Thermo‐oxidative degradation of HDPE as a function of its crystalline content

The composition, the thermal properties, and the kinetics of the thermo‐oxidative degradation of high‐density polyethylene (HDPE) were studied as a function of the increasing crystalline fraction, which resulted from the selective extraction of the amorphous part, through digestion by immersion in fuming nitric acid (HNO₃) for different periods of time. The chemical and thermodynamic changes in HDPE, brought about by digestion in nitric acid for different periods of time, are discussed. Changes in the chemistry and microstructure of the HDPE, as a function of acid treatment for different periods of time, were studied using infra‐red spectroscopy (FTIR), gel permeation chromatography (GPC), and thermal analysis (DSC and TGA), as well as scanning electron microscopy (SEM). These studies were carried out as a function of the extracted amorphous fraction of HDPE samples via digestion in HNO₃. These studies showed that in the first stages of the acid chemical attack, the amorphous part first undergoes a chemical modification and then dissolves into the strong acid medium. The total crystalline fraction apparently decreases during the first stages of the chemical attack and then increases as the amorphous part is extracted. TGA results show that as the selective extraction of the amorphous part occurs, there is a displacement of the thermo‐oxidative degradation toward higher temperatures. The kinetics of the thermo‐oxidative degradation as a function of the extraction of the amorphous part was followed according to the Horowitz‐Metzger method, and it was found that as the concentration of the crystalline fraction increases, the activation energy for the thermo‐oxidative degradation increases. SEM studies show that the extraction of the amorphous part does not affect the size of the crystalline lamellar thickness of HDPE. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1906–1915, 2009     

A new volume of fluid method in three dimensions—Part II: Piecewise‐planar interface reconstruction with cubic‐Bézier fit

A new interface reconstruction method in 3D is presented. The method involves a conservative level‐contour reconstruction coupled to a cubic‐Bézier interpolation. The use of the proposed piecewise linear interface calculation (PLIC) reconstruction scheme coupled to a multidimensional time integration provides solutions of second‐order spatial and temporal accuracy. The accuracy and efficiency of the proposed reconstruction algorithm are demonstrated through several tests, whose results are compared with those obtained with other recently proposed methods. An overall improvement in accuracy with respect to other recent methods has been achieved, along with a substantial reduction in the central processing unit time required. Copyright © 2008 John Wiley & Sons, Ltd.     

An adaptive cut‐cell method for environmental fluid mechanics

In this work we present a numerical method for solving the incompressible Navier–Stokes equations in an environmental fluid mechanics context. The method is designed for the study of environmental flows that are multiscale, incompressible, variable‐density, and within arbitrarily complex and possibly anisotropic domains. The method is new because in this context we couple the embedded‐boundary (or cut‐cell) method for complex geometry with block‐structured adaptive mesh refinement (AMR) while maintaining conservation and second‐order accuracy. The accurate simulation of variable‐density fluids necessitates special care in formulating projection methods. This variable‐density formulation is well known for incompressible flows in unit‐aspect ratio domains, without AMR, and without complex geometry, but here we carefully present a new method that addresses the intersection of these issues. The methodology is based on a second‐order‐accurate projection method with high‐order‐accurate Godunov finite‐differencing, including slope limiting and a stable differencing of the nonlinear convection terms. The finite‐volume AMR discretizations are based on two‐way flux matching at refinement boundaries to obtain a conservative method that is second‐order accurate in solution error. The control volumes are formed by the intersection of the irregular embedded boundary with Cartesian grid cells. Unlike typical discretization methods, these control volumes naturally fit within parallelizable, disjoint‐block data structures, and permit dynamic AMR coarsening and refinement as the simulation progresses. We present two‐ and three‐dimensional numerical examples to illustrate the accuracy of the method. Copyright © 2008 John Wiley & Sons, Ltd.     

A computational study of gas flow in a De‐Laval micronozzle at different throat diameters

A numerical study has been carried out to investigate the gas flows in a micronozzle using a continuum model under both slip and no‐slip boundary conditions. The governing equations were solved with a finite volume method. The numerical model was validated with available experimental data. Numerical results of exit thrust showed good agreement with experimental data except at very low Reynolds numbers. For parametric studies on the effect of geometric scaling, the nozzle throat diameter was varied from 10 to 0.1 mm, whereas throat Reynolds number was varied from 5 to 2000. A correlation has also been developed to calculate the specific impulse at specified throat diameter and Reynolds number. The effect of different gases on the specific impulse of the nozzle, such as helium, nitrogen, argon and carbon dioxide, was also examined. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and applications of novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite nanocomposites

Novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite (HAp) nanocomposites were prepared by the reaction of calcium nitrate tetrahydrate and phosphoric acid in the presence of the corresponding oligomer. These fluorinated oligomer/HAp composites thus obtained are nanometer size‐controlled fine particles (83–173 nm), and were found to exhibit good dispersibility in methanol, ethanol, and isopropyl alcohol. These fluorinated HAp nanocomposites were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleophobic characteristics imparted by fluorine on their surface. In addition, the surface structural changes of the modified polyethylene terephtalate and PMMA films treated with these fluorinated nanocomposites before and after soaking in a simulated body fluid (SBF) were analyzed by using SEM, XRD, and EDX to observe the formation of spherical HAp deposits on the surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of variable viscosity on the peristaltic transport of a Newtonian fluid in an asymmetric channel

The effect of variable viscosity on the peristaltic flow of a Newtonian fluid in an asymmetric channel has been discussed. Asymmetry in the flow is induced due to travelling waves of different phase and amplitude which propagate along the channel walls. A long wavelength approximation is used in the flow analysis. Closed form analytic solutions for velocity components and longitudinal pressure gradient are obtained. The study also shows that, in addition to the effect of mean flow parameter, the wave amplitude also effect the peristaltic flow. This effect is noticeable in the pressure rise and frictional forces per wavelength through numerical integration.     

On the use of characteristic‐based split meshfree method for solving flow problems

This study presents characteristic‐based split (CBS) algorithm in the meshfree context. This algorithm is the extension of general CBS method which was initially introduced in finite element framework. In this work, the general equations of flow have been represented in the meshfree context. A new finite element and MFree code is developed for solving flow problems. This computational code is capable of solving both time‐dependent and steady‐state flow problems. Numerical simulation of some known benchmark flow problems has been studied. Computational results of MFree method have been compared to those of finite element method. The results obtained have been verified by known numerical, analytical and experimental data in the literature. A number of shape functions are used for field variable interpolation. The performance of each interpolation method is discussed. It is concluded that the MFree method is more accurate than FEM if the same numbers of nodes are used for each solver. Meshfree CBS algorithm is completely stable even at high Reynolds numbers. Copyright © 2007 John Wiley & Sons, Ltd.     

Homo‐ and heteropolynuclear copper(II) complexes containing a new diimine–dioxime ligand and 1,10‐phenanthroline: synthesis,characterization, solvent‐extraction studies,catalase‐like functions and DNA cleavage abilities

A series of homo‐, heterodinuclear and homotrinuclear copper(II) complexes containing a new Schiff base ligand and 1,10‐phenanthroline were synthesized. Based on results of elemental analyses, FTIR, ¹H‐ and ¹³C‐NMR spectra, conductivity measurements and magnetic susceptibility measurements, the complexes had general compositions {[Cu(L)(H₂O)M(phen)₂](ClO₄)₂ [M = Cu(II), Mn(II), Co(II)]} and {[Cu₃(L)₂(H₂O)₂](ClO₄)₂}. The metal:L:phen ratio is 2:1:2 for the dinuclear copper(II) complexes and the metal:L ratio was 3:2 for the trinuclear copper(II) complex. The liquid–liquid extraction of various transition metal cations [Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II), Hg(II)] from the aqueous phase to the organic phase was carried out using the diimine–dioxime ligand. It was concluded that the ligand can effectively be used in solvent extraction of copper(II) from the aqueous phase to the organic phase. Furthermore, catalytic activitiy of the complexes for the disproportionation of hydrogen peroxide was also investigated in the presence of imidazole. Dinuclear copper(II)–manganese(II) complex has some similarity to manganese catalase in structure and activity. The interaction between these complexes and DNA has also been investigated by agarose gel electrophoresis; we found that the homo‐ and heterodinuclear copper complexes can cleave supercoiled pBR322 DNA to nicked and linear forms in the presence of H₂O₂. Copyright © 2009 John Wiley & Sons, Ltd.     

A numerical technique for laminar swirling flow at the interface between porous and homogenous fluid domains

There have been a few recent numerical implementations of the stress‐jump condition at the interface of conjugate flows, which couple the governing equations for flows in the porous and homogenous fluid domains. These previous demonstration cases were for two‐dimensional, planar flows with simple geometries, for example, flow over a porous layer or flow through a porous plug. The present study implements the interfacial stress‐jump condition for a non‐planar flow with three velocity components, which is more realistic in terms of practical flow applications. The steady, laminar, Newtonian flow in a stirred micro‐bioreactor with a porous scaffold inside was investigated. It is shown how to implement the interfacial jump condition on the radial, axial, and swirling velocity components. To avoid a full three‐dimensional simulation, the flow is assumed to be independent of the azimuthal direction, which makes it an axisymmetric flow with a swirling velocity. The present interface treatment is suitable for non‐flat surfaces, which is achieved by applying the finite volume method based on body‐fitted and multi‐block grids. The numerical simulations show that a vortex breakdown bubble, attached to the free surface, occurs above a certain Reynolds number. The presence of the porous scaffold delays the onset of vortex breakdown and confines it to a region above the scaffold. Copyright © 2008 John Wiley & Sons, Ltd.     

The intrinsic XFEM for two‐fluid flows

In two‐fluid flows, jumps and/or kinks along the interfaces are present in the resulting velocity and pressure fields. Standard methods require mesh manipulations with the aim that either element edges align with the interfaces or that the mesh is sufficiently refined near the interfaces. In contrast, enriched methods, such as the extended finite element method (XFEM), enable the representation of arbitrary jumps and kinks inside elements. Thereby, optimal convergence can be achieved for two‐fluid flows with meshes that remain fixed throughout the simulation. In the intrinsic XFEM, in contrast to other enriched methods, no more unknowns are present in the approximation than in a standard finite element approximation. In this work, the intrinsic XFEM is employed for the simulation of incompressible two‐fluid flows. Numerical results are shown for a number of test cases and prove the success of the method. Copyright © 2008 John Wiley & Sons, Ltd.