Interfacial interactions and structure of polyurethane intercalated nanocomposite

Understanding the interfacial interactions between the nanofiller and polymer matrix is important to improve the design and manufacture of polymer nanocomposites. This paper reports a molecular dynamic Study on the interfacial interactions and structure of a clay-based polyurethane intercalated nanocomposite. The results show that the intercalation of surfactant (i.e. dioctadecyldlmethyl ammonium) and polyurethane (PU) into the nanoconfined gallery of clay leads to the multilayer structure for both surfactant and PU, and the absence of phase separation for PU chains. Such structural characteristics are attributed to the result of competitive interactions among the surfactant, PU and the clay surface, including van der Waals, electrostatic and hydrogen bonding.

Clay-based polymer nanocomposites: Research and commercial development

This paper reviews the recent research and development of clay-based polymer nanocomposites. Clay minerals, due to their unique layered structure, rich intercalation chemistry and availability at low cost, are promising nanoparticle reinforcements for polymers to manufacture low-cost, lightweight and high performance nanocomposites. We introduce briefly the structure, properties and surface modification of clay minerals, followed by the processing and characterization techniques of polymer nanocomposites. The enhanced and novel properties of such nanocomposites are then discussed, including mechanical, thermal, barrier, electrical conductivity, biodegradability among others. In addition, their available commercial and potential applications in automotive, packaging, coating and pigment, electrical materials, and in particular biomedical fields are highlighted. Finally, the challenges for the future are discussed in terms of processing, characterization and the mechanisms governing the behaviour of these advanced materials.

Effect of exfoliation and dispersion on the yield behavior of melt-compounded polyethylene-montmorillonite nanocomposites

The yield behavior of melt-mixed nanocomposites containing 5 wt % organically modified montmorillonite in matrices of a linear low-density polyethylene (LLDPE) or a modified polyethylene was studied as a function of the temperature. and strain rate. In the melt-mixed LLDPE nanocomposite, the montmorillonite showed a slight increase in the clay spacing, which suggested that the clay was at best intercalated. Transmission electron microscopy (TEM) images showed that the dispersion in this nanocomposite was poor. The use of the modified polyethylene promoted exfoliation of the clay tactoids in the nanocomposite, as assessed by X-ray diffraction and TEM. In both nanocomposites, the yield mechanisms were insensitive to the addition of the organoclay, even though modest increases in the modulus were produced. (c) 2006 Wiley Periodicals, Inc.

Raman microscopic investigation of paint samples from the Rosalila building, Copan, Honduras

Micro-Raman spectroscopy was applied to the study of multiple layered wall paints from the Rosalila temple, Copan, Honduras, which dates to the Middle Classic period (A.D. 520 to 655). Samples of red, green and grey paint and a thick white overcoating were analysed. The paint pigments have been identified as hematite, celadonite or green earth and a combined carbon/mica mixture. By combining Raman spectroscopy with micro-ATR infrared spectroscopy and environmental scanning electron microscopy (ESEM), a detailed study has been made of the materials and processes used to make the stucco and paints. The use of green earth as a green pigment on Maya buildings has not been reported before. The combination of carbon and muscovite mica to create a reflective paint is also a novel finding.

Inorganic nanoparticles as carriers for efficient cellular delivery

Cellular delivery involving the transfer of various drugs and bio-active molecules (peptides, proteins and DNAs, etc.) through the cell membrane into cells has attracted increasing attention because of its importance in medicine and drug delivery. This topic has been extensively reviewed. The direct delivery of drugs and biomolecules, however, is generally inefficient and suffering from problems such as enzymic degradation of DNAs. Therefore, searching for efficient and safe transport vehicles (carriers) to delivery genes or drugs into cells has been challenging yet exciting area of research. In past decades, many carriers have been developed and investigated extensively which can be generally classified into four major groups: viral carriers, organic cationic compounds, recombinant protiens and inorganic nanoparticles. Many inorganic materials, such as calcium phosphate, gold, carbon materials, silicon oxide, iron oxide and layered double hydroxide (LDH), have been studied. Inorganic nanoparticles show low toxicity and promise for controlled delivery properties, thus presenting a new alternative to viral carriers and cationic carriers. Inorganic nanoparticles generally possess versatile properties suitable for cellular delivery, including wide availability, rich functionality, good biocompatibility, potential capability of targeted delivery (e.g. selectively destroying cancer cells but sparing normal tissues) and controlled release of carried drugs. This paper reviews the latest advances in inorganic nanoparticle applications as cellular delivery carriers and highlights some key issues in efficient cellular delivery using inorganic nanoparticles. Critical proper-ties of inorganic nanoparticles, surface functionalisation (modification), uptake of biomolecules, the driving forces for delivery, and release of biomolecules will be reviewed systematically. Selected examples of promising inorganic nanoparticle delivery systems, including gold, fullerences and carbon nanotubes, LDH and various oxide nanoparticles in particular their applications for gene delivery will be discussed. The fundamental understanding of properties of inorganic nanoparticles in relation to cellular delivery efficiency as the most paramount issue will be highlighted. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of the average soft-segment length on the morphology and properties of segmented polyurethane nanocomposites

Two organically modified layered silicates (with small and large diameters) were incorporated into three segmented polyurethanes with various degrees of microphase separation. Microphase separation increased with the molecular weight of the poly(hexamethylene oxide) soft segment. The molecular weight of the soft segment did not influence the amount of polyurethane intercalating the interlayer spacing. Small-angle neutron scattering and differential scanning calorimetry data indicated that the layered silicates did not affect the microphase morphology of any host polymer, regardless of the particle diameter. The stiffness enhancement on filler addition increased as the microphase separation of the polyurethane decreased, presumably because a greater number of urethane linkages were available to interact with the filler. For comparison, the small nanofiller was introduced into a polyurethane with a poly(tetramethylene oxide) soft segment, and a significant increase in the tensile strength and a sharper upturn in the stress-strain curve resulted. No such improvement occurred in the host polymers with poly(hexamethylene oxide) soft segments. It is proposed that the nanocomposite containing the more hydrophilic and mobile poly(tetramethylene oxide) soft segment is capable of greater secondary bonding between the polyurethane chains and the organosilicate surface, resulting in improved stress transfer to the filler and reduced molecular slippage. (c) 2006 Wiley Periodicals, Inc.

Stirring in 3-d spherical models of convection in the Earth's mantle

On a global scale basalts from mid-ocean ridges are strikingly more homogeneous than basalts from intraplate volcanism. The observed geochemical heterogeneity argues strongly for the existence of distinct reservoirs in the Earth's mantle. It is an unresolved problem of Geodynamics as to how these findings can be reconciled with large-scale convection. We review observational constraints, and investigate stirring properties of numerical models of mantle convection. Conditions in the early Earth may have supported layered convection with rapid stirring in the upper layers. Material that has been altered near the surface is transported downwards by small-scale convection. Thereby a layer of homogeneous depleted material develops above pristine mantle. As the mantle cools over Earth history, the effects leading to layering become reduced and models show the large-scale convection favoured for the Earth today. Laterally averaged, the upper mantle below the lithosphere is least affected by material that has experienced near-surface differentiation. The geochemical signature obtained during the previous episode of small-scale convection may be preserved there for the longest time. Additionally, stirring is less effective in the high viscosity layer of the central lower mantle [1, 2], supporting the survival of medium-scale heterogeneities there. These models are the first, using 3-d spherical geometry and mostly Earth-like parameters, to address the suggested change of convective style. Although the models are still far from reproducing our planet, we find that proposal might be helpful towards reconciling geochemical and geophysical constraints.

Modeling and exploiting behavior patterns in dynamic environments

This paper presents a new approach to improving the effectiveness of autonomous systems that deal with dynamic environments. The basis of the approach is to find repeating patterns of behavior in the dynamic elements of the system, and then to use predictions of the repeating elements to better plan goal directed behavior. It is a layered approach involving classifying, modeling, predicting and exploiting. Classifying involves using observations to place the moving elements into previously defined classes. Modeling involves recording features of the behavior on a coarse grained grid. Exploitation is achieved by integrating predictions from the model into the behavior selection module to improve the utility of the robot's actions. This is in contrast to typical approaches that use the model to select between different strategies or plays. Three methods of adaptation to the dynamic features of the environment are explored. The effectiveness of each method is determined using statistical tests over a number of repeated experiments. The work is presented in the context of predicting opponent behavior in the highly dynamic and multi-agent robot soccer domain (RoboCup)

Effect of fluoromica platelet size on the properties of segmented polyurethane nanocomposites

Segmented polyurethane nanocomposites containing three different size fractions of SomasifTM ME100 (synthetic fluoromica) have been prepared via solvent casting. The platelet size was adjusted via a proprietary milling process, and average diameters of approximately 500 nm, 100 nm and 30 nm were measured via TEM. To the best of our knowledge this is the first time the effect of aspect ratio has been studied with the same t-o-t structured mineral. The mechanical properties of these nanocomposites have been found to be highly dependent upon the platelet size. Depending on the aspect ratio and surface treatment selected, significant improvements in tensile strength can be achieved with a minimal reduction in resilience: a problem encountered with elastomeric layered silicate nanocomposites.

Tracking the states of a nonlinear system in the weight-space of a feed-forward neural network

Nonlinear, non-stationary signals are commonly found in a variety of disciplines such as biology, medicine, geology and financial modeling. The complexity (e.g. nonlinearity and non-stationarity) of such signals and their low signal to noise ratios often make it a challenging task to use them in critical applications. In this paper we propose a new neural network based technique to address those problems. We show that a feed forward, multi-layered neural network can conveniently capture the states of a nonlinear system in its connection weight-space, after a process of supervised training. The performance of the proposed method is investigated via computer simulations.

Anisotropy model for mantle convection

The paper presents a new theory for modeling flow in anisotropic, viscous rock. This theory has originally been developed for the simulation of large deformation processes including folding and kinking in multi-layered visco-elastic rock. The orientation of slip planes in the context of crystallographic slip is determined by the normal vector, the so-called director of these surfaces. The model is applied to simulate anisotropic natural mantle convection. We compare the evolution of the director and approximately steady states of isotropic and anisotropic convection. The isotropic case has a simple steady state solution, whereas the orthotropic convection model produces a continuously evolving patterning in tile core of the convection cell which makes only a near-steady condition possible, in which the thermal boundary layer appears to be well aligned with the flow and hence as observed in seismic tomomgraphy strong anistropic.

Cracks of higher modes in Cosserat continua

Rotational degrees of freedom in Cosserat continua give rise to higher fracture modes. Three new fracture modes correspond to the cracks that are surfaces of discontinuities in the corresponding components of independent Cosserat rotations. We develop a generalisation of J- integral that includes these additional degrees of freedom. The obtained path-independent integrals are used to develop a criterion of crack propagation for a special type of failure in layered materials with sliding layers. This fracture propagates as a progressive bending failure of layers – a “bending crack that is, a crack that can be represented as a distribution of discontinuities in the layer bending. This situation is analysed using a 2D Cosserat continuum model. Semi-infinite bending crack normal to layering is considered. The moment stress concentrates along the line that is a continuation of the crack and has a singularity of the power − 1/4. A model of process zone is proposed for the case when the breakage of layers in the process of bending crack propagation is caused by a crack (microcrack in our description) growing across the layer adjacent to the crack tip. This growth is unstable (in the moment-controlled loading), which results in a typical descending branch of moment stress – rotation discontinuity relationship and hence in emergence of a Barenblatt-type process zone at the tip of the bending crack.

On-line learning in neural networks

On-line learning is one of the most powerful and commonly used techniques for training large layered networks and has been used successfully in many real-world applications. Traditional analytical methods have been recently complemented by ones from statistical physics and Bayesian statistics. This powerful combination of analytical methods provides more insight and deeper understanding of existing algorithms and leads to novel and principled proposals for their improvement. This book presents a coherent picture of the state-of-the-art in the theoretical analysis of on-line learning. An introduction relates the subject to other developments in neural networks and explains the overall picture. Surveys by leading experts in the field combine new and established material and enable non-experts to learn more about the techniques and methods used. This book, the first in the area, provides a comprehensive view of the subject and will be welcomed by mathematicians, scientists and engineers, whether in industry or academia.

Dynamics of learning with restricted training sets

The dynamics of supervised learning in layered neural networks were studied in the regime where the size of the training set is proportional to the number of inputs. The evolution of macroscopic observables, including the two relevant performance measures can be predicted by using the dynamical replica theory. Three approximation schemes aimed at eliminating the need to solve a functional saddle-point equation at each time step have been derived.

Mixed communities: a new approach to spatially-concentrated poverty in England

This article examines the adoption, by the New Labour government, of a mixed communities approach to the renewal of disadvantaged neighbourhoods in England. It argues that while there are continuities with previous policy, the new approach represents a more neoliberal policy turn in three respects: its identification of concentrated poverty as the problem; its faith in market-led regeneration; and its alignment with a new urban policy agenda in which cities are gentrified and remodelled as sites for capital accumulation through entrepreneurial local governance. The article then draws on evidence from the early phases of the evaluation of the mixed community demonstration projects to explore how the new policy approach is playing out at a local level, where it is layered upon existing policies, politics and institutional relationships. Tensions between neighbourhood and strategic interests, community and capital are evident as the local projects attempt neighbourhood transformation, while seeking to protect the rights and interests of existing residents. Extensive community consultation efforts run parallel with emergent governance structures, in which local state and capital interests combine and communities may effectively be disempowered. Policies and structures are still evolving and it is not yet entirely clear how these tensions will be resolved, especially in the light of a collapsing housing market, increased poverty and demand for affordable housing, and a shortage of private investment.