Russian metals for arctic offshore structures

With an increasingly growing demand for natural resources, the Arctic region has become an attractive area, holding about 15% of world oil. Ice shrinkage caused by global warming encourages the development of offshore and ship-building sectors. Russia, as one of the leading oil and gas production countries is participating actively in cold resistant materials research, since half of its territory belongs to the Arctic environment, which held considerable stores of oil. Nowadays most Russian offshore platforms are located in the Sakhalin Island area, which geographically does not belong to the Arctic, but has com-parable environmental conditions. Russia recently has manufactured several offshore platforms. It became clear that further development of the Arctic off-shore structures with necessary reliability is highly depending on the materials employed. This work pursues the following objectives:  to provide a comprehensive review on Russian metals used for Arctic offshore structures on the base of standards, books, journal articles and companies reports  to overview various Arctic offshore structures and its structural characteristics  briefly discuss materials testing methods for low temperatures Master`s thesis focuses on specifications and description of Russian metals which are already in use and can be used for Arctic offshore structures. Work overviews several groups of steel, such as low carbon, low alloy, chromium containing steels, stainless steels, aluminium and nanostructured steels. Materials under discussion are grouped based on the standards, for instance the work covers shipbuilding and structural steels at the different sections. This paper provides an overview of important Russian Arctic offshore projects built for use in Russia and ordered by foreign countries. Future trends in development of the Arctic materials are discussed. Based on the information provided in this Master`s thesis it is possible to learn about Russian metals used for ships and offshore platforms operated in the Arctic region. Paper can be used as the comprehensive review of current materials, such as various steels, aluminium and nanomaterials.

Evaluation of the efficacy of hydrated sodium aluminosilicate in the prevention of aflatoxin-induced hepatic cancer in rainbow trout

The use of aluminum silicates for decontaminating animal feed containing aflatoxins has yielded encouraging results in chicken and turkey poults. In contrast, very few studies have tested these substances in aquaculture. In this work, we investigated the efficacy of a trout diet containing 0.5% hydrated sodium aluminosilicate (HSAS) in protecting against contamination with aflatoxin B1. Trout were reared on these diets for one year and the experimental groups were examined monthly for hepatic presumptive preneoplastic and neoplastic lesions. Regardless of the presence of HSAS, all of the fish that received aflatoxin in their diet have shown hepatic lesions indicative of a carcinogenic process, presenting also the development of cancer in some fish. The concentration of HSAS used in this study was ineffective in preventing the onset of hepatic lesions induced by aflatoxin B1 in rainbow trout.

Ohutseinämäisten putkien hitsauksen robotisointi

Tämän diplomityön tavoitteena on ollut selvittää, kuinka robotisoitua hitsausta on mahdollista hyödyntää teollisuuskaiteiden valmistuksessa. Tutkimusmenetelminä käytettiin kirjallisuusselvitystä, hitsauskokeita ja makrohietutkimuksia. Työssä keskityttiin robottihitsauksen menetelmiin ja työstä on rajattu pois kaikki kustannuslaskelmat sekä alumiinin hitsaus. Hitsattavat materiaalit olivat rakenneteräs ja ruostumaton teräs. Rakenneteräsputken koko oli 42,4 x 2,6 mm ja ruostumattoman putken koko 42,4 x 2,0 mm. Käytetyt liitosmuodot olivat T-liitoksia, joista suorassa T-liitoksessa putkien välinen kulma oli 90 astetta ja vinossa T-liitoksessa noin 45 astetta. Tehdyn selvitystyön ja hitsauskokeiden perusteella voidaan sanoa, että kaiteissa käytettävien materiaalipaksuuksien ja liitosmuotojen hitsaaminen robotilla on mahdollista. Hitsauksen lopputulos riippuu hitsausasennosta ja paras tulos saavutetaan, kun kappaletta pyöritetään hitsauksen aikana siten, että hitsaus tapahtuu koko ajan jalkoasennossa.

Treatment of NI-containing acidic mine waters with calcite side-stones

Acid mine drainage (AMD) presents a serious problem for the environment for the massive formation of acidic leachates containing heavy metals. The present work deals with the AMD treatment using neutralizing limestone side-products. The conventional methods for prevention, mitigating and control of AMD formation are described. The experimental testing of Nordkalk Oy calcite-containing side-stones for acid neutralizing and removal of nickel from solutions presents the research objective. The batch experiments in acid neutralizing with subsequent metal content analysis were carried out. The results showed the dependence of pH on the dose of neutralizing material and the exposure time. The nickel removal, unlike iron, within the pH range from 1.2 to 6.0 appeared to be inadequate. The further research on nickel co-precipitation with iron and aluminium may appear to be necessary together with testing of alkalinity strengthening materials.

Laser-TIG hybrid welding process

Joining processes and techniques need to meet the trend of new applications and the development of new materials. The application in connection with thick and thin plates in industrial fields is wide and the joining technology is in very urgent need. The laser-TIG hybrid welding technology can play the respective advantages of both of them. One major advantage of the hybrid laser-TIG welding technology is its efficient use of laser energy. Additionally, it can develop into a high and new advanced welding technology and become a hot spot in both the application and research area. This thesis investigated laser –TIG hybrid welding with the aim of enlightening the reader on its advantages, disadvantages and future areas of improvement. The main objective is to investigate laser-TIG hybrid on the welding of various metals (steels, magnesium, aluminium etc.). In addition, it elaborates on various possible combinations on hybrid laser-TIG welding technology and their benefits. The possibility of using laser-TIG hybrid in welding of thick materials was investigated. The method applied in carrying out this research is by using literature review. The results showed that hybrid laser-TIG is applicable to almost all weldable metals. Also it proves to be effective in welding refractive metals. The possibility of welding with or without filler materials is of economic advantage especially in welding of materials with no filler material. Thick plate’s hybrid laser-TIG welding is showing great prospects although it normally finds its used in welding thin materials in the range of 0.4 to 0.8 mm. The findings show that laser-TIG hybrid welding can be a versatile welding process and therefore will be increasingly used industrially due to its numerous advantages and the development of new TIG arc that enhances its capabilities.

Influence of duty factor on the die-sinking Electrical Discharge Machining of high-strength aluminum alloy under rough machining

The use of high-strength aluminium alloys as material for injection molding tools to produce small and medium batches of plastic products as well as prototyping molds is becoming of increasing demand by the tooling industry. These alloys are replacing the traditional use of steel in the cases above because they offer many advantages such as very high thermal conductivity associated with good corrosion and wear resistance presenting good machinability in milling and electrical discharge machining operations. Unfortunately there is little technological knowledge on the Electrical Discharge Machining (EDM) of high-strength aluminium alloys, especially about the AMP 8000 alloy. The duty factor, which means the ratio between pulse duration and pulse cycle time exerts an important role on the performance of EDM. This work has carried out an experimental study on the variation of the duty factor in order to analyze its influence on material removal rate and volumetric relative wear under roughing conditions of EDM process. The results showed that high values of duty factor are possible to be applied without bringing instability into the EDM process and with improvement of material removal rate and volumetric relative wear.

Lehmijärven valuma-alueen happamuus sekä alumiini- ja rikkipitoisuus

Lehmijärvi on 63 ha laajuinen kirkasvetinen ja vähähumuksinen latvajärvi Salossa. Lehmijärven suojeluyhdistys pyysi Varsinais-Suomen ELY-keskukselta ja Suomen metsäkeskukselta apua järvivedessä havaittujen korkeiden alumiinipitoisuuksien ja happamuuspiikkien sekä mahdollisten metsätaloustoimenpiteiden haittojen ehkäisemiseen valuma-alueella. Suomen metsäkeskuksen ja Varsinais-Suomen ELY-keskuksen yhteistyönä selvitettiin maanäytteiden avulla maaperän happamuutta ja alumiinipitoisuutta Lehmijärven valuma-alueella. Tulokset ja johtopäätökset on esitetty tässä raportissa. Tulosten perusteella näyttää siltä, että Lehmijärven happamuuspiikit (pH:n jyrkät laskut vedessä) johtuvat pääosin happamista lumensulamisvesistä, johon on jo aiemmissakin selvityksissä viitattu eikä alunamaa ongelmasta valuma-alueella. Myös ojitettujen soiden suuri osuus valuma-alueesta ja turvemaiden yleinen happamuus lisäävät osaltaan valuma-alueelta virtaavien vesien happamuutta varsinkin tulva-aikoina. Mustikkasuon eteläpuolisella suokuviolla, jonka läpi pääosa pohjoispuolen valumavesistä virtaa, voi kuitenkin esiintyä ohuen turpeen alla pienialaisesti alunamaata. Vertailtaessa tämän aineiston liukoisen alumiinin määriä turpeessa aikaisempien tutkimusten vertailulukuihin, voidaan sanoa Lehmijärven valuma-alueen ojitetuilla soilla olevan keskimääräistä korkeampia alumiinipitoisuuksia. Paikoin liukoiset alumiinipitoisuudet olivat jopa erittäin korkeita. Mustikkasuon eteläpuolisella suokuviolla, jonka kautta vedet suurelta osin virtaavat, alumiinipitoisuus oli korkeimmillaan 11 267 mg/kg ja Miilussuolla 7 044 mg/kg, kun Niemisen ja Jarvan (1996) tutkimuksessa alumiinipitoisuuden maksimiarvo oli 5 577 mg/kg. Alumiinin ajoittain korkeat pitoisuudet Lehmijärvessä johtuvat tämän raportin tulosten perusteella todennäköisesti pääosin valuma-alueen soiden turpeen korkeista alumiinipitoisuuksista. Voimakas maanmuokkaus kivennäismailla lisää alumiinin liukoisuutta ja samalla alumiinin huuhtoutumisriskiä vesistöihin. Lehmijärven valuma-alueella on suositeltavaa käyttää metsänuudistamisessa kevyitä maanmuokkausmenetelmiä (laikutus, kääntömätästys ja laikkumätästys) ja välttää ojitusmätästystä. Luontainen uudistaminen (erityisesti alikasvosten hyödyntäminen) pitäisi olla ensisijainen uudistamismenetelmä Lehmijärven valuma-alueella. Kunnostusojituksia toteutettaessa pitäisi ottaa käyttöön mahdollisimman tehokkaat vesiensuojelutoimet. On muistettava, että korkeat alumiinipitoisuudet Lehmijärvellä eivät ole pelkästään negatiivinen asia, koska alumiini sitoo tehokkaasti fosforia ja pahasti rehevöityneitä järviä (esim. Köyliön Ilmijärvi) on yritetty kunnostaa alumiinisulfaatti käsittelyllä. Lisätutkimusta tarvitaan selvittämään, onko Lehmijärven veden alumiinipitoisuus ajoittain jo niin korkea, että siitä on haittaa kalakannalle tai, että se jopa estää rapukannan palauttamisen istuttamalla järveen.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Multiple dormancy and maternal effect on Miconia ferruginata (Melastomataceae) seed germination, Serra de Caldas Novas, Goiás, Brazil

Species with mostly asexual reproduction are interesting subjects for germination studies since variation would be more easily linked to environmental factors. Miconia ferruginata DC. is an apomictic treelet in Brazilian cerrado areas on rocky outcrops. Germination of seeds collected from individuals occurring in the Serra de Caldas Novas State Park, Goiás, was studied in three experiments under controlled conditions. Germination characteristics differed among individuals and were correlated with altitude and soil Al content. Seeds from plants growing at lower altitudes, with lower soil aluminium content, presented malformed seeds with absence of embryo which rendered lower, but better synchronized germination. The nested analysis showed that from the total variance, 78.14% for germinability, 54.56% for uncertainty of the germination process, and 68.30% for the quantity of seeds without embryo was attributed to the altitudinal effect. Individuals nested within altitude contributed up to 16.93% for the total variance. It means that there is low variability among individuals of the same altitude and high variability among individuals from different points of the slope, making clear that for the studied population the environmental effect is stronger than the genetic component to determine the seed quality. The testa of the seeds provides a mechanical dormancy which seems to be associated also with phenolic compounds, which help to disperse germination through time. Photoblastism was also registered for seeds of this species.

Alumiinin oksidikerroksen merkitys hitsauksessa

Tämä kandidaatintyö on kirjallisuuden pohjalta laadittu yhteenveto alumiinin oksidikerroksen vaikutuksesta hitsauksessa. Työssä käsitellään alumiinia alkuaineena, alumiinin oksidikerroksen muodostumista ja rakennetta, seosaineiden vaikutusta oksidikerrokseen, alumiinin hitsattavuutta teräkseen vertaillen, alumiiniseosten hitsattavuutta, oksidikerroksen merkitystä hitsauksessa, alumiinin yleisiä hitsausvirheitä, oksidikerroksen poistotapoja sekä alumiinin eri hitsausmenetelmiä. Hitsausmenetelmistä käsitellään pääasiassa alumiinin MIG-, TIG- ja plasmahitsausta.

Suorituskyvyn mittaaminen lasi- ja alumiinirakentamisen pk-yrityksissä

Diplomityön taustana oli oletus suorituskyvyn mittaamisen vähäisyydestä lasi- ja alumiinirakentamisen pk-yrityksissä. Tämän takia haluttiin tutkia mitataanko suorituskykyä ja jos mitataan, miten sitä tehdään sekä minkälainen järjestelmä sopisi kyseisille yrityksille. Lasi- ja alumiinirakentamisen suorituskyvyn analysoinnin tilannetta kartoitettiin haastattelututkimuksella, jossa kävi ilmi, että se tosiaan on vähäistä. Tutkimukseen osallistuneissa yrityksissä seurattiin pääasiassa liiketaloutta ja tulosta, ja näitäkin suppeasti. Laajemmalle mittaamiselle todettiin kuitenkin olevan tarvetta. Tämän jälkeen haastattelututkimuksen pohjalta suunniteltiin työssä mukana olleelle Case-yritykselle mittaristo. Suunnitteluvaiheessa valittiin yrityksen visioiden ja strategian mukaisesti neljä mitattavaa suorituskyvyn osa-aluetta ja näille mittarit. Mittariston suunnittelun jälkeen siirryttiin rakennusvaiheeseen. Järjestelmäksi valittiin SAKE, joka on helppokäyttöinen ja erityisesti pk-yritysten tarpeisiin suunniteltu työkalu. Tämän suorituskyvyn mittariston avulla lasi- ja alumiinirakentamisen yritykset voivat tehostaa toimintaansa ja ulottaa suorituskyvyn mittauksen osa-alueilla joita ei aiemmin ole huomioitu.

Roll-to-roll atomic layer deposition process for flexible electronics applications

Atomic Layer Deposition (ALD) is the technology of choice where very thin and highquality films are required. Its advantage is its ability to deposit dense and pinhole-free coatings in a controllable manner. It has already shown promising results in a range of applications, e.g. diffusion barrier coatings for OLED displays, surface passivation layers for solar panels. Spatial Atomic Layer Deposition (SALD) is a concept that allows a dramatic increase in ALD throughput. During the SALD process, the substrate moves between spatially separated zones filled with the respective precursor gases and reagents in such a manner that the exposure sequence replicates the conventional ALD cycle. The present work describes the development of a high-throughput ALD process. Preliminary process studies were made using an SALD reactor designed especially for this purpose. The basic properties of the ALD process were demonstrated using the wellstudied Al2O3 trimethyl aluminium (TMA)+H2O process. It was shown that the SALD reactor is able to deposit uniform films in true ALD mode. The ALD nature of the process was proven by demonstrating self-limiting behaviour and linear film growth. The process behaviour and properties of synthesized films were in good agreement with previous ALD studies. Issues related to anomalous deposition at low temperatures were addressed as well. The quality of the coatings was demonstrated by applying 20 nm of the Al2O3 on to polymer substrate and measuring its moisture barrier properties. The results of tests confirmed the superior properties of the coatings and their suitability for flexible electronics encapsulation. Successful results led to the development of a pilot scale roll-to-roll coating system. It was demonstrated that the system is able to deposit superior quality films with a water transmission rate of 5x10-6 g/m2day at a web speed of 0.25 m/min. That is equivalent to a production rate of 180 m2/day and can be potentially increased by using wider webs. State-of-art film quality, high production rates and repeatable results make SALD the technology of choice for manufacturing ultra-high barrier coatings for flexible electronics.

Bauksiittijätteen neutralointi- ja stabilointimenetelmät

Bauksiittijäte on alumiinin jalostuksessa syntyvä sivutuote, jonka alkalisuus on riski lähiympäristön ekosysteemeille. Alkalisuuden aiheuttamaan riskiin etsittiin ratkaisua perehtymällä bauksiittijätteen käsittelyyn. Kandidaatintyössä esitettiin eri menetelmiä bauksiittijätteen neutraloimiseksi, stabiloimiseksi ja varastoimiseksi. Menetelmien periaatteet määritettiin kirjallisuudesta löytyvien tutkimusten pohjalta, joiden perusteella voitiin määrittää toimivimmat menetelmät bauksiittijätteen käsittelemiseksi. Käytännöllisimmiksi käsittelymenetelmiksi osoittautuivat meriveden ja/tai hiilidioksidin lisääminen bauksiittijätteeseen sen neutraloimiseksi. Bauksiittijätteen stabiloimiseksi siihen tulee lisätä kiinteää materiaalia, kuten kalkkia, kiintoainepitoisuuden nostamiseksi sekä kovettuvien yhdisteiden muodostumiseksi.