Substitutional Impurities in PPV Crystals: An Intrinsic Donor-Acceptor System for High V(oc) Photovoltaic Devices

Defects are usually present in organic polymer films and are commonly invoked to explain the low efficiency obtained in organic-based optoelectronic devices. We propose that controlled insertion of substitutional impurities may, on the contrary, tune the optoelectronic properties of the underivatized organic material and, in the case studied here, maximize the efficiency of a solar cell. We investigate a specific oxygen-impurity substitution, the keto-defect -(CH(2)-C=O)- in underivatized crystalline poly(p-phenylenevinylene) (PPV), and its impact on the electronic structure of the bulk film, through a combined classical (force-field) and quantum mechanical (DFT) approach. We find defect states which suggest a spontaneous electron hole separation typical of a donor acceptor interface, optimal for photovoltaic devices. Furthermore, the inclusion of oxygen impurities does not introduce defect states in the gap and thus, contrary to standard donor-acceptor systems, should preserve the intrinsic high open circuit voltage (V(oc)) that may be extracted from PPV-based devices.

Effects of Micelles and Vesicles on the Oximolysis of p-Nitrophenyl Diphenyl Phosphate: A Model System for Surfactant-Based Skin-defensive Formulations against Organophosphates

The rates of oximolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) by Acetophenoxime; 10-phenyl-10-hydi-oxyiminodecanoic acid; 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroyiminononanyl) benzene; 1-dodecyl-2-[(hydroxyimino)methyl]-pyridinium chloride (IV) and N-methylpyridinium-2-aldoxime chloride were determined in micelles of N-hexadecyl-N,N,N-trimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethylammonium propanesulfonate and dioctadecyldimethylammonium chloride (DODAC) vesicles. The effects of CTAC micelles and DODAC vesicles on the rates of oxymolysis of O,O-Diethyl O-(4-nitrophenyl) phosphate (paraoxon) by oxime IV were also determined. Analysis of micellar and vesicular effects on oximolysis of PNPDPP, using pseudophase or pseudophase with explicit consideration of ion exchange models, required the determination of the aggregate`s effects on the pK(a), of oximes and on the rates of PNPDPP hydrolysis. All aggregates increased the rate of oximolysis of PNPDPP and the results were analyzed quantitatively. In particular, DODAC vesicles catalyzed the reaction and increased the rate of oximolysis of PNPDPP by IV several million fold at pH`s compatible with pharmaceutical formulations. The rate increase produced by DODAC vesicles on the rate of oximolysis paraoxon by IV demonstrates the pharmaceutical potential of this system, since the substrate is used as an agricultural defensive agent and the surfactant is extensively employed in cosmetic formulations. (C) 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:1040-1052, 2009

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. All rights reserved.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (lambda = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L(-1) NaCl + 0.5 mol L(-1) H(2)SO(4) solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L(-1) NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min(-1) and 0.069 min(-1), for Pt and Pt/Ti electrodes, respectively.

Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

Videography as production nexus : digital film cameras, media mangement and the distribution of creativity

This thesis is about new digital moving image recording technologies and how they augment the distribution of creativity and the flexibility in moving image production systems, but also impose constraints on how images flow through the production system. The central concept developed in this thesis is ‘creative space’ which links quality and efficiency in moving image production to time for creative work, capacity of digital tools, user skills and the constitution of digital moving image material. The empirical evidence of this thesis is primarily based on semi-structured interviews conducted with Swedish film and TV production representatives.This thesis highlights the importance of pre-production technical planning and proposes a design management support tool (MI-FLOW) as a way to leverage functional workflows that is a prerequisite for efficient and cost effective moving image production.

Film som kommunikation : En studie av gymnasieungdomars filmarbete

The starting point for this work was a discussion between my supervisor and myself during my teaching training. The discussion concerned the appropriateness of allowing students make films with sexual content. Film gives young people the opportunity to express their feelings and broaden their views. If the film then disseminates to unknown people via in-ternet, which it most likely will do, maybe it is no longer so positive. The aim of this study is to shed light on various aspects of identity and ethics that are important to keep in mind when young people in school make films. These aspects are to avoid making young people vulnerable to abuse and improper influence. One aim is also to highlight the advantages of making films in school. The study is inspired by hermeneutic interpretive and based on qualitative interviews. The informants are four students at the age of 18-19 at two different schools in one municipality in Sweden.The results of the study show that it is important for the informants that the films are pro-duced in an aesthetically good way so that it appeals to the audience. Two of the infor-mants have a specific audience and make more conscious choices, so that the audience will understand what is said. The study shows that the more a filmmaker considers the audi-ence, the more consciously he or she uses film as communication. To get positive feedback is important, but it is mostly friends of the filmmakers that actually comment. To get nega-tive comments is regarded as a disadvantage when placing material on the internet. Howev-er, none of the informants in the study have received negative comments on what has been posted. The opinions about what the informants believe is inappropriate to post on inter-net or to make films about regards sexuality and violations. Earlier studies show that mate-rial can, because it is interesting to other people, become widespread. For this reason it is important for teachers to have conversations with students about their preferences and opinions on various issues. Adults need to interfere in the young people's world, while be-ing open to their opinions. Then the young people's value system will be built up and give them a safe tool that helps them to avoid improper influence.

Photovoltaic System Design for a Contaminated Area in Falun – Comparison of South and East- West Layout

In this thesis the solar part of a large grid-connected photovoltaic system design has been done. The main purpose was to size and optimize the system and to present figures helping to evaluate the prospective project rationality, which can potentially be constructed on a contaminated area in Falun. The methodology consisted in PV market study and component selection, site analysis and defining suitable area for solar installation; and system configuration optimization based on PVsyst simulations and Levelized Cost of Energy calculations. The procedure was mainly divided on two parts, preliminary and detailed sizing. In the first part the objective was complex, which included the investigation of the most profitable component combination and system optimization due to tilt and row distance. It was done by simulating systems with different components and orientations, which were sized for the same 100kW inverter in order to make a fair comparison. For each simulated result a simplified LCOE calculation procedure was applied. The main results of this part show that with the price of 0.43 €/Wp thin-film modules were the most cost effective solution for the case with a great advantage over crystalline type in terms of financial attractiveness. From the results of the preliminary study it was possible to select the optimal system configuration, which was used in the detailed sizing as a starting point. In this part the PVsyst simulations were run, which included full scale system design considering near shadings created by factory buildings. Additionally, more complex procedure of LCOE calculation has been used here considered insurances, maintenance, time value of money and possible cost reduction due to the system size. Two system options were proposed in final results; both cover the same area of 66000 m2. The first one represents an ordinary South faced design with 1.1 MW nominal power, which was optimized for the highest performance. According to PVsyst simulations, this system should produce 1108 MWh/year with the initial investment of 835,000 € and 0.056 €/kWh LCOE. The second option has an alternative East-West orientation, which allows to cover 80% of occupied ground and consequently have 6.6 MW PV nominal power. The system produces 5388 MWh/year costs about 4500,000 € and delivers electricity with the same price of 0.056 €/kWh. Even though the EW solution has 20% lower specific energy production, it benefits mainly from lower relative costs for inverters, mounting and annual maintenance expenses. After analyzing the performance results, among the two alternatives none of the systems showed a clear superiority so there was no optimal system proposed. Both, South and East-West solutions have own advantages and disadvantages in terms of energy production profile, configuration, installation and maintenance. Furthermore, the uncertainty due to cost figures assumptions restricted the results veracity.

Caracterização Microestrutural e Tribocorrosiva de Sistemas Metalocerâmicos Odontológicos do Tipo Ni-Cr/Porcelana E Ni-Cr/Ti/Porcelana

The partial fixed prosthodontics restoration is used to rehabilitate form and function of partial or total compromised teeth, having to remain permanently joined to remainder tooth. The most useful material on prosthodontics is the feldspar porcelain, commercialized as aluminosilicate powders. Dental porcelains are presented with limited mechanical properties to rehabilitate extensive spaces. The association with Ni-Cr metallic systems (metal-ceramic system) allows that the metallic substructure compensates the fragile porcelain nature, preserving the thermal insulation and aesthetics desirable, as well as reducing the possibility of cracking during matication efforts. Cohesive flaws by low mechanical strength connect the metallic substructure to the oral environment, characterized by a electrolytic solution (saliva), by aggressive temperature, pH cyclic changes and mechanical requests. This process results on ionic liberation that could promote allergic or inflammatory responses, and/or clinical degradation of ceramometal system. The aim of this study was to evaluate the presence of an intermediate titanium layer on the microscopic fracture behavior of porcelains on ceramometal systems. Plasma deposition of titanium films result in regular passivating oxide layers which act as barriers to protect the metallic substrate against the hazardous effects of corrosive saliva. Tribocorrosion tests were performed to simulate the oral environment and mechanical stress, making it possible the early detection of crack formation and growth on metal-ceramic systems, which estimate the adherence between the compounds of this system. Plain samples consisting of dental feldspar porcelain deposited either onto metallic substrates or titanium films were fired and characterized by scanning electron microscopy. The result showed that the titanium film improved the adherence of the system compared to conventional metal-ceramic interfaces, thus holding crack propagation

Preliminary results of a floating subirrigation system (Aquaforest system) as an alternative to conventional tree nurseries

A new methodology for tree seedling production (Aquaforest system) based on a continuous floating subirrigation system was developed and tested using creeks with different nutrient levels. Eucalyptus grandis seedlings were produced in water from polluted and clean creeks, and compared to conventional tree nursery production. The growth variables analyzed in the seedling phase were: survival, height, diameter, shoot and root dry weight, leaf area, and root/shoot ratio. Water and substrate were analyzed, as well as leaf nutritional status. Plant survival was 100% in all treatments. Height and diameter were greater in the higher nutrient water treatment. Leaf area and dry weight of plants produced in the higher nutrient water treatment were similar to those of the control. The results showed that polluted water can represent a good nutrient source. The preliminary results show that the Aquaforest system can be a viable alternative for tree seedling production. (C) 2004 Elsevier B.V. All rights reserved.

Film based on Y2O3: Eu3+ (5 mol% of Eu3+) for flat panel display

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Spray layer-by-layer films based on phospholipid vesicles aiming sensing application via e-tongue system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Numerical simulation of the liquid phase in SnO2 thin film deposition by sol-gel-dip-coating

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)