Molecular motion in miscible polymer blends .1. Motion in blends of PEO and PVPh studied by solid-state C-13 T-1 rho measurements

Changes in molecular motion in blends of PEO-PVPh have been studied using measurements of C-13 T-1 rho relaxation times. C-13 T-1 rho relaxation has been confirmed as arising from spin-lattice interactions by observation of the variation in T-1 rho with rf field strength and temperature. In the pure homopolymers a minimum in T-1 rho is observed at ca. 50 K above the glass transition temperatures detected by DSC. After blending, the temperature of the minimum in T-1 rho for PEO increased, while that for PVPh decreased, however, the minima, which correspond to the temperatures where the average correlation times for reorientation are close to 3.1 mu s, are separated by 45 K (in a 45% PEO-PVPh blend). These phenomena are explained in terms of the local nature of T-1 rho measurements. The motions of the individual homopolymer chains are only partially coupled in the blend. A short T-1 rho has been observed for protonated aromatic carbons, and assigned to phenyl rings undergoing large-angle oscillatory motion, The effects of blending, and temperature, on the proportion of rings undergoing oscillatory motion are analyzed.

Viscoelasticity of radiation-formed PVA/PVP hydrogel

The dynamic theological behaviour of gamma-irradiated 12.8 wt% poly(vinyl alcohol) (PVA), 12.8 wt% poly(vinyl pyrrolidone) (PVP), and a blend of 8 wt% PVA and 4.8 wt% PVP aqueous solutions have been studied pre- and post-gelation. The non-irradiated solutions displayed theological behaviour typical of dilute to semi-dilute polymer solutions, with the complex viscosity being independent of the frequency and shear rate (i.e. Newtonian behaviour) over the range of frequencies tested and the loss modulus G(omega) and storage modulus G(omega) being nearly proportional to omega and omega(2) respectively. After a set of doses of gamma-radiation, the magnitudes of the dynamic moduli G'(omega) and G(omega) increased as the absorbed dose increased, with notable differences between the two homopolymers and the blend. The stages of gelation were effectively monitored by means of dynamic theological measurements, allowing the possible mechanisms of network formation to be elucidated. The doses required for gelation of the PVA, PVP, and blend samples, determined on the basis of the Winter and Chambon criteria for gelation, were found to be 12 kGy for the 12.8 wt% PVA, 4 kGy for the 12.8 wt% PVP, and 5 kGy for the 8 wt% PVA/4.8 wt% PVP solutions. The unexpected lower gelation dose demonstrated by the blend sample, compared with predictions based on the blend composition, and the associated gelation mechanism are also discussed.

Characterisation of grafted supports used for solid-phase synthesis

A series of 'pellicular' type supports were fabricated by direct gamma-radiation-mediated graft polymerisation of styrene onto polypropylene, followed by aminomethylation. Raman spectroscopy was used for measuring the level of penetration of polystyrene graft into polypropylene, and other structural features such as density of graft and depth of functionalisation. The kinetics of the coupling of fluorenylmethylcarbamate (Fmoc)-labelled amino acids, to the aminomethylated polystyrene grafts have been measured by UV absorption followed cleavage of the Fmoc chromophore. The Raman spectroscopy results showed that for this series of experiments the calculated rate coefficient for coupling of Fmoc-labelled amino acids was primarily dependent on graft thickness, but was also influenced by the proportion of polystyrene graft to polypropylene. In general, it was also shown that with increasing loading capacity of support the calculated rate coefficient for amino-acid coupling decreased correspondingly. In addition, a support that had both a high rate coefficient and a high loading capacity was prepared from polypropylene base material with a co-continuous porous structure (high surface area). (C) 2003 Society of Chemical Industry.

Aplicação de ferramentas de simulação de processos

Este trabalho foi efectuado com o propósito de interpretar, compreender e explicar algumas ferramentas de simulação de processos, em particular o Aspen Energy Analyzer (AEA), o Aspen Economic Evaluation (AEE) e o seu funcionamento integrado com o Aspen Hysys(AH). O AH é uma ferramenta de modelação de processos para a concepção de projectos de engenharia química, o AEA é uma ferramenta de modelação de redes de integração energética. O AEE integrado no AH é uma ferramenta que permite incorporar estudos económicos numa fase preliminar do desenvolvimento de um projecto de engenharia. A abordagem a este trabalho foi efectuada através do estudo de Casos. O Caso I foi baseado na resolução de um problema no AEA através da construção e optimização de uma rede de permutadores de calor. Os Casos II e III foram baseados na construção de um flowsheet de produção de Benzeno e de Cloreto de Vinil, respectivamente, e cada Caso foi dividido em dois cenários diferentes. Para o efeito foram utilizados os softwares AEA para a integração energética dos processos, o AH para construção do fluxograma do processo e o AEE para os estudos económicos dos diferentes cenários. Finalmente, os Casos IV e V dizem respeito à resolução de um problema de integração energética. O Caso IV foi baseado num problema de optimização da rede de permutadores através do aumento da sua área. Já o Caso V foi baseado na informação inicial das correntes do caso anterior e em dois cenários diferentes, nos quais foi estudada a influência dos preços das utilidades na construção da rede de permutadores. A conclusão foi que as ferramentas de modelação, particularmente o AH, o AEA e o AEE são uma mais-valia extraordinária para ajudar o utilizador na tomada de decisões em fases bastante preliminares da engenharia de processos.

Liaisons dangereuses, conservation of modern and contemporary art: a study of the synthetic binding media in Portugal

Dissertação apresentada para obtenção do Grau de Doutor em Conservação e Restauro, especialidade de Ciências da Conservação, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Synthesis and characterization of sugar containing hydrophilic and hydrophobic polymers with potential application in medicine

Dissertation toobtaina Master of Science degree in Bioorganics

Smart macroporous structures for the purification of viral particles

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Double-walled PLLA/PLGA particles for the sustained release of Meloxicam: preparation, characterisation and contolled release studies

There were two main objectives in this thesis investigation, first, the production, characterisation, in vitro degradation and release studies of double walled microspheres for drug release control. The second one, and the most challenging, was the production of double walled nanospheres, also for drug control delivery. The spheres were produced using two polymers, the Poly(L-lactide)Acid, PLLA, and the Poly(L-lactide-co-glycolic)Acid, PLGA.Afterwards, a model drug, Meloxicam, which is an antiinflammatory drug, was encapsulated into the particles. Micro and nanospheres were produced by the solvent extraction/evaporation method, where perfect spherical particles were obtained. By varying the polymers PLLA/PLGA mass ratio, different core and shell composition, as well as several shell and core thickness were observed. In the particles with a PLLA/PLGA mass ratio 1:1, the shell is composed by PLLA and the core by PLGA. It was also verified that the Meloxicam has a tendency to be distributed in the PLGA layer. Micro and nanoparticles were characterised in morphology, size, polymer cristalinity properties and drug distribution. Particles degradation studies was performed, where the particles in a PVA solution of pH 7,4 where placed in an incubator, during approximately 40 days, at 120rpm, and 37ºC, simulating, as much as possible, the human body environment. From these studies, the conclusion was that particles containing a PLGA shell and a PLLA core degrade more rapidly, due to the fact that PLLA is more hydrophobic than the PLGA. Concerning the drug release controlled results, done also for 40 and 50 days, they showed that the microspheres containing a shell of PLLA release more slowly than when the shell is composed of PLGA. This result was predictable, since the drug is solubilised in the PLGA polymer and so, in that case, the PLLA shell works like a barrier between the drug and the outer medium. Another positive aspect presented by this study is the lower initial burst effect, obtained when using double walled particles, which is one of the advantages of the same. In a second part of this investigation, the production of the nanospheres was the main goal, since it was not yet accomplished by other authors or investigators. After several studies, referring to the speed, time and type of agitation, as well as, the concentration and volume of the first aqueous solution of poly-vinyl-alcohol (PVA) during the process of solvent extraction/evaporation it was possible to obtain double walled nanospheres.(...)

Mechanical fatigue performance of PCL-chondroprogenitor constructs after cell culture under bioreactor mechanical stimulus

In tissue engineering of cartilage, polymeric scaffolds are implanted in the damaged tissue and subjected to repeated compression loading cycles. The possibility of failure due to mechanical fatigue has not been properly addressed in these scaffolds. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. This is related to inherent discontinuities in the material due to the micropore structure of the macro-pore walls that act as stress concentration points. In this work, chondrogenic precursor cells have been seeded in Poly-ε-caprolactone (PCL) scaffolds with fibrin and some were submitted to free swelling culture and others to cyclic loading in a bioreactor. After cell culture, all the samples were analyzed for fatigue behavior under repeated loading-unloading cycles. Moreover, some components of the extracellular matrix (ECM) were identified. No differences were observed between samples undergoing free swelling or bioreactor loading conditions, neither respect to matrix components nor to mechanical performance to fatigue. The ECM did not achieve the desired preponderance of collagen type II over collagen type I which is considered the main characteristic of hyaline cartilage ECM. However, prediction in PCL with ECM constructs was possible up to 600 cycles, an enhanced performance when compared to previous works. PCL after cell culture presents an improved fatigue resistance, despite the fact that the measured elastic modulus at the first cycle was similar to PCL with poly(vinyl alcohol) samples. This finding suggests that fatigue analysis in tissue engineering constructs can provide additional information missed with traditional mechanical measurements.

A study of the effects of PVAC on works of art on paper and wood: pH and colour change

This paper presents the preliminary findings of pH and colour measurements carried out on artworks on paperand on wood that had been treated with a poly(vinyl acetate) (PVAC) based adhesive in the 1980s. In both cases, areas treated with PVAC proved to be less acidic than untreated areas. Contrary to expectations, the conservation treatments have not, as yet, increased acidity levels in the objects under study. Colour measurements of the works on paper showed that those that had been backed with a cotton fabric using a mixture of methylcellulose and PVAC were less yellow than those from the same print run that had not been backed. This finding suggests that the backing somehow prevented the natural degradation of the support. In view of these preliminary results, further research is clearly needed. This study forms part of a broader ongoing project to assess the role of PVAC in the conservation of a range of cultural assets.

A study of the effects of PVAC on works of art on paper and wood: pH and colour change

This paper presents the preliminary findings of pH and colour measurements carried out on artworks on paperand on wood that had been treated with a poly(vinyl acetate) (PVAC) based adhesive in the 1980s. In both cases, areas treated with PVAC proved to be less acidic than untreated areas. Contrary to expectations, the conservation treatments have not, as yet, increased acidity levels in the objects under study. Colour measurements of the works on paper showed that those that had been backed with a cotton fabric using a mixture of methylcellulose and PVAC were less yellow than those from the same print run that had not been backed. This finding suggests that the backing somehow prevented the natural degradation of the support. In view of these preliminary results, further research is clearly needed. This study forms part of a broader ongoing project to assess the role of PVAC in the conservation of a range of cultural assets.

A study of the effects of PVAC on works of art on paper and wood: pH and colour change

This paper presents the preliminary findings of pH and colour measurements carried out on artworks on paperand on wood that had been treated with a poly(vinyl acetate) (PVAC) based adhesive in the 1980s. In both cases, areas treated with PVAC proved to be less acidic than untreated areas. Contrary to expectations, the conservation treatments have not, as yet, increased acidity levels in the objects under study. Colour measurements of the works on paper showed that those that had been backed with a cotton fabric using a mixture of methylcellulose and PVAC were less yellow than those from the same print run that had not been backed. This finding suggests that the backing somehow prevented the natural degradation of the support. In view of these preliminary results, further research is clearly needed. This study forms part of a broader ongoing project to assess the role of PVAC in the conservation of a range of cultural assets.

A study of the effects of PVAC on works of art on paper and wood: pH and colour change

This paper presents the preliminary findings of pH and colour measurements carried out on artworks on paperand on wood that had been treated with a poly(vinyl acetate) (PVAC) based adhesive in the 1980s. In both cases, areas treated with PVAC proved to be less acidic than untreated areas. Contrary to expectations, the conservation treatments have not, as yet, increased acidity levels in the objects under study. Colour measurements of the works on paper showed that those that had been backed with a cotton fabric using a mixture of methylcellulose and PVAC were less yellow than those from the same print run that had not been backed. This finding suggests that the backing somehow prevented the natural degradation of the support. In view of these preliminary results, further research is clearly needed. This study forms part of a broader ongoing project to assess the role of PVAC in the conservation of a range of cultural assets.

Processo alternativo para remoção de cobre (II) e níquel (II) de soluções aquosas utilizando cápsulas de quitosana - Álcool Polivinílico

Capsules were prepared from chitosan (QTS)-poly(vinyl alcohol) (PVA) blend by saline coacervation and then by formalization. A adsorbent based on chitosan, insoluble on acid solution, was obtained. The morphology, average diameters of QTS/PVA capsules and their pores were studied by using scanning electron microscopy. The entrapment-adsorption of dimethylglioxime and ethylenediaminetetracetate by the capsules were studied. The removal of the ion nickel (II) and copper (II), was more effective than by using unloaded capsules.

Irradiação de polímeros com feixe de elétrons: caracterização de íons positivos através da técnica de tempo-de-vôo

With the aim of studying the interaction of fast electrons with solid surfaces we have developed an experimental set-up based on electron stimulated desorption (ESD) coupled to time-of-flight (TOF) mass spectrometry. Poly(methyl methacrylate) and poly(vynil chloride) samples have been irradiated by a pulsed electron beam of 1.2 keV and 0.18 µs FWHM. The results show that H+ is the main ionic species to desorb after electron bombardment. In addition, other ionic fragments were also observed and assigned. These results show the potentiality of this technique in the study of ESD of polymers.