Short-Time Elasticity of Polymer Melts: Tobolsky Conjecture and Heterogeneous Local Stiffness

An extended Molecular-Dynamics study of the short-time "glassy" elasticity exhibited by a polymer melt of linear fully-flexible chains above the glass transition is presented. The focus is on the infinite-frequency shear modulus $G_\infty$ manifested in the picosecond time scale and the relaxed plateau $G_p$ reached at later times and terminated by the structural relaxation. The local stiffness of the interactions with the first neighbours of each monomer exhibits marked distribution with average value given by $G_\infty$. In particular, the neighbourhood of the end monomers of each chain are softer than the inner monomers, so that $G_\infty$ increases with the chain length. $G_p$ is not affected by the chain length and is largely set by the non-bonding interactions, thus confirming for polymer melts the conjecture formulated by Tobolsky for glassy polymers.Comment: 18 pages, 6 figure

Cage rattling does not correlate with the local geometry in molecular liquids

Molecular-dynamics simulations of a liquid of short linear molecules have been performed to investigate the correlation between the particle dynamics in the cage of the neighbors and the local geometry. The latter is characterized in terms of the size and the asphericity of the Voronoi polyhedra. The correlation is found to be poor. In particular, in spite of the different Voronoi volume around the end and the inner monomers of a molecule, all the monomers exhibit coinciding displacement distribution when they are caged (as well as at longer times during the structural relaxation). It is concluded that the fast dynamics during the cage trapping is a non-local collective process involving monomers beyond the nearest neighbours.Comment: 15 pages, 6 figure

Aumento da resistência mecanica a penetração em função da perda natural de umidade no solo.

Nosso objetivo foi verificar a variação de umidade e sua interferência sobre a resistência mecânica a penetração em um latossolo amarelo disrófico (Lad) sobre relevo plano em área de pastagem, sob condições de clima Amazônico, através de modelo estatísticos de regressão polinomial de 2º grau

Competition of the connectivity with the local and the global order in polymer melts and crystals

The competition between the connectivity and the local or global order in model fully-flexible chain molecules is investigated by molecular-dynamics simulations. States with both missing (melts) and high (crystal) global order are considered. Local order is characterized within the first coordination shell (FCS) of a tagged monomer and found to be lower than in atomic systems in both melt and crystal. The role played by the bonds linking the tagged monomer to FCS monomers (radial bonds), and the bonds linking two FCS monomers (shell bonds) is investigated. The detailed analysis in terms of Steinhardt's orientation order parameters Q_l (l = 2 - 10) reveals that increasing the number of shell bonds decreases the FCS order in both melt and crystal. Differently, the FCS arrangements organize the radial bonds. Even if the molecular chains are fully flexible, the distribution of the angle formed by adjacent radial bonds exhibits sharp contributions at the characteristic angles {\theta} = 70{\deg}, 122{\deg}, 180{\deg}. The fractions of adjacent radial bonds with {\theta} = 122{\deg}, 180{\deg} are enhanced by the global order of the crystal, whereas the fraction with 70{\deg} < {\theta} < 110{\deg} is nearly unaffected by the crystallization. Kink defects, i.e. large lateral displacements of the chains, are evidenced in the crystalline state.Comment: J. Chem. Phys. in pres

Quantification of aluminium in soil of the Solimões formation, Acre State, Brazil.

The variety of soils in the State of Acre is wide and their chemical profiles are still not fully understood. The nature of the material of origin of these soils is indicated by the high aluminium (Al) content, commonly associated with high calcium (Ca) and magnesium (Mg) contents. The study objective was to use different methods to quantify Al in soils from toposequences formed from material of a sedimentary nature originating from the Solimões Formation, in Acre, Brazil. Trenches were opened at three distinct points in the landscape: shoulder, backslope and footslope positions. Soil samples were collected for physical, chemical, mineralogical analyses. The Al content was quantified using different methods. High Al contents were found in most of these horizons, associated with high Ca and Mg levels, representing the predominant cations in the sum of exchangeable bases. The mineralogy indicates that the soils are still in a low weathering phase, with the presence of significant quantities of 2:1 minerals. Similar Al contents were determined by the methods of NaOH titration, xylenol orange spectrometry and inductively coupled plasma optical emission spectrometry. However, no consistent data were obtained by the pyrocatechol violet method. Extraction with KCl overestimated the exchangeable Al content due to its ability to extract the non-exchangeable Al present in the smectite interlayers. It was observed that high Al contents are related to the instability of the hydroxyl-Al smectite interlayers

Structure-directing factors when introducing hydrogen bond functionality to metal?organic frameworks

The introduction of H-bond donor/acceptor functionality into metal-organic frameworks (MOFs) can have a beneficial effect on their molecular recognition, uptake selectivity and catalytic properties. The changes in ligand geometry induced by incorporation of functional groups may also affect the topology and composition of the resultant MOFs. Herein, we present a comprehensive study of functional group incorporation into MOFs, linked by either Zn2+ paddlewheel units or monomeric Zn2+ corners, which exhibit pcu and dia topology, respectively. Crystallographic analysis shows that amide groups can be easily incorporated into isoreticular pcu pillared-MOFs, whilst integration of urea units results in materials with dia topology. Molecular simulations allow the examination of hypothetical structures with differing constitutions and topologies, and highlight the influence of the urea units in generating the experimentally observed topologies. Noncovalent interactions between independent nets may be significant structure-directing influences, a finding which has great implications for the design of MOFs containing more complex functional groupsFil: Forgan, Ross S.. University Of Glasgow; Reino UnidoFil: Marshall, Ross J.. University Of Glasgow; Reino UnidoFil: Struckmann, Mona. University Of Glasgow; Reino UnidoFil: Bleine, Aurore B.. University Of Glasgow; Reino UnidoFil: Long, De Liang. University Of Glasgow; Reino UnidoFil: Bernini, Maria Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Fairen Jimenez, D.. University of Cambridge; Reino Unid

Frações granulométricas e oxidáveis da matéria orgânica do solo em sucessão floresta - pastagem no Acre.

A conversão de floresta nativa em pastagem provoca mudanças no conteúdo das frações da matéria orgânica do solo (MOS). O objetivo deste trabalho foi avaliar as alterações ocorridas nas frações granulométricas e oxidáveis da MOS em Sucessão Floresta - Pastagem no Acre. Após a derrubada e queima da floresta, implantou-se a pastagem de braquiária. Nas duas áreas foram coletadas amostras de solo nas profundidades de 0-5 e 5-10 cm. Nestas, foram avaliados os conteúdos de carbono orgânico total (COT), carbono orgânico particulado (COp), carbono orgânico associado aos minerais (COam) e carbono das frações oxidáveis (F1, F2, F3 e F4). Verificou-se que, independente da profundidade, os maiores valores de COT, COp e carbono na F1 e F3 foram encontrados na área de floresta. A retirada da vegetação original para a implantação da pastagem diminuiu os teores de COT, COp e na F1, demonstrando a maior fragilidade desses ecossistemas.Edição dos Resumos do VI CBA e II CLAA

Taxonomia de solos desenvolvidos sobre depósitos sedimentares da Formação Solimões no Estado do Acre.

Os solos do Estado do Acre na maioria são formados sobre material de origem com grande influência da orogênese Andina, com elevados teores de Ca2+, Mg2+ e Al3+ concomitantemente, associado às combinações diferenciadas dos valores da CTC, V e m. O objetivo deste trabalho foi caracterizar e classificar os solos de uma topossequência sobre material sedimentar da Formação Solimões, no município de Feijó, Acre. Foram abertas trincheiras em três pontos de uma topossequência: terço superior (P1), terço médio (P2) e terço inferior (P3). Os solos foram analisados quanto a morfologia, granulometria (areia, silte e argila), complexo sortivo (Ca2+, Mg2+, Na+, K+ e Al3+), acidez potencial (H+Al), P assimilável, pH (água e KCl), superfície específica, ataque sulfúrico (óxidos de Fe, Al, Ti e Si), mineralogia (frações areia, silte e argila). Os solos foram classificados segundo o Sistema Brasileiro de Classificação de Solos (SiBCS, 2006) e apresentada uma proposta de classificação considerando as peculiaridades do solos da região. Os solos têm baixo grau de desenvolvimento pedogenético, com minerais da fração argila de alta atividade, além da presença de minerais primários, como feldspatos e plagioclásios, nas frações areia e silte. Os solos foram classificados segundo o SiBCS atual como Argissolo Vermelho Álitico plíntico (P1), Argissolo Acinzentado Distrófico plíntico (P2) e Cambissolo Háplico Ta Eutrófico típico (P3)