Analytical Chemistry for the Study of Paintings and the Detection of Forgeries (Cultural Heritage Science)

Forgeries present a daunting problem to art historians, museums, galleries and curators who face challenges in determining the authenticity of paintings. Recent progress in science has led to the development of new methods for investigating works of art, and can provide new insights into the materials found in paintings. The rise in the value of paintings together with the knowledge and skills of forgers highlights the need to develop reliable scientific procedures to identify fakes. Given the complexity of materials in paintings and the convergence of various disciplines, a methodological approach for nvestigations of paintings is based on art historical, curatorial, aesthetic, technical and scientific evaluation. In this book sophisticated digital and analytical techniques are reviewed for the identification of materials (pigments, binders, varnishes, adhesives) and the physical characteristics of paintings such as brushstrokes, craquelure and canvas weaves. This book presents an updated overview of both non-invasive and micro-invasive techniques that enable the material characterization of paintings. The materials constituting a painting are reviewed, as are ways that changes in materials over time can provide insights into chronology and physical history. State-of the art digital metods including multi and hyper-spectral imaging and computational approaches to data treatment will be presented. Analytical techniques developed and optimized to characterize binders, varnishes, and pigments are reviewed, focusing on materials which can provide information on ageing or provenance. Case studies of applications of synchrotron-based methods and the analysis of paintings are given, as are chapters devoted to legal aspects related to authenticity. Chapter 1 is available open access under a Creative Commons Attribution 4.0 International License via link.springer.com. Preface Contents Part I: Approaches to the Authentication of Works of Art Chapter 1: The Eye Versus Chemistry? From Twentieth to Twenty-First Century Connoisseurship 1.1 Connoisseurship, the Humanities and Some Recent Insights from Cognitive Psychology 1.2 The Eye Versus Chemistry: Early Interactions Between Connoisseurs and Chemists 1.3 The Van Meegeren Scandal: A Turning Point 1.4 Excessive Optimism: The Potential and Limitations of Scientific Techniques 1.5 Paradigm Change and Myriad New Techniques 1.6 The Digitally Enhanced Eye: Connoisseurship and Smart Tools 1.6.1 The Curtain Viewer 1.6.2 Morelli’s Vision 1.6.3 Draper 1.6.4 PixelSwarm 1.7 Concluding Remarks: Challenges and Opportunities References Chapter 2: Scientific Study, Condition Challenges, and Attribution Questions in Yves Tanguy’s Oeuvre 2.1 Introduction 2.1.1 Attribution Challenges for Yves Tanguy and His Contemporaries 2.1.2 Science, Attribution, and the Art Market 2.1.3 Background Information on Yves Tanguy’s Influences and Life 2.1.4 Current Resources for Yves Tanguy Attribution Research 2.1.5 Condition and the Surrealists 2.2 Background 2.2.1 Prior Technical Art History Studies of Surrealist Works 2.3 The Extant Problems of Yves Tanguy and His Oeuvre 2.3.1 Condition Issues in Surrealist Paintings That Challenge Authenticity as a Dichotomy 2.3.2 Current Status of Yves Tanguy’s Oeuvre 2.4 Extant Information on Tanguy’s Working Methods 2.5 Tanguy’s Methods 2.6 Tanguy’s Materials 2.7 Scientific Study of Yves Tanguy Works 2.7.1 Technical Imaging 2.8 Conclusions 2.9 Experimental Methods 2.9.1 Imaging methods 2.9.2 Spectroscopic methods 2.9.3 Elemental Analysis – X-Ray Fluorescence (XRF) References Chapter 3: Analytical Approaches to the Analysis of Paintings: An Overview of Methods and Materials 3.1 Introduction 3.2 Materials 3.2.1 Supports 3.2.2 Pigments 3.2.3 Traditional Paint Binders 3.2.4 Modern Paint Binders 3.2.5 Varnishes 3.3 Conclusions References Part II: Characterization of Paintings by Digital Techniques Chapter 4: Visible and Infrared Reflectance Imaging Spectroscopy of Paintings and Works on Paper 4.1 Introduction 4.2 Definition of Diffuse Reflectance Imaging Spectroscopy 4.3 Use of Diffuse Reflectance Imaging Spectroscopy in Cultural Heritage Science 4.4 Spectral Range of Hyperspectral Reflectance Cameras Used in Cultural Heritage Science 4.5 Instrumentation and Experimental Procedures for Reflectance Imaging Spectroscopic Studies (350–2500 nm) 4.6 Image Processing and Exploitation of Reflectance Image Cubes (350–2500 nm) 4.7 The Mid-IR Instrumentation, Experimental Procedures, and Image Processing (4000 cm−1 to 650 cm−1, 2.5 to 15.4 μm) 4.8 The Future of Reflectance Imaging Spectroscopy 4.9 Case Studies 4.9.1 Identification and Mapping of Artists’ Materials: Pigments 4.9.2 Identification and Mapping of Artists’ Materials: Paint Binders 4.9.3 The Earlier Composition of Fragonard’s Young Girl Reading References Chapter 5: Automated Analysis of Drawings at the Stroke Level for Attribution and Authentication Using Artificial Intelligence 5.1 Introduction 5.2 From Pictology to AI-Pictology 5.3 Challenges with Drawings 5.3.1 Case Study: Picasso, Matisse, and Schiele 5.4 Stroke Segmentation 5.5 Stroke Analysis and Recognition 5.5.1 Quantifying Stroke Characteristics 5.5.1.1 Stroke Shape Characteristics 5.5.1.2 Stroke Tonal Variations: Deep Learned Features Using RNNs 5.5.2 Stroke-Level Classification 5.5.3 Drawing Classification 5.6 Example Results and Validations 5.6.1 Segmentation Validation 5.6.2 Stroke Classification 5.6.2.1 Stroke Classification Validation – Technique Specific – Pairwise 5.6.2.2 Stroke Classification Validation – One-vs-All 5.6.3 Drawing Classification and Detection of Fakes 5.7 Conclusions References Part III: Material Characterization of Paintings by Instrumental Techniques Chapter 6: Analytical Pyrolysis of Organic Paint Materials for Authentication and Attribution 6.1 Introduction 6.2 The Analysis of Original and Restoration Materials in Ancient Polychromies and Paintings 6.2.1 An Etruscan Sarcophagus from the Fourth Century BC: “Sarcofago delle Amazzoni” 6.2.2 Mural Painting in a Roman Villa Dated 10 BC–5 AD: The Casa del Bicentenario in Herculaneum 6.2.3 Hierapolis of Phrygia First-Third Century AD (Pamukkale, Denizli, Turkey) 6.2.4 1385 AD ca – Annunciation and Saints by Giovanni del Biondo 6.2.5 Fourteenth–Seventeenth Century – Wall Paintings of the Monumental Cemetery of Pisa 6.2.6 Sixteenth Century Madonna con Bambino, Giovanni Pietro Rizzoli 6.3 Py-GC-MS Analysing Modern Paint Materials 6.4 Characterization of Organic Pigments 6.5 Conclusions References Chapter 7: Direct and Hyphenated Mass Spectrometry to Detect Glycerolipids and Additives in Paint 7.1 Introduction 7.1.1 Overview of the Use of Oil Paint Binders 7.1.1.1 Oil Paint 7.1.1.2 Oil Varnishes 7.1.1.3 Additives and Modifications 7.1.2 Chemistry of Oil Paints 7.1.2.1 Oil Composition 7.1.2.2 Pre-heating Process 7.1.2.3 Drying Process 7.1.2.4 Ageing Process 7.1.2.5 Degradation Phenomena 7.2 Mass Spectrometry 7.3 Chromatography – Mass Spectrometry 7.3.1 GC-MS 7.3.2 LC-MS 7.4 Direct MS 7.4.1 Spray Ionisation 7.4.1.1 ESI-MS 7.4.1.2 SAWN-MS 7.4.1.3 DESI-MS 7.4.2 MALDI MS 7.4.3 ToF-SIMS 7.4.4 Thermal Desorption and Pyrolysis Techniques 7.4.4.1 DTMS 7.4.4.2 EGA-MS 7.5 Glycerolipid Markers, Modifications and Additives 7.5.1 Lipid Markers and Relation to Ageing 7.5.1.1 Detection and Identification of Glycerolipid Binders 7.5.1.2 Distinction of Glycerides, Free Fatty Acids and Metal Carboxylates 7.5.1.3 Influence of Heat Treatment on Degree of Oxidation 7.5.2 Lipid Additives 7.5.3 Oil Paint Modifications 7.5.3.1 Oleoresinous Media 7.5.3.2 Alkyd Paints 7.5.3.3 Oil/Protein Mixtures 7.5.4 Degradation Studies 7.5.4.1 Saponification 7.5.4.2 Influence of Moisture 7.5.4.3 Water Sensitivity 7.5.5 Studies on Forgeries 7.6 Conclusion References Chapter 8: Fluorescence for the Analysis of Paintings 8.1 Introduction 8.2 Documentation of Paintings 8.3 Capturing Fluorescence Images 8.4 On the Fluorescence of Varnishes 8.4.1 Examples of Inspection of Varnish and Restorations on Paintings 8.4.2 A Note on UV Stabilised Varnishes and Assessing Condition 8.5 UV Fluorescence for the Analysis of Binding media 8.6 UV Fluorescence for the Analysis of Pigments 8.6.1 Inorganic Pigments 8.6.2 Organic Pigments 8.7 Conclusions References Chapter 9: Analysis of Natural and Synthetic Organic Lakes and Pigments by Chromatographic and Mass Spectrometric Techniques 9.1 Introduction 9.1.1 Natural Organic Lakes 9.1.2 Synthetic Organic Pigments (SOPs) 9.2 Analysis: Methods, Instrumentation, and Specific Issues 9.2.1 High Performance Liquid Chromatography (HPLC) and Ultra Performance Liquid Chromatography (UPLC) 9.2.2 Gas Chromatography – Mass Spectrometry (GC/MS) and Analytical Pyrolysis (Py-GC/MS) 9.2.3 Mass Spectrometry Based Techniques 9.2.4 Sample Preparation 9.2.5 Data Interpretation 9.3 A Further Analytical Issue: Photo-Degradation of Coloured Compounds 9.4 Case Studies 9.4.1 Commercial Paint Materials: Database of Manufacturers 9.4.2 Commercial Paint Materials: Comparison of Yellow Formulations 9.4.3 Ageing and a Cautionary Tale 9.4.4 Ageing and a Tale of Success 9.5 Conclusions References Chapter 10: Raman Analysis of Inorganic and Organic Pigments 10.1 Introduction 10.2 Theory of the Raman Effect 10.3 Laboratory Raman Spectroscopy 10.4 Direct and Mobile Raman Spectroscopy 10.5 Non-invasive Stratigraphic Analysis: SORS 10.6 Surface-Enhanced Raman Spectroscopy (SERS) 10.7 Conclusions References Chapter 11: Non-invasive and Non-destructive Examination of Artists’ Pigments, Paints and Paintings by Means of X-Ray Imaging Methods 11.1 Introduction 11.2 Principles of XRF and XRD Mapping 11.2.1 Principles of XRF 11.2.1.1 XRF Mapping: Regular and Confocal Mapping 11.2.1.2 Depth-Selective XRF 11.2.2 Principles of XRD 11.2.2.1 XRD Mapping in Two and Three Dimensions 11.3 Applications of MA-XRF and/or MA-XRD Mapping 11.3.1 Virtual Reconstructions and Retracing the Composition of the Original Artists’ Materials 11.3.1.1 Crystallite Orientation Within Paint Layers 11.3.2 Mapping of Degradation Products 11.4 Distinguishing Original from Add-On Paint and Detection of Counterfeit Artefacts 11.4.1 Example 1. Identification and localization of Different Smalt Types in ‘Saul and David’, Rembrandt 11.4.2 Example 2: Pigment Use and Layer Buildup of a Counterfeit ‘seventeenth century’ Flowerpiece 11.4.3 Example 3: Mary Magdalene, a Counterfeit ‘fifteenth century’ Panel by Renowned Restorer Jef Van der Veken 11.5 Conclusions References Chapter 12: Microchemical Imaging of Oil Paint Composition and Degradation: State-of-the-Art and Future Prospects 12.1 Introduction 12.2 Infrared-based Methods 12.2.1 μ-FTIR 12.2.2 AFM-IR 12.3 Methods Based on UV and Visible Light 12.3.1 PL Microimaging 12.3.2 Raman Microspectroscopy 12.4 Methods Based on X-Rays 12.4.1 μ-XRF 12.4.2 μ-XAS 12.4.3 μ-XRD 12.5 Methods Based on Charged Particle Beams 12.5.1 SEM-EDX 12.5.2 TEM 12.5.3 Imaging SIMS 12.6 Future Prospects 12.6.1 Improved Retrieval of Spatial Information 12.6.1.1 Improvements in Spatial Resolution 12.6.1.2 Increasing the Number of Analyzed Spatial Points 12.6.2 Improved Retrieval of Chemical Information 12.6.2.1 Semi-hyperspectral Total Synchronous PL Microimaging 12.6.2.2 Site-Selective and High-Energy Resolution μ-XANES 12.6.2.3 Energy-Dispersive μ-EXAFS 12.6.2.4 X-Ray Raman Scattering 12.6.2.5 SEM-Raman & Electron Backscatter Diffraction 12.6.2.6 Imaging MALDI Mass Spectrometry 12.6.3 Addressing the Limited Statistical Relevance of Analysis on Paint Microsamples 12.6.3.1 Three-Dimensional Microchemical Imaging 12.6.3.2 Object-Based Sub-surface Microchemical Imaging 12.6.4 Integrating Computational Methodologies in the Processing of Microchemical Data 12.7 Conclusion Glossary References Part IV: Isotopic Analysis for Authentication Chapter 13: Dating of Artwork by Radiocarbon 13.1 Radiocarbon Dating 13.1.1 Introduction 13.1.2 The 14C Dating Method 13.2 Measuring Techniques 13.2.1 Sample Pretreatment 13.2.2 Radiometry 13.2.3 Accelerator Mass Spectrometry 13.3 Timescale Calibration 13.4 Dating Artwork 13.4.1 General 13.4.2 Dating of Wood 13.4.3 Contamination 13.4.4 New Materials 13.4.5 Forgeries 13.4.6 The Radiocarbon “Artwork Convention” 13.5 Conclusions References Chapter 14: Lead Isotope Ratios of Lead White: From Provenance to Authentication 14.1 Introduction 14.2 Lead White Production 14.3 Lead Ore Deposits 14.4 The Isotopes of Lead 14.5 Lead Production 14.5.1 European Lead Production (Fifteenth to Seventeenth Century) 14.6 Lead Isotope Analysis 14.7 Current State-of-the-Art 14.7.1 Lead Isotope Ratios in Paintings: Provenance and Identification 14.7.2 Post Production Retouching and Modification 14.7.3 From Macro to Micro: Lead Isotope Ratios Within a Painting 14.7.4 Temporal Change in Lead Isotope Ratios of Lead White: A Case of Study for Seventeenth Century Dutch Paintings 14.8 Lead Isotope Tool Box for Identification 14.9 Conclusion Bibliography Part V: Case Studies Chapter 15: The Role of Technical Study and Chemical Analysis on Questions of Attribution and Dating of Paintings and on Easel Painting Conservation Practice: Selected Case Studies 15.1 Introduction 15.2 Case Studies 15.2.1 Dating, Assigning Geographical Origin 15.2.2 Physical History 15.2.2.1 Characterising and Imitating the Aging of Materials 15.2.3 Attribution 15.2.3.1 Signatures, Studio Practice and Collaborative Production 15.2.3.2 Review of Attribution Using New Analytical Evidence 15.3 Conclusion References Chapter 16: Approaches to Current Issues with Art Forgery, Restoration and Conservation: Legal and Scientific Perspectives 16.1 Case Studies Involving Art Forgery 16.2 Defining the Terminology: Fake v. Forgery 16.2.1 Contractual Protections for Buyers of Art 16.2.2 Tort Claims 16.3 Case Studies Involving Art Conservation 16.4 Defining Terminology: Distinctions Between Conservation, Restoration and Preservation 16.4.1 Artwork Owner’s Claims Against Conservators 16.4.2 Tort Claims 16.4.3 Contract Claims 16.4.4 Remedies 16.4.5 City of Amsterdam v. Daniel Goldreyer (1995) 16.4.6 Practical Considerations for Drafting Conservation Contracts 16.4.7 Moral Rights of Artists and Art Conservation 16.5 Conclusion References Forgeries present a daunting problem to art historians, museums, galleries and curators who face challenges in determining the authenticity of paintings. Recent progress in science has led to the development of new methods for investigating works of art, and can provide new insights into the materials found in paintings. The rise in the value of paintings together with the knowledge and skills of forgers highlights the need to develop reliable scientific procedures to identify fakes. Given the complexity of materials in paintings and the convergence of various disciplines, a methodological approach for investigations of paintings is based on art historical, curatorial, aesthetic, technical and scientific evaluation. In this book sophisticated digital and analytical techniques are reviewed for the identification of materials (pigments, binders, varnishes, adhesives) and the physical characteristics of paintings such as brushstrokes, craquelure and canvas weaves. This book presents an updated overview of both non-invasive and micro-invasive techniques that enable the material characterization of paintings. The materials constituting a painting are reviewed, as are ways that changes in materials over time can provide insights into chronology and physical history. State-of the art digital metods including multi and hyper-spectral imaging and computational approaches to data treatment will be presented. Analytical techniques developed and optimized to characterize binders, varnishes, and pigments are reviewed, focusing on materials which can provide information on ageing or provenance. Case studies of applications of synchrotron-based methods and the analysis of paintings are given, as are chapters devoted to legal aspects related to authenticity. Chapter 1 is available open access under a Creative Commons Attribution 4.0 International License via link.springer.com "Forgeries present a daunting problem to art historians, museums, galleries and curators who face challenges in determining the authenticity of paintings. Recent progress in science has led to the development of new methods for investigating works of art, and can provide new insights into the materials found in paintings. The rise in the value of paintings together with the knowledge and skills of forgers highlights the need to develop reliable scientific procedures to identify fakes. Given the complexity of materials in paintings and the convergence of various disciplines, a methodological approach for investigations of paintings is based on art historical, curatorial, aesthetic, technical and scientific evaluation. In this book sophisticated digital and analytical techniques are reviewed for the identification of materials (pigments, binders, varnishes, adhesives) and the physical characteristics of paintings such as brushstrokes, craquelure and canvas weaves. This book presents an updated overview of both non-invasive and micro-invasive techniques that enable the material characterization of paintings. The materials constituting a painting are reviewed, as are ways that changes in materials over time can provide insights into chronology and physical history. State-of the art digital metods including multi and hyper-spectral imaging and computational approaches to data treatment will be presented. Analytical techniques developed and optimized to characterize binders, varnishes, and pigments are reviewed, focusing on materials which can provide information on ageing or provenance. Case studies of applications of synchrotron-based methods and the analysis of paintings are given, as are chapters devoted to legal aspects related to authenticity.--Page 4 de la couverture