Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.

Suurnopeuskuvaustekniikan soveltaminen hitsausvalokaaren tutkimuksessa

Työn tavoitteena oli suurnopeuskuvaustekniikan ottaminen osaksi Kemppi Oy:n tuotekehitystä. Työn teoriaosa sisältää hitsausvalokaaren ja lisäaineensiirtymisen teoriaa,sekä perehtymisen suurnopeuskuvaustekniikkaan ja siihen vaadittaviin laitteistoihin. Teoriassa tarkastellaan myös MIG/MAG -päittäisliitoksen olemassa oleviin pohjapalon hitsausprosesseihin. Kokeellisen osan tuloksena syntyi suurnopeuskuvaustekniikkaan pohjautuva tutkimusmenetelmä. Rakennetulla järjestelmällä nähtiin hyvin teoriassa esitetyt MIG/MAG -hitsauksen kaarityypit ja lisäaineensiirtymisen muodot. Kuvattuja tuloksia kyettiin analysoimaan ja vertaamaan teoriaan. Päittäisliitoksen pohjapalon hitsaukseen soveltuvan prosessin kehitys oli osa käytännön osuutta. Tehdyillä kuvauksilla onnistuttiin havainnoimaan kehitetyn valokaaren ja aineensiirtymisen ilmiöitä. Näiden ymmärtäminen helpottui kuvauksien ansiosta ja tämä nopeutti ja mahdollisti tuotekehitystyötä. Tuloksena valmistui uusi pulssitettu lyhytkaariprosessi. Työn tuloksena syntyi uusi suurnopeuskuvaustekniikkaan nojautuva tuotekehitysprosessi, jossa uusi tekniikka kyetään liittämäänosaksi tutkimus- ja kehitystyötä. Tuloksia voidaan käyttää myös markkinoinnin ja myynnin edistämiseen.

Value added logistics in supply and demand chains. Smile. Part 1. eBusiness between global company and itslocal sme supplier network

VALOSADE (Value Added Logistics in Supply and Demand Chains) is the research project of Anita Lukka's VALORE (Value Added Logistics Research) research team inLappeenranta University of Technology. VALOSADE is included in ELO (Ebusiness logistics) technology program of Tekes (Finnish Technology Agency). SMILE (SME-sector, Internet applications and Logistical Efficiency) is one of four subprojects of VALOSADE. SMILE research focuses on case network that is composed of small and medium sized mechanical maintenance service providers and global wood processing customers. Basic principle of SMILE study is communication and ebusiness insupply and demand network. This first phase of research concentrates on creating backgrounds for SMILE study and for ebusiness solutions of maintenance case network. The focus is on general trends of ebusiness in supply chains and networksof different industries; total ebusiness system architecture of company networks; ebusiness strategy of company network; information value chain; different factors, which influence on ebusiness solution of company network; and the correlation between ebusiness and competitive advantage. Literature, interviews and benchmarking were used as research methods in this qualitative case study. Networks and end-to-end supply chains are the organizational structures, which can add value for end customer. Information is one of the key factors in these decentralized structures. Because of decentralization of business, information is produced and used in different companies and in different information systems. Information refinement services are needed to manage information flows in company networksbetween different systems. Furthermore, some new solutions like network information systems are utilised in optimising network performance and in standardizingnetwork common processes. Some cases have however indicated, that utilization of ebusiness in decentralized business model is not always a necessity, but value-add of ICT must be defined case-specifically. In the theory part of report, different ebusiness and architecture models are introduced. These models are compared to empirical case data in research results. The biggest difference between theory and empirical data is that models are mainly developed for large-scale companies - not for SMEs. This is due to that implemented network ebusiness solutions are mainly large company centered. Genuine SME network centred ebusiness models are quite rare, and the study in that area has been few in number. Business relationships between customer and their SME suppliers are nowadays concentrated more on collaborative tactical and strategic initiatives besides transaction based operational initiatives. However, ebusiness systems are further mainly based on exchange of operational transactional data. Collaborative ebusiness solutions are in planning or pilot phase in most case companies. Furthermore, many ebusiness solutions are nowadays between two participants, but network and end-to-end supply chain transparency and information systems are quite rare. Transaction volumes, data formats, the types of exchanged information, information criticality,type and duration of business relationship, internal information systems of partners, processes and operation models (e.g. different ordering models) differ among network companies, and furthermore companies are at different stages on networking and ebusiness readiness. Because of former factors, different customer-supplier combinations in network must utilise totally different ebusiness architectures, technologies, systems and standards.

Value added logistics in supply and demand chain. Smile. Part 2. eBusiness in a service business. Case: A maintenance and operations network in forest industry

VVALOSADE is a research project of professor Anita Lukka's VALORE research team in the Lappeenranta University of Technology. The VALOSADE includes the ELO technology program of Tekes. SMILE is one of four subprojects of the VALOSADE. The SMILE study focuses on the case of the company network that is composed of small and micro-sized mechanical maintenance service providers and forest industry as large-scale customers. The basic principle of the SMILE study is the communication and ebusiness in supply and demand networks. The aim of the study is to develop ebusiness strategy, ebusiness model and e-processes among the SME local service providers, and onthe other hand, between the local service provider network and the forest industry customers in a maintenance and operations service business. A literature review, interviews and benchmarking are used as research methods in this qualitative case study. The first SMILE report, 'Ebusiness between Global Company and Its Local SME Supplier Network', concentrated on creating background for the SMILE study by studying general trends of ebusiness in supply chains and networks of different industries. This second phase of the study concentrates on case network background, such as business relationships, information systems and business objectives; core processes in maintenance and operations service network; development needs in communication among the network participants; and ICT solutions to respond needs in changing environment. In the theory part of the report, different ebusiness models and frameworks are introduced. Those models and frameworks are compared to empirical case data. From that analysis of the empirical data, therecommendations for the development of the network information system are derived. In process industry such as the forest industry, it is crucial to achieve a high level of operational efficiency and reliability, which sets up great requirements for maintenance and operations. Therefore, partnerships or strategic alliances are needed between the network participants. In partnerships and alliances, deep communication is important, and therefore the information systems in the network also are critical. Communication, coordination and collaboration will increase in the case network in the future, because network resources must be optimised to improve competitive capability of the forest industry customers and theefficiency of their service providers. At present, ebusiness systems are not usual in this maintenance network. A network information system among the forest industry customers and their local service providers actually is the only genuinenetwork information system in this total network. However, the utilisation of that system has been quite insignificant. The current system does not add value enough either to the customers or to the local service providers. At present, thenetwork information system is the infomediary that share static information forthe network partners. The network information system should be the transaction intermediary, which integrates internal processes of the network companies; the network information system, which provides common standardised processes for thelocal service providers; and the infomediary, which share static and dynamic information on right time, on right partner, on right costs, on right format and on right quality. This study provides recommendations how to develop this system in the future to add value to the network companies. Ebusiness scenarios, vision, objectives, strategies, application architecture, ebusiness model, core processes and development strategy must be considered when the network information system will be developed in the next development step. The core processes in the case network are demand/capacity management, customer/supplier relationship management, service delivery management, knowledge management and cash flow management. Most benefits from ebusiness solutions come from the electrifying of operational level processes, such as service delivery management and cash flow management.

Investigation of interaction between native and impurity defects in ZnSe

Zinc selenide is a prospective material for optoelectronics. The fabrication of ZnSe­based light-emitting diodes is hindered by complexity of p-type doping of the component materials. The interaction between native and impurity defects, the tendency of doping impurity to form associative centres with native defects and the tendency to self-compensation are the main factors impeding effective control of the value and type of conductivity. The thesis is devoted to the study of the processes of interaction between native and impurity defects in zinc selenide. It is established that the Au impurity has the most prominent amphoteric properties in ZnSe among Cu, Ag and Au impurities, as it forms a great number of both Au; donors and Auz„ acceptors. Electrical measurements show that Ag and Au ions introduced into vacant sites of the Zn sublattice form simple single-charged Agz„+ and Auzn+ states with d1° electron configuration, while Cu ions can form both single-charged Cuz„ (d1) and double-charged Cuzr`+ (d`o) centres. Amphoteric properties of Ag and Au transition metals stimulated by time are found for the first time from both electrical and luminescent measurements. A model that explains the changes in electrical and luminescent parameters by displacement of Ag ions into interstitial sites due to lattice deformation forces is proposed. Formation of an Ag;-donor impurity band in ZnSe samples doped with Ag and stored at room temperature is also studied. Thus, the properties of the doped samples are modified due to large lattice relaxation during aging. This fact should be taken into account in optoelectronic applications of doped ZnSe and related compounds.

Fiber-reinforced Composite as Oral Implant Material. Experimental studies of glass fiber and bioactive glass in vitro and in vivo

Fiber-reinforced composite as oral implant material: Experimental studies of glass fiber and bioactive glass in vitro and in vivo Department of Prosthetic Dentistry and Biomaterials Science, Institute of Dentistry, University of Turku, Turku, Finland 2008. Biocompatibility and mechanical properties are important variables that need to be determined when new materials are considered for medical implants. Special emphasis was placed on these characteristics in the present work, which aimed to investigate the potential of fiber-reinforced composite (FRC) material as an oral implant. Furthermore, the purpose of this study was to explore the effect of bioactive glass (BAG) on osseointegration of FRC implants. The biocompatibility and mechanical properties of FRC implants were studied both in vitro and in vivo. The mechanical properties of the bulk FRC implant were tested with a cantilever bending test, torsional test and push-out test. The biocompatibility was first evaluated with osteoblast cells cultured on FRC substrates. Bone bonding was determined with the mechanical push-out test and histological as well as histomorplanimetric evaluation. Implant surface was characterized with SEM and EDS analysis. The results of these studies showed that FRC implants can withstand the static load values comparably to titanium. Threaded FRC implants had significantly higher push-out strength than the threaded titanium implants. Cell culture study revealed no cytotoxic effect of FRC materials on the osteoblast-like-cells. Addition of BAG particles enhanced cell proliferation and mineralization of the FRC substrates The in vivo study showed that FRC implants can withstand static loading until failure without fracture. The results also suggest that the FRC implant is biocompatible in bone. The biological behavior of FRC was comparable to that of titanium after 4 and 12 weeks of implantation. Furthermore, addition of BAG to FRC implant increases peri-implant osteogenesis and bone maturation.

Lämpötilamuutosten vaikutukset metallien liimaliitoksiin

Diplomityön tavoitteena oli tutkia lämpötilan ja sen muutosten vaikutusta kahden metallin tai metallin ja magneetin väliseen liimaliitokseen. Tutkimuksen päätavoitteena oli tutkia magneettien liimaukseen käytetyn akryyliliiman lujuutta lämpösyklitysten jälkeen ja eri käyttölämpötilojen seurauksena. Teoriaosassa on käsitelty erilaisia liimauksen toteutukseen ja liimaliitoksen lujuuteen vaikuttavia tekijöitä. Erilaiset metallien liimaukseen soveltuvat liimatyypit ja niiden tarttumiseen liittyvät tekijät, kuten esikäsittelyt on myös käyty läpi teoriaosassa. Myös liiman- ja liimatyypin valintaa koskevia periaatteita ja tekniikoita on käsitelty. Käytännön osassa on esitelty koejärjestelyt sekä tutkittavat materiaalit ja niille suoritetut esikäsittelyt. Käytännön kokeissa suoritettavissa liimaliitoksissa käytettiin akryyli- ja silikoniliimoja, joille suoritettiin erilaisia vetokokeita. Akryyliliimalla liimatuille liitoksille suoritettiin myös lämpösyklityksiä, joita vertailtiin käsittelemättömiin liitoksiin. Magneettien ja metallien välisten liitosten lujuuden lisäksi liimalta saavutettavia lujuuksia arvioitiin rakenneterästen välisen liimaliitoksen sisältävillä vetosauvoilla. Suoritettujen kokeiden perusteella havaittiin lämpötilan vaikuttavan radikaalisesti liimaliitosten lujuuteen. Magneettien liimaliitoksilla saavutettiin käytännön sovellukseen riittävän suuria leikkauslujuuden arvoja vain huoneenlämpötilassa vedettäessä. Lämpösyklitysten todettiin myös heikentävän liitosta selvästi. Silikoniliiman lujuus oli alle sovelluskohteessa vaikuttavien voimien optimaalisissakin olosuhteissa. Metallien välisten liimaliitosten lujuuden todettiin heikentyvän nopeasti kasvatettaessa vetokokeissa käytettyä lämpötilaa. Liitoksen heikkenemistä havaittiin myös lämpötilaa laskettaessa.

Performance of high power fibre laser cutting of thick-section steel and mediumsection aluminium

Cutting of thick section stainless steel and mild steel, and medium section aluminium using the high power ytterbium fibre laser has been experimentally investigated in this study. Theoretical models of the laser power requirement for cutting of a metal workpiece and the melt removal rate were also developed. The calculated laser power requirement was correlated to the laser power used for the cutting of 10 mm stainless steel workpiece and 15 mm mild steel workpiece using the ytterbium fibre laser and the CO2 laser. Nitrogen assist gas was used for cutting of stainless steel and oxygen was used for mild steel cutting. It was found that the incident laser power required for cutting at a given cutting speed was lower for fibre laser cutting than for CO2 laser cutting indicating a higher absorptivity of the fibre laser beam by the workpiece and higher melting efficiency for the fibre laser beam than for the CO2 laser beam. The difficulty in achieving an efficient melt removal during high speed cutting of the 15 mmmild steel workpiece with oxygen assist gas using the ytterbium fibre laser can be attributed to the high melting efficiency of the ytterbium fibre laser. The calculated melt flow velocity and melt film thickness correlated well with the location of the boundary layer separation point on the 10 mm stainless steel cut edges. An increase in the melt film thickness caused by deceleration of the melt particles in the boundary layer by the viscous shear forces results in the flow separation. The melt flow velocity increases with an increase in assist gas pressure and cut kerf width resulting in a reduction in the melt film thickness and the boundary layer separation point moves closer to the bottom cut edge. The cut edge quality was examined by visual inspection of the cut samples and measurement of the cut kerf width, boundary layer separation point, cut edge squareness (perpendicularity) deviation, and cut edge surface roughness as output quality factors. Different regions of cut edge quality in 10 mm stainless steel and 4 mm aluminium workpieces were defined for different combinations of cutting speed and laserpower.Optimization of processing parameters for a high cut edge quality in 10 mmstainless steel was demonstrated

Biogeochemistry in acid sulphate soil landscapes and small urban centres in Western Finland

The overall purpose of this thesis was to increase the knowledge on the biogeochemistry of rural acid sulphate (AS) soil environments and urban forest ecosystems near small towns in Western Finland. In addition, the potential causal relationship between the distribution of AS soils and geographical occurence of multiple sclerosis (MS) disease was assessed based on a review of existing literature and data. Acid sulphate soils, which occupy an area of approximately 17–24 million hectare worldwide, are regarded as the nastiest soils in the world. Independent of the geographical locality of these soils, they pose a great threat to their surrounding environment if disturbed. The abundant metal-rich acid drainage from Finnish AS soils, which is a result of sulphide oxidation due to artificial farmland drainage, has significant but spatially and temporally variable ecotoxicological impacts on biodiversity and community structure of fish, benthic invertebrates and macrophytes. This has resulted in mass fish kills and even eradication of sensitive fish species in affected waters. Moreover, previous investigations demonstrated significantly enriched concentrations of Co, Ni, Mn and Al, metals which are abundantly mobilised in AS soils, in agricultural crops (timothy grass and oats) and approximately 50 times higher concentrations of Al in cow milk originating from AS soils in Western Finland. Nevertheless, the results presented here demonstrate, in general, relatively moderate metal concentrations in oats and cabbage grown on AS soils in Western Finland, although some of the studied fields showed anomalous values of metals (e.g. Co and Ni) in both the soil and target plants (especially oats), similar to that of the previous investigations. The results indicated that the concentrations of Co, Ni, Mn and Zn in oats and Co and Zn in cabbage were governed by soil geochemistry as these metals were correlated with corresponding concentrations extracted from the soil by NH4Ac-EDTA and NH4Ac, respectively. The concentrations of Cu and Fe in oats and cabbage were uncorrelated to that of the easily soluble concentrations in the soils, suggesting that biological processes (e.g. plant-root processes) overshadow geochemical variation. The concentrations of K and Mg in cabbage, which showed a low spread and were strongly correlated to the NH4Ac extractable contents in the soil, were governed by both the bioavailable fractions in the topsoil and plant-uptake mechanisms. The plant´s ability to regulate its uptake of Ca and P (e.g. through root exudates) seemed to be more important than the influence of soil geochemistry. The distribution of P, K, Ca, Mg, Mn and S within humus, moss and needles in and around small towns was to a high degree controlled by biological cycling, which was indicated by the low correlation coefficients for P, K, Ca, Mg and S between humus and moss, and the low spread of these nutrients in moss and needles. The concentration variations of elements in till are mainly due to natural processes (e.g. intrusions, weathering, mineralogical variations in the bedrock). There was a strong spatial pattern for B in humus, moss and needles, which was suggested to be associated with anthropogenic emissions from nearby town centres. Geogenic dust affected the spatial distribution of Fe and Cr in moss, while natural processes governed the Fe anomaly found in the needles. The spatial accumulation patterns of Zn, Cd, Cu, Ni and Pb in humus and moss were strong and diverse, and related to current industry, the former steel industry, coal combustion, and natural geochemical processes. An intriguing Cu anomaly was found in moss. Since it was located close to a main railway line and because the railway line´s electric cables are made of Cu, it was suggested that the reason for the Cu anomaly is corrosion of these cables. In Western Finland, where AS soils are particularly abundant and enrich the metal concentrations of stream waters, cow milk and to some extent crops, an environmental risk assessment would be motivated to elucidate if the metal dispersion affect human health. Within this context, a topic of concern is the distribution of multiple sclerosis as high MS prevalence rates are found in the main area of AS soils. Regionally, the AS soil type in the Seinäjoki area has been demonstrated to be very severe in terms of metal leaching, this area also shows one of the highest MS rates reported worldwide. On a local scale, these severe AS soil types coincide well with the corresponding MS clustering along the Kyrönjoki River in Seinäjoki. There are reasons to suspect that these spatial correlations are causal, as multiple sclerosis has been suggested to result from a combination of genetic and environmental factors.

DPS-Like Peroxide Resistance Protein: Structural and Functional Studies on a Versatile Nanocontainer

Oxidative stress is a constant threat to almost all organisms. It damages a number of biomolecules and leads to the disruption of many crucial cellular functions. It is caused by reactive oxygen species (ROS), such as hydrogen peroxide (H2O₂), superoxide (•O₂ -), and hydroxyl radical (•OH). The most harmful of these compounds is •OH, which is only formed in cells in the presence of redox-cycling transition metals, such as iron and copper. Bacteria have developed a number of mechanisms to cope with ROS. One of the most widespread means employed by bacteria is the DNA-binding proteins from starved cells (Dps). Dps proteins protect the cells by binding and oxidizing Fe2+, thus greatly reducing the production of •OH. The oxidized iron is stored inside the protein as an iron core. In addition, Dps proteins bind directly to DNA forming a protective coating that shields DNA from harmful agents. Moreover, Dps proteins have been found to elicit other protective functions in cells and to participate in bacterial virulence. Dps proteins are of special importance to Streptococci owing to the lack of catalase in this genus of bacteria.This study was focused on structural and functional characterization of streptococcal Dpslike peroxide resistance (Dpr) proteins. Initially, crystal structures of Streptococcus pyogenes Dpr were determined. The data confirmed the presence of a di-metal ferroxidase center (FOC) in Dpr proteins and revealed the presence of a novel N-terminal helix as well as a surface metal-binding site. The crystal structures of Streptococcus suis Dpr complexed with transition metals demonstrated the metal specificity of the FOC. Solution binding studies also indicated the presence of a di-metal FOC. These results suggested a possible role for Dpr in the detoxification of various metals. Iron was found to mineralize inside the protein as ferrihydrite based on X-ray absorption spectroscopy data. The iron core was found to exhibit clear superparamagnetic behaviour using magnetic and Mössbauer measurements. The results from this study are expected to further increase our understanding on the binding, oxidation, and mineralization of iron and other metals in Dpr proteins. In particular, the structural and magnetic properties of the iron core can form a basis for potential new applications in nanotechnology. From the streptococcal viewpoint, the results would help in understanding better the complicated picture of bacterial pathogenesis. Dpr proteins may also provide a novel target for drug design due to their tight involvement in bacterial virulence.

Corrosion behaviour of boiler tube materials during combustion of fuels containing Zn and Pb

Många förbränningsanläggningar som bränner utmanande bränslen såsom restfraktioner och avfall råkar ut för problem med ökad korrosion på överhettare och/eller vattenväggar pga. komponenter i bränslena som är korrosiva. För att minimera problemen i avfallseldade pannor hålls ångparametrarna på en relativt låg nivå, vilket drastiskt minskar energiproduktionen. Beläggningarna i avfallseldade pannor består till största delen av element som är förknippade med högtemperaturkorrosion: Cl, S, alkalimetaller, främst K och Na, och tungmetaller som Pb och Zn, och det finns också indikationer av Br-förekomst. Det låga ångtrycket i avfallseldade pannor påverkar också stålrörens temperatur i pannväggarna i eldstaden. I dagens läge hålls temperaturen normalt vid 300-400 °C. Alkalikloridorsakad (KCl, NaCl) högtemperaturkorrosion har inte rapporterats vara relevant vid såpass låga temperaturer, men närvaro av Zn- och Pb-komponenter i beläggningarna har påvisats förorsaka ökad korrosion redan vid 300-400 °C. Vid förbränning kan Zn och Pb reagera med S och Cl och bilda klorider och sulfater i rökgaserna. Dessa tungmetallföreningar är speciellt problematiska pga. de bildar lågsmältande saltblandningar. Dessa lågsmältande gasformiga eller fasta föreningar följer rökgasen och kan sedan fastna eller kondensera på kallare ytor på pannväggar eller överhettare för att sedan bilda aggressiva beläggningar. Tungmetallrika (Pb, Zn) klorider och sulfater ökar risken för korrosion, och effekten förstärks ytterligare vid närvaro av smälta. Motivet med den här studien var att få en bättre insikt i högtemperaturkorrosion förorsakad av Zn och Pb, samt att undersöka och prediktera beteendet och motståndskraften hos några stålkvaliteter som används i överhettare och pannväggar i tungmetallrika förhållanden och höga materialtemperaturer. Omfattande laboratorie-, småskale- och fullskaletest utfördes. Resultaten kan direkt utnyttjas i praktiska applikationer, t.ex. vid materialval, eller vid utveckling av korrosionsmotverkande verktyg för att hitta initierande faktorer och förstå deras effekt på högtemperaturkorrosion.

Laser-TIG–hybridihitsauksen soveltuvuustutkimus

Tässä tutkimuksessa selvitetään ilman hitsauslisäainetta tapahtuvan laser–TIG–hybridihitsausprosessin soveltuvuus 6 mm ja 8 mm paksujen päittäisliitettyjen S355 K2 ja Laser 355 MC rakenneterästen hitsaukseen. Hitsien tarkastelussa huomio kiinnitetään hitsausnopeuteen, hitsien tunkeumaan, liittämistehokkuuteen, hitsien kovuuteen ja hitsausliitoksen ulkonäköön. Muita tutkittavia asioita ovat laser-TIG-hybridihitsattujen levyjen muodonmuutokset ja suuresta hitsausnopeudesta sekä pienestä t8/5 jäähtymisajasta johtuvat mahdolliset kylmähalkeamat. Laser-TIG-hybridihitsejä verrataan robotti-MAG- ja käsin MAG-hitseihin sekä kaarihitsausstandardin SFS-EN ISO 5817 hitsiluokkien mukaisiin raja-arvoihin. Laser-TIG-hybridihitsausprosessissa TIG-valokaari mahdollistaa tasaisen ja lähes roiskeettoman hitsin ja lasersäde aikaansaa syvän tunkeuman sekä tasalaatuisen juurihitsin. Laser-TIG-hybridihitsausprosessilla 6 mm paksut S355 K2 rakenneteräslevyt on mahdollista hitsata levyn yhdeltä puolelta kerralla valmiiksi. Paksummat 8 mm levyt voidaan hitsata levyn yhdeltä tai molemmilta puolilta suoritettavalla laser-TIG-hybridihitsauksella. Laser-TIG-hybridihitsausprosessilla hitsatut hitsit ovat hyvin siistejä ja lähes roiskeettomia. Verrattaessa laser-TIG-hybridihitsausprosessia muihin hitsausprosesseihin sen voidaan todeta olevan erittäin kilpailukykyinen 6 mm paksujen päittäisliitettyjen rakenneterästen hitsaamisessa, mutta se soveltuu myös 8 mm paksujen rakenneterästen hitsaamiseen. Tutkitut hitsit täyttävät kaarihitsausstandardin SFS-EN ISO 5817 B- ja D-hitsiluokkien mukaiset raja-arvot. Vertailukokeet 6 mm paksulla S355 rakenneteräksellä osoittavat, että yhdeltä puolelta suoritettavan laser-TIG-hybridihitsauksen hitsausnopeus on robotti-MAG-hitsaukseen verrattuna yli nelinkertainen ja MAG-käsinhitsaukseen verrattuna yli viisinkertainen. Laser-TIG-hybridihitsauksessa liittämistehokkuus on noin viisinkertainen robotti-MAGhitsaukseen verrattuna. Molemmilta puolilta suoritettavalla laser-TIG-hybridihitsauksella voidaan 8 mm paksulla S355 rakenneteräksellä saavuttaa noin kolminkertainen hitsausnopeus ja liittämistehokkuus robotti-MAG-hitsaukseen verrattuna. Laser-TIG-hybridihitsauksessa TIG-kaaren tuoman lisälämmön ansiosta suurillakin hitsausnopeuksilla (1 m/min) voidaan saavuttaa edulliset kovuusarvot. Kovuusmittausten tulosten perusteella 6 mm ja 8 mm paksujen S355 K2 ja Laser 355 MC rakenneterästen hitsit eivät ylittäneet kaarihitsausstandardin määrittelemää 350 HV kovuuden enimmäisrajaa. Laser-TIG-hybridihitsauksen edullisesta lämmöntuonnista johtuen levyjen pituus- ja poikittaissuuntaiset muodonmuutokset ovat noin 80 prosenttia pienemmät kuin käsin suoritettavassa MAG-hitsauksessa. Laser-TIG-hybridihitsausprosessilla käytetään I-railoa, mutta robotti-MAG- ja käsin MAG-hitsausprosesseilla joudutaan käyttämään V-railoa, jolloin lämmöntuonti ja siitä johtuvat muodonmuutokset ovat suuremmat. Korkea liittämistehokkuus ja edullinen lämmöntuonti merkitsevät vähäisempiä muodonmuutoksia ja siten merkittäviä säästöjä työ-, materiaali- ja energiakustannuksissa. 8 mm ja sitä paksummilla S355 rakenneteräksillä levyn yhdeltä puolelta suoritettava päittäisliitoksen hitsaaminen on laser-TIG hybridihitsauksella haastavaa, koska yli 200 A:n TIG-kaarivirralla suuri metallisula aiheuttaa avaimenreiän sulkeutumisen ja avaimenreiän alaosaan muodostuu kaasukuplia. Tästä voidaan tehdä sellainen johtopäätös, että päittäisliitettävien levyjen ilmarakoa pitäisi kasvattaa niin suureksi, että avaimenreiän sulavirtaus ei pääse estymään. Yli 0,25 mm:n ilmarako edellyttää lasersäteen vaaputusta tai säteen halkaisijan kasvattamista. Ilmaraon kasvattaminen edellyttää myös lisäaineen käyttöä. Tutkimustulosten perusteella laser-TIG-hybridihitsausprosessilla voidaan saavuttaa merkittäviä etuja ja kustannussäästöjä, joten sen hyödyntämistä kannattaa harkita 8 mm ja sitä ohuempien päittäisliitettävien tuotteiden konepaja- ja tehdastuotannossa. Laser-TIGhybridihitsausprosessi soveltuu esimerkiksi seuraavien tuotteiden hitsaamiseen: päittäisliitettävät levyt, palkit, koneenosat, putket, säiliöt ja erilaiset pyörähdyskappaleet.

Factors predicting mortality in type 2 diabetes. With special reference to physical exercise, blood pressure, proteinuria, inflammation and P wave duration

Background: Type 2 diabetes patients have a 2-4 fold risk of cardiovascular disease (CVD) compared to the general population. In type 2 diabetes, several CVD risk factors have been identified, including obesity, hypertension, hyperglycemia, proteinuria, sedentary lifestyle and dyslipidemia. Although much of the excess CVD risk can be attributed to these risk factors, a significant proportion is still unknown. Aims: To assess in middle-aged type 2 diabetic subjects the joint relations of several conventional and non-conventional CVD risk factors with respect to cardiovascular and total mortality. Subjects and methods: This thesis is part of a large prospective, population based East-West type 2 diabetes study that was launched in 1982-1984. It includes 1,059 middle-aged (45-64 years old) participants. At baseline, a thorough clinical examination and laboratory measurements were performed and an ECG was recorded. The latest follow-up study was performed 18 years later in January 2001 (when the subjects were 63-81 years old). The study endpoints were total mortality and mortality due to CVD, coronary heart disease (CHD) and stroke. Results: Physically more active patients had significantly reduced total, CVD and CHD mortality independent of high-sensitivity C-reactive protein (hs-CRP) levels unless proteinuria was present. Among physically active patients with a hs-CRP level >3 mg/L, the prognosis of CVD mortality was similar to patients with hs-CRP levels ≤3 mg/L. The worst prognosis was among physically inactive patients with hs-CRP levels >3 mg/L. Physically active patients with proteinuria had significantly increased total and CVD mortality by multivariate analyses. After adjustment for confounding factors, patients with proteinuria and a systolic BP <130 mmHg had a significant increase in total and CVD mortality compared to those with a systolic BP between 130 and 160 mmHg. The prognosis was similar in patients with a systolic BP <130 mmHg and ≥160 mmHg. Among patients without proteinuria, a systolic BP <130 mmHg was associated with a non-significant reduction in mortality. A P wave duration ≥114 ms was associated with a 2.5-fold increase in stroke mortality among patients with prevalent CHD or claudication. This finding persisted in multivariable analyses. Among patients with no comorbidities, there was no relationship between P wave duration and stroke mortality. Conclusions: Physical activity reduces total and CVD mortality in patients with type 2 diabetes without proteinuria or with elevated levels of hs-CRP, suggesting that the anti-inflammatory effect of physical activity can counteract increased CVD morbidity and mortality associated with a high CRP level. In patients with proteinuria the protective effect was not, however, present. Among patients with proteinuria, systolic BP <130 mmHg may increase mortality due to CVD. These results demonstrate the importance of early intervention to prevent CVD and to control all-cause mortality among patients with type 2 diabetes. The presence of proteinuria should be taken into account when defining the target systolic BP level for prevention of CVD deaths. A prolongation of the duration of the P wave was associated with increased stroke mortality among high-risk patients with type 2 diabetes. P wave duration is easy to measure and merits further examination to evaluate its importance for estimation of the risk of stroke among patients with type 2 diabetes.

Flexible multibody dynamics and intelligent control of a hydraulically driven hybrid redundant robot machine

The assembly and maintenance of the International Thermonuclear Experimental Reactor (ITER) vacuum vessel (VV) is highly challenging since the tasks performed by the robot involve welding, material handling, and machine cutting from inside the VV. The VV is made of stainless steel, which has poor machinability and tends to work harden very rapidly, and all the machining operations need to be carried out from inside of the ITER VV. A general industrial robot cannot be used due to its poor stiffness in the heavy duty machining process, and this will cause many problems, such as poor surface quality, tool damage, low accuracy. Therefore, one of the most suitable options should be a light weight mobile robot which is able to move around inside of the VV and perform different machining tasks by replacing different cutting tools. Reducing the mass of the robot manipulators offers many advantages: reduced material costs, reduced power consumption, the possibility of using smaller actuators, and a higher payload-to-robot weight ratio. Offsetting these advantages, the lighter weight robot is more flexible, which makes it more difficult to control. To achieve good machining surface quality, the tracking of the end effector must be accurate, and an accurate model for a more flexible robot must be constructed. This thesis studies the dynamics and control of a 10 degree-of-freedom (DOF) redundant hybrid robot (4-DOF serial mechanism and 6-DOF 6-UPS hexapod parallel mechanisms) hydraulically driven with flexible rods under the influence of machining forces. Firstly, the flexibility of the bodies is described using the floating frame of reference method (FFRF). A finite element model (FEM) provided the Craig-Bampton (CB) modes needed for the FFRF. A dynamic model of the system of six closed loop mechanisms was assembled using the constrained Lagrange equations and the Lagrange multiplier method. Subsequently, the reaction forces between the parallel and serial parts were used to study the dynamics of the serial robot. A PID control based on position predictions was implemented independently to control the hydraulic cylinders of the robot. Secondly, in machining, to achieve greater end effector trajectory tracking accuracy for surface quality, a robust control of the actuators for the flexible link has to be deduced. This thesis investigates the intelligent control of a hydraulically driven parallel robot part based on the dynamic model and two schemes of intelligent control for a hydraulically driven parallel mechanism based on the dynamic model: (1) a fuzzy-PID self-tuning controller composed of the conventional PID control and with fuzzy logic, and (2) adaptive neuro-fuzzy inference system-PID (ANFIS-PID) self-tuning of the gains of the PID controller, which are implemented independently to control each hydraulic cylinder of the parallel mechanism based on rod length predictions. The serial component of the hybrid robot can be analyzed using the equilibrium of reaction forces at the universal joint connections of the hexa-element. To achieve precise positional control of the end effector for maximum precision machining, the hydraulic cylinder should be controlled to hold the hexa-element. Thirdly, a finite element approach of multibody systems using the Special Euclidean group SE(3) framework is presented for a parallel mechanism with flexible piston rods under the influence of machining forces. The flexibility of the bodies is described using the nonlinear interpolation method with an exponential map. The equations of motion take the form of a differential algebraic equation on a Lie group, which is solved using a Lie group time integration scheme. The method relies on the local description of motions, so that it provides a singularity-free formulation, and no parameterization of the nodal variables needs to be introduced. The flexible slider constraint is formulated using a Lie group and used for modeling a flexible rod sliding inside a cylinder. The dynamic model of the system of six closed loop mechanisms was assembled using Hamilton’s principle and the Lagrange multiplier method. A linearized hydraulic control system based on rod length predictions was implemented independently to control the hydraulic cylinders. Consequently, the results of the simulations demonstrating the behavior of the robot machine are presented for each case study. In conclusion, this thesis studies the dynamic analysis of a special hybrid (serialparallel) robot for the above-mentioned special task involving the ITER and investigates different control algorithms that can significantly improve machining performance. These analyses and results provide valuable insight into the design and control of the parallel robot with flexible rods.

Public and private sector cooperative opportunities in the Finnish healthcare internationalization : views from the public sector’s perspective

Traditionally mostly publicly provided Finnish healthcare services are confronted today by the evident challenge of rising healthcare costs as the expenditure on health and social case has exceeded Finland’s national GDP growth significantly since the new millennium. While the opening of the traditional barriers through the EU’s new patient directive resulting in increasing international competition and the free flow of patients within the EU present opportunities for the Finnish healthcare services industry there are also several challenges for the existing healthcare system as proposed by the Ministry of Employment and the Economy in 2011. Due to the structure and nature of the current Finnish healthcare service system the greatest potential for internationalization is seen from a joint cooperation of the public and private sectors in an internationalization network for Finnish healthcare services. As its formation has recently also taken as a strategic initiative to be completed by the Ministry of Employment and the Economy and no earlier research exists on how this is seen in practice by the network actors, the purpose of this study is to examine the proposed solution of forming an internationalization network between the public and private sector actors in Finland in practice from the viewpoint of public sector actors. The research relied heavily on the reports by the Finnish Ministries in understanding the current situation of the Finnish healthcare services internationalization and its potential. Suitable theories were also used to build a more comprehensive view of the matter. The study applied a qualitative research approach on the explorative research problem. The data collection was achieved through expert interviews in two of the largest Finnish public healthcare service providers; the Turku and Helsinki Central University Hospitals. Expert interviews were considered as the most suitable method for data collection in order to create an in-depth understanding of the topic within the limitations of this thesis. In turn, two different public healthcare service providers were chosen to give a broader view of the field instead of focusing on a specific unit and also to allow a possible comparison between the two different organizations. The latter however was shown not to be suitable for the purposes of this study as the opinions of the respondents varied largely also within their own organizations. The conclusion is that while the actors agree on the evident internationalization of Finnish healthcare services, there are several large-scale structural challenges effectively preventing such activities while at the same time the opportunities within Finland vary, as there are several niches but no real large-scale advantages in the highly competitive industry. Interest towards cooperation between the sectors are seen especially in exploiting the advantages offered by the private sector in commercialization and marketization, yet however no clear views exist on how these activities should be governed or structured in the short-term as a larger reform of the entire Finnish healthcare service sector is needed in the long-term.