Influence of stationary phase and eluent properties on chromatographic separation of carbohydrates

In this thesis, the sorption and elastic properties of the cation-exchange resins were studied to explain the liquid chromatographic separation of carbohydrates. Na+, Ca2+ and La3+ form strong poly(styrene-co-divinylbenzene) (SCE) as well as Na+ and Ca2+ form weak acrylic (WCE) cation-exchange resins at different cross-link densities were treated within this work. The focus was on the effects of water-alcohol mixtures, mostly aqueous ethanol, and that of the carbohydrates. The carbohydrates examined were rhamnose, xylose, glucose, fructose, arabinose, sucrose, xylitol and sorbitol. In addition to linear chromatographic conditions, non-linear conditions more typical for industrial applications were studied. Both experimental and modeling aspectswere covered. The aqueous alcohol sorption on the cation-exchangers were experimentally determined and theoretically calculated. The sorption model includes elastic parameters, which were obtained from sorption data combined with elasticity measurements. As hydrophilic materials cation-exchangers are water selective and shrink when an organic solvent is added. At a certain deswelling degree the elastic resins go through glass transition and become as glass-like material. Theincreasing cross-link level and the valence of the counterion decrease the sorption of solvent components in the water-rich solutions. The cross-linkage or thecounterions have less effect on the water selectivity than the resin type or the used alcohol. The amount of water sorbed is higher in the WCE resin and, moreover, the WCE resin is more water selective than the corresponding SCE resin. Theincreased aliphatic part of lower alcohols tend to increase the water selectivity, i.e. the resins are more water selective in 2-propanol than in ethanol solutions. Both the sorption behavior of carbohydrates and the sorption differences between carbohydrates are considerably affected by the eluent composition and theresin characteristics. The carbohydrate sorption was experimentally examined and modeled. In all cases, sorption and moreover the separation of carbohydrates are dominated by three phenomena: partition, ligand exchange and size exclusion. The sorption of hydrophilic carbohydrates increases when alcohol is added into the eluent or when carbohydrate is able to form coordination complexes with the counterions, especially with multivalent counterions. Decreasing polarity of the eluent enhances the complex stability. Size exclusion effect is more prominent when the resin becomes tighter or carbohydrate size increases. On the other hand,the elution volumes between different sized carbohydrates decreases with the decreasing polarity of the eluent. The chromatographic separation of carbohydrateswas modeled, using rhamnose and xylose as target molecules. The thermodynamic sorption model was successfully implemented in the rate-based column model. The experimental chromatographic data were fitted by using only one adjustable parameter. In addition to the fitted data also simulated data were generated and utilized in explaining the effect of the eluent composition and of the resin characteristics on the carbohydrate separation.

A novel procedure for establishing clinching parameters for high strength steel sheet

The building industry has a particular interest in using clinching as a joining method for frame constructions of light-frame housing. Normally many clinch joints are required in joining of frames.In order to maximise the strength of the complete assembly, each clinch joint must be as sound as possible. Experimental testing is the main means of optimising a particular clinch joint. This includes shear strength testing and visual observation of joint cross-sections. The manufacturers of clinching equipment normally perform such experimental trials. Finite element analysis can also be used to optimise the tool geometry and the process parameter, X, which represents the thickness of the base of the joint. However, such procedures require dedicated software, a skilled operator, and test specimens in order to verify the finite element model. In addition, when using current technology several hours' computing time may be necessary. The objective of the study was to develop a simple calculation procedure for rapidly establishing an optimum value for the parameter X for a given tool combination. It should be possible to use the procedure on a daily basis, without stringent demands on the skill of the operator or the equipment. It is also desirable that the procedure would significantly decrease thenumber of shear strength tests required for verification. The experimental workinvolved tests in order to obtain an understanding of the behaviour of the sheets during clinching. The most notable observation concerned the stage of the process in which the upper sheet was initially bent, after which the deformation mechanism changed to shearing and elongation. The amount of deformation was measured relative to the original location of the upper sheet, and characterised as the C-measure. By understanding in detail the behaviour of the upper sheet, it waspossible to estimate a bending line function for the surface of the upper sheet. A procedure was developed, which makes it possible to estimate the process parameter X for each tool combination with a fixed die. The procedure is based on equating the volume of material on the punch side with the volume of the die. Detailed information concerning the behaviour of material on the punch side is required, assuming that the volume of die does not change during the process. The procedure was applied to shear strength testing of a sample material. The sample material was continuously hot-dip zinc-coated high-strength constructional steel,with a nominal thickness of 1.0 mm. The minimum Rp0.2 proof stress was 637 N/mm2. Such material has not yet been used extensively in light-frame housing, and little has been published on clinching of the material. The performance of the material is therefore of particular interest. Companies that use clinching on a daily basis stand to gain the greatest benefit from the procedure. By understanding the behaviour of sheets in different cases, it is possible to use data at an early stage for adjusting and optimising the process. In particular, the functionality of common tools can be increased since it is possible to characterise the complete range of existing tools. The study increases and broadens the amount ofbasic information concerning the clinching process. New approaches and points of view are presented and used for generating new knowledge.

Analytical Study on the Influence of Geometrical Parameters on the Fatigue Strength of Welds with Undercuts

The purpose of this study is to analyze the influence of geometric parameters on the fatigue strength of the welded joint. The thesis includes the analytical study pertaining to variation of undercut and the weld toe radius. The theoretical part includes the concepts of fracture mechanics, different stages of the crack propagation and finally the results. The numerical results are obtained from FRANC2D/L. The results show that the fatigue strength of the welded structure depends on the parameters of the welds such as the weld toe radius, weld angle, height of the undercut and plate thickness. The results show that the fatigue life can be improved by having the undercut as minimum as possible. However there has been significant variation on the fatigue life of the structure when the weld toe radius is increased.

The Optimization of Flotation Process Parameters in the Deinking Plant

Tämän diplomityön tavoitteena oli sekundäärisen esiflotaation optimointi Stora Enso Sachsen GmbH:n tehtaalla. Optimoinnin muuttujana käytettiin vaahdon määrää ja optimointiparametreinä ISO-vaaleutta, saantoja sekä tuhkapitoisuutta. Lisäksi tutkittiin flotaatiosakeuden vaikutusta myös muihin tehtaan flotaatioprosesseihin. Kirjallisuusosassa tarkasteltiin flotaatiotapahtumaa, poistettavien partikkeleiden ja ilmakuplien kontaktia, vaahdon muodostumista sekä tärkeimpiä käytössä olevia siistausflotaattoreiden laiteratkaisuja. Kokeellisessa osassa tutkittiin flotaatiosakeuden pienetämisen vaikutuksia tehtaan flotaatioprosesseihin tuhkapitoisuuden, ISO-vaaleuden, valon sironta- ja valon absorpiokerrointen kannalta. Sekundäärisen esiflotaation optimonti suoritettiin muuttamalla vaahdon määrää kolmella erilaisella injektorin koolla, (8 mm, 10 mm ja 13 mm), joista keskimmäinen kasvattaa 30 % massan tilavuusvirtaa ilmapitoisuuden muodossa. Optimonnin tarkoituksena oli kasvattaa hyväksytyn massajakeen ISO-vaaleutta, sekä kasvattaa kuitu- ja kokonaissaantoa sekundäärisessä esiflotaatiossa. Flotaatiosakeuden pienentämisellä oli edullisia vaikutuksia ISO-vaaleuteen ja valon sirontakertoimeen kussakin flotaatiossa. Tuhkapitoisuus pieneni sekundäärisissä flotaatioissa enemmän sakeuden ollessa pienempi, kun taas primäärisissä flotaatiossa vaikutus oli päinvastainen. Valon absorptiokerroin parani jälkiflotaatioissa alhaisemmalla sakeudella, kun taas esiflotaatioissa vaikutus oli päinvastainen. Sekundäärisen esiflotaation optimoinnin tuloksena oli lähes 5 % parempi ISO-vaaleus hyväksytyssä massajakeessa. Kokonaissaanto parani optimoinnin myötä 5 % ja kuitusaanto 2 %. Saantojen nousu tuottaa vuosittaisia säästöjä siistauslaitoksen tuotantokapasiteetin noustessa 0,5 %. Tämän lisäksi sekundäärisessä esiflotaatiossa rejektoituvan massavirran pienentyminen tuottaa lisäsäästöjä tehtaan voimalaitoksella.

Stock and Bond Market Integration: Evidence from Russian Financial Markets

Minimizing the risks of an investment portfolio but not in the favour of expected returns is one of the key interests of an investor. Typically, portfolio diversification is achieved using two main strategies: investing in different classes of assets thought to have little or negative correlations or investing in similar classes of assets in multiple markets through international diversification. This study investigates integration of the Russian financial markets in the time period of January 1, 2003 to December 28, 2007 using daily data. The aim is to test the intra-country and cross-country integration of the Russian stock and bond markets between seven countries. Our test methodology for the short-run dynamics testing is the vector autoregressive model (VAR) and for the long-run cointegration testing we use the Johansen cointegration test which is an extension to VAR. The empirical results of this study show that the Russian stock and bond markets are not integrated in the long-run either at intra-country or cross-country level which means that the markets are relatively segmented. The short-run dynamics are also relatively low. This implies a presence of potential gains from diversification.

Analysis of Earnings, Stock Prices and Bond Yields: The Fed Model Approach

Prediction of the stock market valuation is a common interest to all market participants. Theoretically sound market valuation can be achieved by discounting future earnings of equities to present. Competing valuation models seek to find variables that affect the equity market valuation in a way that the market valuation can be explained and also variables that could be used to predict market valuation. In this paper we test the contemporaneous relationship between stock prices, forward looking earnings and long-term government bond yields. We test this so-called Fed model in a long- and short-term time series analysis. In order to test the dynamics of the relationship, we use the cointegration framework. The data used in this study spans over four decades of various market conditions between 1964-2007, using data from United States. The empirical results of our analysis do not give support for the Fed model. We are able to show that the long-term government bonds do not play statistically significant role in this relationship. The effect of forward earnings yield on the stock market prices is significant and thus we suggest the use of standard valuation ratios when trying to predict the future paths of equity prices. Also, changes in the long-term government bond yields do not have significant short-term impact on stock prices.

Korkokäyrän estimointi Suomen aineistolla

Tutkimuksen tavoitteena on estimoida korkokäyrä Suomen aineistolla pe-riodeittain vuosille 2001–2007. Data koostuu Eonia- ja Euribor-korkojen sekä Suomen valtion joukkolainojen maturiteettituottojen poikkileikkaus aikasarjoista. Korkokäyrän estimointiin käytetään Svenssonin (1995) kehittämää laajennettua Nelson & Siegel -mallia. Kyseinen malli soveltui hyvin korkokäyrän estimointiin Suomen aineistolla. Lisäksi tutkimuksessa tarkastellaan Nelson & Siegel -mallin parametrien sopivuutta korkokäyrän ennustamiseen.

Flash Memory Cells Reliability Parameters Investigation

The present work is a part of the large project with purpose to qualify the Flash memory for automotive application using a standardized test and measurement flow. High memory reliability and data retention are the most critical parameters in this application. The current work covers the functional tests and data retention test. The purpose of the data retention test is to obtain the data retention parameters of the designed memory, i.e. the maximum time of information storage at specified conditions without critical charge leakage. For this purpose the charge leakage from the cells, which results in decrease of cells threshold voltage, was measured after a long-time hightemperature treatment at several temperatures. The amount of lost charge for each temperature was used to calculate the Arrhenius constant and activation energy for the discharge process. With this data, the discharge of the cells at different temperatures during long time can be predicted and the probability of data loss after years can be calculated. The memory chips, investigated in this work, were 0.035 μm CMOS Flash memory testchips, designed for further use in the Systems-on-Chips for automotive electronics.

Energy efficiency parameters in variable speed drives

The main purpose of this thesis is to measure and evaluate how accurately the current energy saving calculation in ABB’s new variable speed drive ACS850 works. The main topic of this thesis is energy-efficiency parameters. At the beginning of this thesis centrifugal pump, squirrel cage motor and variable speed drive, including some equations related to them, are being introduced. Also methods of throttling control and variable speed drive control of centrifugal pumps are being introduced. These subjects are introduced because the energy saving calculation in ACS850 is related to the centrifugal pumps usually driven by squirrel cage motors. The theory also includes short section about specific energy of pumping. Before measurements the current energy saving calculation of ACS850 is being introduced and analyzed. The measurements part includes introduction of measuring equipment, measurement results, summary and analysis of the measurements. At the end of this thesis a proposal for an improvement to the current energy saving calculation is being introduced and few proposals are made for new energy-efficiency parameters, which could be added to variable speed drives. At the end are also thoughts

On the effects of welding parameters on weld quality of plasma arc keyhole welding of structural steels

The possibility and the usefulness of applying plasma keyhole welding to structural steels with different compositions and material thicknesses, and in various welding positions has been examinated. Single pass butt welding with I groove in flat, horizontal vertical and vertical positions and root welding with V , Y and U grooves of thick plate material in flat position have been studied and the welds with high quality has been obtained. The technological conditions for successful welding are presented. The single and interactive effects of welding parameters on weld quality, especially on surface weld defects, geometrical form errors, internal defects and mechanical properties (strength, ductility, impact toughness, hardness and bendability) of weld joint, are presented. Welding parameter combinations providing the best quality welds are also presented.

The effects of real time control of welding parameters on weld quality in plasma arc keyhole welding

Joints intended for welding frequently show variations in geometry and position, for which it is unfortunately not possible to apply a single set of operating parameters to ensure constant quality. The cause of this difficulty lies in a number of factors, including inaccurate joint preparation and joint fit up, tack welds, as well as thermal distortion of the workpiece. In plasma arc keyhole welding of butt joints, deviations in the gap width may cause weld defects such as an incomplete weld bead, excessive penetration and burn through. Manual adjustment of welding parameters to compensate for variations in the gap width is very difficult, and unsatisfactory weld quality is often obtained. In this study a control system for plasma arc keyhole welding has been developed and used to study the effects of the real time control of welding parameters on gap tolerance during welding of austenitic stainless steel AISI 304L. The welding tests demonstrated the beneficial effect of real time control on weld quality. Compared with welding using constant parameters, the maximum tolerable gap width with an acceptable weld quality was 47% higher when using the real time controlled parameters for a plate thickness of 5 mm. In addition, burn through occurred with significantly larger gap widths when parameters were controlled in real time. Increased gap tolerance enables joints to be prepared and fit up less accurately, saving time and preparation costs for welding. In addition to the control system, a novel technique for back face monitoring is described in this study. The test results showed that the technique could be successfully applied for penetration monitoring when welding non magnetic materials. The results also imply that it is possible to measure the dimensions of the plasma efflux or weld root, and use this information in a feedback control system and, thus, maintain the required weld quality.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.