Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

FOREST LITTER DECOMPOSITION AS AFFECTED BY EUCALYPTUS STAND AGE AND TOPOGRAPHY IN SOUTH-EASTERN BRAZIL1

Forest litter decomposition is a major process in returning nutrients to soils and thus promoting wood productivity in the humid tropic. This study aimed to assess decomposition of eucalypt litter in the Rio Doce region, Brazil. Leaf litter was sampled under clonal eucalypt stands aged 2, 4 and 6 years on hillslopes and footslopes. Soil and soil+litter samples were incubated at two levels of soil moisture, temperature and fertilization. C-CO2 emissions from soil measured during 106 days were higher at 32 °C than at 23°C, mainly for the 2-yr-old stand on footslope. When leaf litter was added on soils, C-CO2 emissions were eight times higher, mainly on footslopes, with no effect of stand age. Leaf decomposition in situ, assessed with a litterbag experiment showed a mean weight loss of at least 50% during 365 days, reaching 74% for 2 yr-old stands on footslopes. In comparison with data from the native forest and the literature, no apparent restrictions were found in eucalypt litter decomposition. Differences between in vitro and in situ results, and between eucalypt and native forest, were most likely related to the response of diverse decomposer communities and to substrate quality.

DYNAMICS AND PREDICTION OF DIAMETRIC STRUCTURE IN TWO ATLANTIC FOREST FRAGMENTS IN NORTHEASTERN BRAZIL

ABSTRACT Monitoring analyses aim to understand the processes that drive changes in forest structure and, along with prediction studies, may assist in the management planning and conservation of forest remnants. The objective of this study was to analyze the forest dynamics in two Atlantic rainforest fragments in Pernambuco, Brazil, and to predict their future forest diameter structure using the Markov chain model. We used continuous forest inventory data from three surveys in two forest fragments of 87 ha (F1) and 388 ha (F2). We calculated the annual rates of mortality and recruitment, the mean annual increment, and the basal area for each of the 3-year periods. Data from the first and second surveys were used to project the third inventory measurements, which were compared to the observed values in the permanent plots using chi-squared tests (a = 0.05). In F1, a decrease in the number of individuals was observed due to mortality rates being higher than recruitment rates; however, there was an increase in the basal area. In this fragment, the fit to the Markov model was adequate. In F2, there was an increase in both the basal area and the number of individuals during the 6-year period due to the recruitment rate exceeding the mortality rate. For this fragment, the fit of the model was unacceptable. Hence, for the studied fragments, the demographic rates influenced the stem density more than the floristic composition. Yet, even with these intense dynamics, both fragments showed active growth.

CLASSIFICATION OF FOREST ROADS AND DETERMINATION OF ROUTE USING GEOGRAPHIC INFORMATION SYSTEM

ABSTRACT Geographic Information System (GIS) is an indispensable software tool in forest planning. In forestry transportation, GIS can manage the data on the road network and solve some problems in transportation, such as route planning. Therefore, the aim of this study was to determine the pattern of the road network and define transport routes using GIS technology. The present research was conducted in a forestry company in the state of Minas Gerais, Brazil. The criteria used to classify the pattern of forest roads were horizontal and vertical geometry, and pavement type. In order to determine transport routes, a data Analysis Model Network was created in ArcGIS using an Extension Network Analyst, allowing finding a route shorter in distance and faster. The results showed a predominance of horizontal geometry classes average (3) and bad (4), indicating presence of winding roads. In the case of vertical geometry criterion, the class of highly mountainous relief (4) possessed the greatest extent of roads. Regarding the type of pavement, the occurrence of secondary coating was higher (75%), followed by primary coating (20%) and asphalt pavement (5%). The best route was the one that allowed the transport vehicle travel in a higher specific speed as a function of road pattern found in the study.

Pienahitsin sijainnin vaikutus kuormaa kantamattoman T-liitoksen väsymiskestävyyteen

Hitsatuissa rakenteissa on paljon hitsien aiheuttamia epäjatkuvuuskohtia, jotka ovat alttiita vaurioitumaan väsyttävän kuormituksen alaisina. Standardit ja normit auttavat suunnittelua rakenneyksityiskohtien analysoinnissa, mutta ohjeiden arvot vaihtelevat paljon. Onkin tär-keää päättää, mitä standardia tai normia käytetään ja saada tutkimustuloksia tukemaan ohjeen käyttöä. Tämä työ on tehty Konecranes Finland Oy:lle. Työn tarkoituksena on etsiä käytössä olevi-en ohjeiden joukosta suunnittelun kannalta parhaiten todellista rakennetta kuvaava. Työssä esitellään käytössä olevia standardeja ja normeja sekä vertaillaan niiden välisiä eroja rakenneyksityiskohdan väsymiskestävyyden määrittämisessä. Työssä tarkastellaan myös hitsatun rakenteen väsymiseen vaikuttavia tekijöitä sekä väsymisanalyysissä käytet-täviä menetelmiä. Tutkittavaan liitokseen valittiin kolme erilaista hitsiä, yksi –ja kaksipuolinen pienahitsi sekä katkopienahitsi. Elementtimenetelmän avulla luotiin malleja koekappaleista ja laskettiin niille väsymiskestävyydet. Tämä lisäksi väsymistä tarkasteltiin väsytyskokeilla, jotka suoritti Lappeenrannan Teknillisen Yliopiston Teräsrakenteiden laboratorio. Lopputuloksena työstä saatiin tietoa hitsien väsymiskestävyyksistä. Liitosten väsymiskes-tävyydet olivat hyviä ja varsinkin katkopienahitsin tulokset olivat odotettua paremmat. Kat-kopienahitsin väsymiskestävyys vaatii tämän työn tulosten perusteella lisää tutkimista.

Relative reduction in annual soil loss in micro watersheds due to the relief and forest cover

With the intense debate, in Brazil, between landowners and public agencies about the amount of area with forest cover needed in different regions, there is an increase of the need for provision of technical data used as a basis for decision making. One of the criteria to evaluate the effect of forest cover in protecting water resources is the soil loss, which leads to several consequences on the environment, including the silting of the rivers. Therefore, this study aimed to evaluate the reduction in the soil loss in micro watersheds with different reliefs, size and location of forest cover, in the Corumbataí River watershed, in the state of São Paulo, using the Revised Universal Soil Loss Equation (RUSLE) in a GIS environment. For this study, 18 watersheds in three degrees of slope were selected, and 20 scenarios for land-use were established, by analyzing the influence of the PPA size, and the size and the location of the Legal Reserve. The results showed that: a) the effect of forest cover in reducing annual soil loss varies depending on the average slope of the watershed; b) the PPA width must be determined taking into account the slope of the watershed; c) the Legal Reserve must be located along the PPA. These provide better results in reducing annual soil loss.

CSR standards and financial performance in forest industry - Empirical analysis

The definition of corporate social responsibility (CSR) has been developed since 1950s but even today there is no consensus what CSR includes. The main purpose of this thesis was to find out whether financial performance is better among first adopters of CSR standards in forest industry. To support the main purpose it was critical also investigate what kind of companies adopt CSR standards. The empirical part of the thesis based on a survey which was done in 2010 to forest industry companies and financial data that was gathered from different databases from years 2003-2010. According to the research results it seems the early CSR standards adopters benefits the position of the first adopter many times. Especially cash position and solvency of early adopter companies were better than later adopters or those who did not adopt CSR standards at all. Profitability seemed to be better among CSR standards adopters but early adopters did not have significantly better position compared to later adopters. CSR standards adopters were companies that considered themselves as environmental performance pioneers and had employee oriented management.

Reaaliaikaisen PMU-mittaustiedon hyödyntäminen voimajärjestelmän valvonnassa

Tämä työ on tehty Fingrid Oyj:lle. Työn tavoitteena oli tutkia, miten reaaliaikaista PMU-mittaustietoa voidaan hyödyntää voimajärjestelmän valvonnassa. Voimajärjestelmän dynaamisia ilmiöitä ovat jännite- ja kulmastabiilius. Työssä tutkittiin voimajärjestelmän kulmastabiiliutta PSS/E-ohjelmalla simuloitujen mittaustulosten perusteella. Fouriermuunnoksen tulokset osoittavat, että huonoiten vaimeneva taajuuskomponentti on 0,3 Hz taajuus. Lisäksi tiedetään, että huonosti vaimeneva taajuuskomponentti rajoittaa siirtokapasiteettia. Voimajärjestelmän stabiiliutta voidaan esittää Wide Area Monitoring -järjestelmien (WAMS) avulla. WAMS perustuu Phasor Measurement -laitteen (PMU) reaaliaikaiseen mittaustekniikkaan. Jännitteen vaihekulman mittaaminen mahdollistaa voimajärjestelmän tilan määrittämisen reaaliajassa. Työssä on esitelty Fingridin käytössä oleva WAMS ja lisäksi esitelty kolmen eri laitetoimittajan WAMS:n rakennetta ja operaattorin käyttöön tarkoitettuja käyttöliittymiä. WAMS:n rakenteet ovat pääpiirteittäin samanlaisia, mutta stabiiliuden visuaalisessa esittämisessä on eroja. PMU -mittaustietoja on mahdollista tuoda käytönvalvontajärjestelmään erillisellä tiedonsiirtoprotokollalla. PMU-mittaustiedon hyödyntäminen käytönvalvontajärjestelmän toimintaaluenäytöllä mahdollistaa verkon tilan esittämisen reaaliajassa. Roottorin kulmastabiilius esitetään Fingridin käytönvalvontajärjestelmässä vaihekulmaerojen avulla ja työssä on esitetty, kuinka vaihekulmaeron arvolla on vaikutus tehonsiirtoon. Vaihekulmaeron arvo kuvaa vian jälkeisen tehoheilahtelun voimakkuutta. PMU-mittaustiedon esittäminen antaa operaattorille selkeämmän kuvan ylläpitää tehonsiirto turvallisella tasolla ja epästabiilin heilahtelun havainnoiminen vähentää suurhäiriön riskiä. Tulevaisuudessa siirtoverkon kehittyessä tarvitaan operaattorin käyttöön myös nopeita stabiilisuutta esittäviä työkaluja.

The effect of dynamic capabilities on operational-level innovation – Empirical study in magazine publishing industry

This master’s thesis aims to examine the relationship between dynamic capabilities and operational-level innovations. In addition, measures for the concept of dynamic capabilities are developed. The study was executed in the magazine publishing industry which is considered favourable for examining dynamic capabilities, since the sector is characterized by rapid change. As a basis for the study and the measure development, a literary review was conducted. Data for the empirical section was gathered by a survey targeted to chief-editors of Finnish consumer magazines. The relationship between dynamic capabilities and innovation was examined by multiple linear regression. The results indicate that dynamic capabilities have effect on the emergence of radical innovations. Environmental dynamism’s effect on radical innovations was not detected. Also, dynamic capabilities’ effect on innovation was not greater in turbulent operating environment.

A Farewell to Flat Biology. Three-dimensional Cell Culture Models in Cancer Drug Target Identification and Validation

Cells of epithelial origin, e.g. from breast and prostate cancers, effectively differentiate into complex multicellular structures when cultured in three-dimensions (3D) instead of conventional two-dimensional (2D) adherent surfaces. The spectrum of different organotypic morphologies is highly dependent on the culture environment that can be either non-adherent or scaffold-based. When embedded in physiological extracellular matrices (ECMs), such as laminin-rich basement membrane extracts, normal epithelial cells differentiate into acinar spheroids reminiscent of glandular ductal structures. Transformed cancer cells, in contrast, typically fail to undergo acinar morphogenic patterns, forming poorly differentiated or invasive multicellular structures. The 3D cancer spheroids are widely accepted to better recapitulate various tumorigenic processes and drug responses. So far, however, 3D models have been employed predominantly in the Academia, whereas the pharmaceutical industry has yet to adopt a more widely and routine use. This is mainly due to poor characterisation of cell models, lack of standardised workflows and high throughput cell culture platforms, and the availability of proper readout and quantification tools. In this thesis, a complete workflow has been established entailing well-characterised 3D cell culture models for prostate cancer, a standardised 3D cell culture routine based on high-throughput-ready platform, automated image acquisition with concomitant morphometric image analysis, and data visualisation, in order to enable large-scale high-content screens. Our integrated suite of software and statistical analysis tools were optimised and validated using a comprehensive panel of prostate cancer cell lines and 3D models. The tools quantify multiple key cancer-relevant morphological features, ranging from cancer cell invasion through multicellular differentiation to growth, and detect dynamic changes both in morphology and function, such as cell death and apoptosis, in response to experimental perturbations including RNA interference and small molecule inhibitors. Our panel of cell lines included many non-transformed and most currently available classic prostate cancer cell lines, which were characterised for their morphogenetic properties in 3D laminin-rich ECM. The phenotypes and gene expression profiles were evaluated concerning their relevance for pre-clinical drug discovery, disease modelling and basic research. In addition, a spontaneous model for invasive transformation was discovered, displaying a highdegree of epithelial plasticity. This plasticity is mediated by an abundant bioactive serum lipid, lysophosphatidic acid (LPA), and its receptor LPAR1. The invasive transformation was caused by abrupt cytoskeletal rearrangement through impaired G protein alpha 12/13 and RhoA/ROCK, and mediated by upregulated adenylyl cyclase/cyclic AMP (cAMP)/protein kinase A, and Rac/ PAK pathways. The spontaneous invasion model tangibly exemplifies the biological relevance of organotypic cell culture models. Overall, this thesis work underlines the power of novel morphometric screening tools in drug discovery.

Dynamic Ownership in Family Business System – A Portfolio Business Approach

Family businesses are among the longest-lived most prevalent institutions in the world and they are an important source of economic development and growth. Ownership is a key to the business life of the firm and also one main key in family business definition. There is only a little portfolio entrepreneurship or portfolio business research within family business context. The absence of empirical evidence on the long-term relationship between family ownership and portfolio development presents an important gap in the family business literature. This study deals with the family business ownership changes and the development of portfolios in the family business and it is positioned in to the conversation of family business, growth, ownership, management and strategy. This study contributes and expands the existing body of theory on family business and ownership. From the theoretical point of view this study combines insights from the fields of portfolio entrepreneurship, ownership, and family business and integrate them. This crossfertilization produces interesting empirical and theoretical findings that can constitute a basis for solid contributions to the understanding of ownership dynamics and portfolio entrepreneurship in family firms. The research strategy chosen for this study represents longitudinal, qualitative, hermeneutic, and deductive approaches.The empirical part of study is using a case study approach with embedded design, that is, multiple levels of analysis within a single study. The study consists of two cases and it begins with a pilot case which will form a preunderstanding on the phenomenon. Pilot case develops the methodology approach to build in the main case and the main case will deepen the understanding of the phenomenon. This study develops and tests a research method of family business portfolio development focusing on investigating how ownership changes are influencing to the family business structures over time. This study reveals the linkages between dimensions of ownership and how they give rise to portfolio business development within the context of the family business. The empirical results of the study suggest that family business ownership is dynamic and owners are using ownership as a tool for creating business portfolios.

Understanding the in vitro dissolution rate of glasses with respect to future clinical applications

Glass is a unique material with a long history. Several glass products are used daily in our everyday life, often unnoticed. Glass can be found not only in obvious applications such as tableware, windows, and light bulbs, but also in tennis rackets, windmill turbine blades, optical devices, and medical implants. The glasses used at present as implants are inorganic silica-based melt-derived compositions mainly for hard-tissue repair as bone graft substitute in dentistry and orthopedics. The degree of glass reactivity desired varies according to implantation situation and it is vital that the ion release from any glasses used in medical applications is controlled. Understanding the in vitro dissolution rate of glasses provides a first approximation of their behavior in vivo. Specific studies concerning dissolution properties of bioactive glasses have been relatively scarce and mostly concentrated to static condition studies. The motivation behind this work was to develop a simple and accurate method for quantifying the in vitro dissolution rate of highly different types of glass compositions with interest for future clinical applications. By combining information from various experimental conditions, a better knowledge of glass dissolution and the suitability of different glasses for different medical applications can be obtained. Thus, two traditional and one novel approach were utilized in this thesis to study glass dissolution. The chemical durability of silicate glasses was tested in water and TRIS-buffered solution at static and dynamic conditions. The traditional in vitro testing with a TRISbuffered solution under static conditions works well with bioactive or with readily dissolving glasses, and it is easy to follow the ion dissolution reactions. However, in the buffered solution no marked differences between the more durable glasses were observed. The hydrolytic resistance of the glasses was studied using the standard procedure ISO 719. The relative scale given by the standard failed to provide any relevant information when bioactive glasses were studied. However, the clear differences in the hydrolytic resistance values imply that the method could be used as a rapid test to get an overall idea of the biodegradability of glasses. The standard method combined with the ion concentration and pH measurements gives a better estimate of the hydrolytic resistance because of the high silicon amount released from a glass. A sensitive on-line analysis method utilizing inductively coupled plasma optical emission spectrometer and a flow-through micro-volume pH electrode was developed to study the initial dissolution of biocompatible glasses. This approach was found suitable for compositions within a large range of chemical durability. With this approach, the initial dissolution of all ions could be measured simultaneously and quantitatively, which gave a good overall idea of the initial dissolution rates for the individual ions and the dissolution mechanism. These types of results with glass dissolution were presented for the first time during the course of writing this thesis. Based on the initial dissolution patterns obtained with the novel approach using TRIS, the experimental glasses could be divided into four distinct categories. The initial dissolution patterns of glasses correlated well with the anticipated bioactivity. Moreover, the normalized surface-specific mass loss rates and the different in vivo models and the actual in vivo data correlated well. The results suggest that this type of approach can be used for prescreening the suitability of novel glass compositions for future clinical applications. Furthermore, the results shed light on the possible bioactivity of glasses. An additional goal in this thesis was to gain insight into the phase changes occurring during various heat treatments of glasses with three selected compositions. Engineering-type T-T-T curves for glasses 1-98 and 13-93 were stablished. The information gained is essential in manufacturing amorphous porous implants or for drawing of continuous fibers of the glasses. Although both glasses can be hot worked to amorphous products at carefully controlled conditions, 1-98 showed one magnitude greater nucleation and crystal growth rate than 13-93. Thus, 13-93 is better suited than 1-98 for working processes which require long residence times at high temperatures. It was also shown that amorphous and partially crystalline porous implants can be sintered from bioactive glass S53P4. Surface crystallization of S53P4, forming Na2O∙CaO∙2SiO2, was observed to start at 650°C. The secondary crystals of Na2Ca4(PO4)2SiO4, reported for the first time in this thesis, were detected at higher temperatures, from 850°C to 1000°C. The crystal phases formed affected the dissolution behavior of the implants in simulated body fluid. This study opens up new possibilities for using S53P4 to manufacture various structures, while tailoring their bioactivity by controlling the proportions of the different phases. The results obtained in this thesis give valuable additional information and tools to the state of the art for designing glasses with respect to future clinical applications. With the knowledge gained we can identify different dissolution patters and use this information to improve the tuning of glass compositions. In addition, the novel online analysis approach provides an excellent opportunity to further enhance our knowledge of glass behavior in simulated body conditions.

Simulation of structural stress history based on dynamic analysis

Modern machine structures are often fabricated by welding. From a fatigue point of view, the structural details and especially, the welded details are the most prone to fatigue damage and failure. Design against fatigue requires information on the fatigue resistance of a structure’s critical details and the stress loads that act on each detail. Even though, dynamic simulation of flexible bodies is already current method for analyzing structures, obtaining the stress history of a structural detail during dynamic simulation is a challenging task; especially when the detail has a complex geometry. In particular, analyzing the stress history of every structural detail within a single finite element model can be overwhelming since the amount of nodal degrees of freedom needed in the model may require an impractical amount of computational effort. The purpose of computer simulation is to reduce amount of prototypes and speed up the product development process. Also, to take operator influence into account, real time models, i.e. simplified and computationally efficient models are required. This in turn, requires stress computation to be efficient if it will be performed during dynamic simulation. The research looks back at the theoretical background of multibody dynamic simulation and finite element method to find suitable parts to form a new approach for efficient stress calculation. This study proposes that, the problem of stress calculation during dynamic simulation can be greatly simplified by using a combination of floating frame of reference formulation with modal superposition and a sub-modeling approach. In practice, the proposed approach can be used to efficiently generate the relevant fatigue assessment stress history for a structural detail during or after dynamic simulation. In this work numerical examples are presented to demonstrate the proposed approach in practice. The results show that approach is applicable and can be used as proposed.

On Dynamic Monitoring Methods for Networks-on-Chip

Rapid ongoing evolution of multiprocessors will lead to systems with hundreds of processing cores integrated in a single chip. An emerging challenge is the implementation of reliable and efficient interconnection between these cores as well as other components in the systems. Network-on-Chip is an interconnection approach which is intended to solve the performance bottleneck caused by traditional, poorly scalable communication structures such as buses. However, a large on-chip network involves issues related to congestion problems and system control, for instance. Additionally, faults can cause problems in multiprocessor systems. These faults can be transient faults, permanent manufacturing faults, or they can appear due to aging. To solve the emerging traffic management, controllability issues and to maintain system operation regardless of faults a monitoring system is needed. The monitoring system should be dynamically applicable to various purposes and it should fully cover the system under observation. In a large multiprocessor the distances between components can be relatively long. Therefore, the system should be designed so that the amount of energy-inefficient long-distance communication is minimized. This thesis presents a dynamically clustered distributed monitoring structure. The monitoring is distributed so that no centralized control is required for basic tasks such as traffic management and task mapping. To enable extensive analysis of different Network-on-Chip architectures, an in-house SystemC based simulation environment was implemented. It allows transaction level analysis without time consuming circuit level implementations during early design phases of novel architectures and features. The presented analysis shows that the dynamically clustered monitoring structure can be efficiently utilized for traffic management in faulty and congested Network-on-Chip-based multiprocessor systems. The monitoring structure can be also successfully applied for task mapping purposes. Furthermore, the analysis shows that the presented in-house simulation environment is flexible and practical tool for extensive Network-on-Chip architecture analysis.