Characterization of medieval glass artefacts from Miranduolo site, Chiusdino, Italy

This archaeovitreological study deals with artefacts of Miranduolo site, Tuscany region (Italy), dated 1250-1350 AD. The Miranduolo site is a medieval hill-village dated from 7th to 14th century. The information obtained reveal that Miranduolo was under control of noble families, which displayed the social, economic and political power. It is marked by controlling the farmers and metal workers on the site, as well as having control over agricultural surpluses. No in situ glass workshop has been recovered, implying that the glass artefacts were imported. One aim of this work is application of SEM-EDS to visualize textural characteristics and thickness of the pristine glass and corrosion layers. Preliminary qualification and semi-quantification of major and minor chemical elements will provide the data on the glass group present and fluxes employed. The data obtained will be integrated with the one obtained by more sensitive techniques such as PIXE/PIGE and LA-ICP-MS. Twenty cross-sections of transparent glasses (colorless, azure, and different hues of yellow and) have been analyzed by VP-SEM. All the analyzed glasses display a homogenous matrix. Only four samples (MD 24, MD 139, MD 143, MD 259) show corrosion layers of various thickness with 2.25μm, 136-500 μm, 26.8 μm and 17.01 μm. EDS linescan analyses indicate strong depletion in the corrosion layers of Na and K, while Ca depletes to a minor extent. In general, both glass composition and the burial conditions were favorable for preservation. Samples can be classified as mainly plant ash Na-Ca-Si glasses made with both unpurified and purified Levantine ash. Only sample MD 243 is made from Barilla plant ash. Sample MD 139 cannot be classified into main compositional groups as K2O is 1.33 wt% and MgO 5.92 wt%. In 8 samples MnO content is lower than 0.8 wt%, meaning that in these samples MnO is naturally present. In other 12 samples, MnO above 0.8 wt% indicates deliberate addition as a decolorant agent to intentionally obtain different hues or the amount added was not successful in making the glass transparent. The results considering fluxes are compatible with archaeovitreological study from contemporary primary glass workshops in Tuscany. For determining the provenance of silica sources, further analysis with more sensitive techniques has to be carried out; Resumo: Este estudo “arqueovitreologia” lida com artefatos do local Miranduolo, região da Toscana (Itália), datados de 1250-1350 AD. O sitio de Miranduolo é uma colina vila medieval datada do séc.VII ao séc.XIV. As informações obtidas revelam que Miranduolo estava sob o controle de famílias nobres, que exibiu o poder social, económico e político. É marcado por controlar os agricultores e trabalhadores do metal no sitio, bem como ter controlo sobre os excedentes agrícolas. Não há na oficina de vidro in situ foi recuperado, o que implica que os artefactos de vidro foram importados. Um dos objetivos deste trabalho é a aplicação de SEM-EDS para visualizar características de textura e espessura das camadas de corrosão do vidro também como da áreas originais. qualificação preliminar e semi-quantificação de maiores e menores elementos químicos irá fornecer os dados sobre o grupo presente vidro e fluxos empregado. Os dados obtidos são integrados com os dados obtidos por meio de técnicas mais sensíveis, como PIXE / PIGE e LA-ICP-MS. Vinte secções transversais de vidros transparentes (incolor, azul celeste, e diferentes tons de amarelo) foram analisados por VP-SEM. Todos os vidros analisados exibir uma matriz homogénea. Apenas quatro amostras (MD 24, MD 139, MD 143, MD 259) mostram camadas de corrosão de várias espessuras com 2.25μm, 136-500μm, 26,8μm e 17,01μm. Análises Linescan EDS indicam forte esgotamento nas camadas de corrosão de Na e K, enquanto Ca esgota, em menor grau. Em geral, tanto a composição de vidro e as condições de depósito foram favoráveis para a preservação. As amostras podem ser classificados como vidros principalmente Na-Ca-Si feitas com cinzas de plantas do tipo levantino, não purificada e purificada. Apenas a amostra MD 243 é feita a partir de cinzas vegetais tipo “Barilla”. A amostra MD 139 não pode ser classificada em grupos principais de composição porque K2O é 1,33% em peso e MgO 5,92% em peso. Em 8 amostras, o teor de MnO é menor do que 0,8% em peso, o que significa que nestas amostras MnO está naturalmente presente. Em outras 12 amostras, MnO acima de 0,8% em peso indica adição intencional como um agente de colorante para obter intencionalmente diferentes matizes ou o valor acrescentado não foi bem sucedido em fazer o vidro transparente. Os resultados, considerando os fluxos são compatíveis com o estudo “arqueovitreologico” com as principais oficinas de vidro contemporâneos na Toscana. Para determinar a origem das fontes de sílica, uma análise mais aprofundada com técnicas mais sensíveis tem de ser levada a cabo.

Study of the most suitable new glass laser to incorporate ytterbium: alkali niobium tellurite, lead fluorborate or heavy metal oxide

Diode-pumped Yb-doped glass lasers have received considerable attention for applications such as high-power beam production or femtosecond pulses generation. In this paper, we evaluate the laser potential of three different glass families doped with Yb3+ : alkali lead fluorborate (PbO-PbF2-B2O3), heavy metal oxide (Bi2O3-PbO-Ga2O3) and niobium tellurite (TeO2-Nb2O5-K2O-Li2O). Spectroscopic properties were studied for the samples and calculations of the minimum laser pump intensity (I-min), saturation fluence (U-sat) and the theoretical limit of peak power (P-max) are also presented. A comparison of laser properties of these three different glasses and their importance is shown and analyzed. (C) 2002 Elsevier B.V. B.V. All rights reserved.

The provenance and technology of Near Eastern glass: Oxygen isotopes by laser fluorination as a complement to strontium

The ability to make rapid measurements on small samples using laser fluorination enhances the potential of oxygen isotopes in the investigation of early inorganic materials and technologies. delta O-18 and Sr-87/Sr-86 values are presented for glass from two primary production sites, four secondary production sites and a consumer site in the Near East, dating from Late Antiquity to the medieval period. delta O-18 is in general slightly less effective than Sr-87/Sr-86 in discriminating between sources, as the spread of measured values from a single source is somewhat broader relative to the available range. However, while Sr-87/Sr-86 is derived predominantly from either the lime-bearing fraction of the glass-making sand or the plant ash used as a source of alkali, delta O-18 derives mainly from the silica. Thus the two measurements can provide complementary information. A comparison of delta O-18 for late Roman - Islamic glasses made on the coast of Syria-Palestine with those of previously analysed glasses from Roman Europe suggests that the European glasses are relatively enriched in O-18. This appears to contradict the view that most Roman glass was made using Levantine sand and possible interpretations are discussed.

Directional bend sensor based on an asymmetric modification of the fiber cladding by femtosecond laser

A femtosecond laser was used to modify a part of the cladding of a standard LPG bend sensor. The device produced wavelength shifts depending upon the direction of bend, thus making a shape sensor.

Bending characteristics of fiber long-period gratings with cladding index modified by femtosecond laser

A femtosecond laser has been used to asymmetrically modify the cladding of fiber containing long-period gratings. Following modification, devices in single-mode fiber are shown to be capable of sensing the magnitude and direction of bending in one plane by producing blue and red wavelength shifts depending upon the orientation of the bend. The resulting curvature sensitivities were -1.62 and +3.82 nm&middotm. Devices have also been produced using an elliptical core fiber to study the effects of the cladding modification on the two polarization eigenstates. A cladding modification applied on the fast axis of the fiber is shown to affect the light in the fast axis much more significantly than the light in the orthogonal state; this behavior may ultimately lead to a sensor capable of detecting the direction of bending in two dimensions for applications in shape sensing.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Bending characteristics of fiber long-period gratings with cladding index modified by femtosecond laser

A femtosecond laser has been used to asymmetrically modify the cladding of fiber containing long-period gratings. Following modification, devices in single-mode fiber are shown to be capable of sensing the magnitude and direction of bending in one plane by producing blue and red wavelength shifts depending upon the orientation of the bend. The resulting curvature sensitivities were -1.62 and +3.82 nm·m. Devices have also been produced using an elliptical core fiber to study the effects of the cladding modification on the two polarization eigenstates. A cladding modification applied on the fast axis of the fiber is shown to affect the light in the fast axis much more significantly than the light in the orthogonal state; this behavior may ultimately lead to a sensor capable of detecting the direction of bending in two dimensions for applications in shape sensing. © 2006 IEEE.

Directional bend sensor based on an asymmetric modification of the fiber cladding by femtosecond laser

A femtosecond laser was used to modify a part of the cladding of a standard LPG bend sensor. The device produced wavelength shifts depending upon the direction of bend, thus making a shape sensor. © 2005 Optical Society of America.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Trace elemental analysis of glass by inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

This work evaluated the capabilities of inductively coupled plasma mass spectrometry (ICP-MS) for elemental analysis of trace evidence. A method was developed and validated for the analysis of glass by ICP-MS. A database of ∼700 glass samples was analyzed for elemental composition by external calibration with internal standardization (EC) ICP-MS and refractive index (RI). Additional methods were developed during the course of this work using two well-known techniques, isotope dilution (ID) and laser ablation (LA). These methods were then applied to analyze subsets of this database. ICP-MS data from 161 containers, 45 headlamps, and 458 float glasses (among them at least 143 vehicle windows) are presented and summarized. Data from the analysis of ∼190 glass samples collected from a single glass manufacturing facility over a period of 53 months at different intervals, including 97 samples collected in a 24 hour period are presented. Data from the analysis of 125 glass samples representing 36 manufacturing plants in the U.S. are also presented. ^ The three methods used, ICP-MS, ID-ICP-MS and LA-ICP-MS, were shown to be excellent methods for distinguishing between different glass samples. The database provided information about the variability of refractive index and elemental composition in glasses from diverse population types. Using the proposed methods, the database supports the hypothesis that different glass samples have different elemental profiles and a comparison between fragments from the same source results in indistinguishable profiles. ^

Evaluation of the evidential value of the elemental composition of glass, ink and paper by laser-based microspectrochemical methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87–100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling's T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Evaluation of the Evidential Value of the Elemental Composition of Glass, Ink and Paper by Laser-Based Micro-Spectrochemical Methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87 – 100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling’s T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y(2)O(3))(0.2)-(Al(2)O(3))(x)-(B(2)O(3))(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 <= x <= 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three-and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly ""aluminate-like'' with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.

Laser cooling of a solid from ambient temperature

A 250 mum diameter fibre of ytterbium-doped ZBLAN was cooled by 13 K from room temperature. The cooling was performed in vacuum to limit the thermal load on the fibre. 0.85 W of laser light at 1015 nm was coupled into the fibre. The ytterbium ions absorbed this light, and the excited atoms thermalized phononically and on average emitted light at a wavelength of 996 nm. Since the quantum efficiency of the transition was high, this resulted in a net loss of energy from the glass, producing net bulk cooling.

Particle shape and orientation in laser diffraction and static image analysis size distribution analysis of micrometer sized rectangular particles

Laser diffraction (LD) and static image analysis (SIA) of rectangular particles [United States Pharmacopeia, USP30-NF25, General Chapter <776>, Optical Miroscopy.] have been systematically studied. To rule out sample dispersion and particle orientation as the root cause of differences in size distribution profiles, we immobilize powder samples on a glass plate by means of a dry disperser. For a defined region of the glass plate, we measure the diffraction pattern as induced by the dispersed particles, and the 2D dimensions of the individual particles using LD and optical microscopy, respectively. We demonstrate a correlation between LD and SIA, with the scattering intensity of the individual particles as the dominant factor. In theory, the scattering intensity is related to the square of the projected area of both spherical and rectangular particles. In traditional LD the size distribution profile is dominated by the maximum projected area of the particles (A). The diffraction diameters of a rectangular particle with length L and breadth B as measured by the LD instrument approximately correspond to spheres of diameter ØL and ØB respectively. Differences in the scattering intensity between spherical and rectangular particles suggest that the contribution made to the overall LD volume probability distribution by each rectangular particle is proportional to A2/L and A2/B. Accordingly, for rectangular particles the scattering intensity weighted diffraction diameter (SIWDD) explains an overestimation of their shortest dimension and an underestimation of their longest dimension. This study analyzes various samples of particles whose length ranges from approximately 10 to 1000 μm. The correlation we demonstrate between LD and SIA can be used to improve validation of LD methods based on SIA data for a variety of pharmaceutical powders all with a different rectangular particle size and shape.