The initial oxidation of transition metal surfaces

Due to their numerous novel technological applications ranging from the example of exhaust catalysts in the automotive industry to the catalytic production of hydro- gen, surface reactions on transition metal substrates have become to be one of the most essential subjects within the surface science community. Although numerous applications exist, there are many details in the different processes that, after many decades of research, remain unknown. There are perhaps as many applications for the corrosion resistant materials such as stainless steels. A thorough knowledge of the details of the simplest reactions occuring on the surfaces, such as oxidation, play a key role in the design of better catalysts, or corrosion resistant materials in the future. This thesis examines the oxidation of metal surfaces from a computational point of view mostly concentrating on copper as a model material. Oxidation is studied from the initial oxidation to the oxygen precovered surface. Important parameters for the initial sticking and dissociation are obtained. The saturation layer is thoroughly studied and the calculated results arecompared with available experimental results. On the saturated surface, some open questions still remain. The present calculations demonstrate, that the saturated part of the surface is excluded from being chemically reactive towards the oxygen molecules. The results suggest, that the reason for the chemical activity of the saturated surface is due to a strain effect occuring between the saturated areas of the surface.

The effects of some variables on CO2 laser-MAG hybrid welding

The CO2-laser-MAG hybrid welding process has been shown to be a productive choice for the welding industry, being used in e.g. the shipbuilding, pipe and beam manufacturing, and automotive industries. It provides an opportunity to increase the productivity of welding of joints containing air gaps compared with autogenous laser beam welding, with associated reductions in distortion and marked increases in welding speeds and penetration in comparison with both arc and autogenous laser welding. The literature study indicated that the phenomena of laser hybrid welding are mostly being studied using bead-on-plate welding or zero air gap configurations. This study shows it very clearly that the CO2 laser-MAG hybrid welding process is completely different, when there is a groove with an air gap. As in case of industrial use it is excepted that welding is performed for non-zero grooves, this study is of great importance for industrial applications. The results of this study indicate that by using a 6 kW CO2 laser-MAG hybrid welding process, the welding speed may also be increased if an air gap is present in the joint. Experimental trials indicated that the welding speed may be increased by 30-82% when compared with bead-on-plate welding, or welding of a joint with no air gap i.e. a joint prepared as optimum for autogenous laser welding. This study demonstrates very clearly, that the separation of the different processes, as well as the relative configurations of the processes (arc leading or trailing) affect welding performance significantly. These matters influence the droplet size and therefore the metal transfer mode, which in turn determined the resulting weld quality and the ability to bridge air gaps. Welding in bead-onplate mode, or of an I butt joint containing no air gap joint is facilitated by using a leading torch. This is due to the preheating effect of the arc, which increases the absorptivity of the work piece to the laser beam, enabling greater penetration and the use of higher welding speeds. With an air gap present, air gap bridging is more effectively achieved by using a trailing torch because of the lower arc power needed, the wider arc, and the movement of droplets predominantly towards the joint edges. The experiments showed, that the mode of metal transfer has a marked effect on gap bridgeability. Transfer of a single droplet per arc pulse may not be desirable if an air gap is present, because most of the droplets are directed towards the middle of the joint where no base material is present. In such cases, undercut is observed. Pulsed globular and rotational metal transfer modes enable molten metal to also be transferred to the joint edges, and are therefore superior metal transfer modes when bridging air gaps. It was also found very obvious, that process separation is an important factor in gap bridgeability. If process separation is too large, the resulting weld often exhibits sagging, or no weld may be formed at all as a result of the reduced interaction between the component processes. In contrast, if the processes are too close to one another, the processing region contains excess molten metal that may create difficulties for the keyhole to remain open. When the distance is optimised - i.e. a separation of 0-4 mm in this study, depending on the welding speed and beam-arc configuration - the processes act together, creating beneficial synergistic effects. The optimum process separation when using a trailing torch was found to be shorter (0-2 mm) than when a leading torch is used (2-4 mm); a result of the facilitation of weld pool motion when the latter configuration is adopted. This study demonstrates, that the MAG process used has a strong effect on the CO2-laser-MAG hybrid welding process. The laser beam welding component is relatively stable and easy to manage, with only two principal processing parameters (power and welding speed) needing to be adjusted. In contrast, the MAG process has a large number of processing parameters to optimise, all of which play an important role in the interaction between the laser beam and the arc. The parameters used for traditional MAG welding are often not optimal in achieving the most appropriate mode of metal transfer, and weld quality in laser hybrid welding, and must be optimised if the full range of benefits provided by hybrid welding are to be realised.

Dekontaminointimenetelmien arviointi ja toimintaprosessien tehostaminen Loviisan voimalaitoksella

Tämän diplomityön lähtökohtana oli Loviisan voimalaitoksella 2006 käynnistyneen valvonta-alueen laajennusprojektin (VAJAKO) uudistettavien dekontaminointitilojen tehostaminen. Diplomityössä arvioitiin Loviisan voimalaitoksen dekontaminointikeskuksissa käytössä olevien puhdistusmenetelmien tehokkuutta ja toimivuutta. Tämän lisäksi työssä tutkittiin tarkemmin kahta "uutta" dekontaminointimenetelmää, joista toisen menetelmän toimivuutta kokeiltiin pienimuotoisen kokeen avulla. Dekontaminointimenetelmien arviointi ja toimintaprosessien tehostaminen tehtiin kirjalliseen materiaaliin, käyttäjiltä saatuihin kommentteihin sekä kokeista saatuihin tuloksiin perustuen. Dekontaminointimenetelmien arviointi aloitettiin kirjallisen materiaalin tutustumisella, jonka perusteella valittiin kaksi tarkemmin tutkittavaa menetelmää. Kirjalliseen materiaaliin pohjautuvaa tietoa verrattiin käytännön kokemuksiin vierailemalla mm. Forsmarkin, Oskarshamnin, Olkiluodon ja Ringhalsin ydinvoimalaitoksissa. Työntekijöiltä saatujen tietojen sekä kirjalliseen materiaaliin pohjautuen valittiin toinen tutkituista menetelmistä käytännön kokeeseen. Kokeessa tutkittiin menetelmän toimivuutta mm. dekontaminointituloksen, puhdistusajan ja syntyvän nestemäisen jätteen määrän perusteella. Kokeista saadut tulokset yhdistettiin kirjallisen materiaalin ja käyttäjiltä saatujen kokemusten kanssa yhdeksi kokonaisuudeksi. Työssä tarkasteltiin myös Loviisan voimalaitoksen metalliromujen käsittelyprosessin toimivuutta. Toimivuuden arvioinnissa kiinnitettiin erityistä huomiota syntyperäisen lajittelun parantamiseen, jonka seurauksena puhtaiden metalliromujen dekontaminointitarve vähenee käytännössä.

A model of gender prejudice, power, and discrimination: How hierarchy-enhancing factors predominate over hierarchy-attenuating factors

Gender inequalities remain an issue in our society and particularly in the workplace. Several factors can explain this gender difference in top-level managerial positions such as career ambitions but also biases against women. In our chapter, we propose a model explaining why gender inequalities and particularly discrimination against women is still present in our societies despite social norms and existing legislation on gender equality. To this purpose, we review research on discrimination through two different approaches, (a) a prejudice approach through the justification-suppression model developed by Crandall and Eshleman (2003) and (b) a power approach through the social dominance theory (Pratto, Sidanius, Stallworth, & Malle, 1994; Sidanius & Pratto, 1999). In our work, we integrate these two approaches and propose a model of gender prejudice, power and discrimination. The integration of these two approaches contributes to a better understanding of how discrimination against women is formed and maintained over time.

Supplier Energy Audits in Thermal Power Plants

This master’s thesis handles an operating model for an electric equipment supplier conducted sale oriented energy audit for pumping, fan and other motor applications at power plants. The study goes through the largest factors affecting internal electricity use at a power plant, finds an energy audit –like approach for the basis of information gathering and presents the information needed for conducting the analysis. The model is tested in practice at a kraft recovery boiler of a chemical pulping mill. Targets chosen represent some of the largest electric motor applications in the boiler itself and in its fuel handling. The energy saving potential of the chosen targets is calculated by simulating the energy consumption of the alternatives for controlling the targets, and thereafter combining the information with the volume flow duration curve. Results of the research are somewhat divaricated, as all the information needed is not available in the automation system. Some of the targets could be simulated and their energy saving potential calculated quite easily. At some of the targets chosen the monitoring was not sufficient enough for this and additional measurements would have been needed to base the calculations on. In traditional energy audits, energy efficiency of pump and fan applications is not necessarily examined. This means that there are good possibilities for developing the now presented targeted energy audit procedure basis further.

Systematic review with meta-analysis: self-expanding metal stents in patients with cirrhosis and severe or refractory oesophageal variceal bleeding.

BACKGROUND: The prognosis of patients with cirrhosis and acute variceal bleeding is very poor when the standard-of-care fails to control bleeding. New treatment modalities are needed in these patients. AIM: To synthesise the available evidence on the efficacy of self-expanding metal stents (SEMS) in patients with cirrhosis and severe or refractory oesophageal variceal bleeding. METHODS: Meta-analysis of trials evaluating SEMS in patients with cirrhosis and severe or refractory oesophageal variceal bleeding. RESULTS: Thirteen studies were included. The pooled estimate rates were 0.40 (95% confidence interval, CI = 0.31-0.49) for death, 0.41 (95% CI = 0.29-0.53) for liver-related death and 0.36 (95% CI = 0.26-0.47) for death at day 30, with low heterogeneity between studies. The pooled estimate rates were 0.12 (95% CI = 0.07-0.21) for mortality related to variceal bleeding, and 0.18 (95% CI = 0.11-0.29) for failure to control bleeding with SEMS, with no or low heterogeneity between studies. The pooled estimate rate were 0.16 (95% CI = 0.04-0.48) for rebleeding after stent removal and 0.28 (95% CI = 0.17-0.43) for stent migration, with high heterogeneity. A significant proportion of patients had access to liver transplantation or to TIPSS [pooled estimate rate 0.10 (95% CI = 0.04-0.21) and 0.26 (95% CI = 0.18-0.36), respectively]. CONCLUSIONS: Fewer than 40% of patients treated with SEMS were dead at 1 month. SEMS can be used as a bridge to TIPSS or to liver transplantation in a significant proportion of patients. Additional studies are required to identify potential risk factors leading to a poor prognosis in patients with acute variceal bleeding in whom the use of SEMS could be considered.

Suitability of human and mammalian cells of different origin for the assessment of genotoxicity of metal and polymeric engineered nanoparticles.

Nanogenotoxicity is a crucial endpoint in safety testing of nanomaterials as it addresses potential mutagenicity, which has implications for risks of both genetic disease and carcinogenesis. Within the NanoTEST project, we investigated the genotoxic potential of well-characterised nanoparticles (NPs): titanium dioxide (TiO2) NPs of nominal size 20 nm, iron oxide (8 nm) both uncoated (U-Fe3O4) and oleic acid coated (OC-Fe3O4), rhodamine-labelled amorphous silica 25 (Fl-25 SiO2) and 50 nm (Fl-50 SiO) and polylactic glycolic acid polyethylene oxide polymeric NPs - as well as Endorem® as a negative control for detection of strand breaks and oxidised DNA lesions with the alkaline comet assay. Using primary cells and cell lines derived from blood (human lymphocytes and lymphoblastoid TK6 cells), vascular/central nervous system (human endothelial human cerebral endothelial cells), liver (rat hepatocytes and Kupffer cells), kidney (monkey Cos-1 and human HEK293 cells), lung (human bronchial 16HBE14o cells) and placenta (human BeWo b30), we were interested in which in vitro cell model is sufficient to detect positive (genotoxic) and negative (non-genotoxic) responses. All in vitro studies were harmonized, i.e. NPs from the same batch, and identical dispersion protocols (for TiO2 NPs, two dispersions were used), exposure time, concentration range, culture conditions and time-courses were used. The results from the statistical evaluation show that OC-Fe3O4 and TiO2 NPs are genotoxic in the experimental conditions used. When all NPs were included in the analysis, no differences were seen among cell lines - demonstrating the usefulness of the assay in all cells to identify genotoxic and non-genotoxic NPs. The TK6 cells, human lymphocytes, BeWo b30 and kidney cells seem to be the most reliable for detecting a dose-response.

Dial M for Murder: A Case of Passion Killing, Criminal Evidence and Sultanic Power in Medieval India

This paper considers the structures and applications of the criminal judicial system in the Islamic Later Middle Period as it developed in India under the sultans of Delhi (1200-1400 CE). A fundamental issue in crime and punishment is the relationship between sultanic power and religious authority. Particularly at stake in this relationship is the question of who can sanction the highest form of punishment, i.e. the death penalty (siyāsa). Contemporary historians and scholars in the study of religion investigating the relationship between sharīʿa and siyāsa to reveal the extent and limits of sultanic power show a system of governance that allowed for the delegation of authority, particularly in the area of the judiciary, from the sultan down to viziers and judges. Some scholars depict the relationship between the ʿulamāʾ and the sultan as a kind of stand off. The actual dynamics of legal jurisdiction were much more complex. This study proposes a new interpretive framework for understanding the relationship between political power and religious authority through a critical analysis of the criminal judicial system, law, and historical narrative. In particular, I consider a murder case described by Shams al-dīn Sirāj ʿAfīf in one of the most significant histories written in the later Delhi Sultanate, the Tārīkh-i Fīrūzshāhī.

Sulfitos duplos contendo cobre (I) e um metal de transição M(II) tipo Cu2SO3.M(II)SO3.2H 2O [M(II) = Cu(II), Fe(II), Mn(II) e Cd(II)]: preparação e seletividade na incorporação de M(II)

The metal-catalyzed autooxidation of S(IV) has been studied for more than a century without a consensus being obtained as to reaction rates, rate laws or mechanisms. The main objective in this work was to explore the reaction between Cu(II) and SO2 in the presence of M(II), paying special attention to the formation of double sulfites like Cu2SO3.M(II)SO3.2H 2O. The two principal aspects studied were: i) a new way to prepare double sulfites with high purity degree and the selectivity in the M(II) incorporation during the salt formation.

Power line communication in motor cables of variable-speed electric drives − analysis and

Data transmission between an electric motor and a frequency converter is required in variablespeed electric drives because of sensors installed at the motor. Sensor information can be used for various useful applications to improve the system reliability and its properties. Traditionally, the communication medium is implemented by an additional cabling. However, the costs of the traditional method may be an obstacle to the wider application of data transmission between a motor and a frequency converter. In any case, a power cable is always installed between a motor and a frequency converter for power supply, and hence it may be applied as a communication medium for sensor level data. This thesis considers power line communication (PLC) in inverter-fed motor power cables. The motor cable is studied as a communication channel in the frequency band of 100 kHz−30 MHz. The communication channel and noise characteristics are described. All the individual components included in a variable-speed electric drive are presented in detail. A channel model is developed, and it is verified by measurements. A theoretical channel information capacity analysis is carried out to estimate the opportunities of a communication medium. Suitable communication and forward error correction (FEC) methods are suggested. A general method to implement a broadband and Ethernet-based communication medium between a motor and a frequency converter is proposed. A coupling interface is also developed that allows to install the communication device safely to a three-phase inverter-fed motor power cable. Practical tests are carried out, and the results are analyzed. Possible applications for the proposed method are presented. A speed feedback motor control application is verified in detail by simulations and laboratory tests because of restrictions for the delay in the feedback loop caused by PLC. Other possible applications are discussed at a more general level.

Assessment of Environmental Impacts of Power Generation

Through indisputable evidence of climate change and its link to the greenhouse gas emissions comes the necessity for change in energy production infrastructure during the coming decades. Through political conventions and restrictions energy industry is pushed toward using bigger share of renewable energy sources as energy supply. In addition to climate change, sustainable energy supply is another major issue for future development plans, but neither of these should come with unbearable price. All the power production types have environmental effects as well as strengths and weaknesses. Although each change comes with a price, right track in minimising the environmental impacts and energy supply security can be found by combining all possible low-carbon technologies and by improving energy efficiency in all sectors, for creating a new power production infrastructure of tolerable energy price and of minor environmental effects. GEMIS-Global Emission Model for Integrated Systems is a life-cycle analysis program which was used in this thesis to make indicative energy models for Finland’s future energy supply. Results indicate that the energy supply must comprise both high capacity nuclear power as well as large variation of renewable energy sources for minimization of all environmental effects and keeping energy price reasonable.