Creación de una filmoteca de prácticas para la Facultad de Ciencias de la Información de la UCM: Adecuación de espacio y estrategias de catalogación

En el presente trabajo se da el primer paso para la creación de una Filmoteca de Prácticas en la facultad de Ciencias de la Información de la Universidad Complutense de Madrid. El Patrimonio Fílmico se ve gravemente expuesto al paso del tiempo y el abandono por lo que se necesita un rescate urgente. Mediante un riguroso trabajo de investigación, en el que se estudian diferentes propuestas y normativas expuestas por organismos especializados, se redacta un manual de inicio. Se han investigado, diseñado y propuesto las herramientas básicas y útiles para poner en funcionamiento la primera Filmoteca de Prácticas en el ámbito universitario español.

Degradation of poly-L-lactide. Part 1: in vitro and in vivo physiological temperature degradation

Poly-L-Lactide is a bioresorbable polymer which degrades through hydrolysis of its ester linkage influenced by initial molecular weight and degree of crystallinity. Polymers belonging to the aliphatic polyester family currently represent the most attractive group of polymers that meet the medical and physical demands for safe clinical applications. Compression moulded PLLA pellets were produced as rods, sterilized and degraded both in vitro and in vivo (sub-dermal implantation model). The material molecular weight, crystallinity, mechanical strength and thermal properties were evaluated. In both in vitro and in vivo environments, degradation proceeded at the same rate and followed the general sequence of aliphatic polyester degradation, ruling out enzymes accelerating the degradation rate in vivo. By 44 weeks duration of implantation the PLLA rods were still biocompatible, before any mass loss was observed.

Influence of plasticizer type and storage conditions on properties of poly(methyl vinyl ether-co-maleic anhydride) bioadhesive films

Poly(methyl vinyl ether-co-maleic anhydride) formed films from aqueous formulations with characteristics that are ideal as a basis for producing a drug-containing bioadhesive delivery system when plasticized with a monohydroxyl functionalized plasticizer. Hence, films containing a novel plasticizer, tripropylene glycol methyl ether (TPME), maintained their adhesive strength and tensile properties when packaged in aluminized foil for extended periods of time. Films plasticized with commonly used polyhydric alcohols, such as the glycerol in this study, underwent an esterification reaction that led to polymer crosslinking, as shown in NMR studies. These revealed the presence of peaks in the ester/carbonyl region, suggesting that glyceride residue formation had been initiated. Given the polyfunctional nature of glycerol, progressive esterification would result in a polyester network and an accompanying profound alteration in the physical characteristics. Indeed, films became brittle over time with a loss of both the aqueous solubility and bioadhesion to porcine skin. In addition, a swelling index was measurable after 7 days, a property not seen with those films containing TPME. This change in bioadhesive strength and pliability was independent of the packaging conditions, rendering the films that contain glycerol as unsuitable as a basis for topical bioadhesive delivery of drug substances. Consequently, films containing TPME have potential as an alternative formulation strategy.

The influence of video games with apocalyptic content in adolescents

The aim of this study is the dissertation and analysis of the influence (sociological, psychological and cultural) exerted on adolescents by the concept of Apocalypse. Become a key thought of visual culture, the called doomsday theory achieves one of its highest expressions in video games, possibly the favorite entertainment for young people in their leisure time. The results obtained in this research represent a first approach to the subject through the selected samples, two secondary schools from the city of Seville with disparate locations and divergent socioeconomic backgrounds. To reinforce the comparative study, we have included issues related to parental control, principal gaming platforms used by respondents or the number of hours dedicated to this type of entertainment. The conclusions demonstrate an irremediable attraction from our youth towards apocalyptic universes, plotter consciously with leisure and entertainment as escape from their routine of everyday life.

Performance enhancement of polymer nanocomposites via multiscale modelling of processing and properties

This paper provides an overview of research on modelling of the structure–property interactions of polymer nanocomposites in manufacturing processes (stretch blow moulding and thermoforming) involving large-strain biaxial stretching of relatively thin sheets, aimed at developing computer modelling tools to help producers of materials, product designers and manufacturers exploit these materials to the full, much more quickly than could be done by experimental methods alone. The exemplar systems studied are polypropylene and polyester terephalate, with nanoclays. These were compounded and extruded into 2mm thick sheet which was then biaxially stretched at 155°C for the PP and 90 to 100°C for the PET. Mechanical properties were determined for the unstretched and stretched materials, together with TEM and XRD studies of structure. Multi-scale modelling, using representative volume elements is used to model the properties of these products.

New methods in Biomass Depolymerisation: Catalytic Hydrogenolysis of Barks

Hydrogenolysis of bark from three different species of tree using heterogeneous platinum group metal catalysts produces two major product streams. Aromatic substituted guaiacols are produced from lignin and the lignin-like regions of suberin and a range of saturated fatty acids and alcohols, including a,?-functionalised species, are produced from the polyester regions of suberin. Control experiments demonstrate clear advantages of catalytic hydrogenolysis over base hydrolysis, both in terms of conversion and product selectivity.

Application of fibre assemblies as damping elements in the automotive industry

This investigation aims to characterise the damping properties of the nonwoven materials with potential applications in automotive and aerospace industry. Nonwovens are a popular choice for many applications due to their relatively low manufacturing cost and unique properties. It is known that nonwovens are efficient energy dispersers for certain applications such as acoustic damping and ballistic impact. It is anticipated that these energy absorption properties could eventually be used to provide damping for mechanical vibrations. However the behaviour of nonwovens under dynamic load and vibration has not been investigated before. Therefore we intend to highlight these aspects of the behaviour of the nonwovens through this research. In order to obtain an insight to the energy absorption properties of the nonwoven fabrics, a range of tests has been performed. Forced vibration of the cantilever beam is used to explore damping over a range of resonance modes and input amplitudes. The tests are conducted on aramid, glass fibre and polyester fabrics with a range of area densities and various coatings. The tests clarified the general dynamic behaviour of the fabrics tested and the possible response in more real application condition as well. The energy absorption in both thickness and plane of the fabric is tested. The effects of the area density on the results are identified. The main absorption mechanism is known to be the friction. The frictional properties are improved by using a smaller fibre denier and increasing fibre length, this is a result of increasing contact surface between fibres. It is expected the increased friction result in improving damping. The results indicate different mechanism of damping for fiber glass fabrics compared to the aramid fabrics. The frequency of maximum efficiency of damping is identified for the fabrics tested. These can be used to recommend potential applications.

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Although the use of ball milling to induce reactions between solids (mechanochemical synthesis) can provide lower-waste routes to chemical products by avoiding solvent during the reaction, there are further potential advantages in using one-pot multistep syntheses to avoid the use of bulk solvents for the purification of intermediates. We report here two-step syntheses involving formation of salen-type ligands from diamines and hydroxyaldehydes followed directly by reactions with metal salts to provide the corresponding metal complexes. Five salen-type ligands 2,2'-[1,2-ethanediylbis[(E)-nitrilomethylidyne]] bisphenol, ` salenH2', 1; 2,2'-[(+/-)-1,2-cyclohexanediylbis-[(E)-nitrilomethylidyne]] bis-phenol, 2; 2,2'-[1,2-phenylenebis( nitrilomethylidyne)]-bis-phenol, ` salphenH2' 3; 2-[[(2-aminophenyl) imino] methyl]-phenol, 4; 2,2'-[(+/-)-1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]]-bis[4,6-bis(1,1-dimethylethyl)]-phenol, ` Jacobsen ligand', 5) were found to form readily in a shaker-type ball mill at 0.5 to 3 g scale from their corresponding diamine and aldehyde precursors. Although in some cases both starting materials were liquids, ball milling was still necessary to drive those reactions to completion because precipitation of the product and or intermediates rapidly gave in thick pastes which could not be stirred conventionally. The only ligand which required the addition of solvent was the Jacobsen ligand 5 which required 1.75 mol equivalents of methanol to go to completion. Ligands 1-5 were thus obtained directly in 30-60 minutes in their hydrated forms, due to the presence of water by-product, as free-flowing yellow powders which could be dried by heating to give analytically pure products. The one-armed salphen ligand 4 could also be obtained selectively by changing the reaction stoichiometry to 1 : 1. SalenH(2) 1 was explored for the onepot two-step synthesis of metal complexes. In particular, after in situ formation of the ligand by ball milling, metal salts (ZnO, Ni(OAc)2 center dot 4H(2)O or Cu(OAc)(2)center dot H2O) were added directly to the jar and milling continued for a further 30 minutes. Small amounts of methanol (0.4-1.1 mol equivalents) were needed for these reactions to run to completion. The corresponding metal complexes [M(salen)] (M = Zn, 6; Ni, 7; or Cu, 8) were thus obtained quantitatively after 30 minutes in hydrated form, and could be heated briefly to give analytically pure dehydrated products. The all-at-once ` tandem' synthesis of [Zn(salen)] 6 was also explored by milling ZnO, ethylene diamine and salicylaldehyde together in the appropriate mole ratio for 60 minutes. This approach also gave the target complex selectively with no solvent needing to be added. Overall, these syntheses were found to be highly efficient in terms of time and the in avoidance of bulk solvent both during the reaction and for the isolation of intermediates. The work demonstrates the applicability of mechanochemical synthesis to one-pot multi-step strategies.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)(2)(PPh3)(2) as well as the commercially important metal organic frameworks (MOFs) Cu-3(BTC)(2) (HKUST-1), Zn(2-methylimidazolate)(2) (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h(-1) rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3-4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h(-1). The space time yields (STYs) for these methods of up to 144 x 10(3) kg per m(3) per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

Weathering resistance of thin plasma polymer films on pre-coated steel

O trabalho apresentado teve origem no projecto de investigação “Tailored Thin Plasma Polymers Films for Surface Engineering of Coil Coated Steel”, financiado pelo Programa Europeu ECSC Steel Research. Sistemas de aço galvanizado pré-pintado em banda à base de poliéster e poliuretano foram submetidos a um processo de polimerização por plasma onde um filme fino foi depositado de modo a modificar as propriedades de superfície. Foram usados reactores de cátodo oco, microondas e rádio frequência para a deposição do polímero fino. Os sistemas preparados foram analisados de modo a verificar a influência do processo de polimerização por plasma na alteração das propriedades barreira dos sistemas pré-pintados em banda. Foi estudado o efeito dos diferentes passos do processo de polimerização por plasma, bem como o efeito de diferentes variáveis operatórias. A mistura precursora foi variada de modo a modificar as propriedades da superfície de modo a poder vir a obter maior hidrofobicidade, maior resistência a marcas digitais, bem como maior facilidade de limpeza. Os testes foram conduzidos em solução de NaCl 0,5 M. Para o trabalho foram usadas técnicas de análise da morfologia da superfície como Microscopia de Força Atómica e Microscopia Electrónica de Varrimento. As propriedades electroquímicas dos sistemas foram estudadas por Espectroscopia de Impedância Electroquímica. A estrutura dos filmes gerados no processo de polimerização por plasma foi caracterizada por Microscopia de Transmissão Electrónica. A modificação das propriedades ópticas devido ao processo de polimerização por plasma foi também obtida.

Electrospun fibrous mats for skin and abdominal wall repair

Esta tese centra-se no desenvolvimento de materiais biodegradáveis e nãodegradáveis produzidos por eletrofiação com aplicação na área biomédica. O poli(3-hidroxibutirato-co-3-hidroxivalerato) (PHBV), um poliéster biodegradável, foi selecionado como base dos materiais biodegradáveis, enquanto o poli(tereftalato de etileno) (PET), um polímero sintético, estável e biocompatível, foi selecionado para a produção das matrizes não degradáveis. Adicionou-se quitosana aos sistemas com o objetivo de melhorar o processo de eletrofiação e as propriedades morfológicas, físico-químicas e biológicas dos materiais resultantes. A composição química, bem como as características morfológicas e físicoquímicas dos materiais em estudo, foram manipuladas de modo a otimizar a sua performance como suportes celulares para engenharia de tecidos. Foram realizados estudos in vitro com cultura de fibroblastos L929 para avaliar o comportamento das células, i.e. viabilidade, adesão, proliferação e morte, quando cultivadas nas matrizes produzidas por eletrofiação. Adicionalmente foram realizados ensaios in vivo para investigar o potencial dos materiais em estudo na regeneração cutânea e como tela abdominal. Os principais resultados encontrados incluem: o desenvolvimento de novas matrizes híbridas (PHBV/quitosana) adequadas ao crescimento de fibroblastos e ao tratamento de lesões de pele; o desenvolvimento de um sistema de eletrofiação com duas seringas para a incorporação de compostos bioativos; diversas estratégias para manipulação das características morfológicas dos materiais de PHBV/quitosana e PET/quitosana produzidos por eletrofiação; uma melhoria do conhecimento das interações fibroblastos-suporte polimérico; a verificação de uma resposta inflamatória desencadeada pelos materiais nãodegradáveis quando utilizados no tratamento de defeitos da parede abdominal, o que sugere a necessidade de novos estudos para avaliar a segurança do uso de biomateriais produzidos por eletrofiação.

Synthesis of new vegetable oil-based polymeric materials

A crescente procura de recursos fosseis a que se tem assistido nos ultimos anos, tem resultado num crescimento sem precedentes dos precos, com consequencias imprevisiveis e que levara, no espaco de decadas, ao seu inevitavel esgotamento. A procura de um modelo de desenvolvimento sustentavel, baseado em recursos renovaveis e o grande desafio que se coloca a civilizacao no seculo XXI. A biomassa vegetal, atraves das designadas gBio-refinarias h, e uma alternativa logica para a producao de produtos quimicos e de materiais mas tambem de combustiveis e energia. Os oleos vegetais constituem uma das fracoes da biomassa vegetal, cuja exploracao tem merecido redobrada atencao nos ultimos anos, como fonte de materiais e de combustiveis. Assim, a presente dissertacao tem por objetivo o desenvolvimento de novos materiais polimericos derivados de oleos vegetais, seguindo duas abordagens distintas, nomeadamente a preparacao de polimeros atraves de polimerizacao por etapas e polimerizacao em cadeia (Parte B e C, respetivamente). Em primeiro lugar, foram sintetizados poliesteres alifaticos de cadeia longa a partir de monomeros provenientes do oleo de colza (Capitulo III). A auto-metatese do acido erucico com catalisadores de rutenio, seguida de hidrogenacao da ligacao dupla, originou o acido 1,26-hexacosanodioico, que por sua vez foi convertido em hexacosano-1,26-diol. Subsequentemente, a policondensacao do acido ƒ¿,ƒÖ-dicarboxilico de cadeia longa com o hexacosano-1,26-diol originou o poliester 26,26. O diacido C26 foi tambem polimerizado com outros alcano-diois de cadeia curta, nomeadamente o dodecano-1,12-diol e o butano-1,2-diol, produzindo, respetivamente, os poliesteres 12,26 e 4,26. Estes poliesteres de fontes 100% renovaveis possuem valores de Mn na ordem dos 8-14 kDa e valores de PDI entre 2.1 e 2.7. As propriedades destes poliesteres alifaticos foram avaliadas atraves de varias tecnicas, revelando elevada cristalinidade (com uma estrutura cristalina como a do polietileno) e elevadas temperaturas de fusao (74-104 ‹C), cristalizacao (68-92 ‹C) e degradacao (323-386 ‹C). Em segundo lugar, foram sintetizados polimeros lineares termo-reversiveis a partir de derivados do oleo de ricinio (Capitulo IV). Para tal foram preparados monomeros que incorporam aneis furanicos inseridos atraves do acoplamento tiol-eno, e que posteriormente foram polimerizados pela reacao de Diels-Alder (DA) entre os grupos furano (dieno A) e estruturas complementares do tipo maleimida (dienofilo B). Para as polimerizacoes DA foram consideradas duas abordagens diferentes, nomeadamente (i) o uso de monomeros com dois aneis furanicos terminais em conjunto com uma bismaleimida (sistemas AA+BB) e (ii) a utilizacao de um monomero que incorpora ambos os grupos reativos, furano e maleimida, na sua estrutura (sistema AB). Este estudo demonstrou claramente que ambas as estratégias foram bem sucedidas embora com diferentes resultados em termos da natureza dos produtos obtidos. Estes polímeros lineares apresentam valores relativamente baixos de Tg (-40 to -2 °C) devido à natureza flexível dos grupos separadores das funções reativas, e de Mn (4.5-9.0 kDa) dada a observada tendência de ciclização associada a concentrações baixas de monómero. A aplicação da reação de retro-DA aos polímeros em causa confirmou o seu caráter reversível, ou seja, a possibilidade de promover, em condições controladas, a despolimerização com recuperação dos monómeros de partida. Esta particularidade abre caminhos para materiais macromoleculares originais com aplicações promissoras tais como auto-reparação e reciclabilidade. Em terceiro lugar, sintetizaram-se polímeros não-lineares termo-reversíveis a partir de derivados do óleo de ricínio (Capítulo V). Para tal foram preparados monómeros trifuncionais e posteriormente polimerizados através da reação de DA entre os grupos reativos complementares furano/maleimida. Foram consideradas três abordagens distintas para preparar estes polímeros não-lineares, nomeadamente através da utilização de (i) um monómero bisfurânico em combinação com uma trismaleimida (sistema A2+B3) e (ii) um monómero trisfurânico em conjunto com uma bismaleimida (sistema A3+B2) que originaram materiais ramificados ou reticulados, e ainda (iii) a utilização de monómeros assimetricamente substituídos do tipo A2B ou AB2 capazes de originar estruturas macromoleculares hiper-ramificadas. Todos os sistemas apresentaram valores de Tg perto de 0 °C, o que era de esperar para estes materiais não-lineares. A aplicação da reação de retro-DA comprovou mais uma vez o caráter termo-reversível das polimerizações em causa. Em quarto lugar e último lugar, foram preparados copolímeros de acetato de vinilo (VAc) com monómeros derivados de óleo de girassol (Capítulo VI). Ésteres vinílicos de ácidos gordos (FAVE) foram sintetizados por transvinilação dos ácidos oleico e linoleico com VAc catalisada por um complexo de irídio. Os monómeros vinílicos preparados foram caracterizados e posteriormente homopolimerizados e copolimerizados com VAc através do uso dos grupos vinílicos terminais como função inicial de polimerização. A variação do tipo e quantidade de monómero FAVE e da quantidade de iniciador radicalar originou copolímeros de VAc com valores de Mn na gama de 1.2-3.0 kDa e valores de Tg de -5 a 16 °C. Os copolímeros foram avaliados em testes de cura oxidativa através das insaturações nas suas cadeias alifáticas para formar materiais reticulados, e os resultados sugerem que eles podem ser sistemas efetivos de cura para aplicações como tintas, vernizes e outros tipos de revestimento. Todos os materiais poliméricos preparados ao longo deste trabalho constituem contribuições atrativas para a área dos polímeros oriundos de recursos renováveis e representam uma prova indiscutível de que os óleos vegetais são percursores promissores de materiais macromoleculares com potenciais aplicações.

Study of the production of polyesters for polyurethanes at pilot plant scale

Dissertação para obtenção do grau de Mestre em Engenharia Química

Amarração de plataformas offshore flutuantes com cabos de poliéster

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Estruturas

Re-use assessment of thermoset composite wastes as aggregate and filler replacement for concrete-polymer composite materials: a case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.