Determination of the components of the gyration tensor of quartz by oblique incidence transmission two-modulator generalized ellipsometry

The two independent components of the gyration tensor of quartz, g11 and g33, have been spectroscopically measured using a transmission two-modulator generalized ellipsometer. The method is used to determine the optical activity in crystals in directions other than the optic axis, where the linear birefringence is much larger than the optical activity.

In-line Monitoring of Precipitation Process using Raman Spectroscopy and ATR-FTIR

Polymorfian jatkuva seuranta saostuksessa on hyödyllistä suunnittelun ja kidetuotteen ominaisuuksien sekä kiteytystä seuraavan jatkoprosessoinnin kannalta. Tässä diplomityössä on tutkittu L-glutamiinihapon kahden (- ja ß) polymorfimuodon liukoisuuden riippuvuutta pH:sta ja lämpötilasta.Tulokseksi saatiin, että kummankin polymorfin liukoisuus kasvoi sekä pH:ta ettälämpötilaa kasvatettaessa. ¿¿muodon liukoisuus oli korkeampi kuin ß-muodon liukoisuus valituilla pH-arvoilla eri lämpötiloissa. Lisäksi seurattiin puolipanostoimisen saostuksen aikana 1-litraisella laboratoriokiteyttimellä muodostuvan kiteisen polymorfiseoksen koostumusta hyödyntäen in-line Raman-spektroskopiaa. Myös liuoksen pH-muutosta seurattiin sekä liuoksen koostumusta ATR FTIR-spektroskopian (Attenuated Total Reflection Fourier Transform Infrared Spectrometer) avulla. Tutkittavina muuttujina olivat mm. sekoitusintensiteetti, sekoitintyyppi, reaktanttien (natriumglutamaatti ja rikkihappo) konsentraatiot sekä syötetyn rikkihapon syöttökohta kiteyttimessä. Työhön sisältyi 36 koetta ja osa kokeista toistettiin tulosten oikeellisuuden tarkistamiseksi. Inline-mittaustulosten verifioimiseksi kidenäytteet analysoitiin myös käyttämällä konfokaali Raman-mikroskooppia. Kidemorfologiaa tutkittiin SEM-kuvien (Scanning Eletronic Microscope) avulla. Työ osoitti, että Raman-spektroskopia on joustava ja luotettava menetelmä saostusprosessin jatkuvaan seurantaan L-glutamiinihapolla. Alhaiset lähtöainepitoisuudet tuottivat pääasiassa ¿¿muotoa, kun taas alhainen sekoitusteho edisti ß-muodon muodostumista. Syöttökohta vaikutti merkittävästi polymorfiaan. Kun rikkihapon syöttökohta oli epäideaalisesti sekoitetulla vyöhykkeellä, nousi ylikylläisyystaso korkeaksi ja päätuote oli tällöin ß-muotoa. 6-lapainen vinolapaturbiini (nousukulma 45o) ja 6-lapainen levyturbiini eivät merkittävästi poikenneet toisistaan muodostuvien polymorfien osalta.

The Mont Collon mafic complex (Austroalpine Dent Blanche nappe) : permian evolution of the Western European mantle

Résumé: Le complexe du Mont Collon (nappe de la Dent Blanche, Austroalpin) est l'un des exemples les mieux préservés du magmatisme mafique permien des Alpes occidentales. Il est composé d'affleurements discontinus et d'une stratification magmatique en son centre (Dents de Bertol) et est composé à 95% de roches mafiques cumulatives (gabbros à olivine et/ou cpx, anorthositiques, troctolites, wehrlites et wehrlites à plagioclase) et localement de quelques gabbros pegmatitiques. Ces faciès sont recoupés par de nombreux filons acides (aphtes, pegmatites quartziques, microgranodiorites et filons anorthositiques) et mafiques tardifs (dikes mélanocrates riches en Fe et Ti). Les calculs thermométriques (équilibre olivine-augite) montrent des températures de 1070-1120 ± 6°C, tandis que le thermomètre amphibole-plagioclase indique une température de 740 ± 40°C à 0.5 GPa pour les amphiboles magmatiques tardives. La geobarométrie sur pyroxène donne des pressions moyennes de 0.3-0.6 GPa, indiquant un emplacement dans la croûte moyenne. De plus, les températures obtenues sur des amphiboles coronitiques indiquent des températures de l'ordre de 700 ± 40°C confirmant que les réactions coronitiques apparaissent dans des conditions subsolidus. Les âges concordants U/Pb sur zircons de 284.2 ± 0.6 et 282.9 ± 0.6 Ma obtenus sur un gabbro pegmatitique et une pegmatitique quartzique, sont interprétés comme des âges de cristallisation. Les datations 40Ar/39Ar sur amphiboles des filons mélanocrates donnent un âge plateau de 260.2 ± 0.7 Ma, qui est probablement très proche de l'âge de cristallisation. Ainsi, cet age 40Ar/39Ar indique un second évènement magmatique au sein du complexe. Les compositions des roches totales en éléments majeurs et traces montrent peu de variations, ainsi que le Mg# (75-80). Les éléments traces enregistrent le caractère cumulatif des roches (anomalie positive en Eu) et révèlent des anomalies négatives systématiques en Nb, Ta, Zr, Hf et Ti dans les faciès basiques. Le manque de corrélation entre éléments majeurs et traces est caractéristique d'un processus de cristallisation in situ impliquant une quantité variable de liquide interstitiel (L) entre les phases cumulus. Les distributions des éléments traces dans les minéraux sont homogènes, indiquant une rééquilibration .subsolidus entre cristaux et liquide interstitiel. Un modèle quantitatif basé sur les équations de cristallisation in situ de Langmuir reproduisent correctement les concentrations en terres rares légères des minéraux cumulatifs montrant la présence de 0 à 35% de liquide interstitiel L pour des degrés de différenciation F de 0 à 45%, par rapport au faciès les moins évolués du complexe. En outre, les valeurs de L sont bien corrélées avec les proportions modales d'amphibole interstitielle et les concentrations en éléments incompatibles des roches (Zr, Nb). Le liquide parental calculé des cumulats du Mont Collon est caractérisé par un enrichissement relatif en terres rares légères et Th, un appauvrissement en terres rares lourdes typique d'une affinité transitionnelle (T-MORB) et une forte anomalie négative en Nb-Ta. Les roches cumulatives montrent des compositions isotopiques en Nd-Sr proches de la terre globale silicatée (BSE), soit 0.6<εNdi<+3.2, 0.7045<87Sr/86Sri<0.7056. Les rapports initiaux en Pb indiquent une source dans le manteau enrichi subcontinental lithosphérique, préalablement contaminé par des sédiments océaniques. Les dikes mélanocrates Fe-Ti sont représentatifs de liquides et ont des spectres de terres rares enrichis, une anomalie positive en Nb-Ta et des εNdi de +7, des 87Sr/86Sri de 0.703 et des rapports initiaux en Pb, similaires à ceux des basaltes d'île océanique, indiquant une source asthénosphérique modérément appauvrie. Ainsi, la fusion partielle du manteau lithosphérique subcontinental est induite par l'amincissement post-orogénique et la remontée de l'asthénosphère. Les filons mélanocrates proviennent, après délamination du manteau lithosphérique, de la fusion de l'asthénosphère. Abstract The early Permian Mont Collon mafic complex (Dent Blanche nappe, Austroalpine nappe system) is one of the best preserved examples of the Permian mafic magmatism in the Western Alps. It is composed of discontinuous exposures and a well-preserved magmatic layering (the Dents de Bertol cliff) crops out in the center part of the complex. It mainly consists of cumulative mafic rocks, which represent 95 vol-% of the mafic complex (ol- and cpx-bearing gabbros and rare anorthositic layers, troctolites, wehrlites and plagioclase-wehrlites) and locally pegmatitic gabbros. All these facies are crosscut by widespread acidic (aplites, quartz-rich pegmatites, microgranodiorites) and late mafic Fe-Ti melanocratic dikes. Olivine-augite thermometric calculations yield a range of 1070-1120 ± 6°C, while amphibole-plagioclase thermometer yields a temperature of 740 ± 40°C at 0.5 GPa. Pyroxene geobarometry points to a pressure of 0.3-0.6 GPa, indicating a middle crustal level of emplacement. Moreover, temperature calculations on the Mont Conon coronitic amphiboles indicate temperatures of 700 ± 40°C, close to those calculated for magmatic amphiboles. These temperatures confirm that coronitic reactions occurred at subsolidus conditions. ID-TIMS U/Pb zircon ages of 284.2 ± 0.6 and 282.9 ± 0.6 Ma obtained on a pegmatitic gabbro and a quartz-pegmatitic dike, respectively, were interpreted as the crystallization ages of these rocks. 40Ar/39Ar dating on amphiboles from Fe-Ti melanocratic dikes yields a plateau age of 260.2 ± 0.7 Ma, which is probably very close to the crystallization age. Consequently, this 40Ar/P39Ar age indicates a second magmatic event. Whole-rock major- and trace-element compositions show little variation across the whole intrusion and Mg-number stays within a narrow range (75-80). Trace-element concentrations record the cumulative nature of the rocks (e.g. positive Eu anomaly) and reveal systematic Nb, Ta, Zr, Hf and Ti negative anomalies for all basic facies. The lack of correlation between major and trace elements is characteristic of an in situ crystallization process involving variable amounts of interstitial liquid (L) trapped between the cumulus mineral phases. LA-ICPMS measurements show that trace-element distributions in minerals are homogeneous, pointing to subsolidus re-equilibration between crystals and interstitial melts. A quantitative modeling based on Langmuir's in situ crystallization equation successfully reproduced the Rare Earth Element (REE) concentrations in cumulitic minerals. The calculated amounts of interstitial liquid L vary between 0 and 35% for degrees of differentiation F of 0 to 45%, relative to the least evolved facies of the intrusion. Furthermore, L values are well correlated with the modal proportions of interstitial amphibole and whole-rock incompatible trace-element concentrations (e.g. Zr, Nb) of the tested samples. The calculated parental melt of the Mont Collon cumulates is characterized by a relative enrichment in Light REE and Th, a depletion in Heavy REE, typical of a transitional affinity (T-MORB), and strong negative Nb-Ta anomaly. Cumulative rocks display Nd-Sr isotopic compositions close to the BSE (-0.6 < εNdi < +3.2, 0.7045 < 87Sr/86Sri < 0.7056). Initial Pb ratios point to an origin from the melting of an enriched subcontinental lithospheric mantle source, previously contaminated at the source by oceanic sediments. The contrasted alkaline Fe-Ti melanocratic dikes are representative of liquids. They display enriched fractionated REE patterns, a positive Nb-Ta anomaly and εNdi of +7, 87Sr/86Sri of 0.703 and initial Pb ratios, all reminiscent of Ocean Island Basalt-type rocks, pointing to a moderately

Cryo-electron microscopy of vitreous sections of native biological cells and tissues : methodology and applications

Résumé L'eau est souvent considérée comme une substance ordinaire puisque elle est très commune dans la nature. En fait elle est la plus remarquable de toutes les substances. Sans l'eau la vie sur la terre n'existerait pas. L'eau représente le composant majeur de la cellule vivante, formant typiquement 70 à 95% de la masse cellulaire et elle fournit un environnement à d'innombrables organismes puisque elle couvre 75% de la surface de terre. L'eau est une molécule simple faite de deux atomes d'hydrogène et un atome d'oxygène. Sa petite taille semble en contradiction avec la subtilité de ses propriétés physiques et chimiques. Parmi celles-là, le fait que, au point triple, l'eau liquide est plus dense que la glace est particulièrement remarquable. Malgré son importance particulière dans les sciences de la vie, l'eau est systématiquement éliminée des spécimens biologiques examinés par la microscopie électronique. La raison en est que le haut vide du microscope électronique exige que le spécimen biologique soit solide. Pendant 50 ans la science de la microscopie électronique a adressé ce problème résultant en ce moment en des nombreuses techniques de préparation dont l'usage est courrant. Typiquement ces techniques consistent à fixer l'échantillon (chimiquement ou par congélation), remplacer son contenu d'eau par un plastique doux qui est transformé à un bloc rigide par polymérisation. Le bloc du spécimen est coupé en sections minces (d’environ 50 nm) avec un ultramicrotome à température ambiante. En général, ces techniques introduisent plusieurs artefacts, principalement dû à l'enlèvement d'eau. Afin d'éviter ces artefacts, le spécimen peut être congelé, coupé et observé à basse température. Cependant, l'eau liquide cristallise lors de la congélation, résultant en une importante détérioration. Idéalement, l'eau liquide est solidifiée dans un état vitreux. La vitrification consiste à refroidir l'eau si rapidement que les cristaux de glace n'ont pas de temps de se former. Une percée a eu lieu quand la vitrification d'eau pure a été découverte expérimentalement. Cette découverte a ouvert la voie à la cryo-microscopie des suspensions biologiques en film mince vitrifié. Nous avons travaillé pour étendre la technique aux spécimens épais. Pour ce faire les échantillons biologiques doivent être vitrifiés, cryo-coupées en sections vitreuse et observées dans une cryo-microscope électronique. Cette technique, appelée la cryo- microscopie électronique des sections vitrifiées (CEMOVIS), est maintenant considérée comme étant la meilleure façon de conserver l'ultrastructure de tissus et cellules biologiques dans un état très proche de l'état natif. Récemment, cette technique est devenue une méthode pratique fournissant des résultats excellents. Elle a cependant, des limitations importantes, la plus importante d'entre elles est certainement dû aux artefacts de la coupe. Ces artefacts sont la conséquence de la nature du matériel vitreux et le fait que les sections vitreuses ne peuvent pas flotter sur un liquide comme c'est le cas pour les sections en plastique coupées à température ambiante. Le but de ce travail a été d'améliorer notre compréhension du processus de la coupe et des artefacts de la coupe. Nous avons ainsi trouvé des conditions optimales pour minimiser ou empêcher ces artefacts. Un modèle amélioré du processus de coupe et une redéfinitions des artefacts de coupe sont proposés. Les résultats obtenus sous ces conditions sont présentés et comparés aux résultats obtenus avec les méthodes conventionnelles. Abstract Water is often considered to be an ordinary substance since it is transparent, odourless, tasteless and it is very common in nature. As a matter of fact it can be argued that it is the most remarkable of all substances. Without water life on Earth would not exist. Water is the major component of cells, typically forming 70 to 95% of cellular mass and it provides an environment for innumerable organisms to live in, since it covers 75% of Earth surface. Water is a simple molecule made of two hydrogen atoms and one oxygen atom, H2O. The small size of the molecule stands in contrast with its unique physical and chemical properties. Among those the fact that, at the triple point, liquid water is denser than ice is especially remarkable. Despite its special importance in life science, water is systematically removed from biological specimens investigated by electron microscopy. This is because the high vacuum of the electron microscope requires that the biological specimen is observed in dry conditions. For 50 years the science of electron microscopy has addressed this problem resulting in numerous preparation techniques, presently in routine use. Typically these techniques consist in fixing the sample (chemically or by freezing), replacing its water by plastic which is transformed into rigid block by polymerisation. The block is then cut into thin sections (c. 50 nm) with an ultra-microtome at room temperature. Usually, these techniques introduce several artefacts, most of them due to water removal. In order to avoid these artefacts, the specimen can be frozen, cut and observed at low temperature. However, liquid water crystallizes into ice upon freezing, thus causing severe damage. Ideally, liquid water is solidified into a vitreous state. Vitrification consists in solidifying water so rapidly that ice crystals have no time to form. A breakthrough took place when vitrification of pure water was discovered. Since this discovery, the thin film vitrification method is used with success for the observation of biological suspensions of. small particles. Our work was to extend the method to bulk biological samples that have to be vitrified, cryosectioned into vitreous sections and observed in cryo-electron microscope. This technique is called cryo-electron microscopy of vitreous sections (CEMOVIS). It is now believed to be the best way to preserve the ultrastructure of biological tissues and cells very close to the native state for electron microscopic observation. Since recently, CEMOVIS has become a practical method achieving excellent results. It has, however, some sever limitations, the most important of them certainly being due to cutting artefacts. They are the consequence of the nature of vitreous material and the fact that vitreous sections cannot be floated on a liquid as is the case for plastic sections cut at room temperature. The aim of the present work has been to improve our understanding of the cutting process and of cutting artefacts, thus finding optimal conditions to minimise or prevent these artefacts. An improved model of the cutting process and redefinitions of cutting artefacts are proposed. Results obtained with CEMOVIS under these conditions are presented and compared with results obtained with conventional methods.

Cryo-negative staining: advantages and applications for three-dimensional electron microscopy of biological macromolecules

Les échantillons biologiques ne s?arrangent pas toujours en objets ordonnés (cristaux 2D ou hélices) nécessaires pour la microscopie électronique ni en cristaux 3D parfaitement ordonnés pour la cristallographie rayons X alors que de nombreux spécimens sont tout simplement trop << gros D pour la spectroscopie NMR. C?est pour ces raisons que l?analyse de particules isolées par la cryo-microscopie électronique est devenue une technique de plus en plus importante pour déterminer la structure de macromolécules. Néanmoins, le faible rapport signal-sur-bruit ainsi que la forte sensibilité des échantillons biologiques natifs face au faisceau électronique restent deux parmi les facteurs limitant la résolution. La cryo-coloration négative est une technique récemment développée permettant l?observation des échantillons biologiques avec le microscope électronique. Ils sont observés à l?état vitrifié et à basse température, en présence d?un colorant (molybdate d?ammonium). Les avantages de la cryo-coloration négative sont étudiés dans ce travail. Les résultats obtenus révèlent que les problèmes majeurs peuvent êtres évités par l?utilisation de cette nouvelle technique. Les échantillons sont représentés fidèlement avec un SNR 10 fois plus important que dans le cas des échantillons dans l?eau. De plus, la comparaison de données obtenues après de multiples expositions montre que les dégâts liés au faisceau électronique sont réduits considérablement. D?autre part, les résultats exposés mettent en évidence que la technique est idéale pour l?analyse à haute résolution de macromolécules biologiques. La solution vitrifiée de molybdate d?ammonium entourant l?échantillon n?empêche pas l?accès à la structure interne de la protéine. Finalement, plusieurs exemples d?application démontrent les avantages de cette technique nouvellement développée.<br/><br/>Many biological specimens do not arrange themselves in ordered assemblies (tubular or flat 2D crystals) suitable for electron crystallography, nor in perfectly ordered 3D crystals for X-ray diffraction; many other are simply too large to be approached by NMR spectroscopy. Therefore, single-particles analysis has become a progressively more important technique for structural determination of large isolated macromolecules by cryo-electron microscopy. Nevertheless, the low signal-to-noise ratio and the high electron-beam sensitivity of biological samples remain two main resolution-limiting factors, when the specimens are observed in their native state. Cryo-negative staining is a recently developed technique that allows the study of biological samples with the electron microscope. The samples are observed at low temperature, in the vitrified state, but in presence of a stain (ammonium molybdate). In the present work, the advantages of this novel technique are investigated: it is shown that cryo-negative staining can generally overcome most of the problems encountered with cryo-electron microscopy of vitrified native suspension of biological particles. The specimens are faithfully represented with a 10-times higher SNR than in the case of unstained samples. Beam-damage is found to be considerably reduced by comparison of multiple-exposure series of both stained and unstained samples. The present report also demonstrates that cryo-negative staining is capable of high- resolution analysis of biological macromolecules. The vitrified stain solution surrounding the sample does not forbid the access to the interna1 features (ie. the secondary structure) of a protein. This finding is of direct interest for the structural biologist trying to combine electron microscopy and X-ray data. developed electron microscopy technique. Finally, several application examples demonstrate the advantages of this newly

Monitoring of crystallization processes by using infrared spectroscopy and multivariate methods

Väitöstutkimuksessa on tarkasteltuinfrapunaspektroskopian ja monimuuttujaisten aineistonkäsittelymenetelmien soveltamista kiteytysprosessin monitoroinnissa ja kidemäisen tuotteen analysoinnissa. Parhaillaan kiteytysprosessitutkimuksessa maailmanlaajuisesti tutkitaan intensiivisesti erilaisten mittausmenetelmien soveltamista kiteytysprosessin ilmiöidenjatkuvaan mittaamiseen niin nestefaasista kuin syntyvistä kiteistäkin. Lisäksi tuotteen karakterisointi on välttämätöntä tuotteen laadun varmistamiseksi. Erityisesti lääkeaineiden valmistuksessa kiinnostusta tämäntyyppiseen tutkimukseen edistää Yhdysvaltain elintarvike- ja lääkeaineviraston (FDA) prosessianalyyttisiintekniikoihin (PAT) liittyvä ohjeistus, jossa määritellään laajasti vaatimukset lääkeaineiden valmistuksessa ja tuotteen karakterisoinnissa tarvittaville mittauksille turvallisten valmistusprosessien takaamiseksi. Jäähdytyskiteytyson erityisesti lääketeollisuudessa paljon käytetty erotusmenetelmä kiinteän raakatuotteen puhdistuksessa. Menetelmässä puhdistettava kiinteä raaka-aine liuotetaan sopivaan liuottimeen suhteellisen korkeassa lämpötilassa. Puhdistettavan aineen liukoisuus käytettävään liuottimeen laskee lämpötilan laskiessa, joten systeemiä jäähdytettäessä liuenneen aineen konsentraatio prosessissa ylittää liukoisuuskonsentraation. Tällaiseen ylikylläiseen systeemiin pyrkii muodostumaan uusia kiteitä tai olemassa olevat kiteet kasvavat. Ylikylläisyys on yksi tärkeimmistä kidetuotteen laatuun vaikuttavista tekijöistä. Jäähdytyskiteytyksessä syntyvän tuotteen ominaisuuksiin voidaan vaikuttaa mm. liuottimen valinnalla, jäähdytyprofiililla ja sekoituksella. Lisäksi kiteytysprosessin käynnistymisvaihe eli ensimmäisten kiteiden muodostumishetki vaikuttaa tuotteen ominaisuuksiin. Kidemäisen tuotteen laatu määritellään kiteiden keskimääräisen koon, koko- ja muotojakaumansekä puhtauden perusteella. Lääketeollisuudessa on usein vaatimuksena, että tuote edustaa tiettyä polymorfimuotoa, mikä tarkoittaa molekyylien kykyä järjestäytyä kidehilassa usealla eri tavalla. Edellä mainitut ominaisuudet vaikuttavat tuotteen jatkokäsiteltävyyteen, kuten mm. suodattuvuuteen, jauhautuvuuteen ja tabletoitavuuteen. Lisäksi polymorfiamuodolla on vaikutusta moniin tuotteen käytettävyysominaisuuksiin, kuten esim. lääkeaineen liukenemisnopeuteen elimistössä. Väitöstyössä on tutkittu sulfatiatsolin jäähdytyskiteytystä käyttäen useita eri liuotinseoksia ja jäähdytysprofiileja sekä tarkasteltu näiden tekijöiden vaikutustatuotteen laatuominaisuuksiin. Infrapunaspektroskopia on laajalti kemian alan tutkimuksissa sovellettava menetelmä. Siinä mitataan tutkittavan näytteenmolekyylien värähtelyjen aiheuttamia spektrimuutoksia IR alueella. Tutkimuksessa prosessinaikaiset mittaukset toteutettiin in-situ reaktoriin sijoitettavalla uppoanturilla käyttäen vaimennettuun kokonaisheijastukseen (ATR) perustuvaa Fourier muunnettua infrapuna (FTIR) spektroskopiaa. Jauhemaiset näytteet mitattiin off-line diffuusioheijastukseen (DRIFT) perustuvalla FTIR spektroskopialla. Monimuuttujamenetelmillä (kemometria) voidaan useita satoja, jopa tuhansia muuttujia käsittävä spektridata jalostaa kvalitatiiviseksi (laadulliseksi) tai kvantitatiiviseksi (määrälliseksi) prosessia kuvaavaksi informaatioksi. Väitöstyössä tarkasteltiin laajasti erilaisten monimuuttujamenetelmien soveltamista mahdollisimman monipuolisen prosessia kuvaavan informaation saamiseksi mitatusta spektriaineistosta. Väitöstyön tuloksena on ehdotettu kalibrointirutiini liuenneen aineen konsentraation ja edelleen ylikylläisyystason mittaamiseksi kiteytysprosessin aikana. Kalibrointirutiinin kehittämiseen kuuluivat aineiston hyvyyden tarkastelumenetelmät, aineiston esikäsittelymenetelmät, varsinainen kalibrointimallinnus sekä mallin validointi. Näin saadaan reaaliaikaista informaatiota kiteytysprosessin ajavasta voimasta, mikä edelleen parantaa kyseisen prosessin tuntemusta ja hallittavuutta. Ylikylläisyystason vaikutuksia syntyvän kidetuotteen laatuun seurattiin usein kiteytyskokein. Työssä on esitetty myös monimuuttujaiseen tilastolliseen prosessinseurantaan perustuva menetelmä, jolla voidaan ennustaa spontaania primääristä ytimenmuodostumishetkeä mitatusta spektriaineistosta sekä mahdollisesti päätellä ydintymisessä syntyvä polymorfimuoto. Ehdotettua menetelmää hyödyntäen voidaan paitsi ennakoida kideytimien muodostumista myös havaita mahdolliset häiriötilanteet kiteytysprosessin alkuhetkillä. Syntyvää polymorfimuotoa ennustamalla voidaan havaita ei-toivotun polymorfin ydintyminen,ja mahdollisesti muuttaa kiteytyksen ohjausta halutun polymorfimuodon saavuttamiseksi. Monimuuttujamenetelmiä sovellettiin myös kiteytyspanosten välisen vaihtelun määrittämiseen mitatusta spektriaineistosta. Tämäntyyppisestä analyysistä saatua informaatiota voidaan hyödyntää kiteytysprosessien suunnittelussa ja optimoinnissa. Väitöstyössä testattiin IR spektroskopian ja erilaisten monimuuttujamenetelmien soveltuvuutta kidetuotteen polymorfikoostumuksen nopeaan määritykseen. Jauhemaisten näytteiden luokittelu eri polymorfeja sisältäviin näytteisiin voitiin tehdä käyttäen tarkoitukseen soveltuvia monimuuttujaisia luokittelumenetelmiä. Tämä tarjoaa nopean menetelmän jauhemaisen näytteen polymorfikoostumuksen karkeaan arviointiin, eli siihen mitä yksittäistä polymorfia kyseinen näyte pääasiassa sisältää. Varsinainen kvantitatiivinen analyysi, eli sen selvittäminen paljonko esim. painoprosentteina näyte sisältää eri polymorfeja, vaatii kaikki polymorfit kattavan fysikaalisen kalibrointisarjan, mikä voi olla puhtaiden polymorfien huonon saatavuuden takia hankalaa.

Theoretical and numerical study of thermomagnetic convection in magnetic fluids

In this thesis, the magnetic field control of convection instabilities and heat and mass transfer processesin magnetic fluids have been investigated by numerical simulations and theoretical considerations. Simulation models based on finite element and finite volume methods have been developed. In addition to standard conservation equations, themagnetic field inside the simulation domain is calculated from Maxwell equations and the necessary terms to take into account for the magnetic body force and magnetic dissipation have been added to the equations governing the fluid motion.Numerical simulations of magnetic fluid convection near the threshold supportedexperimental observations qualitatively. Near the onset of convection the competitive action of thermal and concentration density gradients leads to mostly spatiotemporally chaotic convection with oscillatory and travelling wave regimes, previously observed in binary mixtures and nematic liquid crystals. In many applications of magnetic fluids, the heat and mass transfer processes including the effects of external magnetic fields are of great importance. In addition to magnetic fluids, the concepts and the simulation models used in this study may be applied also to the studies of convective instabilities in ordinary fluids as well as in other binary mixtures and complex fluids.

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.

Ash Particle Erosion on Steam Boiler Convective Section

In this study, equations for the calculation of erosion wear caused by ash particles on convective heat exchanger tubes of steam boilers are presented. Anew, three-dimensional test arrangement was used in the testing of the erosion wear of convective heat exchanger tubes of steam boilers. When using the sleeve-method, three different tube materials and three tube constructions could be tested. New results were obtained from the analyses. The main mechanisms of erosionwear phenomena and erosion wear as a function of collision conditions and material properties have been studied. Properties of fossil fuels have also been presented. When burning solid fuels, such as pulverized coal and peat in steam boilers, most of the ash is entrained by the flue gas in the furnace. In bubbling andcirculating fluidized bed boilers, particle concentration in the flue gas is high because of bed material entrained in the flue gas. Hard particles, such as sharp edged quartz crystals, cause erosion wear when colliding on convective heat exchanger tubes and on the rear wall of the steam boiler. The most important ways to reduce erosion wear in steam boilers is to keep the velocity of the flue gas moderate and prevent channelling of the ash flow in a certain part of the cross section of the flue gas channel, especially near the back wall. One can do this by constructing the boiler with the following components. Screen plates can beused to make the velocity and ash flow distributions more even at the cross-section of the channel. Shield plates and plate type constructions in superheaters can also be used. Erosion testing was conducted with three types of tube constructions: a one tube row, an inline tube bank with six tube rows, and a staggered tube bank with six tube rows. Three flow velocities and two particle concentrations were used in the tests, which were carried out at room temperature. Three particle materials were used: quartz, coal ash and peat ash particles. Mass loss, diameter loss and wall thickness loss measurements of the test sleeves were taken. Erosion wear as a function of flow conditions, tube material and tube construction was analyzed by single-variable linear regression analysis. In developing the erosion wear calculation equations, multi-variable linear regression analysis was used. In the staggered tube bank, erosion wear had a maximum value in a tube row 2 and a local maximum in row 5. In rows 3, 4 and 6, the erosion rate was low. On the other hand, in the in-line tube bank the minimum erosion rate occurred in tube row 2 and in further rows the erosion had an increasing value, so that in a six row tube bank, the maximum value occurred in row 6.

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.

Xanthine oxidoreductase regulates macrophage IL1β secretion upon NLRP3 inflammasome activation.

Activation of the NLRP3 inflammasome by microbial ligands or tissue damage requires intracellular generation of reactive oxygen species (ROS). We present evidence that macrophage secretion of IL1β upon stimulation with ATP, crystals or LPS is mediated by a rapid increase in the activity of xanthine oxidase (XO), the oxidized form of xanthine dehydrogenase, resulting in the formation of uric acid as well as ROS. We show that XO-derived ROS, but not uric acid, is the trigger for IL1β release and that XO blockade results in impaired IL1β and caspase1 secretion. XO is localized to both cytoplasmic and mitochondrial compartments and acts upstream to the PI3K-AKT signalling pathway that results in mitochondrial ROS generation. This pathway represents a mechanism for regulating NLRP3 inflammasome activation that may have therapeutic implications in inflammatory diseases.

Micronization of Pharmaceuticals and Food Ingredients using Supercritical Fluid Techniques

Micronization techniques based on supercritical fluids (SCFs) are promising for the production of particles with controlled size and distribution. The interest of the pharmaceutical field in the development of SCF techniques is increasing due to the need for clean processes, reduced consumption of energy, and to their several possible applications. The food field is still far from the application of SCF micronization techniques, but there is increasing interest mainly for the processing of products with high added value. The aim of this study is to use SCF micronization techniques for the production of particles of pharmaceuticals and food ingredients with controlled particle size and morphology, and to look at their production on semi-industrial scale. The results obtained are also used to understand the processes from the perspective of broader application within the pharmaceutical and food industries. Certain pharmaceuticals, a biopolymer and a food ingredient have been tested using supercritical antisolvent micronization (SAS) or supercritical assisted atomization (SAA) techniques. The reproducibility of the SAS technique has been studied using physically different apparatuses and on both laboratory and semi-industrial scale. Moreover, a comparison between semi-continuous and batch mode has been performed. The behaviour of the system during the SAS process has been observed using a windowed precipitation vessel. The micronized powders have been characterized by particle size and distribution, morphology and crystallinity. Several analyses have been performed to verify if the SCF process modified the structure of the compound or caused degradation or contamination of the product. The different powder morphologies obtained have been linked to the position of the process operating point with respect to the vapour-liquid equilibrium (VLE) of the systems studied, that is, mainly to the position of the mixture critical point (MCP) of the mixture. Spherical micro, submicro- and nanoparticles, expanded microparticles (balloons) and crystals were obtained by SAS. The obtained particles were amorphous or with different degrees of crystallinity and, in some cases, had different pseudo-polymorphic or polymorphic forms. A compound that could not be processed using SAS was micronized by SAA, and amorphous particles were obtained, stable in vials at room temperature. The SCF micronization techniques studied proved to be effective and versatile for the production of particles for several uses. Furthermore, the findings of this study and the acquired knowledge of the proposed processes can allow a more conscious application of SCF techniques to obtain products with the desired characteristics and enable the use of their principles for broader applications.

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

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.