Development of fire-resistant (B1 & B2) winter 1 KPU foams applied by gun or straw adapter and optimization of a gun applied winter 1 KPU foam

A realização do presente trabalho teve como principais objectivos o desenvolvimento de espumas de poliuretano de um componente com propriedades de resistência à chama superiores (B1 & B2), aplicadas por pistola ou por adaptador/tubo e a optimização de uma espuma de poliuretano de um componente de inverno aplicada por pistola. Todo o trabalho desenvolvido está dividido em dois projectos distintos: i. O primeiro projecto consistiu em desenvolver espumas de um componente com propriedades de resistência à chama (classificadas como B1 e B2 de acordo com a norma alemã DIN 4102), aplicadas por pistola (GWB1 e GWB2) ou por adaptador/tubo (AWB), utilizando polióis poliésteres aromáticos modificados e aditivos retardantes de chama halogenados. Estas espumas deveriam apresentar também propriedades aceitáveis a baixas temperaturas. Após realizar várias formulações foi possível desenvolver uma espuma AWB2 com apenas 3,3% de poliol poliéster no pré-polímero e com propriedades equivalentes às da melhor espuma comercial mesmo a 5/-10 (temperatura da lata/cura da espuma em °C) e também com uma altura de chama de apenas 11 cm. A partir de duas formulações (AWB2) que passaram o Teste B2, foram obtidas também, uma espuma GWB2 e outra GWB1 com propriedades equivalentes às da melhor espuma da concorrência a -10/-10 e a 23/5, respectivamente, embora não tenham sido submetidas ao teste B2 e B1 após as modificações efectuadas. ii. O segundo projecto consistiu em optimizar uma espuma de poliuretano de um componente de inverno aplicada por pistola (GWB3). A espuma inicial tinha problemas de glass bubbles quando esta era dispensada a partir de uma lata cheia, sendo necessário ultrapassar este problema. Este problema foi resolvido diminuindo a razão de GPL/DME através do aumento da percentagem em volume de DME no pré-polímero para 14% no entanto, a estabilidade dimensional piorou um pouco. O reagente FCA 400 foi removido da formulação anterior (6925) numa tentativa de diminuir o custo da espuma, obtendo-se uma espuma aceitável a 23/23 e a 5/5, com uma redução de 4% no custo da produção e com uma redução de 5,5% no custo por litro de espuma dispensada, quando comparada com a sua antecessora. Por último, foi avaliada a influência da concentração de diferentes surfactantes na formulação 6925, verificando-se o melhoramento da estrutura celular da espuma para concentrções mais elevadas de surfactante, sendo este efeito mais notório a temperaturas mais baixas (5/5). Dos surfactantes estudados, o B 8871 mostrou o melhor desempenho a 5/5 com a concentração mais baixa, sendo portanto o melhor surfactante, enquanto o Struksilon 8003 demonstrou ser o menos adequado para esta formulação específica, apresentando piores resultados globais. Pode-se ainda acrescentar que os surfactantes L-5351, L-5352 e B 8526 também não são adequados para esta formulação uma vez que as espumas resultantes apresentam cell collapse, especialmente a 5/5. No caso dos surfactantes L-5351 e L-5352, esta propriedade piora com concentrações mais elevadas. Em cada projecto foram também efectuados testes de benchmark em determinadas espumas comerciais com o principal objectivo de comparar todos os resultados das espumas desenvolvidas, em ambos os projectos, com espumas da concorrência.

Contributo da análise ergonómica do trabalho para o estudo de acidentes de trabalho em enfermeiros no serviço de urgência

Mestrado em Segurança e Higiene no Trabalho.

Dispositional optimism is unidimensional or bidimensional? The Portuguese Revised Life Orientation Test

The aim of the study is to adapt and then discuss the appropriateness of the Life Orientation Test as a one or two dimension scale. The research includes two studies; one is composed of a sequential sample of 280 people with multiple sclerosis, 71% female, and another includes a convenience sample of 615 individuals from the community, 51.1% female. Because the construct is built upon a theoretical assumption that has one dimension, we examine the hypothesis of one or two factor solutions through confirmatory factor analysis, and the two-dimension solution premise demonstrates better adjustment for both samples. The other psychometric properties explored show appropriate results for the Portuguese sample, and similar to the original ones; the Test therefore seems appropriate for use in cross cultural studies. Based on our results, we discuss whether the questionnaire is a one or two dimension instrument, concluding that it appears appropriate to accept the recommendations of the original authors to use it as a one-dimensional tool and, when necessary, to use both dimensions. - RESUMO: El objetivo del estudio es adaptar y discutir la adecuación de la prueba de Orientación de la Vida en una o dos escalas de dimensión. La investigación engloba dos estudios, uno constituido por una muestra secuencial de 280 personas con esclerosis múltiple, 71% mujeres y otro con una muestra de conveniencia de la comunidad de 615 individuos, 51,1% del sexo femenino. Como el constructo se asienta sobre la presunción teórica de que tiene una dimensión, inspeccionamos la hipótesis de una o dos soluciones de factor a través del análisis factorial confirmatorio y la hipótesis de dos dimensiones manifiesta un mejor ajuste para ambas muestras. Las otras propiedades psicométricas exploradas muestran los resultados apropiados para la muestra portuguesa, y semejantes a los originales. Parece apropiado para los estudios culturales transversales. Basándonos en nuestros resultados, discutimos si el cuestionario es un instrumento de una o dos dimensiones, concluyéndose que parece conveniente seguir las recomendaciones de los autores originales, para utilizarlo como un instrumento unidimensional y, si fuera necesario necesario, utilizar cada una de las dimensiones.

O regime de exigibilidade de caixa no IVA

Mestrado em Contabilidade

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.

Models with three Higgs doublets in the triplet representations of A(4) or S-4

We consider the quark sector of theories containing three scalar SU(2)(L) doublets in the triplet representation of A(4) (or S-4) and three generations of quarks in arbitrary A(4) (or S-4) representations. We show that for all possible choices of quark field representations and for all possible alignments of the Higgs vacuum expectation values that can constitute global minima of the scalar potential, it is not possible to obtain simultaneously nonvanishing quark masses and a nonvanishing CP-violating phase in the Cabibbo-Kobayashi-Maskawa quark mixing matrix. As a result, in this minimal form, models with three scalar fields in the triplet representation of A(4) or S-4 cannot be extended to the quark sector in a way consistent with experiment. DOI: 10.1103/PhysRevD.87.055010.

Capacitive effects in pinpin photodiodes

The application of a-SiC:H/a-Si:H pinpin photodiodes for optoelectronic applications as a WDM demultiplexer device has been demonstrated useful in optical communications that use the WDM technique to encode multiple signals in the visible light range. This is required in short range optical communication applications, where for costs reasons the link is provided by Plastic Optical Fibers. Characterization of these devices has shown the presence of large photocapacitive effects. By superimposing background illumination to the pulsed channel the device behaves as a filter, producing signal attenuation, or as an amplifier, producing signal gain, depending on the channel/background wavelength combination. We present here results, obtained by numerical simulations, about the internal electric configuration of a-SiC:H/a-Si:H pinpin photodiode. These results address the explanation of the device functioning in the frequency domain to a wavelength tunable photo-capacitance due to the accumulation of space charge localized at the bottom diode that, according to the Shockley-Read-Hall model, it is mainly due to defect trapping. Experimental result about measurement of the photodiode capacitance under different conditions of illumination and applied bias will be also presented. The combination of these analyses permits the description of a wavelength controlled photo-capacitance that combined with the series and parallel resistance of the diodes may result in the explicit definition of cut off frequencies for frequency capacitive filters activated by the light background or an oscillatory resonance of photogenerated carriers between the two diodes. (C) 2013 Elsevier B.V. All rights reserved.

Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives - Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies

The compounds [mPTA][CoCl4] (1, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [CoCl(H2O)(DION)(2)][BF4] (2, DION = 1,10-phenanthroline-5,6-dione), [Zn(DION)(2)]Cl-2 (3) and [ZnCl(O-PTA=O)(DION)][BF4] (4) were synthesized by reaction of CoCl2 with [mPTA]I or DION and ZnCl2 with DION or 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTA=O) and DION, respectively. All complexes are water soluble and have been characterized by IR, far-IR, H-1, C-13 and P-31{H-1} NMR spectroscopy, ESI-MS, elemental analyses and single-crystal X-ray diffraction structural analysis (for 1). They were screened against the human tumour cell lines HCT116, HepG2 and MCF7. Complexes 2 and 3 exhibit the highest in vitro cytotoxicity and show lower cytotoxic activities in normal human fibroblast cell line than in HCT116 tumour cell line, which demonstrates their slight specificity for this type of tumour cell.

Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer-Villiger Oxidation of Ketones

New rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

An application of structural equation modeling of test dispositional optimism as mediator or moderator in quality of life in patients with chronic disease

The aim of the present study was to test a hypothetical model to examine if dispositional optimism exerts a moderating or a mediating effect between personality traits and quality of life, in Portuguese patients with chronic diseases. A sample of 540 patients was recruited from central hospitals in various districts of Portugal. All patients completed self-reported questionnaires assessing socio-demographic and clinical variables, personality, dispositional optimism, and quality of life. Structural equation modeling (SEM) was used to analyze the moderating and mediating effects. Results suggest that dispositional optimism exerts a mediator rather than a moderator role between personality traits and quality of life, suggesting that “the expectation that good things will happen” contributes to a better general well-being and better mental functioning.

O processo de reconhecimento, validação e certificação de competências em adultos com deficiências e incapacidades

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ciências da Educação - Especialidade Educação Especial

Coordenação e fiscalização de obras na empresa Landway, S.A.

Relatório de Estágio para obtenção do grau de Mestre em Engenharia na Área de Especialização em Edificações

O Balanced Scorecard: estudo do processo e mecanismos para ser uma ferramenta imprescindível no contexto organizacional

Mestrado em Contabilidade

A liquidação do IRS: uma análise à actuação oficiosa

Mestrado em Fiscalidade

A importância do follow-up na auditoria interna em Portugal

Mestrado em Auditoria