Products from iron and copper mining are among Sweden’s top exports. However, as the metals are excavated, they often end up in the aquatic environment where they can cause toxicity. To implement the Water Framework Directive (WFD) within the European Union, all member states must classify their waters and set local environmental quality standards (EQS). These EQS are used to set the maximum concentration of a metal allowed in water and can be set both by the Swedish EPA and EU. The WFD EQS are to be based on the bioavailable metal fraction, as compared to the total metal concentration as have been used previously. As a tool in setting EQS, bioavailability models, like the biotic ligand model (BLM), have been proposed. BLMs can calculate toxicity endpoints based on water chemistry and organismal response and these predictions can be used for regional EQS values. However, BLMs are often calibrated toward hard waters with neutral or high pH, containing low concentrations of natural organic material (NOM), a water chemistry most commonly found in the central and southern parts of Europe. The overarching aim of this doctoral thesis was, therefore, to assess the regulatory applicability of Cu BLMs for Swedish conditions. Results from Paper I and II show that for at least 50% of Fennoscandinavian (Sweden, Finland and Norway) freshwater bodies, the models are not fully applicable. This due to crucial model input parameters being outside of the current calibration range of the Cu BLM. Papers II and III further showed that BLM calculated results differed from measured Cu toxicity to daphnids and algae, indicating that model-based EQS will not be protective for these organisms. Moreover, Paper III showed that Al had an impact on Cu speciation and, hence, toxicity. In conclusion, the present thesis shows that several available Cu BLMs are not yet fully applicable for Swedish or Scandinavian freshwater bodies due to incomplete parameterisation of the models.  To improve the applicability of the models, there is a need to calibrate the models for soft freshwater bodies and include Al and NOM properties as input parameters. / Produkter från metallindustrin är bland Sveriges viktigaste exportprodukter. Metallutvinning leder dock till utsläpp som kan hamna i den akvatiska miljön och där orsaka toxicitet. Europeiska Unionens Vattendirektiv syftar till att alla medlemsstater ska klassificera sina vatten och ta fram miljökvalitetsnormer. Dessa normer ska baseras på den biotillgängliga fasen av metaller istället för den totala som tidigare. Biotiska ligand modeller (BLM) har förts fram som verktyg i denna process. BLM kan beräkna utsläppsnivåer för sötvatten baserat på rådande vattenkemi samt vattenorganismers känslighet och ger användaren en specifikt anpassad rekommendation (LC/EC50, NOEC, PNEC o.s.v.). Dock är dessa modeller ofta kalibrerade för en vattenkemi gällande i de centrala och södra delarna av Europa. I Sverige är det vanligt med sura mjuka vatten, vilka har en högre koncentration av biotillgängliga metaller vilka kan orsaka toxicitet. Det övergripande syftet med denna doktorsavhandling var att undersöka hur dagens BLM för koppar (Cu) fungerar för svenska sötvatten. Resultaten från Artikel I och II visar att en stor del av de Fennoskandinaviska vatten som testats faller utanför kalibreringsintervallet för BLM. Vidare visar Artikel III och IV att de testade modellerna inte på ett korrekt sätt kunde uppskatta toxicitet för alger och vattenloppor, vilket innebär att de inte räknar ut skyddande rekommendationer för dessa arter. Det var även tydligt i Artikel IV att aluminium (Al) påverkar kopparspecieringen och genom detta även koppars toxicitet. Sammanfattningsvis visar denna avhandling att flera tillgängliga BLM inte är helt applicerbara i mjuka vatten, ofta p.g.a. opassande intervall för de kemiska parametrarna. För att förbättra tillämpbarheten av BLMs i Sverige krävs det att modellerna dels kalibreras för den rådande vattenkemin och dels att Al och NOMs egenskaper inkluderas.

Neste trabalho estudamos a influencia da temperatura e tempo de reação e sinterização na preparação de amostras cerâmicas supercondutoras pelo método de reação no estado sólido. Os resultados indicam claramente que algumas propriedades destes supercondutores, tais como: temperatura crítica (Tc), susceptibilidade magnética (X), resistividade (&#961), microestruturas, densidade e porosidade aparente, sofrem forte influencia das condições de tratamento térmico. Foram preparadas várias amostras dos sistemas YBa2Cu3O6.5+x e TmBa2Cu3O6.5+x, sendo que a temperatura e tempo ideal de reação encontrados foram de 950&#176C por 6 horas e 925&#176C por 48 horas, respectivamente; ambas tratadas em fluxo de oxigênio. A caracterização destas amostras foram feitas pelas técnicas de difração de raios-x, técnica de quatro-pontas (medida da variação da resistividade pela temperatura), ponte de Hartshorn (para a medida da variação da susceptibilidade magnética pela temperatura), microscopia eletrônica de varredura (para análise das microestruturas) e método de imersão (para a medida da densidade e porosidade aparente). A maior temperatura crítica encontrada foi de aproximadamente 94K para YBa2Cu3O6.5+x e de aproximadamente 91K para o TmBa2Cu3O6.5+x / The influence of the temperature and time in the reaction and sinterization of superconducting ceramics prepared by a solid state reaction was determined. The results clearly showed that some of its properties, such as critical temperature (Tc), magnetic susceptibility (X), resistivity (&#961), microstructure, apparent density, and porosity undergo a strong influence of the preparation conditions. Some samples in the YBa2Cu3O6.5+x and TmBa2Cu3O6.5+x systems were prepared. The ideal reaction temperature and time were 950&#176C for 6 hours and 925&#176C for 48 hours, respectively. Both annealed in O2 flow. The sample characterization was made by using X-ray diffraction, standard four probe (measures the variation of resistivity versus temperature), Bridge of Hartshorn (the variation of susceptibility versus temperature), scanning electron micrograph (microstructure analysis), and immersion method (measures the apparent density and porosity). The greatest critical temperature was approximately 94K for YBa2Cu3O6.5+x and 91K for TmBa2Cu3O6.5+x

Copper is an essential biological metal. Many enzymes such as cytochrome C oxidase and superoxide dismutase use copper as a prosthetic group. However, free copper can be harmful by generating reactive oxygen species through Fenton reactions (Linder and Hazegh-Azam 1996). Therefore, copper is tightly regulated throughout the cell. Cu+ ATPases are transporters that regulate Cu+ homeostasis. Mutations to these Cu+ ATPases can cause diseases (Wilson's and Menkes diseases) (Ferenci 2005). CopA from Archaeoglobus fulgidus is a model Cu+ ATPase; it contains eight transmembrane helices and a cytosolic ATP binding domain. CopA is assisted by a Cu+ chaperone (CopZ) which we have shown delivers Cu+ to CopA via protein-protein interactions (Guerrero-Guerrero and Arguello 2008). CopZ has two domains which are both able to bind Cu+ (Guerrero-Guerrero and Arguello 2008). The N-domain has a mononuclear Zn2+ site, a [2Fe-2S] cluster and is extremely rich in cysteines (Sazinsky, LeMoine et al. 2007). To explore the role of cysteines and their Cu+ binding capacity, each cysteine was mutated to serine. All resulting proteins were able to activate CopA ATPase. However, mutation of two Cysteines (Cys4 and Cys38) led to binding of two additional Cu+ ions. Since these two Cys participate in Zn2+ coordination we hypothesized that the coordination of Cu+ might take place with the displacement of Zn2+. In order to explore this hypothesis, CopZ-WT was incubated with an excess amount of Cu+, followed by atomic absorption to measure the presence of Zn2+. These experiments demonstrate a displacement of Zn2+ by Cu+. Thus, our results show that the second Cu+ binding site in A. fulgidus CopZ is constituted by the same Cysteines participating in Zn2+ binding.

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In this paper, there are two major investments consisted of ¡§Failure Mechanism of Inner Lead Au-Sn Bonds in Tape Automated Bonding (TCP) Packages¡¨ and ¡§Cu Wire bond microstructure analysis and failure mechanism¡¨. In view of the advantages of low cost, simple manufacturing process and significant miniaturization in size, TCP technology is widely applied in consumer electronic products. Inner lead bonding (ILB) process is especially crucial for the production of high quality TCP packages and components. The ILB process is extremely dynamic since the bonding time is around 0.2 second to complete the thermo-compress and soldering processes. The composition of liquid pool varied with the bond temperature and pressure and is crucial to exhibit different structure. One type of unusual failure bond happened during the process parameters optimization. ILB joints microstructure was examined by electron microprobe (EPMA) for detail phase analysis. The phase formation sequence of normal and failure bonds can be explained from the Au-Sn-Cu ternary phase diagram and thermo-chemistry data of Au-Sn binary. According to Part I study, the hypo-eutectic composition (<30 at% Sn) liquid pool could maintain the normal ILB bonds. And the hyper-eutectic composition (>30 at% Sn) has the potential risk to form this unusual failure bond. In the Part II study, copper wire bonding samples were aged at 205¢XC in air from 0 h to 2000 h. It was found that the bonding of a Cu wire and an Al pad formed Cu9Al4, CuAl, and CuAl2 intermetallic compounds, and an initial crack was formed by the ultrasonic squeeze effect during thermosonic wire bonding. The cracks grew towards the ball bond center with an increase in the aging time, and the Cl ions diffused through the crack into the ball center. This diffusion caused a corrosion reaction between the Cl ions and the Cu-Al intermetallic phases, which in turn caused copper wire bonding damage.

Zirconium base alloys have very good metallic glass forming ability. In this study,the Zr-Cu-Ni ternary isotherm at 800¢J were determined by using metallography,electron-probe microanalysis and X-ray diffraction.The main objective is to provide the necessary information for alloy design to form new Zr-base with better glass forming ability.

This thesis is divided into two parts. The main purpose of the first part is only to confirm further whether adding B can really improve the glass forming ability (GFA) and thermal stability. It is recently suggested that the addition of the even smaller sized B (0.08 nm) in the Mg65Cu25Y10 alloys to a certain level can further enhance GFA and provide the chance in fabricating larger bulk amorphous billet. The current study extends the concept of adding B to the Mg65Ni25Y10 based alloy, including the replacement of Ni by 1-5 at % (1, 3, and 5 at %) using the arc melting and melt spinning methods. The second part, this experiment drops magnesium element to 58 at% boldly, even lower, and the big element atom neodymium (Nd) improves to 11 at% or more upwards, different from everybody commonly used 65 at %, 25 at % , 10 at % as the main proportion composition , then to observe whether its supercooled liquid region

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A comparative investigation of electrochemical characteristics of two complex systems, viz. Cu|Cu(II), glycine and Cu|Cu(II), maleic acid, was carried out. The equations were obtained for quantitative description of pH-metric and spectrophotometric data, which were used for determination of equilibrium characteristics in Cu(II)-maleic acid solutions. Thermodynamic analysis shows that deep changes are possible in this system resulting in 90 % transform of Cu(II) into Cu(I). The rates of Cu corrosion and Cu2O formation are estimated to be of the same order (nmol cm-2 s-1). Regularities of formal electrochemical kinetics, which account for the mass transport of chemically interacting particles and for step-wise charge transfer process, are suitable for interpretation of voltammetric data of the Cu|Cu(II), glycine system. Kinetic parameters Cu(II) glycinate complex depend on the nature of the supporting electrolyte: the exchange current density decreases and the cathodic charge transfer coefficient increases in the sequence: Li+ - Na+ - K+ - Cs+. To enhance the Cu(I) generation in maleic acid system, the pre-electrolysis procedure was applied. It was found that its effect depends on solution pH. Applied theoretical model describes satisfactorily the steady-state voltammetric characteristics of Cu|Cu(II), maleic acid system, but some contradictory results were obtained in the case of time-dependent processes. Theoretical and experimental problems to be solved are discussed. / Atliktas palyginamasis dviejų kompleksinių sistemų - Cu|Cu(II), glicinas ir Cu|Cu(II), maleino rūgštis - elektrocheminių charakteristikų tyrimas. Nustatytos maleino rūgšties tirpalų pusiausvyrinės charakteristikos. Kiekybiniam titravimo kreivių aprašymui išvestos lygtys, kuriose įvertinti medžiagų bei krūvių balansai bei atsižvelgta į praskiedimo efektus. Jų taikymas pH-metrinių duomenų analizei davė tokias maleato anijonų protonizacijos konstantų reikšmes: log = 6,05, log = 7,48. Nustatyta, kad tirpaluose su 0,3 M K2SO4 priedu protonizuotų ligando formų stabilumas sumažėja (log = 5,75, log = 7,30). Cu(II) maleatinių kompleksų stabilumui nustatyti panaudotas spektrofotometrijos metodas ir pasiūlyta duomenų analizės procedūra. Ji remiasi kiekybiniu absorbcijos spektrų aprašymu, taikant lygtis, išplaukiančias iš valdomo harmoninio osciliatoriaus teorijos. Išanalizavus įvairių sudėčių tirpalų absorbcijos maksimumo dydžius, prieita išvados, kad rūgščiose terpėse vyrauja monoligandinis kompleksas, kurio koncentracinė stabilumo konstanta log b1 = 2,2. Atlikta sistemos Cu|Cu(II), maleino rūgštis pusiausvyrų termodinaminė analizė. Nustatyta, kad esant metalinio vario ir tirpalų sąlyčiui, sistemoje galimi gilūs virsmai, kurių metu iki 90 % Cu(II) transformuojasi į Cu(I). Teorines išvadas patvirtina eksperimentiniai duomenys, gauti spektrofotometrijos ir elektrocheminės kvarco kristalo mikrogravimetrijos metodais. Įvertinti Cu korozijos bei fazinių Cu2O sluoksnių susidarymo... [toliau žr. visą tekstą]

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