Development of Raman microscopy methods for polymer coatings of polyfilms

Työn tavoitteena oli tutkia Raman-spektrometrin soveltuvuutta muovipäällystettyjen kartonkien syvyyssuuntaisiin mittauksiin. Lisäksi pyrittiin selvittämään voidaanko kiteisyyttä nähdä Raman-laitteistolla. Työn kirjallisessa osassa on selvitetty Raman-laitteiston teknisiä ominaisuuksia. Kokeellinen osa suoritettiin Lappeenrannan teknillisessä yliopistossa Membraanitekniikan ja teknillisen polymeerikemian laboratoriossa. Työssä käytettiin Horiban Jobin Yvon¿in valmistamaa konfokaalista Raman-spektrometri-laitteistoa (LabRam). Syvyyssuuntaisissa mittauksissa käytettiin apuna motorisoitua x-, y- ja z-suuntaan liikkuvaa tasoa. Mittaukset suoritettiin pistemäisesti tietyllä askelvälillä fokusoimalla näytteen pinnasta sisällepäin. Syvyysprofilointimittaukset aloitettiinmäärittelemällä laitteiston syvyysresoluutio eri konfokaalireikäkoolla. Lisäksityössä tehtiin syvyysprofilointimittauksia sekä läpinäkyvillä monikerrosmuoveilla että muovipäällystetyillä kartongeilla. Työssä mitatut muovipäällysteet sisälsivät pääasiassa polyeteeniä. Tulokset osoittivat, että Raman laitteistolla voidaan havainnoida Raman-aktiiviset ryhmät näytteen eri kerroksista. Lisäksi polyeteenin kiteisyysaste voidaan havaita tietyillä aallonpituuksilla.

Fibre-reinforced composites as root canal posts

Fibre-reinforced composite (FRC) root canal posts are suggested to have biomechanical benefits over traditional metallic posts, but they lack good adhesion to resin composites. The aim of this series of studies was to evaluate the adhesion of individually formed fibre-reinforced composite material to composite resin and dentin, as well as some mechanical properties. Flexural properties were evaluated and compared between individually formed FRC post material and different prefabricated posts. The depth of polymerization of the individually formed FRC post material was evaluated with IR spectrophotometry and microhardness measurements, and compared to that of resin without fibres. Bonding properties of the individually formed FRC post to resin cements and dentin were tested using Pull-out- and Push-out-force tests, evaluated with scanning electron microscopy, and compared to those of prefabricated FRC and metal posts. Load-bearing capacity and microstrain were evaluated and failure mode assessment was made on incisors restored with individually formed FRC posts of different structures and prefabricated posts. The results of these studies show that the individually polymerized and formed FRC post material had higher flexural properties compared to the commercial prefabricated FRC posts. The individually polymerized FRC material showed almost the same degree of conversion after light polymerization as monomer resin without fibres. Moreover, it was found that the individually formed FRC post material with a semiinterpenetrating polymer network (IPN) polymer matrix bonded better to composite resin luting cement, than did the prefabricated posts with a cross-linked polymer matrix. Furthermore, it was found that, contrary to the other posts, there were no adhesive failures between the individually formed FRC posts and composite resin luting cement. This suggests better interfacial adhesion of cements to these posts. Although no differences in load-bearing capacity or microstrain could be seen, the incisors restored with individually formed FRC posts with a hollow structure showed more favourable failures compared to other prefabricated posts. These studies suggest that it is possible to use individually formed FRC material with semi-IPN polymer matrix as root canal post material. They also indicate that there are benefits especially regarding the bonding properties to composite resin and dentin with this material compared to prefabricated FRC post material with a cross-linked matrix. Furthermore, clinically more repairable failures were found with this material compared to those of prefabricated posts.

Management of Nitrogen Oxides Reduction Project in a Cement Plant

The main aim of this study was to develop the project management framework model which would serve as the new model to follow for upcoming projects at the Lappeenranta cement plant. The other goal was to execute the SNCR (selective non catalytic reduction) project successfully so that the nitrogen oxides emissions are below the stated emission limit when the new emission limit comes into effect beginning in July, 2008. Nitrogen oxides, project management aspects, SNCR and the invested system are explained in the theory part. In the practical part of the study, the SNCR project in the Lappeenranta cement plant was executed and the findings were documented. In order to reach the aim of this study, a framework of project management was made. The framework is based on the executed SNCR project, previous projects in the cement plant and on the available literature relating to the subject matter. The developed project turned out to be successful.

Rigid Rod Polymer Fillers in Acrylic Denture and Dental Adhesive Resin Systems

Polymeric materials have been used in dental applications for decades. Adhesion of polymeric materials to each other and to the tooth substrate is essential to their successful use. The aim of this series of studies was two-folded. First, to improve adhesion of poly(paraphenylene) based rigid rod polymer (RRP) to other dental polymers, and secondly, to evaluate the usability of a new dentin primer system based on RRP fillers. Poly(paraphenylene) based RRP would be a tempting material for dental applications because of its good mechanical properties. To be used in dental applications, reliable adhesion between RRP and other dental polymers is required. In this series of studies, the adhesion of RRP to denture base polymer and the mechanical properties of RRP-denture base polymer-material combination were evaluated. Also adhesion of BisGMA-TEGDMA-resin to RRP was determined. Different surface treatments were tested to improve the adhesion of BisGMA-TEGDMA-resin to RRP. Results were based on three-point bending testing, Vickers surface hardness test and scanning electron microscope analysis (SEM), which showed that no reliable adhesion between RRP and denture base polymer was formed. Addition of RRP filler to denture base polymer increased surface hardness and flexural modulus but flexural strength decreased. Results from the shear bond strength test and SEM revealed that adhesion between resin and RRP was possible to improve by surface treatment with dichloromethane (DCM) based primer and a new kind of adhesive surface can be designed. The current dentin bonding agents have good immediate bond strength, but in long term the bond strength may decrease due to the detrimental effect of water and perhaps by matrix metalloproteinases. This leads to problems in longevity of restorations. Current bonding agents use organic monomers. In this series of studies, RRP filled dentin primer was tested in order to decrease the water sorption of the monomer system of the primers. The properties of new dentin primer system were evaluated in vitro by comparing it to commercial etch and rinse adhesive system. The results from the contact angle measurements and SEM showed that experimental primer with RRP reinforcement provided similar resin infiltration to dentin collagen and formed the resin-dentin interface as the control primer. Microtensile bond strength test and SEM revealed that in short term water storing, RRP increased bond strength and primer with BMEP-monomer (bis[2-(methacryloyloxy)-ethyl]phosphate) and high solvent concentration provided comparable bonding properties to the commercial control primers. In long term water storing, the high solvent-monomer concentration of the experimental primers decreased bond strength. However, in low solvent-monomer concentration groups, the long-term water storing did not decrease the bond strength despite the existence of hydrophilic monomers which were used in the system. These studies demonstrated that new dentin primer system reached the mechanical properties of current traditional etch and rinse adhesive system in short time water storing. Improved properties can be achieved by further modifications of the monomer system. Studies of the adhesion of RRP to other polymers suggest that adhesion between RRP and other dental polymers is possible to obtain by certain surface treatments.

Formation of polyelectrolyte multilayers and polyelectrolyte complexes in dual polymer treatment of papermaking pulp

The goal of this study was to find a new approach to modify chemically the properties of paper by improving fiber quality. This Master’s thesis includes the multiple polymer treatment in general and themeasurement methods with which the formation of multilayers and complexes can be noticed. The treatment by an oppositely charged dual polymer system is a good approach to increase paper strength. In this work, starch, a cationic polymer, and carboxymethyl cellulose (CMC), an anionic polymer, were used step-by-step to improve paper strength. The adsorption of cationic starch and CMC on cellulose fibers were analyzed via polyelectrolyte titration. The results showed that paper strength was enhanced slightly with a layer-by-layer assembly of the polymers. However, if the washing stage, which was required for layer-by-layer assembly, was eliminated, the starch/CMC complex was deposited on fibers more efficiently, and the paper strength was improved more significantly.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Feasibility study of metal to polymer hybrid joining

The increasing demand for lightweight components has led to a huge exploitation of non-metallic materials such as polymers, fibers and elastomers in industrial and manufacturing processes. Recent trends towards cost effectiveness, weight reduction and production flexibility in industrial production and manufacturing processes has led to a growing interest in hybrid components where two or more dissimilar materials coexist to achieving specifically optimized characteristics. The importance of this research is to serve as a bridge to understanding the theories behind various joining techniques and the adaptation of the process for metal to polymer hybrid joints. Moreso, it helps companies to select the most productive and yet economical joining process for realization of lightweight metal to polymer hybrid components. This thesis is a literature review analyzing various materials that has been published on various joining methods for metal to polymer hybrid joints on the feasibility and eventual realization of the joint between these dissimilar materials. This study is aimed at theoretically evaluating the feasibility of joining processes between metal and plastic components by exploiting exhaustively joining and welding sources.

Future trends of Finnish cement based construction

The construction material sector, as a capital intensive industry, is highly vulnerable to rapid fluctuations in the economic cycles. In Finland this was witnessed especially during the late 2000s, as in 2007 and 2008 the demand for several construction materials exceeded their supply and right after this, in 2009 the demand collapsed fast as a result of an international recession. These factors brought about the need to study the future trends of the market place of the commissioning company, Finnsementti Oy. As reliable short term market forecasts for the sector are difficult to compose, the study concentrates primarily in examining and identifying the trends that are likely to affect the Finnish cement industry, and as an extension, the concrete industry in a frame of 10 to 15 years. The study’s scope comprehends also the examination of the domestic construction sector, as it represents the end user industry of both cement and concrete. These motives for the study produce the research problem, which is to conduct a trend analysis for cement based building in the Finnish market area in the 2020s. The theoretical frame for composing a trend analysis in the case of this study is twofold. This is due to the fact that both, the macro and micro environments of the examined industries are studied. The main methods used are the PESTE-model (macro) and Porter’s five forces model (micro). The study applies a qualitative approach and the data is gathered by interviewing a group of experts from the cement, concrete and construction industries. The result of the paper is an overall trend analysis for the Finnish cement based building sector, which is based on ‘sub trend analyses’ concerning four identified sub-sectors of the Finnish construction industry. The results are a combination of findings from these sub-sectors and the analyzed data that deals with the studied sector’s macro and micro environment. The conclusions provide an overall picture of the examined sectors’ potential future as a whole and by defined sub-sectors of the construction industry. The recognition of future trends in different areas of the construction industry can be applied as a means for an industry actor’s decision making and in estimating the types of construction that are likely to grow or decline. Finally, based on the analyzed data and conclusions, the commissioning company is provided with a brief SWOT analysis, that provides additional tools for decision making and planning processes regarding the future.

Microstructural and environmental effects on the mechanical properties of porous particle-polymer composites

Papper kan anses vara ett av de mest använda materialen i det dagliga livet. Tidskrifter, tidningar, böcker och diverse förpackningar är några exempel på pappersbaserade produkter. Papperets egenskaper måste anpassas till användningsändamålet. En tidskrift kräver t.ex. hög ljushet, opacitet och en slät yta hos papperet, medan dessa egenskaper är mindre viktiga för en dagstidning. Allt tryckpapper behöver vissa mekaniska egenskaper för att tåla vidarebearbetning såsom kalandrering, tryckning och vikning. Man kan bestryka papper för att förbättra dess optiska egenskaper och tryckbarhetsegenskaper. Vid bestrykning appliceras en dispersion av mineralpigment och polymerbindemedel som ett tunt lager på papperets yta. Bestrykningsskiktet kan ses som ett komplext, poröst kompositmaterial som även bidrar till papperets mekaniska egenskaper och dess processerbarhet i diverse konverteringsoperationer. Kravet på framställning av förmånligt papper med tillräckliga styrkeegenskaper ställer allt högre krav på optimeringen av pappersbestrykningsskiktets egenskaper och produktionskostnader. Målet med detta arbete var att förstå sambandet mellan pigmentbestrykningsskiktets mikrostruktur och dess makroskopiska, mekaniska egenskaper. Resultaten visar att adhesionen i gränsytan mellan pigment och bindemedel är kritisk för bestrykningsskiktets förmåga att bära mekanisk belastning. Polära vätskor är vanliga i tryckfärger och kan, eftersom de påverkar syra/bas-interaktionerna mellan pigment och latexbindemedel, försvaga denna adhesion. Resultaten tyder på att ytstyrkan hos bestruket papper kan höjas genom användning av bifunktionella dispergeringsmedel för mineralpigment. Detta medför inbesparingar i pappersproduktionen eftersom mängden bindemedel, den dyraste komponenten i bestrykningsskiktet, kan minskas.

Unidirectional fiber-reinforced composite as an oral implant abutment material: Experimental studies of E-glass fiber/BisGMA-TEGDMA polymer in vitro

Fiber-reinforced composites (FRCs) are a new group of non-metallic biomaterials showing a growing popularity in many dental and medical applications. As an oral implant material, FRC is biocompatible in bone tissue environment. Soft tissue integration to FRC polymer material is unclear. This series of in vitro studies aimed at evaluating unidirectional E-glass FRC polymer in terms of mechanical, chemical, and biological properties in an attempt to develop a new non-metallic oral implant abutment alternative. Two different types of substrates were investigated: (a) Plain polymer (BisGMA 50%–TEGDMA 50%) and (b) Unidirectional FRC. The mechanical behavior of high fiber-density FRCs was assessed using a three-point bending test. Surface characterization was performed using scanning electron and spinning disk confocal microscopes. The surface wettability/energy was determined using sessile drop method. The blood response, including blood-clotting ability and platelet morphology was evaluated. Human gingival fibroblast cell responses - adhesion kinetics, adhesion strength, and proliferation activity - were studied in cell culture environment using routine test conditions. A novel tissue culture method was developed and used to evaluate porcine gingival tissue graft attachment and growth on the experimental composite implants. The analysis of the mechanical properties showed that there is a direct proportionality in the relationship between E-glass fiber volume fraction and toughness, modulus of elasticity, and load bearing capacity; however, flexural strength did not show significant improvement when high fiber-density FRC is used. FRCs showed moderate hydrophilic properties owing to the presence of exposed glass fibers on the polymer surface. Blood-clotting time was shorter on FRC substrates than on plain polymer. The FRC substrates also showed higher platelet activation state than plain polymer substrates. Fibroblast cell adhesion strength and proliferation rate were highly pronounced on FRCs. A tissue culture study revealed that gingival epithelium and connective tissue established an immediate close contact with both plain polymer and FRC implants. However, FRC seemed to guide epithelial migration outwards from the tissue/implant interface. Due to the anisotropic and hydrophilic nature of FRC, it can be concluded that this material enhances biological events related with soft tissue integration on oral implant surface.

Karta öfver Degerhamn och trakten deromkring med husbyggnader tillhörige Ölands Cement Aktiebolag

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

The Possibility of Greenhouse Gas Mitigation in Ethiopian Cement Industry

Cement industry significantly associated with high greenhouse gas (GHG) emissions. Considering the environmental impact, particularly global warming potential, it is important to reduce these emissions to air. The aim of the study is to investigate the mitigation possibility of GHG emissions in Ethiopian cement industry. Life cycle assessment (LCA) method used to identify and quantify GHG emissions during one ton of ordinary portland cement (OPC) production. Three mitigation scenarios: alternative fuel use, clinker substitution and thermal energy efficiency were applied on a representative gate-to-gate flow model developed with GaBi 6 software. The results of the study indicate that clinker substitution and alternative fuel use play a great role for GHG emissions mitigation with affordable cost. Applying most energy efficient kiln technology, which in turn reduces the amount of thermal energy use, has the least GHG emissions reduction intensity and high implementation cost comparing to the other scenarios. It was found that the cumulative GHG emissions mitigation potential along with other selected mitigation scenarios can be at least 48.9% per ton of cement production.