Surface Modification of Polyethylene with Multi-End-Functional Polyethylene Additives

We have prepared and characterized a series of multifluorocarbon end-functional polyethylene additives, which when blended with polyethylene matrices increase surface hydrophobicity and lipophobicity. Water contact angles of >112° were observed on spin-cast blended film surfaces containing less than 1% fluorocarbon in the bulk, compared to 98° in the absence of any additive. Crystallinity in these films gives rise to surface roughness that is an order of magnitude greater than is typical for amorphous spin-cast films but is too little to give rise to superhydrophobicity. X-ray photoelectron spectroscopy (XPS) confirms the enrichment of the multifluorocarbon additives at the air surface by up to 80 times the bulk concentration. Ion beam analysis was used to quantify the surface excess of the additives as a function of composition, functionality, and molecular weight of either blend component. In some cases, an excess of the additives was also found at the substrate interface, indicating phase separation into self-stratified layers. The combination of neutron reflectometry and ion beam analysis allowed the surface excess to be quantified above and below the melting point of the blended films. In these films, where the melting temperatures of the additive and matrix components are relatively similar (within 15 °C), the surface excess is almost independent of whether the blended film is semicrystalline or molten, suggesting that the additive undergoes cocrystallization with the matrix when the blended films are allowed to cool below the melting point

Responsive brushes and gels as components of soft nanotechnology<br />

Progress in the development of generic molecular devices based on responsive polymers is discussed. Characterisation of specially synthesised polyelectrolyte gels, “grafted from” brushes and triblock copolymers is reported. A Landolt pH-oscillator, based on bromate/sulfite/ferrocyanide, with a room temperature period of 20 min and a range of 3.1 < pH < 7.0, has been used to drive periodic oscillations in volume in a pH responsive hydrogel. The gel is coupled to the reaction and changes volume by a factor of at least 6. A continuously stirred, constant volume, tank reactor was set-up on an optical microscope and the reaction pH and gel size monitored. The cyclic force generation of this system has been measured directly in a modified JKR experiment. The responsive nature of polyelectrolyte brushes, grown by surface initiated ATRP, have been characterised by scanning force microscopy, neutron reflectometry and single molecule force measurements. Triblock copolymers, based on hydrophobic end-blocks and either polyacid or polybase mid-block, have been used to produce polymer gels where the deformation of the molecules can be followed directly by SAXS and a correlation between molecular shape change and macroscopic deformation has been established. The three systems studied allow both the macroscopic and a molecular response to be investigated independently for the crosslinked gels and the brushes. The triblock copolymers demonstrate that the individual response of the polyelectrolyte molecules scale-up to give the macroscopic response of the system in an oscillating chemical reaction

Espacialização da precipitação pluvial por meio de krigagem e cokrigagem

O objetivo deste trabalho foi avaliar a cokrigagem ordinária, com dados de altitude e distância do mar, em comparação à krigagem ordinária, na espacialização da precipitação pluvial dos períodos anual, seco e úmido, no Estado do Espírito Santo. Os dados de altitude e distância do mar foram obtidos de pontos de amostragem em grades regulares e irregulares. Foram utilizados dados de 108 postos pluviométricos. A avaliação dos métodos e das variáveis foi realizada com base na validação cruzada, tendo-se considerado os erros dos valores preditos e o ajuste dos modelos de regressão linear para valores observados e preditos. A grade regular para amostragem das covariáveis apresentou melhor acurácia de predição em comparação à grade irregular. A cokrigagem produziu resultados mais acurados do que a krigagem, verificados por pequenas diferenças nos erros médios absolutos, capazes de produzir mapas estatisticamente diferentes. A interpolação por cokrigagem e o uso de grades regulares para amostragem são preferíveis, principalmente se as covariáveis são de fácil obtenção e de baixo custo