Atomikerroskasvatuksen soveltaminen kemiantekniikassa

Tässä kirjallisuustyössä tutkittiin atomikerroskasvatuksen (ALD) soveltamista kemiantekniikassa. Työn alussa kerrottiin atomikerroskasvatuksesta, sen toimintaperiaatteista ja prosessitekniikasta. Tämän jälkeen tutkittiin viittä eri kemiantekniikan sovellusta, jotka olivat polymeerien pinnoittaminen, heterogeenisten katalyyttien syntetisointi, membraanien modifiointi, korroosionesto ja kaasunilmaisimet. ALD on ohutkalvotekniikka, jolla voidaan valmistaa nanometrin tai jopa Ångströmin (1 Å = 0.1 nm) tarkkuudella epäorgaanisia materiaalikerroksia, jotka yleensä ovat metallioksideja, kuten alumiinioksidi. ALD perustuu kaasu-kiintoainereaktioihin, joissa kaasumaiset kemialliset prekursorit reagoivat vuorotellen kasvualustan kanssa. Tyypilliset prekursorit ovat metalliligandi ja vesi, joka on yleisin hapen lähde ALD-reaktioissa. ALD−reaktiot suoritetaan yleensä matalassa paineessa (100−200 Pa) ja korkeassa lämpötilassa (200–400 °C) suljetussa reaktorikammiossa. ALD-prosesseissa voidaan hyödyntää myös plasmaa alentamaan reaktiolämpötiloja. Plasman avulla prekursoreista luodaan hyvin reaktiivisia radikaaleja, jotka voivat reagoida jopa huoneenlämmössä. Lämpöherkkiä polymeerejä voidaan pinnoittaa ohutkalvoilla, joilla voidaan lisätä esimerkiksi pakkausmateriaalien suojaa happea ja vesihöyryä vastaan. ALD:llä voidaan syntetisoida tarkasti nanomittakaavan heterogeenisiä katalyyttejä, joilla on korkea dispersio tukimateriaalin pinnalla. ALD:n avulla voidaan säästää katalyyttimateriaalia menettämättä katalyytin aktiivisuutta, mikä on tärkeää monien katalyyttisovellusten taloudellisuuden kannalta, esimerkiksi polttokennot. ALD soveltuu hyvin membraanien modifiointiin, koska kaasumaiset prekursorit leviävät tasaisesti membraanin huokosiin. Membraanien pinnoittamisella pyritään vaikuttamaan, selektiivisyyteen, hydrofiilisyyteen, liuotinkestävyyteen, huokoskokoon ja sen jakaumaan. Lisäksi membraaneja voidaan pinnoittaa katalyyttisillä ohutkalvoilla, mikä on tärkeää nanoreaktoreiden kehityksen kannalta. ALD:llä voidaan pinnoittaa esimerkiksi terästä, ja vähentää täten teräksen korroosiota. Puolijohtavia metallioksideja voidaan käyttää kaasunilmaisimina, joiden valmistuksessa ALD:n tarkkuudesta on suurta hyötyä.

The Possibilities and Dosimetric Limitations of MLC-Based Intensity-Modulated Radiotherapy Delivery and Optimization Techniques

The use of intensity-modulated radiotherapy (IMRT) has increased extensively in the modern radiotherapy (RT) treatments over the past two decades. Radiation dose distributions can be delivered with higher conformality with IMRT when compared to the conventional 3D-conformal radiotherapy (3D-CRT). Higher conformality and target coverage increases the probability of tumour control and decreases the normal tissue complications. The primary goal of this work is to improve and evaluate the accuracy, efficiency and delivery techniques of RT treatments by using IMRT. This study evaluated the dosimetric limitations and possibilities of IMRT in small (treatments of head-and-neck, prostate and lung cancer) and large volumes (primitive neuroectodermal tumours). The dose coverage of target volumes and the sparing of critical organs were increased with IMRT when compared to 3D-CRT. The developed split field IMRT technique was found to be safe and accurate method in craniospinal irradiations. By using IMRT in simultaneous integrated boosting of biologically defined target volumes of localized prostate cancer high doses were achievable with only small increase in the treatment complexity. Biological plan optimization increased the probability of uncomplicated control on average by 28% when compared to standard IMRT delivery. Unfortunately IMRT carries also some drawbacks. In IMRT the beam modulation is realized by splitting a large radiation field to small apertures. The smaller the beam apertures are the larger the rebuild-up and rebuild-down effects are at the tissue interfaces. The limitations to use IMRT with small apertures in the treatments of small lung tumours were investigated with dosimetric film measurements. The results confirmed that the peripheral doses of the small lung tumours were decreased as the effective field size was decreased. The studied calculation algorithms were not able to model the dose deficiency of the tumours accurately. The use of small sliding window apertures of 2 mm and 4 mm decreased the tumour peripheral dose by 6% when compared to 3D-CRT treatment plan. A direct aperture based optimization (DABO) technique was examined as a solution to decrease the treatment complexity. The DABO IMRT technique was able to achieve treatment plans equivalent with the conventional IMRT fluence based optimization techniques in the concave head-and-neck target volumes. With DABO the effective field sizes were increased and the number of MUs was reduced with a factor of two. The optimality of a treatment plan and the therapeutic ratio can be further enhanced by using dose painting based on regional radiosensitivities imaged with functional imaging methods.

Dynaamisen lämmönsiirtomallin kehittäminen

Dynaamisia simulointimalleja tarvitaan, jotta voidaan tarkastella järjestelmän käyttäytymistä ajan funktiona. Simulointimallilla voidaan simuloida järjestelmän lähtö erilaisilla herätteillä. Mallin avulla saadaan myös tarkempi käsitys järjestelmästä ja sen osa-alueista, koska simulointimallista voidaan tarkastella sellaisia asioita, jotka voivat olla oikeasta järjestelmästä vaikeasti mitattavia. Tässä työssä kehitetään LUT Energian hyötysuhdemittapaikan keskikokoista kalorimetriä approksimoiva dynaaminen lämmönsiirtomalli käyttäen Matlab® Simulink -ohjelmistoa. Kehitetyn lämmönsiirtomallin tarkkuutta arvioidaan todellisella järjestelmällä tehdyillä mittauksilla. Työssä käytetään karkeita approksimaatioita, jotka tulee korvata tarkemmilla matemaattisilla malleilla jatkokehitystä varten. Työssä kehitetty dynaaminen lämmönsiirtomalli approksimoi todellisen järjestelmän vastetta lämmitysvaiheessa keskimääräisenvirheen ±0,19 °C tarkkuudella.

Accuracy Analysis of Frequency Converter Estimates in Diagnostic Applications

Transportation of fluids is one of the most common and energy intensive processes in the industrial and HVAC sectors. Pumping systems are frequently subject to engineering malpractice when dimensioned, which can lead to poor operational efficiency. Moreover, pump monitoring requires dedicated measuring equipment, which imply costly investments. Inefficient pump operation and improper maintenance can increase energy costs substantially and even lead to pump failure. A centrifugal pump is commonly driven by an induction motor. Driving the induction motor with a frequency converter can diminish energy consumption in pump drives and provide better control of a process. In addition, induction machine signals can also be estimated by modern frequency converters, dispensing with the use of sensors. If the estimates are accurate enough, a pump can be modelled and integrated into the frequency converter control scheme. This can open the possibility of joint motor and pump monitoring and diagnostics, thereby allowing the detection of reliability-reducing operating states that can lead to additional maintenance costs. The goal of this work is to study the accuracy of rotational speed, torque and shaft power estimates calculated by a frequency converter. Laboratory tests were performed in order to observe estimate behaviour in both steady-state and transient operation. An induction machine driven by a vector-controlled frequency converter, coupled with another induction machine acting as load was used in the tests. The estimated quantities were obtained through the frequency converter’s Trend Recorder software. A high-precision, HBM T12 torque-speed transducer was used to measure the actual values of the aforementioned variables. The effect of the flux optimization energy saving feature on the estimate quality was also studied. A processing function was developed in MATLAB for comparison of the obtained data. The obtained results confirm the suitability of this particular converter to provide accurate enough estimates for pumping applications.

Kartongin reunaimeytymän hallittavuus

Kuppikartongin yksi tärkeimmistä ominaisuuksista on reunaimeytymän vastustuskyky, joka tulee olla riittävällä tasolla laadun takaamiseksi. Koska yksinkertainen juomakuppi on bulkki¬tuote, ei sen raakareunaa kannata taloudellisuuden vuoksi suojata tätä varten kehitellyillä menetelmillä vaan itse kartongin tulee vastustaa nesteitä riittävässä määrin. Tämän diplomityön tarkoituksena oli selvittää hydrofobointiin käytettävän massaliiman (hartsi) sekä pintaliiman joukkoon annosteltavan lisäaineen välinen optimaalinen suhde parhaan vastustuskyvyn saavuttamiseksi. Lisäksi selvitettiin joidenkin liimapuristimen ajo-olosuhteiden vaikutusta pintaliiman pick-upiin sekä koneen pH-tason oikeellisuus. Jauhatuksen vaikutusta tutkittiin lähinnä historiatietojen avulla. Tutkimus koostui viidestä tehdasmittakaavaisesta koeajosta, joiden avulla selvitettiin muuttujien vaikutus sisäisellä reunaimeytymän määritysmenetelmällä sekä määrittä¬mällä koepisteistä kulloinkin mielenkiinnon kohteena olleet kemikaalipitoisuudet. Viimeisen koeajon koepisteet jalostettiin lisäksi valmiiksi kupeiksi. Käytetty reunaimeytymän määritysmenetelmä osoittautui virhealttiiksi eivätkä raakakartongista tehtyjen määritysten tulokset korreloineet kovinkaan voimakkaasti PE-päällystettyjen näytteiden kanssa. Menetelmän kehitystä on viety eteenpäin tämän työn rinnalla ja työ jatkuu edelleen. Lisäksi kartongin hartsipitoisuusmääritysten tuloksista paljastui ristiriitaisuuksia, joiden vuoksi menetelmää uusittiin voimakkaasti. Reunaimeytymän vastustuksen riittävyydeksi koneella käytettävien massaliima-annosten tulee olla vähintään valitulla nollatasolla kaikissa kerroksissa ja pintaliiman lisäaine tulee pitää käytössä. Mikäli lisäaine jätetään pois käytöstä, tulee massaliima-annokset olla hyvin korkeita, eikä tämäkään takaa täysin reunaimeytymätöntä lopputuotetta. Lisäaineen ollessa käytössä ei suuremmalla massaliima-annoksella ole puolestaan merkittävää vaikutusta. Konetta ajetaan nykyisin hyvin alhaisella pH-tasolla, mutta tason nostaminen aiheuttaa selvän liimauksen heikkenemisen. Liimapuristimelle tulevan radan kosteudella ja pintaliiman kuiva-aineella ei näyttäisi olevan vaikutusta kartongin reunaimeytymän vastustuskykyyn. Myöskään taustakerroksen koivun jauhatusasteella ei ole merkitystä alueella, jolla koneella operoidaan. CTMP-massan jauhatuksen tulee sen sijaan olla riittävä, jotta keskikerrokseen ei synny yksittäisiä, pitkiä imeytymiä.

Statistical analysis of survey-based event history data with application to modeling of unemployment duration

Longitudinal surveys are increasingly used to collect event history data on person-specific processes such as transitions between labour market states. Surveybased event history data pose a number of challenges for statistical analysis. These challenges include survey errors due to sampling, non-response, attrition and measurement. This study deals with non-response, attrition and measurement errors in event history data and the bias caused by them in event history analysis. The study also discusses some choices faced by a researcher using longitudinal survey data for event history analysis and demonstrates their effects. These choices include, whether a design-based or a model-based approach is taken, which subset of data to use and, if a design-based approach is taken, which weights to use. The study takes advantage of the possibility to use combined longitudinal survey register data. The Finnish subset of European Community Household Panel (FI ECHP) survey for waves 1–5 were linked at person-level with longitudinal register data. Unemployment spells were used as study variables of interest. Lastly, a simulation study was conducted in order to assess the statistical properties of the Inverse Probability of Censoring Weighting (IPCW) method in a survey data context. The study shows how combined longitudinal survey register data can be used to analyse and compare the non-response and attrition processes, test the missingness mechanism type and estimate the size of bias due to non-response and attrition. In our empirical analysis, initial non-response turned out to be a more important source of bias than attrition. Reported unemployment spells were subject to seam effects, omissions, and, to a lesser extent, overreporting. The use of proxy interviews tended to cause spell omissions. An often-ignored phenomenon classification error in reported spell outcomes, was also found in the data. Neither the Missing At Random (MAR) assumption about non-response and attrition mechanisms, nor the classical assumptions about measurement errors, turned out to be valid. Both measurement errors in spell durations and spell outcomes were found to cause bias in estimates from event history models. Low measurement accuracy affected the estimates of baseline hazard most. The design-based estimates based on data from respondents to all waves of interest and weighted by the last wave weights displayed the largest bias. Using all the available data, including the spells by attriters until the time of attrition, helped to reduce attrition bias. Lastly, the simulation study showed that the IPCW correction to design weights reduces bias due to dependent censoring in design-based Kaplan-Meier and Cox proportional hazard model estimators. The study discusses implications of the results for survey organisations collecting event history data, researchers using surveys for event history analysis, and researchers who develop methods to correct for non-sampling biases in event history data.

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.

Segmentation of overlapping convex objects

This thesis presents a framework for segmentation of clustered overlapping convex objects. The proposed approach is based on a three-step framework in which the tasks of seed point extraction, contour evidence extraction, and contour estimation are addressed. The state-of-art techniques for each step were studied and evaluated using synthetic and real microscopic image data. According to obtained evaluation results, a method combining the best performers in each step was presented. In the proposed method, Fast Radial Symmetry transform, edge-to-marker association algorithm and ellipse fitting are employed for seed point extraction, contour evidence extraction and contour estimation respectively. Using synthetic and real image data, the proposed method was evaluated and compared with two competing methods and the results showed a promising improvement over the competing methods, with high segmentation and size distribution estimation accuracy.

Heterogeneous mass transfer in fluidized beds by computational fluid dynamics

The main objective of this research is to estimate and characterize heterogeneous mass transfer coefficients in bench- and pilot-scale fluidized bed processes by the means of computational fluid dynamics (CFD). A further objective is to benchmark the heterogeneous mass transfer coefficients predicted by fine-grid Eulerian CFD simulations against empirical data presented in the scientific literature. First, a fine-grid two-dimensional Eulerian CFD model with a solid and gas phase has been designed. The model is applied for transient two-dimensional simulations of char combustion in small-scale bubbling and turbulent fluidized beds. The same approach is used to simulate a novel fluidized bed energy conversion process developed for the carbon capture, chemical looping combustion operated with a gaseous fuel. In order to analyze the results of the CFD simulations, two one-dimensional fluidized bed models have been formulated. The single-phase and bubble-emulsion models were applied to derive the average gas-bed and interphase mass transfer coefficients, respectively. In the analysis, the effects of various fluidized bed operation parameters, such as fluidization, velocity, particle and bubble diameter, reactor size, and chemical kinetics, on the heterogeneous mass transfer coefficients in the lower fluidized bed are evaluated extensively. The analysis shows that the fine-grid Eulerian CFD model can predict the heterogeneous mass transfer coefficients quantitatively with acceptable accuracy. Qualitatively, the CFD-based research of fluidized bed process revealed several new scientific results, such as parametrical relationships. The huge variance of seven orders of magnitude within the bed Sherwood numbers presented in the literature could be explained by the change of controlling mechanisms in the overall heterogeneous mass transfer process with the varied process conditions. The research opens new process-specific insights into the reactive fluidized bed processes, such as a strong mass transfer control over heterogeneous reaction rate, a dominance of interphase mass transfer in the fine-particle fluidized beds and a strong chemical kinetic dependence of the average gas-bed mass transfer. The obtained mass transfer coefficients can be applied in fluidized bed models used for various engineering design, reactor scale-up and process research tasks, and they consequently provide an enhanced prediction accuracy of the performance of fluidized bed processes.

Accuracy improvement of a demand forecasting model

This research concerns different statistical methods that assist to increase the demand forecasting accuracy of company X’s forecasting model. Current forecasting process was analyzed in details. As a result, graphical scheme of logical algorithm was developed. Based on the analysis of the algorithm and forecasting errors, all the potential directions for model future improvements in context of its accuracy were gathered into the complete list. Three improvement directions were chosen for further practical research, on their basis, three test models were created and verified. Novelty of this work lies in the methodological approach of the original analysis of the model, which identified its critical points, as well as the uniqueness of the developed test models. Results of the study formed the basis of the grant of the Government of St. Petersburg.

Accuracy in book papers' sales forecasting

The main objective of this thesis was to study if the quantitative sales forecasting methods will enhance the accuracy of the sales forecast in comparison to qualitative sales forecasting method. A literature review in the field of forecasting was conducted, including general sales forecasting process, forecasting methods and techniques and forecasting accuracy measurement. In the empirical part of the study the accuracy of the forecasts provided by both qualitative and quantitative methods is being studied and compared in the case of short, medium and long term forecasts. The SAS® Forecast Server –tool was used in creating the quantitative forecasts.

Finite size effects in superconducting nanocomposites

The present Master’s thesis presents theoretical description of the extraodinary behavior of the confined Indium nanoparticles. Superconducting properties of nanoparticles and nanocomposites are extensively reviewed. Special attention has been paid to phase fluctuation, shell and disordered effects. The experimental data has been obtained and provided by Dmitry Shamshur from Ioffe Physical Technical Institute. The investigated material represents a highly ordered system of silicate spheres filled with indium metal, where the In nanoparticles are interconnected between each other. Bulk indium is a superconductor with crititcal superconducting temperature Tc0 = 3:41 K. But indium nanoparticles exhibit different behavior, the critical temperature rise by approximately 20% up to 4.15 K. As well as transition of the indium particles to type-II superconductivity with high critical magnetic fields. Such diversity is explained by finite size effects which originate from nanosize of the samples.