Paper- and membrane-based ion-modulated electronics

Avhandlingen handlar om pappers- och membranbaserad jonmodulerad elektronik. Målet med forskningen har varit att utveckla billig, miljövänlig och brännbar elektronik, som kan användas i vardagliga engångsprodukter. Baskomponenterna som utvecklas och presenteras i avhandlingen är transistorer och kondensatorer. Mer komplicerad logisk kretselektronik demonstreras också med hjälp av dessa komponenter. Substraten som utnyttjas vid framställningen av dessa elektroniska komponenter är papper och membran. Dessa substrat är flexibla, hållbara, billiga, miljövänliga, etc. och därför väl anpassade för befintliga tryckteknologier. Själva baskomponenterna framställs sedan på dessa substrat genom att trycka flera skikt på varandra, där varje enskilt skikt är ett individuellt material. Detta är möjligt eftersom de organiska materialen som används i dessa komponenter är upplösta i ett lösningsmedel och kan därmed tryckas på samma sätt som ett vanligt bläck. Ett tredimensionellt objekt kan på detta sätt framställas. I avhandlingen presenteras flera olika typer av transistorer, men den gemensamma nämnaren bland dessa är att isolatorn är en jonledare. Denna, ganska ovanliga, transistormodellen har den stora fördelen att lågspänningskomponenter kan relativt enkelt framställas. Det som är speciellt med våra transistorer är att vi har använt miljövänliga jonledare. Detta, bl.a., leder till att våra komponenter visar både god prestanda, tillika som de är miljövänliga. I avhandlingen demonstrerar vi även tryckta superkondensatorer, en motsvarighet till laddningsbara batterier, konstruerade på papper med aktiverat kol och miljövänliga jonledare. De mest komplicerade logiska kretsar som demonstreras i denna avhandling är ring-oscillatorer och 1-bits-minnen konstruerade på papper. --------------------------------------------- Väitöskirja käsittelee paperille ja polymeerikalvolle tulostettua ionimoduloitua elektroniikkaa. Tutkimuksen tavoitteena oli kehittää edullista, ympäristöystävällistä ja polttokelpoista elektroniikkaa, jota voidaan käyttää esim. tavanomaisissa kertakäyttötuotteissa. Väitöskirjassa esitellään erilaisia transistoreita ja kondensaattoreita. Näitä elektronisia peruskomponentteja käyttäen demonstroidaan myös monimutkaisempia loogisia piirejä. Komponenttien valmistuksessa alustana käytettiin paperia ja polymeerikalvoa. Valitut alustat ovat joustavia ja kestäviä, ja ovat siksi hyvin yhteensopivia olemassa olevien tulostusmenetelmien kanssa. Peruskomponentit valmistettiin tulostamalla eri materiaaleja päällekkäin. Komponenteissa käytettävät orgaaniset aineet ovat liuenneessa muodossa musteessa, joka voidaan tulostaa samalla periaatteella kuin mikä tahansa normaali muste. Tällä menetelmällä voidaan valmistaa myös kolmiulotteisia tuotteita. Väitöskirjassa esitellään useita erityyppisiä transistoreita, joissa yhdistävänä tekijänä on ionisesti johtava eriste. Tällaista suhteellisen harvinaista transistorityyppiä käyttämällä voidaan mahdollistaa matala-jännitteisten komponenttien yksinkertainen valmistus. Valmistettujen transistoreiden etu on ionisten nesteiden ympäristöystävällisyys. Elektroniset komponentit ovat täten hyviä suorituskyvyltään, mutteivät haitallisia ympäristölle. Väitöskirjassa demonstroidaan myös tulostettujen superkondensaattoreiden, eli ladattavien paristojen vastineiden, valmistus paperille aktiivihiiltä ja ionisia nesteitä käyttäen. Kaikkein monimutkaisimmat loogiset piirit, jotka tässä väitöskirjassa esitellään, ovat rengasoskillaattorit sekä 1-bittinen paperille valmistettu muisti.

Heavy metals investigation in bovine tissues in Brazil

The aim of this study was to investigate the presence of arsenic, lead, and cadmium residues in samples of liver, kidney, and muscle of cattle during the years of 2002 to 2008. A total of 1017 samples from 20 Brazilian States were used. The samples were analyzed at the National Agricultural Laboratory using the atomic absorption spectrometry technique. Arsenic residues were detected in 15.7% of liver samples and 28.7% of kidney samples although no results have exceeded the MRL. With regard to lead, 16 samples of liver and 74 samples of kidney were contaminated (5.2 and 10.9%, respectively). Among these samples, only one liver and two of kidney samples had lead levels above the MRL. Cadmium was found with levels below the MRL in 12.5% of the liver samples, and only 3 samples (1%) were quantified above the MRL. Among the kidney samples, 420 (60.8% of the total tested) had cadmium residues, and five of them exceeded the limits established by legislation. It is concluded that the Brazilian meat meets the legislation requirements without putting consumer's healthy at risk since as it satisfies the national and international food-safety conditions.

Metal-Ion-Binding Oligonucleotides: High-Affinity Probes for Nucleic Acid Sequences

Small non-coding RNAs have numerous biological functions in cell and are divided into different classes such as: microRNA, snoRNA, snRNA and siRNA. MicroRNA (miRNA) is the most studied non-coding RNA to date and is found in plants, animals and some viruses. miRNA with short sequences is involved in suppressing translation of target genes by binding to their mRNA post-transcriptionally and silencing it. Their function besides silencing of the viral gene, can be oncogenic and therefore the cause of cancer. Hence, their roles are highlighted in human diseases, which increases the interest in using them as biomarkers and drug targets. One of the major problems to overcome is recognition of miRNA. Owing to a stable hairpin structure, chain invasion by conventional Watson-Crick base-pairing is difficult. One way to enhance the hybridization is exploitation of metal-ion mediated base-pairing, i. e. oligonucleotide probes that tightly bind a metal ions and are able to form a coordinative bonds between modified and natural nucleobases. This kind of metallo basepairs containing short modified oligonucleotides can also be useful for recognition of other RNA sequences containing hairpin-like structural motives, such as the TAR sequence of HIV. In addition, metal-ion-binding oligonucleotides will undoubtedly find applications in DNA-based nanotechnology. In this study, the 3,5-dimethylpyrazol-1-yl substituted purine derivatives were successfully incorporated within oligonucleotides, into either a terminal or non-terminal position. Among all of the modified oligonucleotides studied, a 2-(3,5-dimethylpyrazol-1-yl)-6-oxopurine base containing oligonucleotide was observed to bind most efficiently to their unmodified complementary sequences in the presence of both Cu2+ or Zn2+. The oligonucleotide incorporating 2,6-bis(3,5-dimethylpyrazol-1-yl)purine base also markedly increased the stability of duplexes in the presence of Cu2+ without losing the selectivity.

Thermal modelling of commercial lithium-ion batteries

The accelerating adoption of electrical technologies in vehicles over the recent years has led to an increase in the research on electrochemical energy storage systems, which are among the key elements in these technologies. The application of electrochemical energy storage systems for instance in hybrid electrical vehicles (HEVs) or hybrid mobile working machines allows tolerating high power peaks, leading to an opportunity to downsize the internal combustion engine and reduce fuel consumption, and therefore, CO2 and other emissions. Further, the application of electrochemical energy storage systems provides an option of kinetic and potential energy recuperation. Presently, the lithium-ion (Li-ion) battery is considered the most suitable electrochemical energy storage type in HEVs and hybrid mobile working machines. However, the intensive operating cycle produces high heat losses in the Li-ion battery, which increase its operating temperature. The Li-ion battery operation at high temperatures accelerates the ageing of the battery, and in the worst case, may lead to a thermal runaway and fire. Therefore, an appropriate Li-ion battery cooling system should be provided for the temperature control in applications such as HEVs and mobile working machines. In this doctoral dissertation, methods are presented to set up a thermal model of a single Li-ion cell and a more complex battery module, which can be used if full information about the battery chemistry is not available. In addition, a non-destructive method is developed for the cell thermal characterization, which allows to measure the thermal parameters at different states of charge and in different points of cell surface. The proposed models and the cell thermal characterization method have been verified by experimental measurements. The minimization of high thermal non-uniformity, which was detected in the pouch cell during its operation with a high C-rate current, was analysed by applying a simplified pouch cell 3D thermal model. In the analysis, heat pipes were incorporated into the pouch cell cooling system, and an optimization algorithm was generated for the estimation of the optimalplacement of heat pipes in the pouch cell cooling system. An analysis of the application of heat pipes to the pouch cell cooling system shows that heat pipes significantly decrease the temperature non-uniformity on the cell surface, and therefore, heat pipes were recommended for the enhancement of the pouch cell cooling system.

Recognition of nucleic acids by metal ion complexes

Metal-ion-mediated base-pairing of nucleic acids has attracted considerable attention during the past decade, since it offers means to expand the genetic code by artificial base-pairs, to create predesigned molecular architecture by metal-ion-mediated inter- or intra-strand cross-links, or to convert double stranded DNA to a nano-scale wire. Such applications largely depend on the presence of a modified nucleobase in both strands engaged in the duplex formation. Hybridization of metal-ion-binding oligonucleotide analogs with natural nucleic acid sequences has received much less attention in spite of obvious applications. While the natural oligonucleotides hybridize with high selectivity, their affinity for complementary sequences is inadequate for a number of applications. In the case of DNA, for example, more than 10 consecutive Watson-Crick base pairs are required for a stable duplex at room temperature, making targeting of sequences shorter than this challenging. For example, many types of cancer exhibit distinctive profiles of oncogenic miRNA, the diagnostics of which is, however, difficult owing to the presence of only short single stranded loop structures. Metallo-oligonucleotides, with their superior affinity towards their natural complements, would offer a way to overcome the low stability of short duplexes. In this study a number of metal-ion-binding surrogate nucleosides were prepared and their interaction with nucleoside 5´-monophosphates (NMPs) has been investigated by 1H NMR spectroscopy. To find metal ion complexes that could discriminate between natural nucleobases upon double helix formation, glycol nucleic acid (GNA) sequences carrying a PdII ion with vacant coordination sites at a predetermined position were synthesized and their affinity to complementary as well as mismatched counterparts quantified by UV-melting measurements.

Performance Degradation Modelling and Techno-Economic Analysis of Lithium-Ion Battery Energy Storage Systems

Transmission system operators and distribution system operators are experiencing new challenges in terms of reliability, power quality, and cost efficiency. Although the potential of energy storages to face those challenges is recognized, the economic implications are still obscure, which introduce the risk into the business models. This thesis aims to investigate the technical and economic value indicators of lithium-ion battery energy storage systems (BESS) in grid-scale applications. In order to do that, a comprehensive performance lithium-ion BESS model with degradation effects estimation is developed. The model development process implies literature review on lifetime modelling, use, and modification of previous study progress, building the additional system parts and integrating it into a complete tool. The constructed model is capable of describing the dynamic behavior of the BESS voltage, state of charge, temperature and capacity loss. Five control strategies for BESS unit providing primary frequency regulation are implemented, in addition to the model. The questions related to BESS dimensioning and the end of life (EoL) criterion are addressed. Simulations are performed with one-month real frequency data acquired from Fingrid. The lifetime and cost-benefit analysis of the simulation results allow to compare and determine the preferable control strategy. Finally, the study performs the sensitivity analysis of economic profitability with variable size, EoL and system price. The research reports that BESS can be profitable in certain cases and presents the recommendations.

Quest/ion of Identities in African American Feminist Postmodern Drama: A Study of Selected Plays by Suzan-Lori Parks

Innovative and unconventional, Pulitzer Prize-winning playwright Suzan-Lori Parks belongs to the continuum of African American playwrights who have contributed to the quest/ion – the quest for and question – of identities for African Americans. Her plays are sites in which the quest/ion of identities for African Americans is pursued, raised and enacted. She makes use of both page and stage to emphasize the exigency of reshaping African Americans’ identities through questioning the dominant ideologies and metanarratives, delegitimizing some of the prevailing stereotypes imposed on them, drawing out the complicity of the media in perpetuating racism, evoking slavery, lynching and their aftereffects, rehistoricizing African American history, catalyzing reflections on the various intersections of sex, race, class and gender orientations, and proffering alternative perspectives to help readers think more critically about issues facing African Americans. In my dissertation, I approach three plays by Parks – The Death of the Last Black Man in the Whole Entire World (1990), Venus (1996) and Fucking A (2000) – from the standpoints of postmodern drama and African American feminism with a focus on the terrains that reflect the quest/ion of identities for African Americans, especially African American women. I argue that postmodern drama and African American feminism provide the ground for Parks to promote the development of a political agenda in order to call into question a number of dominant ideologies and metanarratives with regard to African Americans and draw upon the roles of those metanarratives as a powerful apparatus of racial and sexual oppressions. I also explore how Parks engages with postmodern drama and African American feminism to incorporate her own mininarratives in the dominant discourses. I argue that Parks in these plays uses postmodern drama and African American feminism to encourage reflections on intersectionality in order to reveal the concerns of African Americans, particularly African American women. Her plays challenge the dominant order of hierarchy and patriarchy, while in some cases urging unity and solidarity between African American men and women by showing how unity and solidarity can help them confront race, class and gender oppressions. Furthermore, I discuss how the utilization of postmodern techniques and devices helps Parks to transform the conventional features of playwriting, to create incredulity toward the dominant systems of oppression and to incorporate her mininarratives within the context of dominant discourses.

Geochemistry and mineralogical association of heavy metal contaminants in fine grained sediment, Welland River, Southern Ontario /

This investigation of geochemistry and mineralogy of heavy metals in fine grained (<63^m) sediment of the Welland River was imdertaken to: 1) describe metal dispersion patterns relative to a source, identify minerals forming and existing at the outfall region and relate sediment particle size to chemistry; 2) to delineate sample handling, preparation and evaluate, modify and develop analytical methods for heavy metal analysis of complex environmental samples. Ajoint project between Brock University and Geoscience Laboratories was initiated to test a contaminated site of the Welland River at the base of Atlas Speciality Steels Co. Methods were developed and utilized for particle size separation and two acid extraction techniques: 1) Partial extraction; 2) Total extraction. The mineralogical assessment identified calcite, dolomite, quartz and clays. These minerals are typical of the carbonate-shale rock basement of the Niagara Peninsula. Minerals such as, mullite and ferrocolumbite were found at the outfall region. These are not typical of the local geology and are generally associated with industrial pollutants. Partial and total extraction techniques were used to characterize the sediments based on chemical distribution, elemental behaviour and analytical differences. The majority of elements were lower in concentration in the partial extraction technique; suggesting these elements are bound in an acid extractable phase (exchangeable, organic and carbonate phases). The total extraction technique yielded higher elemental concentrations taking difficult oxides and silicates into solution. Geochemical analyses of grain size separates revealed that heavy metal (Co, Ni, V, Mn, Fe, Ba) concentrations did not increase with decreasing grain size. This is a function of the anthropogenic mill scale input into the river. The background elements (Sc, Y, Sr, Mg, Al and Ti) showed an increase in concentration to the finest grain size suggesting that it is directly related to the local mineralogy and geology. Dispersion patterns ofmetals fall into two distinct categories: 1) the heavy metals (Co, Cu, Ni, Zn, V and Cr), and 2) the background elements (Be, Sc, Y, Sr, Al and Ti). The heavy metals show a marked increase in the outfall region, while the background elements show a significant decrease at the outfall. This pattern is attributed to a "dilution effect" ofthe natural sediments by the anthropogenic mill scale sediments. Multivariant statistical analysis and correlation coefficient matrix results clearly support these results and conclusions. These results indicate the outfall region ofthe Welland River is highly contaminated with to heavy metals from the industrialized area of Welland. A short distance downstream, the metal concentrations return to baseline geochemical levels. It appears, contaminants rapidly come out of suspension and are deposited in close proximity to the source. Therefore, it is likely that dredging the sediment from the river may cause resuspension of contaminated sediments, but may not distribute the sediment as far as initially anticipated.

Sample preparation and heavy metal determination by atomic spectrometry /

Microwave digestions of mercury in Standards Reference Material (SRM) coal samples with nitric acid and hydrogen peroxide in quartz vessels were compared with Teflon® vessel digestion by using flow injection cold vapor atomic absorption spectrometry. Teflon® vessels gave poor reproducibiUty and tended to deliver high values, while the digestion results from quartz vessel show good agreement with certificate values and better standard deviations. Trace level elements (Ag, Ba, Cd, Cr, Co, Cu, Fe, Mg, Mn, Mo, Pb, Sn, Ti, V and Zn) in used oil and residual oil samples were determined by inductively coupled plasma-optical emission spectrometry. Different microwave digestion programs were developed for each sample and most of the results are in good agreement with certified values. The disagreement with values for Ag was due to the precipitation of Ag in sample; while Sn, V and Zn values had good recoveries from the spike test, which suggests that these certified values might need to be reconsidered. Gold, silver, copper, cadmium, cobalt, nickel and zinc were determined by continuous hydride generation inductively coupled plasma-optical emission spectrometry. The performance of two sample introduction systems: MSIS™ and gas-liquid separator were compared. Under the respective optimum conditions, MSIS^"^ showed better sensitivity and lower detection limits for Ag, Cd, Cu, Co and similar values for Au, Ni and Zn to those for the gas-liquid separator.

An experimental investigation of dechanneling in copper single crystals

This investigation comprises a comparison of experimental and theoretical dechanneling of MeV protons in copper single crystals. Dechanneling results when an ion's transverse energy increases to the value where the ion can undergo small impact parameter collisions with individual atoms. Depth dependent dechanneling rates were determined as functions of lattice temperature, ion beam energy and crystal axis orientation. Ion beam energies were IMeV and 2MeV,temperatures ranged from 35 K to 280 K and the experiment was carried out along both the (lOa) and <110) axes. Experimental data took the form of aligned and random Rutherford backscattered energy spectra. Dechanneling rates were extracted from these spectra using a single scattering theory that took explicit account of the different stopping powers experienced by channeled and dechanneled ions and also included a correction factor to take into account multiple scattering effects along the ion's trajectory. The assumption of statistical equilibrium and small angle scattering of the channeled ions allows a description of dechanneling in terms of the solution of a diffusion like equation which contains a so called diffusion function. The diffusion function is shown to be related to the increase in average transverse energy. Theoretical treatments of increase in average transverse energy due to collisions of projectiles with channel electrons and thermal perturbations in the lattice potential are reviewed. Using the diffusion equation and the electron density in the channel centre as a fitting parameter dechanneling rates are extracted. Excellent agreement between theory and experiment has been demonstrated. Electron densities determined in the fitting procedure appear to be realistic. The surface parameters show themselves to be good indicators of the quality of the crystal.

Arsenic speciation by ion-exchange chromatography with on- line determination by hydride generation: electronic modification of the D.C. plasma by photon counting

A method using L-cysteine for the determination of arsenous acid (As(III)), arsenic acid (As(V)), monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) by hydride generation was demonstrated. The instrument used was a d.c. plasma atomic emission spectrometer (OCP-AES). Complete recovery was reported for As(III), As(V), and DMAA while 86% recovery was reported for MMAA. Detection limits were determined, as arsenic for the species listed previously, to be 1.2, 0.8, 1.1, and 1.0 ngemL-l, respectively. Precision values, at 50 ngemL-1 arsenic concentration, were f.80/0, 2.50/0, 2.6% and 2.6% relative standard deviation, respectively. The L-cysteine reagent was compared directly with the conventional hydride generation technique which uses a potassium iodide-hydrochloric acid medium. Recoveries using L-cysteine when compared with the conventional method provided the following results: similar recoveries were obtained for As(III), slightly better recoveries were obtained for As(V) and MMAA, and significantly better recoveries for DMAA. In addition, tall and sharp peak shapes were observed for all four species when using L-cysteine. The arsenic speciation method involved separation by ion exchange .. high perfonnance liquid chromatography (HPLC) with on-line hydride generation using the L.. cysteine reagent and measurement byOCP-AES. Total analysis time per sample was 12 min while the time between the start of subsequent runs was approximately 20 min. A binary . gradient elution program, which incorporated the following two eluents: 0.01 and 0.5 mM tri.. sodium citrate both containing 5% methanol (v/v) and both at a pH of approximately 9, was used during the separation by HPLC. Recoveries of the four species which were measured as peak area, and were normalized against As(III), were 880/0, 290/0, and 40% for DMAA, MMAA and As(V), respectively. Resolution factors between adjacent analyte peaks of As(III) and DMAA was 1.1; DMAA and MMAA was 1.3; and MMAA and As(V) was 8.6. During the arsenic speciation study, signals from the d.c. plasma optical system were measured using a new photon-signal integrating device. The_new photon integrator developed and built in this laboratory was based on a previously published design which was further modified to reflect current available hardware. This photon integrator was interfaced to a personal computer through an AID convertor. The .photon integrator has adjustable threshold settings and an adjustable post-gain device.

Far-infrared optical properties of the heavy fermion superconductor UB[E13]

Temperature dependent resistivity, p, magnetic susceptibility, X, and far-infrared reflectance measurements were made on the low Tc superconductor UBe13. Two variants of UBe13 have been proposed, named 'L'- (for low Tc ) and 'H'-type (for high Tc ). Low temperature resistivity measurements confirmed that our sample was of H-type and that the transition temperature was at 0.9 K. This was further confirmed with the observation of this transition in the AC-susceptibility. Low temperature reflectance measurements showed a decrease in the reflectivity as the temperature is lowered from 300 to 10 K, which is in qualitative agreement with the increasing resistivity in this temperature range as temperature is lowered. No dramatic change in the reflectivity was observed between 10 and 0.75 K. A further decrease of the reflectance was observed for the temperature of 0.5 K. The calculated optical conductivity shows a broad minimum near 80 cm-1 below 45 K. Above 45 K the conductivity is relatively featureless. As the temperature is lowered, the optical conductivity decreases. The frequency dependent scattering rate was found to be flat for temperatures between 300 and 45 K. The development of a peak, at around 70 cm-1 was found for temperatures of 45 K and below. This peak has been associated with the energy at which the transition to a coherent state occurs from single impurity scattering in other heavy fermion systems. The frequency dependent mass enhancement coefficient was found to increase at low frequencies as the frequency decreases. Its' magnitude as frequency approaches zero also increased as the temperature decreased.

Far infrared spectroscopy of heavy fermion superconductor CeCoIn5

The optical response to far infrared radiation has been measured on a mosaic of heavy fermion CeColnssingle crystals. The superconducting transition temperature of the crystals has been determined by van der Pauw resistivity and ac-susceptibility measurements as Tc = 2.3 K. The optical measurements were taken above and below the transition temperature using a 3He cryostat and step and integrate Martin-Puplett type polarizing interferometer. The absolute reflectance of the heavy fermion CeColns in the superconducting state in range (0, 100)cm-1 was calculated from the measured thermal reflectance, using the normal state data of Singley et al and a low frequency extrapolation for a metallic material in the Hagen-Rubens regime. By means of Kramers-Kronig analysis the absolute reflectance was used to calculate the optical conductivity of the sample. The real part of the calculated complex conductivity 0-(w) ofCeColns indicates a possible opening of an energy gap close to 50 em-I.

NMR studies of strong hydrogen bond to fluoride ion

Systems such as MF/diol (M = alkali metal) and }1F/carboxylic acid were subjected to IH, I9F and 13C nmr study to investigate the nature of the very strong H-bonding of fluoride ions with these systems. Evidence indicates a strong H-bond in diol-fluoride systems (~H ~ -(56) kJ mol-I) which is stronger than most 'typical' H-bonds (~H = -(12-40) kJ mol-I), but weaker than that reported for carboxylic acid-fluoride systems (~H ~ -(120) kJ mol-I). Approximate fluoride H-bonded shifts (o(OH)OHF) were evaluated for MF/diol systems from IH chemical shift measurements. No direct correlation was observed between I9F chemical shift and H-bond strength. Thermodynamic parameters were calculated from temperature dependent IH and 19F shifts. Preliminary studies of BUn 4NF-acetylacetone by I9F nmr were conducted at low temperatures and a possible Jmax (ca. 400 Hz) is reported for the fluoride ion H-bonded to acetylacetone. Highfield shift for non-protonated carbons and downfield shift for protonated carbons were observed in carboxylic acid/KF systems. Significant decreas$in I3C TI due to strong H-bonding to fluoride ions were also detected in both diol and carboxylic acid systems. Anomalous results were obtained, such as increasing NOE with increasing temperature in neat 1,2-ethanediol (values above the theoretical maximum of 1.988) and in 1,2-ethanediol/KF. The large 13C NOE's for carboxy carbons in neat carboxylic acids which are. further enhanced by the addition of KF are also unusual.