New insight on the in situ crystallization of calcium antimonate opacified glass during the Roman period

Glass is usually opacified by small crystalline particles, called opacifiers, dispersed in the translucent vitreous matrix. To understand the glassmaking conditions used to produce calcium antimonate opacified glass, the in situ crystallization process has been studied through synthetic glasses made in the laboratory. The effects of the nature and the concentration of the antimony source, the temperature and the duration of heat-treatments on the calcium antimonates crystallization have been tested. The physico-chemical characteristics of these glasses were compared to Roman mosaic tesserae from Aquilea and Rome (1st cent. B.C.–6th cent. A.D.). We show that the glass composition (EDX), the microstructure (SEM-BSE, imaging treatment), the oxidation state of antimony in the vitreous matrices (μ-XANES) and the proportion of the crystalline phases (XRD with Rietveld refinement) are suitable parameters to assess glassmaking conditions used in ancient times. We demonstrate that opaque Roman glasses were obtained by in situ crystallization, probably using roasted stibnite Sb₂O₄ and by doing heat-treatment between 1 or 2 days.     

Rediscovering ancient glass technologies through the examination of opacifier crystals

The aim of the study is to understand how antimonate opacifying crystals were obtained throughout history. Two archaeological glass productions opacified with calcium and lead antimonates are studied in this paper, in order to rediscover ancient opaque glass technologies: Roman mosaic tesserae (1^st cent. B.C.–4^th cent. A.D.) and Nevers lampworking glass (18^th cent. A.D.). The fine examination of crystalline phases and of the vitreous matrix is undertaken using various and complementary techniques. Results are compared with a modern reference production, for which the technological process is well known. We demonstrate that Ca-antimonate opacifiers in Roman mosaic tesserae, as well as in Nevers lampworking glass, were obtained by in situ crystallization. Nevertheless, Roman and Nevers glass would have undergone different firing processes. We propose that the addition of previously synthesized crystals or the use of “anime” could be the process used to obtain Pb-antimonate opacified glass, for both productions studied. We demonstrate that CaO, PbO and Sb₂O₃ concentrations in the bulk compositions and in the matrices, and their evolution with the crystallinity ratio, offer robust criteria for the distinction of the opacification process used. Also, the different crystalline structures help to provide information on the experimental conditions. PACS  81.05.Kf; 81.10.Fq; 61.50.Lt; 61.05.cp; 82.80.Ej     

Characterization of microcrystals in some ancient glass beads from china by means of confocal Raman microspectroscopy

A total of ten ancient colored glass beads were analyzed by confocal Raman microspectroscopy for the non‐destructive identification of microcrystals within them. These beads were excavated from different regions of China, including Xinjiang, Henan, Hubei and Guangxi Provinces, and were dated mainly from the 10^th century BC to the 9^th century AD. For the first time, either tin or antimony‐based opacifiers/colorants including calcium antimonate (CaSb₂O₆, Ca₂Sb₂O₇), bindheimite (Pb₂Sb₂O₇), lead tin yellow type II (PbSn_1‐xSi_xO₃) and cassiterite (SnO₂) were identified in nine samples. In addition, other crystalline phases such as cuprite (Cu₂O), α‐wollastonite (CaSiO₃), diopside (CaMgSi₂O₆), feldspar (KAlSi₃O₈), calcite (CaCO₃) and quartz (SiO₂) were also detected. Another interesting phenomenon first observed in this study was the coexistence of Sn‐ and Sb‐based opacifiers/colorants in one mosaic bead from Guangxi. The possibility to use Sb‐ and Sn‐based opacifiers/colorants for dating and provenance study of ancient glass found in China is discussed briefly. Copyright © 2013 John Wiley & Sons, Ltd.     

Analysis of glass tesserae from the mosaics of the ‘Villa del Casale’ near Piazza Armerina (Enna, Italy). Chemical composition, state of preservation and production technology

This paper represents a contribution to the safeguard project of The ‘Villa del Casale’ near Piazza Armerina (3rd–early 4th century AD), among the most important examples of Sicilian mosaic art, glass materials used for the mosaics execution have been investigated by several techniques. Optical Microscopy and Scanning Electron Microscopy (SEM) were used to give information about the porosity (microstructure) of glass pastes and the presence of crystalline areas or alteration layers at the surface inside the glass paste itself. SEM-EDX, X-ray Photoelectron Spectroscopy (XPS), X-ray Fluorescence (XRF) and UV-VIS-NIR reflectance analysis have provided information to obtain the chemical composition of the tesserae and on the chromophore groups. X-ray diffraction (XRD) was employed to identify opacifiers. The analytical results indicate that all tesserae are silica-soda-lime and silica-soda-lime-lead glasses. Chromophore ions consist of Cu(II) (green and pale blue tesserae), Cu(0) (red sample), Fe(II) (pale blue and the green glasses), Co(II) (deep blue samples) and Mn as a decolourant, while opacifiers found out are Pb _x Sb_2−z (O,OH,H₂O)₆ (bindheimite) in the yellow and green tesserae, CaSb₂O₆ (calcium antimony oxide) in the pale blue samples, and Ca₂Sb₂O₇ (calcium antimony oxide) in the blue tesserae. The glasses that show the greatest signs of degradation processes are those of a pale blue hue.     

Baroque glass mosaics from the Capela de São João Baptista (Chapel of Saint John the Baptist,Lisbon): unveiling the glassmaking records

For the first time, 18th‐century glass mosaics from the Capela de São João Baptista (Chapel of St. John the Baptist, Lisbon) were analysed by Raman microscopy (RM). This masterpiece in baroque mosaic art had one of its major contributors the most famous glassmaker in Rome, Alessio Mattioli. Mattioli was celebrated because of the opacity of his mosaics and the astonishing number of hues he was able to produce for mosaic decorating Saint Peter's Basilica in Rome. This study had two goals in mind: (1) characterising the materials involved in the manufacture of these glass mosaics and (2) lengthening the understanding of what was left of Mattioli's glassmaking records. As expected the mosaics presented a high ratio of crystalline phases, making RM the ideal technique for non‐destructive analysis. The mosaics contained a white ‘background’ or opacifier added identified as Ca₂Sb₂O₇. The yellow tesserae are opacified with lead antimonate (Pb₂Sb₂O₇) and ternary oxides, structures related to lead antimonate but with other ions entering the position of Sb⁴⁺ (namely Sn⁴⁺). Those ternary oxides are pervasive in most colours, admixed with other colorants. The red, orange, pink and brown colours were accomplished with cuprous oxide (Cu₂O) and admixed with a ternary oxide to create the latter three colours. The red copper‐based colours were made according to the procedure to make a ruby copper glass and with the exception of the red colour; all mosaics exhibited a dark layer on each side of the mosaic, named scorzetta. This layer is the outcome of an oxidation reaction because of a quick cooling process and is composed of CuO. Finally the blue and green colours are accomplished with cobalt oxide and copper oxide, respectively, and the purple/black colour with manganese oxide. Copyright © 2015 John Wiley & Sons, Ltd.     

New alkali antimonate glasses

Glass formation has been investigated in ternary systems Sb₂O₃-PbO-M₂O in which M is alkali Li, Na and K and antimony oxide is the glass former. Alkali elements were introduced as carbonates. The size of the glass forming region is enlarged as alkali ionic radius increases. Binary Sb₂O₃-M₂O glasses were obtained: (100−x) Sb₂O₃-xLi₂O, (10<x<30), (100−x) Sb₂O₃-xNa₂O, (10<x<70), and (100−x) Sb₂O₃-xK₂O, (10<x<90). In ternary systems, PbO content could reach 60 mol%. Temperatures of glass transition, T_g, onset of crystallization, T_x, and maximum of crystallization, T_p, have been measured using differential scanning calorimetry. Depending on composition, glass transition temperature ranges from 240 to 330 °C. The incorporation of alkali oxide increases T_g while lead oxide has the reverse effect. Thermal stability range (T_x-T_g) was usually between 65 and 266 °C, while no crystallization exotherm was observed in some cases. Density and thermal expansion increases as lead concentration increases. Optical transmission has been measured. The UV cut-off depends on alkali content: samples are yellow and turn green for large K and Na content. These glasses have potential applications as low phonon energy glasses for infrared transmission or active devices.     

Low temperature elastic behaviour of As-Sb-Se and Ge-Sb-Se glasses

The ternary glasses of arsenic and germanium with antimony and selenium can be prepared in large sizes for optical purposes. The elastic behaviour of eight compositions of each glass has been studied down to 4.2 K using a 10 MHz ultrasonic pulse echo interferometer. The glasses have a normal elastic behaviour, with the velocities gradually increasing as the temperature is lowered. An anharmonic solid model of Lakkad satisfactorily explains the temperature variations. The elastic moduli of Ge _x Sb₁₀Se_90?x glasses increase linearly as the Ge content is increased up to 25 at. % and beyond this the increase is nonlinear. (AsSb)₄₀Se₆₀ glasses show a linear increase in elastic moduli with increasing Sb content. The elastic moduli of As _x Sb₁₅Se_85?x glasses exhibit a drastic change near the stoichiometric composition As₂₅Sb₁₅Se₆₀. These behaviours have been qualitatively explained on the basis of the structural changes in glasses.     

Induced crystallization and the physical properties of PbO–Sb2O3–As2O3: MoO3 glass system

PbO–Sb₂O₃–As₂O₃ glasses mixed with different concentrations of MoO₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. The X-ray diffraction and the scanning electron microscopic studies have revealed the presence of Pb₅Sb₂O₈, PbSb₂O₆, SbAsO₄, Sb₂MoO₆, Sb₄Mo₁₀O₃₁, As₄Mo₃O₁₅, Pb₅Sb₄O₁₁ crystalline phases in these samples. The differential thermal analysis indicated that the surface crystallization prevails over the bulk crystallization as the concentration of the crystallizing agent is increased. The infrared (IR) spectral studies exhibit bands due to MoO₄ structural units in addition to the conventional bands due to various antimonate and arsenate structural groups. The studies on PbO–Sb₂O₃–As₂O₃: MoO₃ glass-ceramics with respect to various physical properties viz., dielectric properties over a range of frequency and temperature, optical absorption, electron spin resonance (ESR) and magnetic susceptibility at room temperature have also been reported. The optical absorption, ESR and magnetic susceptibility studies indicated that the molybdenum ions exist in Mo⁵⁺ state in addition to Mo⁶⁺ state in these samples. The redox ratio found to increase as the concentration of the MoO₃ is increased. The variations observed in all these properties with the concentration of the crystallizing agent have been analyzed in the light of different oxidation states and environment of molybdenum ions in the glass ceramic network.     

Glass formation in the Sb2O3-ZnBr2 binary system

Glass formation has been investigated in the Sb₂O₃-ZnBr₂ binary system. Vitreous samples have been obtained for batches containing 20-90 mol% Sb₂O₃. Chemical analysis shows that bromine concentration is smaller than expected and real compositions belong to the Sb₂O₃-ZnBr₂-ZnO ternary system. However, the discrepancy between nominal and analyzed compositions is fair for Sb₂O₃ content larger than 50 mol%. Optical transmission lies between 400 nm and 7 μm and refractive index ranges from 2.0 to 2.1. Glass transition occurs around 300 °C, and crystallization exotherm does not appear in the differential scanning calorimetry scan at 10 K s⁻¹ for samples containing 50-60 mol% Sb₂O₃. Thermal expansion varies between 120 and 220×10⁻⁷ K⁻¹ as antimony content decreases. Microhardness is close to 200 kg/mm². These glasses have low phonon energy and make potential materials for infrared transmission and active fibers.     

In situ analysis of stratified glass eye beads from the tomb of Marquis Yi of the Zeng State in Hubei Province,China using XRF and micro‐Raman spectrometry

A total of 46 stratified glass eye beads in Hubei Provincial Museum, Wuhan, China were analyzed in situ by means of portable X‐ray fluorescence and Raman spectrometers. These beads were excavated from the famous tomb of Marquis Yi of the Zeng State, which was dated back to the early Warring States Period (433 bc or little late), in Hubei Province. It is determined that most of these elegant glass beads belong to the typical soda‐lime‐silicate glasses with low contents of MgO and K₂O. The colorants used within these beads are attributed to two types: antimony‐based compound opacifiers/colorants and the transition metals in their oxidized state such as Co, Cu, and Fe ions. According to their characteristics of typology, chemical composition, and micro‐crystals within samples, we classified them into three subtypes and evaluated the possible relations among them. In addition, through comparing with the similar contemporary samples unearthed from Xu Jialing Tomb (5th–4th century bc ) in Henan Province, we discussed the provenance of these stratified glass eye beads and relative issues briefly. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of silver nanoparticles and antimony oxide nanocrystals by pulsed laser ablation in liquid media

Pulsed laser ablation in liquid media (PLALM) is a prominent technique for the controlled fabrication of nanomaterials via rapid reactive quenching of ablated species at the interface between the plasma and liquid. Results on nanoparticles and nanocrystals formed by PLALM of silver (Ag) and antimony (Sb) solid targets in different liquid environments (Sodium Dodecyl Sulfate, distilled water) are presented. These experiments were done by irradiating solid targets of Ag and Sb with a nanosecond pulsed Nd:YAG laser output of wavelength 532 nm. Nanoparticles of silver and nanocrystals of antimony oxide (Sb₂O₃) obtained were characterized using UV-Vis spectrometry, Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), X-ray Energy Dispersion Analysis (EDAX) and X-ray diffractometry (XRD). The morphology of nanomaterials formed is studied as a function of surfactant environment. The silver nanoparticles obtained were spherical of size in the order of 10–35 nm in solution of SDS having different concentrations. In case of the Sb target, ablation was performed in two different molarities of SDS solution and distilled water. Nanocrystals of Sb₂O₃ in powder form having cubic and orthorhombic phases were formed in SDS solution and as fibers of nanocrystals of cubic Sb₂O₃ in distilled water.     

Optical absorption and thermoluminescence studies on LiF-Sb2O3-B2O3 glasses doped with Ni ions

20LiF-(30−x)Sb₂O₃-50B₂O₃:xNiO glasses with the value of x (ranging from 0 to 1.0 mol% in steps of 0.2) were prepared. A number of studies, viz. differential scanning calorimetry, optical absorption, magnetic susceptibility and thermoluminescence, on these glasses were carried out as a function of nickel ion concentration. An anomaly has been observed in all the properties of these glasses when NiO concentration is about 0.6 mol%. The results of these studies were analysed in the light of different environments of nickel ions in the glass network.     

Scientific analysis of some glazed pottery unearthed from Warring States Chu tombs in Jiangling,Hubei Province: Indication for the origin of the low-fired glazed pottery in China

A portable energy dispersive X-ray fluorescence spectrometer and a micro-Raman spectrometer are used for the nondestructive analysis of a batch of glazed pottery ornaments unearthed from Warring States Chu (楚) tombs (B.C.475–B.C.221) in Jiangling, Hubei Province, China. According to the chemical compositions obtained, all of the glazes belong to the lead–barium–silicate (PbO–BaO–SiO₂) system and contain certain levels of copper. The man-made barium copper silicate pigment crystals, such as Chinese blue (BaCuSi₄O₁₀) and Chinese purple (BaCuSi₂O₆), are identified from several samples by micro-Raman spectrometer. Besides, gypsum and hematite are found in the white and brown regions of two eye beads. Combined with other glazed pottery and the related silicate artifacts (e.g., lead–barium glass and faience, potash–lime glass and glazed pottery, high-lead glazed pottery, etc.), the origin, development, and affected factors of ancient Chinese low-fired glazed pottery have been discussed preliminarily. The present study provides principal evidences for the technological provenance, raw material recipes, and the relationship between low-fired glazed pottery and related vitreous materials of ancient China. It also provides some significant clues for the origin and the development of ancient Chinese lead–barium glass.     

The structural, optical, and dielectric spectroscopy studies of novel ZnO–As2O3 glass system with Sb2O3 as additive

ZnO–As₂O₃–Sb₂O₃ glasses of varying concentrations of Sb₂O₃ with ZnO (ranging from 5 to 45 mol%) are prepared. A number of studies, including differential thermal analysis, and study of spectroscopic properties (viz., optical absorption and IR spectra) and dielectric properties (constant ε′, loss tan δ and ac conductivity σ_ac) over a wide range of frequency and temperature of these glasses are carried out. Analyses of the results of these investigations have indicated that the glasses containing higher concentrations of Sb₂O₃ are more suitable for non-linear optical (NLO) applications.     

Electrodeposition of Sb2Se3 on indium-doped tin oxides substrate: Nucleation and growth

The mechanisms related to the initial stages of the nucleation and growth of antimony selenide (Sb₂Se₃) semiconductor compounds onto the indium-doped tin oxides (ITO) coated glass surface have been investigated using chronoamperometry (CA) technique. The fabrication was conducted from nitric acid bath containing both Sb³⁺ and SeO₂ species at ambient conditions. No underpotential deposition (UPD) of antimony and selenium onto ITO substrate was observed in the investigated systems indicating a weak precursor-substrate interaction. Deposition of antimony and selenium onto ITO substrate occurred with large overvoltage through 3D nucleation and growth mechanism followed by diffusion limited growth. FE-SEM and XRD results show that orthorhombic phase Sb₂Se₃ particles with their size between 90 and 125 nm were obtained and the atomic ratio for antimony and selenium was 2:2.63 according to the EDX results.     

119Sn and121Sb Mössbauer studies of BaSn1−x Sb x O3 Perovskite system

The relations between the electrical characteristics of BaSn_1?x Sb _x O₃ perovskite system and the contents of BaO, Sb₂O₃ and silicate sintering agent were studied by X-ray diffraction analysis and Mössbauer spectroscopy. It was found that the electrical conductivity is related to the substitution of Sb³⁺ for Sn⁴⁺, the content of sintering agent and the phase constitutents in samples. BaSnO₃, Ba₃Sn₂O₇, Ba₂SnO₄ and SnO₂ phases might appear in different fractions when the contents of BaO change from 0.5 mole to 3.5 mole. In low antimony percentage condition, pentavalent Sb³⁺ ions inserted in Sn⁴⁺ sites and formed the donor center. In high antimony percentage (x≥0.20) condition, the existence of an insulating phase (BaSb₂O₆) was confirmed.     

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.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Electrical,structural, and thermal studies of antimony trioxide-doped poly(acrylic acid)-based composite polymer electrolytes

In this work, we investigate the electrical, structural, and thermal properties of composite polymer electrolytes (CPEs). Different mass fractions of antimony trioxide filler, Sb₂O₃, are added into poly(acrylic acid) (PAA)-based polymer electrolytes with N-lithiotrifluoromethane sulphonamide [LiN(SO₂CF₃)₂] (LiTFSI) as doping salt. Characteristics such as alternating current (AC)–impedance spectroscopy, attenuated total reflectance–Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) are analyzed. The highest ionic conductivity of (2.15?±?0.01)?×?10^?4 S cm^?1 is achieved at room temperature with addition of 6 wt% of fillers. The ionic transportation is further proven in a transference number study under DC polarization, whereas ATR-FTIR is employed to explore the complexation between PAA, LiTFSI, and Sb₂O₃. TGA reveals the improved thermal stability of CPEs. The glass transition temperature (T _g) is reduced upon addition of Sb₂O₃ as shown in DSC analysis.     

Effect of replacement of Se by S on structural and physical properties of Ge–Sb–As–Se–S chalcogenide glasses

In the present study, the structural and opto-mechanical properties of Ge–Sb–As–Se–S chalcogenide glasses have been investigated. For this purpose, different bulk glasses of Ge₂₀Sb₅As₁₅Se_60?xS_x (0 ≤ x≤50) were prepared by conventional melt quenching technique in quartz ampoule and different characteristics of prepared glasses such as glass transition temperature, density, hardness, transmittance, optical band gap energy and refractive index were determined. The value of hardness and glass transition temperature of prepared glasses were found to increase with increasing the sulfur content as a result of formation of GeS₄ tetrahedral units and increasing the network connectivity and average bonding energy. The optical energy gap (according to Tauc’s relation), transmittance and refractive index of prepared glasses are in direct relation with sulfur content. In this study, the highest value of transmittance (about 70%) and lowest value of refractive index (2–2.3) was achieved in Ge₂₀Sb₅As₁₅Se₄₀S₂₀ and Ge₂₀Sb₅As₁₅Se₁₀S₅₀ glasses, respectively.