Survey on batch-to-batch variation in spray paints: a collaborative study

This study represents the most extensive analysis of batch-to-batch variations in spray paint samples to date. The survey was performed as a collaborative project of the ENFSI (European Network of Forensic Science Institutes) Paint and Glass Working Group (EPG) and involved 11 laboratories. Several studies have already shown that paint samples of similar color but from different manufacturers can usually be differentiated using an appropriate analytical sequence. The discrimination of paints from the same manufacturer and color (batch-to-batch variations) is of great interest and these data are seldom found in the literature. This survey concerns the analysis of batches from different color groups (white, papaya (special shade of orange), red and black) with a wide range of analytical techniques and leads to the following conclusions. Colored batch samples are more likely to be differentiated since their pigment composition is more complex (pigment mixtures, added pigments) and therefore subject to variations. These variations may occur during the paint production but may also occur when checking the paint shade in quality control processes. For these samples, techniques aimed at color/pigment(s) characterization (optical microscopy, microspectrophotometry (MSP), Raman spectroscopy) provide better discrimination than techniques aimed at the organic (binder) or inorganic composition (fourier transform infrared spectroscopy (FTIR) or elemental analysis (SEM - scanning electron microscopy and XRF - X-ray fluorescence)). White samples contain mainly titanium dioxide as a pigment and the main differentiation is based on the binder composition (Csingle bondH stretches) detected either by FTIR or Raman. The inorganic composition (elemental analysis) also provides some discrimination. Black samples contain mainly carbon black as a pigment and are problematic with most of the spectroscopic techniques. In this case, pyrolysis-GC/MS represents the best technique to detect differences. Globally, Py-GC/MS may show a high potential of discrimination on all samples but the results are highly dependent on the specific instrumental conditions used. Finally, the discrimination of samples when data was interpreted visually as compared to statistically using principal component analysis (PCA) yielded very similar results. PCA increases sensitivity and could perform better on specific samples, but one first has to ensure that all non-informative variation (baseline deviation) is eliminated by applying correct pre-treatments. Statistical treatments can be used on a large data set and, when combined with an expert's opinion, will provide more objective criteria for decision making

Inorganic Niobium and Tantalum Octahedral Cluster Halide Compounds with Three-dimensional Frameworks: A Review on their Crystallographic and Electronic Structures

International audienceThis review summarizes the development of the rich crystal and bonding chemistry of face-capped and edge-bridged inorganic niobium and tantalum octahedral cluster halide compounds, with a particular emphasis on those showing three-dimensional cluster frameworks. Discussion is made on varied structures and bonding which are intimately linked to the valence electron concentration, i.e., the number of electrons that held the octahedral metal cluster architecture. Exploration of the literature indicates that apart from Nb6I11 and derivatives, which show electron-deficient face-capped M6Xi8Xa6 units, compounds containing edge-bridged M6Xi12Xa6 motifs are the most largely encountered. Closed-shell compounds with a valence electron concentration of 16 are predominant, although a few 15-electron open-shell magnetic compounds or even 14-electron closed-shell species have also been reported. Particularly interesting from a structural point of view is the fashion in which these face-capped and edge-bridged clusters “pack” in crystals. The astonishing diversity of structural types, which are observed, is mainly due to the flexibility of the halogen ligands to coordinate in various manners to metal atoms. However, a rigorous structural analysis of these compounds reveals no close relationship between the valence electron concentration and the variability of the intercluster connections and/or the nature of the counterions. Indeed, the main bonding features of these compounds can be understood from the delocalized bonding picture of isolated “molecular-like” M6Xi8Xa6 or M6Xi12Xa6 clusters