Suojakaasuseoksen koostumuksen vaikutus CO2-laser-MAG-hybridihitsauksessa

Hitsaavassa teollisuudessa kilpailukyvyn säilyttäminen edellyttää hitsauksen tehokkuuden nostoa. Niinpä metalliteollisuus etsii kuumeisesti uusia yhä tehokkaampia hitsausmenetelmiä. CO2-laserin ja MAG:in yhdistelmän muodostamalla hybridihitsauksella saadaan aikaan syvä tunkeuma kuten laserhitsauksessa, mutta sallitaan laserhitsausta väljemmät railotoleranssit. Samalla muodonmuutokset vähenevät huomattavasti verrattuna perinteiseen kaarihitsaukseen. Kaariavusteisessa laserhitsauksessa yhdistetään laserhitsaukseen perinteinen kaarihitsaus eli MIG/MAG-, TIG- tai plasmahitsaus. Menetelmää voidaan kutsua myös hybridihitsaukseksi ja sillä hyödynnetään molempien prosessien edut välttyen yksittäisten prosessien haitoilta. Prosessin haittapuolena on parametrien suuri määrä, joka on rajoittanut menetelmän käyttöönottoa. Diplomityössä tutkittiin suojakaasuseoksen koostumuksen vaikutusta rakenneteräksen CO2-laser-MAG-hybridihitsauksessa. Laserhitsauksen ja MAG-hitsauksen suojakaasuvirtaukset yhdistettiin siten, että heliumseosteinen suojakaasu tuotiin MAG-polttimen kaasukuvun kautta. Suojakaasun heliumpitoisuus nostettiin niin korkeaksi, että estettiin laserhitsauksen muodostaman plasman syntyminen. Samalla hitsauskokeissa opittiin paremmin ymmärtämään prosessia ja sen parametrien riippuvuutta toisiinsa. Tutkitut suojakaasuseokset koostuivat heliumista, argonista ja hiilidioksidista. Hitsauskokeiden perusteella havaittiin, että suojakaasuseoksen optimaalinen heliumpitoisuus on 40-50 %. Tällöin laserin tunkeumaa häiritsevää plasmapilveä ei synny ja prosessi on stabiili. Päittäisliitosten hitsauksessa suojakaasuseoksen 2 %:n CO2-pitoisuudella saadaan aikaan hyvin vähän huokosia sisältävä hitsi, jonka tunkeumaprofiilin muoto ja liittymä perusaineeseen on juoheva. Pienaliitoksilla 7 %:n CO2-pitoisuudella prosessi pysyy stabiilina ja vähäroiskeisena. Tunkeuma hieman levenee hitsin keskeltä ja hitsin liittyminen perusaineeseen on juoheva.CO2-laser-MAG-hybridihitsauksella aikaansaadaan laadukkaita hitsejä taloudellisesti, mikäli käytetyt parametrit ovat oikein valittuja. Parametrit on sovitettava jokaiseen hitsaustapaukseen erikseen, eikä niitä välttämättä voida suoraan käyttää toisessa tapauksessa.

Kylmämuokatun austeniittisen ruostumattoman teräsputkipalkin hitsaus

Diplomityön tavoitteena on selvittää kylmälujitetusta austeniittisesta ruostumattomasta teräksestä valmistettavan putkipalkin pituussuunnassa hitsaamalla tapahtuvaa valmistusta. Työssä tarkastellaan eri hitsausprosessien lämmöntuonnin ja putkipalkin kylmämuovaamalla tapahtuvan valmistuksen ja hitsin jälkikäsittelynvaikutuksia putkipalkin pituushitsin mekaanisiin ominaisuuksiin. Teoriaosassa on perehdytty austeniittisen ruostumattoman teräksen hitsaukseen, kylmämuokkaamalla lujitetun teräksen käyttäytymiseen hitsauksessa, monipoltinkaari-, TIG-suurtaajuuspulssi- ja kaariavusteiseen laserhitsaukseen. Kokeellisessa osassaon suoritettu koehitsauksia edellä mainituilla menetelmillä kylmälujitetulle austeniittiselle ruostumattomalle teräkselle ja suoritettu saatujen koehitsien mekaanisien ominaisuuksien arviointia. Saatujen koetulosten perusteella ontodettu, että huolimatta hitsauksen lämmöntuonnin kylmämuokatun teräksen lujuusarvoja alentavasta vaikutuksesta on mahdollista valmistaa hitsin osalta perusaineen lujuusluokituksen täyttäviä putkipalkkeja. Tämä johtuu putkipalkin kylmämuovaamalla tapahtuvan valmistuksen ja hitsin jälkikäsittelyn hitsauksessa pehmentyneen vyöhykkeen lujuusarvoja takaisin perusaineen tasolle palauttavasta vaikutuksesta.

Intensification of hemicellulose hot-water extraction from spruce wood by parameter tuning

The growing population on earth along with diminishing fossil deposits and the climate change debate calls out for a better utilization of renewable, bio-based materials. In a biorefinery perspective, the renewable biomass is converted into many different products such as fuels, chemicals, and materials, quite similar to the petroleum refinery industry. Since forests cover about one third of the land surface on earth, ligno-cellulosic biomass is the most abundant renewable resource available. The natural first step in a biorefinery is separation and isolation of the different compounds the biomass is comprised of. The major components in wood are cellulose, hemicellulose, and lignin, all of which can be made into various end-products. Today, focus normally lies on utilizing only one component, e.g., the cellulose in the Kraft pulping process. It would be highly desirable to utilize all the different compounds, both from an economical and environmental point of view. The separation process should therefore be optimized. Hemicelluloses can partly be extracted with hot-water prior to pulping. Depending in the severity of the extraction, the hemicelluloses are degraded to various degrees. In order to be able to choose from a variety of different end-products, the hemicelluloses should be as intact as possible after the extraction. The main focus of this work has been on preserving the hemicellulose molar mass throughout the extraction at a high yield by actively controlling the extraction pH at the high temperatures used. Since it has not been possible to measure pH during an extraction due to the high temperatures, the extraction pH has remained a “black box”. Therefore, a high-temperature in-line pH measuring system was developed, validated, and tested for hot-water wood extractions. One crucial step in the measurements is calibration, therefore extensive efforts was put on developing a reliable calibration procedure. Initial extractions with wood showed that the actual extraction pH was ~0.35 pH units higher than previously believed. The measuring system was also equipped with a controller connected to a pump. With this addition it was possible to control the extraction to any desired pH set point. When the pH dropped below the set point, the controller started pumping in alkali and by that the desired set point was maintained very accurately. Analyses of the extracted hemicelluloses showed that less hemicelluloses were extracted at higher pH but with a higher molar-mass. Monomer formation could, at a certain pH level, be completely inhibited. Increasing the temperature, but maintaining a specific pH set point, would speed up the extraction without degrading the molar-mass of the hemicelluloses and thereby intensifying the extraction. The diffusion of the dissolved hemicelluloses from the wood particle is a major part of the extraction process. Therefore, a particle size study ranging from 0.5 mm wood particles to industrial size wood chips was conducted to investigate the internal mass transfer of the hemicelluloses. Unsurprisingly, it showed that hemicelluloses were extracted faster from smaller wood particles than larger although it did not seem to have a substantial effect on the average molar mass of the extracted hemicelluloses. However, smaller particle sizes require more energy to manufacture and thus increases the economic cost. Since bark comprises 10 – 15 % of a tree, it is important to also consider it in a biorefinery concept. Spruce inner and outer bark was hot-water extracted separately to investigate the possibility to isolate the bark hemicelluloses. It was showed that the bark hemicelluloses comprised mostly of pectic material and differed considerably from the wood hemicelluloses. The bark hemicelluloses, or pectins, could be extracted at lower temperatures than the wood hemicelluloses. A chemical characterization, done separately on inner and outer bark, showed that inner bark contained over 10 % stilbene glucosides that could be extracted already at 100 °C with aqueous acetone.

Simplified sample handing in mass spectrometry based protein research - focus on protein phosphorylation

The human genome comprises roughly 20 000 protein coding genes. Proteins are the building material for cells and tissues, and proteins are functional compounds having an important role in many cellular responses, such as cell signalling. In multicellular organisms such as humans, cells need to communicate with each other in order to maintain a normal function of the tissues within the body. This complex signalling between and within cells is transferred by proteins and their post-translational modifications, one of the most important being phosphorylation. The work presented here concerns the development and use of tools for phosphorylation analysis. Mass spectrometers have become essential tools to study proteins and proteomes. In mass spectrometry oriented proteomics, proteins can be identified and their post-translational modifications can be studied. In this Ph.D. thesis the objectives were to improve the robustness of sample handling methods prior to mass spectrometry analysis for peptides and their phosphorylation status. The focus was to develop strategies that enable acquisition of more MS measurements per sample, higher quality MS spectra and simplified and rapid enrichment procedures for phosphopeptides. Furthermore, an objective was to apply these methods to characterize phosphorylation sites of phosphopeptides. In these studies a new MALDI matrix was developed which allowed more homogenous, intense and durable signals to be acquired when compared to traditional CHCA matrix. This new matrix along with other matrices was subsequently used to develop a new method that combines multiple spectra from different matrises from identical peptides. With this approach it was possible to identify more phosphopeptides than with conventional LC/ESI-MS/MS methods, and to use 5 times less sample. Also, phosphopeptide affinity MALDI target was prepared to capture and immobilise phosphopeptides from a standard peptide mixture while maintaining their spatial orientation. In addition a new protocol utilizing commercially available conductive glass slides was developed that enabled fast and sensitive phosphopeptide purification. This protocol was applied to characterize the in vivo phosphorylation of a signalling protein, NFATc1. Evidence for 12 phosphorylation sites were found, and many of those were found in multiply phosphorylated peptides

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.