Ancient Glass Beads Research Articles

Interpretation of Chemical Compositions and Making Techniques for Ancient Glass Beads from Suchonri Tomb Complex in Gongju, Korea

The Suchonri tomb complex in Uidang of Gongju has been excavated several times, and the remains and artifacts from various periods have been unearthed. Tomb No. 8, known as a Baekje Kingdom, collected a large quantity of blue-colored glass beads, quartz bead and gold-gilded glass beads. In this study, we analyzed the occurrences, internal textures and chemical compositions of representative glass beads, and interpreted the making techniques based on the study. As a result, quartz bead, which are different from glass, were confirmed, and the glass beads were classified into potassium, sodium and gold-gilded beads. The internal texture of the glass beads contained a mixture of bubbles and unmelted additives. The additives consisted of fluxes, stabilizers and colorants compositions, and were observed in various crystals and shapes. Based on internal textures, arrangement of bubbles and shape of impurities within the glass beads, it seems that various making techniques such as the winding, the drawing and the molding methods were applied. In this way, the glass beads used in a single location have slightly different characteristics suggests the diversity of the manufacturing site, materials used and producers, as well as the possibility of external introduction. It can also be interpreted that the beads were likely procured and assembled for the funeral rites to serve the purpose of the interred individual.

SEM-EDS, PIXE and Raman spectroscopies analysis of Khlong Thom ancient glass bead, southern Thailand

Various colors of glass beads excavated at the Khlong Thom archaeological site in southern Thailand were characterized non-destructively using proton-induced X-ray emission spectroscopy (PIXE), scanning electron microscope coupled with energy dispersive X-ray spectrometer (SEM-EDS), and Raman spectroscopy in order to determine the glass composition and production technology in ancient time. The results show that most of them are alkali-based glass matrices. Some of them are high lead-bearing glass. The glass compositions are approximately the same as the Mediterranean, Islamic, and Indian glasses, but with a higher concentration of aluminum. The colors are influenced by transition metal-ions content such as copper, iron, and manganese. High content of lead has been found in the samples with opaque colors, especially the yellow opaque. The corroded and flaked surface of the glass bead has been revealed by SEM. In a comparison of glass composition, it can be proposed that there is some relationship in production technology between Khlong Thom archaeological site and other sites: South-East Asia; South Asia; East Asia; Asia Minor; and South Africa. This information indicates the historical link of both land and maritime networks for long-distance trade and exchange in ancient time.

X-ray spectroscopy study of ancient glass beads at Hor-Ek, Thailand

In ancient time, it is well known that glasses have been used in ornament and decorative objects in Thailand for several hundred years as implied by archaeological evidences such as glass beads and decorative glasses. In this work, the blue and red colored glass beads selected from the Hor-Ek archaeological site in Nakhon Pathom province (central Thailand) have been characterized chemical composition using a scanning electron microscope coupled with energy dispersive X-ray spectroscopy (SEM-EDS) and a particle induced X-ray emission spectroscopy (PIXE). Cu-K-edge XANES (X-ray absorption near edge structure) of the selected samples is also carried out in fluorescent mode in order to determine the oxidation state. The results showed that the beads are all the LMHK-based glass (low magnesia, high potash). The red and blue tonalities are affected by copper with different oxidation states, and/or the summation of copper and cobalt. The shape and composition of these ancient glass beads are similar to those collected from other four sites in southern Thailand such as Khlong Thom, Phu Khao Thong, Nang Yon, and Thung Thuk and the foreign countries such as India, China, and Vietnam. These detailsindicate the long-distance trade and exchange network in ancient maritime.

A Characteristics on the Ancient Glass Beads Excavated from the Site of Hapgang-ri in Sejong, Korea

A Characteristics on the Ancient Glass Beads Excavated from the Site of Hapgang-ri in Sejong, Korea

Shedding New Light on Ancient Glass Beads by Synchrotron, SEM-EDS, and Raman Spectroscopy Techniques

The oxidation states of colouring elements and the pigments in ancient rare glasses have been investigated in this study. Synchrotron X-ray, SEM-EDS, and Raman techniques revealed that Cu2+plays a major role in blue and green glasses. The lead stannate pigment gives glasses a yellow colour. Copper and lead stannate can cause the green colour in glasses, and iron gives rise to the colour of black glasses. Microcomputed tomography reveals the distribution of the heavy elements, pigments, and inclusions in the glasses. The Dvaravati glasses in Southeast Asia may have been imported or technologically transferred to domestic manufacturers during trading on the Silk Road that connected the East and the West.

A Phoenician glass eye bead from 7th–5th c. cal BCE Nin-Bèrè 3, Mali: Compositional characterisation by LA–ICP–MS

The so-called Phoenician or Punic eye beads are a well-known type of glass artefacts circulating all over the Mediterranean Basin and Europe for most of the 1st millennium BCE. Glass beads were mostly produced in secondary workshops from imported raw glass or recycled artefacts but the specific sites of manufacture remain difficult to locate. Nevertheless, numerous chemical studies of glass from the area of interest proved that natron-based soda-lime-silica glass was the most widespread from 10th–9th century BCE to 8th–9th century CE.A glass eye bead typologically consistent with the Phoenician ones was unearthed during the archaeological excavation of the Nin-Bèrè 3 settlement site in Mali in a context dating between the 7th and the 5th centuries cal BCE. The chemical analysis by means of Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA–ICP–MS) has been carried out in order to confirm the characteristic composition of Mediterranean Iron Age glass. Results show the bead to be soda-lime silica glass fluxed with mineral soda, and coloured and opacified with cobalt, copper, and antimony. The minor and trace elements are also consistent with said composition.This exceptional find this far south expands greatly the area of distribution of these artefacts and it suggests a very early indirect contact between sub-Saharan Africa and the Mediterranean Basin. At the current state of research, this is the most ancient glass bead found south of the Sahara desert.

Elemental analysis by field-emission scanning electron microscope of ancient glass beads sample from Pulau Kalumpang archaeological site, (Perak, Malaysia)

Elemental analysis by field-emission scanning electron microscope of ancient glass beads sample from Pulau Kalumpang archaeological site, (Perak, Malaysia)

The glass beads from Ingombe Ilede

Analysis of glass beads from the Ingombe Ilede burials provides additional information that supports McIntosh and Fagan's new dating of burials 3 and 8, and that also clarifies the chronology of some of the other burials. Following an unsuccessful attempt to locate the Ingombe Ilede beads in the Livingstone Museum, we analysed beads from a card with samples of Ingombe Ilede beads that had been originally prepared by A.P. du Toit (1965), and later sold to MuseuMAfricA in Johannesburg (Figure 1). The beads were chemically analysed using LA-ICP-MS, as part of a larger project on ancient African glass bead chemistry (Robertshaw et al.2003). All analysed beads from burials 3 and 8 belong to the Khami series produced in India and traded into southern and south-central Africa from the mid fifteenth to mid seventeenth centuries. Some beads of an earlier type were present in other graves, and may have been kept as heirlooms.

Ancient Glass Bead from U-Thong Ancient City Site, Central Thailand

The goal of this research is to build a database for the ancient glass beads from U-Thong excavation site (Dvaravati Period, 6th to 13th centuries). We can compare the chemical properties among the ancient glass beads from different sites in order to learn about the ancient trading route of those glass beads. The 30 samples and 12 colors (translucent to opaque and various colors) were collected from U-Thong archaeological site, Suphanburi Province, Central Thailand. The ancient glass bead samples were studied about the physical and chemical characteristics as well as the surface features. The glass beads were analyzed by the scanning electron microscope coupled with energy dispersive x-ray spectrometer (SEM-EDS), Fourier transform infrared spectrometer (FTIR) and Atomic Force Microscope (AFM). The chemical composition of the dark blue bead for example contained 2.25 wt% MgO, 90.98 wt% SiO2, 1.26 wt% K2O, 4.17 wt% CaO and 0.59 wt% CuO. The FTIR spectrum of ancient glass beads is rarely to interpret their molecular vibration. The AFM allowed us to see the glass corrosion in nano scale on the surface. This research can help Thai archaeologists to identify the characteristics of ancient glass bead in the Central Thailand.

Quantification of elemental mapping of heterogeneous geological sample by laser ablation inductively coupled plasma mass spectrometry

Quantification procedures based on the external calibration with total sum content standardization (ECTSCS) and the external calibration with internal standardization (ECIS) were compared in the analysis of glass materials by laser ablation inductively coupled plasma spectrometry (LA-ICP-MS) with a 213nm Nd:YAG laser ablation device and a quadrupole mass spectrometer. Silicon was used as the internal reference element for ECIS. Applicability of these approaches was statistically tested using both homogeneous and inhomogeneous samples. The former type was represented by the standard reference material NIST 612 and an ancient glass bead (Early Bronze Age), while the latter was a mediaeval glass artefact (8th – 9th century). Homogeneity of samples was examined by EMP analysis. Identical results were obtained by both calibration methods for homogeneous samples, while underestimated contents resulted from quantification with ECIS method in comparison to EMP analyses of the same target area of inhomogeneous glass. Finally, elemental maps of zonal muscovite grain were recorded and quantified using ECTSCS method and verified by EMP analysis.

Physical and chemical properties of the ancient glass beads from the highland log-coffin culture and the lowland areas, Thailand: Considerations on their colors and technology

The ancient glass beads from a log coffin cave at Pang Mapha, Mae Hong Son as well as from Sa Kaeo, Thailand, were studied for their physical and chemical properties. The samples have an average specific gravity of 2.25, and an average refractive index of 1.55. The glasses show typical inclusions of swirls and gas bubbles, suggesting drawn production. Copper and iron are the main sources of the blue and green glasses, confirmed by the UV–Vis–NIR spectra, whereas the lead stannate is responsible for the yellow and iron for the black beads. Lead, as a color intensifier, is dominant in a gradual change from yellow to green, to blue samples, respectively. The main raw materials could possibly be silica sand, reh, and stannate. There are some evidences indicating recycled raw materials. We found that people on the northern highland of the log coffin culture had a connection to the low land community in the central and eastern regions of the country during the years of ~260–560CE. The technology of glass making for the studied glasses is the same as those used in the Dvaravati Kingdom glasses found in the sites of central Thailand.

Morphological Studies on Microstructure of Thai Ancient Glass Beads

Various ancient glass beads in prehistorical - historical period (around 2500-1200 BP) from the collection of the Banraiprachasawan local museum (A. Pisalee, Nakhon Sawan) were studied to determine elemental compositions and morphologies using electron probe microanalysis (EPMA) and scanning electron microscopy/energy dispersive x-ray analysis (SEM/EDX). The colors of the beads range from blue to red brown. From the EPMA data, all beads contain copper in the glass matrices. The SEM/EDX showed differences in the microstructures of the glass beads. The transparent blue, greenish blue and light green beads contain small particles of tin oxide while the opaque orange or red brown beads contain both copper oxide and tin oxide particles. The forms of copper oxide in the orange and red brown beads were proposed from previous work: Cu2O in the orange glass and copper metal in the red brown glass.

Investigation of Ancient Chinese Potash Glass by Laser Ablation Inductively Coupled Plasma Atomic Emission Spectroscopy

ABSTRACT In the present study, laser ablation inductively coupled plasma atomic emission spectroscopy (LA-ICP-AES) was successfully used to classify 26 ancient potash glass beads. These samples, mainly dated from the Han Dynasty to the Jin Dynasty, were from several provinces of both China and Vietnam. Quantitative analyses were done with both weathered and polished samples in order to consider the effects of surface weathering. Based on the characteristics of major, minor, and trace elements, we divided the samples into three subgroups (the percentage for each subgroup was 50%, 42%, and 8%, respectively) and also determined their main colorants. The results obtained provide new clues to trace the possible producing centers of ancient potash glasses in Asia. This study also reveals a complex network related to the trade of ancient potash glasses.

Characterization of some ancient glass beads unearthed from theKizil reservoir andWanquan cemeteries inXinjiang,China

A total of 33 ancient glass beads unearthed from theKizil reservoir cemetery andWanquan cemetery inXinjiang are studied usingRaman spectroscopy, scanning electron microscopy with energy‐dispersive spectrometry (SEM–EDS) and other methods. The detailed study of the glassy matrices, the crystalline inclusions and the microstructural heterogeneities for these glass beads has revealed some valuable information to help in the understanding of their possible manufacturing technology and provenance. At least two different types of glass were present in the two cemeteries. For the first time, antimony‐based colourant/opacifier—for example,Pb2Sb2O7orCaSb2O6—was systematically identified in some beads of plant‐ash type soda–lime glass dated to about 1000–500bc. The limited number of potash glass beads from theKizil reservoir cemetery, which were dated to about 500–300bc, used tin oxide as an opacifier. The diverse resources of the soda–lime and potash glasses indicate the existence of a complex trade network betweenChina and theWest much earlier than theWesternHanDynasty.

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

AbstractA 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 10th century BC to the 9th 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 (PbSn1‐xSixO3) 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.

Characterization of some tin‐contained ancient glass beads found in China by means of SEM–EDS and raman spectroscopy

A total of nine tin-contained ancient glass beads were characterized by a combination of scanning electron microscopy coupled with energy-dispersive X-ray spectrometry and Raman spectroscopy. These glass beads dated from 1st century BC to 10th century AD were excavated from the Xinjiang and Guangxi provinces of China. Two kinds of tin-based opacifiers/colorants included crystalline cassiterite (SnO(2)) and lead-tin yellow types II were first found in these soda lime glass beads. The tentative chronology of the tin-based opacifiers/colorants used in ancient glasses from China and the West was compared. In addition, several transition metal ions colorants were also found in these beads. The detailed study of the glassy matrices, crystalline inclusions, and the microstructural heterogeneities for these glass beads has revealed some valuable information to trace the possible making technology and provenances.

Corrosion of ancient glass beads found in Southern Thailand

Glass has been used as ornaments and decorations in Thailand for several hundred years. The archaeological resources suggested that the ancient glass beads excavated in southern Thailand were made more than 1300 years ago. Initial findings revealed that there were number of difference in shade between the glass beads of difference colors. Energy dispersive X-ray spectrometer (EDS) system attached with scanning electron microscope (SEM) and particle-induced X-ray emission spectroscopy (PIXE) were firstly used to study the surface corrosion of the samples. SEM micrographs showed more corroded and flaked microstructure. These were contributed to the interaction of both the ground water and its dissolved chemical compounds.

The new external ion beam analysis setup at the Demokritos Tandem accelerator and first applications in cultural heritage

At the 5.5 MV Tandem VdG accelerator of the Institute of Nuclear Physics of N.C.S.R. “Demokritos”, Athens, Greece, an external ion-beam set-up has been recently developed and installed. The aim of this development was to integrate the analytical capabilities of the PIXE, RBS and PIGE ion beam techniques in one experimental set-up, so that to attain a complete elemental and near surface structural characterization of samples in an almost non-destructive way and without any limitation concerning their size or conductive state. A careful 3D mechanical drawing optimized the set-up experimental parameters achieving probe dimensions at the millimeter range (1 mm 2) and fulfilling the special requirements imposed for optimum performance of the aforementioned techniques, including the possibility to use heavier, than protons, ion beams. For the digital pulse processing of the X-ray, γ-ray and charged particle detector signals, novel hardware and software tools were developed based on a custom FPGA configuration. The first applications were focused in the quality control of materials that have been intentionally contaminated with a particular tracer-element (“tagged” materials). The tagged materials which were developed and tested are technologically authentic replicas of ancient attic ceramics with black glazed decoration. Analytical diagnostic studies were carried out for a few representative paintings of contemporary Greek painters in order to identify and document materials/pigments and techniques and eventually to prevent trade of fakes. Finally, ancient glass beads were also examined with respect to the sodium concentration and its in-depth homogeneity.

XAS study on copper red in ancient glass beads from Thailand

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.

Combined elemental analysis of ancient glass beads by means of ion beam, portable XRF, and EPMA techniques

Ion beam analysis (IBA)- and X-ray fluorescence (XRF)-based techniques have been well adopted in cultural-heritage-related analytical studies covering a wide range of diagnostic role, i.e., from screening purposes up to full quantitative characterization. In this work, a systematic research was carried out towards the identification and evaluation of the advantages and the limitations of laboratory-based (IBA, electron probe microanalyzer) and portable (milli-XRF and micro-XRF) techniques. The study focused on the analysis of an Archaic glass bead collection recently excavated from the city of Thebes (mainland, Greece), in order to suggest an optimized and synergistic analytical methodology for similar studies and to assess the reliability of the quantification procedure of analyses conducted in particular by portable XRF spectrometers. All the employed analytical techniques and methodologies proved efficient to provide in a consistent way characterization of the glass bead composition, with analytical range and sensitivity depending on the particular technique. The obtained compositional data suggest a solid basis for the understanding of the main technological features related to the raw major and minor materials utilized for the manufacture of the Thebian ancient glass bead collection.