Use of portable X-ray fluorescence instrument for bulk alloy analysis on low corroded indoor bronzes

One of the most often used non-destructive methods for elemental analysis when performing field measurements on bronze sculptures is X-ray fluorescence (XRF) analysis based on portable instrumentation. However, when performing routine in-situ XRF analysis on corroded objects obtained results are sometimes considerably influenced by the corrosion surface products.In this work the suitability of portable XRF for bulk analysis of low corroded bronzes, which were initially precisely characterized using sophisticated and reliable laboratory methods, was investigated and some improvements in measuring technique and data processing were given. Artificially corroded bronze samples were analyzed by a portable XRF instrument using the same methodology and procedures as when performing in-situ analysis on real objects. The samples were first investigated using sophisticated complementary laboratory techniques: Scanning Electron Microscopy, Proton-Induced X-ray Emission Spectroscopy and Rutherford Backscattering Spectrometry, in order to gain precise information on the formation of the corrosion product layers and in-depth elemental profile of corrosion layers for different aging parameters. It has been shown that for corrosion layers of up to ca. 25 μm a portable XRF can yield very accurate quantification results.     

Nanorods of transition metal oxalates: A versatile route to the oxide nanoparticles

A versatile route has been explored for the synthesis of nanorods of transition metal (Cu, Ni, Mn, Zn, Co and Fe) oxalates using reverse micelles. Transmission electron microscopy shows that the as-prepared nanorods of nickel and copper oxalates have diameter of 250 nm and 130 nm while the length is of the order of 2.5 μm and 480 nm, respectively. The aspect ratio of the nanorods of copper oxalate could be modified by changing the solvent. The average dimensions of manganese, zinc and cobalt oxalate nanorods were 100 μm, 120 μm and 300 nm, respectively, in diameter and 2.5 μm, 600 nm and 6.5 μm, respectively, in length. The aspect ratio of the cobalt oxalate nanorods could be modified by controlling the temperature.The nanorods of metal (Cu, Ni, Mn, Zn, Co and Fe) oxalates were found to be suitable precursors to obtain a variety of transition metal oxide nanoparticles. Our studies show that the grain size of CuO nanoparticles is highly dependent on the nature of non-polar solvent used to initially synthesize the oxalate rods. All the commonly known manganese oxides could be obtained as pure phases from the single manganese oxalate precursor by decomposing in different atmospheres (air, vacuum or nitrogen). The ZnO nanoparticles obtained from zinc oxalate rods are ～55 nm in diameter. Oxides with different morphology, Fe₃O₄ nanoparticles faceted (cuboidal) and Fe₂O₃ nanoparticles (spherical) could be obtained.     

3D homometallic carboxylate ferrimagnet constructed from a manganese(II) succinate carboxylate layer motif pillared by isonicotinate spacers

A manganese succinate having a layer structure in which the layers are pillared by the isonicotinate spacers in a 3D architecture exhibits long-range ferrimagnetic order below 5.0 K, with the ferrimagnetism arising, for topological reasons, from the nature of the carboxylate binding modes. The compound is the first structurally authenticated example of a 3D ferrimagnet, featuring a homometallic topological ferrimagnetic sheet among metal carboxylates.     

Attenuated Total Reflection-Fourier transform infrared microspectroscopic mapping for the characterisation of paint cross-sections

Paint cross-sections have been analysed using the attenuated total reflection technique combined with FTIR mapping microspectroscopy in order to characterise the nature of the compounds present and map their localisation in the stratigraphy. The study reveals the possibilities offered by micro-ATR devices for obtaining informations about the organic substances employed in painting techniques and in particular their distribution in the different layers, showing a real improvement over traditional analytical investigations in use for the detection of organic substances. Limitations, such as the contamination of the embedding resin and the typical spectral resolution (20 μm) are presented and alternative methods were proposed to obtain better results. In particular, the use of an infrared transparent salt (KBr) as embedding material for the cross-sections is evaluated and seems to be very promising. Furthermore, ATR mapping represent a useful non-destructive analytical technique complementary to others molecular and elemental analyses to be performed afterwards such as SEM-EDX.     

Formation of soluble hexanuclear neptunium(IV) nanoclusters in aqueous solution: growth termination of actinide(IV) hydrous oxides by carboxylates

Complexation of Np(IV) with several carboxylates (RCOO(-); R = H, CH(3), or CHR'NH(2); R' = H, CH(3), or CH(2)SH) in moderately acidic aqueous solutions was studied by using UV-vis-NIR and X-ray absorption spectroscopy. As the pH increased, all investigated carboxylates initiated formation of water-soluble hexanuclear complexes, Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4), in which the neighboring Np atoms are connected by RCOO(-)syn-syn bridges and the triangular faces of the Np(6) octahedron are capped with μ(3)-O(2-)/μ(3)-OH(-). The structure information of Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4) in aqueous solution was extracted from the extended X-ray absorption fine structure data: Np-O(2-) = 2.22-2.23 ? (coordination number N = 1.9-2.2), Np-O(RCOO(-)) and Np-OH(-) = 2.42-2.43 ? (N = 5.6-6.7 in total), Np···C(RCOO(-)) = 3.43 ? (N = 3.3-3.9), Np···Np(neighbor) = 3.80-3.82 ? (N = 3.6-4.0), and Np···Np(terminal) = 5.39-5.41 ? (N = 1.0-1.2). For the simpler carboxylates, the gross stability constants of Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4) and related monomers, Np(RCOO)(OH)(2)(+), were determined from the UV-vis-NIR titration data: when R = H, log β(6,12,-12) = 42.7 ± 1.2 and log β(1,1,-2) = 2.51 ± 0.05 at I = 0.62 M and 295 K; when R = CH(3), log β(6,12,-12) = 52.0 ± 0.7 and log β(1,1,-2) = 3.86 ± 0.03 at I = 0.66 M and 295 K.     

Single-Phase Precursors for the Preparation of Spinel Ferrites via Oxalate Route: the Study of Cobalt Ferrite Synthesis

This work explores the benefits of single-phase oxalate precursors for the preparation of spinel ferrites by thermal decomposition. A direct comparison between the genuine oxalate solid solution and the physical mixture of simple oxalates is presented using the case study of cobalt ferrite preparation. The mixing of metal cations within a single oxalate structure could be verified prior to its thermal decomposition by several non-destructive experimental techniques, namely Mössbauer spectroscopy, X-ray powder diffraction (XRD) and energy-dispersive X-ray spectroscopy. In situ XRD experiments were conducted to compare the decomposition processes of the solid solution and the physical mixture. Additionally, the decomposition products of the FeCo oxalate solid solution were studied ex situ by means of N₂ adsorption, Mössbauer spectroscopy and XRD. The results obtained for different reaction temperatures demonstrate the possibilities to easily control the physical properties of the prepared oxides.     

Ligand Effects on the Chemoselectivity of Transition Metal Catalyzed Reactions of α-Diazo Carbonyl Compounds

The transition metal catalyzed reaction of α-diazo carbonyl compounds has found numerous applications in organic synthesis, and its use in either heterocyclic or carbocyclic ring formation is well precedented. Early work in this area made use of insoluble copper catalysts. Although these catalysts are still employed today, their use has decreased significantly with the advent of homogeneous copper catalysts and catalysts based on other metals. The discovery that Rh^II carboxylates facilitate nitrogen loss from diazo compounds rekindled significant interest in the field of diazo/carbenoid chemistry. Since the realization that Rh^II carboxylates are superior catalysts for the generation of transient electrophilic metal carbenoids from α-diazo carbonyl compounds, intramolecular carbenoid addition and insertion reactions have assumed strategic importance in C? C bond-forming reactions in organic synthesis. In contrast to other catalysts that are suitable for carbenoid reactions of diazo compounds, those constructed with the dirhodium(II ) framework are most amenable to ligand modifications that, in turn, can influence reaction selectivity. This article will emphasize the chemical behavior of transition metal carbenoid complexes that are greatly affected by the nature of the ligand groups attached to the metal center. Much of the discussion will center on the ability of the dirhodium(II ) ligands to determine reaction preference toward different functional groups on the same molecule.     

Identification of Different Copper Green Pigments in Renaissance Paintings by Cluster-TOF-SIMS Imaging Analysis

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging using cluster primary ion beams is used for the identification of a green painting layer on the scene The Angels Concert from the Issenheim Altarpiece (painted in 1516) from a German Renaissance painter, Matthias Grünewald. Copper carboxylate clusters inside a basic copper chloride (atacamite) layer have been identified and located in the copper green layer. The mechanisms of transformation of atacamite into copper carboxylates may be initiated by an aging of the paint layers. The combination of the high mass resolution of the technique together with a micrometer spatial resolution and the possibility to simultaneously identify both minerals and organics, has proven to be the method of choice for the study of the stratigraphy of a paint cross-section.     

Manganese triacetate oxidation of methyl 1-hydroxy-2-naphthalene carboxylates

Manganese-triacetate mediated oxidation of 1-hydroxy-2-napthalene carboxylates in benzene under anhydrous conditions delivers the dimerized product. However, acetoxylation on the ortho- or para-position, or oxidation to quinones occurs on the 1-hydroxy-3-substituted 2-napthalene carboxylates depending on the nature of the substituents when the reaction is carried out in a mixture of acetic acid/acetonitrile.     

Triorganotin 4-isopropylbenzoates as model transesterification catalysts for triorganotin carboxylates grafted to cross-linked polystyrene

Starting from 4-isopropylbenzoic acid, three new triorganotin carboxylates bearing methyl, butyl and phenyl substituents at tin, respectively, were prepared and fully characterized by spectroscopic and thermal techniques, with particular regard to the coordination number of tin atom, in solution as well as in the solid state. The triorganotin compounds, tested as transesterification catalysts in the reaction between ethyl acetate and primary, secondary or tertiary alcohol, respectively, displayed, as expected, a strong decrease of activity on passing from the primary to the tertiary alcohol reactant. Different activities by the tin carboxylates were also observed in the reaction between primary alcohol and ethyl acetate. The reaction mechanism, as elucidated by Sn NMR, involves coordination of both ester substrate and alcohol reactant to the triorganotin compound, the reaction conversion appearing related not only to the Lewis acidity of the tin atom, but also to the nature of the reactants. Preliminary catalytic tests were also carried out in the reaction between glyceryl tridodecanoate (as a model of natural triglyceride) and ethanol, mimicking the preparation of biodiesel fuel. Although in this case lower conversions were obtained with respect to the reactions on ethyl acetate, the catalytic activity of organotin derivatives appears considerable.     

A conventional new procedure for N-acylation of unprotected amino acids

The preparation of amide derivatives (4) by N-acylation of unprotected alpha-amino acids is easily achieved via readily available benzotriazolyl carboxylates (2a-d) or succinimidyl carboxylates (2e-f). These intermediates (2) are prepared from reaction of carboxylic acids (1) with 1-hydroxybenzotriazole (HO-Bt) or N-hydroxysuccinimide (HO-Su) in the presence of equimolar amounts of 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride (WSCI). The overall yields of the target compounds (4) were excellent, and this two-stage procedure could be applicable as an alternative procedure for one-pot reaction.     

Black crusts and patinas on Pentelic marble from the Parthenon and Erechtheum (Acropolis, Athens): characterization and origin

This study describes an analytical approach for the characterization and origin of the encrustation formed on the surface of monuments from the Acropolis in Athens. The morphology of encrustation was investigated by optical and scanning electronic microscopy. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), energy-dispersive X-ray fluorescence (EDXRF) and scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDS) identify and quantify the key elements and compounds associated with the genesis of encrustation. Black crusts (>200 μm thick), consisting of gypsum, calcite and elements such as Si, Al, Fe, Pb, Ti, Zn and Mn, were being formed from interaction between the marble surface and atmospheric pollutants. Orange-brown accretions on the Parthenon, called patinas (∼150 μm thick), comprise calcite, calcium oxalates, low amount of S, and both in the inner and outer parts significant and almost constant amounts of Si, P and Fe; P and Fe identified as hydroxyapatite and hematite, respectively. In the Parthenon patinas, the EDS distribution maps of Si, Fe and P indicate an origin that may be attributed to the residue and transformation of ancient treatments rich in these elements. Patinas from the Erechtheum (∼100 μm thick) resemble plasters consisting of calcite, siliceous sand, hydroxyapatite, calcium oxalates and hematite. EDXRF highlighted the presence of Pb in the patinas from the Erechtheum; FTIR revealed that Pb is in the form of cerussite most probably from the use of attic ochre. The patinas from the Parthenon and Erechtheum, as opposed to black crusts, are associated with the best-preserved surfaces and should remain intact during conservation interventions.     

Surface morphology and dispersity of europium heteroligand compounds subjected to mechanical activation

The methods of scanning electron and atomic-force microscopy were used to study the surface shape, size, and morphology of the particles in a reaction mixture (rare-earth salts with organic ligands) before and after mechanical processing in a centrifugal planetary ball mill. It was established that, after mechanical treatment, the luminescent europium and terbium heteroligand carboxylates and β-diketonates with neutral nitrogen-containing ligands turn into 10–12-μm globules composed of smaller particles with sizes 0.3–0.01 μm.     

A novel method for the construction of (z,e)- or (z,z)-conjugated alkadienyl carboxylates

[reaction: see text] The stereocontrolled dehydrobromination of 1,2-dibromoethyl carboxylates giving (Z)-2-bromovinyl carboxylates could readily be approached by using DBU and a catalytic amount of hydroquinone as a base at -78 degrees C. The first investigation on the Suzuki-type cross-coupling of (Z)-2-bromovinyl carboxylates as electrophiles with stereodefined alkenylboronic acids provides a novel method for the construction of (Z,E)- or (Z,Z)-conjugated alkadienyl carboxylate moieties, which are often present in a range of natural products.     

Metals produced as nano-snow layers for converters of laser light into X-ray for indirect targets and as intensive EUV sources

Low-density nano-snow metal layers down to 1 % of solid material density are considered. Specification of such structures and their parameters is required for pre-experimental non-destructive target characterization. The intrinsic structures have nano-sized average cells. Such low-density structures can be used inside indirect laser targets and as a cover of inner walls of advanced hohlraum to increase radiation temperature and X-ray emission.     

Old acid,new chemistry. Negative metal anions generated from alkali metal oxalates and others

A brief search in Sci Finder for oxalic acid and oxalates will reward the researcher with a staggering 129,280 hits. However, the generation of alkali metal and silver anions via collision-induced dissociation of the metal oxalate anion has not been previously been reported, though Tian and coworkers recently investigated the dissociation of lithium oxalate [18]. The exothermic decomposition of alkali metal oxalate anion to carbon dioxide in the collision cell of a triple quadrupole mass spectrometer leaves no place for the electron to reside, resulting in a double electron-transfer reaction to produce an alkali metal anion. This reaction is facilitated by the negative electron affinity of carbon dioxide and, as such, the authors believe that metal oxalates are potentially unique in this respect. The observed dissociation reactions for collision with argon gas (1.7−1.8 × 10⁻³ mbar) for oxalic acid and various alkali metal oxalates are discussed and summarized. Silver oxalate is also included to demonstrate the propensity of this system to generate transition-metal anions, as well.     

Monitoring the moisture-related degradation of ethylene propylene rubber cable by electrical and SEM methods

Several electrical approaches were used to monitor the electrical degradation of ethylene propylene rubber (EPR) cable under (1) high temperature water submerged for long-term, (2) room temperature water submerged after thermal and radiation aging, and (3) loss-of-coolant accident simulation conditions. The moisture-related degradation behavior was investigated by the correlation of electrical measurements, moisture content analysis, and scanning electron microscope (SEM) observation. The results indicate that void size and density of insulation material strongly affect the material's water resistant capability and electrical degradation. Also, the void size of insulation material after moisture-related degradation is much bigger than that after thermal and radiation aging, and the former causes material swelling. Combining insulation resistance and dissipation factor condition monitoring (CM) techniques can provide useful means for monitoring cable degradation while the cable is exposed to moisture and high temperature/radiation environment. The Arrhenius model is applied together with appropriate acceptance criteria obtained by insulation resistance measurement to calculate cable remaining life. According to test results and the remaining life calculation, it is shown that the moisture-related degradation of EPR cable can be early assessed by insulation resistance measurement, which is a non-destructive prognostic CM technique.     

Confocal microscopic X-ray fluorescence at the HASYLAB microfocus beamline: characteristics and possibilities

The possibilities of performing non-destructive elemental analysis in three dimensions on a variety of heterogeneous materials by means of an innovative variation of the microscopic X-ray fluorescence analysis (μ-XRF) method are described. Next to employing focusing optics for concentration of the primary beam of X-rays, a second optical element between the sample and the energy-dispersive detector is used in confocal μ-XRF. Thus, only X-ray fluorescence signals from a cube-like volume (within certain limits imposed by the absorption of the radiation in the sample) can be arbitrarily positioned within the sample. The distribution of major, minor and trace elements (down to the sub-ppm concentration level in some matrices) along lines and planes within the sample can be visualized with a spatial resolution of the order of 15–40 μm. The lowest detectable amounts in confocal mode using pink-beam excitation are situated at the sub-femtogram level.     

The non-destructive determination of REE in fossilized bone using synchrotron radiation induced K-line X-ray microfluorescence analysis

The sensitivity and applicability of the synchrotron radiation induced X-ray microfluorescence (μ-SRXRF) spectrometer at the Hamburg synchrotron laboratory Hasylab for the determination of the distribution of trace concentrations of rare-earth elements (REE) in fossilized bone are discussed and critically compared to those of other trace analytical methods such as instrumental neutron activation analysis (INAA) and LAMP-ICPMS (laser ablation microprobe inductively-coupled plasma mass spectrometry). Measurements were carried out on two bone samples from contrasting terrestrial depositional environments at Olduvai Gorge (Tanzania). Results indicate that the microdistribution of the REE in these biological materials is not homogeneous and that the relative abundance of these elements can provide information on the palaeoenvironment during the fossilization process. The heterogeneous distribution of the REE can be determined in a quantitative and completely non-destructive manner provided the concentrations of individual REE are above 10 μg/g.