Thermoplastic bioactive composite – with special reference to dissolution behaviour and tissue response

Bioactive glasses are surface-active ceramic materials which support and accelerate bone growth in the body. During the healing of a bone fracture or a large bone defect, fixation is often needed. The aim of this thesis was to determine the dissolution behaviour and biocompatibility of a composite consisting of poly(ε-caprolactone-co-DL-lactide) and bioactive glass (S53P4). In addition the applicability as an injectable material straight to a bone defect was assessed. In in vitro tests the dissolution behaviour of plain copolymer and composites containing bioactive glass granules was evaluated, as well as surface reactivity and the material’s capability to form apatite in simulated body fluid (SBF). The human fibroblast proliferation was tested on materials in cell culture. In in vivo experiments, toxicological tests, material degradation and tissue reactions were tested both in subcutaneous space and in experimental bone defects. The composites containing bioactive glass formed a unified layer of apatite on their surface in SBF. The size and amount of glass granules affected the degradation of polymer matrix, as well the material’s surface reactivity. In cell culture on the test materials the human gingival fibroblasts proliferated and matured faster compared with control materials. In in vitro tests a connective tissue capsule was formed around the specimens, and became thinner in the course of time. Foreign body cell reactions in toxicological tests were mild. In experimental bone defects the specimens with a high concentration of small bioactive glass granules (<45 μm) formed a dense apatite surface layer that restricted the bone ingrowth to material. The range of large glass granules (90-315 μm) with high concentrations formed the best bonding with bone, but slow degradation on the copolymer restricted the bone growth only in the superficial layers. In these studies, the handling properties of the material proved to be good and tissue reactions were mild. The reactivity of bioactive glass was retained inside the copolymer matrix, thus enabling bone conductivity with composites. However, the copolymer was noticed to degradate too slowly compared with the bone healing. Therefore, the porosity of the material should be increased in order to improve tissue healing.

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Active sulphide mine tailings impoundments as sources of contaminated drainage: controlling factors, methods of characterisation and geochemical constraints for mitigation

Low quality mine drainage from tailings facilities persists as one of the most significant global environmental concerns related to sulphide mining. Due to the large variation in geological and environmental conditions at mine sites, universal approaches to the management of mine drainage are not always applicable. Instead, site-specific knowledge of the geochemical behaviour of waste materials is required for the design and closure of the facilities. In this thesis, tailings-derived water contamination and factors causing the pollution were investigated in two coeval active sulphide mine sites in Finland: the Hitura Ni mine and the Luikonlahti Cu-Zn-Co-Ni mine and talc processing plant. A hydrogeochemical study was performed to characterise the tailingsderived water pollution at Hitura. Geochemical changes in the Hitura tailings were evaluated with a detailed mineralogical and geochemical investigation (solid-phase speciation, acid mine drainage potential, pore water chemistry) and using a spatial assessment to identify the mechanisms of water contamination. A similar spatial investigation, applying selective extractions, was carried out in the Luikonlahti tailings area for comparative purposes (Hitura low-sulphide tailings vs. Luikonlahti sulphide-rich tailings). At both sites, hydrogeochemistry of tailings seepage waters was further characterised to examine the net results of the processes observed within the impoundments and to identify constraints for water treatment. At Luikonlahti, annual and seasonal variation in effluent quality was evaluated based on a four-year monitoring period. Observations pertinent to future assessment and mine drainage prevention from existing and future tailings facilities were presented based on the results. A combination of hydrogeochemical approaches provided a means to delineate the tailings-derived neutral mine drainage at Hitura. Tailings effluents with elevated Ni, SO₄ ^2- and Fe content had dispersed to the surrounding aquifer through a levelled-out esker and underneath the seepage collection ditches. In future mines, this could be avoided with additional basal liners in tailings impoundments where the permeability of the underlying Quaternary deposits is inadequate, and with sufficiently deep ditches. Based on the studies, extensive sulphide oxidation with subsequent metal release may already initiate during active tailings disposal. The intensity and onset of oxidation depended on e.g. the Fe sulphide content of the tailings, water saturation level, and time of exposure of fresh sulphide grains. Continuous disposal decreased sulphide weathering in the surface of low-sulphide tailings, but oxidation initiated if they were left uncovered after disposal ceased. In the sulphide-rich tailings, delayed burial of the unsaturated tailings had resulted in thick oxidized layers, despite the continuous operation. Sulphide weathering and contaminant release occurred also in the border zones. Based on the results, the prevention of sulphide oxidation should already be considered in the planning of tailings disposal, taking into account the border zones. Moreover, even lowsulphide tailings should be covered without delay after active disposal ceases. The quality of tailings effluents showed wide variation within a single impoundment and between the two different types of tailings facilities assessed. The affecting factors included source materials, the intensity of weathering of tailings and embankment materials along the seepage flow path, inputs from the process waters, the water retention time in tailings, and climatic seasonality. In addition, modifications to the tailings impoundment may markedly change the effluent quality. The wide variation in the tailings effluent quality poses challenges for treatment design. The final decision on water management requires quantification of the spatial and seasonal fluctuation at the site, taking into account changes resulting from the eventual closure of the impoundment. Overall, comprehensive hydrogeochemical mapping was deemed essential in the identification of critical contaminants and their sources at mine sites. Mineralogical analysis, selective extractions, and pore water analysis were a good combination of methods for studying the weathering of tailings and in evaluating metal mobility from the facilities. Selective extractions with visual observations and pH measurements of tailings solids were, nevertheless, adequate in describing the spatial distribution of sulphide oxidation in tailings impoundments. Seepage water chemistry provided additional data on geochemical processes in tailings and was necessary for defining constraints for water treatment.

Active du/dt Filtering for Variable-Speed AC Drives

An oscillating overvoltage has become a common phenomenon at the motor terminal in inverter-fed variable-speed drives. The problem has emerged since modern insulated gate bipolar transistors have become the standard choice as the power switch component in lowvoltage frequency converter drives. Theovervoltage phenomenon is a consequence of the pulse shape of inverter output voltage and impedance mismatches between the inverter, motor cable, and motor. The overvoltages are harmful to the electric motor, and may cause, for instance, insulation failure in the motor. Several methods have been developed to mitigate the problem. However, most of them are based on filtering with lossy passive components, the drawbacks of which are typically their cost and size. In this doctoral dissertation, application of a new active du/dt filtering method based on a low-loss LC circuit and active control to eliminate the motor overvoltages is discussed. The main benefits of the method are the controllability of the output voltage du/dt within certain limits, considerably smaller inductances in the filter circuit resulting in a smaller physical component size, and excellent filtering performance when compared with typical traditional du/dt filtering solutions. Moreover, no additional components are required, since the active control of the filter circuit takes place in the process of the upper-level PWM modulation using the same power switches as the inverter output stage. Further, the active du/dt method will benefit from the development of semiconductor power switch modules, as new technologies and materials emerge, because the method requires additional switching in the output stage of the inverter and generation of narrow voltage pulses. Since additional switching is required in the output stage, additional losses are generated in the inverter as a result of the application of the method. Considerations on the application of the active du/dt filtering method in electric drives are presented together with experimental data in order to verify the potential of the method.

UCL Discovery: raising the Open Access profile at the institution

Presentation at the "Tutkimus vapaaksi verkkoon!" seminar in Helsinki, January 25, 2011

Multifrequency VLBI Observations of Selected Active Galactic Nuclei

In this dissertation, active galactic nuclei (AGN) are discussed, as they are seen with the high-resolution radio-astronomical technique called Very Long Baseline Interferometry (VLBI). This observational technique provides very high angular resolution (_ 10−300 = 1 milliarcsecond). VLBI observations, performed at different radio frequencies (multi-frequency VLBI), allow to penetrate deep into the core of an AGN to reveal an otherwise obscured inner part of the jet and the vicinity of the AGN’s central engine. Multi-frequency VLBI data are used to scrutinize the structure and evolution of the jet, as well as the distribution of the polarized emission. These data can help to derive the properties of the plasma and the magnetic field, and to provide constraints to the jet composition and the parameters of emission mechanisms. Also VLBI data can be used for testing the possible physical processes in the jet by comparing observational results with results of numerical simulations. The work presented in this thesis contributes to different aspects of AGN physics studies, as well as to the methodology of VLBI data reduction. In particular, Paper I reports evidence of optical and radio emission of AGN coming from the same region in the inner jet. This result was obtained via simultaneous observations of linear polarization in the optical and in radio using VLBI technique of a sample of AGN. Papers II and III describe, in detail, the jet kinematics of the blazar 0716+714, based on multi-frequency data, and reveal a peculiar kinematic pattern: plasma in the inner jet appears to move substantially faster that that in the large-scale jet. This peculiarity is explained by the jet bending, in Paper III. Also, Paper III presents a test of the new imaging technique for VLBI data, the Generalized Maximum Entropy Method (GMEM), with the observed (not simulated) data and compares its results with the conventional imaging. Papers IV and V report the results of observations of the circularly polarized (CP) emission in AGN at small spatial scales. In particular, Paper IV presents values of the core CP for 41 AGN at 15, 22 and 43 GHz, obtained with the help of the standard Gain transfer (GT) method, which was previously developed by D. Homan and J.Wardle for the calibration of multi-source VLBI observations. This method was developed for long multi-source observations, when many AGN are observed in a single VLBI run. In contrast, in Paper V, an attempt is made to apply the GT method to single-source VLBI observations. In such observations, the object list would include only a few sources: a target source and two or three calibrators, and it lasts much shorter than the multi-source experiment. For the CP calibration of a single-source observation, it is necessary to have a source with zero or known CP as one of the calibrators. If the archival observations included such a source to the list of calibrators, the GT could also be used for the archival data, increasing a list of known AGN with the CP at small spatial scale. Paper V contains also calculation of contributions of different sourced of errors to the uncertainty of the final result, and presents the first results for the blazar 0716+714.

Broadband excitation in the system identification of active magnetic bearing rotor systems

One of the targets of the climate and energy package of the European Union is to increase the energy efficiency in order to achieve a 20 percent reduction in primary energy use compared with the projected level by 2020. The energy efficiency can be improved for example by increasing the rotational speed of large electrical drives, because this enables the elimination of gearboxes leading to a compact design with lower losses. The rotational speeds of traditional bearings, such as roller bearings, are limited by mechanical friction. Active magnetic bearings (AMBs), on the other hand, allow very high rotational speeds. Consequently, their use in large medium- and high-speed machines has rapidly increased. An active magnetic bearing rotor system is an inherently unstable, nonlinear multiple-input, multiple-output system. Model-based controller design of AMBs requires an accurate system model. Finite element modeling (FEM) together with the experimental modal analysis provides a very accurate model for the rotor, and a linearized model of the magneticactuators has proven to work well in normal conditions. However, the overall system may suffer from unmodeled dynamics, such as dynamics of foundation or shrink fits. This dynamics can be modeled by system identification. System identification can also be used for on-line diagnostics. In this study, broadband excitation signals are adopted to the identification of an active magnetic bearing rotor system. The broadband excitation enables faster frequency response function measurements when compared with the widely used stepped sine and swept sine excitations. Different broadband excitations are reviewed, and the random phase multisine excitation is chosen for further study. The measurement times using the multisine excitation and the stepped sine excitation are compared. An excitation signal design with an analysis of the harmonics produced by the nonlinear system is presented. The suitability of different frequency response function estimators for an AMB rotor system are also compared. Additionally, analytical modeling of an AMB rotor system, obtaining a parametric model from the nonparametric frequency response functions, and model updating are discussed in brief, as they are key elements in the modeling for a control design. Theoretical methods are tested with a laboratory test rig. The results conclude that an appropriately designed random phase multisine excitation is suitable for the identification of AMB rotor systems.

Active inverter output filtering methods

Frequency converters are widely used in the industry to enable better controllability and efficiency of variable speed AC motor drives. Despite these advantages, certain challenges concerning the inverter and motor interfacing have been present for decades. As insulated gate bipolar transistors entered the market, the inverter output voltage transition rate significantly increased compared with their predecessors. Inverters operate based on pulse width modulation of the output voltage, and the steep voltage edge fed by the inverter produces a motor terminal overvoltage. The overvoltage causes extra stress to the motor insulation, which may lead to a prematuremotor failure. The overvoltage is not generated by the inverter alone, but also by the sum effect of the motor cable length and the impedance mismatch between the cable and the motor. Many solutions have been shown to limit the overvoltage, and the mainstream products focus on passive filters. This doctoral thesis studies an alternative methodology for motor overvoltage reduction. The focus is on minimization of the passive filter dimensions, physical and electrical, or better yet, on operation without any filter. This is achieved by additional inverter control and modulation. The studied methods are implemented on different inverter topologies, varying in nominal voltage and current.For two-level inverters, the studied method is termed active du/dt. It consists of a small output LC filter, which is controlled by an independent modulator. The overvoltage is limited by a reduced voltage transition rate. For multilevel inverters, an overvoltage mitigation method operating without a passive filter, called edge modulation, is implemented. The method uses the capability of the inverter to produce two switching operations in the same direction to cancel the oscillating voltages of opposite phases. For parallel inverters, two methods are studied. They are both intended for two-level inverters, but the first uses individual motor cables from each inverter while the other topology applies output inductors. The overvoltage is reduced by interleaving the switching operations to produce a similar oscillation accumulation as with the edge modulation. The implementation of these methods is discussed in detail, and the necessary modifications to the control system of the inverter are presented. Each method is experimentally verified by operating industrial frequency converters with the modified control. All the methods are found feasible, and they provide sufficient overvoltage protection. The limitations and challenges brought about by the methods are discussed.

Performance of active portfolio management and the effect of stock market trend

Purpose of the study is to evaluate performance of active portfolio management and the effect of stock market trend on the performance. Theory of efficient markets states that market prices reflect all available information and that all investors share a common view of future price developments. This view gives little room for the success of active management, but the theory has been disputed – at least the level of efficiency. Behavioral finance has developed theories that identify irrational behavior patterns of investors. For example, investment decisions are not made independent of past market developments. These findings give reason to believe that also the performance of active portfolio management may depend on market developments. Performance of 16 Finnish equity funds is evaluated during the period of 2005 to 2011. In addition two sub periods are constructed, a bull market period and a bear market period. The sub periods are created by joining together the two bull market phases and the two bear market phases of the whole period. This allows for the comparison of the two different market states. Performance of the funds is measured with risk-adjusted performance by Modigliani and Modigliani (1997), abnormal return over the CAPM by Jensen (1968), and market timing by Henriksson and Merton (1981). The results suggested that in average the funds are not able to outperform the market portfolio. However, the underperformance was found to be lower than the management fees in average which suggests that portfolio managers are able to do successful investment decisions to some extent. The study revealed substantial dependence on the market trend for all of the measures. The risk-adjusted performance measure suggested that in bear markets active portfolio managers in average are able to beat the market portfolio but not in bull markets. Jensen´s alpha and the market timing model also showed striking differences between the two market states. The results of these two measures were, however, somewhat problematic and reliable conclusions about the performance could not be drawn.

Occurrence and photochemical fate of selected pharmaceutical active ingredients in the aquatic environment

Läkemedel konsumeras årligen i enorma mängder världen över. Efter intag kommer en del av läkemedlets aktiva förening(ar) att utsöndras från kroppen med urin och fekalier för att sedan transporteras till avloppsreningsverk. Till följd av att reningsverken inte fullständigt förmår rena avloppsvattnet från dessa föreningar kommer de att kontinuerligt tillföras vattenmiljön. Således är det viktigt att utveckla analytiska metoder för att kunna studera halterna av de aktiva föreningarna i reningsverkens utloppsvatten och den närliggande vattenmiljön. Ute i naturen kommer föreningarna att utsättas för olika fysikaliska, kemiska och biologiska processer, vilka kan orsaka förändringar i deras kemiska struktur och därigenom deras identitet och biologiska aktivitet. En stor del av de befintliga aktiva föreningarna genomgår kemisk förändring då de i vattenmiljön utsätts för solljus (fototransformation). Genom fototransformation kan nya föreningar (transformationsprodukter) med andra kemiska och biologiska egenskaper bildas. Denna avhandling inriktar sig på de aktiva föreningarnas förekomst och fotokemiska öde i miljön. I avhandlingen presenteras framtagna analytiska metoder för kvantifiering av läkemedelsföreningar i avloppsvatten och ytvatten samt för studier av vissa utvalda föreningars fotokemiska transformationsvägar. Därtill beskrivs några syntetiska metoder för att få tillgång till transformationsprodukter av det antiinflammatoriska ämnet diklofenak.

One chip solution for low-cost active magnetic bearing system

In this work the implementation of the active magnetic bearing control system in a single FPGA is studied. Requirements for the full magnetic bearing control system are reviewed. Different control methods for active magnetic bearings are described shortly. Flux and the current base controllers are implemented in a FPGA. Suitability of the con-trollers for a low-cost magnetic bearing application is studied. Floating-point arithmetic’s are used in the controllers to ease designing burden and improve calculation precision. Per-formance of the flux controller is verified with simulations.

Chaotic Behaviour of Active Magnetic Bearing System by Time Series Analysis

Chaotic behaviour is one of the hardest problems that can happen in nonlinear dynamical systems with severe nonlinearities. It makes the system's responses unpredictable. It makes the system's responses to behave similar to noise. In some applications it should be avoided. One of the approaches to detect the chaotic behaviour is nding the Lyapunov exponent through examining the dynamical equation of the system. It needs a model of the system. The goal of this study is the diagnosis of chaotic behaviour by just exploring the data (signal) without using any dynamical model of the system. In this work two methods are tested on the time series data collected from AMB (Active Magnetic Bearing) system sensors. The rst method is used to nd the largest Lyapunov exponent by Rosenstein method. The second method is a 0-1 test for identifying chaotic behaviour. These two methods are used to detect if the data is chaotic. By using Rosenstein method it is needed to nd the minimum embedding dimension. To nd the minimum embedding dimension Cao method is used. Cao method does not give just the minimum embedding dimension, it also gives the order of the nonlinear dynamical equation of the system and also it shows how the system's signals are corrupted with noise. At the end of this research a test called runs test is introduced to show that the data is not excessively noisy.