An Archaeometric Investigation of Gems and Glass Beads Decorating the Double-Arm Reliquary Cross from Liège, Belgium

In 1914, a magnificent reliquary cross dating from the early XIIIth century was discovered in a safe from the Liège Cathedral. This double-arm cross shows a wooden structure, covered by gold-coated copper on the front, and by carved silver plates on the back. Its total length is 34 cm, and it is covered by filigrees, gems, glass beads, and pearls on its front. The reliquary cross was analysed by Raman spectrometry and X-ray fluorescence spectrometry (pXRF) to determine the mineralogical and chemical compositions of gems, glass beads, and metals that have been used to decorate it. The results confirm the identification of twenty-five turquoises from Egypt, one garnet from Sri Lanka, as well as six quartz and one opal whose origin is difficult to certify. Twelve glass beads, showing green, blue, or amber tints, were also identified. Their compositions either correspond to soda lime glasses with natron or to potash–lead glasses similar to those of Central Europe. Moreover, a small polished red cross and a green stone appear to be constituted by nice doublets, composed of coloured glass covered by quartz. The filigrees contain Au and Cu, while carved plates covering the edges and the back of the cross are made of silver.

A combination of invasive and non-invasive techniques for the study of the palette and painting structure of a copy of Raphael's Transfiguration of Christ

The main objective of this study is to establish an appropriate method for the characterization of the pigments, materials and structure of the paint layers in a copy of the painting the Transfiguration of Christ by Raffaello Sanzio. A multi-technique approach that combines elemental, molecular and structural analyses and involves optical microscopy (OM), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM–EDX), μ-Attenuated Total Reflection–Fourier Transform InfraRed (µATR-FTIR), μ-Raman spectrometry (µRS) and non-invasive portable diffractometer (pXRD) was used. Our results revealed that this copy of the Transfiguration was executed with a palette, which includes white lead (cerussite and hydrocerussite), lazurite from lapis lazuli pigment, red and yellow earths (goethite, hematite and lepidocrocite), lead tin yellow, cinnabar, red lake, smalt and bone black, and fillers such as calcite, baryte (an impurity associated to some pigments), and traces of colorless powdered glass. A secondary objective of this research was the application of non-invasive in situ pXRD measurements, which do not require painting sampling and helped to confirm some inconclusive results obtained with other techniques regarding the artist's palette. The results showed the crystalline nature of all the pigments identified, which were known from ancient times and available during the 16th and 17th. Lastly, the used of 14C accelerator mass spectrometry determined that the canvas date was 1451–1633 AD (with a 95% confidence level). Although the main focus of the work was to improve the analytical methodology to better understand the artist’s palette, our results will further help us to explore the authorship of the copy or the school that executed it. Graphical Abstract

Investigation of Friction and Wear Performance of Diamond Coating under Si3N4 Friction Pair

In this study, diamond coatings were deposited through the hot filament chemical vapor deposition method on cemented carbide under different methane concentrations, ranging from 1% to 5%, to analyze the performance of the diamond coatings under different loads and lubrication conditions . Friction and wear tests were carried out using ball-disk friction and wear tester under different loads and lubrication conditions. Scanning electron microscopy, high-resolution Raman spectrometry, optical microscopy, and a surface profiler were used to observe the surface morphology and quality of the coatings after the wear test. The results revealed that the coating prepared under 3% methane concentration was more stable during the friction test than that prepared under other methane concentrations. In addition, the coating prepared under 5% methane concentration had poor adhesion and experienced failure under excessive load. Furthermore, lubricating the friction surface with water effectively reduced the formation of abrasive wear and the friction coefficient, and thus the sample reached the stable stage faster. In addition, the wear rate of the coating under wet condition was approximately 4–5 times less than that under dry friction conditions.

Vitamin C-Assisted Fabrication of Aerogels from Industrial Graphene Oxide for Gaseous Hexamethyldisiloxane Adsorption

Volatile methyl siloxanes (VMSs) as a trace impurity in biogas decreases its energy utilization, and thus need to be removed. In this paper, a one-step hydrothermal reduction was performed to produce three-dimensional reduced graphene oxide aerogels (rGOAs) using industrial-grade graphene oxide (IGGO) as raw material and vitamin C (VC) as a reductant to facilitate the fabrication of rGOAs. The synthesis of rGOAs was a simple, green, and energy-efficient process. The developed rGOAs were characterized using the Brunauer–Emmett–Teller method, Raman spectrometry, scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction measurements and contact angle. The results obtained showed that rGOA-1 with a VC/IGGO ratio of 1/1 (m/m) exhibited a hierarchical porous structure and super-hydrophobicity, yielding a high specific surface area (137.9 m2 g−1) and superior water contact angle (143.8°). The breakthrough adsorption capacity of rGOA-1 for hexamethyldisiloxane (L2, a VMS model) was 11 times higher than that of IGGO. Low inlet concentration and bed temperature were considered beneficial for the L2 adsorption. Interestingly, rGOA-1 was less sensitive to water, and it was readily regenerated for reuse by annealing at 80 °C. The rGOAs have been demonstrated to have great potential for the removal of siloxanes from biogas.

Exchange Counterion in Polycationic Hydrogels: Tunability of Hydrophobicity, Water State, and Floating Capability for a Floating pH Device

Smart gel materials are capable of controlling and switching swelling, water state, and wettability properties triggered by external stimuli. In this study, we fabricated a series of polyelectrolyte hydrogels bearing a 3-trimethylammoniumpropyl pendant to a methacrylamide-based backbone and examined the switchability with hydrophobic-like counteranions. The exchange between the initial chloride and camphor sulfate (CaS), dodecyl sulfate (DS), and perfluorooctanoate (PFO) counterions was investigated. The kinetics of the exchange showed that the fast exchange (within 4 h) of PFO allowed for a favorable coordination for ion pairing, resulting in a decrease in hydration. The reversibility of the exchange to the Cl- ion was only enabled for the CaS ion due to its bulkiness, while the PFO and DS hydrogels were unable to exchange, even by using tetrabutylammonium chloride, which is a structurally similar reagent, due to aggregation or the coagulates in the collapsed state of the linear tails of the counterions. The hydrogels exhibited a modulable water state and water swelling. Moreover, the hydrogels containing DS and PFO, as counterions, showed surface hydrophobic (contact angle 90°) and high hydrophobic (110°) behavior, respectively. The Raman spectrometry fluorescence with a pyrene probe indicated an increase in strong hydrogen-bonded water molecules, water confinement, and hydrophobic domains in the PFO hydrogel. Moreover, the PFO-modified hydrogel demonstrated a free-floating ability on the water surface, with a strong water repellency, showing that it has the potential to be applied in a floating pH detection device to distinguish between volatile and nonvolatile bases in a controlled manner.

Effect of Different Deposition Pressure on Diamond Films Deposited by Hot Filament Chemical Vapor Deposition

A hot filament chemical vapor deposition (HFCVD) method was adopted to deposit diamond films at deposition pressures ranging from 2–6 kPa. The effects of deposition pressure on the deposition rate, phase structure, and microstructure of diamond films were investigated. The surface morphology, grain size, micro-structure, and growth rate of the diamond films were analyzed using scanning electron microscopy, X-ray diffraction (XRD), and Raman spectrometry. The experimental results showed that granules on the surface exhibited increasingly compact structure with increasing deposition pressure. The diamond films deposited at various pressures have good compactness, and the particles on the film surfaces are arranged in an ordered manner. All films exhibited orientation along the (111) plane, which was the significant characteristic XRD peak of each diamond film. The (111) peak intensity was the strongest for the film prepared at 2 kPa deposition pressure. Overall, the deposition rate and grain size decreased with increasing deposition pressure, provided other deposition conditions remained unchanged. However, the densification of the microstructure and the nucleation density increased with increasing deposition pressure. Secondary nucleation became more pronounced as deposition pressure increased, and grain size decreased as nucleation density increased.

An Attractive Blue Diopside from Sissone Valley, Western Alps, Italy

In this work a rare and attractive blue diopside present in Sissone valley in the Western Alps was investigated through different methodologies: geological survey; standard gemological methods; X-Ray Powder Diffraction; SEM observations; Raman spectrometry; EMP analyses of major elements; and LA-ICP-MS analyses for minor and trace elements. The host rock of investigated gems is represented by a Mg-calcite bearing marble, belonging to the Suretta nappe and composed of blue diopside, lizardite, phlogopite, forsterite, Ca-Mg-amphibole, and thomsonite; the rock was metamorphosed by the intrusion of Masino-Bregaglia pluton. The diopside is generally found in the core of veins in contact with green–blue tremolite and, more externally, with green–yellowish lizardite. The diopside samples show opaque diaphaneity, are inert to long and short-waves UV radiation, and their specific density varies between 3.24 and 3.30 g/cm3 while medium refraction between 1.680–1.683. The diopside shows a polycrystalline texture with interstitial Mg-calcite which acts as binder. The characteristic blue–turquoise color is mainly determined by traces of V and subordinately of Fe, Mn, Cr and Ti. The contents of V and Ti show a good positive correlation. The minerals associated with diopside in the lenticular veins also show enrichments in V. The blue diopside of the Sissone valley could certainly present a good commercial value, but unfortunately it is difficult to reach the outcrop sites.

“Horsetail” Inclusions in the Ural Demantoids: Growth Formations

The term “demantoid”, first proposed in 1856 by the famous Finnish mineralogist Nils von Nordensheld, refers to a highly dispersed yellow-green mineral from the Central Urals placers. In 1874, it was found to be a gem variety of andradite garnet. “Horsetail” inclusions are considered a sign of the Ural type demantoid. Although these inclusions are large (visible to the naked eye), their diagnostics remains debatable: some researchers attribute them to byssolite (amphibole-asbestos), others consider them chrysotile. We investigated the horsetail inclusions in the Ural demantoids through various methods: optical microscopy, scanning electron microscopy (SEM), Raman spectrometry, X-ray powder diffraction, and thermal analysis. In most cases, “horsetail” inclusions in the Ural demantoid were represented by hollow channels and only the outcrops, on the demantoid surface, were occasionally filled with serpentine (established by SEM); in one case, magnetite was observed. Hollow canals were usually collected not in bundles, such as a “horsetail”, but in fans, sometimes curved into cones. The structure of the grains was spheroidal, sectorial, and sometimes had induction surfaces, which, to the periphery of the grain, were replaced by tubular channels assembled in a fan. The specifics of the growth of the “horsetail” inclusions of the demantoid grains can be explained by the decompression conditions that arose when the ultrabasites (a crust-mantle mixture) were squeezed upwards during collision.