Modern Methods for Analysing Archaeological and Historical Glass

Professor Koen Janssens is based in the Center for Micro- and Trace Analysis at the Department of Chemistry at the University of Antwerp in Belgium. He currently teaches undergraduates on General Chemistry — Theory, Instrumental Analytical Chemistry, Radiochemistry, Micro- and Surface Analysis Methods and Practical Exercises in Analytical Chemistry. Since 1999 he has presented over 100 lectures and has published, since 1990, over 140 papers, book chapters/books. From 1999-2004 he served as an Associate Editor for Journal of Micro- and Trace Analysis, and since 2004 has served as an editorial board member of Spectrochimica Acta.His main area of research is as head of the x-ray microbeam analysis research group at the University of Antwerp which specializes in the use of X-ray microbeams for the non-destructive (trace) analysis and materials characterization.

• List of Contributors xixPreface xxiii1.1 What is Glass? 11.1.1 Introduction 11.1.2 Fundamentals of the Glassy State 21.1.3 Chemical Classification of Glasses 71.1.3.1 Silicate Glasses 71.1.4 Properties of Glasses 9References 211.2 Raw Materials, Recipes and Procedures Used for Glass Making 231.2.1 Introduction 231.2.2 Other Sources of Information on Ancient Glass Production Technology 251.2.3 Raw Materials of the past 281.2.4 Composition Characteristics of Ancient Glass Varieties 321.2.5 Present-Day Raw Materials (from the Nineteenth Century Onwards) 341.2.6 The Melting Process of the past 371.2.7 Glass Furnaces of Today 43References 451.3 Colouring, Decolouring and Opacifying of Glass 491.3.1 Introduction 491.3.2 Conclusion 62References 631.4 Glass Compositions over Several Millennia in theWestern World 671.4.1 Making Silica-Based Glass: Physico-Chemcial Constraints 671.4.2 Evolution of Glass Compositions 691.4.3 Summary 75References 762.1 X-Ray Based Methods of Analysis 792.1.1 Introduction 792.1.2 X-Ray Analysis Employing Table-Top Instrumentation 802.1.3 X-Ray Methods of Investigation Available at Synchrotron Facilities 113References 1262.2 Electron Microscopy 1292.2.1 Introduction 1292.2.2 Electron–Matter Interactions 1332.2.3 Analytical Investigations Using Scanning or Transmission Electron Microscopy 1342.2.4 Additional Analytical Possibilities Using Transmission Electron Microscopy 150References 1542.3 Ion-Beam Analysis Methods 1552.3.1 Introduction 1552.3.2 Principles of the Methods 1562.3.3 Applications: Bulk Analysis 1652.3.4 Surface Analysis 1712.3.5 Conclusion 179References 1802.4 Application of Neutron Activation Analysis to Archaeological Studies of Natural and Man-Made Glasses 1832.4.1 Introduction 1832.4.2 Theory of Activation Analysis 1832.4.3 Application of NAA to Obsidian 1922.4.4 Application of NAA to Man-Made Glass 1932.4.5 Conclusions 195Acknowledgements 195References 1953.1 Glass Characterisation Using Laser Ablation Inductively Coupled Plasma Mass Spectrometry Methods 1993.1.1 Introduction 1993.1.2 Instrumentation 2003.1.3 Analytical Procedure and Parameters 2023.1.4 The Mass Spectrometer 2023.1.5 The Laser Ablation 2033.1.6 Calculation of Concentrations 2073.1.7 Interferences, Detection Limits, Reproducibility and Accuracy 2073.1.8 Examples of Results Obtained by Using Different Analytical Procedures 2083.1.9 Conclusion 230Acknowledgements 230References 2303.2 Isotope-Ratio Techniques in Glass Studies 2333.2.1 Introduction 2333.2.2 Principles 2343.2.3 Methodology 2343.2.4 Isotope Systems in Glass Studies 2353.2.5 Perspectives 241Acknowledgements 241References 2414.1 Surface Analysis 2454.1.1 Atomic Force Microscopy (AFM) 2464.1.2 Infrared Reflection Absorption Spectroscopy (IRRAS) 2564.1.3 Secondary Ion Mass Spectrometry (SIMS) 263Acknowledgements 269References 2694.2 Non-Destructive Raman Analysis of Ancient Glasses and Glazes 2734.2.1 Introduction 2734.2.2 Fundamentals of Vibrational Spectroscopy 2754.2.3 The SiO4 Vibrational Unit and an Understanding of its IR and Raman Signatures 2784.2.4 Polymerisation Degree, Qn Model and Raman Identification of Glass Types 2794.2.5 Raman Resonance and Pigment Identification 2814.2.6 Glass Weathering 2834.2.7 Raman Technique 2874.2.7.1 On-site Measurements 2874.2.8 Case Studies 288Acknowledgments 295References 2954.3 The Use of X-Ray Absorption Spectroscopy in Historical Glass Research 2994.3.1 Introduction 2994.3.2 Iron and Manganese 3004.3.3 Copper 3034.3.4 Calcium, Antimony and Lead 306References 3065.1 Provenance Analysis of Glass Artefacts 3095.1.1 Introduction 3105.1.2 Obsidian, a Natural Glass Used since the Paleolithic 3105.1.3 The First Neolithic Artificial Glassy Materials, and the Discovery of Glass duringthe Bronze Age 3145.1.4 When Trade Beads Reached Europe 3145.1.5 Middle Bronze Age Plant-Ash Soda–Lime Glasses 3165.1.6 Late Bronze Age Mixed Soda–Potash Glasses 3165.1.7 Iron Age and Antiquity Natron–Soda–Lime Glasses 3195.1.8 Protohistoric Glass Trade Routes 3195.1.9 Glass Chrono-Typo-Chemical Models: a Dating Tool? 3195.1.10 Glass Trade to and from Central Asia and the Indian World during Antiquity 3215.1.11 Carolingian Glass Production: Some Unusual Lead Glass Composition Smoothers 3265.1.12 Late Middle Age Recycled Glass 3285.1.13 Trade Beads: the Glass Trade Internationalisation, during the Post Medieval Period 3345.1.14 Conclusion 337Acknowledgements 338References 3385.2 Glass at el-Amarna 3435.2.1 Introduction 3435.2.2 The Evidence from Amarna 3445.2.3 Scientific Investigation 3445.2.4 Conclusions 348References 3495.3 Evolution of Vitreous Materials in Bronze Age Italy 3535.3.1 Introduction 3535.3.2 Materials: Definitions 3545.3.3 Faiences 3545.3.4 Glassy Faiences 3575.3.5 Glass 3585.3.6 Conclusive Notes and Open Problems 362Acknowledgements 364References 3645.4 Black-Appearing Roman Glass 3675.4.1 Introduction 3675.4.2 Background 3675.4.3 Origin and Typology of the Analyzed Material 3705.4.4 Methods of Analysis 3715.4.5 Results 3725.4.6 Chronological Evolution of the Recipes Used for Producing Black-Appearing Glass 3775.4.7 Conclusions and Implications on the General Models for Roman Glassmaking andDistribution 379Acknowledgements 382References 3825.5 Glass Compositions of the Merovingian Period inWestern Europe 3855.5.1 Introduction 3855.5.2 Data Sets Considered 3865.5.3 Comments 3885.5.4 A Special Case 3925.5.5 Summary 394References 3945.6 Glass in South Asia 3975.6.1 Introduction 3975.6.2 The Origin of Glass in South Asia 3985.6.3 Mineral-Soda-Alumina or m-Na-Al Glass 4005.6.4 Arikamedu: The Best-Studied Glass-Bead-Making Site in South Asia 4045.6.5 Discussion 4065.6.6 Conclusion 408Acknowledgements 409References 4095.7 Early Glass in Southeast Asia 4135.7.1 Introduction 4135.7.2 Evaluating the Evidence 4145.7.3 The First Glass Bead in Southeast Asia? 4155.7.4 Khao Sam Kaeo and Early Southeast Asian Glass 4165.7.5 Ban Don Ta Phet 4305.7.6 The Turn of the New Millennium, Khlong Thom and the Southern Silk Road 4315.7.7 Glass Evidence from Khlong Thom 4335.7.8 Khlong Thom and the Southern Silk Road 4375.7.9 Conclusion 438Acknowledgements 439References 4395.8 Glass Trade between the Middle East and Asia 4435.8.1 Introduction 4435.8.2 Portable XRF Suitable for Glass Analysis 4445.8.3 Asian Glass Beads Excavated from Ancient Tombs in Japan 4455.8.4 Glass at Shosoin Temple 4485.8.5 Islamic Glass Excavated from the Raya Site, Egypt 4495.8.6 The Flow of Islamic Glass to Asia, a Glass Vessel at Toshodaiji Temple 4515.8.7 The Glass Road to East Asia via the Sea Silk Road 4515.8.8 Conclusion 454References 4545.9 European Glass Trade Beads in Northeastern North America 4575.9.1 Blue Beads 4595.9.2 White Beads 4615.9.3 Opaque Red Glass 4645.9.4 Black Beads from Amsterdam 4655.9.5 Gold-Coloured Beads from Amsterdam 4665.9.6 Conclusions 467Acknowledgements 467References 4676.1 Medieval Glass-Making and -Working in Tuscany and Liguria (Italy). Towards aStandard Methodology for the Classification of Glass-Making and Glass-WorkingIndicators 4716.1.1 Introduction 4716.1.2 Medieval Glass-Making and -Working in Tuscany and Liguria (Italy) 4736.1.3 Towards a Standard Methodology for the Classification of Glass Making and GlassWorking Indicators 4796.1.4 Conclusions 509Acknowledgements 509References 5106.2 Venetian Soda Glass 5136.2.1 Introduction 5136.2.2 Analysed Samples 5146.2.3 The Origins (Early Medieval Glass) and the Levantine Influence 5166.2.4 Middle Ages and Renaissance 5216.2.5 Eighteenth Century: the Decline 5286.2.6 Fac¸on de Venise Glass 5296.2.7 Other Glasses 5296.2.8 Conclusion 530References 5316.3 Transfer of Glass Manufacturing Technology in the Sixteenth and Seventeenth Centuriesfrom Southern to Northern Europe: Using Trace Element Patterns to Reveal the Spreadfrom Venice via Antwerp to London 5356.3.1 Introduction 5356.3.2 Background Information 5386.3.3 Materials and Methods 5396.3.4 Results and Discussion 5456.3.5 Conclusions 557Acknowledgements 558References 5586.4 Seventeenth-Century Varec Glass from the Great Hall of Mirrors at Versailles 5616.4.1 Introduction 5616.4.2 Experimental Determinations 5636.4.3 Experimental Results 5646.4.4 Analysis of the Results: What Came from Where? 5656.4.5 Discussion 5676.4.6 Conclusions 567Acknowledgements 569References 5696.5 Seventeenth- and Eighteenth-Century English Lead Glass 5716.5.1 Introduction 5716.5.2 Historical Background 5716.5.3 Previous Research 5726.5.4 Objectives 5736.5.5 Analytical Method 5746.5.6 Study Results and Discussion 5756.5.7 Manufacture and Weathering of Replica Glasses 5786.5.8 Conclusions 579Acknowledgements 579References 5797.1 Metal Nanoparticles in Glass: Lustre 5817.1.1 Introduction 5817.1.2 Historical Notes 5837.1.3 Lustre Composition and Morphology 5847.1.4 Lustre Formation Process 5927.1.5 Optical Properties of Lustre 5967.1.6 Conclusion 602References 6027.2 Glass Degradation by Liquids and Atmospheric Agents 6077.2.1 Introduction 6077.2.2 The Corrosion of Glass 6127.2.3 The Weathering of Glass 6247.2.4 Summary and Conclusion 6397.2.5 Acknowledgements 640References 6407.3 Corrosion of Stained GlassWindows: Applied Study of Spanish Monuments ofDifferent Periods 6517.3.1 Introduction 6517.3.1.1 Previous Considerations 6537.3.2 Mechanisms of Chemical Attack 6537.3.3 Environmental Degradation Effects 6547.3.4 Conclusions and Outlook 670Acknowledgements 671References 6717.4 Novel Methods of Evaluation for the Conservation of Browned Historical Stained Glass 6757.4.1 Introduction 6757.4.2 Background 6767.4.3 Corroded Glass Material 6787.4.4 Methods of Analysis 6807.4.5 Results Provided by the μ-XANES Measurements 6817.4.6 Computed Tomography Monitoring of the Conservation Treatment 6827.4.7 Conclusions 685Acknowledgements 686References 687