surface diffusion. This work aims to overcome these limitations by developing experimental and computational frameworks to study voiding and phase transformations within interconnects. To this end, test devices, termed inline microjoints, are developed for non-destructively tracking phase evolution in micro scale interconnects under thermal aging. The test devices are demonstrated on CuSn microbumps and SnBi solder joints. Results on the CuSn microbumps demonstrate that void growth in smaller sized bumps stop earlier due to the conversion of the entire solder region into Cu₆Sn₅. In the SnBi inline joints, the effective electromigration diffusivity was characterized using both thickness of Bi accumulation imaged under back scatter electron (BSE) imaging, and the rate of resistance growth. Both thickness and resistance was obtained on the same bumps due to the non-destructive nature of the test. The diffusivity values obtained were found to match closely with those reported in literature. During the interrupted testing, a nonlinear transient resistance growth was observed at the beginning of each test. The nonlinear growth could not be attributed to joule heating and the cause for it needs further investigation. </p><p dir="ltr">To complement these experimental findings, a sharp interface simulation framework based on Enriched Isogeometric Analysis (EIGA) is developed in this thesis to model intermetallic and void growth in microbumps, which aligns well with experimental outcomes. An extension to the modeling methodology is developed to simulate surface diffusion with imposed flux boundary conditions on open surfaces. The simulations are applied to model surface diffusion in Cu surface during the anneal step in hybrid bonding. The results of the simulations are shown to agree with trends reported in literature. Finally, future applications of the experimental procedure developed in this thesis in the context of hybrid bonding is also discussed. By integrating experimental and simulation techniques, this work contributes tools to analyze phase evolution in interconnects in advanced electronic packages.</p>

Published Article / Health effects associated with Ni-Cu mining on learners living within the mining area at Selebi Phikwe were investigated through the administration of questionnaires. Results depicted learners suffering from a wide range of different symptoms and illnesses. 70% of the learners complained of coughs, 77% had influenza / common cold, and 80% had headaches. The repeated coughing, constant influenza / common cold and persistent headaches from which learners suffered, were very significantly higher than those at the control site; and incidences of their occurrence increased with closeness to the mining area. The unusual high occurrences of these ailments and illnesses coupled with associated diseases among learners were attributed to several environmental factors including contaminated particulate air matter (PAM) (rich in sulphur and heavy metals) linked to the mining and smelting of Ni-Cu.

No description available.

A new materials system of a single layered Co(W) barrier/liner coupled with a Cu(Mn) alloy seed was investigated. Atom probe tomography visualized the sub-nanoscale structure of Cu(Mn)/Co(W) system, and thereby revealed Cu diffusion behavior of Co(W). Grain boundaries of Co were found to be the diffusion path, and successfully stuffed by W. Mn in Cu(Mn) also segregated to stuff the grain boundaries of Co. Combination of these two additives enabled high barrier property against Cu diffusion of Cu(Mn)/Co(W). Foreseeing tiny and high-aspect-ratio Cu interconnect features, Cu(Mn)/Co(W) was fabricated by ALD/CVD processes. To maximize the performance, minor impurities of the film incorporated from the ligand of the precursors were controlled by precursor selection. Thin, conformal, and smooth films were finally demonstrated onto a trench substrate.

Bumpless interconnects and ultra-thinning of 300 mm wafers for three-dimensional (3D) stacking technology has been studied [1, 2]. In our previous studies, wafer thinning effect using device wafers less than 10 μm was investigated [3, 4]. There was no change for the retention time before and after thinning even at 4 μm in thickness of DRAM wafer [5]. In this study, the behavior of Cu contamination on an ultra-thin Si stacked structure was investigated. Thinned Si wafers were intentionally contaminated with Cu on the backside and 250 °C of heating was carried out during the adhesive bonding and de-bonding processing. An approximately 200 nm thick damaged layer was formed at the backside of the Si wafer after thinning process and Cu particle precipitates ranged at 20 nm were observed by cross-sectional transmission electron microscopy (X-TEM). With secondary ion mass spectrometry (SIMS) and EDX analyses, Cu diffusion was not detected in the Si substrate, suggesting that the damaged layer prevents Cu diffusion from the backside.