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Intro; Foreword; Preface; Contents; Contributors; About the Editors; 1 A Brief History of Metal Soaps in Paintings from a Conservation Perspective; 1.1 Introduction; 1.2 Past History; 1.3 Lead Soap Aggregates; 1.3.1 International Survey; 1.4 Other Lead Soap Manifestations; 1.5 Zinc, Potassium, Calcium, Copper, and Aluminum Soap Manifestations; 1.6 Time Frame; 1.7 Conservation Perspectives; 1.8 Outlook; References; Part I Formation, Migration and Environmental Influences; 2 Zinc Soaps: An Overview of Zinc Oxide Reactivity and Consequences of Soap Formation in Oil-Based Paintings
2.1 Introduction2.2 Zinc Oxide; 2.3 Fatty Acid Composition in Oil Mediums; 2.4 FTIR Characterization of Zinc Soaps; 2.5 Morphology Change; 2.6 Zinc White Paints with Added Stearates; 2.7 Formation of Crystalline Zinc Soaps; 2.8 Zinc Soaps and Paint Cleavage; 2.9 Zinc Soap Aggregates; 2.10 Mineralized Zinc Soap Aggregates; 2.11 Zinc Salt Formation and Surface Bloom; 2.12 Environmental Influences; 2.13 Conclusion; References; 3 Toward a Complete Molecular Model for the Formation of Metal Soaps in Oil Paints; 3.1 Introduction; 3.2 Oil Paint Drying: The Formation of Ionomer Networks
3.2.1 Carboxylate Formation During Oil Paint Drying3.2.2 Migration of Metal Ions Throughout the Polymeric Medium; 3.2.3 Formation of Ionomer-Like Binding Medium; 3.3 Oil Paint Deterioration: Metal Soap Formation in Ionomer Networks; 3.3.1 Free Fatty Acid Generation Through Ester Bond Hydrolysis; 3.3.2 The Crystallization of Metal Soaps; 3.4 Outlook; 3.5 Conclusions; References; 4 Understanding the Dynamics and Structure of Lead Soaps in Oil Paintings Using Multinuclear NMR; 4.1 Introduction; 4.2 Materials and Methods; 4.2.1 Synthesis of Materials; 4.2.2 NMR Methods; 4.2.3 Fitting Methods
4.2.4 Reaction of Samples at Different Relative Humidities4.3 Results; 4.3.1 Structure of Lead Soaps; 4.3.2 Local Molecular Dynamics of Soaps; 4.3.3 Kinetics of Soap Formation; 4.4 Conclusions; References; 5 Historical Evolutions of Lead-Fat/Oil Formula from Antiquity to Modern Times in a Set of European Pharmaceutical and Painting Treatises; 5.1 Introduction; 5.1.1 Pharmaceutical Domain; 5.1.2 Paint Domain; 5.2 Text Corpus; 5.2.1 Pharmaceutical Treatises; 5.2.2 Painting Treatises; 5.3 Choice of Ingredients and Proportions; 5.3.1 Lead-Based Ingredients; 5.3.1.1 Pharmaceutical Domain
5.3.1.2 Paint Domain5.3.2 Fat Ingredients; 5.3.2.1 Pharmaceutical Domain; 5.3.2.2 Paint Domain; 5.3.3 Proportions of Lead and Fat/Oil Compounds; 5.3.3.1 Pharmaceutical Domain; 5.3.3.2 Paint Domain; 5.4 Controlling the Operating Conditions: Use of Fire, Water, and Sunlight and the Grinding Level of Lead-Based Compounds; 5.4.1 Use of Fire and Control of the Temperature by the Use of Water; 5.4.1.1 Pharmaceutical Domain; 5.4.1.2 Paint Domain; 5.4.2 Use of Sunlight; 5.5 Conclusions; References; 6 Impact of Lead Soaps on the Formation of Age Craquelure; 6.1 Introduction; 6.2 Results and Discussion
2.1 Introduction2.2 Zinc Oxide; 2.3 Fatty Acid Composition in Oil Mediums; 2.4 FTIR Characterization of Zinc Soaps; 2.5 Morphology Change; 2.6 Zinc White Paints with Added Stearates; 2.7 Formation of Crystalline Zinc Soaps; 2.8 Zinc Soaps and Paint Cleavage; 2.9 Zinc Soap Aggregates; 2.10 Mineralized Zinc Soap Aggregates; 2.11 Zinc Salt Formation and Surface Bloom; 2.12 Environmental Influences; 2.13 Conclusion; References; 3 Toward a Complete Molecular Model for the Formation of Metal Soaps in Oil Paints; 3.1 Introduction; 3.2 Oil Paint Drying: The Formation of Ionomer Networks
3.2.1 Carboxylate Formation During Oil Paint Drying3.2.2 Migration of Metal Ions Throughout the Polymeric Medium; 3.2.3 Formation of Ionomer-Like Binding Medium; 3.3 Oil Paint Deterioration: Metal Soap Formation in Ionomer Networks; 3.3.1 Free Fatty Acid Generation Through Ester Bond Hydrolysis; 3.3.2 The Crystallization of Metal Soaps; 3.4 Outlook; 3.5 Conclusions; References; 4 Understanding the Dynamics and Structure of Lead Soaps in Oil Paintings Using Multinuclear NMR; 4.1 Introduction; 4.2 Materials and Methods; 4.2.1 Synthesis of Materials; 4.2.2 NMR Methods; 4.2.3 Fitting Methods
4.2.4 Reaction of Samples at Different Relative Humidities4.3 Results; 4.3.1 Structure of Lead Soaps; 4.3.2 Local Molecular Dynamics of Soaps; 4.3.3 Kinetics of Soap Formation; 4.4 Conclusions; References; 5 Historical Evolutions of Lead-Fat/Oil Formula from Antiquity to Modern Times in a Set of European Pharmaceutical and Painting Treatises; 5.1 Introduction; 5.1.1 Pharmaceutical Domain; 5.1.2 Paint Domain; 5.2 Text Corpus; 5.2.1 Pharmaceutical Treatises; 5.2.2 Painting Treatises; 5.3 Choice of Ingredients and Proportions; 5.3.1 Lead-Based Ingredients; 5.3.1.1 Pharmaceutical Domain
5.3.1.2 Paint Domain5.3.2 Fat Ingredients; 5.3.2.1 Pharmaceutical Domain; 5.3.2.2 Paint Domain; 5.3.3 Proportions of Lead and Fat/Oil Compounds; 5.3.3.1 Pharmaceutical Domain; 5.3.3.2 Paint Domain; 5.4 Controlling the Operating Conditions: Use of Fire, Water, and Sunlight and the Grinding Level of Lead-Based Compounds; 5.4.1 Use of Fire and Control of the Temperature by the Use of Water; 5.4.1.1 Pharmaceutical Domain; 5.4.1.2 Paint Domain; 5.4.2 Use of Sunlight; 5.5 Conclusions; References; 6 Impact of Lead Soaps on the Formation of Age Craquelure; 6.1 Introduction; 6.2 Results and Discussion