Title Details

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 xix

Preface xxiii

1.1 What is Glass? 1

1.1.1 Introduction 1

1.1.2 Fundamentals of the Glassy State 2

1.1.3 Chemical Classification of Glasses 7

1.1.3.1 Silicate Glasses 7

1.1.4 Properties of Glasses 9

References 21

1.2 Raw Materials, Recipes and Procedures Used for Glass Making 23

1.2.1 Introduction 23

1.2.2 Other Sources of Information on Ancient Glass Production Technology 25

1.2.3 Raw Materials of the past 28

1.2.4 Composition Characteristics of Ancient Glass Varieties 32

1.2.5 Present-Day Raw Materials (from the Nineteenth Century Onwards) 34

1.2.6 The Melting Process of the past 37

1.2.7 Glass Furnaces of Today 43

References 45

1.3 Colouring, Decolouring and Opacifying of Glass 49

1.3.1 Introduction 49

1.3.2 Conclusion 62

References 63

1.4 Glass Compositions over Several Millennia in theWestern World 67

1.4.1 Making Silica-Based Glass: Physico-Chemcial Constraints 67

1.4.2 Evolution of Glass Compositions 69

1.4.3 Summary 75

References 76

2.1 X-Ray Based Methods of Analysis 79

2.1.1 Introduction 79

2.1.2 X-Ray Analysis Employing Table-Top Instrumentation 80

2.1.3 X-Ray Methods of Investigation Available at Synchrotron Facilities 113

References 126

2.2 Electron Microscopy 129

2.2.1 Introduction 129

2.2.2 Electron–Matter Interactions 133

2.2.3 Analytical Investigations Using Scanning or Transmission Electron Microscopy 134

2.2.4 Additional Analytical Possibilities Using Transmission Electron Microscopy 150

References 154

2.3 Ion-Beam Analysis Methods 155

2.3.1 Introduction 155

2.3.2 Principles of the Methods 156

2.3.3 Applications: Bulk Analysis 165

2.3.4 Surface Analysis 171

2.3.5 Conclusion 179

References 180

2.4 Application of Neutron Activation Analysis to Archaeological Studies of Natural and Man-Made Glasses 183

2.4.1 Introduction 183

2.4.2 Theory of Activation Analysis 183

2.4.3 Application of NAA to Obsidian 192

2.4.4 Application of NAA to Man-Made Glass 193

2.4.5 Conclusions 195

Acknowledgements 195

References 195

3.1 Glass Characterisation Using Laser Ablation Inductively Coupled Plasma Mass Spectrometry Methods 199

3.1.1 Introduction 199

3.1.2 Instrumentation 200

3.1.3 Analytical Procedure and Parameters 202

3.1.4 The Mass Spectrometer 202

3.1.5 The Laser Ablation 203

3.1.6 Calculation of Concentrations 207

3.1.7 Interferences, Detection Limits, Reproducibility and Accuracy 207

3.1.8 Examples of Results Obtained by Using Different Analytical Procedures 208

3.1.9 Conclusion 230

Acknowledgements 230

References 230

3.2 Isotope-Ratio Techniques in Glass Studies 233

3.2.1 Introduction 233

3.2.2 Principles 234

3.2.3 Methodology 234

3.2.4 Isotope Systems in Glass Studies 235

3.2.5 Perspectives 241

Acknowledgements 241

References 241

4.1 Surface Analysis 245

4.1.1 Atomic Force Microscopy (AFM) 246

4.1.2 Infrared Reflection Absorption Spectroscopy (IRRAS) 256

4.1.3 Secondary Ion Mass Spectrometry (SIMS) 263

Acknowledgements 269

References 269

4.2 Non-Destructive Raman Analysis of Ancient Glasses and Glazes 273

4.2.1 Introduction 273

4.2.2 Fundamentals of Vibrational Spectroscopy 275

4.2.3 The SiO4 Vibrational Unit and an Understanding of its IR and Raman Signatures 278

4.2.4 Polymerisation Degree, Qn Model and Raman Identification of Glass Types 279

4.2.5 Raman Resonance and Pigment Identification 281

4.2.6 Glass Weathering 283

4.2.7 Raman Technique 287

4.2.7.1 On-site Measurements 287

4.2.8 Case Studies 288

Acknowledgments 295

References 295

4.3 The Use of X-Ray Absorption Spectroscopy in Historical Glass Research 299

4.3.1 Introduction 299

4.3.2 Iron and Manganese 300

4.3.3 Copper 303

4.3.4 Calcium, Antimony and Lead 306

References 306

5.1 Provenance Analysis of Glass Artefacts 309

5.1.1 Introduction 310

5.1.2 Obsidian, a Natural Glass Used since the Paleolithic 310

5.1.3 The First Neolithic Artificial Glassy Materials, and the Discovery of Glass during

the Bronze Age 314

5.1.4 When Trade Beads Reached Europe 314

5.1.5 Middle Bronze Age Plant-Ash Soda–Lime Glasses 316

5.1.6 Late Bronze Age Mixed Soda–Potash Glasses 316

5.1.7 Iron Age and Antiquity Natron–Soda–Lime Glasses 319

5.1.8 Protohistoric Glass Trade Routes 319

5.1.9 Glass Chrono-Typo-Chemical Models: a Dating Tool? 319

5.1.10 Glass Trade to and from Central Asia and the Indian World during Antiquity 321

5.1.11 Carolingian Glass Production: Some Unusual Lead Glass Composition Smoothers 326

5.1.12 Late Middle Age Recycled Glass 328

5.1.13 Trade Beads: the Glass Trade Internationalisation, during the Post Medieval Period 334

5.1.14 Conclusion 337

Acknowledgements 338

References 338

5.2 Glass at el-Amarna 343

5.2.1 Introduction 343

5.2.2 The Evidence from Amarna 344

5.2.3 Scientific Investigation 344

5.2.4 Conclusions 348

References 349

5.3 Evolution of Vitreous Materials in Bronze Age Italy 353

5.3.1 Introduction 353

5.3.2 Materials: Definitions 354

5.3.3 Faiences 354

5.3.4 Glassy Faiences 357

5.3.5 Glass 358

5.3.6 Conclusive Notes and Open Problems 362

Acknowledgements 364

References 364

5.4 Black-Appearing Roman Glass 367

5.4.1 Introduction 367

5.4.2 Background 367

5.4.3 Origin and Typology of the Analyzed Material 370

5.4.4 Methods of Analysis 371

5.4.5 Results 372

5.4.6 Chronological Evolution of the Recipes Used for Producing Black-Appearing Glass 377

5.4.7 Conclusions and Implications on the General Models for Roman Glassmaking and

Distribution 379

Acknowledgements 382

References 382

5.5 Glass Compositions of the Merovingian Period inWestern Europe 385

5.5.1 Introduction 385

5.5.2 Data Sets Considered 386

5.5.3 Comments 388

5.5.4 A Special Case 392

5.5.5 Summary 394

References 394

5.6 Glass in South Asia 397

5.6.1 Introduction 397

5.6.2 The Origin of Glass in South Asia 398

5.6.3 Mineral-Soda-Alumina or m-Na-Al Glass 400

5.6.4 Arikamedu: The Best-Studied Glass-Bead-Making Site in South Asia 404

5.6.5 Discussion 406

5.6.6 Conclusion 408

Acknowledgements 409

References 409

5.7 Early Glass in Southeast Asia 413

5.7.1 Introduction 413

5.7.2 Evaluating the Evidence 414

5.7.3 The First Glass Bead in Southeast Asia? 415

5.7.4 Khao Sam Kaeo and Early Southeast Asian Glass 416

5.7.5 Ban Don Ta Phet 430

5.7.6 The Turn of the New Millennium, Khlong Thom and the Southern Silk Road 431

5.7.7 Glass Evidence from Khlong Thom 433

5.7.8 Khlong Thom and the Southern Silk Road 437

5.7.9 Conclusion 438

Acknowledgements 439

References 439

5.8 Glass Trade between the Middle East and Asia 443

5.8.1 Introduction 443

5.8.2 Portable XRF Suitable for Glass Analysis 444

5.8.3 Asian Glass Beads Excavated from Ancient Tombs in Japan 445

5.8.4 Glass at Shosoin Temple 448

5.8.5 Islamic Glass Excavated from the Raya Site, Egypt 449

5.8.6 The Flow of Islamic Glass to Asia, a Glass Vessel at Toshodaiji Temple 451

5.8.7 The Glass Road to East Asia via the Sea Silk Road 451

5.8.8 Conclusion 454

References 454

5.9 European Glass Trade Beads in Northeastern North America 457

5.9.1 Blue Beads 459

5.9.2 White Beads 461

5.9.3 Opaque Red Glass 464

5.9.4 Black Beads from Amsterdam 465

5.9.5 Gold-Coloured Beads from Amsterdam 466

5.9.6 Conclusions 467

Acknowledgements 467

References 467

6.1 Medieval Glass-Making and -Working in Tuscany and Liguria (Italy). Towards a

Standard Methodology for the Classification of Glass-Making and Glass-Working

Indicators 471

6.1.1 Introduction 471

6.1.2 Medieval Glass-Making and -Working in Tuscany and Liguria (Italy) 473

6.1.3 Towards a Standard Methodology for the Classification of Glass Making and Glass

Working Indicators 479

6.1.4 Conclusions 509

Acknowledgements 509

References 510

6.2 Venetian Soda Glass 513

6.2.1 Introduction 513

6.2.2 Analysed Samples 514

6.2.3 The Origins (Early Medieval Glass) and the Levantine Influence 516

6.2.4 Middle Ages and Renaissance 521

6.2.5 Eighteenth Century: the Decline 528

6.2.6 Fac¸on de Venise Glass 529

6.2.7 Other Glasses 529

6.2.8 Conclusion 530

References 531

6.3 Transfer of Glass Manufacturing Technology in the Sixteenth and Seventeenth Centuries

from Southern to Northern Europe: Using Trace Element Patterns to Reveal the Spread

from Venice via Antwerp to London 535

6.3.1 Introduction 535

6.3.2 Background Information 538

6.3.3 Materials and Methods 539

6.3.4 Results and Discussion 545

6.3.5 Conclusions 557

Acknowledgements 558

References 558

6.4 Seventeenth-Century Varec Glass from the Great Hall of Mirrors at Versailles 561

6.4.1 Introduction 561

6.4.2 Experimental Determinations 563

6.4.3 Experimental Results 564

6.4.4 Analysis of the Results: What Came from Where? 565

6.4.5 Discussion 567

6.4.6 Conclusions 567

Acknowledgements 569

References 569

6.5 Seventeenth- and Eighteenth-Century English Lead Glass 571

6.5.1 Introduction 571

6.5.2 Historical Background 571

6.5.3 Previous Research 572

6.5.4 Objectives 573

6.5.5 Analytical Method 574

6.5.6 Study Results and Discussion 575

6.5.7 Manufacture and Weathering of Replica Glasses 578

6.5.8 Conclusions 579

Acknowledgements 579

References 579

7.1 Metal Nanoparticles in Glass: Lustre 581

7.1.1 Introduction 581

7.1.2 Historical Notes 583

7.1.3 Lustre Composition and Morphology 584

7.1.4 Lustre Formation Process 592

7.1.5 Optical Properties of Lustre 596

7.1.6 Conclusion 602

References 602

7.2 Glass Degradation by Liquids and Atmospheric Agents 607

7.2.1 Introduction 607

7.2.2 The Corrosion of Glass 612

7.2.3 The Weathering of Glass 624

7.2.4 Summary and Conclusion 639

7.2.5 Acknowledgements 640

References 640

7.3 Corrosion of Stained GlassWindows: Applied Study of Spanish Monuments of

Different Periods 651

7.3.1 Introduction 651

7.3.1.1 Previous Considerations 653

7.3.2 Mechanisms of Chemical Attack 653

7.3.3 Environmental Degradation Effects 654

7.3.4 Conclusions and Outlook 670

Acknowledgements 671

References 671

7.4 Novel Methods of Evaluation for the Conservation of Browned Historical Stained Glass 675

7.4.1 Introduction 675

7.4.2 Background 676

7.4.3 Corroded Glass Material 678

7.4.4 Methods of Analysis 680

7.4.5 Results Provided by the μ-XANES Measurements 681

7.4.6 Computed Tomography Monitoring of the Conservation Treatment 682

7.4.7 Conclusions 685

Acknowledgements 686

References 687