Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Ydinvoimalaitoksen höyryturbiinin suorituskyvyn laskenta

Diplomityön tavoitteena on selvittää Loviisan ydinvoimalaitoksen höyryturbiinin hyötysuhteen parantamismahdollisuuksia. Työn kuvaan liittyvät oleellisesti höyryturbiinin siipivyöhykkeiden nopeuskolmioiden sekä hyötysuhteiden laskenta. Höyryturbiinien kehityskaarta sekä turbiinin häviökerrointen laskentayhtälöitä on esitetty useasta eri lähteestä ja vuosikymmeniltä. Työssä selvitettiin uusimpia ydinvoimalaitosten kostea höyryturbiinien suunnitteluperusteita lukuisista eri lähteistä. Kaikkien lähteiden mukaan kostean höyryn alueella tapahtuvaa paisuntaa on haasteellista mallintaa. Työssä on esitelty artikkeleissa tulleita eri näkökulmia höyryturbiinien suorituskyvyn parantamiseksi, sekä rakenteellisia että laskennallisia. Työssä esitellään monia turbiinin virtauksen ja suorituskyvyn laskentamenetelmiä. Esimerkiksi Baumannin säännön laskenta on yksinkertainen tapa käsitellä turbiinin suorituskykyä kostean höyryn alueella. Keskeisimpiä tehtyjä havaintoja oli se, että korkeapaineturbiinin ensimmäisestä vaiheesta löytyi mahdollista parannuspotentiaalia Loviisaan ydinvoimalaitoksen tehon lisäämiseksi. Ensimmäisessä vaiheessa on oletettu siipien olevan Laval –tyyppisiä, mutta käytännössä näin ei ole. Korkeapaineturbiinin nykyisen turbosuuttimen toimintaa voitaisiin tehostaa. Lisäksi Loviisan matalapaineturbiinin viimeisen siipivaiheen jälkeen aiheutuu suuret ulosvirtaushäviöt. Osa suurinopeuksisen virtauksen energiasta pystyttäisiin kuitenkin hyödyntämään vielä ulosvirtauskanavassa olevalla diffuusorilla.

Effects of Weight Loss on Adipose Tissue, Liver and Heart Metabolism in Humans

Obesity has become the leading cause of many chronic diseases, such as type 2 diabetes and cardiovascular diseases. The prevalence of obesity is high in developed countries and it is also a major cause of the use of health services. Ectopic fat accumulation in organs may lead to metabolic disturbances, such as insulin resistance.Weight loss with very-low-energy diet is known to be safe and efficient. Weight loss improves whole body insulin sensitivity, but its effects on tissue and organ level in vivo are not well known. The aims of the studies were to investigate possible changes of weight loss in glucose and fatty acid uptake and perfusion and fat distribution at tissue and organ level using positron emission tomography and magnetic resonance imaging and spectroscopy in 34 healthy obese subjects. The results showed that whole-body insulin sensitivity increased after weight loss with very-low-energy diet and this is associated with improved skeletal muscle insulin-stimulated glucose uptake, but not with adipose tissue, liver or heart glucose uptake. Liver insulin resistance decreased after weight loss. Liver and heart free fatty acid uptakes decreased concomitantly with liver and heart triglyceride content. Adipose tissue and myocardial perfusion decreased. In conclusion, enhanced skeletal muscle glucose uptake leads to increase in whole-body insulin sensitivity when glucose uptake is preserved in other organs studied. These findings suggest that lipid accumulation found in the liver and the heart in obese subjects without co-morbidies is in part reversible by reduced free fatty acid uptake after weight loss. Reduced lipid accumulation in organs may improve metabolic disturbances, e.g. decrease liver insulin resistance. Keywords: Obesity, weight loss, very-low-energy diet, adipose tissue metabolism, liver metabolism, heart metabolism, positron emission tomography

Leimuhitsauksen kokonaisvaltainen laadunhallinta päättymättömässä valssauksessa

Leimuhitsauksen laadunhallinnassa tärkeää on prosessimainen toiminta ja toimintojen kokonaisvaltaisuuden hahmottaminen. Leimuhitsauksen ollessa osana päättymätöntä valssausta hitsauksen laadunhallinta voidaan jakaa kolmeen päävaiheeseen: ennen hitsausta, hitsauksen aikana ja hitsauksen jälkeen vaikuttaviin laaduntuottotekijöihin. Leimuhitsauksen laaduntuottotekijöiden määritys ja jaottelu kaavioiksi on toteutettu tässä työssä. Leimuhitsin tekniseen laatuun vaikuttavat monet ilmiöt ja parametrit hitsauksen aikana. Tärkeimpiä hitsausparametreista ovat hitsausjännite, alustan liikenopeus, tyssäysmatka sekä leimutusaika. Väärät hitsausolosuhteet tai hitsausparametrit aiheuttavat erilaisia mekaanisia ja metallurgisia vikoja leimuhitsiin. Eräs metallurginen vikatyyppi ovat oksidisulkeumat hitsialueella. Nämä hapettuneet alueet voivat johtaa juurensa erilaisista syistä ja esimerkiksi leimutusajan ja epätasaisen liitospinnan yhteyttä sulkeumien syntyyn on epäilty. Pidennetyillä leimutusajoilla tehtyjen hitsauskokeiden ja hitsien rikkovien aineenkoetuskokeiden tuloksena todettiin tässä tutkittujen koehitsien oksidisulkeumien syntyvän hapettumalla leimutuksen aikana tai juuri hetkellä ennen tyssäystä, minkä lisäksi kosteat olosuhteet hitsausatmosfäärin ympärillä heikentävät lopputuloksen laatua. Leimutusajalla on tärkein osa leimutettavia pintoja tasaavana tekijänä ja mitä epätasaisempi liitettävä pinta on, sitä pidemmän leimutusajan se tarvitsee.

Microwave Slot Transmission Line Filled with Ferroelectric and Ferromagnetic Layers

Now when the technology is fast developing it is very important to investigate new hybrid structures. One way is to use ferrite ferroelectric layered structures. Theoretical and experimental investigation of such structures was made. These structures have advantages of both layers and it is possible to tune the behavior of this structure by external electric and magnetic field. But these structures have some disadvantages connected with presence of thick ferroelectric layer. One way to overcome this problem is to use slotline. So this is another new way to create hybrid ferrite ferroelectric structures, but it is needed to create new theory and find experimental proof that the behavior of these structures can be tuned with external magnetic and electric fields.

Enhancing Customer Knowledge and Its Sharing At a Paper Production Line

This study has been made for specific paper production line at an international forest industry company in Finland. The main purpose for the study was a need to examine the current situation of the customer knowledge and its’ sharing at case production line, recognize the problems in it and finally, find out the improvement actions. The study is composed of theoretical and empirical parts. In theoretical part, knowledge management and information sharing in addition to customer knowledge management are presented. Empirical data from case production line was collected by using survey questionnaires. The results are analyzed in discussion and conclusions and finally, study ends with summary which includes recommendations. Based on the study, the amount and quality of customer knowledge and gaining and transferring the customer knowledge were found as the main challenges. The proposed solutions were discovered from moving towards more dynamic operating environment and in the area of customer knowledge management, especially from the communities of creation.

The intrinsic mechanisms of softwood fiber damage in brown stock fiber line unit operations Lappeenranta 2010

The effects of pulp processing on softwood fiber properties strongly influence the properties of wet and dry paper webs. Pulp strength delivery studies have provided observations that much of the strength potential of long fibered pulp is lost during brown stock fiber line operations where the pulp is merely washed and transferred to the subsequent processing stages. The objective of this work was to study the intrinsic mechanisms which maycause fiber damage in the different unit operations of modern softwood brown stock processing. The work was conducted by studying the effects of industrial machinery on pulp properties with some actions of unit operations simulated in laboratory scale devices under controlled conditions. An optical imaging system was created and used to study the orientation of fibers in the internal flows during pulp fluidization in mixers and the passage of fibers through the screen openings during screening. The qualitative changes in fibers were evaluated with existing and standardized techniques. The results showed that each process stage has its characteristic effects on fiber properties: Pulp washing and mat formation in displacement washers introduced fiber deformations especially if the fibers entering the stage were intact, but it did not decrease the pulp strength properties. However, storage chests and pulp transfer after displacement washers contributed to strength deterioration. Pulp screening proved to be quite gentle, having the potential of slightly evening out fiber deformations from very deformed pulps and vice versa inflicting a marginal increase in the deformation indices if the fibers were previously intact. Pulp mixing in fluidizing industrial mixers did not have detrimental effects on pulp strength and had the potential of slightly evening out the deformations, provided that the intensity of fluidization was high enough to allow fiber orientation with the flow and that the time of mixing was short. The chemical and mechanical actions of oxygen delignification had two distinct effects on pulp properties: chemical treatment clearly reduced pulp strength with and without mechanical treatment, and the mechanical actions of process machinery introduced more conformability to pulp fibers, but did not clearly contribute to a further decrease in pulp strength. The chemical composition of fibers entering the oxygen stage was also found to affect the susceptibility of fibers to damage during oxygen delignification. Fibers with the smallest content of xylan were found to be more prone to irreversibledeformations accompanied with a lower tensile strength of the pulp. Fibers poor in glucomannan exhibited a lower fiber strength while wet after oxygen delignification as compared to the reference pulp. Pulps with the smallest lignin content on the other hand exhibited improved strength properties as compared to the references.

Line filter optimization in elevator use

The purpose of this thesis was to create design a guideline for an LCL-filter. This thesis reviews briefly the relevant harmonics standards, old filter designs and problems faced with the previous filters. This thesis proposes a modified design method based on the “Liserre’s method” presented in the literature. This modified method will take into account network parameters better. As input parameters, the method uses the nominal power, allowed ripple current in converter and network side and desired resonant frequency of the filter. Essential component selection issues for LCL-filter, such as heating, voltage strength, current rating etc. are also discussed. Furthermore, a simulation model used to verify the operation of the designed filter in nominal power use and in transient situations is included in this thesis.

Optimization of the power cable for low voltage direct current system

The demand for electricity is constantly growing in contemporary world and, in the same time, quality and reliability requirements are becoming more rigid. In addition, renewable sources of energy have been widely introduced for power generation, and they create specific challenges for the network. Consequently, new solution for distribution system is required, and Low Voltage Direct Current (LVDC) system is the proposed one. This thesis focuses on the investigation of specific cable features for low voltage direct current (LVDC) distribution system. The LVDC system is public ±750 VDC distribution system, which is currently being developed at Lappeen-ranta University of Technology. The aspects, considered in the thesis, are reliable and economic power transmission in distribution networks and possible power line communication in the LVDC cable.

Examining the Role of Rebranding in Perceived Image of a Product Line

The main objective for this study was to explore certain organization’s product line rebranding process and its impact on product line’s perceived image. The case company is a global paper, packaging and forest products company, business segment paper board. The audience explored is one of the company’s major customers, merchant in Germany. The research was performed as a descriptive case study with a purpose to provide longitudinal insight into the product line image and its eventual alteration as a result of the case company’s rebranding process. Mainly qualitative methods were used for conducting the research. The data for the empirical part was collected with a web-based survey at two different points of time; before the rebranded products entered the market and after they had been available approximately six months. The results of this study reveal that the case company has performed well in its attempt to improve product line’s brand image through rebranding. It was found that between the two brand image measurements the product brand image seems to have improved in all of the areas which according to theoretical framework of this study contribute to formation of brand image; brand associations, marketing communications and interpersonal relationships, not forgetting the original platform that initiated the change; technical quality modifications. In other words it may be concluded that as technical quality was brought to a new level, also assessments about the brand image improved respectively.