An electrochemical impedance spectroscopy and scanning electron microscopy study of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries

This study has developed an electrochemical impedance spectroscopy (EIS) method for the in situ investigation of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries during charge/discharge cycling. The EIS data for a fully charged and fully discharged battery are internally consistent with the expected kinetics of a battery in the opposite states of charge, and demonstrate that EIS measurements may be recorded with a high level of reproducibility. Furthermore, this study has necessitated the development of a special cell incorporating horizontally orientated battery plates that can be subjected to elevated pressure through the stacking of lead bricks on top of the cell, as well as a physically robust reference electrode system that can withstand the application of pressure. For this purpose, a platinum-wire pseudo-reference electrode has been developed, and has been shown to exhibit sufficient electrode stability over the period of an EIS recording, enabling the measurement of reproducible and meaningful EIS data. Additionally, the influence of positive plate compression on the behaviour of the lead-acid battery has been investigated by using scanning electron microscopy (SEM). Clearly, the experimental data show that plate compression enhances significantly the kinetics and concomitant performance of the lead-acid battery, and this is related to the enhanced reactivity of the active material, as rationalized by using the agglomeration-of-spheres (AOS) model.     

Characterization of polymer‐layered silicate (clay) nanocomposites by transmission electron microscopy and X‐ray diffraction: A comparative study

Several polymer‐layered silicate (clay) nanocomposites (PLSNs) were analyzed by transmission electron microscopy (TEM) and wide‐angle X‐ray diffraction (XRD) in an effort to characterize the nanoscale dispersion of the layered silicate. The PLSNs investigated included thermoset (cyanate esters) and thermoplastic polymers (polystyrene, nylon 6, and polypropylene‐g‐maleic anhydride). The results of this study reveal that the overall nanoscale dispersion of the clay in the polymer is best described by TEM, especially when mixed morphologies are present. XRD is useful for the measurement of d‐spacings in intercalated systems but cannot always observe low clay loadings (<5%) or be used as a method to identify an exfoliated nanocomposite where no XRD peaks are present (constituting a negative result). Most importantly, the study showed that XRD is not a stand‐alone technique, and it should be used in conjunction with TEM. Our studies suggest that new definitions, or a clarification of existing definitions, are needed to properly describe the diversity of PLSN nanostructures seen in various materials. Published 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1329–1338, 2003     

Complex refractive index,single scattering albedo,and mass absorption coefficient of secondary organic aerosols generated from oxidation of biogenic and anthropogenic precursors

Refractive index and optical properties of biogenic and anthropogenic secondary organic aerosol (SOA) particles were investigated. Aerosol precursors, namely longifolene, α-pinene, 1-methylnaphthalene, phenol, and toluene were oxidized in a Teflon chamber to produce SOA particles under different initial hydrocarbon concentrations and hydroxyl radical sources, reflecting exposures to different levels of nitrogen oxides (NO_x). The real and imaginary components (n and k, respectively) of the refractive index at 375?nm and 632?nm were determined by Mie theory calculations through an iterative process, using the χ² function to evaluate the fitness of the predicted optical parameters with the measured scattering, absorption, and extinction coefficients from a Photoacoustic Extinctiometer and Cavity Attenuated Phase Shift Spectrometer. Single scattering albedo (SSA) and bulk mass absorption coefficient (MAC) at 375?nm were calculated. SSA values of SOA particles from biogenic precursors (longifolene and α-pinene) were ～0.98–0.99 (～6.3% uncertainty), reflecting purely scattering aerosols regardless of the NO_x regime. However, SOA particles from aromatic precursors were more absorbing and displayed NO_x-dependent SSA values. For 1-methylnaphthalene SOA particles, SSA values of 0.92–0.95 and ～0.75–0.90 (～6.1% uncertainty) were observed under intermediate- and high-NO_x conditions, respectively, reflecting the absorbing effects of SOA particles and NO_x chemistry for this aromatic system. In mixtures of longifolene and phenol or longifolene and toluene SOA under intermediate- and high-NO_x conditions, k values of the aromatic-related component of the SOA mixture were higher than that of 1-methylnaphthalene SOA particles. With the increase in OH exposure, k_phenol decreased from 0.10 to 0.02 and 0.22 to 0.05 for intermediate- and high-NO_x conditions, respectively. A simple relative radiative forcing calculation for urban environments at λ?=?375?nm suggests the influence of absorbing SOA particles on relative radiative forcing at this wavelength is most significant for aerosol sizes greater than 0.4?µm.

Copyright © 2019 American Association for Aerosol Research     

Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Patterns of Iridoid Glycoside Production and Induction in Plantago lanceolata and the Importance of Plant Age

Induction of allelochemicals is one way that plants efficiently deploy defenses against herbivory. In two separate experiments we investigated the time course of this inductive response and the importance of the timing of herbivory for Plantago lanceolata (Plantaginaceae). We found a localized induced response of catalpol and the ratio of catalpol to total iridoid glycosides in damaged leaves that was evident at d 6 after caterpillars of the specialist Junonia coenia were put onto the plants. On the whole plant level, we detected small, but significant changes in the iridoid glycoside metabolism of P. lanceolata on several different days following herbivory. We also found considerable change in the amounts of allelochemicals produced during P. lanceolata's ontogeny. This ontogenetic effect might help to explain some of the reasons why induction may be difficult to detect in P. lanceolata. We also investigated the importance of the timing of herbivory on P. lanceolata's inductive response, but neither herbivory after 5 wk of growth nor after 6 or 7 wk of growth induced an increase in aucubin or catalpol.     

Thermal and flammability properties of a silica–poly(methylmethacrylate) nanocomposite

PMMA, poly(metheylmethacrylate), nanocomposites were made by in situ radical polymerization of MMA, methylmethacrylate, with colloidal silica (ca. 12 nm) to study the effects of nanoscale silica particles on the physical properties and flammability properties of PMMA. Transparent samples resulted and the dispersity of the particles was examined by transmission electron microscopy and atomic force microscopy. The addition of nanosilica particles (13% by mass) did not significantly change the thermal stability, but it made a small improvement in modulus, and it reduced the peak heat release rate roughly 50%. Last, the flame‐retardant mechanism provided by the addition of nanosilica particles in PMMA is discussed. Published 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2072–2078, 2003     

The relationship between strength and the composition and fineness of cement

Data from new experiments and from work published during the past 40 years are subjected to regression analysis to determine the relationship between strength and the composition and fineness of cement. The original authors differed in their opinions on the relative importance of C₃S and C₃A. The controversy is examined against a background of experience with a group of materials that are representative of Portland cement in general, and in terms of an analysis based on a model in which, during the first weeks of hardening, the strength developed by C₃S depends on the proportion of C₃A in the cement.     

Modelling of a RDC using a combined CFD-population balance approach

In the present study we propose an extension of the Euler/Lagrangian approach for liquid-liquid two phase flows when the volume fraction of the dispersed phase is not small. The continuous phase velocity is obtained by solving the Reynolds-averaged Navier-Stokes equations augmented with the k-ε turbulence model. The motion of the dispersed phase is calculated by solving the equations of motion taking into account inertia, drag and buoyancy forces. The coupling between the phases is described by momentum source terms and the terms that account for turbulence generation by the droplets’ motion. Collision and breakage of the droplets are treated by a single particle Monte-Carlo stochastic simulation method. This method is based on a mass flow formulation and operator splitting technique. For validation of the numerical procedure the droplet size distribution and flow fields in a rotating disc contactor are calculated and compared with the existing experimental results.     

Hydrothermal microwave-assisted synthesis of LaFeO3 catalyst for N2O decomposition

Lanthanum orthoferrite powders were synthesized via one-step hydrothermal reactions under mild conditions using microwave and conventional heating. The use of microwave irradiation during the synthesis allows one to obtain nanocrystalline LaFeO₃ with a higher yield and reduced crystallite and particle size within a 16 times shorter duration (3 hours) at a lower temperature of 220°C as compared to the conventional heating. The catalytic decomposition of nitrous oxide was performed over both samples, it was shown that the sample obtained under microwave conditions demonstrates enhanced activity as a catalyst: N₂O decomposes completely at 700°C over the catalyst formed at microwave conditions, while the comparative catalyst prepared by conventional heating reaches a lower conversion of only 60% at the same temperature and catalytic reaction conditions.     

Impact of sand and filler materials on the hydration behavior of calcium aluminate cement

In earlier work, we have observed discrepancies relating to the early hydration of calcium aluminate cement (CAC) when comparing data from heat flow calorimetry of CAC paste with results from mortar strength tests using the crushing method. Here, we investigated on this phenomenon and found that the sand which is used as a filler exerts a major influence on CAC hydration resulting in acceleration. Furthermore, in particular fine filler materials such as, for example, microsilica, fine limestone powder, and especially α- and γ-Al₂O₃ also produced a strong hydration accelerating effect which is dependent on their specific surface area. The mechanism underlying the acceleration is that under alkaline conditions their negative surface charge attracts calcium ions as was confirmed via inductively coupled plasma atomic emission measurements. Such a layer generates favourable conditions for the nucleation of CAC hydration products (C-A-H phases). The resulting crystalline hydrates which form on the surface of the filler particles submerged in CAC cement pore solution were visualized via SEM imaging. This way, specifically selected fillers can significantly accelerate CAC hydration and save precious lithium salts which are commonly used to boost the early strength of CAC.