Principles of demineralization: modern strategies for the isolation of organic frameworks. Part II. Decalcification

This is the second paper on principles of demineralization. The initial paper is dedicated to the common definitions and the history of demineralization. In present work we review the principles and mechanisms of decalcification, i.e., removing the mineral Ca-containing compounds (phosphates and carbonates) from the organic matrix in its two main aspects: natural and artificial. Natural chemical erosion of biominerals (cavitation of biogenic calcareous substrata by bacteria, fungi, algae, foraminifera, sponges, polychaetes, and mollusks) is driven by production of mineral and organic acids, acidic polysaccharides, and enzymes (cabonic anhydrase, alkaline and phosphoprotein phosphataes, and H(+)-ATPase). Examples of artifical decalcification includes demineralization of bone, dentin and enamel, and skeletal formations of corals and crustacean. The mechanism and kinetics of Ca-containing biomineral dissolution is analyzed within the framework of (i) diffusion-reaction theory; (ii) surface-reaction controlled, morphology-based theories, and (iii) phenomenological surface coordination models. The application of surface complexation model for describing and predicting the effect of organic ligands on calcium and magnesium dissolution kinetics is also described. Use of the electron microscopy-based methods for observation and visualization of the decalcification phenomenon is discussed.     

The effects of aircraft on climate and pollution. Part I: Numerical methods for treating the subgrid evolution of discrete size- and composition-resolved contrails from all commercial flights worldwide

This paper provides and evaluates mass conservative, positive-definite, unconditionally-stable, and non-iterative numerical techniques for simulating the evolution of discrete, size- and composition-resolved aerosol and contrail particles in individual aircraft exhaust plumes in a global or regional 3-D atmospheric model and coupling the subgrid exhaust plume information to the grid scale. Such treatment represents a new method of simulating the effects of aircraft on climate, contrails, and atmospheric composition. Microphysical processes solved within each plume include size-resolved coagulation among and between aerosol and contrail particles and their inclusions, aerosol-to-hydrometeor particle ice and liquid nucleation, deposition/sublimation, and condensation/evaporation. Each plume has its own emission and supersaturation, and the spreading and shearing of each plume’s cross-section are calculated as a function of time. Aerosol- and contrail-particle core compositions are tracked for each size and affect optical properties in each plume. When line contrails sublimate/evaporate, their size- and composition-resolved aerosol cores and water vapor are added to the grid scale where they affect large-scale clouds. Algorithm properties are analyzed, and the end-result model is evaluated against in situ and satellite data.     

The effects of large vibration amplitudes on the axisymmetric mode shapes and natural frequencies of clamped thin isotropic circular plates. Part I: iterative and explicit analytical solution for non-linear transverse vibrations

The effects of large vibration amplitudes on the first two axisymmetric mode shapes of clamped thin isotropic circular plates are examined. The theoretical model based on Hamilton's principle and spectral analysis developed previously by Benamar et al. for clamped-clamped beams and fully clamped rectangular plates is adapted to the case of circular plates using a basis of Bessel's functions. The model effectively reduces the large-amplitude free vibration problem to the solution of a set of non-linear algebraic equations. Numerical results are given for the first and second axisymmetric non-linear mode shapes for a wide range of vibration amplitudes. For each value of the vibration amplitude considered, the corresponding contributions of the basic functions defining the non-linear transverse displacement function and the associated non-linear frequency are given. The non-linear frequencies associated to the fundamental non-linear mode shape predicted by the present model were compared with numerical results from the available published literature and a good agreement was found. The non-linear mode shapes exhibit higher bending stresses near to the clamped edge at large deflections, compared with those predicted by linear theory. In order to obtain explicit analytical solutions for the first two non-linear axisymmetric mode shapes of clamped circular plates, which are expected to be very useful in engineering applications and in further analytical developments, the improved version of the semi-analytical model developed by El Kadiri et al. for beams and rectangular plates, has been adapted to the case of clamped circular plates, leading to explicit expressions for the higher basic function contributions, which are shown to be in a good agreement with the iterative solutions, for maximum non-dimensional vibration amplitude values of 0.5 and 0.44 for the first and second axisymmetric non-linear mode shapes, respectively.     

A multispectrum analysis of the ν2 band of HCN: Part I. Intensities, broadening, and shift coefficients

Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P- and R-branches of the ν₂ band of H¹²C¹⁴N centered near 712 cm⁻¹. Infrared spectra of HCN in the 14-μm region were obtained at high resolution (0.002-0.008 cm⁻¹) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26 and −60 °C. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening, and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman-Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm⁻¹ atm⁻¹ at 296 K, and the air-broadening coefficients range from 0.08 to 0.14 cm⁻¹ atm⁻¹ at 296 K. The temperature dependence exponents of self-broadening range from 1.46 to −0.12 while the corresponding exponents for air broadening vary between 0.58 and 0.86. The present measurements are the first known determination of negative values for the temperature dependence exponents of HCN-broadening coefficients. We were able to support our self-broadening measurements with appropriate theoretical calculations. Our present measurements are compared, where possible, with previous measurements for this and other HCN bands, as well as the parameters that are included in the 2000 and 2004 editions of the high-resolution transmission (HITRAN) database.     

Raman scattering features of lead pyroantimonate compounds: implication for the non‐invasive identification of yellow pigments on ancient ceramics. Part II. In situ characterisation of Renaissance plates by portable micro‐Raman and XRF studies

The effectiveness of Raman spectroscopy (using a bench‐top system on standard pigments) for the characterisation of modified lead antimonate yellows was demonstrated in the already published Part I. The knowledge gained is employed here for the study of yellow glazes on genuine Renaissance plates with the aim of identifying non‐invasively lead pyroantimonate compounds by portable micro‐Raman equipment. The investigation was carried out directly on site, at the Victoria and Albert Museum (London, UK) and at the Museo Statale d'Arte Medievale di Arezzo (Arezzo, Italy), combining Raman and X‐ray fluorescence analyses. In addition to the spectral features of both unmodified Naples yellow and Sn‐ and Zn‐modified lead antimonate compounds, the Raman patterns related to partially modified pyrochlore structures were observed. For this reason, the possible Sn‐induced modification of Naples yellow by cassiterite (SnO₂), present within the glaze as opacifier was explored on lead antimonate yellow glaze mock‐ups fired at different temperatures. Copyright © 2010 John Wiley & Sons, Ltd.