Electrochromic properties of sputter-deposited nickel-based oxide films have been studied with a two-fold goal. From a practical point of view, the optical switching performance has been improved by optimizing the deposition conditions and film stoichiometry with respect to oxygen and hydrogen, and further by adding Mg, Al, Si, Zr, Nb or Ta to the films. From a theoretical point of view, details of the coloration mechanism have been studied by means of electrochemical intercalation (CV, GITT), optical measurements (UV, VIS, NIR and MIR), RBS, XRD, XPS and EXAFS. Optimization of deposition conditions has been illustrated by the example of films made by sputtering of a non-magnetic Ni(93)V(7) % wt. target in an atmosphere of Ar/O2/H2. The optimized films exhibit transmittance modulation between 20% and 75 % at 18 mC/cm2 charge intercalation. The remaining problem with nickel oxide and nickel vanadium oxide films is their residual yellow-brown color tint in the bleached state, which disappears as the short-wavelength transmittance increases upon addition of Mg, Al, Zr or Ta. Optimization of deposition conditions by co-sputtering from two targets and the film composition for mixed oxide films has been illustrated by the example of nickel aluminium oxide. The mechanisms of coloration upon electrochemical charge insertion and ozone exposure have been investigated. In the beginning of the electrochemical cycling, first, a reconstruction and crystallization is observed with the outer most part of the grain surface being transformed from oxygen rich nickel oxide into nickel oxy-hydroxide and hydroxide by transfer of H+ and OH- groups. After the charge capacity has been stabilized, only a transfer of H+ occurs with two reversible reactions involved: the first one from Ni(OH)2 to NiOOH and the second one from NiO and Ni(OH)2 to Ni2O3. Ozone coloration is described by a similar reaction scheme. The ozone molecule is split on the surface and dehydrogenates Ni(OH)2 into NiOOH. Further dehydrogenation produces Ni2O3 as in the electrochemical coloration.

In this study, WO3 and NiO thin films were deposited on the ITO/Glass substrates by radio frequency (RF) magnetron sputtering, respectively. The physical and electrochromic properties of thin films were investigated. On the other hand, the lithium perchlorate (LiClO4) powder was dispersed in propylene carbonate (PC) solvent to complete 1 M electrolyte. Then, as the 4.5 wt.% of ethyl cellulose and 8 wt.% ethylene carbonate (EC) were added to this electrolyte under stirring, a gel polymer electrolyte (GPE) was formed. Finally, the WO3 and NiO thin films obtained with the optimal deposition parameters were combined with the GPE to set up a complementary electrochromic device (CECD). The effects of the various coloring voltages on the electrochromic properties of CECD are investigated. The memory effect, energy-saving efficient, response time and switch lifetime of CECD are also estimated and discussed. Experimental results reveal that the amorphous thin films can be obtained with the RF power of 100 W and oxygen concentration of 60% at room temperature (RT). The thicknesses of WO3 and NiO films were approximately 530 nm and 180 nm, respectively. The stoichiometric of thin films were 2.99 for O/W ratio and 1.01 for O/Ni ratio. The GPE [(1 M LiClO4+PC)+ethyl cellulose(4.5 wt.%)+EC(8 wt.%)] exhibits a viscosity coefficient of 100 mPa∙s, a maximum ion conductivity (£m) of 7.17 mS/cm, a minimum activation energy (Ea) of 0.033 eV and a average visible transmittance of 82% at RT. The optimal electrochromic CECD (Glass/ITO/WO3/GPE/NiO/ITO/Glass) biased with a coloring/bleaching voltage of ¡Ó2.2 V revealed a transmittance variation (£GT%) of 54.53%, an optical density change (£GOD) of 0.790, an intercalation charge (Q) of 6.28 mC/cm2 and a coloration efficiency (£b) of 125.21 cm2/C at a wavelength (£f) of 550 nm. The chromaticity coordinates of CECD were x=0.289 and y=0.365 under the colored state. In addition, the energy-saving efficient of CECD was 15.19 W/V-m2 over the wavelength range between 380 nm and 780 nm. Also, it presented an open-circuit memory effect that the colored transmittance (£f at 550 nm) was 18.9% in 24 h. The total response time of the CECD was about 4 s for coloring and bleaching steps. After the repeated switch of 1,000 times, the £GT% of CECD was 43.57%. In this study, WO3 and NiO thin films with good adhesion, amorphous, and nearly stoichiometric were successfully deposited by RF sputter. Furthermore, high £m and high transmittance of GPE can be prepared easily and inexpensively. Our results demonstrated that the CECD exhibited the advantages of low applied voltage, high £b, fast response time and long-term memory characteristics.

Cette thèse s'intéresse aux problématiques fondamentales d'optimisation combinatoire qui se dégagent de la modélisation structurelle et algorithmique du dimensionnement des réseaux d'infrastructure de télécommunication. L'optimisation de ces réseaux est essentielle aux opérateurs de télécommunication, qui demandent la garantie d'une exploitation efficace des ressources déployées.<br /><br />Nous donnons une nouvelle modélisation des réseaux optiques WDM multifibres. En considérant un routage agrégé au niveau des câbles, nous optons pour une nouvelle lecture des contraintes d'affectation de longueurs d'onde fondée sur des conflits de groupe.<br /><br />Nous étudions aussi le problème de coloration de chemins, issu de l'affectation de longueurs d'onde dans les réseaux optiques monofibres. Nous développons, pour la relaxation linéaire de ce problème, un algorithme polynomial efficace dans les arbres de degré borné, puis, par extension, dans les graphes de largeur arborescente bornée. Nous majorons le coût d'une telle coloration dans les arbres binaires et donnons une (1+5/(3e)+o(1))-approximation aléatoire pour la coloration entière dans les arbres de degré borné, ce qui améliore le meilleur algorithme connu pour ce cas.<br /><br />Nous présentons enfin des avancées algorithmiques pour les problèmes de multiflot entier et fractionnaire. Nous donnons un algorithme d'arrondi aléatoire incrémental pour l'approximation du multiflot entier. Motivés par le besoin d'un calcul rapide de multiflot fractionnaire pour l'algorithme précédent, nous nous intéressons aux approximations combinatoires de ce problème. En employant des techniques de calcul dynamique des plus courts chemins, nous améliorons l'un des meilleurs algorithme de la littérature.<br />Webstats4U - Free web site statistics

Cette thèse présente différents aperçus de problèmes de mathématiques discrètes en lien avec la théorie des graphes. Elle s'intéresse en particulier à la coloration de graphes, i.e. l'assignation de couleurs aux sommets (ou arêtes) d'un graphes sous certaines contraintes locales, notamment l'exclusion de motifs. Pour différents types de coloration (choisissabilité des sommets, des arêtes, coloration acyclique ou linéaire, ...), un état de l'art est présenté, accompagné de résultats d'existence sur les graphes planaires ou leurs sous-classes, ayant pour but de minimiser le nombre de couleurs nécessaires pour un degré maximum ou un degré moyen maximum (Mad) donnés. Cette thèse traite également de décompositions induites de graphes, et démontre qu'il existe pour tout graphe $H$ une suite infinie de graphes denses dont les arêtes peuvent être partitionnées en copies induites de $H$. Cette preuve requiert le formalisme des hypergraphes, pour lesquels un autre résultat de décomposition est démontré, i.e. une décomposition optimale de l'hypergraphe complet 3-régulier en hypergraphes $\alpha$-acycliques. La troisième parti porte sur des questions algorithmiques. Elles consistent en problèmes d'optimisation ou d'existence, motivés par le routage d'information dans les réseaux, analysés par le formalisme classique de complexité algorithmique, ou traitent de la recherche de sous-graphes dans le formalisme de la complexité paramétrée. Dans une quatrième partie sont considérés des problèmes de comptage issus de la chimie, suivis de la présentation de Programmes Linéaires Entiers utilisés dans le logiciel de mathématiques Sage.

Identification of viable vat dye candidates of a trichromatic series (compatible red, yellow and blue colorants) plus an orange based on the developed single-stage acid leuco vat dyeing process for unmodified polypropylene (PP) flat woven fabrics has been achieved with adequate fastness properties to washing, crocking and dry-cleaning: C. I. Vats Orange 1, Yellow 2 and Red 1 have been certified, whereas Vat Blue 6 is a marginal candidate. Vat Blue 1 has been demonstrated to be a viable colorant for dyeing of PP fiber as a single colorant. Molecular dynamics simulation and solubility parameter (SP) approaches have been utilized to screen the potential vat dye candidates for generic PP coloration. Experimental K/S results have exhibited good correlation with the predicted mixing energy of acid leuco vat dyes-PP fiber and the calculated dyes' SP's. The low SP/mixing energy acid leuco vat dyes (e.g., C. I. Vat Red 1) have shown better color-yield/fastness properties than the high SP/mixing energy vat dyes (e.g., C. I. Vat Brown 1), exhibiting that increasing difference of SP between the vat dye and the PP fiber, coupled with a higher mixing energy of dye-PP blend, resulted in decreased interactions between the two. For example, C.I. Vat Brown 1 with its high SP and calculated mixing energy with PP gave least color yield than the certified vat dyes, all with lower SP's and mixing energies. Cross-section micrographs of the dyed fibers revealed the absence of "ring-dyeing". Experimentally determined kinetic parameters such as affinity of dyeing and heat of dyeing quantified the presence of interaction between acid leuco vat dyes and PP fiber. Tensile test and X-ray crystallinity results have confirmed that dyeing process did not alter the tensile strength and modulus of the dyed PP textiles significantly. PP Fabrics dyed with simulated continuous dyeing processes (pad-steam and pad-dry heat) demonstrated good color yields and levelness with adequate fastness to crocking, washing and dry cleaning.

abstract: Differences between males and females can evolve through a variety of mechanisms, including sexual and ecological selection. Because coloration is evolutionarily labile, sexually dichromatic species are good models for understanding the evolution of sex differences. While many jumping spiders exhibit diverse and brilliant coloration, they have been notably absent from such studies. In the genus Habronattus, females are drab and cryptic while males are brilliantly colored, displaying some of these colors to females during elaborate courtship dances. Here I test multiple hypotheses for the control and function of male color. In the field, I found that Habronattus males indiscriminately court any female they encounter (including other species), so I first examined the role that colors play in species recognition. I manipulated male colors in H. pyrrithrix and found that while they are not required for species recognition, the presence of red facial coloration improves courtship success, but only if males are courting in the sun. Because light environment affects transmission of color signals, the multi-colored displays of males may facilitate communication in variable and unpredictable environments. Because these colors can be costly to produce and maintain, they also have the potential to signal reliable information about male quality to potential female mates. I found that both red facial and green leg coloration is condition dependent in H. pyrrithrix and thus has the potential to signal quality. Yet, surprisingly, this variation in male color does not appear to be important to females. Males of many Habronattus species also exhibit conspicuous markings on the dorsal surface of their abdomens that are not present in females and are oriented away from females during courtship. In the field, I found that these markings are paired with increased leg-waving behavior in a way that resembles the pattern and behavior of wasps; this may provide protection by exploiting the aversions of predators. My data also suggest that different activity levels between the sexes have placed different selection pressures on their dorsal color patterns. Overall, these findings challenge some of the traditional ways that we think about color signaling and provide novel insights into the evolution of animal coloration. / Dissertation/Thesis / Ph.D. Biology 2012

Les décompositions de graphes, lorsqu’elles sont de petite largeur, sont souvent utilisées pour résoudre plus efficacement des problèmes étant difficiles dans le cas de graphes quelconques. Dans ce travail de thèse, nous nous intéressons aux limites liées à ces décompositions, et à la construction d’obstructions certifiant leur grande largeur. Dans une première partie, nous donnons un algorithme généralisant et unifiant la construction d’obstructions pour différentes largeurs de graphes, en temps XP lorsque paramétré par la largeur considérée. Nous obtenons en particulier le premier algorithme permettant de construire efficacement une obstruction à la largeur arborescente en temps O(ntw+4). La seconde partie de notre travail porte sur l’étude du problème ENSEMBLE [σ, ρ]-DOMINANT, une généralisation des problèmes de domination sur les graphes et caractérisée par deux ensembles d’entiers σ et ρ. Les diverses études de ce problème apparaissant dans la littérature concernent uniquement les cas ou le problème est FPT, lorsque paramétré par la largeur arborescente. Nous montrons que ce problème ne l’est pas toujours, et que pour certains cas d’ensembles σ et ρ, il devient W[1]-difficile lorsque paramétré par la largeur arborescente. Dans la dernière partie, nous étudions la complexité d’un nouveau problème de coloration appelé k-COLORATION ADDITIVE, combinant théorie des graphes et théorie des nombres. Nous montrons que ce nouveau problème est NP-complet pour tout k ≥ 4 fixé, tandis qu’il peut être résolu en temps polynomial sur les arbres pour k quelconque et non fixé. / Graphs decompositions of small width are usually used to solve efficiently problems which are difficult in general. In this thesis, we focus on some limits of these decompositions, and the construction of some obstructions certifying a large width. First, we give a generic algorithm unifying obstructions’ construction for several graph widths, in XP time when parameterized by the considered width. In particular, it gives the first algorithm computing efficiently an obstruction to tree-width in time O(ntw+4). Secondly, we study the parameterized complexity of [σ, ρ]-DOMINATING SET, a generalization of some domination problems characterized by two sets of integers σ and ρ. All known studies focused only on cases where this problem is FPT when parameterized by tree-width. In this work, we show that there are some cases where the problem is no longer FPT, and become W[1]-hard instead. Finally, we study the computational complexity of a new coloration problem, named k-ADDITIVE COLORING, which combines both graph theory and number theory. We show that this new problem is NP-complete for any fixed number k ≥ 4, while it can be solved in polynomial time on trees for any k.

The aim of this thesis was to establish a photographic database of selected species of diving beetles (Coleoptera: Dytiscidae) and use image analysis to characterize the number and extent of colour spots. Altogether 52 species were analyzed. They were classified into fourgroups based on their environmental characteristics provided in the Catalogue of water beetles of Czech Republic. The results confirmedthe hypothesis that the colour of adult diving beetles is correlated to their habitat preferences.

abstract: Warning coloration deters predators from attacking prey that are defended, usually by being distasteful, toxic, or otherwise costly for predators to pursue and consume. Predators may have an innate response to warning colors or learn to associate them with a defense through trial and error. In general, predators should select for warning signals that are easy to learn and recognize. Previous research demonstrates long-wavelength colors (e.g. red and yellow) are effective because they are readily detected and learned. However, a number of defended animals display short-wavelength coloration (e.g. blue and violet), such as the pipevine swallowtail butterfly (Battus philenor). The role of blue coloration in warning signals had not previously been explicitly tested. My research showed in laboratory experiments that curve-billed thrashers (Toxostoma curvirostre) and Gambel's quail (Callipepla gambelii) can learn and recognize the iridescent blue of B. philenor as a warning signal and that it is innately avoided. I tested the attack rates of these colors in the field and blue was not as effective as orange. I concluded that blue colors may function as warning signals, but the effectiveness is likely dependent on the context and predator. Blue colors are often iridescent in nature and the effect of iridescence on warning signal function was unknown. I reared B. philenor larvae under varied food deprivation treatments. Iridescent colors did not have more variation than pigment-based colors under these conditions; variation which could affect predator learning. Learning could also be affected by changes in appearance, as iridescent colors change in both hue and brightness as the angle of illuminating light and viewer change in relation to the color surface. Iridescent colors can also be much brighter than pigment-based colors and iridescent animals can statically display different hues. I tested these potential effects on warning signal learning by domestic chickens (Gallus gallus domesticus) and found that variation due to the directionality of iridescence and a brighter warning signal did not influence learning. However, blue-violet was learned more readily than blue-green. These experiments revealed that the directionality of iridescent coloration does not likely negatively affect its potential effectiveness as a warning signal. / Dissertation/Thesis / Doctoral Dissertation Biology 2015

Submitted by Daniele Amaral (daniee_ni@hotmail.com) on 2016-09-23T18:23:03Z No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:32:57Z (GMT) No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:33:07Z (GMT) No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Made available in DSpace on 2016-09-26T18:33:15Z (GMT). No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) Previous issue date: 2015-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Horticultural crops are an important food source for global population. However, crops still show high rates of postharvest losses, due to its high perishability. Ethylene is a plant hormone that regulates aspects such as growth, development, maturation and senescence of plants and their organs. Ethylene production varies between crops and its control can extend the life of fruits and vegetables. Many technologies have been developed in order to control the synthesis and reduce ethylene produced by plants. Oxidation through potassium permanganate (KMnO4) has application in storage, transportation and marketing. Typically, KMnO4 is impregnated in porous platforms displaying high specific surface are, which are aimed at removing ethylene within packaging. Ethylene can be oxidized by KMnO4, which subproducts (after subsequent oxidation), can be converted into water (H2O) and carbon dioxide (CO2). The use of platforms based on mesoporous nanoparticles (with diameters of 5-110 nm) impregnated with KMnO4 allows ethylene oxidation to be carried out more efficiently, once it increases the contact surface area. In this context, this study aimed at developing ethylene absorbers based on nanometric platforms (nanosilica and nanoalumina), associated with potassium permanganate (KMnO4), to remove ethylene produced during postharvest and use color changes during ethylene oxidation as a colorimetric indicator. The performance of nanometric platforms was compared to conventional silica and alumina. The following KMnO4 concentrations impregnated in the platforms were tested: 0; 2.5; 5 to 10%, which values are, respectively, half, equal and twice the values found in commercial ethylene removers. Since relative humidity is a factor that influences ethylene oxidation by KMnO4, the following UR were tested: 45, 60, 75, and 90%. The platforms impregnated with different KMnO4 concentrations and subjected to several RH in closed system, were exposed to a standardized amount of ethylene produced in the laboratory. After 1h and 24h of exposition, injection aliquots were collected for analysis by gas chromatography. The color was measured before placing samples in the closed system and after 24 hours. The silica nanoparticles, synthesized silica and alumina showed superior performance for ethylene absorption, especially when aliquots removal was evaluated in 1h. Among the tested nanoparticles, alumina nanoparticles showed to be the most effective, being able to completely remove the ethylene after 1h, under a greater variety of RH conditions and KMnO4 concentrations. The most suitable combinations, in accordance with the highest color difference and high ethylene absorption performance were synthesized nano-silica + 10% KMnO4 and nano-alumina + 10 % KMnO4 for RH = 45%; nanosilica + 10% KMnO4 and nano-alumina + 10% KMnO4 for RH= 60%; nano-silica + 10% of KMnO4, nano-alumina + 5% KMnO4 and nano-alumina + 10% KMnO4 for RH= 75 and 90%. / Os produtos hortícolas são uma importante fonte de alimentação para população global. Todavia, ainda são registrados elevados índices de perdas desses alimentos, devido a sua alta perecibilidade após a colheita. O etileno é um hormônio vegetal que regula aspectos como o crescimento, desenvolvimento, maturação e senescência de plantas e seus órgãos. A produção de etileno varia de acordo com o tipo de fruta e hortaliça, sendo que seu controle pode prolongar a vida útil dos produtos hortícolas. Muitas tecnologias já foram desenvolvidas afim de controlar a síntese e reduzir o etileno produzido pelos frutos. Por exemplo, a oxidação do etileno por meio do uso de permanganato de potássio (KMnO4) apresenta aplicação no armazenamento, transporte e comercialização. Geralmente o KMnO4 é impregnado em plataformas porosas acondicionadas em sachês, visando a remoção do etileno dentro de embalagens. O etileno oxidado gera subprodutos, que após novas oxidações, será convertido em água (H2O) e gás carbônico (CO2). A utilização de nanopartículas mesoporosas, com diâmetros da ordem de 5 a 110 nm, como plataformas para adsorção de KMnO4 permite que a oxidação do etileno seja realizada com maior eficiência, devido a maior área superficial de contato. Neste contexto, o objetivo deste trabalho foi desenvolver absorvedores de etileno baseados em plataformas nanométricas (nano-sílica comercial, nano-sílica sintetizada em laboratório e nano-alumina comercial), impregnadas com permanganato de potássio (KMnO4). Estas plataformas visam à remoção de etileno produzido por frutos durante a póscolheita, as quais causam alterações de coloração do KMnO4 durante a oxidação do etileno, e podem ser empregados como indicador colorimétrico de amadurecimento. O desempenho das plataformas de sílica e alumina nanométricas (comerciais e sintetizada) foram comparadas com sílica e alumina micrométricas (comerciais). Para a impregnação do KMnO4 nas diferentes plataformas, foram utilizadas concentrações (em relação a massa das plataformas) de 0; 2,5; 5 e 10% de KMnO4, cujos valores selecionados representam a metade, o valor médio e o dobro do teor de permanganato encontrado em sachês absorvedores comerciais. Os testes foram realizados em umidades relativas de 45, 60, 75, e 90%, já que esta variável altera fortemente a oxidação do etileno pelo KMnO4. As plataformas impregnadas com diferentes concentrações de KMnO4 em distintas UR, foram submetidas, em sistema fechado, a uma quantidade padronizada de 7480 μL de etileno produzida em laboratório. Após intervalos de 1h e 24h da injeção de etileno padrão, foram retiradas alíquotas para análise por cromatografia gasosa. A coloração foi aferida antes da inserção das amostras em sistema fechado e após 24h. As nanopartículas de sílica, sílica sintetizada e alumina apresentaram desempenho superior na absorção de etileno em relação a sílica e alumina de tamanhos convencionais, especialmente quando a remoção foi avaliada em 1h. Dentre as nanopartículas testadas, a nanopartícula de alumina foi a mais eficiente, sendo capaz de eliminar o montante de etileno injetado após 1h, sob um intervalo maior de condições de UR e concentração de KMnO4. A coloração pode ser indicativa da oxidação do etileno nas plataformas testadas e de acordo com a maior diferença de coloração e melhor desempenho de absorção de etileno, as combinações mais indicadas foram: nano-sílica sintetizada + 10% de KMnO4 e nano-alumina + 10% de KMnO4 para UR=45%; nano-sílica + 10% de KMnO4 e nano-alumina + 10% de KMnO4 para UR=60%; nano-sílica + 10% de KMnO4, nano-alumina + 5 % de KMnO4 e nano-alumina + 10% de KMnO4 para UR=75 e 90%.