Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 2. Original paint layer samples

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (μ-XANES) and X-ray fluorescence spectrometry (μ-XRF) were employed. Additionally, μ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of μ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.     

Virus inactivation by salt (NaCl) and phosphate supplemented salt in a 3D collagen matrix model for natural sausage casings

Due to possible presence and spread of contagious animal viruses via natural sausage casings the international trade in these food products is subject to veterinary and public health requirements. In order to manage these restrictions we determined the effect of casing preservation on four highly contagious viruses for livestock: foot-and-mouth-disease virus (FMDV), classical swine fever virus (CSFV), swine vesicular disease virus (SVDV) and African swine fever virus (ASFV). We used an in vitro 3D collagen matrix model in which cells, infected with the four different viruses were embedded in a bovine collagen type I gel matrix and treated with either saturated salt (NaCl) or phosphate supplemented saturated salt at four different temperatures (4, 12, 20 and 25 °C) during a period of 30 days. The results showed that all viruses were faster inactivated at higher temperatures, but that stability of the various viruses at 4 °C differed. Inactivation of FMDV in the 3D collagen matrix model showed a clear temperature and treatment effect on the reduction of FMDV titres. At 4 and 12 °C phosphate supplemented salt showed a very strong FMDV inactivation during the first hour of incubation. Salt (NaCl) only had a minor effect on FMDV inactivation. Phosphate supplemented salt treatment increased the effect temperature had on inactivation of CSFV. In contrast, the salt (NaCl) treatment only increased CSFV inactivation at the higher temperatures (20 °C and 25 °C). Also SVDV inactivation was increased by phosphate supplemented salt, but salt (NaCl) treatment only resulted in a significant decrease of SVDV titre at a few time points. The ASFV results showed that both salt (NaCl) and phosphate supplemented salt were capable to inactivate ASFV within 48 h. In contrast to the other viruses (FMDV, CSFV and SVDV), ASFV was the most stable virus even at higher temperatures. The results obtained in this in vitro model underline the efficacy of a combined treatment using phosphate supplemented salt and storage at 20 °C or higher for a period of 30 days. This treatment may therefore be useful in reducing the animal health risks posed by spread of contagious animal viruses by international trade of natural sausage casings.     

Mechanical Properties of Phosphate Glass Optical Fibers

In this work, step-index 40/125 μm diameter optical fibers produced from two slightly different lithium phosphate glasses were subjected to mechanical characterization. Tensile tests were carried out on fibers with gage length from 10 to 150 mm, allowing for the determination of the failure stress (ranging from ≈200 to 400 MPa) and the elastic modulus (60 GPa). Some tests were also performed with the fiber “immersed” in water; an important subcritical crack growth effect was pointed out, and a fatigue susceptibility parameter (n) equal to 11.4 was determined. The analysis of fracture mirror allows an estimated fracture toughness equal to 0.5 MPa m^0.5.     

Outdoor weathering performance parameters of exterior wood coating systems on tropical hardwood substrates

Wood coating research almost exclusively focuses on softwood as substrate despite the fact that coatings applied on tropical hardwoods show a different weathering behaviour. The objective of this study was to quantify the impact of wood substrate and coating type on the weathering behaviour of finished wooden joinery in outdoor exposure using a set of statistical methods. Therefore, a broad range of white opaque paints and mid-oak semi-transparent stains were used. The coatings were industrially applied on window frames made of frequently used commercial tropical hardwood species. The general appearance of the wood/coating systems was assessed visually using a rating scale that takes into account the anatomical characteristics of hardwood. For the evaluation, a required minimum exposure time of 2.5 years outdoor weathering for joinery in vertical position and facing south-west was determined. At 30 months best performances were recorded for waterborne alkyd primers with an acrylic topcoat when dry coating film was sufficiently thick. The dry layer thickness also affected the impact of the hiding power on the performance of the wood/coating system. Within hardwood species the degradation rate of coatings on species with a fine texture was the lowest. The significant influence of the substrate’s texture on the weathering behaviour of coated hardwood stressed the need to evaluate the wood/coating system in total.     

Importance of organic matter lability for monomethylmercury production in sulfate-rich marine sediments

Sediment cores were collected from two shallow sites in the Venice Lagoon, Italy, in order to study the lability of organic matter and the methylation rate of inorganic Hg(II). Measurements were made of concentrations of total Hg and monomethylmercury (MMHg), Hg(II) methylation rates, concentrations of total organic carbon and total nitrogen in the sediments, and dissolved sulfate, sulfide, and alkalinity in sedimentary pore waters. A positive linear relationship was detected between the specific Hg(II) methylation rate constant and the fraction of total Hg comprised of MMHg (%MMHg/Hg), indicating that short-term Hg(II) methylation rate reflects a long-term accumulation of MMHg in sediment. In addition, the %MMHg/Hg and specific Hg(II) methylation rate constant in sediment increased with decreasing ratios of total organic carbon to total nitrogen (C/N), whereas concentrations of dissolved sulfate, sulfide, and alkalinity in pore water remained constant. This result suggests that the Hg(II) methylation rate was affected by lability of organic matter. In particular, surface sediments, which contained large fractions of fresh algal organic material (C/N = 5.8-7.8), showed higher Hg(II) methylation rates than did deeper sediments (C/N > 10). Our results indicate that the C/N ratio can be used as a proxy for the lability of organic matter that influences Hg(II) methylation rate in sulfate-rich marine sediments.     

In vitro degradation and in vivo passage kinetics of carvacrol,thymol, eugenol and trans‐cinnamaldehyde along the gastrointestinal tract of piglets

BACKGROUND: The essential oils (EO) carvacrol, thymol, eugenol and trans‐cinnamaldehyde have well‐documented antimicrobial properties and offer therefore an alternative for the antimicrobial growth promoters in pig feeds. The aim of this work was to determine the degradation and kinetics of these EO along the gastrointestinal tract (GIT) of piglets, which is necessary information for correct application in pig feeds. RESULTS: None of these compounds was significantly degraded in in vitro simulations of pig gastric fermentation. Carvacrol and thymol were not degraded in jejunal simulations, but significant losses of up to 29% were found in caecal simulations. Eugenol and trans‐cinnamaldehyde showed a more pronounced degradation in jejunal and caecal simulations. A single dose mixed with feed (13.0, 13.2, 12.5 and 12.7 mg kg^?1 body weight for carvacrol, thymol, eugenol and trans‐cinnamaldehyde respectively) was given orally to piglets. Half‐lives in total digestive tract ranged between 1.84 and 2.05 h, whereby trans‐cinnamaldehyde showed the fastest disappearance. All of these EO were mainly and almost completely absorbed in the stomach and the proximal small intestine. Plasma concentrations (sum of free and conjugated compound) peaked at 1.39, 1.35 and 0.83 h for carvacrol, thymol and eugenol respectively and this was accompanied by high concentrations in urine. CONCLUSION: The four compounds were in vitro poorly degraded in the proximal segments of the GIT of piglets, but degradation is expected in more distal segments. In vivo, the EO were mainly and almost completely absorbed in the stomach and the proximal small intestine. Copyright © 2008 Society of Chemical Industry     

Time-resolved strain and deformation measurement on the vibrating saxophone reed

Single-reed musical instruments, such as the saxophone, generate sound through a complex interplay between the mechanics of the reed and the hydrodynamic and acoustic pressure in the instrument mouthpiece. To understand this complex mechanism, experimental data are lacking. This paper presents full-field, time-resolved measurements of strain and displacement of a vibrating saxophone reed, measured under mimicked realistic playing conditions. It is found that strain along the length axis of the reed is mainly expansive, except in a small zone near the tip where it becomes compressive when the reed touches the front edge of the mouthpiece. At the instant in the vibration phase where the reed touches the mouthpiece, significant bending and compressive strain appear along the direction perpendicular to the reed axis. Strain magnitudes in both directions are similar, with absolute values of 0.1%. Full-field strain maps reveal subtle characteristics which are not revealed by displacement measurements. Bi-axial bending and strain may be an essential component in reed mechanics, which up till now has been fully neglected in modelling.     

Top-down kinetic modeling from power law to elementary steps using KASTER: A methane steam reforming case study

A top-down methodology for kinetic model construction including regression against experimental data is proposed using “KASTER.” As a case study, it is applied in the assessment of methane steam reforming (MSR) including water–gas shift (WGS) on a Ni catalyst at 923 K. The degree of detail in the reaction mechanism and the corresponding model is gradually enhanced, typically ranging from a simple power law to a microkinetic model. The reactor equations are solved transiently, preventing the numerical challenges encountered in the steady-state solution, particularly for microkinetic models. The microkinetic variant indicated that CH₄ dissociative adsorption and CO formation are kinetically relevant steps in MSR, while COOH formation is rate-determining in WGS. However, the model providing the best balance between detail accounted for and parameter significance corresponded to a Langmuir–Hinshelwood–Hougen–Watson (LHHW) mechanism accounting for dissociative adsorption, with CO formation and COOH formation as rate-determining steps for MSR and WGS, respectively.     

Multi-Scale Modeling of Tunneling in Nanoscale Atomically Precise Si:P Tunnel Junctions

Controlling electron tunneling is of fundamental importance in the design and operation of semiconductor nanostructures such as field effect transistors (FETs) and quantum computing device architectures. The exponential sensitivity of tunneling with distance requires precise fabrication techniques to engineer the desired device dimensions to achieve the appropriate tunneling resistances/tunnel rates. This is particularly important for high fidelity spin readout and qubit exchange in quantum computing architectures. Here, it is shown by combining precision fabrication techniques with accurate atomistic modeling, predictive device design criteria are achieved at atomic length scales. Such a tool is useful when devices become more complex or have arbitrary shapes/geometries. In particular, in this study, atomic precision patterning of monolayer degenerately phosphorus-doped silicon tunnel junctions patterned by scanning tunnelling microscopy lithography and tight-binding non-equilibrium Green's function (TB-NEGF) modeling is combined to describe the dependence of tunnel junction resistance R_T on junction length. An agreement with experiment to within a factor of 2 over 4 orders of magnitude in R_T is found, and this model allows to accurately determine the barrier height V₀ = 57.5 ± 1 meV and lateral seam s_xy = 0.39 ± 0.01 nm in these nanoscale junctions. This study confirms the use of the TB-NEGF formalism to accurately model highly doped atomically precise tunnel junctions in silicon. Further applications of this model will enable improved device performance at the nanoscale.