Komposiittipakkausrakenteen valmistustekninen selvitys

Diplomityö on tehty Exel Oyj:lle tuotekehityprojektina. Tarkoituksena on kehittää Exel Oyj:n valmistamaa komposiittipakkausrakennetta. Työssä on keskitytty valmistustekniseen selvitykseen komposiittirakenteen teollisen mittakaavan tuotannossa. Työssä selvitettiin erilaisten tuoterakenteiden valmistettavuutta sekä suoritettiin kyseisen tuotteen vaatimusprofiilin mukaisia testejä valituille rakennevaihtoehdoille. Pakkausrakenteelle asetettuja vaatimuksia ovat mm. kuljetusvaatimukset, jotka määräytyvät lähinnä NATO standardien pohjalta. Lisäksi tuotteelta vaaditaan tiettyä pitkäaikaiskestoa käsittelyn kannalta sekä soveltuvuutta vallitseviin ilmasto-olosuhteisiin. Vaatimusten mukaisia ominaisuuksia tutkittiin lisäksi mm. ballistisilla ja mekaanisilla testeillä sekä kaasuläpäisytesteillä. Testien pohjalta voidaan todeta, etteivät perinteisen alipaineinjektoidun komposiittituotteen ballistiset ominaisuudet ole riittävällä tasolla suojatuotetta ajatellen. Ballististen ja mekaanisten testien kesken havaittiin joitain yhtäläisyyksiä ja tämä vaikuttaa olevan nimenomaan mekaanisesti optimoidun komposiitin ominaisuus. DI-työn lopputuloksena on saatu selkeä kuva pakkausrakenteen materiaalivaihtoehtojen soveltuvuudesta kyseiselle tuotteelle. Lisäksi pakkausrakenteelle on ehdotettu neljä erilaista tuotesuunnitelmaan, niiden valmistustekniikat sekä lopputuotteen kustannusarviointi.

Komposiittivaipan moderni optimisuunnittelu ja toteutus

Tavoitteena tällä tutkimuksella on soveltaa modernin optimisuunnittelun keinoja komposiittimuovisen nestesäiliön lieriömäisen vaipparakenteen suunnittelemiseksi optimaalisen tyydyttäviksi valmistustekniikan ja kustannusten kannalta. Kuormituksia on kahdenlaisia. Säiliön sisällä on neste, joka tuottaa hydrostaattisen painekuorman ja järjestelmään kytketty puhallin tuottaa ulkoisen ylipaineen. Säiliöt ovat pystysäiliöitä ja ne tukeutuvat alustaan suoran pohjalaatan avulla. FEM- malleissa kuoren alaosat ovat jäykästi kiinnitettyjä ja yläosissa säteensuuntaiset siirtymät ovat estettyjä. Materiaaleiksi kuoreen on valittu kahdella eri menetelmällä lujitetut komposiittimateriaalit. Kantavan kerroksen toimintona on kantaa kuormat. Sulkukerros toimii korroosiosuojana ja sen lujuus on kantavaa kerrosta pienempi. Keinoina käytetään ensin innovatiivista suunnittelua optimaalisten lähtövaihtoehtojen ideoimiseksi ja valitsemiseksi jatkokehittelyä varten. Tavoitteena on asiakkaan tyytyväisyyden maksimointi huomioiden tuotteen kustannukset ja kesto. Yhtenä suunnittelun keinona on käytetty kuoriteoriaa ja komposiittien materiaalimalleja. Kestoehtoina on sovellettu komposiiteille soveltuvia kriteerejä. Toisena keinona käytetään FEM-laskentaa. Elementtityypiksi on valittu kaksiulotteinen kuorielementti, jossa on ortotrooppisen ainemallin mukaiset materiaaliominaisuudet. Jännitystuloksien merkittävyys keston kannalta selvitettiin Tsai-Hillin kriteerillä. Tuloksina saatiin ensin innovoitua rakenteelle kaksi päävaihtoehtoa, joita alettiin optimoida. Valitussa ratkaisussa on huomioitu kokonaisuus ja eri yksityiskohdat, kuten paino, jäykisteet kustannustehokkuus, valmistusnopeus, laatu, hävikit, päästöt, lujuus ja kilpailukykyinen myyntihinta. Yhteenvetona voidaan todeta, että käytetyt keinot ovat hyvin tehokkaita ja niillä voidaan suunnitella ja toteuttaa komposiittirakenteita, jotka tyydyttävät optimaalisesti loppukäyttäjän teknis- taloudelliset vaatimukset. Lisäksi tulokset osoittavat, että standardin ja FEM-laskennan ennustukset ovat lähellä toisiaan sylinterimäisillä kuoriosilla, mutta standardit suosittavat suurempia mittoja itse jäykisteille.

Ekologisen kuorilevyn valmistaminen puunjalostusteollisuuden sivutuotteista

Puunjalostusteollisuudessa syntyy huomattavia määriä sivutuotteita, joiden hyödyntäminen on vielä vajavaista. Sahajauhon ja puukuoren pääasiallinen käyttö rajoittuu energiantuotantoon eli polttamiseen voimalaitoksissa. Selostettavassa tutkimustyössä, joka on tehty Lappeenrannan teknillisen yliopiston puunjalostustekniikan levylaboratoriossa, on pyritty selvittämään kotimaisten kuusi-, mänty- ja koivukuorten käyttömahdollisuuksia raaka-aineina lastulevyn tapaan ns. ekologisen kuorilevyn valmistamisessa, mutta ilman liimaa. Tutkimusmateriaalina käytettiin puunjalostusteollisuudesta hankittua tuoretta kuusen ja männyn rumpukuorintajätettä sekä koivun roottorikuorintajätettä, joista kukin raaka-aine pienennettiin kahteen eri partikkelikokoon käyttäen oksasilppuria ja vasaramyllyä. Raaka-ainemäärät mitattiin ja kaadettiin viiran päällä olevaan puusta valmistettuun muottiin ja muotin poisnostamisen jälkeen levyaihio puristettiin 1-välikuumapuristimessa sykleittäin. Valmistetut kuorilevyt olivat 1 -kerroksisia. Koelevyistä tutkittiin kosteuspitoisuus, tilavuuspaino, taivutuslujuus ja Brinell -kovuus.Saadut tulokset osoittavat, että kuusen, männyn ja koivun kuoresta voidaan valmistaa kuorilevyä ilman liima-ainetta, sillä puukuoren sisältämät omat liimaavuutta parantavat uuteaineet antavat riittävän vaikutuksen kuorilevyn rakenteen stabiloimiseksi. Tällaisen kuorilevyn taivutuslujuus on kuitenkin huomattavasti heikompi kuin puulastulevyllä. Kaikki jauhetusta raaka-aineesta sekä pelkästään silputusta koivuraaka-aineesta valmistetut kuorilevyt täyttävät taivutuslujuuden osalta kuitenkin huokoiselle, A-lujuusluokan standardi-kuitulevylle asetetut vaatimukset. Tarkasteltaessa eri raaka-aineista valmistettujen levyjen ominaisuuksia, voidaan todeta, että tilavuuspainoltaan suurinta sekä kovuudeltaan ja taivutuslujuudeltaan parasta levyä saadaan valmistettua jauhetusta koivukuoresta. Jokaisen valmistetun kuorilevyn kovuusarvo ylittää Suomen johtavan lastulevyn valmistajan lastulevyn kovuusarvon lukuun ottamatta pelkästään silputuista kuusi- ja mäntykuorista valmistettuja levyjä.Vaikka tulokset ovat suuntaa-antavia, osoittavat ne selvästi millaisia mahdollisuuksia tarjoaa puun kuoren tai sahajauhon käyttäminen lastulevyn tapaan valmistettavien levyjen raaka-aineena. Koko tutkimuskenttä on tässä käsiteltävänä olevalla alueella varsin laaja, ja tässä tutkimuksessa selvitetyt asiat ovat siitä vain pieni osa antaen kuitenkin suunnan useille tärkeille jatkossa selvitettäville asioille. Näistä mainittakoon mm. ekologisen levyn jatkojalostus ja tuotesuunnittelu, levyn valmistuksen taloudellisuus ja tuotteiden markkinointi, kuorilevyn valmistusprosessin kehittäminen sekä eri raaka-aineyhdistelmien kokeilu kuorilevyn raaka-aineena.

Komposiittirakenteiden soveltamismahdollisuudet pesureissa

Teräksen raaka-ainekustannusten jyrkkä nousu pakottaa prosessiteollisuuden etsimään vaihtoehtoisia rakennemateriaaleja, joiden ominaisuudet ovat vähintään terästä vastaavia. Prosessiteollisuudessa joudutaan käyttämään runsaasti kemikaaleja kestäviä laitteita, jolloin rakennemateriaaliksi sopiva on haponkestävä teräs. Laitteiden kokojen kasvusta seuraa niiden kokonaispainojen kasvu aiheuttaen haasteita niitä kantaville perustuksille. Komposiitti on yksi varteenotettava vaihtoehto haponkestävän teräksen korvaajaksi, sillä komposiitin ominaisuus/painosuhde on terästä parempi. Diplomityön tavoitteena on ollut selvittää Washers & Filters – tuoteperheeseen kuuluvien laitteiden, DD-pesurin (Drum Displacer) ja GF- suotimen (GasFree Filter), rakenteista löytyvien osien mahdollisuutta korvata komposiitilla. Työn pohjaksi on käsitelty komposiittien ominaisuuksia, tyyppejä ja valmistusmenetelmiä sekä perehdytty sellupesureiden toimintaprosessiin. Tältä pohjalta löytyi valintakriteerien avulla rakenteita, joita olisi mahdollista korvata komposiitilla.

Enhancing performance of paper coatings by tailor-made plastic pigments

The paper industry is constantly looking for new ideas for improving paper products while competition and raw material prices are increasing. Many paper products are pigment coated. Coating layer is the top layer of paper, thus by modifying coating pigment also the paper itself can be altered and value added to the final product. In this thesis, synthesis of new plastic and hybrid pigments and their performance in paper and paperboard coating is reported. Two types of plastic pigments were studied: core-shell latexes and solid beads of maleimide copolymers. Core-shell latexes with partially crosslinked hydrophilic polymer core of poly(n-butyl acrylate-co-methacrylic acid) and a hard hydrophobic polystyrene shell were prepared to improve the optical properties of coated paper. In addition, the effect of different crosslinkers was analyzed and the best overall performance was achieved by the use of ethylene glycol dimethacrylate (EGDMA). Furthermore, the possibility to modify core-shell latex was investigated by introducing a new polymerizable optical brightening agent, 1-[(4-vinylphenoxy)methyl]-4-(2-henylethylenyl)benzene which gave promising results. The prepared core-shell latex pigments performed smoothly also in pilot coating and printing trials. The results demonstrated that by optimizing polymer composition, the optical and surface properties of coated paper can be significantly enhanced. The optimal reaction conditions were established for thermal imidization of poly(styrene-co-maleimide) (SMI) and poly(octadecene-co-maleimide) (OMI) from respective maleic anhydride copolymer precursors and ammonia in a solvent free process. The obtained aqueous dispersions of nanoparticle copolymers exhibited glass transition temperatures (Tg) between 140-170ºC and particle sizes from 50-230 nm. Furthermore, the maleimide copolymers were evaluated in paperboard coating as additional pigments. The maleimide copolymer nanoparticles were partly imbedded into the porous coating structure and therefore the full potential of optical property enhancement for paperboard was not achieved by this method. The possibility to modify maleimide copolymers was also studied. Modifications were carried out via N-substitution by replacing part of the ammonia in the imidization reaction with amines, such as triacetonediamine (TAD), aspartic acid (ASP) and fluorinated amines (2,2,2- trifluoroethylamine, TFEA and 2,2,3,3,4,4,4-heptafluorobuthylamine, HFBA). The obtained functional nanoparticles varied in size between 50-217 nm and their Tg from 150-180ºC. During the coating process the produced plastic pigments exhibited good runnability. No significant improvements were achieved in light stability with TAD modified copolymers whereas nanoparticles modified with aspartic acid and those containing fluorinated groups showed the desired changes in surface properties of the coated paperboard. Finally, reports on preliminary studies with organic-inorganic hybrids are presented. The hybrids prepared by an in situ polymerization reaction consisted of 30 wt% poly(styrene- co-maleimide) (SMI) and high levels of 70 wt% inorganic components of kaolin and/or alumina trihydrate. Scanning Electron Microscopy (SEM) images and characterization by Fourier Transform Infrared Spcetroscopy (FTIR) and X-Ray Diffraction (XRD) revealed that the hybrids had conventional composite structure and inorganic components were covered with precipitated SMI nanoparticles attached to the surface via hydrogen bonding. In paper coating, the hybrids had a beneficial effect on increasing gloss levels.

Tuulivoimalan staattoripakan puristusrakenteen kehittäminen

Diplomityössä tutkittiin voidaanko tuulivoimalan generaattorin staattoripakan puristamisessa hyödyntää komposiittista rakenneratkaisua. Tyypillisesti generaattorissa staattorin teräslevyt puristetaan erilaisilla teräsrakenteilla toisiaan vasten. Tavoitteena oli selvittää, voidaanko puristavan komposiittirakenteen osana hyödyntää liimaliitosta tai laminoitua liitosta. Tarkoitus oli etsiä rakenteeseen soveltuva liima ja liimaliitoksen arvot tai laminoitu rakenne ja sille soveltuvat materiaalit ja suoritustapa. Työssä on perehdytty erilaisiin tuulivoimalatyyppeihin, sekä niissä käytettäviin kesto- ja vierasmagnetoituihin generaattorityyppeihin. Tämän lisäksi on tarkasteltu niissä käytettävien staattorien valmistusvaihtoehtoja ja syitä miksi niissä olevat teräslevyt on puristettava toisiaan vasten. Samalla on luotu katsaus nykyisin käytössä oleviin rakenteisiin, joilla puristus voidaan toteuttaa. Liimauksesta on käsitelty perusteoriaa, sekä seikkoja jotka vaikuttavat liimaliitoksen kestoon. Työssä tutkittavaan liitokseen soveltuvien liimojen ominaisuuksia on käsitelty. Myös laminoituun liitokseen jo aiemmin kovettuneeseen komposiittiin on perehdytty. Tutkittavaan rakenteeseen soveltuvia hartsi- ja lasikuitutyyppejä on esitelty. Komposiittien mekaaniseen liittämiseen on lyhyesti perehdytty. Työssä suoritettiin useita vetokokeita, joilla selvitettiin puristusrakenteen tutkimista varten valmistettujen koekappaleiden suurin vetokuormankesto. Vetokokeiden perusteella voitiin valita soveltuvin rakenne staattorin puristamiseksi.

Non-resorbable glass fibre-reinforced composite with porous surface as bone substitute material: Experimental studies in vitro and in vivo focused on bone-implant interface

The development of load-bearing osseous implant with desired mechanical and surface properties in order to promote incorporation with bone and to eliminate risk of bone resorption and implant failure is a very challenging task. Bone formation and resoption processes depend on the mechanical environment. Certain stress/strain conditions are required to promote new bone growth and to prevent bone mass loss. Conventional metallic implants with high stiffness carry most of the load and the surrounding bone becomes virtually unloaded and inactive. Fibre-reinforced composites offer an interesting alternative to metallic implants, because their mechanical properties can be tailored to be equal to those of bone, by the careful selection of matrix polymer, type of fibres, fibre volume fraction, orientation and length. Successful load transfer at bone-implant interface requires proper fixation between the bone and implant. One promising method to promote fixation is to prepare implants with porous surface. Bone ingrowth into porous surface structure stabilises the system and improves clinical success of the implant. The experimental part of this work was focused on polymethyl methacrylate (PMMA) -based composites with dense load-bearing core and porous surface. Three-dimensionally randomly orientated chopped glass fibres were used to reinforce the composite. A method to fabricate those composites was developed by a solvent treatment technique and some characterisations concerning the functionality of the surface structure were made in vitro and in vivo. Scanning electron microscope observations revealed that the pore size and interconnective porous architecture of the surface layer of the fibre-reinforced composite (FRC) could be optimal for bone ingrowth. Microhardness measurements showed that the solvent treatment did not have an effect on the mechanical properties of the load-bearing core. A push-out test, using dental stone as a bone model material, revealed that short glass fibre-reinforced porous surface layer is strong enough to carry load. Unreacted monomers can cause the chemical necrosis of the tissue, but the levels of leachable resisidual monomers were considerably lower than those found in chemically cured fibre-reinforced dentures and in modified acrylic bone cements. Animal experiments proved that surface porous FRC implant can enhance fixation between bone and FRC. New bone ingrowth into the pores was detected and strong interlocking between bone and the implant was achieved.

Repair of segmental bone defects with fiber-reinforced composite: a study of material development and an animal model on rabbits

The Repair of segmental defects in load-bearing long bones is a challenging task because of the diversity of the load affecting the area; axial, bending, shearing and torsional forces all come together to test the stability/integrity of the bone. The natural biomechanical requirements for bone restorative materials include strength to withstand heavy loads, and adaptivity to conform into a biological environment without disturbing or damaging it. Fiber-reinforced composite (FRC) materials have shown promise, as metals and ceramics have been too rigid, and polymers alone are lacking in strength which is needed for restoration. The versatility of the fiber-reinforced composites also allows tailoring of the composite to meet the multitude of bone properties in the skeleton. The attachment and incorporation of a bone substitute to bone has been advanced by different surface modification methods. Most often this is achieved by the creation of surface texture, which allows bone growth, onto the substitute, creating a mechanical interlocking. Another method is to alter the chemical properties of the surface to create bonding with the bone – for example with a hydroxyapatite (HA) or a bioactive glass (BG) coating. A novel fiber-reinforced composite implant material with a porous surface was developed for bone substitution purposes in load-bearing applications. The material’s biomechanical properties were tailored with unidirectional fiber reinforcement to match the strength of cortical bone. To advance bone growth onto the material, an optimal surface porosity was created by a dissolution process, and an addition of bioactive glass to the material was explored. The effects of dissolution and orientation of the fiber reinforcement were also evaluated for bone-bonding purposes. The Biological response to the implant material was evaluated in a cell culture study to assure the safety of the materials combined. To test the material’s properties in a clinical setting, an animal model was used. A critical-size bone defect in a rabbit’s tibia was used to test the material in a load-bearing application, with short- and long-term follow-up, and a histological evaluation of the incorporation to the host bone. The biomechanical results of the study showed that the material is durable and the tailoring of the properties can be reproduced reliably. The Biological response - ex vivo - to the created surface structure favours the attachment and growth of bone cells, with the additional benefit of bioactive glass appearing on the surface. No toxic reactions to possible agents leaching from the material could be detected in the cell culture study when compared to a nontoxic control material. The mechanical interlocking was enhanced - as expected - with the porosity, whereas the reinforcing fibers protruding from the surface of the implant gave additional strength when tested in a bone-bonding model. Animal experiments verified that the material is capable of withstanding load-bearing conditions in prolonged use without breaking of the material or creating stress shielding effects to the host bone. A Histological examination verified the enhanced incorporation to host bone with an abundance of bone growth onto and over the material. This was achieved with minimal tissue reactions to a foreign body. An FRC implant with surface porosity displays potential in the field of reconstructive surgery, especially regarding large bone defects with high demands on strength and shape retention in load-bearing areas or flat bones such as facial / cranial bones. The benefits of modifying the strength of the material and adjusting the surface properties with fiber reinforcement and bone-bonding additives to meet the requirements of different bone qualities are still to be fully discovered.

Prediction of 3D structure and ligand-binding properties : ABC transporters and flavodiiron proteins from Synechocystis sp. strain PCC 6803

Cyanobacteria are unicellular, non-nitrogen-fixing prokaryotes, which perform photosynthesis similarly as higher plants. The cyanobacterium Synechocystis sp. strain PCC 6803 is used as a model organism in photosynthesis research. My research described herein aims at understanding the function of the photosynthetic machinery and how it responds to changes in the environment. Detailed knowledge of the regulation of photosynthesis in cyanobacteria can be utilized for biotechnological purposes, for example in the harnessing of solar energy for biofuel production. In photosynthesis, iron participates in electron transfer. Here, we focused on iron transport in Synechocystis sp. strain PCC 6803 and particularly on the environmental regulation of the genes encoding the FutA2BC ferric iron transporter, which belongs to the ABC transporter family. A homology model built for the ATP-binding subunit FutC indicates that it has a functional ATPbinding site as well as conserved interactions with the channel-forming subunit FutB in the transporter complex. Polyamines are important for the cell proliferation, differentiation and apoptosis in prokaryotic and eukaryotic cells. In plants, polyamines have special roles in stress response and in plant survival. The polyamine metabolism in cyanobacteria in response to environmental stress is of interest in research on stress tolerance of higher plants. In this thesis, the potd gene encoding an polyamine transporter subunit from Synechocystis sp. strain PCC 6803 was characterized for the first time. A homology model built for PotD protein indicated that it has capability of binding polyamines, with the preference for spermidine. Furthermore, in order to investigate the structural features of the substrate specificity, polyamines were docked into the binding site. Spermidine was positioned very similarly in Synechocystis PotD as in the template structure and had most favorable interactions of the docked polyamines. Based on the homology model, experimental work was conducted, which confirmed the binding preference. Flavodiiron proteins (Flv) are enzymes, which protect the cell against toxicity of oxygen and/or nitric oxide by reduction. In this thesis, we present a novel type of photoprotection mechanism in cyanobacteria by the heterodimer of Flv2/Flv4. The constructed homology model of Flv2/Flv4 suggests a functional heterodimer capable of rapid electron transfer. The unknown protein sll0218, encoded by the flv2-flv4 operon, is assumed to facilitate the interaction of the Flv2/Flv4 heterodimer and energy transfer between the phycobilisome and PSII. Flv2/Flv4 provides an alternative electron transfer pathway and functions as an electron sink in PSII electron transfer.

Development of porous glass-fiber reinforced composite for bone implants. Evaluation of antimicrobial effect and implant fixation

Cranial bone reconstructions are necessary for correcting large skull bone defects due to trauma, tumors, infections and craniotomies. Traditional synthetic implant materials include solid or mesh titanium, various plastics and ceramics. Recently, biostable glass-fiber reinforced composites (FRC), which are based on bifunctional methacrylate resin, were introduced as novel implant solution. FRCs were originally developed and clinically used in dental applications. As a result of further in vitro and in vivo testing, these composites were also approved for clinical use in cranial surgery. To date, reconstructions of large bone defects were performed in 35 patients. This thesis is dedicated to the development of a novel FRC-based implant for cranial reconstructions. The proposed multi-component implant consists of three main parts: (i) porous FRC structure; (ii) bioactive glass granules embedded between FRC layers and (iii) a silver-polysaccharide nanocomposite coating. The porosity of the FRC structure should allow bone ingrowth. Bioactive glass as an osteopromotive material is expected to stimulate the formation of new bone. The polysaccharide coating is expected to prevent bacterial colonization of the implant. The FRC implants developed in this study are based on the porous network of randomly-oriented E-glass fibers bound together by non-resorbable photopolymerizable methacrylate resin. These structures had a total porosity of 10–70 volume %, of which > 70% were open pores. The pore sizes > 100 μm were in the biologically-relevant range (50-400 μm), which is essential for vascularization and bone ingrowth. Bone ingrowth into these structures was simulated by imbedding of porous FRC specimens in gypsum. Results of push-out tests indicated the increase in the shear strength and fracture toughness of the interface with the increase in the total porosity of FRC specimens. The osteopromotive effect of bioactive glass is based on its dissolution in the physiological environment. Here, calcium and phosphate ions, released from the glass, precipitated on the glass surface and its proximity (the FRC) and formed bone-like apatite. The biomineralization of the FRC structure, due to the bioactive glass reactions, was studied in Simulated Body Fluid (SBF) in static and dynamic conditions. An antimicrobial, non-cytotoxic polysaccharide coating, containing silver nanoparticles, was obtained through strong electrostatic interactions with the surface of FRC. In in vitro conditions the lactose-modified chitosan (chitlac) coating showed no signs of degradation within seven days of exposure to lysozyme or one day to hydrogen peroxide (H2O2). The antimicrobial efficacy of the coating was tested against Staphylococcus aureus and Pseudomonas aeruginosa. The contact-active coating had an excellent short time antimicrobial effect. The coating neither affected the initial adhesion of microorganisms to the implant surface nor the biofilm formation after 24 h and 72 h of incubation. Silver ions released to the aqueous environment led to a reduction of bacterial growth in the culture medium.

Structure-related magnetic fabric studies : implications for deformed and undeformed Precambrian rocks

The aim of this thesis research was to gain a better understanding of the emplacement of rapakivi granite intrusions, as well as the emplacement of gold-bearing hydrothermal fluids in structurally controlled mineralizations. Based on investigations of the magnetic fabric, the internal structures could be analysed and the intrusion mechanisms for rapakivi granite intrusions and respectively different deformation stages within gold-bearing shear and fault zones identified. Aeromagnetic images revealed circular structures within the rapakivi granite batholiths of Wiborg, Vehmaa and Åland. These circular structures represent intrusions that eventually build up these large batholiths. The rapakivi granite intrusions of Vehmaa, Ruotsinpyhtää within the Wiborg batholith and Saltvik intrusions within the Åland batholith all show bimodal magnetic susceptibilities with paramagnetic and ferromagnetic components. The distribution of the bimodality is related to different magma batches of the studied intrusions. The anisotropy of magnetic susceptibility (AMS) reveals internal structures that cannot be studied macroscopically or by microscope. The Ruotsinpyhtää and Vehmaa intrusions represent similar intrusion geometries, with gently to moderately outward dipping magnetic foliations. In the case of Vehmaa, the magnetic lineations are gently plunging and trend in the directions of the slightly elongated intrusion. The magnetic lineations represent magma flow. The shapes of the AMS ellipsoids are also more planar (oblate) in the central part of the intrusion, whereas they become more linear (prolate) near the margin. These AMS results, together with field observations, indicate that the main intrusion mechanism has involved the subsidence of older blocks with successive intrusion of fractionated magma during repeated cauldron subsidence. The Saltvik area within the Åland batholith consists of a number of smaller elliptical intrusions of different rapakivi types forming a multiple intrusive complex. The magnetic fabric shows a general westward dipping of the pyterlite and eastward dipping of the contiguous even-grained rapakivi granite, which indicates a central inflow of magma batches towards the east and west resulting from a laccolitic emplacement of magma batches, while the main mechanism for space creation was derived from subsidence. The magnetic fabric of structurally controlled gold potential shear and fault zones in Jokisivu, Satulinmäki and Koijärvi was investigated in order to describe the internal structures and define the deformation history and emplacement of hydrothermal fluids. A further aim of the research was to combine AMS studies with palaeomagnetic methods to constrain the timing for the shearing event relative to the precipitation of ferromagnetic minerals and gold. All of the studied formations are dominated by monoclinic pyrrhotite. The AMS directions generally follow the tectonic structures within the formations. However, internal variations in the AMS direction as well as the shapes of the AMS ellipsoids are observed within the shear zones. In Jokisivu and Satulinmäki in particular, the magnetic signatures of the shear zone core differ from the margins. Furthermore, the shape of the magnetic fabric in the shear zone core of Jokisivu is dominated by oblate shapes, whereas the margins exhibit prolate shapes. These variations indicate a later effect of the hydrothermal fluids on the general shear event. The palaeo-magnetic results reveal a deflection from the original Svecofennian age geomagnetic direction. These results, coupled with correlations between the orientation of the NRM vectors and the magnetic and rock fabrics, imply that the gold-rich hydrothermal fluids were emplaced pre/syntectonically during the late stages of the Svecofennian orogeny.

Functionalisation of spruce O-acetyl-galactoglucomannans for barrier and composite applications

The increasing use of energy, food, and materials by the growing population in the world is leading to the situation where alternative solutions from renewable carbon resources are sought after. The growing use of plastics depends on the raw-oil production while oil refining are politically governed and required for the polymer manufacturing is not sustainable in terms of carbon footprint. The amount of packaging is also increasing. Packaging is not only utilising cardboard and paper, but also plastics. The synthetic petroleum-derived plastics and inner-coatings in food packaging can be substituted with polymeric material from the renewable resources. The trees in Finnish forests constitute a huge resource, which ought to be utilised more effectively than it is today. One underutilised component of the forests is the wood-derived hemicelluloses, although Spruce Oacetyl-galactoglucomannans (GGMs) have previously shown high potential for material applications and can be recovered in large scale. Hemicelluloses are hydrophilic in their native state, which restrains the use of them for food packaging as non-dry item. To cope with this challenge, we intended to make GGMs more hydrophobic or amphiphilic by chemical grafting and consequently with the focus of using them for barrier applications. Methods of esterification with anhydrides and cationic etherification with a trimethyl ammonium moiety were established. A method of controlled synthesis to obtain the desired properties by the means of altering temperature, reaction time, the quantity of the reagent, and even the solvent for purification of the products was developed. Numerous analytical tools, such as NMR, FTIR, SEC-MALLS/RI, MALDI-TOF-MS, RP-HPLC and polyelectrolyte titration were used to evaluate the products from different perspectives and to acquire parallel proofs of their chemical structure. Modified GGMs with different degree of substitution and the correlating level of hydrophobicity was applied as coatings on cartonboard and on nanofibrillated cellulose-GGM films to exhibit barrier functionality. The water dispersibility in processing was maintained with GGM esters with low DS. The use of chemically functionalised GGM was evaluated for the use as barriers against water, oxygen and grease for the food packaging purposes. The results show undoubtedly that GGM derivatives exhibit high potential to function as a barrier material in food packaging.