Complex formation of montmorillonite clay with polymers. Part 2: The use of montmorillonite clay–vinyl monomer complex as a comonomer in the copolymerization reaction of styrene–acrylonitrile monomers

The bulk copolymerization of styrene–acrylonitrile monomers using styrene‐N⁺–montmorillonite complex as a comonomer in the polymerization was studied. The X‐ray diffraction (XRD) analysis showed that part of the styrene‐N⁺–montmorillonite complex remained non‐dispersed (immiscible) and the copolymer was excluded from the interlayer of the immiscible part of the clay. The successive chemical extraction process revealed that a reasonable amount of the styrene–acrylonitrile copolymer was directly attached to the styrene‐N⁺–montmorillonite complex and enveloped the clay. Highly exfoliated clay lamella and nanospheres (3–5 nm) were observed by transmission electron microscopy (TEM). The montmorillonite clay assume two different morphologies, immiscible and exfoliated, on the basis of the XRD and TEM data. A simple method of calculation of the ratio of the exfoliated/immiscible amounts of the clay indicated that the amount of the styrene‐N⁺–montmorillonite complex exfoliated into separate lamella was 40 % (w/w) of the amount of the clay samples containing 2 % of the (styrene‐N⁺–montmorillonite complex) clay. This amount of exfoliated clay decreases with the increase of the concentration of the clay. The presence of the styrene‐N⁺–montmorillonite clay in the copolymerization reaction had a minor effect on both the copolymer composition and the molecular weight. Modification of the clay with the derivatized styrene monomer can achieve a nanocomposite using a percentage no more than 4 % (w/w) of complex in the copolymer. Copyright © 2004 Society of Chemical Industry     

Slow eroding biodegradable multiblock poloxamer copolymers

Biodegradable multiblock poloxamers (BMPs) with gel duration of 8 h to several weeks were prepared by varying their molecular weights from 4000 to 40 000 g mol^?1. The molecular weight of the BMP was controlled by changing the poloxamer to coupling agent ratio. Assuming a micelle packing model of the BMP gel, as in the case of a poloxamer gel, the micelle properties and critical gel concentration of BMPs were investigated on the basis of the scaling concept. The findings suggest that the control of molecular weight by hydrolyzable groups can be a facile approach to optimize the gel properties for biomedical applications. Copyright © 2005 Society of Chemical Industry     

Impact of a snow avalanche against an obstacle. Formation of shock waves

The paper is devoted to the effect of compressibility of the avalanche snow impacting an obstacle. Compression shocks generated by obstacle cause high pressure peaks at first instants of impact. That is why the account of compressibility is essential for the understanding of measurements and the design of structures. The main problem in calculation compression shocks in avalanches is to formulate an equation of state for moving snow in impact. Two different types of equations of state are proposed depending on the type of the avalanche (low-density and high-density flows). The approach is not totally new. It was earlier proposed mainly in Russian literature. Here a brief review of the previous work is given with discussion of some gaps in it. The theory is reformulated and further developed to account thermodynamical equations. The simplest case of a normal compression shock in an avalanche flow is studied. Examples of estimations of pressure and density behind a shock are given. It is important to emphasize that the Mach number plays an important role in the theory of compressible flows so it should be taken into account (together with the Froude number) in calculation and modelling an avalanche impact pressure.     

Dynamic response and behavior of reinforced concrete slabs under impact loading

Reinforced concrete slabs are among the most common structural elements. In spite of the large number of slabs designed and built, the effect of their details on their behavior under impact loads are not always appreciated or properly taken into account. This experimental study was aimed at understanding the dynamic behavior of structural concrete slabs under impact loading to improve the state of the art of protective design. This study investigated the effects of different types of slab reinforcements and the applied impact loads on the dynamic response and behavior of reinforced concrete slabs.     

Phase behavior in liquid crystallization for diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components

Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.     

Effects of Seismically Induced Pounding at Expansion Joints of Concrete Bridges

This paper presents the result of a study on the effect of pounding at expansion joints on concrete bridge response to earthquake ground motions. An engineering approach, rather than continuum mechanics approach, is emphasized. First, the dynamic behavior of a damped multidegree-of-freedom bridge system separated by an expansion joint involving an impact is examined by means of the finite element method. Second, the sensitivity analysis of the stiffness in gap elements is performed. Third, usefulness of the analysis method for simulation of pounding phenomena is demonstrated and the effect of pounding on the ductility demands measured in terms of the rotation of column ends is investigated. Two-dimensional finite element analysis using a bilinear hysterestic model for bridge substructure joints and a nonlinear gap element for the expansion joint is performed on a realistic bridge with an expansion joint. The effects of the primary factors on the ductility demand such as gap sizes and characteristics of earthquake ground motion are investigated through a parametric study. The major conclusions are (1) the effect of impact most directly depends on the size of momentum (or pounding magnitude); and (2) the pounding effect is generally found to be negligible on the ductility demand for wide practical ranges of gap size and peak ground acceleration, but is potentially significant at the locations of impact.     

Thin hard coatings fracture propagation during the impact test

One of the most significant applications of the impact test is to investigate thin hard coatings fatigue properties. Herein the test conditions and duration up to the film damage initiation, are considered in order to determine the critical stresses associated with the coating fatigue strength. Moreover, the subsequent film damage propagation is a significant mechanism as well, since it refers to the ability of the coating to withstand loads after its fatigue damage initiation. In order to describe the film fracture propagation the failed area ratio was introduced and an algorithm to determine this magnitude developed, based on the analysis of imprint scanning electron microscopy graphs. The application of the coating failed area ratio will be demonstrated in various impact test film cases, also with superficial thin layers. The top layers do not affect, in general, the failure initiation of the basic coating. However, according to the obtained results, the superficial films influence the basic coating failure propagation rate during the impact test.     

Highly ordered microstructures of poly(styrene-b-isoprene) block copolymers induced by solution meniscus

Microstructures of hundreds of micron thick poly(styrene-block-isoprene) copolymer films solution-cast in a cylindrical tube with the solvent evaporation controlled were investigated by transmission electron microscope (TEM), small angle X-ray scattering (SAXS) and optical microscope (OM). In a block copolymer with cylindrical polyisoprene microdomains, the orientation of the cylinders was varied along radial direction of the cylindrical tube. Highly aligned hexagonal arrays of in-plane polyisoprene cylinders were formed with their cylindrical axis parallel to the circumference of the tube in the regimes close to the wall edge. In contrast randomly ordered microdomains were observed at the center of the tube. We have also found that the orientation depends on the solvent evaporation rate and an intermediate rate (∼2.3 nL/s) provides the best orientation. In the case of a block copolymer with a bicontinuous double gyroid structure, we obtained a globally ordered microstructure where [111] crystallographic direction was parallel to the circumference of the tube. For both block copolymers, the area of highly ordered arrays of nanoscopic domains is over 1 mm². Development of the orientation was explained by coupling two orthogonal fields: (1) The flow of a solution induced by strong capillary force at a meniscus between the cylindrical tube wall and the block copolymer solution and (2) the solvent evaporation.     

Study of the morphology and mechanical properties of polypropylene composites with silica or rice‐husk

The mechanical, morphological behavior and water absorption characteristics of polypropylene (PP) and silica, or PP and rice‐husk, composites have been studied. The silica used in this study as filler was a commercial type produced from soluble glass or rice husks. The compatibilizing effect of PP grafted with monomethyl itaconate (PP‐g‐MMI) and/or with vinyltriethoxysilane (PP‐g‐VTES) as polar monomers on the mechanical properties and water absorption was also investigated. In general, a high loading of the studied fillers in the polymer matrix increases the stiffness and the water absorption capacity. This effect is more noticeable in the tensile modulus of the PP/silica composite with PP‐g‐VTES as compatibilizer. However, the increase of the rice‐husk charge as a natural filler in the PP matrix decreases the stiffness, and in the presence of PP‐g‐MMI as compatibilizer in PP/rice‐husk, the tensile modulus and water absorption of the composite were improved. The better adhesion and phase continuity in the PP/silica and PP/rice‐husk composites with different compatibilizers was confirmed by the morphological study. Copyright © 2004 Society of Chemical Industry     

Numerical solution for shape optimization of an impactor penetrating into a semi-infinite target

The shape of the impactor with the maximum depth of penetration (DOP) for a given impact velocity is found using a numerical procedure for solving a corresponding non-classical variational problem. It is shown that the optimum shape in a general case is close to a blunt cone. The variation of the optimal shape of the impactor and the dependence of the DOP vs. the initial (impact) velocity and friction coefficient is studied. The analysis is performed also for optimal conical impactors.