Gilding and pigments of Renaissance marble of Abatellis Palace: non‐invasive investigation by XRF spectrometry

Most of the artworks constituting the collection of Renaissance statuary of Abatellis Palace in Palermo (Sicily) show evidence of colour layers and fragments of gold foil that probably once covered the whole marble surface. The restoration of some of these statues has allowed to carry out archaeometric studies about the painting technique and to highlight the original materials and inclusion present on the precious marbles by two famous Italian sculptors of the Renaissance, Francesco Laurana and Antonello Gagini. The measurements have been performed in situ through the integrated use of two non‐invasive techniques: visible fluorescence stimulated by ultraviolet light and X‐ray fluorescence. The ultraviolet‐induced fluorescence analysis has provided additional information on the conservation status of marble surfaces by differentiating the pictorial materials and highlighting the presence of gilding and pigment traces through their characteristic fluorescence response. The observation in ultraviolet light has been used as valuable guide for the identification of the significant points to be analysed by X‐ray fluorescence to characterise the original materials. X‐ray fluorescence measurements have cast light about their chemical composition and stratigraphical structure. Pictorial layers were identified: vermilion for red layers, blue pigment based on copper for blue layers and pure gold leaf for gilding layers. Principal component analysis of the data was capable of clustering the different painting materials, discriminating through their chemical content. The results represent an important scientific support both to the hypotheses about the original look of the artworks and to the resolution of restoration and conservation questions still open. Copyright © 2012 John Wiley & Sons, Ltd.     

Colorando Auro: contribution to the understanding of a medieval recipe to colour gilded silver plates

The colour of gildings can be modified by many artistic techniques. This article refers to the possibility of a specific chemical treatment to change the colour of gildings. The model samples—gilded silver plate, the mixture and the application of a medieval recipe based on ancient writings from Theophilius and Cellini have been described. We propose a strategy to identify the chemical processes involved in the change of colour of the metallic surface through the advanced study of these model samples. Synchrotron X-ray photoelectron spectroscopy and X-ray absorption spectroscopy were carried out both on the gilding with and without the application of the treatment with the aim to understand the chemical reactions occurring during the treatment.     

Rembrandt's Old Woman Praying, 1629/30: A look below the surface using X-ray fluorescence mapping

Rembrandt's painting Old Woman Praying, 1629/30, is the most valuable and exceptional work of art of the Residenzgalerie Salzburg (RGS). It is painted on a gilded copper plate with dimensions of only approximately 15 × 12 cm. The painting probably belongs to a series of three small-scale tronies, all executed on gilded copper plates. This particular picture preparation, which represents a special feature in Rembrandt's work, is quite unusual in the history of art. Previous investigations on the comparable paintings The Laughing Man, 1629/30, in the Mauritshuis, The Hague and the Self Portrait, 1630, in the National Museum, Stockholm showed that the gilding of the copper plate was applied over a lead white ground. To characterize the painting in the RGS, X-ray fluorescence (XRF) mapping was performed in a collaboration between the Research Office Residenzgalerie, Land Salzburg, the XGLab S.R.L, Milan, and the Conservation Science Department of the Kunsthistorische Museum Vienna (KHM). The results indicate a different structure for this painting than that used for The Laughing Man and the Self Portrait. The gilding was applied directly onto the copper plate, but with three areas with the gilding missing. It seems likely that in these sections, the gold was purposely removed to provide a different darker effect. XRF mapping yielded valuable insights into the structure of the painting and its technique as well as the principal pigments used for its composition.     

Gold,gildings, and tumbaga from the Moche tomb of the Lady of Cao: An EDXRF test for the internal ratio method

Gold, gilded copper, gilded silver, and tumbaga artifacts from the Moche tomb of the Lady of Cao, dated around 300 A.D., were analyzed by energy-dispersive X-ray fluorescence analysis. These artifacts are multilayered structures, which can be “reconstructed” using the K or L rays ratio of the chemical elements present in the layers. For example, in the case of gilded copper, the ratios Au (Lα/Lß), Cu (Kα/Kß), and Au-Lα/Cu-Kα, altered with respect to bulk gold or copper, can be used to determine the gilding thickness. An ideal test of this method was recently offered by the study of 15 big spears on gilded copper, a necklace composed of 12 small heads on tumbaga (a poor gold-alloy subject to depletion gilding), and a nose decoration on gilded silver. All these artifacts were found in (or close to) the tomb of the Lady of Cao, discovered 10 years ago in the north of Peru, close to Trujillo. The “internal ratio” method is described and discussed.     

Normal-state electrical resistivity and superconducting magnetic penetration depth in Eu<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript> polycrystals

We report measurements of the temperature dependence of the electrical resistivity, ρ(T), and magnetic pen-etration depth, λ(T), for polycrystalline samples of Eu_0.5K_0.5Fe₂As₂ with T _c = 31 K. ρ(T) follows a linear temperature dependence above T _c and bends over to a weaker temperature dependence around 150 K. The magnetic penetration depth, determined by radio frequency technique displays an unusual minimum around 4 K which is associated with short-range ordering of localized Eu³⁺ moments. The article is published in the original.     

Thickness determination of gold layer on pre‐Columbian objects and a gilding frame,combining pXRF and PLS regression

In conservation, restoration and characterization studies of art and archaeological objects, the improvement of analytical techniques is a tendency. X‐ray fluorescence (XRF) is a versatile technique, and it has been widely used in the last decades for characterization of a great variety of materials (metals, glass, paints, inks, ceramics, etc.) applied to cultural heritage studies. Besides the chemical composition, it is possible to infer the layer thickness through XRF, enabling a general knowledge of the manufacturing techniques implemented by the culture of origin, as well as the association with the technological level reached for the production of each kind of artefact. The aim of this study is to introduce an alternative way for gold thickness determination of coatings in cultural heritage objects, combining portable XRF data and partial least square regression. As a case of study, we present the use of this methodology in portable XRF measurements performed in situ on a gilding frame in Brazil and in two pre‐Columbian artefacts from Chavin culture in Peru. Gold layers with thicknesses determined by Rutherford backscattering spectrometry (RBS) were used as standards to perform a calibration model and to check the methodology before its application to unknown artefacts. Copyright © 2016 John Wiley & Sons, Ltd.     

Analysis of the spectacular gold and silver from the Moche tomb ‘Señora de Cao’

On the north coast of present‐day Peru, between the Andes and the Pacific Ocean, approximately between 100 and 600 ad , the Moche civilization prospered. The Moche were very sophisticated artisans and metal smiths, so that they are considered the finest producers of jewels and artifacts of the region. Their metalworking ability was impressively demonstrated by the excavations of the tomb of the ‘Lady of Cao’ (dated around third–fourth century ad ) discovered by Regulo Franco in 2005. Impressive is the beauty of the artifacts, and also the variety of metallurgical solutions, demonstrated by not only the presence of objects composed of gold and silver alloys but also of gilded copper, gilded silver, and tumbaga, a poor gold Cu‐Au alloy subject to depletion gilding. About 100 metal artifacts from the tomb of the Lady of Cao, never before analyzed, were studied by using various portable equipments based on following non‐destructive and non‐invasive methods:

• energy‐dispersive X‐ray fluorescence with completely portable equipments;
• transmission of monenergetic X‐rays;
• radiographic techniques; and
• optical microscopy.

Gold objects and gold areas of nose decorations are characterized by approximately the same composition, that is, Au = (79.5 ± 2.5) %, Ag = (16 ± 3) %, and Cu = (4.5 ± 1.5) %, while silver objects and silver areas of the same nose decorations show completely erratic results, and a systematic high gold concentration. Many gilded copper and tumbaga artifacts were identified and analyzed. Further, soldering gold–silver was specifically studied by radiographs. Additional measurements are needed, particularly because of the suspect that depletion gilding was systematically employed also in the case of some nose decorations. Copyright © 2016 John Wiley & Sons, Ltd.     

Bi系超导材料的微波焊接及其显微结构研究

微波焊接技术近年来发展较快,它有下列优点:1)能耗低;2)升温速度快;3)接头质量高等。本文研究了Bi系超导材料微波焊接的可行性。结果表明,经855℃60h热处理后,焊接试样的T_c可达107K,与焊接前试样的T_c一致,焊区强度已经高于基体。利用电子探针对焊接前后的显微结构进行了比较,发现焊区组织致密,但在后处理过程中发生再结晶,导致焊区晶粒较大,焊缝变宽且焊区内存在较多杂相。 关键词：     

Observation of the magnetic domain structure in Cu<Subscript>0.47</Subscript>Ni<Subscript>0.53</Subscript> thin films at low temperatures

We report on the first experimental visualization of domain structure in films of weakly ferromagnetic Cu_0.47Ni_0.53 alloy with different thickness at liquid helium temperatures. Improved high-resolution Bitter decoration technique was used to map the magnetic contrast on the surface of the films well below the Curie temperature T_Curie (∼60 K). In contrast to magnetic force microscopy, this technique allowed visualization of the domain structure without its disturbance while the larger areas of the sample were probed. Maze-like domain patterns, typical for perpendicular magnetic anisotropy, were observed. The average domain width was found to be about 100 nm. The article is published in the original.     

Ab-initio molecular dynamical study of a single transition metal atom on fullerene C<Subscript>60</Subscript>: the case of Ta

We report the first-principles Car-Parrinello molecular dynamics study of the behaviour of a single transition metal Ta atom on fullerene C₆₀, at different temperatures, and for both neutral and charged clusters. We seek to characterise the motion of the lone Ta metal atom on the C₆₀ surface, contrasting its behaviour both with that of three Ta atoms, as well as with a single alkali metal atom on the cage surface. Our earlier simulations on C₆₀Ta₃ had revealed that the Ta atoms on the surface of the fullerene are affected by a rather high mobility, and that the motion of these atoms is highly correlated due to Ta-atom-Ta-atom attraction. Earlier, experimental studies of a single metal atom (K, Rb) on the surface of a C₆₀ molecule had led to the inference that at room temperature the metal atom skates freely over the surface, the first direct evidence for which was presented by us in earlier first principles molecular dynamical simulations.     

Low temperature electron irradiation of tellurium

Abstract

Tellurium single crystal samples with a hole concentration of 3 × 10¹⁴/cm² were irradiated at 10 K with electrons with an energy of 0.6 and 1 MeV. In the range investigated resistivity and Hall-coeficient R_H both decreased linearly with the integrated electron flux. The hole generation rate was 0.09 cm^?1 and 0.47 cm^?1 for 0.6 and 1 MeV electrons, respectively. The Hall-mobility R_H/P increased with irradiation.

Annealing of the radiation damage by raising the temperature clearly revealed three recovery stages in the resistivity- and Hall-data. At 180K p and R_H returned to their pre-irradiation values. The original Hall-mobility was already restored close to 90 K.

A more detailed study of the first recovery stage, which occurs at about 50 K, revealed an activation energy of 170±40meV. It is most likely, that the observed lattice defects are Frenkel-defects. There are indications, that the point defects interact with dislocations.     

Magnetic ground state and multiferroicity in BiMnO<Subscript>3</Subscript>

We argue that the centrosymmetric C2/c symmetry in BiMnO₃ is spontaneously broken by antiferromagnetic (AFM) interactions existing in the system. The true symmetry is expected to be Cc, which is compatible with the noncollinear magnetic ground state, where the ferromagnetic order along one crystallographic axis coexists with the hidden AFM order and related to it ferroelectric polarization along two other axes. The C2/c symmetry can be restored by the magnetic field B ∼ 35 T, which switches off the ferroelectric polarization. Our analysis is based on the solution of the low-energy model constructed for the 3d-bands of BiMnO₃, where all the parameters have been derived from the first-principles calculations. Test calculations for isostructural BiCrO₃ reveal an excellent agreement with experimental data. The article is published in the original.     

Temperature dependence of photoluminescence from CdSe nanocrystals embedded in silica matrix

In this work, CdSe nanocrystals (NCs) embedded in SiO₂ matrix were grown by radio frequency (RF)-sputtering technique. X-ray technique was used to characterise the structural properties of the system. The NC's size was estimated to be around 4±1 nm in diameter. The temperature dependence of the photoluminescence from the CdSe/SiO₂ system showed carriers thermal exchange between the NCs and deep defects in the matrix. The evolution of the excitonic energy emission with temperature is about 10 meV in the temperature range 15-295 K. This weak shift was explained by thermal mismatch between the matrix and the NCs.     

A scientific approach to the characterization of the painting materials of Fra Mattia della Robbia polychrome terracotta altarpiece

During the last restoration (2008–2011) of the polychrome terracotta altarpiece called Coronation of Virgin between Saints Rocco, Sebastian, Peter martyr and Antonio abbot, located in the collegiate church of S. Maria Assunta in Montecassiano (Macerata, Italy), scientific investigations were carried out to acquire detailed information about the painting technique. The identification of materials allowed a correct restoration. The altarpiece is almost entirely realized by Marco della Robbia (Fra Mattia), dates back to the first half of the XVI century and represents an interesting example of painted terracotta produced by using two different techniques: glazed polychrome terracotta and the “cold painting” technique. The characterization of the samples’ material constituents was obtained by analysing the cross-sections and the fragments by different techniques (optical, SEM-EDS and ATR-FTIR microscopy as well as GC-MS), as the real nature of a component is often difficult to assess with one single technique. The optical microscope examination of paint cross-sections shows the presence of many layers, indicating the complexity of the paint stratigraphic morphologies. The original polychromy of della Robbia’s masterpiece is constituted of cinnabar, red lake, red lead, orpiment, red ochre, lead white, lead tin yellow, green earth and raw umber. Two different types of gilding technique have been distinguished. The first one presents a glue mordant, and the second one shows an oil mordant composed by a mixture of red lead, red ochre, cinnabar and orpiment. The GC-MS analysis allowed the characterisation of linseed oil and a mixture of animal glue and egg as binding media stratigraphically located by the use of ATR-FTIR mapping microscopy. The analytical results of the painted terracotta integrated investigations show that original technique adopted is characterised by the application of pigments in an oil-binding medium directly applied on the substrates, probably treated with oil and animal glue. A large number of overpaintings above the original scheme of polychromy was found, which could be ascribed to almost three different interventions; the absence of modern pigments suggests that they could be realized long ago.     

Effect of high pressure on the crystal and magnetic structure and on the raman spectra in Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structure and the Raman spectra in Pr_0.7Ba_0.3MnO₃ manganite have been studied by the neutron diffraction technique at pressures up to 5 GPa as well as by the X-ray diffraction and Raman spectroscopy at pressures up to 30 GPa. The pressure dependence is determined for the lattice parameters, unit cell volume, Mn-O bond lengths in the orthorhombic structure of the Imma symmetry, and bending and stretching vibration modes for oxygen octahedra. In the low-temperature range at pressure P = 1.9 GPa, the magnetic transition from the initial ferromagnetic (FM) ground state (T _C = 197 K) to the A-type antiferromagnetic (AFM) state (T _N = 153 K) has been revealed. The FM and AFM phases coexist at pressures up to 5.1 GPa and exhibit negative and positive values of the pressure coefficient for the Curie and Néel temperature, respectively (dT _C/dP = −2.3 K/GPa and dT _N/dP = 8 K/GPa). The pressure dependence of the Curie temperature in Pr_0.7Ba_0.3MnO₃ differs drastically from that observed in other manganites of nearly the same composition with the orthorhombic Pnma and rhombohedral R[`3]cR\bar 3c structures, where the FM phase is characterized by the positive values of dT _C/dP. The structural mechanisms of these phenomena are discussed.     

Non‐destructive characterization of 17th century painted silk banner by the combined use of Raman and XRF portable systems

X‐ray fluorescence spectroscopy (XRF) and Raman spectroscopy analysis were performed to examine a 17th century painted silk banner in order to characterize the pigments and materials used. This complementary approach yields information on the elemental (XRF) and on the molecular composition (Raman) of the used compounds. The paint layer, ground layer under gilding, and gilding layer were investigated. For the studied object, vermilion (HgS), lead white (2PbCO₃ · Pb(OH)₂), red lead (Pb₃O₄), and aurichalcite ((Cu,Zn)₅(CO₃)₂(OH)₆) were found. The presence of silver and gold foils was confirmed. The techniques used in the analysis were portable, non‐destructive, and non‐invasive, which is very desirable when analyzing cultural heritage objects. The obtained results were used by the conservators to develop a showcase prototype for safe exhibition. Copyright © 2015 John Wiley & Sons, Ltd.     

The composition and technology of polychrome enamels on Chinese ruby-backed plates identified through nondestructive micro-X-ray fluorescence

This research presents non-destructive analyses of Chinese enamelled copper and porcelain decorated with polychrome enamels. This study utilises two key, high-value art works with complex enamelling in the collection of the Victoria and Albert Museum (London, UK) to elucidate the composition and technology of objects with ruby-backed decoration. These plates date from early Qing dynasty and are associated with the Yongzheng (1723–1735) and early Qianlong (1735–1796) periods. The goal of this research is to investigate the hypothesis that ruby-backed plates in these two mediums are decorated with the same enamels and possibly manufactured in mutual enamelling workshops, which is a current topic of debate among scholars. Ten different enamel colours and the gilding on each plate were analysed and evaluated with micro-X-ray fluorescence to study the opacifiers and pigments. The results show that the enamels on these two works utilise the same opacifier and the consistent pigments in the white, ruby, pink, green, yellow, turquoise green, and blue enamels. Compositional differences were identified in the underdrawings, purple enamels, and gilding. The results demonstrate that Chinese painted enamels and overglazes on porcelain share mutual technology in most, but not all, of the polychrome decoration, which impacts upon our knowledge of technological organisation in the manufacture of these objects. Micro-X-ray fluorescence has been shown to be an effective and robust technique for the nondestructive study of decorative surfaces in these two material types.     

Fensterbierscheiben in the Pena National Palace collection – chemical and iconographic relations

The stained‐glass collection from the Pena National Palace (Sintra, Portugal) includes around 130 ‘rural panels’, also known as Fensterbierscheiben, that were produced between the 16th and 19th centuries. The aim of this investigation is to characterise the glass composition of this collection of Fensterbierscheiben and relate it with the iconographic research made on these panels, in order to establish possible provenance of production. This is the first study on Fensterbierscheiben, where the chemical information of the glass is considered and related with historical information. The micro‐energy dispersive X‐ray fluorescence allowed performing non‐invasive analysis, mostly performed in situ. Micro‐particle‐induced X‐ray emission analysis was performed on the cross section of a small group of fragmented panels for obtaining quantitative chemical composition of the glass. Through the analysis of the colourless glass, and the comparison of micro‐energy dispersive X‐ray fluorescence and micro‐particle‐induced X‐ray emission data, it was concluded that the majority of the panes have a high lime low alkali glass composition. Furthermore, the Fensterbierscheiben panes form a cohesive group in terms of composition, suggesting that they were all manufactured with raw materials from the same region. This study also allowed one to observe the chronological evolution in terms of treatments applied to the used raw materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural study and electrical properties of Zr-doped Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore compounds

Nd₂Sn₂O₇ pyrochlores with the substitution of Zr⁴⁺ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O _h ⁷ ). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates the existence of grain and grain boundary as two separate elements.     

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采用横向磁场驱动的滑移弧等离子体发生器产生非平衡、大气压下的等离子体。用氮分子谱和OH基谱来估算滑移弧等离子体射流中的重粒子温度。从实验数据的比较来看,从氮分子谱获得的重粒子温度相对较低,而从OH基谱获得的重粒子温度与磁稳滑移弧放电的重粒子温度比较接近,大约在2400~ 2700 K的范围内。