Multiwalled-carbon-nanotube-induced miscibility in near-critical PS/PVME blends: assessment through concentration fluctuations and segmental relaxation

The effects of multiwalled carbon nanotubes (MWNTs) on the concentration fluctuations, interfacial driven elasticity, phase morphology, and local segmental dynamics of chains for near-critical compositions of polystyrene/poly(vinyl to methyl ether) (PS/PVME) blends were systematically investigated using dynamic shear rheology and dielectric spectroscopy. The contribution of the correlation length (xi) of the concentration fluctuations to the evolving stresses was monitored in situ to probe the different stages of demixing in the blends. The classical upturn in the dynamic moduli was taken as the rheological demixing temperature (T-rheo), which was also observed to be in close agreement with those obtained using concentration fluctuation variance, <(delta phi)(2)>, versus temperature curves. Further, Fredrickson and Larson's approach involving the mean-field approximation and the double-reptation self-concentration (DRSC) model was employed to evaluate the spinodal decomposition temperature (T-s). Interestingly, the values of both T-rheo and T-s shifted upward in the blends in the presence of MWNTs, manifesting in molecular-level miscibility. These phenomenal changes were further observed to be a function of the concentration of MWNTs. The evolution of morphology as a function of temperature was studied using polarized optical microscopy (POM). It was observed that PVME, which evolved as an interconnected network during the early stages of demixing, coarsened into a matrix-droplet morphology in the late stages. The preferential wetting of PVME onto MWNTs as a result of physicochemical interactions retained the interconnected network of PVME for longer time scales, as supported by POM and atomic force microscopy (AFM) images. Microscopic heterogeneity in macroscopically miscible systems was studied by dielectric relaxation spectroscopy. The slowing of segmental relaxations in PVME was observed in the presence of both ``frozen'' PS and MWNTs interestingly at temperatures much below the calorimetric glass transition temperature (T-g). This phenomenon was observed to be local rather than global and was addressed by monitoring the evolution of the relaxation spectra near and above the demixing temperature.

Non-equilibrium segmental dynamics driven by multiwall carbon nanotubes in PS/PVME blends

The present paper discusses the effect of multiwall carbon nanotubes (MWNTs) on the structural relaxation and the intermolecular cooperativity in dynamically asymmetric blends of PS/PVME (polystyrene/poly(vinyl methyl ether)). The temperature regime where chain connectivity effects dominate the thermodynamic concentration fluctuation (T/T-g > 0.75, T-g is the glass transition temperature of the blends) was studied using dielectric spectroscopy (DS). Interestingly, in the blends with MWNTs a bimodal distribution of relaxation was obtained in the loss modulus spectra. This plausibly is due to different environments experienced by the faster component (PVME) in the presence of MWNTs. The segmental dynamics of PVME was observed to be significantly slowed down in the presence of MWNTs and an Arrhenius-type behavior, weakly dependent on temperature, is observed at higher frequencies. This non-equilibrium dynamics of PVME is presumed to be originating from interphase regions near the surface of MWNTs. The length scale of the cooperative rearranging region (xi CRR) at T-g, assessed by calorimetric measurements, was observed to be higher in the case of blends with MWNTs. An enhanced molecular level miscibility driven by MWNTs in the blends corroborates with the larger xi CRR and comparatively more number of segments in CRR (in contrast to neat blends) around T-g. The configurational entropy and length scale of the cooperative volume was mapped as a function of temperature in the temperature regime, Tg < T < T-g + 60 K. The blends phase separated by spinodal decomposition which further led to an interconnected PVME network in PS. This further led to materials with very high electrical conductivity upon demixing.

An unusual demixing behavior in PS-PVME blends in the presence of nanoparticles

The effect of silver nanoparticles (sNP) on the demixing and the evolution of morphology in off-critical blends of 90/10 and 10/90 (wt/wt) PS/PVME polystyrene/poly(vinyl methyl ether)] was probed here using shear rheology and optical microscopy. The faster component (PVME) has a higher molecular weight (80 kDa) than the slower component (PS, 35 kDa), which makes this system quite interesting to study with respect to the evolving morphology, as the blends transit through the binodal and the spinodal envelopes. An unusual demixing behavior was observed in both PVME rich and PS rich blends. Temperature modulated differential scanning calorimetry measurements showed that the T-g value for the blends with sNP was slightly lower than that of the neat blends. A decreased volume of cooperativity at T-g suggests confined segmental dynamics in the presence of sNP. Although, the addition of sNP had no influence on the thermodynamic demixing temperature, it significantly altered the elasticity of the minor component during the transition of the blend from the homogeneous to the heterogeneous state. This is manifested from energetically driven localization of the sNP in the PVME phase during demixing. As a direct consequence of this, the formation of the microstructures upon demixing was observed to be delayed in the presence of sNP. Interestingly, in the intermediate quench depth, the higher viscoelastic phase evolved as an interconnected network, which subsequently coarsened into discrete droplets in the late stages for the 90/10 PS/PVME blends. Similar observations were made for 10/90 PS/PVME blends where threads of PVME appeared at deeper quench depths in the presence of sNP. The interconnected network formation of the minor phase (here PVME), which is also the faster component in the blend, was different from the usual demixing behavior.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Designer porous antibacterial membranes derived from thermally induced phase separation of PS/PVME blends decorated with an electrospun nanofiber scaffold

We report the development of porous membranes by thermally induced phase separation of a PS/PVME (polystyrene/polyvinylmethyl ether]) blend, which is a typical LCST mixture. The morphology of the membrane after etching out the PVME phase was characterized by scanning electron microscopy. To give the membrane an antibacterial surface, polystyrene (PS) and polyvinyl(methyl ether)]-alt-maleic anhydride (PVME-MAH) with silver nanoparticles (nAg) were electrospun on the membrane surface. Pure water flux was evaluated by using a cross-flow membrane setup. The microgrooved fibers changed the flux across the membrane depending on the surface properties. The antibacterial properties of the membrane were confirmed by the reduction in the colony count of E. coli. The SEM images show the disruption of the bacterial cell membrane and the antibacterial mechanism was discussed.

A strategy to achieve enhanced electromagnetic interference shielding at ultra-low concentration of multiwall carbon nanotubes in P alpha MSAN/PMMA blends in the presence of a random copolymer PS-r-PMMA

A unique strategy was adopted to achieve an ultra-low electrical percolation threshold of multiwall carbon nanotubes (MWNTs) (0.25 wt%) in a classical partially miscible blend of poly-alpha-methylstyrene-co-acrylonitrile and poly(methyl methacrylate) (P alpha MSAN/PMMA), with a lower critical solution temperature. The polymer blend nanocomposite was prepared by standard melt-mixing followed by annealing above the phase separation temperature. In a two-step mixing protocol, MWNTs were initially melt-mixed with a random PS-r-PMMA copolymer and subsequently diluted with 85/15 P alpha MSAN/PMMA blends in the next mixing step. Mediated by the PS-r-PMMA, the MWNTs were mostly localized at the interface and bridged the PMMA droplets. This strategy led to enhanced electromagnetic interference (EMI) shielding effectiveness at 0.25 wt% MWNTs through multiple scattering from MWNT-covered droplets, as compared to the blends without the copolymer, which were transparent to electromagnetic radiation.

Passively harmonically mode-locked vertical-external-cavity surface-emitting laser emitting 1.1 ps pulses at 147 GHz repetition rate

Coupled-cavity passive harmonic mode-locking of a quantum well based vertical-external-cavity surface-emitting laser has been demonstrated, yielding an output pulse train of 1.5 ps pulses at a repetition rate of 80 GHz and with an average power of 80 mW. Harmonic mode-locking results from coupling between the main laser cavity and a cavity formed within the substrate of the saturable absorber structure. Mode-locking on the second harmonic of the substrate cavity allows a train of 1.1 ps pulses to be generated at a repetition rate of 147 GHz with 40 mW average power. © 2010 American Institute of Physics.

História constitucional brasileira : mudança constitucional, autoritarismo e democracia no Brasil pós-1964

Apresenta, com detalhes, aspectos históricos do constitucionalismo contemporâneo brasileiro. Partindo do período pós-1964, quando diversos processos de reforma ou ruptura alteraram as regras relativas a mudanças constitucionais, é apresentado um desenho dos principais instrumentos jurídicos utilizados pelo regime militar a fim de garantir a sua hegemonia política e jurídica. A análise passa pelo processo constituinte de 1987-1988, para verificar em que medida se rompeu com o paradigma instaurado pela ditadura, e investiga as principais tentativas de, sob a vigência da nova Carta Magna, alterar o processo de reforma constitucional.

Brasil Pós-Copa 2014 : Legado e Gestão dos Estádios

Seminário realizado pela Comissão de Turismo e Desporto para debater sobre eventos esportivos que o Brasil sediará nos próximos anos, notadamente a Copa do Mundo de 2014 e os Jogos Olímpicos de 2016”.

Processo legislativo orçamentário federal: evolução das resoluções orçamentárias pós Constituição de 1988

A Constituição de 1988 devolveu ao Parlamento as prerrogativas históricas de emendar o projeto de lei orçamentária. A regulação do processo de apreciação e emendamento do orçamento se dá pela edição de sucessivas Resoluções do Congresso Nacional, as quais, na temática do projeto em epígrafe, são as resoluções orçamentárias. O estudo dos processos é importante porque representa a experiência acumulada e organizada, incorporando ao longo do tempo procedimentos e controles voltados à eficiência, eficácia e efetividade dos trabalhos legislativos. A presente monografia propõe a análise do conteúdo de todas as resoluções orçamentárias pós Constituição de 1988, com o objetivo de melhor compreender a origem e evolução dos institutos relacionados ao processo de elaboração e aprovação orçamentária. A metodologia toma como ponto de partida 16 dispositivos-temas normativos relacionados à disciplina da apreciação e emendamento, valendo-se de pesquisa bibliográfica e entrevistas de profundidade aplicadas a consultores de orçamento e assessores de lideranças com grande experiência no tema, com vistas a rastrear a origem das principais normas contempladas pelas resoluções e, principalmente, as razões para o seu surgimento ou eventual desaparecimento. No referencial teórico far-se-á, em primeiro lugar, um estudo e análise de cada resolução separadamente. Em seguida, far-se-á uma pesquisa comparativa do conteúdo e das diversas resoluções, analisando-se, com apresentações gráficas, a evolução dessas normas à luz do contexto político e institucional. Como resultados da pesquisa, espera-se tirar conclusões acerca da efetividade do atual estágio normativo materializado na Resolução no 01/2006-CN.

Direito das mulheres pós-constituição : um estudo descritivo

Esta pesquisa objetivou construir um mapeamento das normas jurídicas no âmbito federal. que asseguram os direitos das mulheres no aparato normativo brasileiro, aprovadas no período pós-constituição até 2010. Com delineamento descritivo e realização de pesquisa bibliográfica e documental, as normas relativas a gênero foram identificadas e, por meio de análise de conteúdo, classificadas de acordo com a temática de gênero. A análise gerou os seguintes eixos temáticos por conteúdo: Trabalho, Violência, Poder, Saúde, Bioética, Habitação, Maternidade, Paternidade e Homem, Família, Datas, Educação e Sensibilização para Gênero, Sistema Prisional e Previdência. Os resultados mostram que três eixos temáticos perfazem a maior parte das normas voltadas para as mulheres. Normas relacionadas à proteção e promoção da família, principalmente a família que trabalha, à promoção e proteção ao trabalho da mulher e à erradicação e punição da violência e discriminação contra a mulher, perfazem 60,87% das normas para mulheres na legislação brasileira. Os resultados mostram ainda que a maior parte das normas é do tipo leis ordinárias, representam pouco impacto orçamentário para o Estado e foram iniciadas pelo Poder Legislativo. Observou-se que houve aumento significativo e crescente das normas voltadas às mulheres no período estudado.

Participação popular na produção legislativa : o caso da legislação urbanística no Brasil pós-Constituinte

Na década de 1980 a questão urbana no Brasil ganhou visibilidade a partir de uma gama de ocupações de imóveis ociosos que ocorreram em diversas cidades importantes do país. Às mobilizações pela redemocratização somou-se a luta pela reforma urbana. Com o advento do Processo Constituinte, ganhou importância a intervenção dos movimentos populares na esfera institucional, cuja principal ferramenta foi a apresentação da Emenda Popular da Reforma Urbana, convertida numa espécie de manifesto-programa pelos defensores da causa. Com a Constituição já promulgada, o movimento pela reforma urbana celebrou o fato de, pela primeira vez na História Constitucional brasileira, a questão urbana ter sido contemplada. O Capítulo de Política Urbana necessitou, contudo, de regulamentação para ter efeitos práticos, o que veio a acontecer com a aprovação do Estatuto da Cidade em 2001. Fazer um balanço da luta pela reforma urbana no Brasil e a da influência do movimento popular no delineamento da legislação urbanística desde o Processo Constituinte é o objetivo primeiro deste trabalho. A intenção de fundo é refletir acerca do modelo de democracia brasileira, tendo por pressuposto a ideia de que a participação popular modelou um regime democrático que avança em relação ao clássico modelo da democracia representativa vigente no mundo ocidental.