Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry     

Interactions of Impact Shock Waves in a Thin-Walled Explosive Container. II. Impact by a Cone-Nosed Projectile

Interaction of impact shock waves that could detonate an explosive (Composition B) confined in a thin-walled container impacted by a cone-nosed projectile is numerically studied, based on the Forest Fire explosive reaction rate model. The normal impact on the container by a small projectile with a conical nose is considered. Depending on the cone angle of the nose part of the projectile, the zone of interaction of initiating shock waves can be remote from the central axis of the impact. The off-the-central-axis detonation is interpreted from the viewpoint of different interaction modes in the explosive container, which are reflected from the cassette wall, change their directions, and superimpose onto each other, leading to explosive detonation.     

Catalytic degradation of waste polyolefinic polymers using spent FCC catalyst with various experimental variables

Liquid-phase catalytic degradation of waste polyolefinic polymers (HDPE, LDPE, PP) over spent fluid catalytic cracking (FCC) catalyst was carried out at atmospheric pressure with a stirred semi-batch operation. The effect of experimental variables, such as catalyst amount, reaction temperature, plastic types and weight ratio of mixed plastic on the yield and accumulative amount distribution of liquid product for catalytic degradation was investigated. The initial rate of catalytic degradation of waste HDPE was linearly increased with catalyst amount (4-12 wt%), while that was exponentially increased with reaction temperature (350-430 ‡C). Spent FCC catalyst in the liquid-phase catalytic degradation of polymer was not deactivated fast. The product distribution from catalytic degradation using spent FCC catalyst strongly depended on the plastic type. The catalytic degradation of mixed plastic (HDPE: LDPE: PP: PS=3: 2: 3: 1) showed lower degradation temperature by about 20 ‡C than that of pure HDPE.     

Solution copolymerization of methyl methacrylate and alkyl methacrylates in a continuous stirred tank reactor(CSTR)

Continuous solution copolymerization of methyl methacrylate with ethyl methacrylate or n-butyl methacrylate was carried out in a continuous stirred tank reactor. Solvent and initiator used were toluene and benzoyl peroxide, respectively. Reaction volume was 1.2 litters, residence time 3 hours and polymerization temperature 80°C. The copolymerization conversions were analyzed by UV spectrophotometry and confirmed by measuring the solid weights of copolymers obtained after evaporating solvent. The copolymerization of methyl methacrylate and alkyl methacrylates followed the second order kinetics. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three and half times of the residence time.     

Damage zone development in PVC under a multiaxial tensile stress state

The irreversible deformation mechanisms of poly(vinyl chloride) with a semicircular notch under slow tensile loading have been studied as a function of sheet thickness. Initially, core yielding was observed in the optical microscope as two families of slip lines growing from the notch surface in the centre of the specimen. The size and shape of the core yielding zone could be described by plasticity analysis. A stress-whitened zone subsequently initiated near the tip of the slip line zone. The stress whitening was caused by 1 m voids that were visible in the scanning electron microscope. The mean stress for stress whitening was calculated to be 43.0±1.5 MPa by a plastic stress analysis of a pressure-dependent yield material. By assuming a constant mean stress along the boundary of the stress-whitened zone, the one-dimensional shift of the elastic stress distribution was obtained. At higher stresses, hinge shear and intersecting shear were observed for thick and thin sheet, respectively.     

Spatial distribution of silica fillers in phase-separated rubber blends investigated by three-dimensional elemental mapping

The distribution of nano-sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X-ray spectrometry (EDX). 3D distribution of silica is visualized by STEM-EDX tomography with the tilt-series of silicon elemental maps, while the phase-separated morphologies of polyisoprene rubber (IR) and styrene-butadiene rubber (SBR) are visualized by STEM-tomography in high-angle-annular-dark field (HAADF) mode. The combination of STEM-EDX and STEM-HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.     

Preparation and properties of TiC-Ni cermets using Ni-plated TiC

TiC powders were coated with Ni by a chemical plating technique and the pressed compacts sintered at 1623K. The density of the sintered bodies was 98–99%. Compared with mechanically-mixed powder, Ni-plated TiC powders gave a more uniform microstructure in which TiC particles were well dispersed in the Ni matrix. The cermets exhibited ductile fracture for TiC-70 vol.% Ni and brittle fracture for TiC-30 vol.% Ni. The flexural strength was improved by the homogeneous dispersion of TiC. The thermal expansion coefficient increased with a decrease in Ni content, following a nearly linear law of mixtures on the basis of volume fractions of pure TiC and Ni.     

Properties of Induction Plasma Sprayed Iron Based Nanostructured Alloy Coatings for Metal Based Thermal Barrier Coatings

Metal-based thermal barrier coatings (MBTBCs) have been produced using high frequency induction plasma spraying (IPS) of iron-based nanostructured alloy powders. The study of MBTBCs has been initiated to challenge issues associated with current TBC materials such as difficult prediction of their “in-service” lifetime. Reliability of TBCs is an important aspect besides the economical consideration. Therefore, the study of MBTBCs, which should posses higher toughness than the current TBC materials, has been initiated to challenge the mechanical problems of ceramic-based TBCs (CBTBCs) to create a new generation of TBCs. The thermal diffusivity (TD) (α) properties of the MBTBCs were measured using a laser flash method, and density (ρ) and specific heat (C _p) of the MBTBCs were also measured for their thermal conductivity (k) calculation (k = αρ C _p).     

Superplasticity of fine-grained 7475 Al alloy and a proposed new deformation mechanism

A study has been made to investigate the superplastic deformation mechanisms of 7475 Al alloy in relation to the variation of grain size ranging between 5.5 μm and 13 μm. The strain-rate sensitivity (m) was increased with decreasing grain size in the superplastic deformation regime. Microstructural investigation after tension tests revealed that the dispersoid free zones were produced mostly at the grain boundaries normal to the tensile direction. A new model for describing the deformation behavior of the 7475 Al alloy has been proposed based on the assumption that the grain boundary sliding was accommodated by both diffusional flow and slip. This new model well predicts many aspects of experimental results.     

Electrochemical analysis of the microbiologically influenced corrosion of steels by sulfate-reducing bacteria

The differences between the general corrosion and microbiologically influenced corrosion (MIC) of steels were investigated in terms of its electrochemical behavior and surface phenomena. The corrosion potential of steels in the absence of SRB (sulfate-reducing bacteria) shifted to a negative value with the immersion time. However, the potential of the presence of SRB shifted to a positive value after 30 days' incubation, indicating the growth of SRB biofilms on the test metal specimens and the formation of corrosion products. In addition, the color of a medium inoculated with SRB changed from gray to black. The change in color appeared to be caused by the formation of pyrites (FeS) as a corrosion product, while no significant change in color was observed in a medium without SRB inoculation. Moreover, corrosion rates of various steels tested for MIC were higher compared to those of steels in the absence of SRB. In particular, the corrosion current density of TMCP steels in the presence of SRB was larger than that of other steels. Pitting corrosion was also observed at the surface of all steels in the SRB-inoculated medium. The pitting corrosion likely occurred due to SRB that was associated with the increasing corrosion rates through increasing cathodic reactions, which caused a reduction of sulfate to sulfide as well as the formation of an oxygen concentration cell.