Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

Instabilities in electrochemical systems with a rotating disc electrode

Polarization curves experimentally obtained in the electro-dissolution of iron in a 1 M H2SO4 solution using a rotating disc as the working electrode present a current instability region within the range of applied voltage in which the current is controlled by mass transport in the electrolyte. According to the literature (Barcia et. al., 1992) the electro-dissolution process leads to the existence of a viscosity gradient in the interface metal-solution, which leads to a velocity field quantitatively different form the one developed in uniform viscosity conditions and may affect the stability of the hydrodynamic field. The purpose of this work is to investigate whether a steady viscosity profile, depending on the distance to the electrode surface, affects the stability properties of the classic velocity field near a rotating disc. Two classes of perturbations are considered: perturbations monotonically varying along the radial direction, and perturbations periodically modulated along the radial direction. The results show that the hydrodynamic field is always stable with respect to the first class of perturbations and that the neutral stability curves are modified by the presence of a viscosity gradient in the second case, in the sense of reducing the critical Reynolds number beyond which perturbations are amplified. This result supports the hypothesis that the current oscillations observed in the polarization curve may originate from a hydrodynamic instability.

Laser scribing of thin-film PV modules

This study is a literature review on laser scribing in monolithically interconnected thin-film PV modules, focusing on efficiency of modules based on absorber materials CIGS, CdTe and a-Si. In thin-film PV module manufacturing scribing is used to interconnect individual cells monolithically by P1, P2 and P3 scribes. Laser scribing has several advantages compared to mechanical scribing for this purpose. However, laser scribing of thin-films can be a challenging process and may induce efficiency reducing defects. Some of these defects can be avoided by improving optimisation or processing methods.

Electroretinography in dogs using a fiber electrode prototype

We compared two electroretinography (ERG) electrodes in dogs using ERG standards of the International Society for Clinical Electrophysiology of Vision (ISCEV). Ten healthy Yorkshire terrier dogs (mean age, 2.80 ± 1.42 years; 6 females) weighing 5.20 ± 1.56 kg were evaluated using an ERG system for veterinary use. Dark- and light-adapted ERG responses were recorded using an ERG-Jet electrode and a fiber electrode prototype. The examinations were performed during 2 visits, 3 weeks apart. Both electrodes (ERG-Jet or fiber prototype) were used on each animal and the first eye to be recorded (OD × OS) was selected randomly. Three weeks later the examination was repeated on the same animal switching the type of electrode to be used that day and the first eye to be examined. The magnitude and waveform quality obtained with the two electrode types were similar for all ERG responses. ERG amplitudes and implicit times obtained from dogs using the fiber electrode prototype were comparable to those obtained with the ERG-Jet electrode for rod, maximal rod-cone summed, cone, and 30-Hz flicker responses. The fiber electrode prototype is a low-cost device, available as an alternative instrument for clinical veterinary ERG recording for retinal function assessment.

Identification of fatty foods with contamination possibilities by plasticizers when stored in PVC film packaging

Poly-(vinyl chloride) (PVC) requires the addition of plasticizers - additives that give flexibility and malleability for its processing into flexible film. The most used ones are: di-(2-ethylhexyl) adipate (DEHA) and di-(2-ethylhexyl) phthalate (DEHP). Toxic effects of DEHP have been observed by several authors. Phthalates are being replaced by alternative substances in PVC flexible products, because of their possible toxicological effects. DEHA is a substitute for phthalates widely used as a plasticizer in PVC materials for involving food. Some authors have shown that the exposure to DEHA also induces toxicity. A cross-sectional study was performed to identify which fatty foods carry the possibility of contamination by DEHP and DEHA. Eighteen different foods with at least 3% (m/m) fat and the possibility of being wrapped in plastic film were determined. This study suggested that all foods were subject to contamination by DEHP and DEHA in those conditions - in decreasing consumption order of 96 to 22% in the convenience sample. New guidelines on the limits of DEHA and DEHP established by the Brazilian legislation, as additives in PVC film for packaging fatty food, are still relevant to ensure human health.

Film with anthocyanins as an indicator of chilled pork deterioration

An indicator can be defined as a substance which indicates the presence or absence of another substance or the degree of a certain reaction through characteristic changes, especially color. Therefore, the aim of this work is to evaluate the performance of a bio-based film with anthocyanin as an indicator of chilled pork deterioration. A film made of cassava starch, glycerol, and grape anthocyanins was prepared using the casting technique. Pork loin samples were put in Petri dishes containing an anthocyanin film on the bottom and stored at 4 ºC. Psychrotrophic microorganism count and the pH of the pork loin samples were analyzed for a 14 day- period. At the same time, the films were subjected to colorimetric analysis using D65 illuminant and the CIELAB system. Chroma and hue angle data for these films were evaluated by Anova and Dunnett's test. An increase in the microbial population and in the pH was observed over the storage period as result of pork deterioration. Color changes were also identified in the film. However, only at the beginning of the storage period was it possible to establish a correlation between film color and pork deterioration. The shelf life end-point could not be clearly detected by the film.

Effect of previous chilling storage on quality loss in frozen (–20 °C) sierra (Scomberomorus sierra) muscle packed with a low-density polyethylene film containing butylated hydroxytoluene

Rancidity development during frozen storage (–20 °C) of sierra fish (Scomberomorus sierra) was studied. Fillets were packed in low-density polyethylene films with and without butylated hydroxytoluene added (BHT-LDPE and LDPE respectively). Fillets stored with no package were used as control. Special attention was given to the effect of previous ice storage (0, 3, 6, 9 and 15 days) on the quality of the frozen fish. Physical (pH and texture) and chemical (peroxide value, PV and thiobarbituric acid index, TBA-i) analyses were carried out. Lipid oxidation increased with ice storage time in fish muscle without film packing, being greater than the film packed muscle (with and without antioxidant). An effect of previous ice storage time was observed on the frozen product (in all treatments). However, fish muscle with film packing containing antioxidant showed less lipid deterioration. Under the conditions applied in this study, the plastic films with antioxidant prevented the lipids oxidation during the cold handling of the sierra muscle.

The use of film coating on the performance of treated corn seed

The main objective of seed coating technology using polymers is to improve the physical, physiological and sanitary characteristics of seed performance. The objectives of the present study were to determine: the plantability of corn seeds treated with insecticide, fungicide and graphite, covered with a film coating; the dust retention on treated corn seeds; and the leaching of applied products on corn seeds covered by a film coating. Seed plantability was determined by counting the skips and double seeds; dust was determined by using fiberglass paper in mg.100 g-1 of seeds; and the leaching was determined by collecting the material leached in a 10 cm layer of sand after irrigation. The following conclusions were made: seeds covered with film coating effectively reduce skips and double seeds; film coating effectively reduces the formation of dust from the seeds; film coated seeds minimize the leaching of the insecticide applied in seed treatment; and there are differences in effectiveness related to film coating type and dosage.

The Midnight express phenomenon : a historical materialist approach to the reception of the film Midnight express /

This thesis examines the Midnight Express phenomenon focusing on the film's reception by audiences in Europe, North America, and Turkey between 1978-2003. Using and enhancing the "historical materialist approach" to film reception developed by Janet Staiger, the thesis considers the historical determinants of the film's nationally and culturally differential readings in different periods and of the transformations in those readings. The thesis argues that while Midnight Express was most likely read in the late 1970s as an attempt to reaffirm American social identity by projecting Turks as an instance of the negative Other, there has been an important shift in the reception of the film in the West during the 1990s due to the changes in the discursive contexts in which the film has been circulating. One does not observe any specific reference to Turkish prisons as a part of the issue of human rights violations in Turkey in the initial reception of the film by European and American critics, whereas these issues appear to be important constituents of a particular reception of the film in the West in the present. The thesis explains this shift by pointing to the constitution of a particular discourse on human rights violations in Turkey after 1980, and especially throughout the 1990s, which has become a part of the discursive repertoires of the Western audience. Therefore, the thesis argues that today, Midnight Express functions as a more legitimate political statement about Turkey in the eyes of some Western audiences than it had been in the 1970s. On the other hand, parallel to the increasing desire of Turkey to connect itself to the West, particularly to become a member of the European Union, one observes an immense increase in the belief in and defense against the negative effects of Midnight Express on Turkey's international representation since the 1990s. The historical and current discourses that audiences, both in Turkey and abroad, bring into play suggest that these audiences engage with Midnight Express by assuming or denying not only the subject positions constructed by the film text but also certain history-specific extra-filmic subject positions produced by other social and discursive formations.

Fade to black : picturing mortality in contemporary popular film /

This thesis attempts to understand representations of death in contemporary popular film within a framework that posits mortality as a category of particular social and political importance for the way we understand both individual subjectivity and social responsibility in the postmodern cultural moment. It addresses concerns over the social organizing categories of time and space, and performs a sustained consideration of predominant themes related to the popular representation of death, such as contingency, existential.meaning, and temporal finitude. Death consciousness and social consciousness are shown to be not just intertwined, but also vitally dependent on one another, and the analyses undertaken are ultimately aimed at making these intersections explicit in order • l to think through their potential implications for challenging consumer capitalist hegemony and envisioning the possibility of progressive social change through the lens of our mortality.

The new blockbuster film sequel : changing cultural and economic conditions within the film industry

Film sequels are a pervasive part of film consumption practices and have become an important part of the decision making process for Hollywood studios and producers. This thesis indicates that sequels are not homogenous groups of films, as they are often considered, but offer a variety of story construction and utilize a variety of production methods. Three types of blockbuster sequel sets are identified and discussed in this thesis. The Traditional Blockbuster Sequel Set, as exemplified by Back to the Future (1985, 1989, 1990) films, is the most conventional type of sequel set and capitalizes on the winning formula of the first film in the franchise. The MultiMedia Sequel Set, such as The Matrix (1999,2003) trilogy, allows the user/viewer to experience and consume the story as well as the world of the film through many different media. The Lord a/ the Rings (2001, 2002, 2003) set of films is an illustration of The Saga Sequel Set where plot lines are continuous over the entire franchise thus allowing the viewer to see the entire set as a unified work. The thesis also demonstrates how the blockbuster sequel sets, such as the Pirates a/ the Caribbean (2003, 2006, 2007) franchise, restructure the production process of the Hollywood film industry.

Teaching Adolescents to Think and Act Responsibly Through Narrative Film-making: A Qualitative Study

The current qualitative study examined an adapted version of the psychoeducational program, Teaching Adolescents to Think and Act Responsibly: The EQUIP Approach (DiBiase, Gibbs, Potter, & Blount, 2012). The adapted version, referred to as the EQUIP – Narrative Filmmaking Program, was implemented as a means of character education. The purpose of this study was three-fold: 1) to examine how the EQUIP – Narrative Film-making Program influenced student’s thoughts, feelings, and behaviours; 2) to explore the students’ and the teacher’s perception of their experience with the program; and 3) to assess whether or not the integrated EQUIP – Narrative Film-making Program addressed the goals of Ontario’s character education initiative. Purposive sampling was used to select one typical Grade 9 Exploring Technologies class, consisting of 15 boys from a Catholic board of education in the southern Ontario region. The EQUIP – Narrative Film-making Program required students to create moral narrative films that first portrayed a set of self-centered cognitive distortions, with follow-up portrayals of behavioural modifications. Before, during, and after intervention questionnaires were administered to the students and teacher. The student questionnaires invited responses to a set of cognitive distortion vignettes. In addition, data was collected through student and teacher interviews, and researcher observation protocol reports. Initially the data was coded according to an a priori set of themes that were further analyzed according to emotion and values coding methods. The results indicated that while each student was unique in his thoughts, feelings, and behavioural responses to the cognitive distortion vignettes after completing the EQUIP program, the overall trends showed students had a more positive attitude, with a decreased proclivity for antisocial behaviour and self-serving cognitive distortion portrayed in the vignettes. Overall, the teacher and students’ learning experiences were mainly positive and the program met the learning expectations of Ontario’s character education initiative. Based on these results of the present study, it is recommended that the EQUIP – Narrative Film-making Program be further evaluated through quantitative research and longitudinal study.

Vulgaire! Pervers! Dégradant! : le film d'exploitation et le cinéma québécois

Dans l’historiographie du cinéma québécois, un certain manque est notable concernant le cinéma populaire du début des années 1970 (1968-1975). Historiens et chercheurs accordèrent peu d’importance à cette section de notre cinématographie par déni d’un type de cinéma populaire exploitant la sexualité. Ce qui fut péjorativement appelé la vague de « films de fesses » n’eut droit à aucune étude académique sérieuse et nous proposons, donc, de la revisiter afin de mieux comprendre son apparition et son existence. Dans ce dessein, nous suggérons de l’aborder sous l’angle du cinéma d’exploitation, cinéma populaire méconnu et controversé. Pour cela, nous devrons expliquer les contours de ce cinéma puisque, lui aussi, souffre d’un léger manque d’études sérieuses et approfondies. Nous ferons au premier chapitre un panorama de la norme cinématographique qu’est le cinéma hollywoodien, afin de bien cerner, au deuxième chapitre, le cinéma d’exploitation qui selon nous s’efforce d’être en constante opposition avec le cinéma mainstream. Par la suite, nous mettrons en place le contexte socio-historique et cinématographique qui permit l’apparition d’un cinéma d’exploitation québécois et nous ferons l’énumération des différents titres qui se retrouvent dans ce corpus filmique. Les chapitres IV et V présenteront les analyses de différentes œuvres qui, selon nous, récupèrent de façon partielle ou totale des éléments du cinéma d’exploitation afin de créer une résistance culturelle quant au cinéma dominant américain.

Le film de famille, héritier de la tradition orale

Ce mémoire veut démontrer que le film de famille ainsi que ses conditions de réception empruntent, et ce de façon instinctive, au fonctionnement communicatif et rassembleur de la tradition orale. La parole, l’oralité, devrait être considérée comme le catalyseur de la mise en commun du souvenir que le film de famille suscite. Elle est le véhicule de l’interprétation du message du film de famille en tant que discours familial. D’ailleurs, si l’on compare l’influence des deux registres sensoriels présents dans le médium cinématographique (le visuel et l’oralité), le film de famille reprend davantage les modalités de l’oralité. Conséquemment, son contenu, sa forme et sa finalité correspondent à la définition d’un cinéma de l’oralité, un cinéma de la parole défini par Germain Lacasse. En raison d’une absence de travaux portant spécifiquement sur le sujet, l’objectif de cette recherche est de rapprocher et de définir davantage ces liens qui se sont tissés entre la tradition orale et le film de famille. Dans ce dessein, l’approche théorique développée est basée sur les théories de la tradition orale, sur la théorie de la mémoire collective de Maurice Halbwach et sur les rapports entre le cinéma et l’oralité. Ainsi, les aspects suivants sont abordés : Le rôle de l’oralité dans la constitution de la mémoire familiale, l’apport de l’oralité dans les médias stimulateurs de mémoire familiale et finalement, la forme et le contenu du film de famille en tant qu’aspects distinctifs du cinéma oral. Quatre extraits de films de famille québécois des années 20 à aujourd’hui y sont également analysés.

Towards the nanomechanical actuation and controlled assembly of nanomaterials using charge-transfer reactions in electroactive self-assembled monolayers

Les microcantileviers fonctionnalisés offrent une plateforme idéale pour la nano- et micro-mécanique et pour le développement de (bio-) capteurs tres sensible. Le principe d’opération consiste dans des évènements physicochimiques qui se passent du côté fonctionnalisé du microcantilevier induisant une différence de stress de surface entre les deux côtés du cantilevier qui cause une déflexion verticale du levier. Par contre, les facteurs et les phénomènes interfacials qui régissent la nature et l'intensité du stress de surface sont encore méconnus. Pour éclaircir ce phénomène, la première partie de cette thèse porte sur l'étude des réactions de microcantileviers qui sont recouverts d'or et fonctionnalisés par une monocouche auto-assemblée (MAA) électroactive. La formation d'une MAA de ferrocènylundécanethiol (FcC11SH) à la surface d'or d'un microcantilevier est le modèle utilisé pour mieux comprendre le stress de surface induit par l’électrochimie. Les résultats obtenus démontrent qu'une transformation rédox de la MAA de FcC11SH crée un stress de surface qui résulte dans une déflexion verticale du microcantilevier. Dépendamment de la flexibilité du microcantilevier, cette déflexion peut varier de quelques nanomètres à quelques micromètres. L’oxydation de cette MAA de FcC11SH dans un environnement d'ions perchlorate génère un changement de stress de surface compressive. Les résultats indiquent que la déflexion du microcantilevier est due à une tension latérale provenant d'une réorientation et d'une expansion moléculaire lors du transfért de charge et de pairage d’anions. Pour vérifier cette hypothèse, les mêmes expériences ont été répéteés avec des microcantileviers qui ont été couverts d'une MAA mixte, où les groupements électroactifs de ferrocène sont isolés par des alkylthiols inactifs. Lorsqu’un potentiel est appliqué, un courant est détecté mais le microcantilevier ne signale aucune déflexion. Ces résultats confirment que la déflexion du microcantilevier est due à une pression latérale provenant du ferrocènium qui se réorganise et qui crée une pression sur ses pairs avoisinants plutôt que du couplage d’anions. L’amplitude de la déflexion verticale du microcantilevier dépend de la structure moléculaire de la MAA et du le type d’anion utilisés lors de la réaction électrochimique. Dans la prochaine partie de la thèse, l’électrochimie et la spectroscopie de résonance de plasmon en surface ont été combinées pour arriver à une description de l’adsorption et de l’agrégation des n-alkyl sulfates à l’interface FcC11SAu/électrolyte. À toutes les concentrations de solution, les molécules d'agent tensio-actif sont empilées perpendiculairement à la surface d'électrode sous forme de monocouche condensé entrecroisé. Cependant, la densité du film spécifiquement adsorbé s'est avérée être affectée par l'état d'organisation des agents tensio-actifs en solution. À faible concentration, où les molécules d'agent tensio-actif sont présentes en tant que monomères solvatés, les monomères peuvent facilement s'adapter à l’évolution de la concentration en surface du ferrocènium lors du balayage du potential. Cependant, lorsque les molécules sont présentes en solution en tant que micelles une densité plus faible d'agent tensio-actif a été trouvée en raison de l'incapacité de répondre effectivement à la surface de ferrocenium générée dynamiquement.