Characterisation of ancient Roman wall-painting fragments using non-destructive IBA and MA-XRF techniques

Scientific investigation is very important in studies addressing issues of archaeological and historical objects. Ion beam analysis (IBA) and macro X-ray fluorescence (MA-XRF) spectroscopy are remarkable tools to obtain information about elemental composition and imaging of historical artefacts with a non-invasive character. These investigation techniques were employed in the framework of a project aimed at supporting the characterization of materials and techniques related with the Roman wall painting. The archaeological excavations at Villa della Piscina in Rome have revealed a luxury building with a large pool (about 50 m long) and thermal baths and numerous fragments of plaster, coming from intentional demolitions referable to two distinct architectural contexts of the Villa during the imperial age, have been found. This work deals with studying the interesting wall pictorial apparatus of great cultural value of the heritage inherited from the Roman age in the area of the ancient city of Rome. The colour palette of the pigments investigated, in particular, by MA-XRF and particle-induced X-ray emission (PIXE) and has revealed Fe, Cu, Pb, Si and Hg as main elements. Traces of other constituents uncover the choice of the different colours chosen by the artists who had embellished the rooms of the Villa.     

Structural characterization of Rh/pumice SMAD catalysts

The structure of Rh/pumice catalysts prepared by the SMAD (Solvated Metal Atoms Dispersion) technique at different metal loadings has been investigated by EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), SAXS (Small-Angle X-ray Scattering), WAXS (Wide-Angle X-ray Scattering) and TEM (Transmission Electron Microscopy). According to EXAFS and XPS, a fraction of the Rh atoms is oxidised, but a noticeable part is also present as Rh ⁰. The Rh oxidation is attributed to the interaction of the Rh atoms with the hydroxyls of the support; after the formation of the oxide, the nucleation of metallic rhodium becomes possible. The WAXS data do not show evidence of rhodium fcc crystallites; the metal-bearing particles are probably amorphous and/or very small, as results from the SAXS and TEM data analysis. The disagreement between the latter two techniques, resulting in a small-angle determination of the average size of the particles that is about half that of TEM in the catalyst with the higher Rh loading, is acknowledged and discussed. Preliminary catalytic tests are described, demonstrating the suitability of using a low surface area support for the preparation of SMAD catalysts. Received 2 February 1999     

Aqueous electrochemical insertion of Na into the tungsten oxide hybrid WO3(4,4′-bipyridyl)0.5

Aqueous electrochemical insertion of M⁺ (Na⁺ and H⁺) species into WO₃(4,4′-bipyridyl)_0.5 has been carried out. The chemical states and structure of the resulting product were analysed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). XPS showed the presence of W⁶⁺ as well as the usual reduced W species (W⁵⁺) which is responsible for a change in colour. Moreover, the presence of these intercalates correlates with the evolution of the reduced W species. The bulk structure of the layered hybrid, as determined by powder X-ray diffraction, showed no alteration after electrochemistry, in contrast to the same measurements on tungsten trioxide (WO₃). This however concurs with single-crystal X-ray studies, which show little change in lattice parameters with Na⁺ insertion. Four-probe resistance measurements of the layered hybrid coated film display a drop in resistance after electrochemistry, which can be attributed to the injection of charge-carriers into the conduction band.     

Electrosynthesis and characterization of CdSe thin films: Optimization of preparative parameters by photoelectrochemical technique

CdSe thin films have been electrodeposited potentiostatically onto stainless-steel and fluorine-doped tin oxide-coated glass substrates from an aqueous acidic bath using cadmium acetate ((CH₃COO)₂Cd·2H₂O) as a Cd ion source. Preparative parameters such as deposition potential, solution concentration, bath temperature, pH of the electrolytic bath and deposition time have been optimized by using photoelectrochemical (PEC) technique to obtain well adherent and uniform thin films. The electrodeposits were dark brown in colour. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical absorption techniques. XRD studies reveal that films are polycrystalline, with hexagonal crystal structure. SEM shows that the films are compact, with spherical grains. Optical absorption studies reveal that the material exhibits a direct optical transition having band gap energy ∼1.72 eV. PEC study shows that the films are photoactive.     

Physicochemical characterization of an Indian traditional medicine, Jasada Bhasma: detection of nanoparticles containing non-stoichiometric zinc oxide

Herbs and minerals are the integral parts of traditional systems of medicine in many countries. Herbo-Mineral medicinal preparations called Bhasma are unique to the Ayurvedic and Siddha systems of Indian Traditional Medicine. These preparations have been used since long and are claimed to be the very effective and potent dosage form. However, there is dearth of scientific analytical studies carried out on these products, and even the existing ones suffer from incomplete analysis. Jasada Bhasma is a unique preparation of zinc belonging to this class. This particular preparation has been successfully used by traditional practitioners for the treatment of diabetes and age-related eye diseases. This work presents a first comprehensive physicochemical characterization of Jasada Bhasma using modern state-of-the-art techniques such as X-ray photoelectron spectroscopy (XPS), inductively coupled plasma (ICP), elemental analysis with energy dispersive X-ray analysis (EDAX), dynamic light scattering (DLS), and transmission electron microscopy (TEM). Our analysis shows that the Jasada Bhasma particles are in oxygen deficient state and a clearly identifiable fraction of particles are in the nanometer size range. These properties like oxygen deficiency and nanosize particles in Jasada Bhasma might impart the therapeutic property of this particular type of medicine. A. C. Joshi: Private Practitioner (Vaidya).     

Investigation of the mobility in poly(vinylidene fluoride) ferroelectric films with different structures

The molecular mobility in two isotropic poly(vinylidene fluoride) samples crystallized in the α phase from the melt with different crystallinities and lattice perfections has been investigated by broadband dielectric spectroscopy. It has been revealed that the local-mobility parameters are insensitive to structural features. The average relaxation times of micro-Brownian motion in the disordered phase are found to be identical in the samples under consideration, which can be associated with the localization of the mobility in the interphase layer at the crystal-amorphous phase interface. The motion in the crystal (α _c transition) has been described using the soliton mechanism of relaxation. It has been found that, as should be expected, the average relaxation time increases with an increase in the longitudinal crystal size; however, in this case, a strict quantitative correlation is absent. According to the small-angle X-ray scattering data, this is caused by different microstructures of interlamellar amorphous regions. It has been demonstrated that the samples with a higher degree of crystallinity are characterized by a larger difference in the electron densities of the crystalline and amorphous phases and a larger size of the amorphous layer. It has been assumed that an increase in the concentration of chemical defects in the interlamellar layers with a simultaneous increase in their length is responsible for the increased probability of attenuation of the solitary wave (conformational defect) in its passage between neighboring lamellar crystals.     

Spectral imaging system for non-contact colour measurement

This paper describes the development of a non-contact system for measuring colour of printed material at web speeds. The system proposed uses a non-contact spectrophotometer based on a holographic grating, in conjunction with a conventional monochrome area scan camera, from which colour spectral data is extracted, whilst a xenon flash is used to illuminate colour samples. Software and hardware details of the system are given, along with the underlying mathematics for colour space conversion and measurement. Conversion equations from X, Y, Z chromaticity co-ordinates to the RGB system are presented, and also equations to convert from the L^*a^*b^* colour space to X, Y, Z chromaticity co-ordinates. Experimental results are presented whereby the non-contact spectral system is shown to perform to a colour tolerance exceeding that of conventional colour video systems.     

The radiation shielding offered by the commercial glass installed in Bangladeshi dwellings

One sign of a vibrant Bangladeshi economy has been the move away from the use of more traditional housing materials towards a preference for modern constructional media. Glass, one such example, used both decoratively and in a structural context, offers various advantageous properties and facets including a protective feature against radiation that has not previously been considered. Current interest examines the dosimetric possibilities offered by the commercial glass as a secondary shield and also in retrospective ionising radiation exposure analysis. Four popular brands of window glass are investigated, all available within the local market (PHP-Bangladesh, Usmania-Bangladesh, Nasir-Bangladesh and Rider-China), all with the same thickness and colour, varying in terms of elemental weight fractions as evaluated by energy dispersive X-ray analysis. As potential attenuators of transmitted radiation thereby forming secondary barriers against radiation exposure from penetrating radiations, the four brands of glass have been studied using photon energies from 59 up to 1332 keV, a range of values representative of that potentially encountered in incidents. Use has been made of a well-shielded high-purity germanium γ-ray spectrometer and associated electronics, providing for evaluation of the characteristic barrier parameters of half-value layer, radiation protection efficiency and effective atomic number (Z_eff). Of the four brands investigated, Rider provides superior secondary shielding performance. Concerning potential retrospective dosimetry the effective atomic number of the glass samples are comparable with that of the commercial thermoluminescence (TL) dosimeter TLD-200. At high doses, the TL yields are sufficient to provide for retrospective accident dosimetry.     

New and Simple Staining Method for Visualizing UHMWPE Lamellar Structure in TEM

Ultra-high-molecular-weight polyethylene (UHMWPE) is used in arthroplasty as a key component of total joint replacements. In order to increase its wear resistance, the polymer is often cross-linked in a two-step procedure comprising irradiation and thermal treatment. Both modification steps impact UHMWPE lamellar structure. In this study we introduce a new staining method that makes it possible to visualize the UHMWPE lamellae by transmission electron microscopy (TEM). The method consists of one-step staining with oleum (H ₂ SO ₄ solution of SO ₃ ) for 4 days and ultramicrotomy; this is significantly simpler than previously described techniques and yields micrographs of the same quality. The lamellar thicknesses from TEM correlated well with those from small- and wide-angle X-ray scattering and differential scanning calorimetry. It has also been demonstrated that the exact values of lamellar thicknesses obtained from TEM micrographs strongly depend on the place selected for image analysis.     

Nano particle fluidisation in model 2-D and 3-D beds using high speed X-ray imaging and microtomography

Nanoparticles and nanocomposites have become a major focus of interest in science and technology due to exceptional properties they provide. However, handling and processing of ultra-fine powders is very challenging because they are extremely cohesive. Fluidization is one of techniques available to process powders. It has become increasingly important to understand how these nanoparticles can be handled and processed to benefit from their favourable properties. A high spatial (down to 400 nm) and temporal resolution (down to 1 ms) X-ray imaging apparatus has been designed to study nanoparticles in fluidized beds under different gas flow velocities. The mean volume distribution of the nanoparticle agglomerates was determined with X-ray microtomography. The X-ray microtomography technique provides valuable in situ, non-destructive structural information on the morphological changes that take place during fluidisation of powder samples.     

Temperature-induced transformation of metavariscite to berlinite

The phase transition of metavariscite into berlinite has been studied by means of different techniques, namely electron probe micro analysis, environmental scanning electron microscopy, high-temperature X-ray diffraction, differential thermal analysis, thermogravimetry, thermoluminescence, and thermo Raman. The application of these techniques indicates that: (i) from room temperature to 150°C metavariscite (monoclinic dimorph AlPO₄ ? 2H₂O) appears as the main phase, (ii) in the range of 100–300°C metavariscite starts to lose the water molecules giving rise to form α-berlinite (trigonal AlPO₄) that is the stable phase up to ca 540°C, and (iii) from 550°C onwards the structure adopts the more stable configuration, tetragonal β-berlinite.     

Deposition of ZnS thin film by ultrasonic spray pyrolysis: effect of thickness on the crystallographic and electrical properties

Zinc sulfide (ZnS) thin films have been deposited on Si (1 0 0) substrate using ultrasonic spray pyrolysis. X-ray diffraction (XRD) analysis revealed that the films are (0 0 2) preferentially oriented with c-axis-oriented wurtzite structure. The crystallinity has been found to improve with film thickness in the 180–6000 nm range. Film structure has been analyzed by XRD, scanning electron microscope, FTIR, and Raman spectroscopies, while the stoichiometry has been verified by energy-dispersive spectroscopy and particle-induced X-ray emission techniques. Electrical properties of the grown films were characterized by current–voltage and capacitance–voltage measurements where, the films show better conducting behavior at higher thickness.     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

On the electronic structure of graphite

Comprehending investigations of the electronic structure of polycrystalline as well as monocrystalline graphite have been performed by means of X-ray emission, self absorption and X-ray induced photoemission techniques. On the basis of these combined investigations a model for the determination of the relative cross sections for the photoemission process has been established and applied to graphite, where it yields _s / _p =32. The anisotropy and polarization of the CK-radiation of monocrystalline graphite is discussed in terms of the binding properties of the graphite lattice. The predictions are verified by measurements of the CK-emission employing a crystal monochromator which acts simultaneously as a nearly perfect analyzer for the polarization of the monochromatized radiation. By means of the self absorption technique the unoccupied part of the conduction band has been investigated.     

Radiation-induced conductivity of alkali halide crystals in strong electric fields under X-ray and photoexcitation

A study is undertaken into radiation-induced conductivity of alkali halide crystals under X-ray excitation and sequential excitation with X-ray and laser pulses within the absorption band of F-and F ⁻-centers. The basic conduction parameters (concentration and lifetime of carriers upon X-ray and photoexcitation) are estimated. The possible processes responsible for the nonlinearity of the current-voltage characteristics are discussed. It is shown that an increase in the conductivity in strong electric fields may be due to a decrease in the spatial localization of electrons in the conduction band of the insulator.     

Phase transitions and structural studies ofp-n-alkoxybenzyliden-p’-fluoro-anilines

Summary The transition temperatures and phase diagrams of five fluorinated benzylidenaniline derivatives have been studied by TM and X-ray diffraction techniques. A smectic polimorphism appears in all compounds. The structure of smecticB phases has been deeply studied in order to evidence a possible utilization of such phases as solvents able to exert stereochemical effects on polimerization reactions. The parameters of theS _B hexagonal lattice area=b=4.29 ? in all the studied compounds, whilstc varies from 18.9? to 24? as a function of the C atom number of the alkyl chain; its averaged increase is 1.265? for each CH₂ group. In any case, the distance between the smectic planes is equal to the molecular length so that interdigitated structures are to be excluded. Work presented at the First USSR-Italy Bilateral Meeting on Liquid Crystals held in Portonovo, Ancona (Italy), September 30-October 2, 1987.     

High energy X-ray micro-optics

A tremendous progress in X-ray optics development was made in the past decade. Progress has been driven by the unique properties of X-ray beams produced by third generation synchrotron sources. The very low emittance coupled with high brilliance allows one to develop efficient focusing devices for new X-ray microscopy techniques. This article provides an overview of the state-of-the-art in micro-focusing optics and methods for hard X-rays. The main emphasis is put on those methods which aim to produce submicron and nanometer resolution. These methods fall into three broad categories: reflective, refractive and diffractive optics.The basic principles and recent achievements are discussed for all optical devices. To cite this article: A. Snigirev, I. Snigireva, C. R. Physique 9 (2008).     

Copper blue in an ancient glass bead: a XANES study

The blue colour in ancient soda-lime glasses has been attributed to the presence of copper and/or cobalt but the origin of different shades is not yet fully interpreted. As a contribution to this question, a non-destructive X-ray absorption study at [ _Cu]K-edge was undertaken on the blue (turquoise) layer from a “Nueva Cadiz” type tubular glass bead dated pre-XVII century where copper is the unique colouring agent. Minerals configuring two distinct blue tonalities due to Cu (2+) in similar square coordination were selected as basic model compounds: azurite, which is a classical navy-blue pigment used in ancient wall paintings over plaster, and chalcanthite, displaying exactly the same turquoise-blue tonality of tubular glass beads manufactured since the Egyptian Antiquity. Theoretical modelling of the XAFS spectra was undertaken using the FEFF code. The IFEFFIT software package was used for fitting the calculated spectra to experimental data. EXAFS results are discussed in view of the crystal structures of copper minerals chosen to model the speciation state and structural situation of that element prevailing in the turquoise-blue archaeological glass. Special attention is focused on the difficulties in theoretical modelling [ _Cu]K-XANES spectra of ancient glasses with different colourings. PACS 61.43.Fs; 61.46.+w; 41.60.Ap; 61.10.Ht.     

Colouration mechanism of underglaze copper‐red decoration porcelain (AD 13th–14th century), China

Underglaze copper‐red decoration, i.e. the copper colourant used to paint diversified patterns on the surface of a body and then covered by transparent glaze and fired at high temperature in a reductive firing environment, is famous all over the world. However, the red colouration mechanism generated by underglaze copper remains unclear. In particular, the fact that the edges of the red patterns are orange has been ignored in previous research. Here, non‐destructive analysis has been carried out on a precious fragment of early underglaze red porcelain using synchrotron radiation X‐ray fluorescence, X‐ray absorption near‐edge spectroscopy (XANES) and reflection spectrometry techniques. The results suggest that the copper content in the red region is higher than that in the orange region, and other colour generation elements do not have obvious content difference, indicating that the colour generation effect of the underglaze red product is related to the copper content. XANES analysis shows that the valence states of copper in the red and orange regions are similar and metal copper contributes to their hues. The results of reflection spectrometry demonstrate that tiny orange hues could be attributed to the Mie scatting effect. Therefore, light‐scattering effects should be considered when researching the colouration mechanism of underglaze red.     

A study on CoFe/p-Si interfacial structures before and after swift heavy ion irradiation

Interfacial structures of CoFe/p-Si have been studied before and after the swift heavy ion (～100?MeV, Ni⁷⁺) irradiation to investigate its electronic and magnetic behavior. X-ray diffraction (XRD), atomic force microscopy, magnetic force microscopy and magnetization characteristics (M–H) from vibrating sample magnetometer (VSM) techniques have been used for the above. XRD data have confirmed the formation of the CoFe alloy phase along with the silicide phases of Fe and Co. It is observed that there is an irradiation-induced growth in crystallite but surface remains smooth with a surface roughness of ～34?nm. A very significant increase has been observed in the magnetization and that too with irradiation dose as compared with unirradiated ones, maintaining their superparamagnetic behavior. The results could be understood due to the role played by various magnetic phases in the structure. The magnetic field sensitivity on electronic transport across the structures has also increased in a significant manner after the irradiation as compared with unirradiated ones. The magnetic field sensitivity has resulted in an MR of 20%. The results could be understood due to the irradiation induced interfacial intermixing to result in increased magnetic phases of silicide for the observed significant magnetic behavior on the irradiation.