36 resultados para Structural and electronic properties


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In the present work are reported investigations of structural, magnetic and electronic properties of GaAs/Ga1-xInxAs/GaAs quantum wells (QW) having a 0.5 - 1.8 monolayer thick Mn layer, separated from the quantum well by a 3 nm thick spacer. The structure of the samples is analyzed in details by photoluminescence and high-resolution X-ray difractometry and reflectometry, confirming that Mn atoms are practically absent from the QW. Transport properties and crystal structure are analyzed for the first time for this type of QW structures with so high mobility. Observedconductivity and the Hall effect in quantizing magnetic fields in wide temperature range, defined by transport of holes in the quantum well, demonstrate properties inherent to ferromagnetic systems with spin polarization of charge carriersin the QW. Investigation of the Shubnikov ¿ de Haas and the Hall effects gave the possibility to estimate the energy band parameters such as cyclotron mass andFermi level and calculate concentrations and mobilities of holes and show the high-quality of structures. Magnetic ordering is confirmed by the existence of the anomalous Hall effect.

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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.

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Electrolyte solutions are of importance in a wide range of scientific contexts and as such have attracted considerable theoretical and experimental effort over many years. Nuclear Magnetic resonance provides a precise and versatile tool for investigation of electrolyte solutions, both in water and in organic solvents. Many structural and dynamic properties can be obtained through NMR experiments. The solution of aluminum chloride in water was studied. Different concentrations were taken for investigation. Independence of maximum line shift from concentration and acidity was shown. Six-coordinated structure of solvation shell was confirmed by experiments on 'H and 27A1 nuclei. Diffusion coefficients were studied. The solution of nickel chloride in methanol was studied. Lines, corresponding to coordinated and bulk methanol were found. Four-, five- and six-coordinated structures were found in different temperatures. The line for coordinated -OD group of deuterated methanol was observed on 2H spectrum for the first time. Partial deuteration of CH3 group was detected. Inability to observe coordinated -OH group was explained.

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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.

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Concentrated winding permanent magnet machines and their electromagnetic properties are studied in this doctoral thesis. The thesis includes a number of main tasks related to the application of permanent magnets in concentrated winding open slot machines. Suitable analytical methods are required for the first design calculations of a new machine. Concentrated winding machines differ from conventional integral slot winding machines in such a way that adapted analytical calculation methods are needed. A simple analytical model for calculating the concentrated winding axial flux machines is provided. The next three main design tasks are discussed in more detail in the thesis. The magnetic length of the rotor surface magnet machines is studied, and it is shown that the traditional methods have to be modified also in this respect. An important topic in this study has been to evaluate and minimize the rotor permanent magnet Joule losses by using segmented magnets in the calculations and experiments. Determination of the magnetizing and leakage inductances for a concentrated winding machine and the torque production capability of concentrated winding machines with different pole pair numbers are studied, and the results are compared with the corresponding properties of integral slot winding machines. The thesis introduces a new practical permanent magnet motor type for industrial use. The special features of the machine are based on the option of using concentrated winding open slot constructions of permanent magnet synchronous machines in the normal speed ranges of industrial motors, for instance up to 3000 min-1, without excessive rotor losses. By applying the analytical equations and methods introduced in the thesis, a 37 kW 2400 min-1 12-slot 10-pole axial flux machine with rotor-surfacemounted magnets is designed. The performance of the designed motor is determined by experimental measurements and finite element calculations.

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Kulttuuriset ja tekstuaaliset tekijät alluusioiden kääntämisessä ja tulkinnassa. Alluusiot Dorothy L. Sayersin 1940- ja 1980-luvuilla suomennetuissa salapoliisiromaaneissa Väitöskirja käsittelee alluusioiden kääntämistä ja tulkintaa. Alluusio on intertekstuaalinen viittaus, jonka tulkitsemiseen tarvitaan implisiittistä tietoa tutuksi oletetusta viittauskohteesta. Käännösongelma alluusiosta tulee, mikäli kohdekulttuurin lukijat eivät tunne viittauskohdetta eivätkä voi päätellä alluusion merkitystä. Tutkimus pyrkii kuitenkin uuden analyysimenetelmän avulla osoittamaan, että vieraat alluusiot eivät välttämättä johda tulkintaongelmiin. Väitöskirja jakautuu kahteen osaan: analyysimenetelmän kehittämiseen (luvut 1-5) sekä tapaustutkimukseen (luvut 6-7). Kehitetyn menetelmän avulla pystytään analysoimaan aikaisempaa tarkemmin, millaisia tulkintamahdollisuuksia alluusiot tarjoavat eri lukijakunnille ja miten lähdetekstin alluusioiden kulttuuriset ja tekstuaaliset piirteet korreloivat käännösstrategioiden kanssa. Tapaustutkimus selvittää, millaisia tulkintamahdollisuuksia Dorothy L. Sayersin 1940- ja 1980-luvuilla suomennettujen salapoliisiromaanien alluusiot tarjosivat aikansa suomalaisille lukijoille. Tavoitteena on myös hahmottaa, miten suomentajien käännösratkaisut ja alluusioiden tulkintamahdollisuudet liittyvät toisaalta lähdetekstin alluusioiden piirteisiin ja toisaalta kohdekulttuurin kontekstiin. Tapaustutkimus tarjoaa näin uutta tietoa suomennoskirjallisuuden ja salapoliisiromaanien historiasta. Analyysimenetelmä määrittelee aikaisempaa alluusioita ja intertekstuaalisuutta käsitelleen tutkimuksen pohjalta ne kulttuuriset ja tekstuaaliset piirteet, jotka vaikuttavat alluusioiden kääntämiseen ja tulkintaan. Kulttuurisessa mielessä alluusio voi olla tietylle lukijakunnalle tuttu tai tuntematon. Tekstuaalisia tekijöitä ovat alluusion muodon ja tyylin tunnusmerkillisyys sekä alluusion pintamerkityksen koherenttius uudessa tekstikontekstissa, ilman tietoa viittauskohteesta. Alluusioiden tulkinnassa on perinteisesti erotettu toisaalta allusiivinen tulkintamahdollisuus, jossa alluusio on lukijoille tuttu ja yhdistettävissä viittauskohteeseensa, toisaalta kulttuuritöyssy, jonka muodostaa lukijoille tuntematon ja pintamerkitykseltään inkoherentti alluusio. Tutkimuksessa määritellään kulttuuristen ja tekstuaalisten tekijöiden perusteella lisäksi kaksi muuta mahdollisuutta. Pseudo-allusiivisessa tulkinnassa tuntematon alluusio erottuu ympäröivästä tekstikontekstista tyyliltään ja on koherentti ainakin kuvaannollisessa mielessä ilman viittauskohdettaan. Ei-allusiivisessa tulkinnassa taas vieras alluusio sulautuu kontekstiin sekä muodoltaan että merkitykseltään niin, ettei lukija edes huomaa mahdollista alluusiota. Tulkintamahdollisuuksien jakauma antaa yleiskuvan siitä, miten tietty lukijakunta pystyi tulkitsemaan tekstin alluusioita. Lisäksi analyysi tarkastelee lähdetekstin ja käännöksen välillä tulkintamahdollisuuksissa tapahtuneita muutoksia sekä niiden vaikutusta tulkinnan vaatimaan vaivannäköön (effort) ja alluusion funktioihin. Tapaustutkimus perehtyy Sayers-suomennosten kulttuurikonteksteihin tarkastelemalla salapoliisiromaanien asemaa suomalaisessa kirjallisuusjärjestelmässä, suomennoksilta odotettuja piirteitä sekä suomentajien ammattikuvaa, taustoja ja työoloja. Tulosten perusteella alluusioiden kääntäminen oli vaativa tehtävä sekä 1940- että 1980-luvun suomentajille. Lähdetekstien alluusioista 60–70 prosenttia oli todennäköisesti kohdelukijoille vieraita. Molempina aikakausina suomennoksilta odotettiin silti sekä kielellistä sujuvuutta että lähdetekstin merkitysten välittämistä. 1940-luvun suomentajien tehtävää vaikeutti lisäksi mm. se, että suomentaminen oli enimmäkseen sivutoimista ja englanti oli harvoin parhaiten hallittu vieras kieli. Nämä olosuhteet lienevät vaikuttaneet etenkin vähäarvoisena pidetyn salapoliisikirjallisuuden suomennoksiin. 1980-luvulla suomentajien aikataulut olivat realistisempia, englannin taidot parempia ja päätoiminen suomentaminen mahdollista. Myös salapoliisiromaanien arvostus oli lisääntynyt. Sekä 1940- että 1980-luvun suomennoksissa kohdelukijoille vieraitakin alluusioita oli usein säilytetty, mikäli ne olivat koherentteja ilman viittauskohdettaan. Sen sijaan vieraita ja pintamerkitykseltään epäselviä alluusioita oli muokattu tai poistettu. Kuitenkin 1980-luvun suomentajat säilyttivät lähdetekstin alluusioita useammin ja tarkemmin kuin 1940-luvun suomentajat. Varsinkin poisjättämistä esiintyi 1940-luvun suomennoksissa enemmän. Alluusioiden tulkintamahdollisuudet olivat kaikissa käännöksissä muuttuneet sikäli, että melko harvat suomennetut alluusiot olivat enää kohdelukijoiden tunnistettavissa. Toisaalta myös kulttuuritöyssyt olivat harvinaisia. Erot 1940- ja 1980-luvun suomennosten välillä näkyivätkin pseudo-allusiivisissa ja ei-allusiivisissa tulkintamahdollisuuksissa. 1980-luvun suomennoksissa vieraat alluusiot oli johdonmukaisesti säilytetty niin, että käännetyt alluusiot voitiin tulkita pseudo-alluusioiksi. Sen sijaan 1940-luvun suomennoksissa vieraita alluusioita oli usein muokattu tai jätetty pois tavalla, joka johti ei-allusiiviseen tulkintaan. Kohdelukijoiden kannalta 1980-luvun suomennettujen alluusioiden tulkitseminen lienee vaatinut jonkin verran enemmän vaivaa. Toisaalta pseudo-allusiivisten käännösten pohjalta oli useimmiten mahdollista rakentaa koherentti tulkinta, ja monesti ne jopa välittivät samankaltaisia funktioita kuin lähdetekstin alluusiot. 1940-luvun suomennosten muokkaukset ja poistot periaatteessa helpottivat tulkintaa, mutta mahdollisia kulttuuritöyssyjä esiintyi edelleen, jopa kääntäjän tekemien muutosten seurauksena. 1940-luvun suomennoksissa myös käännettyjen alluusioiden funktiot olivat muuttuneet enemmän lähdetekstin alluusioihin nähden. Kaiken kaikkiaan 1980-luvun suomennokset olivat lähempänä oman aikansa hyvän käännöksen piirteitä. Toisaalta alluusioiden muokkaaminen sai 1940-luvun suomennokset muistuttamaan enemmän perinteistä arvoituksen ratkaisuun keskittyvää salapoliisiromaania, joten tältä osin ne lienevät vastanneet kohdelukijoiden odotuksia. Kulttuurikontekstin vaikutus siis näkyi sekä käännösstrategioissa että käännettyjen alluusioiden tulkintamahdollisuuksissa. Tutkimustuloksissa korostui kuitenkin myös se, että lähdetekstin alluusion pintamerkitys saattaa vaikuttaa käännösratkaisuihin. Lisäksi käännetyt pseudo-alluusiot saattavat välittää samankaltaisia funktioita kuin lähdetekstin alluusiot. Toisin kuin yleensä on esitetty, kohdelukijoille vieraiden alluusioiden säilyttäminen saattaakin siis olla toimiva ratkaisu.

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Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

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Background: Atherosclerosis begins in early life progressing from asymptomatic to symptomatic as we age. Although substantial progress has been made in identifying the determinants of atherosclerosis in middle to older age adults at increased cardiovascular risk, there is lack of data examining determinants and prediction of atherosclerosis in young adults. Aims: The current study was designed to investigate levels of cardiovascular risk factors in young adults, subclinical measures of atherosclerosis, and prediction of subclinical arterial changes with conventional risk factor measures and novel metabolic profiling of serum samples. Subjects and Methods: This thesis utilised data from the follow-ups performed in 2001 and 2007 in the Cardiovascular Risk in Young Finns study, a Finnish population-based prospective cohort study that examined 2,204 subjects who were aged 30-45 years in 2007. Subclinical atherosclerosis was studied using noninvasive ultrasound measurements of carotid intima-media thickness (IMT), carotid arterial distensibility (CDist) and brachial flow-mediated dilation (FMD). Measurements included conventional risk factors and metabolic profiling using highthroughput nuclear magnetic resonance (NMR) methods that provided data on 42 lipid markers and 16 circulating metabolites. Results: Trends in lipids were favourable between 2001 and 2007, whereas waist circumference, fasting glucose, and blood pressure levels increased. To study the stability of noninvasive ultrasound markers, 6-year tracking (the likelihood to maintain the original fractile over time) in 6 years was examined. IMT tracked more strongly than CDist and FMD. Cardiovascular risk scores (Framingham, SCORE, Finrisk, Reynolds and PROCAM) predicted subclinical atherosclerosis equally. Lipoprotein subclass testing did not improve the prediction of subclinical atherosclerosis over and above conventional risk factors. However, circulating metabolites improved risk stratification. Tyrosine and docosahexaenoic acid were found to be novel biomarkers of high IMT. Conclusions: Prediction of cardiovascular risk in young Finnish adults can be performed with any of the existing risk scores. The addition of metabonomics to risk stratification improves prediction of subclinical changes and enables more accurate targeting of prevention at an early stage.

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Hen eggs and oats (Avena Sativa) are important materials for the food industry. Today, instead of merely satisfying the feeling of hunger, consumers are asking for healthier, biologically active and environmentally friendly products. The growing awareness of consumers’ increasing demands presents a great challenge to the food industry to develop more sustainable products and utilise modern and effective techniques. The modification of yolk fatty acid composition by means of feed supplements is well understood. Egg yolk phospholipids are polar lipids and are used in several applications including food, cosmetics, pharmaceuticals, and special nutrients. Egg yolk phospholipids are excellent emulsifiers, typically sold as mixtures of phospholipids, triacylglycerols, and cholesterol. However, highly purified and characterised phospholipids are needed in several sophisticated applications. Industrial fractionation of phospholipids is usually based on organic solvents. With these fractionation techniques, some harmful residues of organic solvents may cause problems in further processing. The objective of the present study was to investigate the methods to improve the functional properties of eggs, to develop techniques to isolate the fractions responsible for the specific functional properties of egg yolk lipids, and to apply the developed techniques to plant-based materials, too. Fractionation techniques based on supercritical fluids were utilised for the separation of the lipid fractions of eggs and oats. The chemical and functional characterisation of the fractions were performed, and the produced oat polar lipid fractions were tested as protective barrier in encapsulation processes. Modifying the fatty acid compositions of egg yolks with different types of oil supplements in feed had no affect on their functional or sensory properties. Based on the results of functional and sensory analysis, it is evident that eggs with modified fatty acid compositions are usable in several industrial applications. These applications include liquid egg yolk products used in mayonnaise and salad dressings. Egg yolk powders were utilised in different kinds of fractionation processes. The precipitation method developed in this study resembles the supercritical anti-solvent method, which is typically used in the pharmaceutical industry. With pilot scale supercritical fluid processes, non-polar lipids and polar lipids were successfully separated from commercially produced egg yolk powder and oat flakes. The egg and oat-based polar lipid fractions showed high purities, and the corresponding delipidated fractions produced using supercritical techniques offer interesting starting materials for the further production of bioactive compounds. The oat polar lipid fraction contained especially digalactosyadiacylglycerol, which was shown to have valuable functional properties in the encapsulation of probiotics.

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In this work mathematical programming models for structural and operational optimisation of energy systems are developed and applied to a selection of energy technology problems. The studied cases are taken from industrial processes and from large regional energy distribution systems. The models are based on Mixed Integer Linear Programming (MILP), Mixed Integer Non-Linear Programming (MINLP) and on a hybrid approach of a combination of Non-Linear Programming (NLP) and Genetic Algorithms (GA). The optimisation of the structure and operation of energy systems in urban regions is treated in the work. Firstly, distributed energy systems (DES) with different energy conversion units and annual variations of consumer heating and electricity demands are considered. Secondly, district cooling systems (DCS) with cooling demands for a large number of consumers are studied, with respect to a long term planning perspective regarding to given predictions of the consumer cooling demand development in a region. The work comprises also the development of applications for heat recovery systems (HRS), where paper machine dryer section HRS is taken as an illustrative example. The heat sources in these systems are moist air streams. Models are developed for different types of equipment price functions. The approach is based on partitioning of the overall temperature range of the system into a number of temperature intervals in order to take into account the strong nonlinearities due to condensation in the heat recovery exchangers. The influence of parameter variations on the solutions of heat recovery systems is analysed firstly by varying cost factors and secondly by varying process parameters. Point-optimal solutions by a fixed parameter approach are compared to robust solutions with given parameter variation ranges. In the work enhanced utilisation of excess heat in heat recovery systems with impingement drying, electricity generation with low grade excess heat and the use of absorption heat transformers to elevate a stream temperature above the excess heat temperature are also studied.