Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Portfolio Selection via Composite Measure Analysis: Evidence from the U.S. Stock Market

The aim of this research is to examine the pricing anomalies existing in the U.S. market during 1986 to 2011. The sample of stocks is divided into decile portfolios based on seven individual valuation ratios (E/P, B/P, S/P, EBIT/EV, EVITDA/EV, D/P, and CE/P) and price momentum to investigate the efficiency of individual valuation ratio and their combinations as portfolio formation criteria. This is the first time in financial literature when CE/P is employed as a constituent of composite value measure. The combinations are based on median scaled composite value measures and TOPSIS method. During the sample period value portfolios significantly outperform both the market portfolio and comparable glamour portfolios. The results show the highest return for the value portfolio that was based on the combination of S/P & CE/P ratios. The outcome of this research will increase the understanding on the suitability of different methodologies for portfolio selection. It will help managers to take advantage of the results of different methodologies in order to gain returns above the market.

Weld joint characteristics by nano-materials addition

The need for industries to remain competitive in the welding business, has created necessity to develop innovative processes that can exceed customer’s demand. Significant development in improving weld efficiency, during the past decades, still have their drawbacks, specifically in the weld strength properties. The recent innovative technologies have created smallest possible solid material known as nanomaterial and their introduction in welding production has improved the weld strength properties and to overcome unstable microstructures in the weld. This study utilizes a qualitative research method, to elaborate the methods of introducing nanomaterial to the weldments and the characteristic of the welds produced by different welding processes. The study mainly focuses on changes in the microstructural formation and strength properties on the welded joint and also discusses those factors influencing such improvements, due to the addition of nanomaterials. The effect of nanomaterial addition in welding process modifies the physics of joining region, thereby, resulting in significant improvement in the strength properties, with stable microstructure in the weld. The addition of nanomaterials in the welding processes are, through coating on base metal, addition in filler metal and utilizing nanostructured base metal. However, due to its insignificant size, the addition of nanomaterials directly to the weld, would poses complications. The factors having major influence on the joint integrity are dispersion of nanomaterials, characteristics of the nanomaterials, quantity of nanomaterials and selection of nanomaterials. The addition of nanomaterials does not affect the fundamental properties and characteristics of base metals and the filler metal. However, in some cases, the addition of nanomaterials lead to the deterioration of the joint properties by unstable microstructural formations. Still research are ongoing to achieve high joint integrity, in various materials through different welding processes and also on other factors that influence the joint strength.

Magnetization studies of polystyrene/multiwall carbon nanotube composite films

Lappeenranta University of Technology School of Technology Technical Physics Evgenii Zhukov MAGNETIZATION STUDIES OF POLYSTYRENE/MULTIWALL CARBON NANOTUBE COMPOSITE FILMS Master’s thesis 2015 55 pages, 41 pictures, 9 Tables. Examiners: Professor Erkki Lähderanta D.Sc. Ivan Zakharchuk Keywords: polystyrene, multi-walled carbon nanotubes, MWCNT, composite, magnetization, SQUID. In this thesis magnetic properties of polystyrene/multiwall carbon nanotube (MWCNT) composites are investigated with Quantum Design SQUID magnetometer (MPMS XL). The surface of the composite films is studied via BRUKER Multimode 8 Atomic Force Microscope, as well. The polystyrene/MWCNT composites have been prepared by the group of professor Okotrub (Physics Chemistry of Nanomaterials laboratory, Nikolaev Institute of Inorganic Chemistry, Russia). The composite films have been prepared by solution processing and stretching method. The approximate length and inner diameter of the MWCNTs used in fabrication are 260 μm and 10 nm, respectively. The content of MWCNTs is 1 and 2.5 contents percent (wt%) for studied samples. The stretching of the samples is 30% for samples with 1 and 2.5 wt% content, and one sample with 1 wt% loading of MWCNTs is 100% stretched. MWCNTs aligned perpendicular to a silicon substrate are used as a reference sample. The magnetization field dependencies of the samples exhibit hysteresis behavior. The values of saturation magnetization of composite films are much less compared to that of the reference sample. The saturation magnetization coercitivity field value drops with decrease of MWCNT content. At high magnetic fields strong presence of diamagnetism is observed. Measurements in magnetic field parallel and perpendicular to the composite plate display anisotropy with respect to the direction of stretching. Temperature dependences of magnetization for all samples display difference between zero-field cooled and field-cooled curves of magnetization. This divergence confirms the presence of magnetic interactions in the material. The atomic force microscopy study of the composites’ surfaces revealed that they are relatively smooth and the nanotubes are aligned with the axis of stretching to some extent. 

Development and characterization of thin printed films for gas sensing applications

The monitoring and control of hydrogen sulfide (H2S) level is of great interest for a wide range of application areas including food quality control, defense and antiterrorist applications and air quality monitoring e.g. in mines. H2S is a very poisonous and flammable gas. Exposure to low concentrations of H2S can result in eye irritation, a sore throat and cough, shortness of breath, and fluid retention in the lungs. These symptoms usually disappear in a few weeks. Long-term, low-level exposure may result in fatigue, loss of appetite, headache, irritability, poor memory, and dizziness. Higher concentrations of 700 - 800 ppm tend to be fatal. H2S has a characteristic smell of rotten egg. However, because of temporary paralysis of olfactory nerves, the smelling capability at concentrations higher than 100 ppm is severely compromised. In addition, volatile H2S is one of the main products during the spoilage of poultry meat in anaerobic conditions. Currently, no commercial H2S sensor is available which can operate under anaerobic conditions and can be easily integrated in the food packaging. This thesis presents a step-wise progress in the development of printed H2S gas sensors. Efforts were made in the formulation, characterization and optimization of functional printable inks and coating pastes based on composites of a polymer and a metal salt as well as a composite of a metal salt and an organic acid. Different processing techniques including inkjet printing, flexographic printing, screen printing and spray coating were utilized in the fabrication of H2S sensors. The dispersions were characterized by measuring turbidity, surface tension, viscosity and particle size. The sensing films were characterized using X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and an electrical multimeter. Thin and thick printed or coated films were developed for gas sensing applications with the aim of monitoring the H2S concentrations in real life applications. Initially, a H2S gas sensor based on a composite of polyaniline and metal salt was developed. Both aqueous and solvent-based dispersions were developed and characterized. These dispersions were then utilized in the fabrication of roll-to-roll printed H2S gas sensors. However, the humidity background, long term instability and comparatively lower detection limit made these sensors less favourable for real practical applications. To overcome these problems, copper acetate based sensors were developed for H2S gas sensing. Stable inks with excellent printability were developed by tuning the surface tension, viscosity and particle size. This enabled the formation of inkjet-printed high quality copper acetate films with excellent sensitivity towards H2S. Furthermore, these sensors showed negligible humidity effects and improved selectivity, response time, lower limit of detection and coefficient of variation. The lower limit of detection of copper acetate based sensors was further improved to sub-ppm level by incorporation of catalytic gold nano-particles and subsequent plasma treatment of the sensing film. These sensors were further integrated in an inexpensive wirelessly readable RLC-circuit (where R is resistor, L is inductor and C is capacitor). The performance of these sensors towards biogenic H2S produced during the spoilage of poultry meat in the modified atmosphere package was also demonstrated in this thesis. This serves as a proof of concept that these sensors can be utilized in real life applications.

Fiber-reinforced composite fixed dental prostheses: Studies of the materials used as pontics

Fiber-reinforced composite fixed dental prostheses – Studies of the materials used as pontics University of Turku, Faculty of Medicine, Institute of Dentistry, Department of Biomaterials Science, Finnish Doctoral Program in Oral Sciences – FINDOS, Annales Universitatis Turkuensis, Turku, Finland 2015 Fiber-reinforced composites (FRC), a non-metallic biomaterial, represent a suitable alternative in prosthetic dentistry when used as a component of fixed dental prostheses (FDPs). Some drawbacks have been identified in the clinical performance of FRC restorations, such as delamination of the veneering material and fracture of the pontic. Therefore, the current series of studies were performed to investigate the possibilities of enhancing the mechanical and physical properties of FRC FDPs by improving the materials used as pontics, to then heighten their longevity. Four experiments showed the importance of the pontic design and surface treatment in the performance of FRC FDPs. In the first, the load-bearing capacities of inlay-retained FRC FDPs with pontics of various materials and thicknesses were evaluated. Three different pontic materials were assessed with different FRC framework vertical positioning. Thicker pontics showed increased load-bearing capacities, especially ceramic pontics. A second study was completed investigating the influence of the chemical conditioning of the ridge-lap surface of acrylic resin denture teeth on their bonding to a composite resin. Increased shear bond strength demonstrated the positive influence of the pretreatment of the acrylic surfaces, indicating dissolution of the denture surfaces, and suggesting potential penetration of the monomer systems into the surface of denture teeth. A third study analyzed the penetration depth of different monomer systems on the acrylic resin denture teeth surfaces. The possibility of establishing a durable bond between acrylic pontics and FRC frameworks was demonstrated by the ability of monomers to penetrate the surface of acrylic resin denture teeth, measured by a confocal scanning type microscope. A fourth study was designed to evaluate the load-bearing capacities of FRC FDPs using the findings of the previous three studies. In this case, the performance of pre-shaped acrylic resin denture teeth used as pontics with different composite resins as filling materials was evaluated. The filling material influenced the load-bearing capacities, providing more durable FRC FDPs. It can be concluded that the mechanical and physical properties of FRC FDPs can be improved as has been shown in the development of this thesis. The improvements reported then might provide long lasting prosthetic solutions of this kind, positioning them as potentially permanent rehabilitation treatments. Key words: fiber-reinforced composite, fixed dental prostheses, inlay-retained bridges, adhesion, acrylic resin denture teeth, dental material.

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.

Transmission oflight through individually formed fiber- reinforced composite post (Yksilöllisesti muotoillun kuitukomposiittinastan valonläpäisevyys)

Kuitukomposiitista valmistettuja juurikanavanastoja käytetään apuna, kun restauroidaan juurihoidettuja ja kruunuosastaan runsaasti kudosta menettäneitä hampaita. Kliinisen kestävyyden kannalta on tärkeää että nasta kiinnittyy hampaaseen hyvin. Tarvittavan valomäärän saattaminen valokovetuksella pimeään juurikanavaan on vaikeaa ja sen vuoksi nastojen kiinnittämiseen suositellaan kaksoiskovetteista yhdistelmämuovisementtiä, joka kovettuu vain osittain valolla. Jotta nasta ja sementti polymeroituisivat hyvin, nastan hyvä valonläpäisy- ja sirontakyky olisi eduksi. Tehdasvalmisteisten nastojen valonläpäisykyvyn on todettu heikkenevän niiden pituuden kasvaessa. Yksilöllisesti muotoilluilla kuitukomposiittinastoilla, joilla on osittaislomittaismuoviverkostorakenne (semi-IPN) polymeerimatriisi, on todettu tehdasvalmisteisia kuitunastoja parempi sidos nastan ja yhdistelmämuovisementin välillä. Yksilöllisesti muotoilluilla kuitunastoilla näyttäisi myös olevan hyvä valonjohtamiskyky, mutta lisätutkimuksia tarvitaan. Tässä tutkimuksessa selvitettiin yksilöllisesti muotoillun kuitukomposiittinastan (EverStick Post) ja kahden tehdasvalmisteisen (Relyx Fiber Post ja GC Fiber Post) kuitukomposiittina stan valonläpäisevyyttä sekä pituuden vaikutusta niiden valonläpäisykykyyn laboratorio- olosuhteissa. Tutkimushypoteesi oli, että nastojen valonläpäisykyky heikkenee niiden pidentyessä. Tutkimuksessa kaikista nastatyypeistä valmistettiin eripituisia nastoja (4, 8, 12 ja 16 mm). Nastoille tehtiin samanpituiset testikappaleet muoviputkesta ja polyvinyylisiloksaanista, ja nastat asetettiin niiden sisään. Tämän jälkeen nastoja kovetettiin valokovettimella 10 sekuntia, ja läpi päässyt valo mitattiin MARC Resin Calibrator -laitteella. Kontrollina käytettiin tyhjää testikappaletta ilman nastaa. Keskeiseksi tulokseksi saatiin, että yksilöllisesti muotoillulla kuitukomposiittinastalla oli kaikissa pituusryhmissä muita nastoja merkitsevästi parempi valonläpäisykyky. Tulokset osoittivat myös, että kaikkien nastojen valonläpäisevyys laski merkitsevästi nastan pituuden lisääntyessä aina 12 millimetriin asti. Tulosten perusteella yksilöllisesti muotoillulla kuitukomposiittinastalla on tehdasvalmisteista nastaa parempi valonläpäisykyky. Kuitukomposiittinastojen valonläpäisykyky heikkenee niiden pituuden kasvaessa aiempien tutkimusten mukaisesti. Jatkotutkimuksissa tulisi selvittää, miten valonläpäisevyys ja siroaminen vaikuttavat nastan ja sementin polymeroitumiseen ja siten kliiniseen lopputulokseen.

A software engineering approach to distributed systems for composite modeling

The goal of this thesis is to define and validate a software engineering approach for the development of a distributed system for the modeling of composite materials, based on the analysis of various existing software development methods. We reviewed the main features of: (1) software engineering methodologies; (2) distributed system characteristics and their effect on software development; (3) composite materials modeling activities and the requirements for the software development. Using the design science as a research methodology, the distributed system for creating models of composite materials is created and evaluated. Empirical experiments which we conducted showed good convergence of modeled and real processes. During the study, we paid attention to the matter of complexity and importance of distributed system and a deep understanding of modern software engineering methods and tools.

Optimal distance of the light-curing tip for light transmission through the resin composite

Hammaslääketieteessä käytetettävien komposiittien valonläpäisevyys vaihtelee. Samoin LED-valokovettimet eroavat toisistaan valotehonsa ja muotoilunsa perusteella. On yleisesti tiedossa, että valokovettimesta tulevan valon intensiteetti pinta-alayksikköä kohden heikkenee, kun kovettimen etäisyys kasvaa. Toisaalta ei ole tiedossa, miten valokovetettavan kohteen ja valokovettimen kärjen väliin sijoitettu materiaali tarkalleenottaen vaikuttaa valon intensiteettiin eri etäisyyksiä käytettäessä. Tämän tutkimuksen tarkoituksena on selvittää, miten valokovetettavan kohteen ja valokovettimen kärjen väliin asetettava etukäteen polymerisoitu materiaali vaikuttaa valon intensiteettiin eri etäisyyksillä. Tutkimus suoritettiin käyttämällä kahta eri valokovetinta. Jotta etäisyyden vaikutusta valotustehoon voitiin demonstroida, vaihdettiin kovettimen etäisyyttä sensorista 0,2,4,6,8,10mm välillä. Valotehot rekisteröitiin MARC resin calibrator -laitteella. Sensorin ja valokovettimen kärjen väliin asetettavat erilaiset komposiittilevyt olivat valmiiksi kovetettuja,1mm paksuisia, filleripitoisuuksiltaan neljää erilaista muovia. Valotehot rekisteröitiin jokaiselta etäisyydeltä komposiitin ollessa sensorin päällä. Rinnakkaisesti verrattiin myös etäisyyden vaikutusta valotehoon ilman esikovetettua materiaalia kovettimen kärjen ja valoa mittaavan sensorin välissä. Vertailun suorittamiseksi laskettiin intensiteettisuhdeluku muovillisen ja muovittoman arvon välillä aina tietyllä etäisyydellä Valokovettimen kärjen etäisyyden kasvattaminen sensorista (eli valokovetettavasta kohteesta) odotusten mukaisesti pienensi valotehoa. Laittamalla sensorin ja kovettimen väliin komposiittilevy, valoteho pieneni odotetusti vielä enemmän. Tutkittaessa intensiteettisuhdetta (valoteho muovin kanssa : valoteho ilman muovia) kuitenkin huomattiin, että 4-6mm:n kohdalla suhdeluku oli suurempi kuin 0,2,8 ja 10mm kohdalla. Johtopäätöksenä oli, että suurin mahdollinen valokovetusteho saavutetan laittamalla kovetuskärki mahdollisimman lähelle kohdetta. Jos valokovetettavan kohteen ja valokovettimen kärjen välissä oli kiinteä komposiittipalanen, suurin mahdollinen valokovetusteho kohteeseen saavutetaan edelleen laittamalla kovetuskärki kiinni muoviin. Jos etäisyyttä muovin pinnasta sen sijaan kasvatettiin, valokovetusteho ei laskenutkaan niin nopeasti kuin oli odotettu. Tämä voi liittyä siihen, että tehokkaan valokeilan halkaisijan koko on suurempi verrattuna komposiitin sekä sensorin halkaisian kokoon. Toiseksi on arvioitu, että resiinikomposiitin täyteaineet voisivat fokusoida läpi kulkevaa valoa sensoriin. Se, pitääkö tämä ilmiö paikkansa, vaatii kuitenkin enemmän tutkimusta