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.

Application of Computational Fluid Dynamics in Modeling Blood Flow in Human Thoracic Aorta

The aim of this study was to simulate blood flow in thoracic human aorta and understand the role of flow dynamics in the initialization and localization of atherosclerotic plaque in human thoracic aorta. The blood flow dynamics in idealized and realistic models of human thoracic aorta were numerically simulated in three idealized and two realistic thoracic aorta models. The idealized models of thoracic aorta were reconstructed with measurements available from literature, and the realistic models of thoracic aorta were constructed by image processing Computed Tomographic (CT) images. The CT images were made available by South Karelia Central Hospital in Lappeenranta. The reconstruction of thoracic aorta consisted of operations, such as contrast adjustment, image segmentations, and 3D surface rendering. Additional design operations were performed to make the aorta model compatible for the numerical method based computer code. The image processing and design operations were performed with specialized medical image processing software. Pulsatile pressure and velocity boundary conditions were deployed as inlet boundary conditions. The blood flow was assumed homogeneous and incompressible. The blood was assumed to be a Newtonian fluid. The simulations with idealized models of thoracic aorta were carried out with Finite Element Method based computer code, while the simulations with realistic models of thoracic aorta were carried out with Finite Volume Method based computer code. Simulations were carried out for four cardiac cycles. The distribution of flow, pressure and Wall Shear Stress (WSS) observed during the fourth cardiac cycle were extensively analyzed. The aim of carrying out the simulations with idealized model was to get an estimate of flow dynamics in a realistic aorta model. The motive behind the choice of three aorta models with distinct features was to understand the dependence of flow dynamics on aorta anatomy. Highly disturbed and nonuniform distribution of velocity and WSS was observed in aortic arch, near brachiocephalic, left common artery, and left subclavian artery. On the other hand, the WSS profiles at the roots of branches show significant differences with geometry variation of aorta and branches. The comparison of instantaneous WSS profiles revealed that the model with straight branching arteries had relatively lower WSS compared to that in the aorta model with curved branches. In addition to this, significant differences were observed in the spatial and temporal profiles of WSS, flow, and pressure. The study with idealized model was extended to study blood flow in thoracic aorta under the effects of hypertension and hypotension. One of the idealized aorta models was modified along with the boundary conditions to mimic the thoracic aorta under the effects of hypertension and hypotension. The results of simulations with realistic models extracted from CT scans demonstrated more realistic flow dynamics than that in the idealized models. During systole, the velocity in ascending aorta was skewed towards the outer wall of aortic arch. The flow develops secondary flow patterns as it moves downstream towards aortic arch. Unlike idealized models, the distribution of flow was nonplanar and heavily guided by the artery anatomy. Flow cavitation was observed in the aorta model which was imaged giving longer branches. This could not be properly observed in the model with imaging containing a shorter length for aortic branches. The flow circulation was also observed in the inner wall of the aortic arch. However, during the diastole, the flow profiles were almost flat and regular due the acceleration of flow at the inlet. The flow profiles were weakly turbulent during the flow reversal. The complex flow patterns caused a non-uniform distribution of WSS. High WSS was distributed at the junction of branches and aortic arch. Low WSS was distributed at the proximal part of the junction, while intermedium WSS was distributed in the distal part of the junction. The pulsatile nature of the inflow caused oscillating WSS at the branch entry region and inner curvature of aortic arch. Based on the WSS distribution in the realistic model, one of the aorta models was altered to induce artificial atherosclerotic plaque at the branch entry region and inner curvature of aortic arch. Atherosclerotic plaque causing 50% blockage of lumen was introduced in brachiocephalic artery, common carotid artery, left subclavian artery, and aortic arch. The aim of this part of the study was first to study the effect of stenosis on flow and WSS distribution, understand the effect of shape of atherosclerotic plaque on flow and WSS distribution, and finally to investigate the effect of lumen blockage severity on flow and WSS distributions. The results revealed that the distribution of WSS is significantly affected by plaque with mere 50% stenosis. The asymmetric shape of stenosis causes higher WSS in branching arteries than in the cases with symmetric plaque. The flow dynamics within thoracic aorta models has been extensively studied and reported here. The effects of pressure and arterial anatomy on the flow dynamic were investigated. The distribution of complex flow and WSS is correlated with the localization of atherosclerosis. With the available results we can conclude that the thoracic aorta, with complex anatomy is the most vulnerable artery for the localization and development of atherosclerosis. The flow dynamics and arterial anatomy play a role in the localization of atherosclerosis. The patient specific image based models can be used to diagnose the locations in the aorta vulnerable to the development of arterial diseases such as atherosclerosis.

Auger-type granular fertylizer distributor: matemathical model and dynamic simulation

The objective of this study was to model mathematically and to simulate the dynamic behavior of an auger-type fertilizer applicator (AFA) in order to use the variable-rate application (VRA) and reduce the coefficient of variation (CV) of the application, proposing an angular speed controller θ' for the motor drive shaft. The input model was θ' and the response was the fertilizer mass flow, due to the construction, density of fertilizer, fill factor and the end position of the auger. The model was used to simulate a control system in open loop, with an electric drive for AFA using an armature voltage (V A) controller. By introducing a sinusoidal excitation signal in V A with amplitude and delay phase optimized and varying θ' during an operation cycle, it is obtained a reduction of 29.8% in the CV (constant V A) to 11.4%. The development of the mathematical model was a first step towards the introduction of electric drive systems and closed loop control for the implementation of AFA with low CV in VRA.

Influence of data acquisition geometry on soybean spectral response simulated by the prosail model

View angle and directional effects significantly affect reflectance and vegetation indices, especially when daily images collected by large field-of-view (FOV) sensors like the Moderate Resolution Imaging Spectroradiometer (MODIS) are used. In this study, the PROSAIL radiative transfer model was chosen to evaluate the impact of the geometry of data acquisition on soybean reflectance and two vegetation indices (Normalized Difference Vegetation Index - NDVI and Enhanced Vegetation Index -EVI) by varying biochemical and biophysical parameters of the crop. Input values for PROSAIL simulation were based on the literature and were adjusted by the comparison between simulated and real satellite soybean spectra acquired by the MODIS/Terra and hyperspectral Hyperion/Earth Observing-One (EO-1). Results showed that the influence of the view angle and view direction on reflectance was stronger with decreasing leaf area index (LAI) and chlorophyll concentration. Because of the greater dependence on the near-infrared reflectance, the EVI was much more sensitive to viewing geometry than NDVI presenting larger values in the backscattering direction. The contrary was observed for NDVI in the forward scattering direction. In relation to the LAI, NDVI was much more isotropic for closed soybean canopies than for incomplete canopies and a contrary behavior was verified for EVI.

Influence of distance, geometry and number of control stations on quality of local geodetic networks for the purpose of georeferencing of rural properties

The implementation of local geodetic networks for georeferencing of rural properties has become a requirement after publication of the Georeferencing Technical Standard by INCRA. According to this standard, the maximum distance of baselines to GNSS L1 receivers is of 20 km. Besides the length of the baseline, the geometry and the number of geodetic control stations are other factors to be considered in the implementation of geodetic networks. Thus, this research aimed to examine the influence of baseline lengths higher than the regulated limit of 20 km, the geometry and the number of control stations on quality of local geodetic networks for georeferencing, and also to demonstrate the importance of using specific tests to evaluate the solution of ambiguities and on the quality of the adjustment. The results indicated that the increasing number of control stations has improved the quality of the network, the geometry has not influenced on the quality and the baseline length has influenced on the quality; however, lengths higher than 20 km has not interrupted the implementation, with GPS L1 receiver, of the local geodetic network for the purpose of georeferencing. Also, the use of different statistical tests, both for the evaluation of the resolution of ambiguities and for the adjustment, have enabled greater clearness in analyzing the results, which allow that unsuitable observations may be eliminated.

Dynamic Hedging with Credit Default Swaps: Empirical Evidence from the European Monetary Union

This thesis investigates the effectiveness of time-varying hedging during the financial crisis of 2007 and the European Debt Crisis of 2010. In addition, the seven test economies are part of the European Monetary Union and these countries are in different economical states. Time-varying hedge ratio was constructed using conditional variances and correlations, which were created by using multivariate GARCH models. Here we have used three different underlying portfolios: national equity markets, government bond markets and the combination of these two. These underlying portfolios were hedged by using credit default swaps. Empirical part includes the in-sample and out-of-sample analysis, which are constructed by using constant and dynamic models. Moreover, almost in every case dynamic models outperform the constant ones in the determination of the hedge ratio. We could not find any statistically significant evidence to support the use of asymmetric dynamic conditional correlation model. In addition, our findings are in line with prior literature and support the use of time-varying hedge ratio. Finally, we found that in some cases credit default swaps are not suitable instruments for hedging and they act more as a speculative instrument.

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 multibody dynamic model of the cross-country ski-skating technique

The objective of this thesis is the development of a multibody dynamic model matching the observed movements of the lower limb of a skier performing the skating technique in cross-country style. During the construction of this model, the formulation of the equation of motion was made using the Euler - Lagrange approach with multipliers applied to a multibody system in three dimensions. The description of the lower limb of the skate skier and the ski was completed by employing three bodies, one representing the ski, and two representing the natural movements of the leg of the skier. The resultant system has 13 joint constraints due to the interconnection of the bodies, and four prescribed kinematic constraints to account for the movements of the leg, leaving the amount of degrees of freedom equal to one. The push-off force exerted by the skate skier was taken directly from measurements made on-site in the ski tunnel at the Vuokatti facilities (Finland) and was input into the model as a continuous function. Then, the resultant velocities and movement of the ski, center of mass of the skier, and variation of the skating angle were studied to understand the response of the model to the variation of important parameters of the skate technique. This allowed a comparison of the model results with the real movement of the skier. Further developments can be made to this model to better approximate the results to the real movement of the leg. One can achieve this by changing the constraints to include the behavior of the real leg joints and muscle actuation. As mentioned in the introduction of this thesis, a multibody dynamic model can be used to provide relevant information to ski designers and to obtain optimized results of the given variables, which athletes can use to improve their performance.

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.

Development of racemization catalysts for dynamic kinetic resolution

Preparation of optically active compounds is of high importance in modern medicinal chemistry. Despite recent advances in the field of asymmetric synthesis, resolution of racemates still remains the most utilized way for preparation of single enantiomers in industrial scale due to its cost-efficiency and simplicity. Enzymatic kinetic resolution (KR) of racemates is a classical method for separation of enantiomers. One of its drawbacks is the limitation of target enantiomer yield to 50%. Dynamic Kinetic Resolution (DKR) allows to reach yields up to 100% by in situ racemization of the less reactive enantiomer. In the first part of this thesis, a number of half-sandwich ruthenium complexes were prepared and evaluated as catalysts for racemization of optically active secondary alcohols. A leading catalyst, Bn5CpRu(CO)2Cl, was identified. The catalyst discovered was extensively characterized by its application for DKR of a broad range of secondary alcohols in a wide range of reaction loadings (1 mmol – 1 mol). Cost-efficient chromatography-free procedure for preparation of this catalyst was developed. Further, detailed kinetic and mechanistic studies of the racemization reactions were performed. Comparison of racemization rates in the presence of Bn5CpRu(CO)2Cl and Ph5CpRu(CO)2Cl catalysts reveals that the performance of the catalytic system can be adjusted by matching of the electronic properties of the catalysts and the substrates. Moreover, dependence of the rate-limiting step from the electronic properties of the reagents was observed. Important conclusions about reaction mechanism were made. Finally, an alternative approach to DKR of amines based on space separated vessels was addressed. This procedure allows the combination of thermolabile enzyme with racemization catalysts active only at high temperatures.

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.

Treatment of ununited anconeal process in 8 dogs by osteotomy and dynamic distraction of the proximal part of the ulna

A surgical technique for the treatment of ununited anconeal process in dogs treated by osteotomy and dynamic distraction of the proximal part of the ulna using a linear external skeletal fixator was evaluated. In all cases the osteotomy was distracted 1mm each day after the surgery until desired distraction had been achieved. Eight dogs and 9 joints diagnosed with ununited anconeal process were treated. The success of the procedure was determined by comparing clinical signs of lameness and degree of arthrosis at the time of diagnosis to 6 months after the surgical intervention. Radiographic union occurred in 88.9% of the affected joints between 21 and 42 days after the surgical procedure. Clinically, six elbows were classified as good, two as satisfactory and one as unsatisfactory. Six months after surgery two elbows had no arthrosis, one had Grade 1, two Grade 2 and one Grade 3. It is concluded the combination of ulnar osteotomy and dynamic distraction of the olecranon by a linear external skeletal fixator is a feasible procedure for the treatment of ununited anconeal process in dogs.

Characterisation of Laser Beam and Paper Material Interaction

It is known already from 1970´s that laser beam is suitable for processing paper materials. In this thesis, term paper materials mean all wood-fibre based materials, like dried pulp, copy paper, newspaper, cardboard, corrugated board, tissue paper etc. Accordingly, laser processing in this thesis means all laser treatments resulting material removal, like cutting, partial cutting, marking, creasing, perforation etc. that can be used to process paper materials. Laser technology provides many advantages for processing of paper materials: non-contact method, freedom of processing geometry, reliable technology for non-stop production etc. Especially packaging industry is very promising area for laser processing applications. However, there are only few industrial laser processing applications worldwide even in beginning of 2010´s. One reason for small-scale use of lasers in paper material manufacturing is that there is a shortage of published research and scientific articles. Another problem, restraining the use of laser for processing of paper materials, is colouration of paper material i.e. the yellowish and/or greyish colour of cut edge appearing during cutting or after cutting. These are the main reasons for selecting the topic of this thesis to concern characterization of interaction of laser beam and paper materials. This study was carried out in Laboratory of Laser Processing at Lappeenranta University of Technology (Finland). Laser equipment used in this study was TRUMPF TLF 2700 carbon dioxide laser that produces a beam with wavelength of 10.6 μm with power range of 190-2500 W (laser power on work piece). Study of laser beam and paper material interaction was carried out by treating dried kraft pulp (grammage of 67 g m-2) with different laser power levels, focal plane postion settings and interaction times. Interaction between laser beam and dried kraft pulp was detected with different monitoring devices, i.e. spectrometer, pyrometer and active illumination imaging system. This way it was possible to create an input and output parameter diagram and to study the effects of input and output parameters in this thesis. When interaction phenomena are understood also process development can be carried out and even new innovations developed. Fulfilling the lack of information on interaction phenomena can assist in the way of lasers for wider use of technology in paper making and converting industry. It was concluded in this thesis that interaction of laser beam and paper material has two mechanisms that are dependent on focal plane position range. Assumed interaction mechanism B appears in range of average focal plane position of 3.4 mm and 2.4 mm and assumed interaction mechanism A in range of average focal plane position of 0.4 mm and -0.6 mm both in used experimental set up. Focal plane position 1.4 mm represents midzone of these two mechanisms. Holes during laser beam and paper material interaction are formed gradually: first small hole is formed to interaction area in the centre of laser beam cross-section and after that, as function of interaction time, hole expands, until interaction between laser beam and dried kraft pulp is ended. By the image analysis it can be seen that in beginning of laser beam and dried kraft pulp material interaction small holes off very good quality are formed. It is obvious that black colour and heat affected zone appear as function of interaction time. This reveals that there still are different interaction phases within interaction mechanisms A and B. These interaction phases appear as function of time and also as function of peak intensity of laser beam. Limit peak intensity is the value that divides interaction mechanism A and B from one-phase interaction into dual-phase interaction. So all peak intensity values under limit peak intensity belong to MAOM (interaction mechanism A one-phase mode) or to MBOM (interaction mechanism B onephase mode) and values over that belong to MADM (interaction mechanism A dual-phase mode) or to MBDM (interaction mechanism B dual-phase mode). Decomposition process of cellulose is evolution of hydrocarbons when temperature is between 380- 500°C. This means that long cellulose molecule is split into smaller volatile hydrocarbons in this temperature range. As temperature increases, decomposition process of cellulose molecule changes. In range of 700-900°C, cellulose molecule is mainly decomposed into H2 gas; this is why this range is called evolution of hydrogen. Interaction in this range starts (as in range of MAOM and MBOM), when a small good quality hole is formed. This is due to “direct evaporation” of pulp via decomposition process of evolution of hydrogen. And this can be seen can be seen in spectrometer as high intensity peak of yellow light (in range of 588-589 nm) which refers to temperature of ~1750ºC. Pyrometer does not detect this high intensity peak since it is not able to detect physical phase change from solid kraft pulp to gaseous compounds. As interaction time between laser beam and dried kraft pulp continues, hypothesis is that three auto ignition processes occurs. Auto ignition of substance is the lowest temperature in which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. Three auto ignition processes appears in range of MADM and MBDM, namely: 1. temperature of auto ignition of hydrogen atom (H2) is 500ºC, 2. temperature of auto ignition of carbon monoxide molecule (CO) is 609ºC and 3. temperature of auto ignition of carbon atom (C) is 700ºC. These three auto ignition processes leads to formation of plasma plume which has strong emission of radiation in range of visible light. Formation of this plasma plume can be seen as increase of intensity in wavelength range of ~475-652 nm. Pyrometer shows maximum temperature just after this ignition. This plasma plume is assumed to scatter laser beam so that it interacts with larger area of dried kraft pulp than what is actual area of beam cross-section. This assumed scattering reduces also peak intensity. So result shows that assumably scattered light with low peak intensity is interacting with large area of hole edges and due to low peak intensity this interaction happens in low temperature. So interaction between laser beam and dried kraft pulp turns from evolution of hydrogen to evolution of hydrocarbons. This leads to black colour of hole edges.