Comprehensive Study of Crystal Growth from Solution

Crystal growth is an essential phase in crystallization kinetics. The rate of crystal growth provides significant information for the design and control of crystallization processes; nevertheless, obtaining accurate growth rate data is still challenging due to a number of factors that prevail in crystal growth. In industrial crystallization, crystals are generally grown from multi-componentand multi-particle solutions under complicated hydrodynamic conditions; thus, it is crucial to increase the general understanding of the growth kinetics in these systems. The aim of this work is to develop a model of the crystal growth rate from solution. An extensive literature review of crystal growth focuses on themodelling of growth kinetics and thermodynamics, and new measuring techniques that have been introduced in the field of crystallization. The growth of a singlecrystal is investigated in binary and ternary systems. The binary system consists of potassium dihydrogen phosphate (KDP, crystallizing solute) and water (solvent), and the ternary system includes KDP, water and an organic admixture. The studied admixtures, urea, ethanol and 1-propanol, are employed at relatively highconcentrations (of up to 5.0 molal). The influence of the admixtures on the solution thermodynamics is studied using the Pitzer activity coefficient model. Theprediction method of the ternary solubility in the studied systems is introduced and verified. The growth rate of the KDP (101) face in the studied systems aremeasured in the growth cell as a function of supersaturation, the admixture concentration, the solution velocity over a crystal and temperature. In addition, the surface morphology of the KDP (101) face is studied using ex situ atomic force microscopy (AFM). The crystal growth rate in the ternary systems is modelled on the basis of the two-step growth model that contains the Maxwell-Stefan (MS) equations and a surface-reaction model. This model is used together with measuredcrystal growth rate data to develop a new method for the evaluation of the model parameters. The validation of the model is justified with experiments. The crystal growth rate in an imperfectly mixed suspension crystallizer is investigatedusing computational fluid dynamics (CFD). A solid-liquid suspension flow that includes multi-sized particles is described by the multi-fluid model as well as by a standard k-epsilon turbulence model and an interface momentum transfer model. The local crystal growth rate is determined from calculated flow information in a diffusion-controlled crystal growth regime. The calculated results are evaluated experimentally.

Effect of hydrodynamics on modelling, monitoring and control of crystallization

Crystallization is a purification method used to obtain crystalline product of a certain crystal size. It is one of the oldest industrial unit processes and commonly used in modern industry due to its good purification capability from rather impure solutions with reasonably low energy consumption. However, the process is extremely challenging to model and control because it involves inhomogeneous mixing and many simultaneous phenomena such as nucleation, crystal growth and agglomeration. All these phenomena are dependent on supersaturation, i.e. the difference between actual liquid phase concentration and solubility. Homogeneous mass and heat transfer in the crystallizer would greatly simplify modelling and control of crystallization processes, such conditions are, however, not the reality, especially in industrial scale processes. Consequently, the hydrodynamics of crystallizers, i.e. the combination of mixing, feed and product removal flows, and recycling of the suspension, needs to be thoroughly investigated. Understanding of hydrodynamics is important in crystallization, especially inlargerscale equipment where uniform flow conditions are difficult to attain. It is also important to understand different size scales of mixing; micro-, meso- and macromixing. Fast processes, like nucleation and chemical reactions, are typically highly dependent on micro- and mesomixing but macromixing, which equalizes the concentrations of all the species within the entire crystallizer, cannot be disregarded. This study investigates the influence of hydrodynamics on crystallization processes. Modelling of crystallizers with the mixed suspension mixed product removal (MSMPR) theory (ideal mixing), computational fluid dynamics (CFD), and a compartmental multiblock model is compared. The importance of proper verification of CFD and multiblock models is demonstrated. In addition, the influence of different hydrodynamic conditions on reactive crystallization process control is studied. Finally, the effect of extreme local supersaturation is studied using power ultrasound to initiate nucleation. The present work shows that mixing and chemical feeding conditions clearly affect induction time and cluster formation, nucleation, growth kinetics, and agglomeration. Consequently, the properties of crystalline end products, e.g. crystal size and crystal habit, can be influenced by management of mixing and feeding conditions. Impurities may have varying impacts on crystallization processes. As an example, manganese ions were shown to replace magnesium ions in the crystal lattice of magnesium sulphate heptahydrate, increasing the crystal growth rate significantly, whereas sodium ions showed no interaction at all. Modelling of continuous crystallization based on MSMPR theory showed that the model is feasible in a small laboratoryscale crystallizer, whereas in larger pilot- and industrial-scale crystallizers hydrodynamic effects should be taken into account. For that reason, CFD and multiblock modelling are shown to be effective tools for modelling crystallization with inhomogeneous mixing. The present work shows also that selection of the measurement point, or points in the case of multiprobe systems, is crucial when process analytical technology (PAT) is used to control larger scale crystallization. The thesis concludes by describing how control of local supersaturation by highly localized ultrasound was successfully applied to induce nucleation and to control polymorphism in reactive crystallization of L-glutamic acid.

Particle transport method for convection-diffusion-reaction problems

Convective transport, both pure and combined with diffusion and reaction, can be observed in a wide range of physical and industrial applications, such as heat and mass transfer, crystal growth or biomechanics. The numerical approximation of this class of problemscan present substantial difficulties clue to regions of high gradients (steep fronts) of the solution, where generation of spurious oscillations or smearing should be precluded. This work is devoted to the development of an efficient numerical technique to deal with pure linear convection and convection-dominated problems in the frame-work of convection-diffusion-reaction systems. The particle transport method, developed in this study, is based on using rneshless numerical particles which carry out the solution along the characteristics defining the convective transport. The resolution of steep fronts of the solution is controlled by a special spacial adaptivity procedure. The serni-Lagrangian particle transport method uses an Eulerian fixed grid to represent the solution. In the case of convection-diffusion-reaction problems, the method is combined with diffusion and reaction solvers within an operator splitting approach. To transfer the solution from the particle set onto the grid, a fast monotone projection technique is designed. Our numerical results confirm that the method has a spacial accuracy of the second order and can be faster than typical grid-based methods of the same order; for pure linear convection problems the method demonstrates optimal linear complexity. The method works on structured and unstructured meshes, demonstrating a high-resolution property in the regions of steep fronts of the solution. Moreover, the particle transport method can be successfully used for the numerical simulation of the real-life problems in, for example, chemical engineering.

Towards desired crystalline product properties: In-situ monitoring of batch crystallization

The objective of industrial crystallization is to obtain a crystalline product which has the desired crystal size distribution, mean crystal size, crystal shape, purity, polymorphic and pseudopolymorphic form. Effective control of the product quality requires an understanding of the thermodynamics of the crystallizing system and the effects of operation parameters on the crystalline product properties. Therefore, obtaining reliable in-line information about crystal properties and supersaturation, which is the driving force of crystallization, would be very advantageous. Advanced techniques, such asRaman spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and in-line imaging techniques, offer great potential for obtaining reliable information during crystallization, and thus giving a better understanding of the fundamental mechanisms (nucleation and crystal growth) involved. In the present work, the relative stability of anhydrate and dihydrate carbamazepine in mixed solvents containing water and ethanol were investigated. The kinetics of the solvent mediated phase transformation of the anhydrate to hydrate in the mixed solvents was studied using an in-line Raman immersion probe. The effects of the operation parameters in terms of solvent composition, temperature and the use of certain additives on the phase transformation kineticswere explored. Comparison of the off-line measured solute concentration and the solid-phase composition measured by in-line Raman spectroscopy allowedthe identification of the fundamental processes during the phase transformation. The effects of thermodynamic and kinetic factors on the anhydrate/hydrate phase of carbamazepine crystals during cooling crystallization were also investigated. The effect of certain additives on the batch cooling crystallization of potassium dihydrogen phosphate (KDP) wasinvestigated. The crystal growth rate of a certain crystal face was determined from images taken with an in-line video microscope. An in-line image processing method was developed to characterize the size and shape of thecrystals. An ATR FTIR and a laser reflection particle size analyzer were used to study the effects of cooling modes and seeding parameters onthe final crystal size distribution of an organic compound C15. Based on the obtained results, an operation condition was proposed which gives improved product property in terms of increased mean crystal size and narrowersize distribution.

Sulfatiatsolin leijupetikiteytys

Työssä tutkittiin leijupetikiteyttimen toimivuutta sulfatiatsolikiteiden kasvunopeuksien mittaamisessa. Sulfatiatsoli on lääkeaine, jota käytetään antibioottina. Kirjallisuusosassa on käsitelty kiteytyksen perusteita sekä olosuhteiden vaikutuksia kidemorfologiaan. Koska kyseessä on lääkeaine, on työssä myös selvitetty tekijöitä, jotka vaikuttavat syntyvän kiteen polymorfimuotoon. Näitä ovat mm. siemenkiteen polymorfimuoto sekä käytetty liuotin. Kirjallisuusosassa on myös esitelty teollisia ja laboratoriomittakaavan leijupetikiteyttimiä. Kokeellisessa osassa on keskitytty testaamaan leijupetikiteyttimen toimintaa sekä etsimään sopivia olosuhteita kasvukokeiden suorittamiselle. Kokeissa tutkittiin ylikylläisyyden vaikutusta sulfatiatsolikiteen kasvuun. Kiteen kasvun seurantaan pyrittiin etsimään sopivia hiukkaskokoanalysaattoreita. Mittauksissa käytetyt laitteistot olivat PIA 4000 mod LUT on-line-videomikroskooppi ja laserdiffraktioon perustuva Coulter LS 130 off-line-partikkelikokoanalysaattori.

Epäpuhtauksien vaikutus monokaliumfosfaattikiteen kasvuun

Työssä on tutkittu epäpuhtauksien vaikutusta kastelulannoitesuolojen monokaliumfosfaatin, kaliumnitraatin ja ureafosfaatin kiteytyksessä. Kirjallisuusosassa on käsitelty kastelulannoiteprosessit ja epäpuhtauksien vaikutus kastelulannoitteiden valmistuksessa. Kiteytys ja kiteenkasvu on esitetty perusyhtälöin, joissa on otettu epäpuhtauksien vaikutus huomioon. Tarkemmin on perehdytty monokaliumfosfaatin kiteytykseen ja kolmenarvoisten kationeiden, Al3+, Fe3+ ja Cr3+, vaikutukseen kiteiden kasvuun. Kolmenarvoiset metalli-ionit adsorboituvat kiteen pintaan haitaten kiteenkasvua, mikä vaikuttaa erityisesti kiteen prismapinnan kasvuun. Lisäksi on esitelty muita kiteenkasvuun vaikuttavia olosuhteita. Lopuksi on käsitelty kompleksinmuodostajia metalli-ionien haitallisten vaikutusten ehkäisijöinä. Kokeellisessa osassa suoritettiin liukoisuuskokeita monokaliumfosfaatin liukoisuuden selvittämiseksi eri pH-olosuhteissa. Suoritetuissa yksikidekokeissa tutkittiin pH:n ja kolmenarvoisten kationeiden; Al3+, Fe3+ ja Cr3+, vaikutus monokaliumfosfaattikiteen pituus- ja leveyskasvuun ja kidemuotoon eri ylikylläisyyksillä. Lisäksi tutkittiin voidaanko lämpötilaa ja pH muuttamalla tai pyrofosfaattia lisäämällä poistaa raudan kasvua inhiboima vaikutus. Kiteytyslämpötilaa nostamalla voidaan poistaa raudan haitallinen vaikutus kiteen kasvuun.

Taloushallinnon toimintastrategia

Tämän tutkimuksen tavoitteena on luoda taloushallinnon toimintastrategia voimakkaasti kasvavalle huonekalualan vähittäiskauppakonsernille. Tavoitteena oli tutkia kasvua ja sen vaikutusta yrityksen taloushallinnon prosesseihin sekä luoda toimiva prosessi kasvun eri vaiheisiin. Tutkimus luokitellaan toimintatutkimukseksi, jonka tavoitteena on kehittää toimintoja tutkimuksen aikana ja sen jälkeen. Tutkimuksen teoriaosassa tarkastellaan kasvua käsitteenä sekä kasvun vaikutuksia yrityksen toimintoihin ja johtamiseen. Toisessa vaiheessa tutustutaan huonekalujen vähittäiskauppaan toimialana sekä luodaan katsaus alan tulevaisuudennäkymiin muuttuvassa liiketoimintaympäristössä. Tämän lisäksi tutkitaan taloushallinnon muuttuneita haasteita yleisesti sekä kasvun tuomia lisähaasteita taloushallinnon toiminnoille. Aineiston perusteella voidaan todeta, että kasvu aiheuttaa yritykselle ja sen johtamiselle aina lisää haasteita. Johdon on kyettävä sopeuttamaan yrityksen toimintoja kuhunkin kasvuvaiheeseen dynaamisessa liiketoimintaympäristössä, jossa pysyvää on vain muutos. Yrityksen kasvaessa toiminnot väistämättä ammattimaistuvat ja institutionaalistuvat, niin myös taloushallinnon johtaminen ja prosessit. Taloushallinnon on pystyttävä toimimaan johdon tukena ja sparraajana kaikissa liiketoimintapäätöksissä. Talousjohdon tehtävänä on myös toimia organisaatiossa taloudellisen tietämyksen levittäjänä ja valmentajana.

Mikroyrittäjä ja yrityksen kasvu

Tämän tutkimuksen tarkoituksena on selvittää mitkä tekijät ovat mikroyrityksen kasvun edellytyksenä ja mitkä tekijät ovat kasvun esteinä. Tutkimuksen taustalla on mikroyritysten yleisesti vähäinen kasvuhalukkuus. Tässä tutkimuksessa yrittäjien kasvuaikomuksia tarkastellaan kasvun prosessimalliin tukeutuen ja mikroyritysten kasvuun vaikuttavia tekijöitä tarkastellaan Perrenin mikroyrityksen kasvuun vaikuttavien tekijöiden mallin avulla. Tutkimuksessa on käytetty kvalitatiivista tutkimusmenetelmää. Tutkimus on toteutettu haastattelututkimuksena, jossa on haastateltu mikroyrittäjiä Päijät-Hämeessä Lahden ja Hollolan alueilla. Tämän tutkimuksen mukaan mikroyritysten kasvuun vaikuttavat yrittäjän tahtotila ja kyky yrityksen kehittämiseen sekä yrittäjän riskinottokyky että suotuisat ympäristölliset olosuhteet. Näiden tekijöiden puuttuminen estää kasvun. Yrityksen kasvua estäviä muita tekijöitä ovat tutkimuksen mukaan mikroyritysten liiallinen paikallisuus, yhteistyön vähäisyys sekä yrittäjän liiallinen kietoutuminen liiketoimintaan että toiminnan liian vähäinen strateginen suunnittelu.

Saksan opiskelijasta saksan opettajaksi. Aineenopettajaopiskelijan ammatillinen kasvu ohjatussa harjoitttelussa

Tutkimuksessani tarkastelin, miten ammatillinen kasvu ilmenee saksan opetusharjoittelijoiden näkemyksissä ja toiminnassa opettajan pedagogisiin opintoihin kuuluvan ohjatun harjoittelun aikana. Keräsin tutkimusaineiston lukuvuosina 2007–2010 kaikilta saksan opetusharjoittelijoilta, jotka suorittivat ohjatussa harjoittelussa vähintään 15 op Turun normaalikoulussa. Tutkimusaineistona käytin henkilökohtaisia harjoittelusuunnitelmia (HOPS) ja reflektiovihkoja, jotka ovat ohjatun harjoittelun normaaleja työvälineitä. Täydensin aineistoa ohjatun harjoittelun alussa toteutetulla kyselyllä ja harjoittelun päätteeksi tehdyllä puolistrukturoidulla teemahaastattelulla. Toimin tutkimuksen aikana Turun normaalikoulussa saksan opettajana ja aineryhmän harjoittelusta vastaavana opettajana. Tutkimuskysymykset tarkentuivat aineistolähtöisesti. Ensimmäinen tutkimuskysymys liittyi siihen, miten harjoittelijoiden ideaalit hyvästä vieraan kielen opetuksesta ja henkilökohtaiset tavoitteet toteutuivat ohjatun harjoittelun aikana. Alkukyselyn pohjalta ideaaleiksi nousivat vuorovaikutus ja monipuoliset työtavat, kulttuurin opettaminen, tavoitekielen käyttö luokkakielenä sekä selkeä kieliopin opetus. Tutkimuksessa kävi ilmi, että alkukyselyssä esiin tullut hyvän opettajan tai vieraan kielen opetuksen ideaali ei välttämättä näy opettajaksi opiskelevan HOPSeihin kirjatuissa henkilökohtaisissa tavoitteissa tai toteudu hänen harjoitustunneillaan. Parhaiten opetusharjoittelijat kokivat onnistuneensa vuorovaikutuksen luomisessa oppilaisiin ja opiskelijoihin sekä monipuolisten työtapojen käytössä. Eriyttäminen ja oppimaan oppimisen ohjaaminen koettiin hankalina. Suurin osa harjoittelijoista oli tyytyväisiä siihen, miten he onnistuivat tuomaan kulttuuria opetukseensa, kun taas tavoitekielen käyttö luokkakielenä ja kieliopin opetus koettiin haasteellisiksi. Toisessa tutkimuskysymyksessä tarkasteltiin, millainen ammatillinen näkemys vieraan kielen opiskelijalla on ohjatun harjoittelun jälkeen. Opetusharjoittelijat korostivat opettajan kasvatustyötä ja opettajien välistä yhteistyötä. Ajatus toimia saksan tai vieraan kielen opettajana oli vahvistunut pedagogisten opintojen aikana. Kolmas tutkimuskysymys kohdistui sen selvittämiseen, miten HOPS ja reflektiovihko toimivat harjoittelijoiden kasvun tukena. Harjoittelijoiden kirjallinen itsereflektio vaihteli syvällisistä pohdinnoista niukkiin merkintöihin. Suurimmassa osassa reflektiovihoista harjoittelijat olivat miettineet palautteissa esille tulleita asioita. HOPS ja reflektiovihko ovat tämän tutkimuksen perusteella toimivia harjoittelun ohjauksen välineitä, kunhan harjoittelijoita ohjataan niiden käytössä. Itsereflektion merkityksen puolesta puhuu se, että harjoittelijat, jotka olivat myös kirjallisesti pohtineet saksan käyttöä luokkakielenä, olivat muita tyytyväisempiä siihen, miten he kokivat onnistuneensa luokkakielen käytössä.

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.

Suomen peliteollisuuden kasvu ja kansainvälistyminen

Suomen peliteollisuus on ollut erittäin puhuttu aihe mediassa viime vuosien ajan. Työmme pyrkii selvittämään Suomen peliteollisuuden kasvun ja kansainvälistymisprosessin taustalla olleita tekijöitä sekä niiden suhteita toisiinsa. Työssä keskitytään analysoimaan jo tapahtunutta kasvua ja kansainvälistymistä, joiden tarkastelussa käytetään hyväksi Porterin jalostamaa Klusteri -teoriaa sekä kasvuyritysten uutta kansainvälistymisilmiötä, Born Global -teoriaa. Suomen peliteollisuuden klusterista esitetään hahmotelma pelialan kattavan kokonaiskuvan rakentamiseksi. Lopuksi kootaan havaintoja ja johtopäätöksiä Suomen peliteollisuusalan kasvuprosessista eri aikakausilta sekä analysoidaan kansainvälistymisprosessin kulkua ja metodologiaa. Myös näkemyksiä Suomen peliteollisuuden tulevaisuudesta esitetään. Suomen peliteollisuuden kasvua arvioidessa voidaan havaita, että sen kasvunopeus on lisääntynyt huomattavasti viimeisen muutaman vuoden aikana. Alan yritysten kasvu painottuu erittäin vahvasti globaaleille markkinoille. Peliteollisuus on kuitenkin edelleen erittäin pieni teollisuudenala Suomessa. Tulevaisuudessa sen koko ja merkitys tulevat kasvamaan, ja varsinkin Suomen mobiilipeliteollisuuden tulevaisuus näyttää valoisalta.

Computational modelling of non-equilibrium condensing steam flows in low-pressure steam turbines

The steam turbines play a significant role in global power generation. Especially, research on low pressure (LP) steam turbine stages is of special importance for steam turbine man- ufactures, vendors, power plant owners and the scientific community due to their lower efficiency than the high pressure steam turbine stages. Because of condensation, the last stages of LP turbine experience irreversible thermodynamic losses, aerodynamic losses and erosion in turbine blades. Additionally, an LP steam turbine requires maintenance due to moisture generation, and therefore, it is also affecting on the turbine reliability. Therefore, the design of energy efficient LP steam turbines requires a comprehensive analysis of condensation phenomena and corresponding losses occurring in the steam tur- bine either by experiments or with numerical simulations. The aim of the present work is to apply computational fluid dynamics (CFD) to enhance the existing knowledge and understanding of condensing steam flows and loss mechanisms that occur due to the irre- versible heat and mass transfer during the condensation process in an LP steam turbine. Throughout this work, two commercial CFD codes were used to model non-equilibrium condensing steam flows. The Eulerian-Eulerian approach was utilised in which the mix- ture of vapour and liquid phases was solved by Reynolds-averaged Navier-Stokes equa- tions. The nucleation process was modelled with the classical nucleation theory, and two different droplet growth models were used to predict the droplet growth rate. The flow turbulence was solved by employing the standard k-ε and the shear stress transport k-ω turbulence models. Further, both models were modified and implemented in the CFD codes. The thermodynamic properties of vapour and liquid phases were evaluated with real gas models. In this thesis, various topics, namely the influence of real gas properties, turbulence mod- elling, unsteadiness and the blade trailing edge shape on wet-steam flows, are studied with different convergent-divergent nozzles, turbine stator cascade and 3D turbine stator-rotor stage. The simulated results of this study were evaluated and discussed together with the available experimental data in the literature. The grid independence study revealed that an adequate grid size is required to capture correct trends of condensation phenomena in LP turbine flows. The study shows that accurate real gas properties are important for the precise modelling of non-equilibrium condensing steam flows. The turbulence modelling revealed that the flow expansion and subsequently the rate of formation of liquid droplet nuclei and its growth process were affected by the turbulence modelling. The losses were rather sensitive to turbulence modelling as well. Based on the presented results, it could be observed that the correct computational prediction of wet-steam flows in the LP turbine requires the turbulence to be modelled accurately. The trailing edge shape of the LP turbine blades influenced the liquid droplet formulation, distribution and sizes, and loss generation. The study shows that the semicircular trailing edge shape predicted the smallest droplet sizes. The square trailing edge shape estimated greater losses. The analysis of steady and unsteady calculations of wet-steam flow exhibited that in unsteady simulations, the interaction of wakes in the rotor blade row affected the flow field. The flow unsteadiness influenced the nucleation and droplet growth processes due to the fluctuation in the Wilson point.

Effect of additives, precursors and process conditions on particle morphology

The objective of the thesis was to develop methods to manufacture and control calcium carbonate crystal nucleation and growth in precipitation process. The work consists of experimental part and literature part that addresses theory of nucleation, crystallization and precipitation. In the experimental part calcium carbonate was precipitated using carbonization reaction. Precipitation was carried out in presence of known morphology controlling agents (anionic polymers and sodium silicate) and by using different operation conditions. Formed material was characterized using SEM images, and its thermal stability was assessed. This work demonstrates that carbon dioxide feeding rate and concentrations of calcium hydroxide and additives can be used to control size, shape and amount of precipitating calcium carbonate.