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.

Molecular modeling of asymmetric induction in heterogeneously catalyzed hydrogenation of the C=O bond

Modifiering av metallytor med starkt adsorberade kirala organiska molekyler är eventuellt den mest relevanta teknik man vet i dag för att skapa kirala ytor. Den kan utnyttjas i katalytisk produktion av enantiomeriskt rena kirala föreningar som behövs t.ex. som läkemedel och aromkemikalier. Trots många fördelar av asymmetrisk heterogen katalys jämfört med andra sätt för att få kirala föreningar, har den ändå inte blivit ett allmänt verktyg för storskaliga tillämpningar. Detta beror t.ex. på brist på djupare kunskaper i katalytiska reaktionsmekanismer och ursprunget för asymmetrisk induktion. I denna studie användes molekylmodelleringstekniker för att studera asymmetriska, heterogena katalytiska system, speciellt hydrering av prokirala karbonylföreningar till motsvarande kirala alkoholer på cinchona-alkaloidmodifierade Pt-katalysatorer. 1-Fenyl-1,2-propandion (PPD) och några andra föreningar, som innehåller en prokiral C=O-grupp, användes som reaktanter. Konformationer av reaktanter och cinchona-alkaloider (som kallas modifierare) samt vätebundna 1:1-komplex mellan dem studerades i gas- och lösningsfas med metoder som baserar sig på vågfunktionsteori och täthetsfunktionalteori (DFT). För beräkningen av protonaffiniteter användes också högst noggranna kombinationsmetoder såsom G2(MP2). Den relativa populationen av modifierarnas konformationer varierade som funktion av modifieraren, dess protonering och lösningsmedlet. Flera reaktant–modifierareinteraktionsgeometrier beaktades. Slutsatserna på riktning av stereoselektivitet baserade sig på den relativa termodynamiska stabiliteten av de diastereomeriska reaktant–modifierare-komplexen samt energierna hos π- och π*-orbitalerna i den reaktiva karbonylgruppen. Adsorption och reaktioner på Pt(111)-ytan betraktades med DFT. Regioselektivitet i hydreringen av PPD och 2,3-hexandion kunde förklaras med molekyl–yta-interaktioner. Storleken och formen av klustret använt för att beskriva Pt-ytan inverkade inte bara på adsorptionsenergierna utan också på de relativa stabiliteterna av olika adsorptionsstrukturer av en molekyl. Populationerna av modifierarnas konformationer i gas- och lösningsfas korrelerade inte med populationerna på Pt-ytan eller med enantioselektiviteten i hydreringen av PPD på Pt–cinchona-katalysatorer. Vissa modifierares konformationer och reaktant–modifierare-interaktionsgeometrier var stabila bara på metallytan. Teoretiskt beräknade potentialenergiprofiler för hydrering av kirala α-hydroxiketoner på Pt implicerade preferens för parvis additionsmekanism för väte och selektiviteter i harmoni med experimenten. De uppnådda resultaten ökar uppfattningen om kirala heterogena katalytiska system och kunde därför utnyttjas i utvecklingen av nya, mera aktiva och selektiva kirala katalysatorer.

Mössbauer spectra of iron oxides in the bulk and nanocrystalline states

Magnetic nanoparticles are very important in modern industry. These particles are used in many different spheres of life. Nanoparticles have unusual physical and chemical properties connected both with quantum dimensional effects and with the increased role of the surface atoms. Most clearly the difference between the properties of bulk materials and nanoparticles can be seen in the magnetic properties of these materials. The most typical magnetic properties of nanomaterials are superparamagnetism with the size of the cluster from 1 to 10 nm; single-domain magnetic state of nanoclusters and nanostructures up to 20 nm; magnetization processes connected with magnetic cluster ordering and with its forms and sizes; quantum magnetic tunneling effects when magnetization changes by jumps and giant magnetoresistance effects. For research of the magnetic properties of iron-containing nanostructures, it is convenient to apply Mӧssbauer spectroscopy. In this work a number of nano-sized samples of iron oxides were examined by Mössbauer spectroscopy. The Mössbauer spectra of nanoparticles with various sizes were obtained. Mössbauer spectra of iron oxide nanoparticles were compared with the spectra of bulk samples. It was shown how the spectra of iron oxide nanoparticles change depending on the particle sizes.

Cluster structure of atomic nuclei

Kirjallisuusarvostelu

Activation of supply relationships : a study of main providers in the Turku logistics cluster

Företag inom industri och handel väljer allt oftare att låta ett logistikföretag sköta stora delar av sina logistiska processer. Logistikföretagen i sin tur överlåter utförandet av enskilda tjänster, som t.ex. olika typer av transport, till olika samarbetspartners inom branschen. I avhandlingen studeras hur logistikföretag går till väga då de väljer vilka av deras samarbetspartners som ska engageras för att delta i utförandet av ett logistiktjänstepaket, en arbetsprocess som här kallas aktivering. Fokus ligger på aktiveringens innehåll och de faktorer som inverkar på hur den går till och vilka samarbetsparter som kommer att engageras. Arbetet bygger på nätverksansatsen för studier av företagsrelationer på industriella marknader. Aktiveringsprocessen uppfattas som en rätt ordinär, rutinmässig verksamhet i företaget, men den kan också förväntas inverka på hur företagets samarbetsnätverk utvecklas över tiden, genom att vissa relationer förstärks medan andra försvagas. I den empi riska undersökningen deltog 29 logistikföretag i Åboregionen som utgående från ett diskussionsunderlag fick berätta om hur de går till väga vid aktivering.

Strategic alliances as an international entry strategy: Finnish cleantech SMEs and the Indian market

The demand for environmental technologies, also called cleantech, is growing globally but the need is especially high in emerging markets such as India where the rising economy and rapid industrialisation have led to increasing energy needs and environmental degradation. The market is of great potential also for the Finnish cleantech cluster that represents advanced expertise in several fields of environmental technologies. However, most of the Finnish companies in the field are SMEs that face challenges in their internationalisation due to their limited resources. The objective of this study was to estimate, whether strategic alliances could be an efficient entry strategy for Finnish cleantech SMEs entering the Indian market. This was done by studying what are the key factors influencing the international entry mode decision of Finnish cleantech SMEs, what are the major factors affecting the entry of Finnish cleantech SMEs to the Indian market and how do Finnish cleantech SMEs use strategic alliances in their internationalisation process. The study was realised as a qualitative multi-case study through theme interviews of Finnish cleantech SME representatives. The results indicated that Finnish cleantech SMEs prefer to enter international markets through non-equity and collaborative modes of entry. These entry modes are chosen because of the small size and limited resources of companies, but also because they want to protect their innovative technologies from property rights violations. India is an attracting market for Finnish cleantech SMEs mainly because of its size and growth, but insufficient environmental regulation and high import tariffs have hindered entry to the market. Finnish cleantech SMEs commonly use strategic alliances in their internationalisation process but the use is rather one-sided. Most of the formed strategic alliances are low-commitment, international contractual agreement in sales and distribution. Alliance partner selection receives less attention. In the future, providing Finnish cleantech SMEs with international experience and training could help in diversifying the use of strategic alliances and increase their benefits to SME internationalisation.

Russia, China, India Foresight for Small and Medium size Enterprises in Uusimaa : Changes forecast in the Russian, Chinese and Indian operating environments from the viewpoint of small and middle-sized enterprises in Uusimaa

The report describes those factors of the future that are related to the growth and needs of Russia, China, and India and that may provide significant internationalisation potential for Uusimaa companies. The report examines the emerging trends and market-entry challenges for each country separately. Additionally, it evaluates the training needs of Uusimaa companies in terms of the current offerings available for education on topics related to Russia, China, and India. The report was created via the Delphi method: experts were interviewed, and both Trendwiki material and the latest literature were used to create a summary of experts’ views, statements, and reasons behind recent developments. This summary of views was sent back to the experts with the objective of reaching consensus synthesising the differing views or, at least, of providing argumentation for the various alternative lines of development. In addition to a number of outside experts and business leaders, all heads of Finpro’s Finland Trade Centers participated in the initial interviews. The summary was commented upon by all Finpro consultants and analysts for Russia, China, and India, with each focusing on his or her own area of expertise. The literature used consisted of reports, listed for each country, and an extensive selection of the most recent newspaper articles. The report was created in January-April 2010. On 22 April 2010 its results were reviewed at the final report presentation in cooperation with the Uusimaa ELY Centre.

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.

Enhancing the Usability of Drug Materials by Electrostatic Atomisation

Electrospraying or electrostatic atomisation is a process of liquid disruption by electrostatic forces. When liquid is brought into an electric field, charge is induced to its surface. Once the repulsive electrostatic force exceeds the liquid surface tension, the liquid disrupts into small highly charged droplets. The size of the electrosprayed droplets can range from hundreds of micrometers down to a few tens of nanometers. Electrospraying can be used not only to produce droplets, but also solid particles. The research presented in this thesis concentrates on producing drug particles by this method. In the experiments, a drug powder was dissolved in a convenient solvent and the solution was atomised. The solvent was then evaporated from the formed droplets in a drying medium and inside each droplet, a dense cluster of the dissolved drug remained. From the pharmaceutical point of view, the most important characteristics of the produced particles are size distribution, porosity, crystal form and degree of crystallinity. These properties affect the dissolution behaviour and ultimately the drug bioavailability in the body. The effects of electrostatic atomization on the aforementioned characteristics are generally not well understood. The research focused on studying these particle properties and finding possible correlations with the spraying parameters. The produced droplets were dried either under atmospheric or reduced pressure, the latter in order to improve the drying process. Special emphasis was put on implementing the spraying under reduced pressure, and the effects of the drying pressure on particle properties. Based on the results, the possibilities to enhance the dissolution of poorly soluble drugs by this method were estimated. In the course of experiments, it was also discovered that electrospraying may have a profound effect on the polymorphic form of the produced drug particles. In the light of the obtained results, it was concluded that electrospraying may offer a valuable tool to overcome some of the challenges met in modern drug development and formulation.