Pienitaajuinen radiosekoitin

Normaalisti radiovastaanottimet on luokiteltavissa suoriin vastaanottimiin ja superheterodynevastaanottimiin. Jälkimmäistä nimitetään tavallisesti supervastaanottimeksi. Molemman vastaanottimen oleellisiin osiin kuuluu antennin virityspiiri, supervastaanottimelle lisäksi paikallisoskillaattorin virityspiiri, mikä pitää virittää antennipiirin kanssa samanaikaisesti. Pienillä taajuuksilla, taajuudet luokassa kilo-Hertzejä tai pienemmillä, on antennipiirin viritys resonanssipiirin ominaisuuksista johtuen sitä kapeammalla kaistalla ja sitä hitaampaa mitä pienemmällä taajuudella vastaanotto tapahtuu. Lisäksi virityspiiri hyvyysluku Q on vaikea saada sopivaksi, mikäli viritys on muuten käytännöllinen, säädettävä resonanssipiiri. Vaadittaessa kiinteätaajuista viritystä on käytännöllistä hyödyntää sähkömekaanisia osia, siis keraamisia tai kvartsikiteitä. Koska kiteitten ja korkean hyvyysluvun piirin värähtely jatkuu useita värähtelyjaksoja ennen saapuneitten värähtelyjen sammumista, kestää myös kauan aikaa, ennen kuin värähtely piirissä on loppu. Pienitaajuinen resonanssipiiri saavuttaa maksimivirtansa hitaasti, jos hyvyysluku on iso, kun piiri alkaa johtaa resonanssitaajuista virtaa. Tässä työssä pyritään vastaanotinjärjestelyyn ongelmallisen, pientaajuisen virityspiirin käytön välttämiseksi. Toisena tavoitteena on saada aikaan vastaanotto siten, että tietty pienitaajuinen radiotaajuusalue voidaan kokonaisuudessaan vastaanottaa jatkuva-aikaisesti, ilman antennipiirin jatkuvaa virittämistä erillisille taajuuksille. Laaditaan kytkentä, joka mitoitetaan, simuloidaan ja mitataan.

The influence of crystallization conditions on the filtration characteristics of sulphathiazole suspensions

Cooling crystallization is one of the most important purification and separation techniques in the chemical and pharmaceutical industry. The product of the cooling crystallization process is always a suspension that contains both the mother liquor and the product crystals, and therefore the first process step following crystallization is usually solid-liquid separation. The properties of the produced crystals, such as their size and shape, can be affected by modifying the conditions during the crystallization process. The filtration characteristics of solid/liquid suspensions, on the other hand, are strongly influenced by the particle properties, as well as the properties of the liquid phase. It is thus obvious that the effect of the changes made to the crystallization parameters can also be seen in the course of the filtration process. Although the relationship between crystallization and filtration is widely recognized, the number of publications where these unit operations have been considered in the same context seems to be surprisingly small. This thesis explores the influence of different crystallization parameters in an unseeded batch cooling crystallization process on the external appearance of the product crystals and on the pressure filtration characteristics of the obtained product suspensions. Crystallization experiments are performed by crystallizing sulphathiazole (C9H9N3O2S2), which is a wellknown antibiotic agent, from different mixtures of water and n-propanol in an unseeded batch crystallizer. The different crystallization parameters that are studied are the composition of the solvent, the cooling rate during the crystallization experiments carried out by using a constant cooling rate throughout the whole batch, the cooling profile, as well as the mixing intensity during the batch. The obtained crystals are characterized by using an automated image analyzer and the crystals are separated from the solvent through constant pressure batch filtration experiments. Separation characteristics of the suspensions are described by means of average specific cake resistance and average filter cake porosity, and the compressibilities of the cakes are also determined. The results show that fairly large differences can be observed between the size and shape of the crystals, and it is also shown experimentally that the changes in the crystal size and shape have a direct impact on the pressure filtration characteristics of the crystal suspensions. The experimental results are utilized to create a procedure that can be used for estimating the filtration characteristics of solid-liquid suspensions according to the particle size and shape data obtained by image analysis. Multilinear partial least squares regression (N-PLS) models are created between the filtration parameters and the particle size and shape data, and the results presented in this thesis show that relatively obvious correlations can be detected with the obtained models.

Supersaturation-controlled crystallization

Identification of product requirements and quality, together with the management of production are key issues in chemical engineering. Quality control of crystalline products is part of the quality of many industrially manufactured products like paper, paintings, medicines and fertilizers. In most crystallization cases, quality is described with the size, polymorph, shape and purity of the crystal. The chemical composition, hydrodynamics and driving force, together with the operating temperature are in a key position when the properties of a crystalline product are controlled with the crystallization process. This study concentrates on managing the identified properties of a crystalline product with the control of a driving force. The controlling of the driving force can be based on the change of solubility or the change of concentration. Solubility can be changed with temperature, pressure and an antisolvent. The concentration of crystallizing compound, the solute can be changed with the evaporation of the solvent and with the addition of a reagent. The present study focuses on reagent addition and temperature change as methods of changing the level of the driving force. Three control structures for direct control of supersaturation are built, one for cooling crystallization and two for reactive crystallization. Closed loop feedback control structures are based on the measurement of the solute concentration with attenuated total reflection - Fourier transform infrared spectrometer. The details of the reagent feed are analyzed with experimental studies and with results of computational fluid dynamic simulations of the inert particle pulse in the premixer and inert particle injection to the mixing tank. Nucleation in conditions of controlled reactive crystallization is analyzed with Nielsen’s equation of homogeneous nucleation. The resulting control systems, based on regulation of supersaturation, can be used to produce the desired polymorph of an organic product. The polymorph composition of product crystals is controlled repeatably with the decision of a set value of supersaturation level.

Crystallization characteristics of bioactive glasses

Bioactive glasses are excellent candidates for implant materials, because they can form a chemical bond to bone or guide bone growth, depending on the glass composition. Some compositions have even shown soft tissue attachment and antimicrobial effects. So far, most clinical applications are based on monoliths, plates and particulates of different grain sizes. There is a growing interest in special products such as porous implants sintered from microspheres and fibers drawn from preforms or glass melts. The viscosity range at which these are formed coincides with the crystallization temperature range for most bioactive glasses, thus complicating the manufacturing process. In this work, the crystallization tendency and its kinetics for a series of glasses with their compositions within the range of bioactivity were investigated. The factors affecting crystallization and how it is related to composition were studied by means of thermal analysis and hot stage microscopy. The crystal compositions formed during isothermal and non-isothermal heat treatments were analyzed with SEM-EDXA and X-ray diffraction analysis. The temperatures at which sintering and fiber drawing can take place without interfering with crystallization were determined and glass compositions which are suitable for these purposes were established. The bioactivity of glass fibers and partly crystallized glass plates was studied by soaking them in simulated body fluid (SBF). The thickness of silica, calcium and phosphate rich reaction layers on the glass surface after soaking was used as an indication of the bioactivity. The results indicated that the crystallization tendencies of the experimental glasses are strongly dependent on composition. The main factor affecting the crystallization was found to be the alkali oxide content: the higher the alkali oxide content the lower the crystallization temperature. The primary crystalline phase formed at low temperatures in these glasses was sodium calcium silicate. The crystals were found to form through internal nucleation, leading to bulk crystallization. These glasses had high bioactivity in vitro. Even when partially crystalline, they formed typical reaction layers, indicating bioactivity. In fact, sodium calcium silicate crystals were shown to transform in vitro into hydroxyapatite during soaking. However, crystallization should be avoided because it was shown to retard dissolution, bioactivity reactions and complicate fiber drawing process. Glass compositions having low alkali oxide content showed formation of wollastonite crystals on the surface, at about 300°C above the glass transition temperature. The wide range between glass transition and crystallization allowed viscous flow sintering of these compositions. These glasses also withstood the thermal treatments required for fiber drawing processing. Precipitation of calcium and phosphate on fibers of these glasses in SBF suggested that they were osteoconductive. Glasses showing bioactivity crystallize easily, making their hot working challenging. Undesired crystallization can be avoided by choosing suitable compositions and heat treatment parameters, allowing desired product forms to be attained. Small changes in the oxide composition of the glass can have large effects and therefore a thorough understanding of glass crystallization behavior is a necessity for a successful outcome, when designing and manufacturing implants containing bioactive glasses.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Growth, magnetic and transport properties of InSb and II-IV-As2 semiconductors doped with manganese

This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.

Understanding the in vitro dissolution rate of glasses with respect to future clinical applications

Glass is a unique material with a long history. Several glass products are used daily in our everyday life, often unnoticed. Glass can be found not only in obvious applications such as tableware, windows, and light bulbs, but also in tennis rackets, windmill turbine blades, optical devices, and medical implants. The glasses used at present as implants are inorganic silica-based melt-derived compositions mainly for hard-tissue repair as bone graft substitute in dentistry and orthopedics. The degree of glass reactivity desired varies according to implantation situation and it is vital that the ion release from any glasses used in medical applications is controlled. Understanding the in vitro dissolution rate of glasses provides a first approximation of their behavior in vivo. Specific studies concerning dissolution properties of bioactive glasses have been relatively scarce and mostly concentrated to static condition studies. The motivation behind this work was to develop a simple and accurate method for quantifying the in vitro dissolution rate of highly different types of glass compositions with interest for future clinical applications. By combining information from various experimental conditions, a better knowledge of glass dissolution and the suitability of different glasses for different medical applications can be obtained. Thus, two traditional and one novel approach were utilized in this thesis to study glass dissolution. The chemical durability of silicate glasses was tested in water and TRIS-buffered solution at static and dynamic conditions. The traditional in vitro testing with a TRISbuffered solution under static conditions works well with bioactive or with readily dissolving glasses, and it is easy to follow the ion dissolution reactions. However, in the buffered solution no marked differences between the more durable glasses were observed. The hydrolytic resistance of the glasses was studied using the standard procedure ISO 719. The relative scale given by the standard failed to provide any relevant information when bioactive glasses were studied. However, the clear differences in the hydrolytic resistance values imply that the method could be used as a rapid test to get an overall idea of the biodegradability of glasses. The standard method combined with the ion concentration and pH measurements gives a better estimate of the hydrolytic resistance because of the high silicon amount released from a glass. A sensitive on-line analysis method utilizing inductively coupled plasma optical emission spectrometer and a flow-through micro-volume pH electrode was developed to study the initial dissolution of biocompatible glasses. This approach was found suitable for compositions within a large range of chemical durability. With this approach, the initial dissolution of all ions could be measured simultaneously and quantitatively, which gave a good overall idea of the initial dissolution rates for the individual ions and the dissolution mechanism. These types of results with glass dissolution were presented for the first time during the course of writing this thesis. Based on the initial dissolution patterns obtained with the novel approach using TRIS, the experimental glasses could be divided into four distinct categories. The initial dissolution patterns of glasses correlated well with the anticipated bioactivity. Moreover, the normalized surface-specific mass loss rates and the different in vivo models and the actual in vivo data correlated well. The results suggest that this type of approach can be used for prescreening the suitability of novel glass compositions for future clinical applications. Furthermore, the results shed light on the possible bioactivity of glasses. An additional goal in this thesis was to gain insight into the phase changes occurring during various heat treatments of glasses with three selected compositions. Engineering-type T-T-T curves for glasses 1-98 and 13-93 were stablished. The information gained is essential in manufacturing amorphous porous implants or for drawing of continuous fibers of the glasses. Although both glasses can be hot worked to amorphous products at carefully controlled conditions, 1-98 showed one magnitude greater nucleation and crystal growth rate than 13-93. Thus, 13-93 is better suited than 1-98 for working processes which require long residence times at high temperatures. It was also shown that amorphous and partially crystalline porous implants can be sintered from bioactive glass S53P4. Surface crystallization of S53P4, forming Na2O∙CaO∙2SiO2, was observed to start at 650°C. The secondary crystals of Na2Ca4(PO4)2SiO4, reported for the first time in this thesis, were detected at higher temperatures, from 850°C to 1000°C. The crystal phases formed affected the dissolution behavior of the implants in simulated body fluid. This study opens up new possibilities for using S53P4 to manufacture various structures, while tailoring their bioactivity by controlling the proportions of the different phases. The results obtained in this thesis give valuable additional information and tools to the state of the art for designing glasses with respect to future clinical applications. With the knowledge gained we can identify different dissolution patters and use this information to improve the tuning of glass compositions. In addition, the novel online analysis approach provides an excellent opportunity to further enhance our knowledge of glass behavior in simulated body conditions.

Morfologian hallinta nikkelin sulfidisaostuksessa

Diplomityön tarkoituksena oli tutkia nikkelin sulfidisaostuksessa syntyvien kiteiden morfologiaa ja siihen vaikuttavia parametreja. Syntyvien kiteiden kasvua ja morfologiaa tutkittiin kiteen muodostumisen ja kasvun teorioiden avulla. Saostuksen olosuhteet, kuten lämpötila, paine ja pH vaikuttavat muodostuvien kiteiden morfologiaan. Muilla parametreilla, kuten liuoksen ylikylläisyydellä, epäpuhtauksilla, lisäaineilla, sekoituksella ja reaktioajalla on myös suuri merkitys. Kokeiden avulla haluttiin liuoskoostumuksen, saostusolosuhteiden ja muiden komponenttien vaikutusta nikkelisulfidikiteiden morfologiaan. Kokeissa käytettiin kahta eri sulfidilähdettä: natriumvetysulfidia ja rikkivetyä. Puolipanoskokeissa nikkelipitoisuus oli 1,5 g/l, paine 101,3 kPa ja sekoitusnopeus 650 rpm. Saostuskokeet tehtiin natriumsulfaatti- 5 g/l ja ammoniumsulfaattiliuoksissa 300 g/l. Saostuskokeissa muuttujia olivat saostimen konsentraatio ja määrä, rauta- ja magne-siumepäpuhtaudet, lämpötila ja lisäaineet. Diplomityön kokeellisessa osassa morfologiaa tutkittiin suoraan valomikroskoopin ja pyyhkäisyelektronimikroskoopin (SEM) avulla. Morfologiaa tutkittiin myös epäsuorasti laskeutumisnopeuden, keskimääräisen partikkelikoon, ja ominaispinta-alamittausten avulla. Saostimen pitoisuuden vaikutukset partikkelimuotoon olivat pieniä, mutta vaikutukset ominaispinta-alaan ja partikkelikokoon olivat suuria. Natriumlauryylisul-faatti ja EDTA ohjasivat partikkelien rakennetta levymäisemmäksi, joka johti hitaaseen laskeutumisnopeuteen. Polyakryylihappo lisäaineena muuttaa partikkelien morfologiaa kuutiomaisemmaksi. Flokkulanttien ja raudan morfologiset vaikutukset olivat pieniä. Partikkelikoko ja omaispinta-ala pienenivät selvästi magnesiumpitoisuuden kasvaessa. Lämpötilan kasvattaminen lisäsi epäsäännöllisten kiteiden määrää ja muodostuneet kiteet olivat enemmän neulamaisia.

Selective inhibition of human tankyrases

Tankyrases belong to the Diphtheria toxin-like ADP-ribosyltransferase (ARTD) enzyme superfamily, also known as poly(ADP-ribose) polymerases (PARPs). They catalyze a covalent post-translational modification reaction where they transfer ADP-ribose units from NAD+ to target proteins. Tankyrases are involved in many cellular processes and their roles in telomere homeostasis, Wnt signaling and in several diseases including cancers have made them interesting drug targets. In this thesis project, selective inhibition of human tankyrases was studied. A homogeneous fluorescence-based assay was developed to screen the compound libraries. The assay is inexpensive, operationally easy, and performs well according to the statistical analysis. Assay suitability was confirmed by screening a natural product library. Flavone was identified as the most potent inhibitor in the library and this motivated us to screen a larger flavonoid library. Results showed that flavones were indeed the best inhibitor of tankyrases among flavonoids. To further study the structure-activity relationship, a small library of flavones containing single substitution was screened and potency measurements allowed us to generate structure-activity relationship. Compounds containing substitutions at 4´-position were more potent in comparison to other substitutions, and importantly, hydrophobic groups improved isoenzyme selectivity as well as the potency. A flavone derivative containing a hydrophobic isopropyl group (compound 22), displayed 6 nM potency against TNKS1, excellent isoenzyme selectivity and Wnt signaling inhibition. Protein interactions with compounds were studied by solving complex crystal structures of the compounds with TNKS2 catalytic domain. A novel tankyrase inhibitor (IWR-1) was also crystallized in complex with TNKS2 catalytic domain. The crystal structure of TNKS2 in complex with IWR-1 showed that the compound binds to adenosine site and it was the first known ARTD inhibitor of this kind. To date, there is no structural information available about the substrate binding with any of the ARTD family members; therefore NAD+ was soaked with TNKS2 catalytic domain crystals. However, analysis of crystal structure showed that NAD+ was hydrolyzed to nicotinamide. Also, a co-crystal structure of NAD+ mimic compound, EB-47, was solved which was used to deduce some insights about the substrate interactions with the enzyme. Like EB-47, other ARTD1 inhibitors were also shown to inhibit tankyrases. It indicated that selectivity of the ARTD1 inhibitors should be considered as some of the effects in cells could come from tankyrase inhibition. In conclusion, the study provides novel information on tankyrase inhibition and presents new insight into the selectivity and potency of compounds.

Upconverting diagnostics: Multiplex assays utilizing upconversion luminescence technology

Conventional diagnostics tests and technologies typically allow only a single analysis and result per test. The aim of this study was to propose robust and multiplex array-inwell test platforms based on oligonucleotide and protein arrays combining the advantages of simple instrumentation and upconverting phosphor (UCP) reporter technology. The UCPs are luminescent lanthanide-doped crystals that have a unique capability to convert infrared radiation into visible light. No autofluorescence is produced from the sample under infrared excitation enabling the development of highly sensitive assays. In this study, an oligonucleotide array-in-well hybridization assay was developed for the detection and genotyping of human adenoviruses. The study provided a verification of the advantages and potential of the UCP-based reporter technology in multiplex assays as well as anti-Stokes photoluminescence detection with a new anti- Stokes photoluminescence imager. The developed assay was technically improved and used to detect and genotype adenovirus types from clinical specimens. Based on the results of the epidemiological study, an outbreak of adenovirus type B03 was observed in the autumn of 2010. A quantitative array-in-well immunoassay was developed for three target analytes (prostate specific antigen, thyroid stimulating hormone, and luteinizing hormone). In this study, quantitative results were obtained for each analyte and the analytical sensitivities in buffer were in clinically relevant range. Another protein-based array-inwell assay was developed for multiplex serodiagnostics. The developed assay was able to detect parvovirus B19 IgG and adenovirus IgG antibodies simultaneously from serum samples according to reference assays. The study demonstrated that the UCPtechnology is a robust detection method for diverse multiplex imaging-based array-inwell assays.

Karbamatsepiinin Haihdutuskiteytys

Haihdutuskiteytyksessä haihdutusolosuhteilla on suuri vaikutus kiteiden muodostumiseen, joten toivottujen kidemuotojen saamiseksi prosessia on hallittava tarkasti. Kandidaatintyön tavoitteena oli tutkia puhtaiden liuottimien ja karbamatsepiiniliuosten haihtumisvuota eri olosuhteissa. Lisäksi tutkittiin kiteytysolosuhteiden vaikutusta karbamatsepiinikiteiden muodostumiseen ja rakenteeseen. Puhtaille liuottimille kokeet suoritettiin ilman virtausnopeudella 0,2 m/s lämpötiloissa 30 ºC, 40 ºC, 50 ºC ja 60 ºC, sekä ilman virtausnopeudella 0,3 m/s lämpötiloissa 40 ºC ja 50 ºC. Karbamatsepiiniliuoksille kokeet suoritettiin ilman virtausnopeudella 0,2 m/s lämpötiloissa 30 ºC ja 60 ºC sekä ilman virtausnopeudella 0,3 m/s lämpötiloissa 40 ºC ja 50 ºC. Haihdutuskiteytys suoritettiin suorakulmaisessa haihdutuskammiossa, jonka toisessa päässä oli tuulettimet virtausnopeuden säätämiseksi. Koehuoneessa vallitsi normaali ilmanpaine, ilman suhteellinen kosteus vaihteli välillä 50–65 % ja huoneen lämpötila välillä 21,2–24,1 ºC. Kuivatut kiteet analysoitiin optisella mikroskoopilla. Kaikista karbamatsepiinin vesiliuoksista kiteytyi dihydraatti-muotoa. Muutokset haihdutusolosuhteissa vaikuttivat selvästi haihtumis-voihin ja muodostuvien kiteiden rakenteeseen.

Spectroscopic Studies of III-V Semiconductor Materials for Improved Devices

Defects in semiconductor crystals and at their interfaces usually impair the properties and the performance of devices. These defects include, for example, vacancies (i.e., missing crystal atoms), interstitials (i.e., extra atoms between the host crystal sites), and impurities such as oxygen atoms. The defects can decrease (i) the rate of the radiative electron transition from the conduction band to the valence band, (ii) the amount of charge carriers, and (iii) the mobility of the electrons in the conduction band. It is a common situation that the presence of crystal defects can be readily concluded as a decrease in the luminescence intensity or in the current flow for example. However, the identification of the harmful defects is not straightforward at all because it is challenging to characterize local defects with atomic resolution and identification. Such atomic-scale knowledge is however essential to find methods for reducing the amount of defects in energy-efficient semiconductor devices. The defects formed in thin interface layers of semiconductors are particularly difficult to characterize due to their buried and amorphous structures. Characterization methods which are sensitive to defects often require well-defined samples with long range order. Photoelectron spectroscopy (PES) combined with photoluminescence (PL) or electrical measurements is a potential approach to elucidate the structure and defects of the interface. It is essential to combine the PES with complementary measurements of similar samples to relate the PES changes to changes in the interface defect density. Understanding of the nature of defects related to III-V materials is relevant to developing for example field-effect transistors which include a III-V channel, but research is still far from complete. In this thesis, PES measurements are utilized in studies of various III-V compound semiconductor materials. PES is combined with photoluminescence measurements to study the SiO2/GaAs, SiNx/GaAs and BaO/GaAs interfaces. Also the formation of novel materials InN and photoluminescent GaAs nanoparticles are studied. Finally, the formation of Ga interstitial defects in GaAsN is elucidated by combining calculational results with PES measurements.

Influence of Pulsed-Electric Field Irradiation in Crystallization

The growing pharmaceutical interest, among others, in the polymorphic composition of the emerging solid end-products from production processes has been traced to the need for attainment of high product purity. This is more so as the presence of different polymorphs may constitute physical impurity of the product. Hence, the need for optimization of the yield of desired product component(s) through controlled crystallization kinetics for instance. This study was carried out to investigate the impact of pulsed electric field (PEF) irradiation on the crystal morphology of glycine obtained by cooling crystallization (without seeding) from commercial glycine sample in distilled deionized water solution. In doing so, three different pulse frequencies (294, 950 and 145 Hz) and a case without PEF were studied at three cooling rates (5, 10 and 20 ºC/h). The crystal products obtained were analyzed for polymorphic composition by powder x-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy while the particles characterization was done on Morphologi G3. The results obtained from this study showed that pulsed electric field irradiation had significant impact on metastability of the aqueous solution as well as on the polymorphic composition of the end product. With increasing PEF frequency applied, nucleation started earlier and the γ-glycine polymorph content of the product crystals increased. These were found to have been aided by cooling rate, as the most significant effect was observed at 5 ºC/h. It was also discovered that PEF application had no measurable impact on the pH of the aqueous solution as well as the size distribution of the particles. Cooling on the contrary was believed to be responsible for the broadening of the particle size distribution with a downward shift of the lower limit of the raw material from about 100 μm to between 10 and 50 μm.

Haihdutusnopeuksien määritys glysiinin alipainekiteytyksessä

Alipainekiteytyksessä tasalaatuisen lopputuotteen valmistamiseksi kiteytysolosuhteiden vaikutus liuottimen haihtumisvuohon ja kiteiden ominaisuuksiin on huomioitava. Kandidaatin työn tavoitteena oli selvittää, miten glysiinin alipainekiteytyksessä vesiliuoksesta kiteytysolosuhteet (lämpötila ja paine) vaikuttavat liuottimen haihtumisvuohon ja syntyvien kiteiden polymorfiaan. Haihdutuskokeet suoritettiin puhtaalle vedelle ja alipainekiteytyskokeet glysiinin 95 % kylläiselle vesiliuokselle lämpötiloissa 40 °C, 50 °C ja 60 °C ja paineissa 40 mbar, 60 mbar ja 80 mbar. Kiteyttimenä käytettiin suljettua, virtaushaitoilla, sekoittimella ja ohjausputkella varustettua reaktoria johon oli kytketty alipainepumppu ja termostaatti paineen ja lämpötilan ohjaamiseksi. Nesteen määrä haihdutuskokeissa oli 2 kg ja alipainekiteytyskokeissa 1,2 kg. Osa alipainekiteytyskokeista saaduista kiteistä analysoitiin jauheröntgendiffraktioanalysaattorin (PXRD, engl. powder x-ray diffraction) avulla. Kaikki PXRD-laitteella analysoidut alipainekiteytyskokeissa saadut kiteet osoittautuivat glysiinin γ-polymorfiksi. Kiteytysolosuhteilla oli selkeä vaikutus haihtumisvuohon, mutta vaikutusta glysiinikiteiden polymorfiaan ei havaittu koealueella.