The Role of Surfactant Properties of Extractants in Hydrometallurgical LiquidLiquid Extraction Processes

The amphiphilic nature of metal extractants causes the formation of micelles and other microscopic aggregates when in contact with water and an organic diluent. These phenomena and their effects on metal extraction were studied using carboxylic acid (Versatic 10) and organophosphorus acid (Cyanex 272) based extractants. Special emphasis was laid on the study of phase behaviour in a pre neutralisation stage when the extractant is transformed to a sodium or ammonium salt form. The pre neutralised extractants were used to extract nickel and to separate cobalt and nickel. Phase diagrams corresponding to the pre neutralisation stage in a metal extraction process were determined. The maximal solubilisation of the components in the system water(NH3)/extractant/isooctane takes place when the molar ratio between the ammonia salt form and the free form of the extractant is 0.5 for the carboxylic acid and 1 for the organophosphorus acid extractant. These values correspond to the complex stoichiometry of NH4A•HA and NIi4A, respectively. When such a solution is contacted with water a microemulsion is formed. If the aqueous phase contains also metal ions (e.g. Ni²+), complexation will take place on the microscopic interface of the micellar aggregates. Experimental evidence showing that the initial stage of nickel extraction with pre neutralised Versatic 10 is a fast pseudohomogeneous reaction was obtained. About 90% of the metal were extracted in the first 15 s after the initial contact. For nickel extraction with pre neutralised Versatic 10 it was found that the highest metal loading and the lowest residual ammonia and water contents in the organic phase are achieved when the feeds are balanced so that the stoichiometry is 2NH4+(org) = Nit2+(aq). In the case of Co/Ni separation using pre neutralised Cyanex 272 the highest separation is achieved when the Co/extractant molar ratio in the feeds is 1 : 4 and at the same time the optimal degree of neutralisation of the Cyanex 272 is about 50%. The adsorption of the extractants on solid surfaces may cause accumulation of solid fine particles at the interface between the aqueous and organic phases in metal extraction processes. Copper extraction processes are known to suffer of this problem. Experiments were carried out using model silica and mica particles. It was found that high copper loading, aromacity of the diluent, modification agents and the presence of aqueous phase decrease the adsorption of the hydroxyoxime on silica surfaces.

Size Effect and Notch Size Effect in Metal Fatigue

It is a well known phenomenon that the constant amplitude fatigue limit of a large component is lower than the fatigue limit of a small specimen made of the same material. In notched components the opposite occurs: the fatigue limit defined as the maximum stress at the notch is higher than that achieved with smooth specimens. These two effects have been taken into account in most design handbooks with the help of experimental formulas or design curves. The basic idea of this study is that the size effect can mainly be explained by the statistical size effect. A component subjected to an alternating load can be assumed to form a sample of initiated cracks at the end of the crack initiation phase. The size of the sample depends on the size of the specimen in question. The main objective of this study is to develop a statistical model for the estimation of this kind of size effect. It was shown that the size of a sample of initiated cracks shall be based on the stressed surface area of the specimen. In case of varying stress distribution, an effective stress area must be calculated. It is based on the decreasing probability of equally sized initiated cracks at lower stress level. If the distribution function of the parent population of cracks is known, the distribution of the maximum crack size in a sample can be defined. This makes it possible to calculate an estimate of the largest expected crack in any sample size. The estimate of the fatigue limit can now be calculated with the help of the linear elastic fracture mechanics. In notched components another source of size effect has to be taken into account. If we think about two specimens which have similar shape, but the size is different, it can be seen that the stress gradient in the smaller specimen is steeper. If there is an initiated crack in both of them, the stress intensity factor at the crack in the larger specimen is higher. The second goal of this thesis is to create a calculation method for this factor which is called the geometric size effect. The proposed method for the calculation of the geometric size effect is also based on the use of the linear elastic fracture mechanics. It is possible to calculate an accurate value of the stress intensity factor in a non linear stress field using weight functions. The calculated stress intensity factor values at the initiated crack can be compared to the corresponding stress intensity factor due to constant stress. The notch size effect is calculated as the ratio of these stress intensity factors. The presented methods were tested against experimental results taken from three German doctoral works. Two candidates for the parent population of initiated cracks were found: the Weibull distribution and the log normal distribution. Both of them can be used successfully for the prediction of the statistical size effect for smooth specimens. In case of notched components the geometric size effect due to the stress gradient shall be combined with the statistical size effect. The proposed method gives good results as long as the notch in question is blunt enough. For very sharp notches, stress concentration factor about 5 or higher, the method does not give sufficient results. It was shown that the plastic portion of the strain becomes quite high at the root of this kind of notches. The use of the linear elastic fracture mechanics becomes therefore questionable.

The effect of microfibrillated cellulose addition on drying shrinkage and dimensional stability of wood-free paper

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper. Dimensional instability is due to changes in moisture content of paper; when paper is moistened it expands and when dried, it shrinks. Hygroexpansion is linked to end-use problems and excessive drying shrinkage consumes strength potential. Effective use of materials requires controlling of these phenomena. There isn’t yet data concerning dimensional stability of papers containing MFC which restricts wider use of MFC. Main objective of the work was to evaluate dimensional stability of wood-free paper containing different amounts of MFC. Sheets were dried with different methods to see how drying strains effected on drying shrinkage and hygroexpansion. Also tensile strength was measured to find out the effect of MFC. Results were compared to sheets containing kraft fines and in some test points cationic starch was used alongside with MFC. MFC increased the dimensional instability of freely dried sheets. As the amounts of MFC increased the effects on dimensional stability became more severe. However the fineness of MFC didn’t play any important role. Both hygroexpansion and drying shrinkage were decreased with cationic starch addition. Prevention of drying shrinkage over powered the effects of additives on hygroexpansion. Tensile strength improved up till 7 % addition amount which could be set as the upper limit of MFC addition when paper preparation and tensile strength are concerned.

Free PAPP-A: a Novel Marker in Acute Coronary Syndrome Patients

In recent years, one important objective of cardiovascular research has been to find new markers that would improve the risk stratification and diagnosis of patients presenting with symptoms of acute coronary syndrome (ACS). Pregnancy-associated plasma protein A (PAPP-A) is a large metalloproteinase involved in insulin-like growth factor signalling. It is expressed in various tissues and seems to be involved in many physiological and pathological processes, such as folliculogenesis, bone formation, wound healing, pregnancy and atherosclerosis. The aim of this thesis was to investigate PAPP-A in ACS patients. Circulating concentrations of PAPP-A had been previously shown to be elevated in ACS. In this study it was revealed that the form of PAPP-A causing this elevation was the free noncomplexed PAPP-A. Thus, the form of PAPP-A in the circulation of ACS patients differed from the complexed PAPP-A form abundantly present in the circulation during pregnancy. A point-of-care method based on time-resolved immunofluorometric assays was developed, which enabled the rapid detection of free PAPP-A. The method was found to perform well with serum and heparin plasma samples as well as with heparinized whole blood samples. With this method the concentrations of free PAPP-A in healthy individuals were shown to be negligible. When the clinical performance of the method was evaluated with serum samples from ACS patients, it was shown that the free PAPP-A concentration in the admission sample was an independent predictor of myocardial infarction and death. Moreover, as a prognostic marker, free PAPP-A was revealed to be superior to total PAPPA, i.e. the combination of free and complexed PAPP-A, which has been measured by the other groups in this field. As heparin products are widely used as medication in ACS patients, the effect of heparin products on free PAPP-A molecule and circulating concentrations were also investigated in this study. It was shown that intravenous administration of low molecular weight or unfractionated heparin elicits a rapid release of free PAPP-A into the circulation in haemodialysis patients and patients undergoing angiography. Moreover, the interaction between PAPP-A and heparin was confirmed in gel filtration studies. Importantly, the patients included in the clinical evaluation of the free PAPP-A detection method developed had not received any heparin product medication before the admission sample and thus the results were not affected by the heparin effect. In conclusion, free PAPP-A was identified as a novel marker associated with ACS. The point-of-care methods developed enable rapid detection of this molecule which predicts adverse outcome when measured in the admission sample of ACS patients. However, the effect revealed of heparin products on circulating PAPP-A concentrations should be acknowledged when further studies are conducted related to free or total PAPP-A in ACS.

Free Flap Monitoring. Using Tissue Oxygen Measurement and Positron Emission Tomography

Aims:This study was carried out to evaluate the feasibility of two different methods to determine free flap perfusion in cancer patients undergoing major reconstructive surgery. The hypotheses was that low perfusion in the flap is associated with flap complications. Patients and methods: Between August 2002 and June 2008 at the Department of Otorhinolaryngology – Head and Neck Surgery, Department of Surgery, and at the PET Centre, Turku, 30 consecutive patients with 32 free flaps were included in this study. The perfusion of the free microvascular flaps was assessed with positron emission tomography (PET) and radioactive water ([¹⁵O] H₂O) in 40 radiowater injections in 33 PET studies. Furthermore, 24 free flaps were monitored with a continuous tissue oxygen measurement using flexible polarographic catheters for an average of three postoperative days. Results: Of the 17 patients operated on for head and neck (HN) cancer and reconstructed with 18 free flaps, three re-operations were carried out due to poor tissue oxygenation as indicated by p_tiO₂ monitoring results and three other patients were reoperated on for postoperative hematomas in the operated area. Blood perfusion assessed with PET (BF_PET) was above 2.0 mL / min / 100 g in all flaps and a low flap-to-muscle BFPET ratio appeared to correlate with poor survival of the flap. Survival in this group of HN cancer patients was 9.0 months (median, range 2.4-34.2) after a median follow-up of 11.9 months (range 1.0-61.0 months). Seven HN patients of this group are alive without any sign of recurrence and one patient has died of other causes. All of the 13 breast reconstruction patients included in the study are alive and free of disease at a median follow-up time of 27.4 months (range 13.9-35.7 months). Re-explorations were carried out in three patients due data provided by p_tiO₂ monitoring and one re-exploration was avoided on the basis of adequate blood perfusion assessed with PET. Two patients had donorsite morbidity and 3 patients had partial flap necrosis or fat necrosis. There were no total flap losses. Conclusions: P_tiO₂ monitoring is a feasible method of free flap monitoring when flap temperature is monitored and maintained close to the core temperature. When other monitoring methods give controversial results or are unavailable, [₁₅O] H₂O PET technique is feasible in the evaluation of the perfusion of the newly reconstructed free flaps.

Towards input/output-free modelling of linear infinite-dimensional systems in continuous time

This dissertation describes a networking approach to infinite-dimensional systems theory, where there is a minimal distinction between inputs and outputs. We introduce and study two closely related classes of systems, namely the state/signal systems and the port-Hamiltonian systems, and describe how they relate to each other. Some basic theory for these two classes of systems and the interconnections of such systems is provided. The main emphasis lies on passive and conservative systems, and the theoretical concepts are illustrated using the example of a lossless transfer line. Much remains to be done in this field and we point to some directions for future studies as well.

Faster for the master! : exploring issues of religious expression and alternative Christian identity within the Finnish Christian metal music scene

Populärkulturen har i dagens läge kommit att utgöra en allt mer viktig och central inspirationskälla för allt fler människors konstruktion av den egna religiösa identiteten även inom traditionella och institutionella kristna sammanhang. Denna avhandling belyser denna utveckling i ljuset av den finländska kristna metallmusik-kulturen - en sällsynt stark sammanblanding av protestantisk kristendom och en utpräglad och kontroversiell populärmusikform och dess kultur. Fokus riktas framför allt på hur den kristna metallmusik-kulturen blir meningsfull för sina medlemmar genom de sätt på vilka den konstrueras diskursivt, dvs. genom de sätt på vilka den representeras och talas om bland sina egna anhängare. Den diskursiva konstruktionen av den kristna metallmusik-kulturen utforskas på ett såväl bredare transnationellt som ett finländskt nationellt plan. Studien redogör även för den kristna metalmusikens och -kulturens huvudsakliga verbala, visuella och estetiska kännetecken. Uppbyggnaden och spridningen av dagens transnationella kristna metallmusik-kultur undersöks även i ljuset av det teoretiska konceptet scene. Avhandlingens centrala argument är att den kristna metallmusikscenen erbjuder sina medlemmar en mängd resurser för skapandet av ett alternativt och komplementärt religiöst uttrycksätt, religiös praxis och en alternativ kristen identitet.

Mening genom (kristen) metal

Kirja-arvio

Vibration free machining tools

Appearance of the vibration is the very important problem in long tool turning and milling. Current solutions of minimizing vibrations provided by different tool suppliers are very expensive. This Master’s Thesis is presenting the new type of vibration free machining tools produced by Konepaja ASTEX Gear Oy that have cheaper production costs compare to competitors’ products. Vibration problems in machining and their today’s solutions are analyzed in this work. The new vibration damping invention is presented and described. Moreover, the production, laboratory experimental modal analysis and practical testing of the new vibration free prototypes are observed and analyzed on the pages of this Thesis. Based on the testing results the new invention is acknowledged to be successful and approved for further studies and developments.

Atomic level phenomena on transition metal surfaces

In this study we discuss the atomic level phenomena on transition metal surfaces. Transition metals are widely used as catalysts in industry. Therefore, reactions occuring on transition metal surfaces have large industrial intrest. This study addresses problems in very small size and time scales, which is an important part in the overall understanding of these phenomena. The publications of this study can be roughly divided into two categories: The adsorption of an O2 molecule to a surface, and surface structures of preadsorbed atoms. These two categories complement each other, because in the realistic case there are always some preadsorbed atoms at the catalytically active surfaces. However, all transition metals have an active d-band, and this study is also a study of the in uence of the active d-band on other atoms. At the rst part of this study we discuss the adsorption and dissociation of an O2 molecule on a clean stepped palladium surface and a smooth palladium surface precovered with sulphur and oxygen atoms. We show how the reactivity of the surface against the oxygen molecule varies due to the geometry of the surface and preadsorbed atoms. We also show how the molecular orbitals of the oxygen molecule evolve when it approaches the di erent sites on the surface. In the second part we discuss the surface structures of transition metal surfaces. We study the structures that are intresting on account of the Rashba e ect and charge density waves. We also study the adsorption of suphur on a gold surface, and surface structures of it. In this study we use ab-initio based density functional theory methods to simulate the results. We also compare the results of our methods to the results obtained with the Low-Energy-Electron-Difraction method.

Development of simple and efficient synthetic strategies for production of fine chemicals of pharmaceutical relevance : metal-mediated allylation combined with applied catalysis

Den snart 200 år gamla vetenskapsgrenen organisk synteskemi har starkt bidragit till moderna samhällens välfärd. Ett av flaggskeppen för den organiska synteskemin är utvecklingen och produktionen av nya läkemedel och speciellt de aktiva substanserna däri. Därmed är det viktigt att utveckla nya syntesmetoder, som kan tillämpas vid framställningen av farmaceutiskt relevanta målstrukturer. I detta sammanhang är den ultimata målsättningen dock inte endast en lyckad syntes av målmolekylen, utan det är allt viktigare att utveckla syntesrutter som uppfyller kriterierna för den hållbara utvecklingen. Ett av de centralaste verktygen som en organisk kemist har till förfogande i detta sammanhang är katalys, eller mera specifikt möjligheten att tillämpa olika katalytiska reaktioner vid framställning av komplexa målstrukturer. De motsvarande industriella processerna karakteriseras av hög effektivitet och minimerad avfallsproduktion, vilket naturligtvis gynnar den kemiska industrin samtidigt som de negativa miljöeffekterna minskas avsevärt. I denna doktorsavhandling har nya syntesrutter för produktion av finkemikalier med farmaceutisk relevans utvecklats genom att kombinera förhållandevis enkla transformationer till nya reaktionssekvenser. Alla reaktionssekvenser som diskuteras i denna avhandling påbörjades med en metallförmedlad allylering av utvalda aldehyder eller aldiminer. De erhållna produkterna innehållende en kol-koldubbelbindning med en närliggande hydroxyl- eller aminogrupp modifierades sedan vidare genom att tillämpa välkända katalytiska reaktioner. Alla syntetiserade molekyler som presenteras i denna avhandling karakteriseras som finkemikalier med hög potential vid farmaceutiska tillämpningar. Utöver detta tillämpades en mängd olika katalytiska reaktioner framgångsrikt vid syntes av dessa molekyler, vilket i sin tur förstärker betydelsen för de katalytiska verktygen i organiska kemins verktygslåda.

Feasibility study of metal to polymer hybrid joining

The increasing demand for lightweight components has led to a huge exploitation of non-metallic materials such as polymers, fibers and elastomers in industrial and manufacturing processes. Recent trends towards cost effectiveness, weight reduction and production flexibility in industrial production and manufacturing processes has led to a growing interest in hybrid components where two or more dissimilar materials coexist to achieving specifically optimized characteristics. The importance of this research is to serve as a bridge to understanding the theories behind various joining techniques and the adaptation of the process for metal to polymer hybrid joints. Moreso, it helps companies to select the most productive and yet economical joining process for realization of lightweight metal to polymer hybrid components. This thesis is a literature review analyzing various materials that has been published on various joining methods for metal to polymer hybrid joints on the feasibility and eventual realization of the joint between these dissimilar materials. This study is aimed at theoretically evaluating the feasibility of joining processes between metal and plastic components by exploiting exhaustively joining and welding sources.

Free Prostate-specific Antigen Forms and Kallikrein-related Peptidase 2: Tools for Prostate Cancer Diagnostics

Prostate-specific antigen (PSA) is a marker that is commonly used in estimating prostate cancer risk. Prostate cancer is usually a slowly progressing disease, which might not cause any symptoms whatsoever. Nevertheless, some cases of cancer are aggressive and need to be treated before they become life-threatening. However, the blood PSA concentration may rise also in benign prostate diseases and using a single total PSA (tPSA) measurement to guide the decision on further examinations leads to many unnecessary biopsies, over-detection, and overtreatment of indolent cancers which would not require treatment. Therefore, there is a need for markers that would better separate cancer from benign disorders, and would also predict cancer aggressiveness. The aim of this study was to evaluate whether intact and nicked forms of free PSA (fPSA-I and fPSA-N) or human kallikrein-related peptidase 2 (hK2) could serve as new tools in estimating prostate cancer risk. First, the immunoassays for fPSA-I and free and total hK2 were optimized so that they would be less prone to assay interference caused by interfering factors present in some blood samples. The optimized assays were shown to work well and were used to study the marker concentrations in the clinical sample panels. The marker levels were measured from preoperative blood samples of prostate cancer patients scheduled for radical prostatectomy. The association of the markers with the cancer stage and grade was studied. It was found that among all tested markers and their combinations especially the ratio of fPSA-N to tPSA and ratio of free PSA (fPSA) to tPSA were associated with both cancer stage and grade. They might be useful in predicting the cancer aggressiveness, but further follow-up studies are necessary to fully evaluate the significance of the markers in this clinical setting. The markers tPSA, fPSA, fPSA-I and hK2 were combined in a statistical model which was previously shown to be able to reduce unnecessary biopsies when applied to large screening cohorts of men with elevated tPSA. The discriminative accuracy of this model was compared to models based on established clinical predictors in reference to biopsy outcome. The kallikrein model and the calculated fPSA-N concentrations (fPSA minus fPSA-I) correlated with the prostate volume and the model, when compared to the clinical models, predicted prostate cancer in biopsy equally well. Hence, the measurement of kallikreins in a blood sample could be used to replace the volume measurement which is time-consuming, needs instrumentation and skilled personnel and is an uncomfortable procedure. Overall, the model could simplify the estimation of prostate cancer risk. Finally, as the fPSA-N seems to be an interesting new marker, a direct immunoassay for measuring fPSA-N concentrations was developed. The analytical performance was acceptable, but the rather complicated assay protocol needs to be improved until it can be used for measuring large sample panels.